TW202035556A - Resin composition capable of obtaining a cured product excellent in lamination property and excellent in dielectric property and adhesiveness - Google Patents

Abstract

The present invention relates to a resin composition capable of obtaining a cured product excellent in lamination property and excellent in dielectric property and adhesiveness, and also relate to a resin sheet containing the resin composition, a printed wiring board having an insulating layer formed by using the resin composition, and a semiconductor device. The resin composition of the present invention includes (A) a maleimide compound having a biphenyl-type structure, (B) a liquid or semi-solid curing agent, and (C) a high molecular weight component.

Description

Resin composition

The present invention relates to a resin composition. It further relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition.

As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which an insulating layer and a conductor layer are alternately overlapped is known.

As an insulating material used for a printed wiring board of such an insulating layer, there is a resin composition disclosed in Patent Document 1, for example. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2018-053092

[Problem Solved by Invention]

In recent years, it is required to further improve the dielectric properties such as the dielectric rate and the dielectric loss tangent of the insulating layer, as well as the adhesion to the conductor layer formed by plating and the peel strength of the copper foil. Further improve.

Generally speaking, if the maleimide compound is contained in the resin composition, the dielectric properties can be improved. However, the maleimide compound usually has a high softening point, so if the maleimide compound contains In the case of a resin composition, the resin composition and its hardened product become brittle. In addition, when a resin sheet containing a resin composition with a maleimide compound is laminated on a substrate with irregularities to form an insulating layer, the opposite surface of the substrate of the insulating layer will follow the irregularities of the substrate, thereby reducing insulation The flatness of the layer makes the lamination worse.

The subject of the present invention is to provide a resin composition that can obtain a cured product having excellent lamination properties and excellent dielectric properties and adhesion; a resin sheet containing the resin composition; and a resin composition formed using the resin composition The insulating layer of printed wiring boards, and semiconductor devices. [Means to solve the problem]

The inventors of the present invention conducted a detailed review of the above-mentioned problems, and found that the above-mentioned problems can be solved by containing a predetermined maleimide compound, a curing agent in the form of a liquid or semi-solid component, and a high molecular weight component, and the present invention has been completed.

式(A-3)中，R³ 及R⁸ 表示馬來醯亞胺基，R⁴ 、R⁵ 、R⁶ 及R⁷ 各獨立表示氫原子、烷基或芳基，R⁹ 及R¹⁰ 各獨立表示取代基。a1及b1各獨立表示0～4的整數，m1及m2各獨立表示1～10的整數，n表示1～100的整數。 [3] (A)成分的含有量在將樹脂組成物中之不揮發成分作為100質量%時，為10質量%以上40質量%以下之如[1]或[2]所記載的樹脂組成物。 [4] (B)成分為選自胺系非固體成分狀硬化劑、(甲基)丙烯酸系非固體成分狀硬化劑、烯丙基系非固體成分狀硬化劑、馬來醯亞胺系非固體成分狀硬化劑及丁二烯系非固體成分狀硬化劑的至少1種之如[1]～[3]中任一所記載的樹脂組成物。 [5] (B)成分為烯丙基系非固體成分狀硬化劑，及馬來醯亞胺系非固體成分狀硬化劑中至少任一種之如[4]所記載的樹脂組成物。 [6] (B)成分的含有量在將樹脂組成物中之不揮發成分作為100質量%時，為0.1質量%以上15質量%以下之如[1]～[5]中任一所記載的樹脂組成物。 [7] (C)成分為熱塑性樹脂之如[1]～[6]中任一所記載的樹脂組成物。 [8] 熱塑性樹脂為選自聚醯亞胺樹脂、聚碳酸酯樹脂及苯氧基樹脂的至少1種之[7]所記載的樹脂組成物。 [9] (C)成分的含有量在將樹脂組成物中之不揮發成分作為100質量%時，為0.5質量%以上10質量%以下之如[1]～[8]中任一所記載的樹脂組成物。 [10] 進一步含有(D)無機填充材之如[1]～[9]中任一所記載的樹脂組成物。 [11] (D)成分的含有量在將樹脂組成物中之不揮發成分作為100質量%時，為50質量%以上之如[10]所記載的樹脂組成物。 [12] 絕緣層形成用之如[1]～[11]中任一所記載的樹脂組成物。 [13] 使用於形成導體層時的絕緣層形成上之如[1]～[12]中任一所記載的樹脂組成物。 [14] 含有支持體，與設置於該支持體上之含有如[1]～[13]中任一所記載的樹脂組成物之樹脂組成物層的樹脂薄片。 [15] 含有藉由如[1]～[13]中任一所記載的樹脂組成物之硬化物所形成的絕緣層之印刷配線板。 [16] 含有如[15]所記載的印刷配線板之半導體裝置。 [發明之效果]That is, the present invention includes the following contents. [1] A resin composition containing (A) a maleimide compound having a biphenyl type structure, (B) a liquid or semi-solid component curing agent, and (C) a high molecular weight component. [2] The component (A) is a resin composition as described in [1] represented by the following formula (A-3).

In formula (A-3), R ³ and R ⁸ represent a maleimide group, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ⁹ and R ¹⁰ each Independently represents a substituent. a1 and b1 each independently represent an integer from 0 to 4, m1 and m2 each independently represent an integer from 1 to 10, and n represents an integer from 1 to 100. [3] The content of component (A) is the resin composition as described in [1] or [2] when the non-volatile content in the resin composition is 100% by mass, 10% by mass or more and 40% by mass or less . [4] Component (B) is selected from amine non-solid component hardener, (meth)acrylic non-solid component hardener, allyl-based non-solid component hardener, maleimide non-solid component hardener At least one of the solid component curing agent and the butadiene-based non-solid component curing agent is the resin composition described in any one of [1] to [3]. [5] The component (B) is the resin composition described in [4], which is at least one of an allyl-based non-solid component-like curing agent and a maleimide-based non-solid component-like curing agent. [6] The content of component (B), when the non-volatile content in the resin composition is 100% by mass, is 0.1% by mass to 15% by mass as described in any of [1] to [5] Resin composition. [7] The component (C) is a resin composition as described in any one of [1] to [6], which is a thermoplastic resin. [8] The thermoplastic resin is the resin composition described in [7] of at least one selected from polyimide resins, polycarbonate resins, and phenoxy resins. [9] The content of component (C) is 0.5% by mass or more and 10% by mass or less when the non-volatile content in the resin composition is 100% by mass, as described in any of [1] to [8] Resin composition. [10] The resin composition as described in any one of [1] to [9], which further contains (D) an inorganic filler. [11] The content of the component (D) is the resin composition as described in [10] at 50% by mass or more when the non-volatile content in the resin composition is 100% by mass. [12] The resin composition as described in any one of [1] to [11] for forming an insulating layer. [13] The resin composition as described in any one of [1] to [12] used for forming an insulating layer when forming a conductor layer. [14] A resin sheet containing a support, and a resin composition layer containing the resin composition described in any one of [1] to [13] provided on the support. [15] A printed wiring board containing an insulating layer formed of a cured product of the resin composition as described in any one of [1] to [13]. [16] A semiconductor device containing the printed wiring board as described in [15]. [Effects of Invention]

According to the present invention, there is provided a resin composition that can obtain a cured product having excellent laminate properties, excellent dielectric properties and adhesion; a resin sheet containing the resin composition; and a resin composition having an insulating layer formed using the resin composition Printed wiring boards, and semiconductor devices.

[Type of Implementation of Invention]

Hereinafter, the present invention will be described in detail through the preferred embodiment. However, the present invention is not limited to the following embodiments and exemplified materials, and can be implemented with arbitrarily changed without departing from the scope of the present invention and its equivalent scope.

[Resin composition] The resin composition of the present invention contains (A) a maleimide compound having a biphenyl type structure, and (B) a liquid or semi-solid component hardener (hereinafter referred to as a liquid or semi-solid component hardener Appropriately called "non-solid component-like hardener"), and (C) high molecular weight component. In the present invention, by containing the components (A) to (C), it is possible to obtain a cured product having excellent lamination properties and excellent dielectric properties and adhesion.

The resin composition is combined with components (A) to (C), and may further contain optional components. Examples of optional components include (D) inorganic fillers, (E) curing agents, (F) curing accelerators, (G) epoxy resins, (H) polymerization initiators, and (I) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Maleimide compound with biphenyl type structure> The resin composition contains (A) a maleimide compound having a biphenyl type structure as the component (A). By including the component (A) in the resin composition, a cured product with excellent dielectric properties can be obtained. (A) A component can be used individually by 1 type, and can also use 2 or more types together.

式(A-2)中，R¹ 及R² 各獨立表示取代基。a及b各獨立表示0～4的整數。*表示鍵結處。The component (A) is a compound containing a maleimide group represented by the following formula (A-1) in the molecule. In addition, the component (A) has a biphenyl type structure from the viewpoint of obtaining a cured product having excellent dielectric properties. The biphenyl type structure means a structure represented by the following formula (A-2).

In formula (A-2), R ¹ and R ² each independently represent a substituent. a and b each independently represent an integer of 0-4. * Indicates the bond point.

Examples of the substituents represented by R ¹ and R ² include halogen atoms, -OH, -OC _1-10 alkyl, -N(C _1-10 alkyl) ₂ , C _1-10 alkyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-10 alkyl, -COOH, -C(O)H, -NO ₂ and so on. Here, the term "C _xy "(x and y are positive integers and satisfy x<y) means that the number of carbon atoms of the organic group described after the term is x to y. For example, the expression of "C _1-10 alkyl group" means an alkyl group having 1 to 10 carbon atoms. These substituents may combine with each other to form a ring, and the ring structure may also contain a spiro ring or a condensed ring.

The above-mentioned substituent may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, unless otherwise stated, the same one as the above-mentioned substituent can be used.

a and b each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, preferably 0 or 1, and more preferably 0.

From the viewpoint of obtaining a cured product with excellent dielectric properties for the component (A), the component (A) preferably has a maleimide group at both ends.

(A) From the viewpoint of obtaining a cured product with excellent dielectric properties, component (A) has, in addition to the biphenyl type structure, one of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Both of the group hydrocarbon groups are preferred. The term "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring. However, the aromatic hydrocarbon group does not need to be composed only of an aromatic ring, and may contain a chain structure or an alicyclic hydrocarbon group in this part, and the aromatic ring may be any of monocyclic, polycyclic, and heterocyclic rings.

As the aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group is preferred, a divalent saturated aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. As the alkylene group, an alkylene having 1 to 10 carbon atoms is preferred, an alkylene having 1 to 6 carbon atoms is preferred, and an alkylene having 1 to 3 carbon atoms is more preferred. Methylene is particularly preferred.

As the aromatic hydrocarbon group, a divalent aromatic hydrocarbon group is preferable, an arylene group and an aralkyl group are preferable, and an arylene group is more preferable. As the arylene group, an arylene group having 6 to 30 carbon atoms is preferable, an arylene group having 6 to 20 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Examples of such arylene groups include phenylene, naphthylene, anthrylene, and biphenylene. As the aralkylene group, an aralkylene group having 7 to 30 carbon atoms is preferred, an aralkylene group having 7 to 20 carbon atoms is preferred, and an aralkylene group having 7 to 15 carbon atoms is preferred. Better. As such an aralkylene group, a group having a benzylidene group and a biphenylene-methylene structure can be mentioned. Among these, groups having phenylene, benzylidene, and biphenylene-methylene structures are also preferred, and phenylene is preferred.

(A) The number of maleimide groups per molecule in the component, from the viewpoint of obtaining a cured product with excellent dielectric properties, is preferably 1 or more, preferably 2 or more, and more preferably It is 3 or more, preferably 10 or less, preferably 6 or less, and more preferably 3 or less.

Regarding the component (A), from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable that the nitrogen atom of the maleimide group can be directly bonded to the aromatic hydrocarbon group. Among them, the so-called "direct" in the term means that there is no other group between the nitrogen atom of the maleimide group and the aromatic hydrocarbon group.

式(A-3)中，R³ 及R⁸ 表示馬來醯亞胺基，R⁴ 、R⁵ 、R⁶ 及R⁷ 各獨立表示氫原子、烷基或芳基，R⁹ 及R¹⁰ 各獨立表示取代基。a1及b1各獨立表示0～4的整數，m1及m2各獨立表示1～10的整數，n表示1～100的整數。(A) It is preferable that a component has a structure represented by following formula (A-3), for example.

In formula (A-3), R ³ and R ⁸ represent a maleimide group, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ⁹ and R ¹⁰ each Independently represents a substituent. a1 and b1 each independently represent an integer from 0 to 4, m1 and m2 each independently represent an integer from 1 to 10, and n represents an integer from 1 to 100.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferred.

As the alkyl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ , an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is preferred. The alkyl group of 3 is more preferable. The alkyl group may be linear, branched or cyclic. Examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl and the like.

The aryl group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 15 carbon atoms is more preferred, and an aryl group having 6 to 15 carbon atoms is preferred. The aryl group of 10 is more preferable. The aryl group may be a monocyclic ring or a condensed ring. As such an aryl group, a phenyl group, a naphthyl group, an anthryl group, etc. are mentioned, for example.

The alkyl and aryl groups in R ⁴ , R ⁵ , R ⁶ and R ⁷ may have substituents. The substituent is the same as R ¹ in formula (A-2).

R ⁹ and R ¹⁰ each independently represent a substituent and are the same as R ¹ and R ^{2 in} formula (A-2).

a1 and b1 each independently represent an integer of 0 to 4, and are the same as a and b in formula (A-2).

m1 and m2 each independently represent an integer of 1 to 10, preferably 1 to 6, preferably 1 to 3, more preferably 1 to 2, and 1 is even more preferred.

n represents an integer of 1-100, preferably 1-50, preferably 1-20, more preferably 1-5.

R ³ and R ⁸ represent a maleimide group, and the maleimide group is directly bonded to an aromatic hydrocarbon group. The maleimide group represented by R ³ and R ⁸ is based on (CH ₂ ) _m1 or (CH ₂ ) _m2 bonded to an aromatic hydrocarbon group, and is based on any of the ortho, meta, and para positions The better is better, and the direct bonding is better.

式(A-4)中，R¹¹ 及R¹⁶ 表示馬來醯亞胺基，R¹² 、R¹³ 、R¹⁴ 及R¹⁵ 各獨立表示氫原子、烷基或芳基。m3及m4各獨立表示1～10的整數，n1表示1～100的整數。As the (A) component, it is preferable to have a structure represented by formula (A-4).

In the formula (A-4), R ¹¹ and R ¹⁶ represent a maleimide group, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group. m3 and m4 each independently represent an integer of 1-10, and n1 represents an integer of 1-100.

R ¹¹ and R ¹⁶ represent a maleimide group, and are the same as R ³ and R ^{8 in} formula (A-3).

R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an alkyl group or an aryl group, and are the same as R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formula (A-3).

m3 and m4 each independently represent an integer of 1 to 10, and are the same as m1 and m2 in formula (A-3).

n1 represents an integer of 1-100, and is the same as n in formula (A-3).

式(A-5)中，R¹⁷ 及R¹⁸ 表示馬來醯亞胺基。n2表示1～100的整數。As (A) component, what has a structure represented by formula (A-5) is preferable.

In formula (A-5), R ¹⁷ and R ¹⁸ represent a maleimino group. n2 represents an integer of 1-100.

R ¹⁷ and R ¹⁸ represent a maleimide group, and are the same as R ³ and R ^{8 in} formula (A-3).

n2 represents an integer of 1-100, and is the same as n in formula (A-3).

(A) Ingredients can be sold. As a sold product, for example, "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. can be cited.

(A) The content of component, from the viewpoint of obtaining a cured product with excellent dielectric properties, when the non-volatile content in the resin composition is 100% by mass, 10% by mass or more is preferred, and 20 Mass% or more, more preferably 25% by mass or more, preferably 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less. In addition, in the present invention, the content of each component in the resin composition is a value when the non-volatile component in the resin composition is 100% by mass unless otherwise stated.

＜(B) Liquid or semi-solid component hardener＞ The resin composition contains (B) a liquid or semi-solid component curing agent as the (B) component. By including the component (B) in the resin composition, it is possible to improve the laminating properties, and it is possible to obtain a cured product with excellent adhesion. (B) A component may be used individually by 1 type, and may use 2 or more types together.

Among them, the determination of liquid, semi-solid component and solid component is based on the second "Method of Confirmation of Liquid State" in the Annex of the Provincial Order (Heisei First Year Autonomous Province Order No. 1) concerning the test and properties of dangerous substances. get on. The specific determination method is as follows.

(1) Device Constant temperature water tank: Use pre-mixer, heater, thermometer, automatic temperature regulator (the temperature can be controlled at ±0.1℃) and the depth is 150mm or more. In addition, in the judgment of the thermosetting resin used in the following examples, a combination of a low-temperature thermostatic water tank (model BU300) made by Yamato Scientific Co., Ltd. and an input thermostat Thermomate (model BF500) was used, and approximately 22 liters of tap water was used. Put it into the low temperature constant temperature water tank (type BU300), input the power supply of the Thermo mate (type BF500) installed here and set the set temperature (20℃ or 60℃), and adjust the water temperature to the setting with the Thermo mate (type BF500) The temperature is ±0.1°C, any device can be used if it is a device that can be adjusted in the same way.

Test tube: As the test tube, as shown in Figure 1, it is made of transparent glass with an inner diameter of 30mm and a height of 120mm. The height of 55mm and 85mm from the bottom of the tube is marked as 11A and 12B. The test tube The test tube 10a for judging the liquid state whose mouth is sealed with a rubber plug 13a, is marked with the same size as the same mark, inserts a thermometer in the center, and seals the test tube mouth with a rubber plug 13b with a hole to be inserted and supported. Use The temperature measurement test tube 10b of the thermometer 14 is inserted into the rubber plug 13b. The marking line with a height of 55mm from the bottom of the tube is marked as "Line A", and the marking line with a height of 85mm from the tube bottom is marked as "Line B". As the thermometer 14, although the freezing point tester specified in JIS B7410 (1982) "Glass Thermometer for Petroleum Testing" (SOP-58 scale range 0-100℃) is used, it can only be measured in the temperature range of 0-100℃ Who can.

(2) Implementation procedures of the test Put the samples that have been left for more than 24 hours under the atmospheric pressure of 60±5℃, and put them into the test tube 10a for judging the liquid state shown in Fig. 1(a) and the test for temperature measurement shown in Fig. 1(b) Pipe 10b to 11A line. The two test tubes 10a, 10b are erected and placed in a low-temperature constant-temperature water tank so that line 12B is below the water surface. The thermometer is placed so that its lower end is 30mm lower than the 11A line. After the sample temperature reaches the set temperature ±0.1°C, keep this state for 10 minutes. After 10 minutes, take out the test tube 10a for judging the liquid state from the low temperature and constant temperature water tank, and immediately lay it flat on the horizontal test bench. The movement time of the tip of the liquid level in the test tube from line 11A to line 12B is measured by the stopwatch. Measure and record.

Similarly, for a sample placed at an atmospheric pressure at a temperature of 20±5°C for more than 24 hours, perform the same test as when placed at an atmospheric pressure at a temperature of 60±5°C for more than 24 hours. The liquid level in the test tube The movement time from line 11A to line 12B is measured and recorded with a stopwatch.

At 20°C, those whose measured time is within 90 seconds are judged to be liquid. If the measured time exceeds 90 seconds at 20°C, and if the measured time is less than 90 seconds at 60°C, it is judged as a semi-solid component. At 60°C, those whose measured time exceeds 90 seconds were judged to be solid.

As the (B) component, it is in the form of a liquid or semi-solid component, and what has a function of hardening the (A) component can be used. As such non-solid component hardeners, for example, selected from allyl-based non-solid component hardeners, maleimide-based non-solid component hardeners, (meth)acrylic non-solid component-like hardeners, amines It is preferably at least one of non-solid component hardener and butadiene-based non-solid component hardener. Allyl-based non-solid component hardener and maleimide-based non-solid component hardener are preferred At least any one of the agents is preferred.

The term "allyl-based non-solid component hardener" refers to a compound in the form of a liquid or semi-solid component and having at least one allyl group in its molecule. The allyl group has the function of reacting with the maleimide group in the component (A) to harden the component (A). The allyl-based non-solid component curing agent preferably has one or more allyl groups in one molecule, and preferably has two or more allyl groups. The lower limit is not particularly limited, but is preferably 10 or less, and preferably 5 or less.

In addition, the allyl-based non-solid component hardening agent has a benzoxazine ring, a phenol ring, an epoxy group, and a ring in addition to the allyl group from the standpoint of achieving the desired effect of the present invention. Either one of the carboxylic acid derivatives having a morphological structure is preferable, and from the viewpoint that the desired effect of the present invention can be more remarkably obtained, one having a benzoxazine ring is preferable.

Regarding the allyl-based non-solid component hardener having a benzoxazine ring, the allyl group is from the viewpoint that the desired effect of the present invention can be remarkably obtained, and is combined with the nitrogen atom constituting the benzoxazine ring and the composition It is preferable that any one of the carbon atoms of the benzoxazine ring is bonded, and the one that is bonded to a carbon atom is more preferable.

式(B-1)中，R²⁰ 及R²¹ 表示烯丙基，R²² 表示q價基。q表示1～4的整數，p1表示0～4的整數，p2表示0～2的整數。As an allyl-based non-solid component hardener having a benzoxazine ring, for example, an allyl-based non-solid component hardener having a benzoxazine ring represented by the following formula (B-1) is good.

In the formula (B-1), R ²⁰ and R ²¹ represent an allyl group, and R ²² represents a q-valent group. q represents an integer of 1 to 4, p1 represents an integer of 0 to 4, and p2 represents an integer of 0 to 2.

The q-valent group represented by R ²² is preferably an allyl group, a q-valent aromatic hydrocarbon group, a q-valent aliphatic hydrocarbon group, an oxygen atom, or a q-valent group formed by a combination of these. When R ²² has an allyl group, the allyl group may be a substituent of either a q-valent aromatic hydrocarbon group or a q-valent aliphatic hydrocarbon group. For example, when q is 2, R ²² is preferably a group formed by an arylene group, an alkylene group, an oxygen atom, or a combination of these two or more divalent groups, and an arylene group or two or more divalent groups is preferred. A base formed by a combination of groups is preferable, and a base formed by a combination of two or more divalent groups is more preferable.

As the arylene group in R ²² , an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is preferable, and an arylene group having 6 to 12 carbon atoms is preferable Better. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, biphenylene, and the like, and phenylene is preferred.

The alkylene group in R ²² is preferably an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 1 to 3 carbon atoms. Better. Specific examples of the alkylene group include, for example, a methylene group, an ethylene group, and a propylene group, and a methylene group is preferred.

As the group formed by the combination of two or more divalent groups in R ²² , for example, a group in which 1 or more arylene groups are bonded to 1 or more oxygen atoms; for example, an aryl group- The group of alkylene-arylene structure, etc., is a group in which 1 or more arylene groups are bonded to 1 or more alkylene groups; groups in which 1 or more alkylene groups are bonded to 1 or more oxygen atoms; 1 The above arylene group and 1 or more alkylene groups are bonded to 1 or more oxygen atoms, etc., 1 or more arylene groups are bonded to 1 or more oxygen atoms, and 1 or more arylene groups The group bonded to the alkylene group of 1 or more is preferable.

q represents an integer of 1 to 4, preferably represents an integer of 1 to 3, and preferably represents 1 or 2.

p1 represents an integer of 0 to 4, preferably an integer of 0 to 2, preferably 0 or 1, and more preferably 1. p2 represents an integer of 0-2, preferably 0 or 1, and preferably 0.

式(B-2)中，R²³ 、R²⁴ 及R²⁵ 各獨立表示烯丙基，s1各獨立表示0～4的整數，s2各獨立表示0～3的整數，r表示0～3的整數。Examples of allyl-based non-solid component hardeners having a phenol ring include allyl-containing cresol resins, allyl-containing novolac-type phenol resins, and allyl-containing cresol novolac resins. Wait. Among them, the allyl-based non-solid component-like curing agent having a phenol ring is preferably an allyl-based non-solid component-like curing agent having a phenol ring represented by the following formula (B-2).

In formula (B-2), R ²³ , R ²⁴ and R ²⁵ each independently represent an allyl group, s1 each independently represents an integer from 0 to 4, s2 each independently represents an integer from 0 to 3, and r represents an integer from 0 to 3 .

R ²³ to R ²⁵ each independently represent an allyl group. In the formula (B-2), the number of allyl groups is preferably 1 or more, preferably 2 or more, more preferably 3 or more, preferably 25 or less, preferably 10 or less, and more Preferably it is 5 or less.

s1 each independently represents an integer of 0-4, preferably an integer of 1-3, and preferably an integer of 1-2.

s2 each independently represents an integer of 0 to 3, preferably an integer of 1 to 3, and preferably an integer of 1 to 2.

r represents an integer of 0 to 3, preferably an integer of 0 to 2, and preferably an integer of 1-2.

The allyl-based non-solid component curing agent having epoxy groups is preferably one having two or more epoxy groups in one molecule. In addition, the allyl-based non-solid component curing agent with epoxy groups is preferably one having an aromatic structure. When two or more types of allyl-based non-solid component curing agents with epoxy groups are used, at least 1 Species with aromatic structure are preferred. The so-called aromatic structure generally refers to a chemical structure defined as aromatic, and also contains polycyclic aromatics and aromatic heterocycles. As the allyl-based non-solid component hardener having epoxy groups, those having a bisphenol structure are preferred. Examples of the bisphenol structure include bisphenol A type, bisphenol F type, and bisphenol AF type. Among them, from the viewpoint that the effects of the present invention can be significantly achieved, bisphenol A type is preferred.

As the allyl-based non-solid component hardener containing a carboxylic acid derivative having a cyclic structure, a carboxylic acid allyl group having a cyclic structure is preferred. As the cyclic structure, any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure may be used. In addition, the cyclic group may be a skeleton of a ring formed by heteroatoms other than carbon atoms. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, and a nitrogen atom is preferable. The hetero atom may have one in the aforementioned ring, or may have two or more. The carboxylic acid derivative with a cyclic structure is to improve the compatibility and dispersibility of the resin paint through the network structure of the cyclic structure. As a result, the laminating property can be improved and the curing with excellent adhesion can be further obtained. Things.

Examples of carboxylic acids having a cyclic structure include isocyanuric acid, phthalic acid, phthalic acid, and cyclohexanedicarboxylic acid. Examples of allyl-based non-solid component hardeners containing carboxylic acid derivatives having a cyclic structure include allyl isocyanurate, diallyl isocyanurate, and triene isocyanurate. Propyl ester, diallyl phthalate, allyl phthalate, ortho-diallyl phthalate, meta-diallyl phthalate, para-diallyl Phthalates, allyl cyclohexane dicarboxylate, diallyl cyclohexane dicarboxylate, etc.

Allyl-based non-solid component hardeners can be sold. Examples of commercially available products include "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., "MEH-8005" (an allyl-based non-solid component hardener having a phenol ring); and "RE-810NM manufactured by Nippon Kayaku Co., Ltd." "(Allyl-based non-solid component hardener with epoxy group); "ALP-d" (Allyl-based non-solid component hardener with benzoxazine ring) manufactured by Shikoku Chemical Industry Co., Ltd.; "L-DAIC" made by Shikoku Kasei Kogyo Co., Ltd. (Allyl-based non-solid component hardener with isocyanuric ring); "TAIC" made by Nippon Kasei Co., Ltd. (allyl with isocyanuric ring) Base-based non-solid component hardener (Triallyl isocyanurate); "MDAC" manufactured by Osaka Soda (Allyl-based non-solid component hardener with cyclohexanedicarboxylic acid derivative) ; "DAD" (diallyl phthalate) made by NISSHOKU TECHNO FINE CHEMICAL CO., LTD.; "DAISO DAP™ Monomer" (ortho diallyl phthalate) made by Osaka Soda.

The allyl equivalent of the allyl-based non-solid component hardener, from the viewpoint of remarkably obtaining the desired effect of the present invention, is preferably 20g/eq.～1000g/eq., more preferably 50g/eq.～ 500g/eq., more preferably 100g/eq.～300g/eq. The allyl equivalent is the mass of the allyl-based non-solid component hardener containing 1 equivalent of allyl.

The term "maleimide-based non-solid component hardener" means a compound in the form of a liquid or semi-solid component and having at least one maleimide group in its molecule. However, except for those equivalent to component (A).

The maleimide-based non-solid component hardening agent preferably contains at least one of an alkyl group having 5 or more carbon atoms and an alkylene having 5 or more carbon atoms.

The number of carbon atoms of the alkyl group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, preferably 45 or less, and more preferably 40 or less. The alkyl group may be any one of linear, branched, and cyclic, and among them, linear is preferred. Examples of such alkyl groups include pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group having 5 or more carbon atoms may have an alkylene group having 5 or more carbon atoms as a substituent.

The number of carbon atoms of the alkylene group having 5 or more carbon atoms is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. The alkylene group may be linear, branched, and cyclic, and among them, linear is also preferred. Here, when the cyclic alkylene group is composed of only a cyclic alkylene group, it also includes the concept of including both a linear alkylene group and a cyclic alkylene group. Examples of such alkylene groups include pentylene, hexylene, heptylene, octylene, nonylylene, decylene, undecylene, dodecylene, and tridecylene. , Heptadecyl, Hexatriacontylene, a group with octylene-cyclohexene structure, a group with octylene-cyclohexene-octylene structure, and propylene-cyclohexylene -The base of Xinxin structure, etc.

From the viewpoint that the effect of the present invention can be remarkably obtained, the maleimide-based non-solid component curing agent preferably contains both an alkyl group having 5 or more carbon atoms and an alkylene having 5 or more carbon atoms .

An alkyl group having 5 or more carbon atoms and an alkylene having 5 or more carbon atoms may be bonded to each other to form a ring, and the ring structure may also include a spiro ring or a condensed ring. Examples of the ring formed by bonding to each other include a cyclohexane ring and the like.

The alkyl group having 5 or more carbon atoms and the alkylene having 5 or more carbon atoms preferably have no substituents, but they may also have substituents. As the substituent, the substituent represented by R ¹ in the above formula (A-2) is the same.

For the maleimide-based non-solid component hardener, an alkyl group with 5 or more carbon atoms and an alkylene group with 5 or more carbon atoms are preferably directly bonded to the nitrogen atom of the maleimide group .

The number of maleimide groups per molecule in the maleimide-based non-solid component hardener may be 1, but is preferably 2 or more, preferably 10 or less, more preferably 6 or less, Especially preferred is 3 or less. The effect of the present invention can be remarkably obtained by using a maleimide-based non-solid component-like hardener having two or more maleimide groups per molecule.

一般式(B-3)中，M表示可具有取代基之碳原子數5以上的伸烷基，L表示單鍵或2價連結基。The maleimide-based non-solid component-like hardener is preferably a maleimide-based non-solid component-like hardener represented by the following general formula (B-3).

In general formula (B-3), M represents an optionally substituted alkylene group having 5 or more carbon atoms, and L represents a single bond or a divalent linking group.

M represents an alkylene group having 5 or more carbon atoms which may have a substituent. The alkylene group of M is the same as the alkylene group having 5 or more carbon atoms. The substituent of M is the same as the substituent represented by R ¹ in general formula (A-2), and the substituent is preferably an alkyl group with 5 or more carbon atoms.

L represents a single bond or a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, alkynylene, arylene, -C(=O)-, -C(=O)-O-, -NR ⁰ -(R ⁰ Is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), an oxygen atom, a sulfur atom, C(=O)NR ⁰ -, a divalent group derived from phthalimide, and a dihydric group derived from pyromellitic acid A divalent group of an amine and a group formed by a combination of two or more of these divalent groups, etc. From alkylene, alkenylene, alkynylene, aryl, divalent group derived from phthalimide, divalent group derived from pyromellitic acid diimide, and a combination of two or more divalent groups The formed group may have an alkyl group having 5 or more carbon atoms as a substituent. The divalent group derived from phthalimide means a divalent group derived from phthalimide, and is specifically a group represented by general formula (A). The divalent group derived from pyromellitic acid diimide means a divalent group derived from pyromellitic acid diimide, and is specifically a group represented by general formula (B). In the formula, "*" represents the bonding location.

As the alkylene group of the divalent linking group in L, an alkylene having 1 to 50 carbon atoms is preferred, an alkylene having 1 to 45 carbon atoms is preferred, and an alkylene having 1 to 40 carbon atoms is preferred. The alkylene is particularly preferred. The alkylene group may be linear, branched, or cyclic. As such an alkylene group, for example, methylethylene group, cyclohexylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylylene group, decylene group, undecylene group, hexylene group Dodecyl, tridecylene, heptadecylene, hexadecatrienyl, groups with octylene-cyclohexylene structure, groups with octylene-cyclohexylene-octylene structure, The group of propylene-cyclohexene-octyl and so on.

As the alkenylene group of the divalent linking group in L, an alkenylene group having 2 to 20 carbon atoms is preferred, an alkenylene group having 2 to 15 carbon atoms is preferred, and an alkenylene group having 2 to 10 carbon atoms is preferred. Alkenylene is particularly preferred. The alkenylene group may be linear, branched, or cyclic. Examples of such alkenylene groups include methylvinylene, cyclohexenylene, pentenyl, hexenyl, heptenylene, and octenylene.

As the alkynylene group of the divalent linking group in L, the alkynylene group having 2 to 20 carbon atoms is preferred, the alkynylene group having 2 to 15 carbon atoms is preferred, and the alkynylene group having 2 to 10 carbon atoms is preferred. Alkynylene is particularly preferred. The alkynylene group may be linear, branched, or cyclic. Examples of such alkynylene groups include methylethynylene, cyclohexynylene, pentynylene, hexynylene, heptynylene, and octylenyl.

As the arylene group of the divalent linking group in L, an arylene group having 6 to 24 carbon atoms is preferable, an arylene group having 6 to 18 carbon atoms is preferable, and an arylene group having 6 to 14 carbon atoms is preferable The arylene group is more preferable, and the arylene group having 6 to 10 carbon atoms is more preferable. As the arylene group, for example, a phenylene group, a naphthylene group, an anthrylene group, etc. may be mentioned.

The alkylene group, alkenylene group, alkynylene group, and arylene group of the divalent linking group in L may have a substituent. The substituent is the same as the substituent represented by R ¹ in the general formula (A-2), and is preferably an alkyl group having 5 or more carbon atoms.

As a group formed by a combination of two or more divalent groups in L, for example, a divalent group formed by a combination of an alkylene group, a divalent group derived from phthalimide, and an oxygen atom; A combination of a divalent group derived from phthalimide, an oxygen atom, an aryl group, and an alkylene group; a combination of an alkylene group and a divalent group derived from pyromellitic acid diimidine The resulting divalent base, etc. The group formed by the combination of two or more types of divalent groups may form a ring such as a condensed ring formed by the combination of each group. In addition, the group formed by a combination of two or more divalent groups may be a repeating unit having 1-10 repeating units.

Among them, as L in the general formula (B-3), the oxygen atom may have a substituted C6-C24 arylene group, may have a substituted C1-C50 alkylene group, carbon An alkyl group with 5 or more atoms, a divalent group derived from phthalimide, a divalent group derived from pyromellitic acid diimide, or a divalent group formed by a combination of two or more of these groups Better. Among them, L is also used as an alkylene group; a divalent structure having an alkylene group-a divalent group derived from phthalimide-an oxygen atom-a divalent group derived from phthalimide Group; has an alkylene group-a divalent group derived from phthalimide-oxygen atom-arylene group-alkylene group-an aryl group-oxygen atom-a divalent group derived from phthalimide The divalent group of the structure; the divalent group having the structure of alkylene-derived from pyromellitic acid diimide is preferred.

一般式(B-4)中，M¹ 各獨立表示可具有取代基的碳原子數5以上的伸烷基，A各獨立表示具有可具有取代基的碳原子數5以上的伸烷基或可具有取代基的芳香環之2價基。t表示1～10的整數。The maleimide-based non-solid component-like hardener represented by general formula (B-3) is preferably a maleimide-based non-solid component-like hardener represented by general formula (B-4).

In general formula (B-4), each of M ¹ independently represents an optionally substituted alkylene group having 5 or more carbon atoms, and each independently represents an optionally substituted alkylene group having 5 or more carbon atoms or A divalent group of an aromatic ring having a substituent. t represents an integer of 1-10.

M ¹ each independently represents an alkylene group having 5 or more carbon atoms which may have a substituent. M ¹ is the same as M in the general formula (B-3).

A each independently represents a divalent group having an optionally substituted alkylene group having 5 or more carbon atoms or an optionally substituted aromatic ring. The alkylene group in A may be any of chain, branched, and cyclic. Among them, a sub-ring, that is, a cyclic alkylene having 5 or more carbon atoms having a substituent is preferred. The number of carbon atoms of the alkylene group is preferably 6 or more, more preferably 8 or more, more preferably 50 or less, preferably 45 or less, more preferably 40 or less. As such an alkylene group, for example, a group having an octylene-cyclohexene structure, a group having an octylene-cyclohexene-octylene structure, a group having a propylene-cyclohexene-octylene structure, etc. .

Examples of the aromatic ring in the divalent group having an aromatic ring represented by A include a benzene ring, a naphthalene ring, an anthracene ring, a phthalimide ring, a pyromellitic acid diimide ring, and aromatic Heterocyclic ring, etc., preferably benzene ring, phthalimide ring, and pyromellitic acid diimide ring. That is, as a divalent group having an aromatic ring, a divalent group having an optionally substituted benzene ring, a divalent group having an optionally substituted phthalimide ring, and an optionally substituted divalent group The divalent group of the pyromellitic acid diimide ring is preferred. As the divalent group having an aromatic ring, for example, a group composed of a combination of a divalent group derived from phthalimide and an oxygen atom; a divalent group derived from phthalimide, A group formed by the combination of an oxygen atom, an aryl group, and an alkylene group is a group formed by a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide; the divalent group derived from pyromellitic acid diimide Group; a group formed by a combination of a divalent group derived from phthalimide and an alkylene group, etc. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (B-3).

The divalent group having an alkylene group and an aromatic ring represented by A may have a substituent. The substituent is the same as the substituent represented by R ¹ in the above formula (A-2).

As specific examples of the group represented by A, the following groups can be given. In the formula, "*" represents the bonding location.

一般式(B-5)中，M² 及M³ 各獨立表示可具有取代基之碳原子數5以上的伸烷基，R³⁰ 各獨立表示氧原子、伸芳基、伸烷基，或由此等基2個以上的組合所成的2價基。t1表示1～10的整數。 一般式(B-6)中，M⁴ 、M⁶ 及M⁷ 各獨立表示可具有取代基之碳原子數5以上的伸烷基，M⁵ 各獨立表示具有可具有取代基之芳香環的2價基，R³¹ 及R³² 各獨立表示碳原子數5以上的烷基。t2表示0～10的整數，u1及u2各獨立表示0～4的整數。The maleimide non-solid component hardener represented by general formula (B-3) is the maleimide non-solid component hardener represented by general formula (B-5), and the general formula (B- 6) Any one of the shown maleimide-based non-solid component hardeners is preferred.

In general formula (B-5), M ² and M ³ each independently represent an alkylene group having 5 or more carbon atoms that may have a substituent, and R ³⁰ each independently represents an oxygen atom, an aryl group, an alkylene group, or A divalent group formed by a combination of two or more of these groups. t1 represents an integer of 1-10. In the general formula (B-6), M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms that may have a substituent, and M ⁵ each independently represents 2 having an aromatic ring that may have a substituent Valence group, R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. t2 represents an integer of 0-10, and u1 and u2 each independently represent an integer of 0-4.

M ² and M ³ each independently represent an alkylene group having 5 or more carbon atoms that may have a substituent. M ² and M ³ are the same as the alkylene group having 5 or more carbon atoms represented by M in the general formula (B-3), and a hexacarbatrienyl group is preferred.

R ³⁰ each independently represents an oxygen atom, an arylene group, an alkylene group, or a group formed by a combination of two or more of these divalent groups. The arylene group and the alkylene group are the same as the arylene group and the alkylene group in the divalent linking group represented by L in the general formula (B-3). As R ³⁰ , a group formed by a combination of two or more divalent groups or an oxygen atom is preferred.

Examples of the group formed by a combination of two or more divalent groups in R ³⁰ include a combination of an oxygen atom, an aryl group, and an alkylene group. As a specific example of a group formed by a combination of two or more types of divalent groups, the following groups can be given. In the formula, "*" represents the bonding location.

M ⁴ , M ⁶ and M ⁷ each independently represent an alkylene group having 5 or more carbon atoms which may have a substituent. M ⁴ , M ⁶ and M ⁷ are the same as the alkylene group with 5 or more carbon atoms that may have substituents represented by M in the general formula (B-3), and are the same as hexylene, heptylene, octylene, Nonyl and decyl are preferred, and octyl is preferred.

Each of M ⁵ independently represents a divalent group having an aromatic ring which may have a substituent. M ^{5 is the} same as the divalent group having an optionally substituted aromatic ring represented by A in the general formula (B-4), and is composed of a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide A group formed; a group formed by a combination of a divalent group derived from phthalimide and an alkylene group is preferably a group formed by a combination of an alkylene group and a divalent group derived from pyromellitic acid diimide The base is better. The above-mentioned arylene group and alkylene group are the same as the arylene group and alkylene group in the divalent linking group represented by L in general formula (B-3).

As a specific example of the group represented by M ⁵ , the following groups can be given, for example. In the formula, "*" represents the bonding location.

R ³¹ and R ³² each independently represent an alkyl group having 5 or more carbon atoms. R ³¹ and R ^{32 are the} same as the above-mentioned alkyl group having 5 or more carbon atoms, preferably hexyl, heptyl, octyl, nonyl, and decyl, and more preferably hexyl and octyl.

u1 and u2 each independently represent an integer of 1-15, preferably an integer of 1-10.

Specific examples of the maleimide-based non-solid component hardener include the following compounds (1) to (3). However, the maleimide-based non-solid component hardener is not limited to these specific examples. In the formula, v represents an integer of 1-10.

Specific examples of maleimide-based non-solid component hardeners include "BMI1500" (compound of formula (1)) manufactured by Designer Molecules, "BMI1700" (compound of formula (2)), " BMI689" (compound of formula (3)) and so on.

The maleimide group equivalent of the maleimide-based non-solid component hardener, from the viewpoint of remarkably achieving the desired effect of the present invention, 50g/eq.～2000g/eq. is better, more preferably It is 100g/eq.～1000g/eq., more preferably 150g/eq.～500g/eq. The maleimide equivalent is the mass of the maleimine non-solid component hardener containing 1 equivalent of the maleimine group.

The so-called (meth)acrylic non-solid component hardener means a liquid or semi-solid component, which is a hardener containing acrylic groups and methacrylic groups, and combinations of these. As the (meth)acrylic non-solid component hardening agent, from the viewpoint of remarkably obtaining the desired effect of the present invention, one having two or more (meth)acrylic groups per molecule is preferred. The so-called "(meth)acryloyl group" includes acryloyl group, methacryloyl group, and combinations thereof.

The (meth)acrylic non-solid component-like hardener is preferably one having a cyclic structure from the viewpoint of remarkably obtaining the desired effect of the present invention. As the cyclic structure, a divalent cyclic group is preferred. As the bivalent cyclic group, any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure may be used. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, a cyclic group containing an alicyclic structure is preferred.

From the viewpoint of remarkably obtaining the desired effect of the present invention, a bivalent cyclic group is preferably a ring with 3 members or more, preferably a ring with 4 members or more, more preferably a ring with 5 members or more, and preferably a ring with 20 members or less , Preferably less than 15 members, more preferably less than 10 members. In addition, as a divalent cyclic group, a monocyclic structure or a polycyclic structure may be sufficient.

The ring in the bivalent cyclic group may constitute the skeleton of the ring by heteroatoms other than carbon atoms. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, Preferably it is an oxygen atom. The hetero atom may have one of the aforementioned rings, or may have two or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among them, the divalent cyclic group is preferably (x) or (xi).

The bivalent cyclic group may have a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, aryl groups, arylalkyl groups, silyl groups, acyl groups, acyloxy groups, carboxyl groups, sulfonic acid groups, cyano groups, nitro groups, and hydroxyl groups. , Mercapto, oxo, etc., preferably alkyl.

The (meth)acryloyl group may be directly bonded to the divalent cyclic group, or may be bonded via the divalent linking group. As the divalent linking group, for example, alkylene, alkenylene, arylene, heteroarylene, -C(=O)O-, -O-, -NHC(=O)-, -NC (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., can also be a base combining plural numbers of these. As the alkylene group, an alkylene having 1 to 10 carbon atoms is preferred, an alkylene having 1 to 6 carbon atoms is preferred, and an alkylene having 1 to 5 carbon atoms or an alkylene having 1 to 5 carbon atoms is preferred. The alkylene groups of 1 to 4 are more preferable. The alkylene group may be any of linear, branched, and cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, 1,1-dimethylethylene, etc., such as methylene, Ethylene and 1,1-dimethylethylene are preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is preferable, and an alkenylene group having 2 to 5 carbon atoms is more preferable. As the arylene group and heteroarylene group, an arylene group or heteroarylene group having 6 to 20 carbon atoms is preferable, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is preferable. As the divalent linking group, an alkylene group is preferred, and among them, a methylene group and a 1,1-dimethylethylene group are also preferred.

(式(B-7)中，R³³ 及R³⁶ 各獨立表示丙烯醯基或甲基丙烯醯基，R³⁴ 及R³⁵ 各獨立表示2價連結基。環D表示2價環狀基)The (meth)acrylic non-solid component hardener is preferably one represented by the following formula (B-7).

(In formula (B-7), R ³³ and R ³⁶ each independently represent an acryloyl group or a methacryloyl group, and R ³⁴ and R ³⁵ each independently represent a divalent linking group. Ring D represents a divalent cyclic group)

R ³³ and R ³⁶ each independently represent an acrylic group or a methacryl group, and an acrylic group is preferred.

R ³⁴ and R ³⁵ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group that can be bonded to the (meth)acrylic group.

Ring D represents a divalent cyclic group. The ring D is the same as the aforementioned divalent cyclic group. Ring D may have a substituent. As a substituent, it is the same as the substituent which may have a bivalent cyclic group mentioned above.

As specific examples of the (meth)acrylic non-solid component curing agent, the following may be mentioned, but the present invention is not limited to these.

(Meth)acrylic non-solid component hardeners can be sold. Examples include "A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyoei Chemical Co., Ltd., and Nippon Ka "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" manufactured by the pharmaceutical company, "NK ester DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd., etc.

The (meth)acrylic acid equivalent of the (meth)acrylic non-solid component hardener is preferably 30g/eq. to 400g/eq. from the viewpoint of remarkably obtaining the desired effect of the present invention, and more preferred It is 50g/eq.～300g/eq., more preferably 75g/eq.～200g/eq. The (meth)acrylic equivalent is the mass of the (meth)acrylic non-solid component-like hardener containing 1 equivalent of (meth)acrylic.

As the amine non-solid component hardener, a liquid or semi-solid component amine hardener can be used. In addition, the amine-based non-solid component hardener includes hardeners having one or more amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, Among the aromatic amines, among them, from the viewpoint of achieving the desired effect of the invention, aromatic amines are preferred. The amine-based non-solid component hardener is preferably a first-stage amine or a second-stage amine, and more preferably a first-stage amine.

Specific examples of amine-based non-solid component hardeners include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-methylenebis-2,6- Xylene diamine, m-phenylene diamine, m-xylene diamine, diethyl toluene diamine, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4- Hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)propane, etc. Amine-based resins can be sold, such as "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYAHARD AA", "Kaya HardA-B", "Kaya HardA-S", and manufactured by Mitsubishi Chemical Corporation. "Epicure w", "jER Cure W" and so on.

The so-called butadiene-based non-solid component hardener is a liquid or semi-solid component, and it is a compound having at least one butadiene skeleton in the molecule. The polybutadiene structure may be contained in the main chain or in the side chain. Moreover, the polybutadiene structure may be partially or completely hydrogenated. The butadiene-based non-solid component hardener is selected from resins containing hydrogenated polybutadiene skeleton, butadiene resins containing hydroxyl groups, butadiene resins containing phenolic hydroxyl groups, and butadiene resins containing carboxyl groups , Butadiene resin containing acid anhydride groups, butadiene resin containing epoxy groups, butadiene resin containing isocyanate groups and butadiene resin containing urethane groups more than one type of resin For better.

Specific examples of butadiene-based non-solid component hardeners include "JP-100" manufactured by Soda Corporation, "Ricon100", "Ricon150", "Ricon130MA8", and "Ricon130MA13" manufactured by CRAY VALLEY. "Ricon130MA20", "Ricon131MA5", "Ricon131MA10", "Ricon131MA17", "Ricon131MA20", "Ricon 184MA6", etc.

As the content of component (B), from the viewpoint of improving lamination and obtaining a cured product with excellent adhesion, when the non-volatile content in the resin composition is 100% by mass, 0.1% by mass The above is preferably, preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 5.5% by mass or less.

When the content of the non-volatile component in the resin composition of component (B) as 100% by mass is taken as b1, and the content when the non-volatile component in the resin composition of component (A) is taken as 100% by mass as a1 , A1/b1 is preferably 1 or more, preferably 2 or more, more preferably 3 or more, 4 or more, preferably 30 or less, preferably 25 or less, more preferably 20 or less, 15 or less, or 10 or less. When a1/b1 is set within this range, the effect of the present invention can be obtained significantly.

＜(C) High molecular weight component＞ The resin composition contains a high molecular weight component as the (C) component. When the component (C) is contained in the resin composition, the stress of the resin composition can be alleviated, and as a result, a cured product with excellent dielectric properties can be obtained. (C) A component may be used individually by 1 type, and may use 2 or more types together.

(C) The weight average molecular weight (Mn) of the component is from the viewpoint of obtaining a cured product with excellent dielectric properties, preferably 5000 or more, more preferably 8000 or more, particularly preferably 10000 or more, and more preferably 100000 or less , Preferably below 80,000, particularly preferably below 50,000. (C) The weight average molecular weight of the component is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

As the (C) component, those having a high weight average molecular weight can be used. Examples of such components include polyimide resins, polycarbonate resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyimide resins, polyetherimide resins, and polyimide resins. Thermoplastic resins such as waste resin, polyether waste resin, polyphenylene ether resin, polyether ether ketone resin, polystyrene resin, and polyester resin. Among them, the component (C) is preferably at least one selected from the group consisting of polyimide resin, polycarbonate resin, and phenoxy resin from the viewpoint of obtaining a cured product having excellent dielectric properties.

As the polyimide resin, a resin having an imine structure can be used. The polyimide resin generally contains one obtained by the imidization reaction of a diamine compound and an acid anhydride.

Although it is not specifically limited as a diamine compound used when preparing a polyimide resin, for example, an aliphatic diamine compound and an aromatic diamine compound are mentioned.

As the aliphatic diamine compound, for example, 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6 -Straight-chain aliphatic diamine compounds such as hexamethylene diamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methylpropane , 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane and other branched chain aliphatic diamine compounds; 1,3-bis(aminomethyl Cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), etc. Diamine compound; dimer acid type diamine (hereinafter also referred to as "dimer diamine"), etc. The so-called dimer acid type diamine means that the two terminal carboxylic acid groups (-COOH) of the dimer acid are replaced by aminomethyl (-CH ₂ -NH ₂ ) or amino (-NH ₂ ) The diamine compound. Dimer acid is a known compound obtained by diquantizing unsaturated fatty acids (preferably those with 11-22 carbons, particularly those with 18 carbons). The industrial manufacturing process is almost Has been standardized.

As an aromatic diamine compound, a phenylene diamine compound, a naphthalene diamine compound, a diphenylamine compound, etc. are mentioned, for example.

The phenylene diamine compound means a compound formed from a benzene ring having two amino groups, and the benzene ring may further have any 1 to 3 substituents. The substituent here is not particularly limited. Specific examples of the phenylene diamine compound include 1,4-phenylene diamine, 1,2-phenylene diamine, 1,3-phenylene diamine, and 2,4-diaminotoluene , 2,6-diaminotoluene, 3,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, etc.

The naphthalene diamine compound refers to a compound formed from a naphthalene ring having two amino groups, and the naphthalene ring may further have any 1 to 3 substituents. The substituent here is not particularly limited. Specific examples of the naphthalene diamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, and the like.

The diphenylamine compound refers to a compound containing two aniline structures in the molecule, and further means that each of the two benzene rings of the two aniline structures may further have any 1 to 3 substituents. The substituent here is not particularly limited. The two aniline structures in the diphenylamine compound are directly bonded and/or separated by 1 or 2 linking structures with 1-100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms Obtained by bonding. In the diphenylamine compound, it also contains two aniline structures that are bonded by two bonding bonds.

Specific examples of the "connection structure" in the diphenylamine compound 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-, -C(CH ₃ ) ₂ -Ph-C(CH ₃ ) ₂ -,

Wait. In this specification, "Ph" means 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

In one embodiment, specific examples of the diphenylamine compound include 4,4'-diamino-2,2'-bistrifluoromethyl-1,1'-biphenyl and 3,4'-diamine Diphenyl 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-amino) Phenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylene) 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)phenyl] -1,4-Diisopropylbenzene, 4,4'-(9-fluorene)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'-diamino -2,2'-Dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy )-3-[4-(4-Aminophenoxy)phenyl]-1,1,3-trimethylindan and the like.

As the diamine compound, a commercially available one can be used, or one synthesized by a known method can also be used. The diamine compound may be used alone or in combination of two or more kinds.

The acid anhydride used to prepare the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, anthracene tetracarboxylic dianhydride, diphthalic dianhydride, etc. may be mentioned, and diphthalic dianhydride is preferred. Formic acid dianhydride.

The benzene tetracarboxylic dianhydride means the dianhydride of benzene having 4 carboxyl groups, and the benzene ring may further have any 1 to 3 substituents. Among them, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (the same as the definition of the following formula (1B)). Specific examples of pyromellitic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and the like.

The so-called naphthalenetetracarboxylic dianhydride means a naphthalene dianhydride having 4 carboxyl groups, and the naphthalene ring may further have any 1 to 3 substituents. Among them, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (the same as the definition of the following formula (1B)). Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

The anthracene tetracarboxylic dianhydride means an anthracene dianhydride having 4 carboxyl groups, and the anthracene ring may further have any 1 to 3 substituents. Among them, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (the same as the definition of the following formula (1B)). Specific examples of anthracene tetracarboxylic dianhydride include 2,3,6,7-anthracene tetracarboxylic dianhydride.

The so-called diphthalic dianhydride means a compound containing two phthalic anhydrides in the molecule, and each of the two benzene rings in the two phthalic anhydrides may further have any 1 to 3 substituents. Among them, the substituent is preferably selected from a halogen atom, a cyano group, and -X ³³ -R ³³ (as defined by the following formula (1B)). The two phthalic anhydrides in the diphthalic dianhydride may be directly bonded, or may have a connection structure with 1-100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms and nitrogen atoms. Bonding.

As diphthalic dianhydride, for example, the formula (1B) can be cited:

[In the formula, R ³¹ and R ³² each independently represent a halogen atom, a cyano group, a nitro group or -X ³³ -R ³³ and X ³³ each independently represent a single bond, -NR ^33' -, -O-, -S-, -CO-, -SO ₂ -, -NR ^33' CO-, -CONR ^33' -, -OCO- or -COO-, R ³³ each independently represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkene R ^33' each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond, or has 1 selected from a carbon atom, an oxygen atom, a sulfur atom, and a nitrogen atom A connection structure of ˜100 skeleton atoms, n10 and m10 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. n and m are preferably zero.

The "connected structure" in Y has 1-100 skeleton atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. "Connection structure" preferably represents _{- [A1-Ph] a10 -A1-} [Ph-A1] b10 - [wherein A1 each independently represents a single bond, - (substituted or unsubstituted alkylene) -, - O -, -S-, -CO-, -SO ₂ -, -CONH-, -NHCO-, -COO- or -OCO-, a10 and b10 each independently represent an integer of 0-2 (preferably 0 or 1) ] Shows the divalent base.

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 this specification, "Ph" means 1,4-phenylene, 1,3-phenylene or 1,2-phenylene.

Specific examples of diphthalic dianhydride include 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3' ,4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic acid Dianhydride 2,2'-bis(3,4-dicarboxyphenoxyphenyl) dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-acetylene-4 ,4'-diphthalic dianhydride, 2,2-propyne-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalate Formic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic 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-dicarboxyl) Phenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)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'-isopropylene Diphenoxy)bisphthalic dianhydride and the like.

The acid anhydride can also be a seller, and can also be synthesized by a known method or a method based on this. An acid anhydride may be used individually by 1 type, and may be used in combination of 2 or more types.

Polyimide resins can be sold as products. Examples of sales items include "RIKACOATSN20" and "RIKACOATPN20" manufactured by Nippon Rika Corporation.

Polycarbonate resin is a resin having a carbonate structure. Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing anhydride groups, and carbonate resins containing isocyanate groups. Carbonate resin, urethane group-containing carbonate resin, epoxy group-containing carbonate resin, etc. The term "reactive group" means a functional group obtained by reacting with other components such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

A commercially available product can be used for the carbonate resin. Examples of sold products include "FPC0220" and "FPC2136" manufactured by Mitsubishi Gas Chemical Corporation, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., and "C-1090" manufactured by Kuraray. ", "C-2090", "C-3090" (polycarbonate diol), etc.

Examples of phenoxy resins include those having a skeleton selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, and dicyclopentane skeleton. A phenoxy resin with more than one type of skeleton consisting of a diene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any one of functional groups such as a phenolic hydroxyl group and an epoxy group. The phenoxy resin is preferably a phenoxy resin having a weight average molecular weight of 30,000 or more.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both are phenoxy resins containing a bisphenol A skeleton); and "YX8100" manufactured by Mitsubishi Chemical Corporation (containing double Phenoxy resin with phenol S skeleton); "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; Mitsubishi "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", etc. manufactured by Chemical Corporation.

Polyamide imide resins are resins having an amide imide structure. From the viewpoint of compatibility with other components in the resin composition, polyamide imide resins are used in polyamide imide resins having an alicyclic structure in the molecular structure, Japanese Patent Application Publication No. 05-112760 The polyamide resin with a silicone structure, the polyamide resin with a high volume branched structure, and the polyamide resin with an asymmetric monomer as a raw material described in the Bulletin , Polyamide imine resin with multi-branched structure is preferred.

Among them, the polyamide imide resin has an isocyanuric acid ring structure, so from the viewpoint of improving the compatibility and dispersibility of the resin paint, (i) having isocyanuric acid in the molecular structure The polyamide imide resin of ring structure (that is, the polyamide imide resin having an isocyanuric acid ring structure and an amide skeleton or an amide skeleton) (ii) has a heterotrimeric molecular structure A polyamide resin having a cyanic acid ring structure and an alicyclic structure (ie, a polyamide resin having an isocyanuric acid ring structure and an alicyclic structure and an amide skeleton or an amide skeleton ), (iii) Polyamidoimide resins with repeating units containing isocyanuric acid ring structure and alicyclic structure (that is, having isocyanuric acid ring structure and alicyclic structure and a Polyamide (imide resin) which is a repeating unit of an amine skeleton or an amide skeleton is preferable.

As a preferred embodiment of the polyamideimide resins (i) to (iii), (1) a polyisocyanurate ring-containing polyimide resin derived from an alicyclic structure diisocyanate Isocyanate compound is a compound obtained by reacting with an anhydride of a polycarboxylic acid having 3 or more carboxyl groups. Branched polyamide containing carboxylic acid group (hereinafter sometimes referred to as "(Compound C-1) "), (2) The carboxylic acid group-containing branched polymerizable polymer of the compound obtained by reacting a compound (C-1) having one epoxy group and one or more radically polymerizable unsaturated groups Amidoimines (hereinafter sometimes referred to as "compound (C-2)"), or (3) during the synthesis of compound (C-1), the residual isocyanate group has one hydroxyl group and one or more A compound obtained by reacting a radically polymerizable unsaturated group is a carboxylic acid group-containing branched polymerizable polyimide (hereinafter may be referred to as "compound (C-3)").

(式中，w表示0～15)Specific examples of the compound (C-1) include compounds represented by the following general formula (I). Moreover, the repeating unit in the compound represented by general formula (I) is regarded as the repeating unit (I-1).

(In the formula, w represents 0～15)

(式中，R表示式(I)中之殘基)Examples of the compound (C-2) include the addition of GMA (glycidyl methacrylate) to the carboxyl group and/or terminal carboxyl group of any part of the repeating unit (I-1) in the general formula (I) Compound (II) of structure (I-2).

(In the formula, R represents the residue in formula (I))

The ratio of GMA denaturation of the carboxyl group to the molar number of the carboxyl group of compound (C-1), the range of addition of GMA is preferably 0.3 mol% or more, preferably 0.5 mol% or more, more preferably 0.7 mol% Above or above 0.9mol%. The upper limit is preferably 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less or 20 mol% or less.

(式中，R’表示式(I)中之殘基)As the compound (C-3), any part of the repeating unit (I-1) in the above formula (I) and/or the terminal imino group is an isocyanate residue, which has three additions of pentaerythritol Compound (III) of structure (I-3) of hydroxyl group of acrylate.

(In the formula, R'represents the residue in formula (I))

The addition amount of pentaerythritol triacrylate is preferably 40 mol% or less, preferably 38 mol% or less, and more preferably 35 mol% or less with respect to the mol number of the isocyanate groups of the polyisocyanate charged as such. On the other hand, the amount of addition of pentaerythritol triacrylate is preferably 0.3 mol% or more with respect to the mol number of the isocyanate group of the polyisocyanate at the time of loading from the viewpoint that the effect of the addition can be sufficiently obtained , Preferably 3 mol% or more, more preferably 5 mol% or more.

Polyamide imide resins can be synthesized by various known methods. As a method of synthesizing polyimide resin, for example, reference can be made to the description of paragraphs 0020 to 0030 of International Publication No. 2010/074197, which are described in this specification.

For the polyimide resin, commercially available products can be used. Examples of sold products include "UnidickV-8000" manufactured by DIC, "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Co., Ltd., "KS9100" manufactured by Hitachi Chemical Co., Ltd., and "KS9300" (containing polysiloxane skeleton). The polyamide imide) and other denatured polyamide imide.

As the polystyrene resin, any elastomer containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. In addition, the polystyrene resin may be a copolymer combined with a styrene unit, containing any repeating unit different from the aforementioned styrene unit, or a hydrogenated polystyrene resin.

As the arbitrary repeating unit, for example, a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating this (hydrogenated conjugated diene) Unit), etc. As the conjugated dienes, for example, butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene and other fats Group conjugated dienes; halogenated aliphatic conjugated dienes such as chloroprene, etc. As the conjugated diene, an aliphatic conjugated diene is preferred, and butadiene is preferred from the viewpoint that the effects of the present invention can be significantly obtained. One type of conjugated diene may be used alone, or two or more types may be used in combination. In addition, the polystyrene resin may be a random copolymer or a block copolymer.

Examples of polystyrene resins include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene- Butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), benzene Ethylene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene Block copolymers, hydrogenated styrene-butadiene random copolymers, styrene-maleic anhydride copolymers, etc. Among them, as the polystyrene resin, styrene-maleic anhydride copolymer is preferred.

Specific examples of polystyrene resins include "EF-40" manufactured by CRAY VALLEY, "H1043" manufactured by Asahi Kasei Corporation, and the like.

From the viewpoint of compatibility with other components in the resin composition, the polyester resin preferably has a fluorene structure in the molecular structure. In addition to the fluorene structure, the polyester resin has a structural unit derived from a diol and a structure derived from a dicarboxylic acid. The structural unit of acid is preferred.

As a specific example of the polyester resin, "OKP4HT" manufactured by Osaka Gas Chemical Co., Ltd. can be cited.

As a specific example of the polymer resin, the polymer "P1700" and "P3500" manufactured by Solvay Advanced Polymers can be cited.

Examples of polyvinyl acetal resins include polyvinyl formaldehyde resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include S-LECBH series manufactured by Sekisui Chemical Industry Co., Ltd., BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series.

As a specific example of the polyether sulfide resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. can be cited.

As a specific example of the polyphenylene ether resin, the oligophenylene ether and styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be cited.

As the content of component (C), from the viewpoint of obtaining a cured product with excellent dielectric properties, when the non-volatile content in the resin composition is 100% by mass, 0.5% by mass or more is preferred, and more preferably 1% by mass or more, more preferably 1.5% by mass or more, preferably 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.

When the content of the non-volatile components in the resin composition of component (C) as 100% by mass is taken as c1, and the content when the non-volatile components in the resin composition of component (A) is taken as 100% by mass as a1 , A1/c1 is preferably 2 or more, preferably 5 or more, more preferably 10 or more, 12 or more, preferably 50 or less, preferably 30 or less, more preferably 20 or less, and 15 or less. By setting a1/c1 within this range, the effect of the present invention can be remarkably obtained.

＜(D)Inorganic fillers＞ In addition to the above-mentioned components, the resin composition may further contain an inorganic filler as the (D) component as an optional component.

As the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, 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, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silica is particularly preferred. Examples of the silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, as the silica, spherical silica is preferred. (D) Inorganic fillers may be used alone or in combination of two or more types.

Examples of sales products of the component (D) include "UFP-30" manufactured by Denka; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; and "YC100C manufactured by Admatechs" ", "YA050C", "YA050C-MJE", "YA010C"; "SilfirNSS-3N", "SilfirNSS-4N", "SilfirNSS-5N" manufactured by Tokuyama; "SC2500SQ", "SO-C4" manufactured by Admatechs ", "SO-C2", "SO-C1", etc.

The specific surface area of the component (D) is preferably 1 m ² /g or 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 based on 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 calculating the specific surface area using the BET multipoint method.

(D) 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, preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, and more It is preferably 2 μm or less, more preferably 1 μm or less.

The average particle size of the component (D) can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter can be measured as the average particle size. As a measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone were weighed into a sample bottle and dispersed in ultrasonic for 10 minutes. Use a laser diffraction particle size distribution measuring device for the measurement sample, set the wavelength of the light source used to blue and red, measure the volume-based particle size distribution of component (D) by the flow cell method, and obtain the particle size distribution Calculate the average particle size as the median diameter. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

The component (D) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include vinyl silane coupling agents, (meth)acrylic coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents Mixture, silane coupling agent, alkoxysilane, organosilazane compound, titanate coupling agent. Among them, from the viewpoint that the effects of the present invention can be significantly obtained, 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 combining 2 or more types arbitrarily.

Sales of surface treatment agents include, for example, "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM503" (3-methacryloxypropyl) manufactured by Shin-Etsu Chemical Co., Ltd. Triethoxysilane), "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , Shin-Etsu Chemical Corporation "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Corporation "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu "SZ-31" (hexamethyldisilazane) manufactured by Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long chain ring Oxygen-type silane 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 should be controlled within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, for 100 parts by mass of the inorganic filler, 0.2 to 5 parts by mass of the surface treatment agent is preferably used for surface treatment, preferably 0.2 to 3 parts by mass for the surface treatment, and 0.3 parts by mass to 2 parts by mass are preferably surface-treated.

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. The amount of carbon per unit surface area of the inorganic filler is from the viewpoint of improving the dispersibility of the inorganic filler, preferably 0.02 mg/m ² or more, preferably 0.1 mg/m ² or more, and 0.2 mg/m ² or more For better. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin coating and the melt viscosity of the sheet form, 1 mg/m ² or less is preferable, 0.8 mg/m ² or less is preferable, and 0.5 mg/m ² or less is more preferable.

The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, except for the inorganic filler in which a sufficient amount of MEK as a solvent was surface-treated with a surface treatment agent, ultrasonic cleaning was performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

(D) From the viewpoint of reducing the dielectric properties, the content of component (D) is preferably 50% by mass or more, more preferably 55% by mass or more when the non-volatile content in the resin composition is 100% by mass. It is 60% by mass or more, preferably 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less.

＜(E) Hardener＞ In addition to the above-mentioned components, the resin composition may further contain a curing agent as the (E) component as an optional component. However, the component (E) excludes those equivalent to the component (B). (E) The component is a hardening agent judged to be a solid in the test carried out in accordance with the second "Method of Confirming Liquid State" in the separate volume of the provincial ordinance related to the test and characteristics of the hazardous substance (the first year of Heisei Autonomous Province Order No. 1). Thereby, (E) component is a solid hardening agent. The test method is shown above.

Examples of (E) component include active ester curing agents, phenolic curing agents, naphthol curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. , Amine hardener, acid anhydride hardener, etc. (E) A component may be used individually by 1 type, or may use 2 or more types together.

As an active ester curing agent, it can be used for compounds having one or more active ester groups in one molecule. Among them, as active ester hardeners, phenol esters, thiophenol esters, N-hydroxy amine esters, heterocyclic hydroxyl compound esters are equal to compounds with two or more highly reactive ester groups in one molecule. good. The active ester hardener 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. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is preferred Better.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalazine, methylated bisphenol A, methylated bisphenol F, methyl Alkylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol Compound, phenol novolac, etc. The "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

Preferred specific examples of active ester hardeners include active ester hardeners containing dicyclopentadiene diphenol structure, active ester hardeners containing naphthalene structure, and acetone containing phenol novolac Active ester hardeners, active ester hardeners containing phenol novolac benzoic acid. Among them, an active ester hardener containing a naphthalene structure and an active ester hardener containing a dicyclopentadiene type diphenol structure are also preferred. The "dicyclopentadiene-type diphenol structure" means a bivalent structural unit composed of phenylene-bicyclopentylene-phenylene.

Sales of active ester hardeners include "EXB9451", "EXB9460", "EXB9460S", and "HPC8000-65T" as active ester hardeners containing a dicyclopentadiene diphenol structure. , "HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC Corporation); as an active ester hardener containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC Corporation) can be mentioned as Examples of active ester hardeners containing phenolic novolac-based active ester hardeners include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of active ester hardeners containing phenolic novolac-based active ester hardeners include "YLH1026" "(Manufactured by Mitsubishi Chemical Corporation); as the active ester curing agent of the acetate of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester curing agent of the benzyl of phenol novolak Examples of the agent include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

As the phenolic curing agent and naphthol curing agent, from the viewpoint of heat resistance and water resistance, those having a novolak structure are preferred. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferred, and a phenolic curing agent containing a triazine skeleton is preferred.

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

Specific examples of benzoxazine-based hardeners include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Corporation, and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. .

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, 4,4'-methylenebis(2,6-dimethylphenylcyanate), and hexafluorobisphenol A Dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4 -Cyanate phenyl) thioether and other bifunctional cyanate resins; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs; part of these cyanate resins is triazineized Prepolymer etc. Specific examples of cyanate ester curing agents include "PT60" (phenol novolak type polyfunctional cyanate ester resin) manufactured by Lonza Japan, and "ULL-950S" (polyfunctional cyanate ester resin). ), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazineized to become a trimer), etc.

As specific examples of the carbodiimide-based hardener, "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. can be cited.

Examples of the amine curing agent include curing agents having one or more amine groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like. Among them, from the viewpoint of achieving the desired effect of the invention, aromatic amines are preferred. The amine-based hardener is preferably a first-stage amine or a second-stage amine, and more preferably a first-stage amine. As specific examples of the amine curing agent, 4,4'-diaminodiphenylmethane, diphenyldiaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 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) benzene, bis( 4-(3-Aminophenoxy)phenyl) sulfite and the like. Commercially available products can be used as the amine hardener, and examples include "KAYABOND C-100" manufactured by Nippon Kayaku Co., Ltd. and the like.

Examples of acid anhydride hardeners include hardeners having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, anhydrous trimellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid two Anhydride, naphthalene tetracarboxylic dianhydride, oxodiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5,9b -Hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated partial benzene Triester), styrene and maleic acid copolymerized with styrene, maleic acid resin and other polymeric acid anhydrides.

(E) The content of the component, from the viewpoint of remarkably obtaining the desired effect of the present invention, for 100% by mass of the non-volatile content in the resin composition, 0.1% by mass or more is preferable, and 0.3% by mass is more preferable Above, it is more preferably 0.5% by mass or more, more preferably 5% by mass or less, more preferably 4% by mass or less, and more preferably 3% by mass or less.

＜(F) Hardening accelerator＞ In addition to the above-mentioned components, the resin composition may further contain a hardening accelerator as an optional component (F) component.

(F) Components include, for example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, and the like. (F) A component may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of phosphorus-based hardening accelerators include triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, and tetrabutyl phosphonium decanoate. , (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc., with triphenyl phosphine, tetrabutyl phosphonium thiocyanate Alkanoates are preferred.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diaza Heterobicyclo(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-methyl Imidazole, 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' -Methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 -Methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resin, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole Better.

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

As the guanidine-based hardening accelerator, for example, dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, two Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl -1,5,7-Triazacyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecane Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., Preferably, dicyandiamine and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt (II) acetone and cobalt (III) acetone, organic copper complexes such as copper (II) acetone, and zinc (II) Organic zinc complexes such as acetone, organic iron complexes such as iron (III) acetone, organic nickel complexes such as nickel (II) acetone, organic manganese complexes such as manganese (II) acetone, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(F) The content of 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 0.001% by mass or more, preferably 0.005% by mass Above, more preferably 0.01% by mass or more, more preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and more preferably 0.1% by mass or less.

＜(G)Epoxy resin＞ In addition to the above-mentioned components, the resin composition may further contain an epoxy resin as an optional component (G) component. However, the component (G) excludes those equivalent to the component (B).

(G) 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 epoxy resin, ginseng phenol epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene Type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type ring Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane epoxy resin , Cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane type epoxy resin, etc. (G) A component may be used individually by 1 type, or may be used in combination of 2 or more types.

In the resin composition, it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule as the component (G). From the standpoint of remarkably obtaining the desired effect of the present invention, for 100% by mass of the non-volatile components of component (G), the proportion of epoxy resin having two or more epoxy groups per molecule is 50% by mass The above is preferable, 60% by mass or more is preferable, and 70% by mass or more is particularly preferable.

(G) There are epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter sometimes referred to as "Solid epoxy resin"). The resin composition may contain only the liquid epoxy resin as component (G), or only the solid epoxy resin, or may contain a combination of liquid epoxy resin and solid epoxy resin, but it is notably From the viewpoint of obtaining the desired effect of the present invention, it is preferable to contain only a liquid epoxy resin.

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

As liquid epoxy resins, 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 novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin Resins and epoxy resins with butadiene structure are preferred, and bisphenol A epoxy resins and bisphenol F epoxy resins are preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US" and "jER828EL" manufactured by Mitsubishi Chemical Corporation. 825", "EPICOAT828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "630", "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and double Mixture of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase Chemtex; "CELLOXIDE2021P" manufactured by Daicel Chemical Industries, Ltd. (alicyclic with ester skeleton) Formula epoxy resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel Chemical Industries, Ltd.; "ZX1658" and "ZX1658GS" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (liquid 1 , 4-glycidyl cyclohexane type epoxy resin) and so on. These can be used individually by 1 type or in combination of 2 or more types.

As a solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups in a molecule is preferred, and an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule is preferred For better.

As a solid epoxy resin, bisxylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, Phenolic epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthylene ether epoxy resin, anthracene epoxy resin, bisphenol A epoxy resin, bisphenol AF ring Oxygen resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene tetrafunctional epoxy resin) manufactured by DIC Resin); "N-690" (cresol novolac epoxy resin) manufactured by DIC; "N-695" (cresol novolak epoxy resin) manufactured by DIC; "HP- 7200HH", "HP-7200H", "HP-7200" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation "", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Corporation; manufactured by Nippon Kayaku Corporation "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; Nippon Steel & Sumikin Chemical "ESN475V" (naphthol type epoxy resin) manufactured by the company; "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H" and "YX4000" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin); "YX4000HK" (bisxylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas "PG-100" and "CG-500" manufactured by Chemical Corporation; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used individually by 1 type or in combination of 2 or more types.

When using a combination of a liquid epoxy resin and a solid epoxy resin as the component (G), when these ratios (liquid epoxy resin: solid epoxy resin) are expressed in a mass ratio, it is 1:1 ~1:20 is preferably, preferably 1:1.5 to 1:15, particularly preferably 1:2 to 1:10. When the ratio of the liquid epoxy resin to the solid epoxy resin is within this range, the desired effect of the present invention can be remarkably obtained. And usually when used in the form of a resin sheet, it has moderate adhesiveness. In addition, it is usually used in the form of a resin sheet to obtain sufficient flexibility and improve handling properties. And usually a hardened product with sufficient breaking strength can be obtained.

(G) The epoxy equivalent of the component is preferably 50g/eq.～5000g/eq., preferably 50g/eq.～3000g/eq., more preferably 80g/eq.～2000g/eq., more Preferably, it is 110g/eq.～1000g/eq. When it is in this range, the crosslink density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be obtained. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

(G) The weight average molecular weight (Mw) of the component, from the viewpoint of remarkably obtaining the desired effect of the present invention, is preferably 100-5000, preferably 250-3000, more preferably 400-1500. The weight average molecular weight of the component (G) can be measured in the same way as the weight average molecular weight of the component (C).

(G) 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, preferably 0.3% by mass Above, it is more preferably 0.5% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 2% by mass or less.

＜(H) Polymerization initiator＞ In addition to the above components, the resin composition may further contain a polymerization initiator as an optional component (H) component. (H) A component may be used individually by 1 type, or may use 2 or more types together.

As the (H) component, for example, t-butylperoxycumyl peroxide, t-butylperoxyacetate, α,α'-bis(t-butylperoxy)diisopropylbenzene , T-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate and other peroxides .

As for the sale of component (H), for example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl" manufactured by NOF Corporation Base O", "Per-butyl ND", "Per-butyl Z", "Per-cumyl P", "Per-cumyl D", etc.

(H) The content of 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, 0.01% by mass or more is preferred, and 0.05% by mass is more preferred Above, more preferably 0.1% by mass or more, more preferably 1% by mass or less, more preferably 0.5% by mass or less, more preferably 0.3% by mass or less.

＜(I) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include resin additives such as thickeners, defoamers, leveling agents, and adhesion imparting agents. These additives may be used individually by 1 type, or may be used in combination of 2 or more types. Each content can be set appropriately only for those in the industry.

Although the preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. to a compounding component as needed, and mixing and dispersing using a rotating mixer, etc. are mentioned.

＜Physical properties and application of resin composition＞ The resin composition contains (A) a maleimide compound having a biphenyl type structure, (B) a liquid or semi-solid component curing agent, and (C) a high molecular weight component. Thereby, a cured product having excellent lamination properties and excellent dielectric properties and adhesion can be obtained. And as shown above, generally if maleimide compound is contained in the resin composition, the dielectric properties can be improved. However, because the maleimide compound usually has a higher softening point, the resin composition The material and its hardened material will become brittle. However, by containing (B) a liquid or semi-solid component curing agent, the viscosity of the resin composition before curing can be increased, and the resultant brittleness can be improved. Furthermore, by containing (C) high molecular weight components, the stress in the initial hardened product can be relieved, and the brittleness of the hardened product can also be improved.

The resin composition is cured at 100°C for 30 minutes, and then heat-cured at 180°C for 30 minutes. The peel strength between the cured product and the conductor layer (plated conductor layer) formed by plating is shown Excellent characteristics. Thereby, an insulating layer with excellent peeling strength between the hardened product and the plated conductor layer can be obtained. The peel strength is preferably 0.3 kgf/cm or more, preferably 0.4 kgf/cm or more, and more preferably 0.45 kgf/cm or more. The upper limit of the peel strength is 10 kgf/cm or less. The measurement of the peeling strength of the plated conductor layer can be measured according to the method described in the following Examples.

The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits excellent properties in the tensile strength of the copper foil. Thereby, the above-mentioned hardened product can obtain an insulating layer with excellent tensile strength of the copper foil. The tensile strength of the copper foil is preferably 0.3 kgf/cm or more, preferably 0.4 kgf/cm or more, and more preferably 0.5 kgf/cm or more. The upper limit of the tensile strength of the copper foil may be 10kgf/cm or less. The measurement of the open strength of the copper foil can be measured according to the method described in the examples described later.

The cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits low dielectric constant. In this way, the hardened product can obtain an insulating layer with a low dielectric constant. The permittivity is preferably 4 or less, preferably 3.5 or less, and more preferably 3 or less. The lower limit of the permittivity is 0.001 or more. The dielectric constant can be measured according to the method described in the following examples.

The cured product obtained by thermally curing the resin composition at 200°C for 90 minutes exhibits a low electrical loss tangent. Thereby, the hardened material can obtain an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, preferably 0.004 or less, and more preferably 0.003 or less. The lower limit of the dielectric loss tangent is 0.0001 or more. Measurement of dielectric loss tangent.

The resin composition exhibits excellent characteristics of lamination. Specifically, a glass cloth substrate with a 35μm thick conductor pattern is formed on both sides of the epoxy resin copper laminate laminate conductor, the resin composition is laminated on the conductor, and the resin composition is thermally cured at 100°C for 30 minutes Then, thermal curing was performed at 180°C for 30 minutes to form an insulating layer. Use a non-contact surface roughness meter (WYKO NT3300 manufactured by VICO INSTRUMENTS) on the conductors in the insulating layer to obtain a measurement range of 1.2mm×0.91mm with a 10x lens in the VSI mode. And get it. At this time, there is usually no void after lamination, and the unevenness difference between the conductor and the other parts is less than 5 μm. The details of the evaluation of the lamination can be measured according to the method described in the examples described later.

The resin composition of the present invention has excellent lamination properties, can lower the dielectric properties, and can obtain an insulating layer with excellent adhesion. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, it can be used as a resin composition for forming a conductive layer (including a rewiring layer) to be formed on the insulating layer (resin composition for forming an insulating layer when a conductive layer is to be used) And apply.

In addition, the multilayer printed wiring board described later can be used as a resin composition (resin composition for forming an insulating layer of a multilayer printed wiring board) for forming an insulating layer of a multilayer printed wiring board, and an interlayer insulating layer to be formed on a printed wiring board A resin composition (a resin composition for forming an interlayer insulating layer of a printed wiring board) is suitably used.

In addition, for example, when a semiconductor wafer package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be used as a resin composition for a rewiring forming layer (rewiring layer) of an insulating layer to be formed with a rewiring layer. A resin composition for forming a formation layer, and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer) are suitably used. When semiconductor wafer packaging is manufactured, 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 of the substrate of the semiconductor wafer and the temporary fixing film, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring forming layer

[Resin Sheet] The resin sheet of the present invention contains 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 can provide a thinner printed wiring board, and even if the cured product of the resin composition is a thin film, the cured product has excellent insulation. It is preferably 50μm or less. It is preferably 40 μm or less, more preferably 30 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it is usually 5 μm or more.

Examples of the support include a film made of a plastic material, metal foil, and release paper, and a film made of a plastic material or metal foil is preferred.

When a film made of a plastic material as a support is used, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (Hereinafter sometimes referred to as “PEN”), polycarbonate (hereinafter sometimes referred to as “PC”), acrylic (resin) such as polymethylmethacrylate (PMMA), cyclic polyolefin, triethyl Cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and simple polyethylene terephthalate is particularly preferred.

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

The surface of the support that is layered with the resin composition can be subjected to matting treatment, corona treatment, and anti-static treatment.

In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer can be used. As the mold release agent used for the mold release layer of the support with the mold release layer, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins The above release agent. The support with a release layer can be a commercial product. For example, there is a PET film with a release layer of an alkyd resin-based release agent as the main component of the Lintec company "SK-1", "AL -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, and "Uni Spin-off" 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 using a support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.

In one embodiment, the resin sheet may further contain other layers as necessary. Examples of the other layer include a protective film that can be provided on a surface that is not bonded to the support of the resin composition layer (that is, the surface opposite to the support), and a protective film based on the support. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion or scratches of garbage on the surface of the resin composition layer.

The resin sheet can be manufactured by, for example, preparing a resin paint in which the resin composition is dissolved in an organic solvent, applying the resin paint to the support using a die coating or the like, and further drying to form a resin composition layer. .

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Acetates such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide ( DMAc) and amide-based solvents such as N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by well-known methods, such as heating and blowing hot air. Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is dried to 10% by mass or less, preferably dried to 5% by mass or less. Although it differs depending 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 of an organic solvent, dry it at 50°C to 150°C for 3 to 10 minutes Instead, a resin composition layer can be formed.

The resin sheet can be rolled into a roll for storage. When the resin sheet has a protective film, it can be used after peeling off the protective film.

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

The printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-mentioned resin sheet, for example. (I) Step of bonding the resin composition layer of the synthetic resin sheet on the inner layer substrate and the inner layer substrate (II) The step of thermally curing 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, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, Thermosetting polyphenylene ether substrates, etc. In addition, the substrate may have a conductive layer on the one side or on both sides, and the conductive layer may also be patterned. An inner substrate with a conductor layer (loop) formed on one or both sides of the substrate is called an "inner circuit substrate." In addition, when manufacturing a printed wiring board, an intermediate product in which an insulating layer and/or a conductive layer must be further formed is also included in the so-called "inner substrate" in the present invention. If the printed wiring board is a circuit board with a built-in part, an inner-layer substrate with built-in parts can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet on the inner layer substrate from the support side. As a member that heats and presses the resin sheet on the inner substrate (hereinafter also referred to as "heat press member"), for example, a heated metal plate (SUS mirror plate, etc.) or metal roll (SUS roll) can be cited. In addition, instead of directly pressing the heating and pressing member on the resin sheet, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber in order to make the resin sheet follow the surface irregularities of the inner substrate.

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

Laminating can be done by vacuum lamination. Examples of commercially available vacuum laminates include vacuum press laminates manufactured by Meiji Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko/Materials, and batch vacuum press laminates.

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

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, the thermal curing conditions of the resin composition layer may vary depending on the type of resin composition. The curing temperature is preferably 120°C to 240°C, preferably 150°C to 220°C, and more preferably 170°C to 210°C. The curing time is preferably 5 minutes to 120 minutes, preferably 10 minutes to 100 minutes, and 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, the resin composition layer can be thermally cured first, and the resin composition can be cured at a temperature above 50°C and below 120°C (preferably 60°C or more and 115°C or less, preferably 70°C or more and 110°C or less). The layer is preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of further forming a conductor layer can be further carried out. These steps (III) to (V) are used in the manufacture of printed wiring boards, which can be implemented in accordance with various known methods for the industry. Moreover, when the support can be removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or in step ( IV) and step (V). In addition, the formation of the insulating layer and the conductor layer of steps (II) to (V) can be repeated as necessary to form a multilayer wiring board.

Step (III) is a step of making holes in the insulating layer, whereby holes such as through holes and through holes can be formed in the insulating layer. Step (III) is the composition of the resin composition used in the formation of the insulating layer. For example, it can be implemented using a drill, a laser, a plasma, etc. The size or shape of the 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), stains can also be removed. The procedures and conditions of the roughening treatment are not particularly limited, and known procedures and conditions generally used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment by the swelling liquid, the roughening treatment by the oxidizing agent, and the neutralization treatment by the neutralization liquid can be sequentially performed to make the insulating layer rough. The swelling liquid used in the roughening treatment is not particularly limited, but an alkaline solution, a surfactant solution, etc. can be mentioned. An alkaline solution is preferred. As the alkaline solution, sodium hydroxide solution or potassium hydroxide solution is preferred. . As the swelling liquid sold, for example, "Swelling Dip SecurigansP" manufactured by Atotech Japan, "Swelling Dip SecurigansSBU", "Swelling dip securigantP" and the like can be mentioned. The swelling treatment by the swelling liquid is not particularly limited, and it can be performed, for example, by immersing the insulating layer with a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, but for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferable to immerse the insulating layer in an oxidizing agent solution heated at 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 oxidizing agents include alkaline permanganic acid solutions such as "Concentrate compact CP" manufactured by Atotech Japan and "Dosing Solution Security P". In addition, as the neutralizing liquid used in the roughening treatment, an acidic aqueous solution is preferable, and as a commercially available product, for example, "Reduction Solution Seculigant P" manufactured by Atotech Japan can be cited. The treatment by the neutralization liquid can be performed by immersing the processed surface roughened by the oxidizing agent in the neutralization liquid at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of workability, etc., a method of immersing the object roughened by the oxidizing agent in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes is preferred.

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

Step (V) is a step of forming a conductive layer, forming a conductive layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 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 may be a single metal layer or an alloy layer. As the alloy layer, for example, it may have 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 layer formed. Among them, it is also based on the generality, cost, ease of drawing, etc. of the conductor layer. Single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel, chromium alloy, copper, etc. The alloy layer of 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 preferable. The single metal layer is better.

The conductor layer can be a single-layer structure, a single metal layer made of different types of metals or alloys, or a multiple-layer structure in which two or more alloy layers are laminated. When the conductor layer is a multi-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 is determined by the design of the desired printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

For one embodiment, the conductive layer can be formed by plating. For example, by plating on the surface of the insulating layer by a technique known in the past such as the semi-additive method and the full-additive method, a conductor layer with the desired wiring pattern can be formed. From the viewpoint of the ease of manufacture, The semi-additive method is preferred. The following shows an example in which the conductor layer is formed by the semi-additive method.

First, a plating seed layer is formed by electroless plating on the surface of the insulating layer. Secondly, on the formed plating seed layer, a mask pattern corresponding to the desired wiring pattern with a part of the plating seed layer exposed is formed. 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 is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor Device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices provided in electrical products (for example, computers, mobile phones, digital cameras, and televisions, etc.) and vehicles (for example, bicycles, automobiles, trams, ships, and airplanes).

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor wafers) due to the conduction of the printed wiring board. The so-called "conducting point" is the "place where electrical information in the printed wiring board is transmitted". The place can be either on the surface or in the 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 wafer during the manufacture of semiconductor devices is not particularly limited as long as the semiconductor wafer can effectively perform its functions, but specific examples include wire bonding mounting methods and flip chip mounting Methods, mounting method by bumpless laminated layer (BBUL), mounting method by anisotropic conductive film (ACF), mounting method by non-conductive film (NCF), etc. The so-called "mounting method by bumpless laminated layer (BBUL)" means that "the semiconductor wafer is directly embedded in the recess of the printed wiring board, and the semiconductor wafer is connected to the wiring on the printed wiring board. Mounting method". [Example]

The following examples illustrate the present invention in further detail, but the present invention is not limited to these examples only. In addition, for the following description, unless otherwise stated, "parts" and "%" respectively mean "parts by mass" and "% by mass".

＜(B) Judgment of liquid or semi-solid component of hardener of liquid or semi-solid component> For (B) the liquid or semi-solid composition of hardeners in the form of liquid or semi-solid components, the determination of the liquid state, semi-solid composition state, and solid composition state can be based on the Japanese provincial ordinance concerning the test and properties of dangerous substances (Japan Heisei First Year Autonomous Ministry Order No. 1 No.) attached to the 2nd "Method of Confirming Liquid State". "Method of confirming liquid state" can be performed according to the above method. The results are shown below. "JER Cure W" manufactured by Mitsubishi Chemical Corporation: liquid "KAYAHARD A-A" manufactured by Nippon Kayaku Corporation: Liquid "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd.: liquid "NK ester DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd.: liquid "NK ester A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd.: liquid "RE-810NM" manufactured by Nippon Kayaku Corporation: Liquid "BMI689" Produced by Designer Molecules: Liquid "Ricon100" manufactured by CRAY VALLEY: liquid "Ricon130MA13" manufactured by CRAY VALLEY: liquid "Ricon150" manufactured by CRAY VALLEY: liquid "JP-100" Made by Soda Corporation: Liquid "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.: liquid "L-DAIC" manufactured by Shikoku Chemical Industry Co., Ltd.: liquid "TAIC" manufactured by Nippon Kasei Corporation: Liquid "DAISO DAP™ Monomer" manufactured by Osaka Soda: Liquid "MDAC" manufactured by Osaka Soda: Liquid "DAD" made by NISSHOKU TECHNO FINE CHEMICAL CO., LTD.: Liquid

[Synthesis example: Synthesis of polyimide resin] Prepare a 500mL separable flask 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 cause reaction. Next, the temperature of the reaction solution was raised, and while maintaining the temperature at about 160°C, the condensation water and toluene were simultaneously removed azeotropically under a nitrogen stream. Confirm that the quantitative amount of water has been accumulated in the moisture quantitative receiver, and that no water flows out. After confirmation, the temperature of the reaction solution was further increased, and stirring was performed at 200°C for 1 hour. After cooling, a polyimide solution containing a polyimide resin having a 1,1,3-trimethylindan skeleton (non-volatile content 20% by mass) was obtained. The obtained polyimide resin 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 is 12,000.

[Example 1. Preparation of resin composition 1] Biphenyl aralkyl maleimide resin (MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275g/eq, non-volatile content 70% MEK/toluene mixed Solution) 180 parts, 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Corporation, weight average molecular weight 30,000) were dissolved in 30 parts of toluene and 30 parts of MEK while stirring. After cooling the resulting solution to room temperature, 18 parts of an amine-based non-solid component hardener (manufactured by Mitsubishi Chemical Corporation "jER Cure W") and an inorganic filler (vinyl-based coupling agent (Shin-Etsu Chemical 300 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm)) surface-treated by Kogyo Co., Ltd., and uniformly dispersed in a high-speed rotating mixer to obtain resin composition 1 .

MIR-3000-70MT is a compound represented by the following structural formula. In the formula, e1 represents an integer of 1-100.

[Example 2. Preparation of resin composition 2] For Example 1, 1) Change 18 parts of amine non-solid component hardener (Mitsubishi Chemical Corporation "jER Cure W") to 25 parts of amine non-solid component hardener (Nippon Kayaku Corporation "KAYAHARD A-A"), 2) Change 10 parts of polycarbonate resin ("FPC2136" manufactured by Mitsubishi Gas Chemical Corporation, with a weight average molecular weight of 30,000) to 50 parts of paint containing 20% by mass of polyimide resin obtained in the synthesis example. Except for the above matters, a resin composition 2 was obtained in the same manner as in Example 1.

[Example 3. Preparation of resin composition 3] For Example 1, 1) Change 18 parts of amine-based non-solid component hardener (Mitsubishi Chemical Corporation "jER Cure W") to a phenol resin containing allyl groups (allyl-based non-solid component hardener with a phenol ring, Meiwa "MEH-8000H" manufactured by Kasei Corporation, phenol equivalent 240) 20 parts, 2) Change 10 parts of polycarbonate resin (Mitsubishi Gas Chemical Corporation "FPC2136", weight average molecular weight 30,000) to phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30% by mass MEK and cyclohexanone) 1:1 solution, weight average molecular weight 35000) 33.3 parts, 3) Further use 0.5 part of a polymerization initiator ("Perbutyl C" manufactured by NOF Corporation). Except for the above matters, a resin composition 3 was obtained in the same manner as in Example 1.

[Example 4. Preparation of resin composition 4] For Example 3, 1) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", a 1:1 solution of 30% by mass solid content MEK and cyclohexanone, weight average molecular weight 35000) to contain polyamide obtained from Synthesis Example 50 parts of imine resin 20% by mass paint, 2) Furthermore, 10 parts of a carbodiimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216, solid content of 50% by mass in toluene solution) was used. The resin composition 4 was obtained in the same manner as in Example 3 except for the above matters.

[Example 5. Preparation of resin composition 5] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenol ring, "MEH-8000H" manufactured by Meiwa Chemicals Co., Ltd., phenol equivalent 240) to bifunctional methacrylate ((Meth)acrylic non-solid component hardener, "NK ester DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd., molecular weight 332) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", a 1:1 solution of 30% by mass solid content of MEK and cyclohexanone, weight average molecular weight 35,000) to polyamide imide resin ( "Unidick V-8000" manufactured by DIC, with a weight average molecular weight of 11,000 and a non-volatile content of 40% by mass of ethyl diethylene glycol acetate solution) 25 parts, 3) 300 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (vinyl coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co.)) Change to 300 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (methacrylic coupling agent ("KBM503" manufactured by Shin-Etsu Chemical Co., Ltd.)) . A resin composition 5 was obtained in the same manner as in Example 3 except for the above matters.

Unidick V-8000 is a compound represented by the following structural formula. In the formula, e2 represents an integer of 0-15.

[Example 6. Preparation of resin composition 6] For Example 5, 1) Change 13 parts of bifunctional methacrylate ((meth)acrylic non-solid component hardener, manufactured by Shinnakamura Chemical Industry Co., Ltd. "NK ester DCP", molecular weight 332) to bifunctional acrylate ((meth) ) Acrylic non-solid component hardener, "NK ester A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd., molecular weight 326) 13 parts, 2) 25 parts of polyamide imide resin ("Unidick V-8000" manufactured by DIC Corporation, a weight average molecular weight of 11000, and 40% by mass of non-volatile content of ethyl diglycol acetate solution) was changed to one containing acid anhydride groups 10 parts of vinyl resin (polystyrene resin, "EF-40" manufactured by CRAY VALLEY, weight average molecular weight 11,000). A resin composition 6 was obtained in the same manner as in Example 5 except for the above matters.

EF-40 is a compound represented by the following structural formula. In the formula, e3 represents an integer of 8-12, and e4 represents an integer of 1-8.

[Example 7. Preparation of resin composition 7] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (an allyl-based non-solid component hardener with a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to an epoxy-containing olefin 13 parts of propyl-based non-solid component hardener ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220), 2) Further use 2 parts of hardening accelerator (2P4MZ (2-phenyl-4-methylimidazole) solid content 2.5% MEK solution). Except for the above matters, a resin composition 7 was obtained in the same manner as in Example 3.

RE-810NM is a compound represented by the following structural formula. e5 represents an integer of 0-5.

[Example 8. Preparation of resin composition 8] For Example 7, 1) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", a 1:1 solution of 30% by mass solid content of MEK and cyclohexanone, weight average molecular weight 35,000) to hydrogenated styrene-based thermoplastic elastomer ( 10 parts of "H1043" manufactured by Asahi Kasei Corporation, weight average molecular weight 35000), 2) Further use 10 parts of active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of 223, solid content of 65% by mass toluene solution), 3) Change 2 parts of hardening accelerator (MEK solution with 2.5% solid content of 2P4MZ) to 2 parts of hardening accelerator (MEK solution with 2.5% solid content of 1B2PZ (1-benzyl-2-phenylimidazole)) , 4) 300 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (vinyl coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co.)) Changed to spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 copies. Except for the above matters, a resin composition 8 was obtained in the same manner as in Example 7.

[Example 9. Preparation of resin composition 9] For Example 5, 1) Change 13 parts of bifunctional methacrylate ((meth)acrylic non-solid component hardener, "NK ester DCP" manufactured by Shinnakamura Chemical Industry Co., Ltd., molecular weight 332) to liquid bismaleimide (Maleimide-based non-solid component hardener, "BMI689" manufactured by Designer Molecules, Maleimide equivalent 345) 13 parts, 2) 25 parts of polyamide imine resin ("Unidick V-8000" manufactured by DIC Corporation, a weight average molecular weight of 11,000, and 40% by mass of non-volatile content of ethyl diethylene glycol acetate solution) was changed to polyester resin ( "OKP4HT" manufactured by Osaka Gas Chemical Corporation, with a weight average molecular weight of 50,000) 10 parts. Except for the above matters, a resin composition 9 was obtained in the same manner as in Example 5.

BMI689 is a compound represented by the following structural formula.

[Example 10. Preparation of resin composition 10] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (an allyl-based non-solid component hardener with a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., 240 phenol equivalent) to liquid styrene butadiene Olefin polymer (butadiene-based non-solid component hardener, "Ricon100" manufactured by CRAY VALLEY, 25% styrene content, Mn about 4500) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to hydrogenated styrene-based thermoplastic elastomer ( "H1043" manufactured by Asahi Kasei Corporation, with a weight average molecular weight of 35,000) 10 parts. Except for the above matters, a resin composition 10 was obtained in the same manner as in Example 3.

[Example 11. Preparation of resin composition 11] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to a liquid state containing anhydride groups Butadiene polymer (butadiene-based non-solid component hardener, "Ricon130MA13" manufactured by CRAY VALLEY, acid anhydride equivalent 732, Mn about 2900) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight of 35000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to vinyl resin containing acid anhydride groups ("EF-40" manufactured by CRAY VALLEY, weight average molecular weight 11,000) 10 parts. Except for the above matters, a resin composition 11 was obtained in the same manner as in Example 3.

[Example 12. Preparation of resin composition 12] For Example 3, 1) 20 parts of phenol resin containing allyl groups (allyl-based non-solid component hardener with phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) 20 parts are changed to liquid butadiene polymer (Butadiene-based non-solid component hardener, "Ricon150" manufactured by CRAY VALLEY, Mn approximately 3900) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight of 35000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to contain polyamide obtained from the synthesis example 50 parts of imine resin 20% by mass paint. Except for the above matters, a resin composition 12 was obtained in the same manner as in Example 3.

[Example 13. Preparation of resin composition 13] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenolic ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to epoxidized polybutadiene (Butadiene-based non-solid component hardener, "JP-100" manufactured by Soda Corporation, epoxy equivalent 210, Mn about 1300) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polyamide imide resin ( "Unidick V-8000" manufactured by DIC Corporation, 25 parts of ethyl diethylene glycol acetate solution with a weight average molecular weight of 11,000 and a non-volatile content of 40% by mass, 3) Further use 2 parts of hardening accelerator (1B2PZ solid content 2.5% MEK solution). Except for the above matters, a resin composition 13 was obtained in the same manner as in Example 3.

[Example 14. Preparation of resin composition 14] For Example 7, 1) Change 13 parts of an epoxy-based allyl-based non-solid component hardener ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220) to epoxidized polybutadiene (butadiene-based Non-solid component hardener, "JP-100" manufactured by Japan Soda Corporation, epoxy equivalent 210, Mn about 1300) 13 parts, 2) Further use 3 parts of benzoxazine-based hardener ("ODA-BOZ" manufactured by JFE Chemical Company), 3) 300 parts of spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (vinyl coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co.)) Changed to spherical silica ("SO-C2" manufactured by Admatechs, average particle size 0.5μm) surface-treated with an inorganic filler (phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) 300 copies. Except for the above matters, a resin composition 14 was obtained in the same manner as in Example 7.

[Example 15. Preparation of resin composition 15] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to bifunctional acrylate (( Meth) acrylic non-solid component hardener, "NK ester A-DOG" manufactured by Shinnakamura Chemical Industry Co., Ltd., molecular weight 326) 5 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35,000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polycarbonate resin (Mitsubishi Gas Chemical "FPC2136" manufactured by the company, with a weight average molecular weight of 30000) 10 parts, 3) Further use 20 parts of MEK solution of 50% solid content of 4,4-diaminodiphenylmethane. Except for the above matters, a resin composition 15 was obtained in the same manner as in Example 3.

[Example 16. Preparation of resin composition 16] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenolic ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to have benzoxazine ring 20 parts of allyl-based non-solid component hardener ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd., MEK solution with 65% solid content), 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35,000, solid content 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polyester resin (Osaka Gas Chemical Corporation) Make "OKP4HT", weight average molecular weight 50000) 10 parts. Except for the above matters, a resin composition 16 was obtained in the same manner as in Example 3.

ALP-d is a compound represented by the following structural formula.

[Example 17. Preparation of resin composition 17] For Example 8, 1) Change 13 parts of allyl-based non-solid component hardeners with epoxy groups ("RE-810NM" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 220) to allyl-based hardeners with benzoxazine ring Non-solid component hardener ("ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd., MEK solution with 65% solid content) 20 parts, 2) Change 10 parts of hydrogenated styrene-based thermoplastic elastomer ("H1043" manufactured by Asahi Kasei Co., Ltd., weight average molecular weight 35,000) to polyamide imide resin ("Unidick V-8000" manufactured by DIC Co., Ltd., weight average molecular weight 11,000). 25 parts of ethyl diethylene glycol acetate solution (40% by mass of volatile components), 3) Change 10 parts of active ester hardener (made by DIC Corporation "HPC-8000-65T", active base equivalent of 223, solid content 65% by mass toluene solution) to bisphenol A epoxy resin (made by Mitsubishi Chemical Corporation) "828US", epoxy equivalent is about 180)5 parts. Except for the above matters, a resin composition 17 was obtained in the same manner as in Example 8.

[Example 18. Preparation of resin composition 18] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenolic ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) with isocyanuric acid 13 parts of cyclic allyl-based non-solid component hardener ("L-DAIC" manufactured by Shikoku Chemical Industry Co., Ltd.), 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35,000, solid content 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polyester resin (Osaka Gas Chemical Corporation) Make "OKP4HT", weight average molecular weight 50000) 10 parts. Except for the above matters, a resin composition 18 was obtained in the same manner as in Example 3.

[Example 19. Preparation of resin composition 19] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenolic ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) with isocyanuric acid 13 parts of cyclic allyl-based non-solid component hardener (Triallyl isocyanurate, "TAIC" manufactured by Nippon Kasei Co., Ltd., molecular weight 249), 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35,000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polycarbonate resin (Mitsubishi Gas Chemical "FPC2136" manufactured by the company, with a weight average molecular weight of 30000) 10 parts. Except for the above matters, a resin composition 19 was obtained in the same manner as in Example 3.

[Example 20. Preparation of resin composition 20] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (allyl-based non-solid component hardener with phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to allyl-based non-solid Composition hardener (ortho diallyl phthalate, "DAISO DAP™ Monomer" manufactured by Osaka Soda, molecular weight 246) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, solid content of 30% by mass of a 1:1 solution of MEK and cyclohexanone) to contain polyamide obtained from the synthesis example 50 parts of imine resin 20% by mass paint. Except for the above matters, a resin composition 20 was obtained in the same manner as in Example 3.

[Example 21. Preparation of resin composition 21] For Example 3, 1) Change 20 parts of allyl-containing phenol resin (an allyl-based non-solid component hardener with a phenol ring, "MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) to cyclohexane dicarboxylic acid Diallyl (allyl-based non-solid component hardener, "MDAC" manufactured by Osaka Soda, molecular weight 252) 13 parts, 2) Change 33.3 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35,000, solid content 30% by mass of a 1:1 solution of MEK and cyclohexanone) to polyester resin (Osaka Gas Chemical Corporation) Make "OKP4HT", weight molecular weight 50000) 10 parts. Except for the above matters, a resin composition 21 was obtained in the same manner as in Example 3.

[Example 22. Preparation of resin composition 22] Biphenyl aralkyl type maleimide resin (MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275g/eq, mixed with 70% non-volatile MEK/toluene Solution) 180 parts, phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", weight average molecular weight 35000, solid content of 30% by mass of MEK and cyclohexanone 1:1 solution) 33.3 parts, toluene 20 parts, MEK 20 parts, 13 parts of diallyl cyclohexanedicarboxylic acid ("MDAC" manufactured by Osaka Soda, molecular weight 252), 5 parts of bisphenol A epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 180), 3 parts of a phenolic hardener containing a triazine skeleton (LA-3018-50P, manufactured by DIC Corporation, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%), active ester hardener (DIC "HPC-8000-65T" manufactured by the company, active group equivalent 223, solid content 65% by mass toluene solution) 5 parts, polymerization initiator (NOF Corporation "perbutyl C") 0.5 parts, hardening accelerator ( 2 parts of 1B2PZ MEK solution with 2.5% solid content), spherical silica (SO-C2, manufactured by Admatechs), surface-treated with an inorganic filler (vinyl-based coupling agent ("KBM1003" manufactured by Shin-Etsu Chemical Co., Ltd.)) , Average particle size 0.5μm)) 150 parts, spherical silica (SO-C2 made by Admatechs) surface-treated with inorganic filler (phenylaminosilane coupling agent ("KBM573" made by Shin-Etsu Chemical Co., Ltd.)) ", an average particle size of 0.5 μm)) 150 parts were uniformly dispersed with a high-speed rotating mixer to obtain a resin composition 22.

[Example 23. Preparation of resin composition 23] For Example 9, 1) Change 13 parts of liquid bismaleimide (maleimide non-solid component hardener, "BMI689" manufactured by Designer Molecules, maleimide equivalent 345) to diphthalic acid Allyl (allyl-based non-solid component hardener, "DAD" manufactured by NISSHOKU TECHNO FINE CHEMICAL CO., LTD., molecular weight 322) 13 parts, 2) Change 10 parts of polyester resin (Osaka Gas Chemical Corporation "OKP4HT", weight average molecular weight 50,000) to 10 parts of polycarbonate resin (Mitsubishi Gas Chemical Corporation "FPC2136", weight average molecular weight 30,000). Except for the above matters, a resin composition 23 was obtained in the same manner as in Example 9.

[Comparative Example 1. Preparation of resin composition 1 for comparison] In Example 3, 20 parts of allyl-containing phenol resin ("MEH-8000H" manufactured by Meiwa Chemical Co., Ltd., phenol equivalent 240) was not used. Except for the above matters, the resin composition 1 for comparison was obtained in the same manner as in Example 3.

[Comparative example 2. Preparation of resin composition 2 for comparison] In Example 11, 10 parts of an acid anhydride group-containing vinyl resin (“EF-40” manufactured by CRAY VALLEY Co., Ltd., weight average molecular weight 11,000) was not used. Except for the above matters, the resin composition 2 for comparison was obtained in the same manner as in Example 11.

[Comparative example 3. Preparation of resin composition 3 for comparison] For Example 2, the biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275g/eq, non-volatile content 70% 180 parts of MEK/toluene mixed solution) was changed to 126 parts of polyphenylmethane maleimide (“BMI2300” manufactured by Daiwa Chemical Co., Ltd.). Except for the above matters, in the same manner as in Example 2, a resin composition 3 for comparison was obtained.

BMI2300 is a compound represented by the following structural formula. n10 represents an integer of 1-10.

[Production of Resin Sheet] As a support, a polyethylene terephthalate film ("Luminor R80" made by Toray Company" with an alkyd resin-based release agent ("AL-5" made by Lintec) subjected to a mold release treatment was prepared, with a thickness of 38μm, softened Point 130°C).

Resin compositions 1 to 23 and comparative resin compositions 1 to 3 were applied on a support with a mold until the thickness of the dried resin composition layer became 40 μm, and dried at 70°C to 95°C for 4 minutes, A resin composition layer is formed on the support. Next, a rough surface of polypropylene film ("Alfan MA-411" made by Prince F-tex, 15μm in thickness), which is a protective film, is attached to the surface that is not bonded to the support of the resin composition layer. Thereby, a resin sheet A which is a support, a resin composition layer and a protective film in this order can be obtained.

[Measurement of peel strength of plating conductor layer] (1) Preparation of inner substrate A copper laminate (copper foil thickness of 18μm, substrate thickness of 0.4mm, Panasonic "R1515A") is applied to both sides of the glass cloth substrate epoxy resin forming the inner circuit with a microetchant (MEC "CZ8101") ") After 1μm etching, the copper surface is roughened.

(2) Laminating of resin sheet The protective film was peeled from the resin sheet A, and the resin composition layer was exposed. A batch-type vacuum press laminate (manufactured by Nikko/Materials, 2-stage accumulation laminate "CVP700") was used to contact the upper synthetic resin composition layer on both sides of the inner substrate with the inner substrate. The lamination is carried out by reducing the pressure for 30 seconds and adjusting the air pressure to 13 hPa or less, and then pressing the pressure at a pressure of 0.74 MPa at 120°C for 30 seconds. Next, hot pressing is performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet was put into an oven at 100°C for heating for 30 minutes, and then moved to an oven at 180°C for heating for 30 minutes to heat the resin composition layer to form an insulating layer. After that, the support was peeled off to obtain a cured substrate A having an insulating layer, an inner substrate, and an insulating layer in this order.

(4) Coarse treatment On the hardened substrate A, the stain removal treatment is performed as a roughening treatment. As the stain removal treatment, the following wet stain removal treatment can be implemented. (Wet stain removal treatment) The hardened substrate A was immersed in a swelling solution ("Swelling Dip Securigant P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then in an oxidizing agent solution (Atotech Japan "Concentrate compactCP" manufactured by the company, immersed in an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4% at 80°C for 15 minutes, followed by a neutralization solution ("Reduction Solution SeculigantP" manufactured by Atotech Japan) , Sulfuric acid aqueous solution) was immersed in 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

(5) The formation of the conductor layer is based on the semi-additive method, and the conductor layer is formed on the roughened surface of the insulating layer. That is, the roughened substrate was immersed in an electroless plating solution containing PdCl ₂ at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Next, after heating at 150° C. for 30 minutes and annealing treatment, an etching resist is formed, and a pattern is formed by etching. After that, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm, and annealing treatment was performed at 200° C. for 60 minutes. The resulting substrate is called "evaluation substrate B".

＜Measurement of peel strength of plated conductor layer＞ The measurement of the peel strength between the insulating layer and the conductor layer was performed in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, cut a portion of 10mm wide and 100mm long into the conductor layer of the evaluation substrate B, peel off the end and clamp it with a jig. At room temperature, it is measured when it is pulled 35mm in the vertical direction at a speed of 50mm/min. The load (kgf/cm) to obtain the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE Corporation) was used for the measurement.

[Determination of the tensile strength of copper foil] (1) Basic treatment of copper foil The glossy surface of "3EC-III" (electric field copper foil, 35μm) manufactured by Mitsui Metals Mining Co., Ltd. is etched with a microetching agent ("CZ8101" manufactured by MEC Corporation) for 1μm to roughen the copper surface. Rust treatment (CL8300). Further heat treatment in an oven at 130°C for 30 minutes. This copper foil is called CZ copper foil.

(2) Preparation of the inner substrate The glass cloth substrate epoxy resin with the inner circuit formed on both sides of the copper laminate (the thickness of the copper foil is 18μm, the thickness of the substrate is 0.4mm, Panasonic company "R1515A") with a microetchant (MEC company " CZ8101”) After 1μm etching, the copper surface is roughened.

(3) Laminating of copper foil and formation of insulating layer The protective film is peeled from the resin sheet A to expose the resin composition layer. A batch-type vacuum press laminate (manufactured by Nikko/Materials, 2-stage accumulation laminate "CVP700") was used to bring the resin composition layer into contact with the inner substrate and laminate it on both sides of the inner substrate. The lamination is performed by adjusting the air pressure to 13 hPa or less by reducing the pressure for 30 seconds, and then performing pressing at 120° C. and 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds. The processed surface of the CZ copper foil was laminated on the resin composition layer under the same conditions as described above. Then, the resin composition layer was cured under curing conditions of 200° C. and 90 minutes to form an insulating layer, and a sample A was made.

＜Measurement of copper foil pull-out strength (copper foil adhesion)＞ The prepared sample A was cut into small pieces of 150×30 mm. Use a cutter to cut out a 10mm wide and 100mm long part of the copper foil part of the small piece, peel off one end of the copper foil and clamp it with a jig, and measure when it is pulled 35mm vertically at a speed of 50mm/min at room temperature The load (kgf/cm), the peel strength is obtained. The measurement used a tensile tester ("AC-50C-SL" manufactured by TSE Corporation). The measurement was performed in accordance with Japanese Industrial Standards (JIS C6481).

[Measurement of dielectric properties (dielectric rate, dielectric loss tangent)] The protective film was peeled off from the resin sheet A produced in the example and the comparative example, and after heating at 200° C. for 90 minutes to thermally cure the resin composition layer, the support was peeled off. The obtained cured product is called "evaluation cured product C". The cured product C for evaluation was cut into a test piece with a width of 2 mm and a length of 80 mm. For this test piece, "HP8362B" manufactured by Agilent Technologies was used, and the dielectric constant and dielectric loss tangent were measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The measurement was performed on 3 test pieces, and the average value was calculated. Moreover, the evaluation hardened|cured material C of the comparative example 2 which does not use (C) component is too weak in strength, and it is difficult to handle. Therefore, the dielectric properties of Comparative Example 2 cannot be measured.

[Assessment of Laminarity] (1) Preparation of inner substrate The conductor thickness is 35μm to form L (line: wiring width)/S (space: interval width)=160μm/160μm, a glass cloth base material with a grid-like conductor pattern, epoxy resin laminate on both sides of copper (substrate thickness 0.8 mm, "R1515A" manufactured by Panasonic), both sides are etched with a micro-etching agent ("CZ8101" manufactured by MEC) for 1 μm, and then the copper surface is roughened.

(2) Laminating of resin sheet The protective film was peeled from the resin sheet A to expose the resin composition layer. Using a batch-type vacuum press laminate (two-stage accumulation laminate "CVP700" manufactured by Nikko/Materials), the resin composition layer is to be in contact with the glass cloth substrate epoxy resin on both sides of the copper laminate, and then laminated The epoxy resin on both sides of the glass cloth substrate is pasted on both sides of the copper laminate. The lamination was carried out by adjusting the air pressure to 13 hPa or less under reduced pressure for 30 seconds, and then performing pressing at 120°C and 0.74 MPa for 30 seconds. Next, hot pressing is performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Thermal curing of resin composition layer After that, the glass cloth substrate epoxy resin double-sided copper-clad laminate of the laminated resin sheet was put into an oven at 100°C for 30 minutes heating, and then moved to an oven at 180°C and heated for 30 minutes to make the resin composition The layer is thermally cured to form an insulating layer. After that, the support was peeled off to obtain a hardened substrate D having an insulating layer, a glass cloth base epoxy resin double-sided copper laminate, and an insulating layer in this order.

(4) Laminarity evaluation The value of the unevenness difference (Rt: maximum peak-to-valley) between the conductor in the insulating layer of the hardened substrate D and the other parts is using a non-contact surface roughness meter (WYKO NT3300 manufactured by VICO INSTRUMENTS). VSI mode, and 10 times lens, the measurement range is set to 1.2mm × 0.91mm to obtain the value. And when there is no void after lamination, and the unevenness difference between the conductor and the other part is less than 5μm, it is evaluated as "○". There is no void after lamination, but the unevenness difference between the conductor and the other part When it is 5μm or more, it is evaluated as "△", and when voids are generated after lamination, it is evaluated as "×".

Regarding Examples 1 to 23, even when the components (D) to (H) are not contained, and there is a certain degree of difference, the same results as the above-mentioned examples were confirmed.

11A: Marking 12B: Marking 13a: Rubber plug 13b: Rubber plug 14: Thermometer 10a: Test tube for temperature measurement 10b: Test tube for temperature measurement

[Fig. 1] Fig. 1 shows a schematic side view of an example of two test tubes used for judging liquid, semi-solid and solid components of thermosetting resin.

Claims (16)

A resin composition characterized by containing (A) a maleimide compound having a biphenyl type structure, (B) Hardener in liquid or semi-solid form, and (C) High molecular weight components. The resin composition of claim 1, wherein component (A) is represented by the following formula (A-3);

In formula (A-3), R ³ and R ⁸ represent a maleimide group, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ⁹ and R ¹⁰ each Each independently represents a substituent; a1 and b1 each independently represent an integer of 0-4, m1 and m2 each independently represent an integer of 1-10, and n represents an integer of 1-100. The resin composition of claim 1, wherein the content of the component (A) is 10% by mass or more and 40% by mass when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein component (B) is selected from the group consisting of amine-based non-solid component-like hardeners, (meth)acrylic-based non-solid component-like hardeners, allyl-based non-solid component-like hardeners, At least one of maleimide-based non-solid component-like hardeners and butadiene-based non-solid component-like hardeners. The resin composition of claim 4, wherein the component (B) is at least one of an allyl-based non-solid component-like hardener and a maleimide-based non-solid component-like hardener. The resin composition of claim 1, wherein the content of component (B) is 0.1% by mass or more and 15% by mass or less when the nonvolatile content in the resin composition is 100% by mass. The resin composition of claim 1, wherein component (C) is a thermoplastic resin. The resin composition of claim 7, wherein the thermoplastic resin is at least one selected from the group consisting of polyimide resin, polycarbonate resin and phenoxy resin. The resin composition of claim 1, wherein the content of component (C) is 0.5% by mass or more and 10% by mass or less when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, which further contains (D) an inorganic filler. The resin composition of claim 10, wherein the content of component (D) is 50% by mass or more when the non-volatile content in the resin composition is 100% by mass. The resin composition of claim 1, which is used for forming an insulating layer. The resin composition of claim 1, which is used for forming an insulating layer when forming a conductor layer. A resin sheet characterized by comprising a support, and a resin composition layer containing the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board characterized by including an insulating layer formed of a cured product of the resin composition of any one of claims 1-13. A semiconductor device characterized by including a printed wiring board as claimed in claim 15.

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