TW202128871A - Resin composition, cured product of resin composition, resin sheet, printed wiring board, flexible substrate, and semiconductor device wherein the resin composition contains a polymer containing a butadiene skeleton, an inorganic filler, and a benzoxazine compound containing a substituted or unsubstituted allyl group - Google Patents

Abstract

The subject of the present invention is to provide a resin composition which can obtain a cured product having excellent heat resistance and moisture resistance; a cured product of the resin composition; a resin sheet containing the resin composition; a printed wiring board or a flexible substrate containing an insulating layer formed by the cured product of the resin composition and a semiconductor device. The solution of the invention is the resin composition, containing (A) a polymer containing a butadiene skeleton, (B) an inorganic filler, and (C) a benzoxazine compound containing a substituted or unsubstituted allyl group. The resin composition is characterized in that if the nonvolatile component in the resin composition is set to be 100 mass%, the content of the inorganic filler (B) is more than 0 mass% and less than 60 mass%.

Description

Resin composition, cured resin composition, resin sheet, printed wiring board, flexible substrate, and semiconductor device

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

A semiconductor device including a thin and light flexible substrate as a printed wiring board is known. The so-called flexible substrate is generally inserted into a flexible printed wiring board (FPC) that has flexibility. Depending on the circumstances, there may also be a circuit board where components are further mounted on the printed wiring board. In the printed wiring board, there is a printed wiring board composed of an insulating layer formed by a cured product of a resin composition. Since the insulating layer of the printed wiring board is formed of a hardened resin composition, thinning and weight reduction can be achieved.

As a resin composition for forming an insulating layer of a printed wiring board, for example, Patent Document 1 discloses a bismaleimide resin composition. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-074871 A

[The problem to be solved by the invention]

However, when a resin composition containing a polymer containing a butadiene skeleton and an inorganic filler is used, the heat resistance and moisture resistance of the cured product of the resin composition may decrease. Here, the so-called polymer containing a butadiene skeleton refers to a polymer containing a butadiene skeleton including a butadiene structure, a polybutadiene structure, etc., and is expected to contribute to the flexibility of the flexible substrate Material. Furthermore, although the above-mentioned problems occur significantly on flexible substrates, it is not limited to the fact that flexible substrates also occur on rigid substrates.

Accordingly, there is a demand for a resin composition that can obtain a cured product having excellent heat resistance and moisture resistance.

The subject of the present invention is to provide a resin composition that can obtain a cured product excellent in heat resistance and moisture resistance; a cured product of the resin composition; a resin sheet containing the resin composition; Printed wiring boards or flexible substrates and semiconductor devices with insulating layers formed by objects. [Means to solve the problem]

As a result of diligent research, the inventors found that (A) a polymer containing a butadiene skeleton, (B) an inorganic filler, and (C) a benzoxazine compound containing a substituted or unsubstituted allyl group When the non-volatile content in the resin composition is set to 100% by mass, (B) a resin composition with an inorganic filler content of 60% by mass or less and more than 0% by mass can solve the above problems , And finally completed the present invention.

(上述式(A2-2)中，A^a1 及A^a2 為鍵結部，A^a3 ～A^a6 分別獨立為氫原子、鹵素原子或取代或非取代之碳數1～5的直鏈狀的烷基)。 [5] 如[2]～[4]中任一項所記載之樹脂組成物，其中，(A)成分係一個芳香族基介在二個丁二烯骨架之間的含有丁二烯骨架之聚合物。 [6] 如[1]～[5]中任一項所記載之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(A)成分的含量為15質量%以上。 [7] 如[1]～[6]中任一項所記載之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(A)成分的含量為50質量%以下。 [8] 如[1]～[7]中任一項所記載之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(B)成分的含量為未滿50質量%。 [9] 如[1]～[8]中任一項所記載之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(B)成分的含量為10質量%以上。 [10] 如[1]～[9]中任一項所記載之樹脂組成物，其中，(C)成分係於分子中包含二個以上苯并噁嗪構造的苯并噁嗪化合物。 [11] 如[1]～[10]中任一項所記載之樹脂組成物，其中，(C)成分係於分子中包含二個以上烯丙基的苯并噁嗪化合物。 [12] 如[1]～[11]中任一項所記載之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100質量%時，(C)成分的含量為0.01質量%以上。 [13] 如[1]～[12]中任一項所記載之樹脂組成物，其中，硬化物的吸水率為未滿0.2%。 [14] 如[1]～[13]中任一項所記載之樹脂組成物，其係絕緣層形成用。 [15] 一種如[1]～[14]中任一項所記載之樹脂組成物的硬化物。 [16] 一種樹脂薄片，其係包含支持體、與包含設置在該支持體上之如[1]～[14]中任一項所記載之樹脂組成物的樹脂組成物層。 [17] 一種印刷配線板，其係包含藉由如[1]～[14]中任一項所記載之樹脂組成物之硬化物，或如[15]所記載之硬化物所形成之絕緣層。 [18] 一種可撓性基板，其係包含藉由如[1]～[14]中任一項所記載之樹脂組成物之硬化物，或如[15]所記載之硬化物所形成之絕緣層。 [19] 一種半導體裝置，其係包含如[17]所記載之印刷配線板或如[18]所記載之可撓性基板。 [發明效果]That is, the present invention includes the following contents. [1] A resin composition comprising (A) a polymer containing a butadiene skeleton, (B) an inorganic filler, and (C) a resin containing a substituted or unsubstituted allyl group benzoxazine compound The composition is characterized in that when the non-volatile content in the resin composition is 100% by mass, the content of the (B) inorganic filler is 60% by mass or less and more than 0% by mass. [2] The resin composition as described in [1], wherein the component (A) is a butadiene skeleton-containing polymer containing one or two or more aromatic groups in the molecule. [3] The resin composition according to [2], wherein at least one of the aromatic groups constitutes a part of the phenoxy structure. [4] The resin composition according to [3], wherein the phenoxy structure includes a phenoxy structure represented by the following formula (A2-2).

(In the above formula (A2-2), A ^a1 and A ^a2 are bonding parts, and A ^a3 to A ^a6 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear alkane with 1 to 5 carbon atoms base). [5] The resin composition according to any one of [2] to [4], wherein the component (A) is a polymerization containing butadiene skeleton in which an aromatic group is interposed between two butadiene skeletons Things. [6] The resin composition as described in any one of [1] to [5], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 15% by mass above. [7] The resin composition as described in any one of [1] to [6], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 50% by mass the following. [8] The resin composition as described in any one of [1] to [7], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (B) is less than 50 quality%. [9] The resin composition as described in any one of [1] to [8], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (B) is 10% by mass above. [10] The resin composition according to any one of [1] to [9], wherein the component (C) is a benzoxazine compound containing two or more benzoxazine structures in the molecule. [11] The resin composition according to any one of [1] to [10], wherein the component (C) is a benzoxazine compound containing two or more allyl groups in the molecule. [12] The resin composition as described in any one of [1] to [11], wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (C) is 0.01% by mass above. [13] The resin composition according to any one of [1] to [12], wherein the water absorption rate of the cured product is less than 0.2%. [14] The resin composition as described in any one of [1] to [13], which is used for forming an insulating layer. [15] A cured product of the resin composition as described in any one of [1] to [14]. [16] A resin sheet including a support and a resin composition layer including the resin composition described in any one of [1] to [14] provided on the support. [17] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [14], or a cured product as described in [15] . [18] A flexible substrate comprising a cured product of the resin composition described in any one of [1] to [14], or an insulation formed of the cured product described in [15] Floor. [19] A semiconductor device comprising the printed wiring board as described in [17] or the flexible substrate as described in [18]. [Effects of the invention]

According to the present invention, it is possible to provide a resin composition that can obtain a cured product having excellent heat resistance and moisture resistance; a cured product of the resin composition; a resin sheet containing the resin composition; Printed wiring boards or flexible substrates and semiconductor devices with insulating layers formed by objects.

Hereinafter, the present invention will be described in detail with respect to its suitable embodiments. 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 includes (A) a polymer containing a butadiene skeleton (hereinafter also referred to as "Bu polymer"), (B) an inorganic filler, and (C) a substituted or unsubstituted olefin When the propyl benzoxazine compound has a non-volatile content of 100% by mass in the resin composition, the content of the (B) inorganic filler is 60% by mass or less and more than 0% by mass. In order to ensure the flexibility of the cured product, the resin composition of the present invention contains the (A) component, and further contains a specific amount of the (B) component and (C) component, so that a cured product with excellent heat resistance and moisture resistance can be obtained. Things.

The resin composition can be combined with (A) component-(C) component, and further contains arbitrary components. As optional components, for example, (D) thermosetting resin (excludes (A) component and (C) component), (E) hardening accelerator (excludes (A) component, (C) component, and (D) component), and (F) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

＜(A) Polymer containing butadiene skeleton (Bu polymer)＞ The resin composition contains a butadiene skeleton-containing polymer as the (A) component. The polymer containing a butadiene skeleton refers to a polymer containing a butadiene skeleton (a1) described later. Since the resin composition contains the component (A), in addition to a cured product having flexibility, a flexible substrate including the cured product as an insulating layer can also be expected. (A) A component may be used individually by 1 type, and may use 2 or more types together.

(Butadiene skeleton (a1)) The component (A) contains one or more butadiene skeletons (a1) in the molecule. The butadiene skeleton (a1) refers to a skeleton including a butadiene structure. Here, the so-called butene diyl structure is cis-2-butene-1,4-diyl, trans-2-butene-1,4-diyl, ethylene ethylene (that is, 3-butene -1,2-diyl) and the hydrogen atoms contained in these groups, and the general term for groups substituted by other atoms or groups of atoms. The number of butene diyl structures contained in the butadiene skeleton (a1) may be one or plural. From the viewpoint of obtaining a cured product with more excellent flexibility, it is preferable that the number of butadiene diyl structures contained in the butadiene skeleton (a1) is plural, and it is more preferable that the butadiene skeleton (a1) contains one type. Or a polybutadiene structure in which two or more butene diyl structures are bonded to each other (hereinafter, also referred to as "PBu structure"). However, the double bond contained in a part of the polybutadiene structure can be hydrogenated.

An example of the butene diyl structure is a structure represented by the following formula (A1-1), the following formula (A1-2), or the following formula (A1-3).

(上述式(A1-1)中，X¹ 分別獨立為氫原子或鹵素原子)。

(In the above formula (A1-1), X ^{1 is} each independently a hydrogen atom or a halogen atom).

(上述式(A1-2)中，X² 分別獨立為氫原子或鹵素原子)。

(In the above formula (A1-2), X ^{2 is} each independently a hydrogen atom or a halogen atom).

(上述式(A1-3)中，X³ 分別獨立為氫原子或鹵素原子)。

(In the above formula (A1-3), X ^{3 is} each independently a hydrogen atom or a halogen atom).

In the above formula (A1-1), formula (A1-2) and formula (A1-3), ^{specific examples of the halogen atom that can form the group X 1} , X ² , and X ³ include a chlorine atom, a fluorine atom, etc. . In the above formula (A1-1), formula (A1-2) and formula (A1-3), the groups X ¹ , X ² and X ³ are preferably hydrogen from the viewpoint of obtaining a cured product with excellent dielectric properties atom.

The butadiene skeleton (a1), from the viewpoint of the structure represented by the above formula (A1-1), formula (A1-2) and formula (A1-3), inhibits the reaction with other molecules or other resins at the double bond site In view of this, it is preferable to include the structure represented by the above formula (A1-1) or the structure represented by the above formula (A1-2), whereby the expected flexibility of the cured product can be maintained.

The polybutadiene structure (PBu structure) is preferably a polybutadiene structure represented by the following formula (A1). However, the polybutadiene structure represented by the following formula (A1) includes at least the structure represented by the above formula (A1-1) or the structure represented by the above formula (A1-2). The polybutadiene structure represented by the following formula (A1) may include both the structure represented by the above formula (A1-1) and the structure represented by the above formula (A1-2).

(上述式(A1)中，n為2以上之整數)。

(In the above formula (A1), n is an integer of 2 or more).

(Aromatic group (a2)) The component (A) is preferably a Bu polymer containing the above-mentioned butadiene skeleton (a1) and one or two or more aromatic groups (a2) in the molecule. The aromatic group (a2) is preferably a divalent or trivalent aromatic group. (A) When the component (A) is close to the butadiene skeleton (a1) in the molecule and contains an aromatic group (a2), a cured product with excellent heat resistance can be obtained. When the number of aromatic groups (a2) contained in the component (A) is plural, a cured product with more excellent heat resistance can be obtained. (A) The plural aromatic groups (a2) contained in one molecule of the component may be the same or different from each other.

(上述式(A2-1)中，A¹ ～A⁶ 當中，2個或3個為鍵結部，並非鍵結部之A¹ ～A⁶ 分別獨立為氫原子、鹵素原子，或取代或非取代之碳數1～5之直鏈狀的烷基)。An example of the aromatic group (a2) is a divalent or trivalent group having a structure represented by the following formula (A2-1).

(In the formula ^{(A2-1), A 1 ~ A} 6 among the two or three portions a bond, A is not bonded portions of ¹ ~ A ⁶ are each independently a hydrogen atom, a halogen atom, or a substituted or The substituted linear alkyl group with 1 to 5 carbon atoms).

In the above formula (A2-1), ^{specific examples of the halogen atom that can form A 1} to A ⁶ that are not the bonding portion include a chlorine atom, a fluorine atom, and the like. ^{Specific examples of the linear alkyl group that can form A 1} to A ⁶ that are not the bonding portion include methyl, ethyl, n-propyl, n-butyl, etc. Among them, methyl is preferred. .

^{Examples of the substituents that the linear alkyl group of A 1} to A ⁶ may have in the above formula (A2-1) include substituted or unsubstituted linear and branched carbon atoms of 1-20 Either a cyclic alkyl group, a substituted or unsubstituted aryl group with 6 to 15 carbon atoms, a halogen atom, a sulfo group, a cyano group, a nitro group, a mercapto group, or a hydroxyl group. In addition, at least one carbon atom contained in a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms may be selected from -O-, -S- , -SO ₂ -, -NH-, -CO-, -CONH-, -NHCO-, -CO-O- and -O-CO- are substituted with heteroatom-containing groups. Specific examples of the linear alkyl group that can constitute a substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like. As a specific example of the branched alkyl group which can constitute a substituent, an isobutyl group etc. are mentioned. As a specific example of the cyclic alkyl group which can comprise a substituent, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. As a specific example of an aryl group, a phenyl group, a naphthyl group, etc. are mentioned.

The first example of the aromatic group (a2) is ^{that two of A 1} to A ⁶ are bonding portions (that is, divalent groups), and all of A ¹ to A ^{6 that} are not bonding portions are hydrogen atoms. In the second example of the aromatic group (a2), two of A ¹ to A ⁶ are bonding portions, and at least one ^{of A 1} to A ⁶ that is not a bonding portion is a methyl group. In the third example of the aromatic group (a2), three of A ¹ to A ⁶ are bonding portions (that is, trivalent groups), and all of A ¹ to A ^{6 that} are not bonding portions are hydrogen atoms.

Among the plurality of bonding parts of the aromatic group (a2), at least one bonding part is preferably bonded to an oxygen atom. That is, it is preferable that the aromatic group (a2) constitutes a part of the phenoxy structure (a2-1) described later. In one embodiment, the aromatic group (a2) constitutes a part of the phenoxy structure (a2-1) described later.

The so-called phenoxy structure (a2-1) refers to a divalent group obtained by removing two hydrogen atoms of the hydrogen bonded to the carbon atom or the oxygen atom of the substituted or unsubstituted phenol.

Preferably, the phenoxy structure (a2-1) includes a divalent phenoxy structure represented by the following formula (A2-2). Since the phenoxy structure is a rigid structure, a cured product with excellent heat resistance can be obtained.

(上述式(A2-2)中，A^a1 ～A^a6 當中，2個為鍵結部，殘餘之4個分別獨立為氫原子、鹵素原子，或取代或非取代之碳數1～5之直鏈狀的烷基，惟，A^a1 並非為鍵結部時，為氫原子)。

(In the above formula (A2-2), two of A ^a1 to A ^a6 are bonding parts, and the remaining four are independently hydrogen atoms, halogen atoms, or substituted or unsubstituted straight carbon atoms with 1 to 5 A chain alkyl group, however, when A ^a1 is not a bonding part, it is a hydrogen atom).

In the above formula (A2-2), ^{specific examples of the halogen atom that can form A a1} to A ^a6 that are not the bonding portion include a chlorine atom, a fluorine atom, and the like. ^{Specific examples of the linear alkyl group that can form A a1} to A ^a6 that are not a bonding portion include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. From the viewpoint of obtaining a cured product having excellent dielectric properties, ^{A a1} to A ^a6 that are not the bonding portion are preferably a hydrogen atom or a methyl group.

^{Examples of the substituents that the linear alkyl group of A a1} to A ^a6 may have in the above formula (A2-2) include substituted or unsubstituted linear and branched carbon atoms of 1-20 Either a cyclic alkyl group, a substituted or unsubstituted aryl group with 6 to 15 carbon atoms, a halogen atom, a sulfo group, a cyano group, a nitro group, a mercapto group, or a hydroxyl group. In addition, at least one carbon atom contained in a linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms may be selected from -O-, -S- , -SO ₂ -, -NH-, -CO-, -CONH-, -NHCO-, -CO-O- and -O-CO- are substituted with heteroatom-containing groups. Specific examples of the linear alkyl group that can constitute a substituent include a methyl group, an ethyl group, a propyl group, an n-butyl group, and the like. As a specific example of the branched alkyl group which can constitute a substituent, an isobutyl group etc. are mentioned. As a specific example of the cyclic alkyl group which can comprise a substituent, a cyclopentyl group, a cyclohexyl group, etc. are mentioned. As a specific example of an aryl group, a phenyl group, a naphthyl group, etc. are mentioned.

In the first example of the phenoxy structure (a2-1), in the above formula (A2-2), A ^a1 is a hydrogen atom, and ^{at least one of A a2} to A ^a6 that is not a bonding portion is a methyl group. In the second example of the phenoxy structure (a2-1), in the above formula (A2-2), A ^a1 is a bonding part, and ^{at least one of A a2} to A ^a6 that is not a bonding part is a methyl group. In the third example of the phenoxy structure (a2-1), in the above formula (A2-2), A ^a1 to A ^{a6 that} are not the bonding portion are all hydrogen atoms.

(上述式(A2-3)中，A^b1 及A^b2 為鍵結部，A^b3 ～A^b6 分別獨立為氫原子、鹵素原子，或取代或非取代之碳數1～5之直鏈狀的烷基)。In one embodiment, the phenoxy structure (a2-1) includes the phenoxy structure represented by the following formula (A2-3).

(In the above formula (A2-3), A ^b1 and A ^b2 are bonding parts, and A ^b3 to A ^b6 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear chain with 1 to 5 carbon atoms alkyl).

In the above formula (A2-3), A ^b3 to A ^{b6 that} are not a bonding portion are independent of each other, and are the same as ^{A a1} to A ^a6 that are not a bonding portion in the above formula (A2-2). Among A ^b3 to A ^b6 , at least one is preferably a methyl group.

(A) The component is preferably a Bu polymer having plural phenoxy structures (a2-1) described above. (A) The plural phenoxy structures (a2-1) contained in one molecule of the component may be the same or different from each other. It is more preferable that the component (A) includes a polyphenoxy structure (hereinafter, also referred to as "PPO structure") in which phenoxy structures (a2-1) of the same species or different species are bonded to each other. When the number of the phenoxy structure (a2-1) contained in one molecule of the component (A) is plural, a cured product with more excellent heat resistance can be obtained.

The polyphenoxy structure (PPO structure) preferably contains a poly(phenylene ether) skeleton selected from (a2-a) (hereinafter, also referred to as "PPE skeleton") and (a2-b) cresol novolac A skeleton, and (a2-c) a skeleton of at least one of the group of (a2-c) phenol novolac skeletons. From the viewpoint of obtaining a cured product with more excellent moisture resistance, it is more preferable that the polyphenoxy structure (PPO structure) contains a PPE skeleton. This is considered to be because the PPE skeleton has a tendency to be low in polarity compared with the phenol novolak skeleton and the cresol novolak skeleton. Even in the cured product obtained, the affinity with water is also low. As a result, excellent moisture resistance is obtained. The hardened object.

The PPE skeleton (a2-a) is a skeleton including the structure represented by the following formula (A2-4) as a repeating unit. The average number per molecule of the PPE backbone of the Bu polymer is preferably adjusted so as to satisfy the range of the weight average molecular weight or the range of the number average molecular weight described later.

(上述式(A2-4)中，A^c1 ～A^c6 係與在前述之(A2-2)的A^c1 ～A^c6 相同。惟，A^c1 為第一鍵結部，A^c2 ～A^c6 當中之一個為第2鍵結部)。

(In the formula ^{(A2-4), A c1 ~ A} c6 system and the A ^c1 ~ A ^c6 of the aforementioned (A2-2) is the same. However, A ^c1 first bonding portion, A ^c2 ~ A ^c6 which One of them is the second bonding part).

In the above formula (A2-4), it is preferred that A ^c4 is located at the p-position relative to the carbon bonded to the oxygen atom and is the second bonding part, that is, the PPE skeleton contains poly(p-phenylene Ether) skeleton (hereinafter also referred to as "p-PPE skeleton"). The p-PPE skeleton is preferably a structure represented by the above formula (A2-4), including a 2,6-dimethyl-1,4-phenylene oxide structure represented by the following formula (A2-4a) p-PPE skeleton.

(上述式(A2-4a)中，*為鍵結部)。

(In the above formula (A2-4a), * is a bonding part).

The p-PPE skeleton preferably includes the p-PPE skeleton represented by the following formula (1), formula (2), formula (3) or formula (4). As shown in formula (2), formula (3) and formula (4), a plurality of PPE skeletons can be bonded to each other through a linking group.

(式(1)中，na表示重複單位之數，為2以上之整數)。

(In formula (1), na represents the number of repeating units and is an integer of 2 or more).

(式(2)中，nb表示重複單位之數，為1以上之整數)。

(In formula (2), nb represents the number of repeating units and is an integer of 1 or more).

(式(3)中，nc表示重複單位之數，分別獨立為1以上之整數)。

(In formula (3), nc represents the number of repeating units, each independently being an integer of 1 or more).

(式(4)中，nd表示重複單位之數，分別獨立為1以上之整數)。

(In formula (4), nd represents the number of repeating units, and each is independently an integer of 1 or more).

The cresol novolak skeleton (a2-b) includes a structure represented by the following formula (A2-5). The average number per molecule of the cresol novolak skeleton of the Bu polymer is preferably adjusted so as to satisfy the range of the weight average molecular weight or the range of the number average molecular weight described later.

(上述式(A2-5)中，A^d1 及A^d4 為鍵結部，A^d2 及A^d3 分別獨立為氫原子、鹵素原子，或取代或非取代之碳數1～5之烷基。R^d1 及R^d2 分別獨立為氫原子、取代或非取代之直鏈狀的碳數1～10的烷基，或取代或非取代之碳數6～15的芳基。na2表示重複單位之數，為2以上之整數)。

(In the above formula (A2-5), A ^d1 and A ^d4 are bonding parts, and A ^d2 and A ^d3 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group with 1 to 5 carbon atoms. R ^d1 and R ^d2 are each independently a hydrogen atom, a substituted or unsubstituted linear alkyl group with 1 to 10 carbons, or a substituted or unsubstituted aryl group with 6 to 15 carbons. na2 represents the number of repeating units, Is an integer greater than 2).

As the alkyl (A2-5) in linear R ^d1 and R ^d2 of the above formula include methyl, ethyl, N- propyl, N- butyl and the like. As R ^d1 and R ^d2 of the aryl group include phenyl, benzyl, tolyl, naphthyl and the like. In A ^d2, linear A ^d3, R ^d1 and R ^d2 of the alkyl group and the aryl group may have a substituent group, and in the line of group A ^b3 ~ A straight-chain alkyl group and the aryl group ^b6 may The substituents are the same.

When the solubility of the above formula (A2-5), R ^d1 and R ^d2 prepare a resin varnish improving viewpoint, preferably are hydrogen atoms. Carbon atoms which may constitute R ^d1 and R ^d2 of the linear alkyl group is preferably from 1 to 3, more preferably 1 to 2, particularly preferably 1.

The phenol novolak skeleton (a2-c) includes a structure represented by the following formula (A2-6). The average number per molecule of the phenol novolak skeleton of the Bu polymer is preferably adjusted so as to satisfy the range of the weight average molecular weight or the range of the number average molecular weight described later.

(上述式(A2-6)中，A^e1 及A^e5 為鍵結部，A^e2 ～A^e4 分別獨立為氫原子、鹵素原子，或取代或非取代之碳數1～5的烷基(惟，排除A^e2 ～A^e4 當中之至少一個以上為甲基的情況)。R^e1 及R^e2 分別獨立為氫原子或取代或非取代之直鏈狀的碳數1～10的烷基，或取代或非取代之碳數6～15的芳基。na3表示重複單位之數，為2以上之整數)。

(In the above formula (A2-6), A ^e1 and A ^e5 are bonding parts, and A ^e2 to A ^e4 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group with 1 to 5 carbon atoms (but , Excluding the case where at least one of ^{A e2} to A ^{e4 is a methyl group). R e1} and R ^e2 are each independently a hydrogen atom or a substituted or unsubstituted linear alkyl group with 1 to 10 carbon atoms, or substituted Or an unsubstituted aryl group with 6 to 15 carbon atoms. na3 represents the number of repeating units and is an integer of 2 or more).

^{Examples of the linear alkyl group of Re1} and ^Re2 in the above formula (A2-6) include ethyl, n-propyl, n-butyl, and the like. Examples of the aryl group in ^Re1 and ^Re2 include phenyl, naphthyl and the like. The substituents that the linear alkyl and aryl groups of A ^e2 to A ^e4 , ^Re1 and ^Re2 may have are the same as the linear alkyl and aryl groups of the aforementioned groups A ^b3 to A ^b6 . The substituents are the same.

In the above formula (A2-6), ^Re1 and ^Re2 are preferably both hydrogen atoms from the viewpoint of improving the solubility when preparing the resin varnish. The number of carbon atoms of the linear alkyl group that can constitute ^Re1 and ^Re2 is preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

The component (A) is preferably a butadiene skeleton-containing polymer in which an aromatic group (a2) is interposed between two butadiene skeletons (a1). With one aromatic group (a2) interposed between two butadiene skeletons (a1), a cured product with more excellent heat resistance can be obtained. This is considered to be because the aromatic group (a2) with higher heat resistance exists in the vicinity of the butadiene skeleton (a1) compared to the butadiene skeleton (a1). From this point of view, it is preferable that the aromatic group (a2) constitute a part of the above-mentioned phenoxy structure (a2-1), and it is more preferable that the phenoxy structure (a2-1) includes a polyphenoxy structure (PPO). structure).

In one embodiment, the Bu polymer is a block copolymer containing a first block of a polybutadiene structure (PBu structure) and a second block of a PPO structure. Such block copolymerization can polymerize, for example, the first monomer corresponding to the first block (for example, "G3000" manufactured by Nippon Soda Corporation, "SA90" manufactured by SABIC), and the second monomer corresponding to the second block. Made by a single body.

In addition, the component (A) is preferably interposed between the butadiene skeleton (a1) and the aromatic group (a2) selected from the group consisting of a urethane bond and an ester bond (but excluding the urethane bond Bu polymer of one or more linking groups among the ester bond included), the amide bond, and the amide structure described later. By controlling the molecular structure (for example, the chain length of the block containing the butadiene skeleton (a1), the chain length of the block containing the aromatic group (a2)) by the linking group, a curing with more excellent heat resistance can be obtained Things. In one embodiment, the Bu polymer contains cresol novolac resin, phenol novolak resin, or poly(phenylene ether) resin with a PBu structure and a PPO structure. In another embodiment, the Bu polymer contains a PBu structure. Polyimide resin structured with imine. The so-called imine structure refers to a structure in which two carbonyl groups are bonded to a primary amine or an ammonia, and the two carbonyl groups are at the ends of the two carbonyl groups as the bonding part. From the viewpoint of obtaining a cured product having excellent heat resistance, the imine structure preferably forms a conjugated system together with an aromatic group. In order to include a polar group in the imidine structure, in general, although there is a tendency to lower the moisture resistance, according to the present invention, even if it is a resin composition containing a Bu polymer containing an imidine structure, the moisture resistance can be obtained And a hardened product with excellent heat resistance.

As the poly(phenylene ether) resin containing the PBu structure and the PPE structure, commercially available products can be used. For example, "BX-360", "BX-660", "BX-660M", and "BX-660" manufactured by Nippon Kayaku Co., Ltd. can be used. BX-660T". As the polyimide resin containing a PBu structure and an imine structure, for example, Bu polymer a or its derivatives synthesized by Synthesis Example 1 described later can be cited. As a cresol novolak resin containing a PBu structure and a PPO structure, for example, Bu polymer b or its derivatives synthesized by Synthesis Example 2 described later can be cited.

The urethane bond that can be interposed between the butadiene skeleton (a1) and the aromatic group (a2) may be a part of the linking group. The linking group is, for example, a divalent linking group. As such a divalent linking group, a group derived from diisocyanate (for example, a group derived from toluene diisocyanate (ie -O(C=O) NH-ph(CH ₃ ))-NH(C=O) )O-represented group), a group derived from diphenylmethane diisocyanate (that is, -O(C=O)NH-ph-CH ₂ -ph-NH(C=O)O-represented group), Derived from the group of isophorone diisocyanate (IPDI) (ie -O(C=O) NH-Ch(CH ₃ ) ₃ -CH ₂ -NH(C=O)O-represented group)). The ester bond that can be interposed between the butadiene skeleton (a1) and the aromatic group (a2) may be a part of the linking group. The linking group is, for example, a divalent linking group. As such a linking group, a group derived from dicarboxylic acid (for example, a group derived from terephthalic acid, a group derived from isophthalic acid (ie -O(C=O)-ph-( C=O)O-represented base)). However, in the above formula, "ph" means a benzene ring, and "Ch" means a cyclohexane ring. In addition, in the above formula, the hydrogen bonded to the nitrogen atom may be substituted with any substituent.

In addition, the component (A) is preferably a monovalent group containing one or more vinyl groups (but excluding a monovalent group containing 3-butene-1,2-diyl group). Examples of the monovalent group containing the above vinyl group include (meth)acryloyl group and (meth)acryloyloxy group. Here, the so-called (meth)acryloyl group includes an acryloyl group, a methacryloyl group, and a combination thereof. In addition, the term “(meth)acryloxy group” includes acryloxy group, methacryloxy group, and combinations thereof.

In addition to the double bond contained in the butadiene skeleton, the vinyl group also exists as a group that can form a cross-linking point. Therefore, the cross-linking point can be increased by this. The monovalent group containing the aforementioned vinyl group preferably exists as a terminal group of the molecule constituting the component (A), and more preferably exists as at least one terminal group among the two terminals of the molecule of the Bu polymer.

The above-mentioned component (A) can be polymerized by block polymerization, for example, into a first resin containing a butadiene skeleton (a1) precursor (corresponding to the first monomer of the first block, for example, "G3000" manufactured by Soda Corporation of Japan "(Number average molecular weight: 3000) or "SA90" manufactured by SABIC), and a second resin (corresponding to the second monomer of the second block) that becomes a precursor containing the aromatic group (a2).

(A) The number average molecular weight (Mn) of the component is preferably 4000 or more, more preferably 4500 or more, particularly preferably 5000 or more from the viewpoint of obtaining a cured product that more significantly exhibits the desired effect of the present invention. It is preferably 100,000 or less, more preferably 90,000 or less, and particularly preferably 80,000 or less.

(A) The weight average molecular weight (Mw) of component (Mw) is preferably 4000 or more, more preferably 10000 or more, particularly preferably 20000 or more, from the viewpoint of obtaining a cured product that more significantly exhibits the desired effect of the present invention. It is preferably 120,000 or less, more preferably 110,000 or less, and particularly preferably 105,000 or less. (A) The weight average molecular weight of the component is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

The value (Mw/Mn) of the ratio (Mw/Mn) of the number average molecular weight of the weight average molecular weight of the component (A) is preferably 1-30 from the viewpoint of obtaining a cured product that more remarkably exhibits the desired effect of the present invention between. (A) The weight average molecular weight and number average molecular weight of the component are the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

(A) The content ratio (percentage) of the butadiene skeleton of the component is preferably 30% by mass or more or 40% by mass or more from the viewpoint of obtaining a flexible hardened product, so as to obtain a hardened product with excellent flexibility From the viewpoint of, it is more preferable to be 50% by mass or more, 60% by mass or more, or 65% by mass or more. From the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance, the content (percentage) of the butadiene skeleton of the component (A) can be, for example, 98% by mass or less, 95% by mass or less, and less than 90% by mass. % Or less than 85% by mass. Here, the content ratio (percentage) of the butadiene skeleton can be calculated from the ratio of the amount (parts by mass) of each material used to synthesize the component (A), instead of this, the ratio of the component (A) can be specified The molecular structure was calculated as the ratio of the molecular weight to the formula weight of the butadiene skeleton site. (A) When there are plural kinds of components, it is preferable that the content ratio (percentage) of the butadiene skeleton of each component is within the aforementioned range because the average value of the mass ratio of the components is within the aforementioned range.

(A) The content of component, when the non-volatile content in the resin composition is set to 100% by mass, from the viewpoint of obtaining a flexible hardened product, it is more than 0% by mass, preferably 0.1% by mass Or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 5% by mass or more, 9% by mass or more, or 10% by mass or more. From the viewpoint of obtaining a cured product with excellent flexibility, when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is preferably 15% by mass or more, 16% by mass or more, and 17% by mass. % Or more, 18% by mass or more, 19% by mass or more, or 20% by mass or more. From the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance, the content of component (A) is preferably determined in accordance with the relative ratio with component (B) described later, and the non-volatile components in the resin composition When it is set to 100% by mass, for example, it can be set to 50% by mass or less, less than 50% by mass, 49% by mass or less, 45% by mass or less, 43% by mass or less, or 40% by mass or less.

＜(B) Inorganic fillers＞ The resin composition system contains an inorganic filler as the (B) component. By including the component (B) in the resin composition containing the component (A), it is possible to obtain a hardening that does not significantly impair the flexibility of the cured product expected from the component (A), and is excellent in heat resistance and moisture resistance Things. (B) A component may be used individually by 1 type, and may use 2 or more types together.

As the material of the inorganic filler, an inorganic compound is used. Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as the silica, spherical silica is preferred. (B) Inorganic fillers may be used alone or in combination of two or more types.

Commercial products of (B) component include, for example, "UFP-30" manufactured by Denki Chemical Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; and "YC100C manufactured by Admatechs Co., Ltd." ", "YA050C", "YA050C-MJE", "YA010C"; "SYLFIL NSS-3N", "SYLFIL NSS-4N", "SYLFIL NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ" manufactured by Admatechs, "SO-C4", "SO-C2", "SO-C1"; etc.

The component (B) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include amine coupling agents, (meth)acrylic (Arcyl) coupling agents, and vinyl coupling agents. Among them, amine coupling agents and (meth)acrylic (Arcyl) coupling agents are used. It is preferable from the viewpoint of obtaining a cured product excellent in environmental test resistance (HAST resistance). Here, the so-called amine-based coupling agent refers to a coupling agent having an amine group. The so-called (meth)acrylic acid (Arcyl) coupling agent refers to a coupling agent having a methacryloxy group or an acryloxy group. The so-called vinyl-based coupling agent refers to a coupling agent having a vinyl group, which is not a (meth)acrylic-based coupling agent. Each of the above-mentioned amine coupling agents, (meth)acrylic (Arcyl) coupling agents and vinyl coupling agents includes silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. Coupling agents, etc., may also belong to any of the silane coupling agents. As the silane coupling agent, for example, a fluorine-containing silane coupling agent, an epoxy silane coupling agent, and a mercaptosilane coupling agent can be cited. Among them, from the viewpoint of remarkably obtaining the effects of the present invention, silane coupling agents are preferred, amine coupling agents belonging to silane coupling agents, and (meth)acrylic acid (Arcyl) coupling agents belonging to silane coupling agents are more preferred . In addition, one type of surface treatment agent may be used alone, or two or more types may be used in any combination.

Commercial products of the surface treatment agent include, for example, "KBM1003" (vinyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM503" (3-methacryloxypropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Ethoxysilane), "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" manufactured by the company (hexamethyldisilazane, "KBM103" manufactured by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), and "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy-type silane) Coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. Among them, it is preferable to use a group selected from the group of (meth)acryloyloxy groups. One or more of the coupling agent "KBM503" and the amine coupling agent "KBM573" and "KBE903", it is more preferable to use at least one of "KBM503" and "KBM573".

The degree of surface treatment by the surface treatment agent is preferably contained in a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 parts by mass to 5 parts by mass of the surface treatment agent, preferably 0.2 parts by mass to 3 parts by mass, and preferably 0.3 parts by mass. Parts to 2 parts by mass for surface treatment.

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

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

The specific surface area of the component (B) is preferably 1 m ² /g or more, more preferably 2 m ² /g or more, and particularly ^{preferably 3 m 2} /g or more. Although the upper limit is not particularly limited, it 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 obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) in accordance with the BET method, adsorbing nitrogen on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

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

(B) The average particle size of the component can be measured by the laser diffraction and scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter can be determined as the average particle size for measurement. The measurement sample can be obtained by weighing 100 mg of the inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing it for 10 minutes by ultrasonic waves. Use a laser diffraction particle size distribution measuring device for the measurement sample, and set the wavelength of the light source to blue and red, and measure the volume-based particle size distribution of component (B) by the flow cell method. The obtained particle size can be obtained from The distribution is used as the median diameter to calculate the average particle size. As a laser diffraction type particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

(B) The content of component, when the non-volatile content in the resin composition is set to 100% by mass, from the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance, it is more than 0% by mass, for example, it can be set as 0.1 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, 6 mass% or more, 7 mass% or more, 8 mass% or more, 9 mass% or more or 10% by mass or more. (B) The content of the component, when the non-volatile content in the resin composition is set to 100% by mass, from the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance, it can be set at 60% by mass or less and 55% by mass. % Or less, 50% by mass or less, less than 50% by mass, 45% by mass or less, 41% by mass or less, or 40% by mass or less. From the viewpoint of obtaining a cured product with excellent flexibility, when the non-volatile content in the resin composition is set to 100% by mass, the content of component (B) can be set to 50% by mass or less, less than 50% by mass, 45 Mass% or less, 43% by mass or less, 41% by mass or less, or 40% by mass or less.

The mass ratio (mass%) of the amount (parts by mass) of component (B) of the resin composition to the amount (parts by mass) of component (A) (hereinafter, also referred to as "B/A ratio"), preferably In order not to significantly impair the flexibility of the cured product exerted by the component (A), it is determined from the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance. For example, it can be set at 50% by mass or more and 75% by mass. % Or more or 100% by mass or more. Here, the B/A ratio refers to the ratio (percentage) of the content of the component (B) when the content of the component (A) is 100% by mass. From the viewpoint of obtaining a cured product excellent in flexibility, heat resistance, and moisture resistance, the B/A ratio can be set to 250% by mass or less, 200% by mass or less, or 175% by mass or less.

(B) The mass ratio (mass%) of the amount (parts by mass) of the component to the total of the amount (parts by mass) of the component (A) and the amount (parts by mass) of the component (C) described later (hereinafter also referred to as " B/(A+C) ratio") is preferably in a range that does not significantly impair the flexibility of the cured product exerted by the (A) component, from the viewpoint of obtaining a cured product having excellent heat resistance and moisture resistance The decision may be, for example, 15% by mass or more, 20% by mass or more, or 25% by mass or more. Here, the B/(A+C) ratio refers to the ratio (percentage) of the content of the (B) component when the total of the content of the (A) component and the content of the (C) component is 100% by mass. From the viewpoint of obtaining a cured product excellent in flexibility, heat resistance, and moisture resistance, the B/(A+C) ratio can be set to 70% by mass or less, 65% by mass or less, or 60% by mass or less.

＜(C) Benzoxazine compounds containing substituted or unsubstituted allyl groups＞ The resin composition contains a substituted or unsubstituted allyl group-containing benzoxazine compound (hereinafter, also referred to as an "allyl-containing benzoxazine compound") as the (C) component. The benzoxazine compound refers to a compound having a benzoxazine structure described later. The inclusion of the (C) component in the resin composition containing the (A) component and (B) component makes it possible to obtain the flexibility of the hardened product expected from the (A) component, as well as heat resistance and moisture resistance. More excellent hardened materials become possible. This is considered to be because the component (C) is used as a curing agent for thermosetting the resin composition through the reactivity of the allyl group and the reactivity of the benzoxazine structure, forming a cross-linked structure in the cured product ( Matrix (Matrix)), as a result, even if the components (A) and (B) include parts with deteriorated heat resistance (for example, butadiene skeleton (a1)) and hydrophilic or hygroscopic parts (polar groups, The imine structure and the hydrophilic group on the surface of silica) can also be embedded in the cross-linked structure by the components (A) and (B) to form a hardened body with excellent hydrophobicity and excellent heat resistance as a whole, and the hardened product The heat resistance of (A) component and (B) component contains excellent heat resistance parts (for example, aromatic group (b1) and inorganic filler particles themselves) synergistically improved. Here, when the component (A) has a vinyl group at the molecular terminal, it can react with the component (C) to form a cross-linked structure. In addition, according to the present invention, by combining the (B) component and the (C) component, a resin containing a component (for example, the (A) component) having a part (for example, butadiene skeleton) that has deteriorated heat resistance in the molecule It is also possible for the composition to improve both the heat resistance and moisture resistance of the cured product.

The component (C) contains a benzoxazine structure in at least one molecule. The benzoxazine structure may be substituted with any substituent as long as it does not excessively hinder the ring-opening reaction of the benzoxazine structure. In addition, part of the double bonds contained in the benzoxazine structure may be hydrogenated. The benzoxazine structure includes, for example, a 1,2-benzoxazine structure and a 1,3-benzoxazine structure. Among them, from the viewpoint of obtaining the desired effect of the present invention, the following are preferred The 3,4-dihydro-2H-1,3-benzoxazine structure represented by formula (c1).

(上述式(c1)中，*表示鍵結部或氫原子)。

(In the above formula (c1), * represents a bonding part or a hydrogen atom).

The number of benzoxazine structures per molecule of component (C) is one or more. From the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance, it is preferably two or more. Although the upper limit is not Limited, but can be set to 10 or less, 6 or less, 4 or less, or 3 or less.

In addition, the component (C) contains a substituted or unsubstituted allyl group in at least one molecule. The unsubstituted allyl group is 2-propenyl. The allyl group may have any substituent as long as it does not excessively hinder its reactivity. An example of the substituted allyl group is 2-methylallyl. The number of allyl groups per molecule of component (C) is preferably the same as the number of allyl groups per molecule of component (C) from the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance. The number of oxazine structures is the same or more, preferably 2 or more, more preferably 4 or more. Although the upper limit is not limited, it can be 20 or less, 12 or less, 8 or less, or 6 or less.

In the component (C), the allyl group is preferably one of the nitrogen atom constituting the benzoxazine structure and the carbon atom constituting the benzoxazine structure from the viewpoint of remarkably obtaining the desired effect of the present invention The bonding is more preferably bonding to the carbon atom constituting the benzoxazine structure.

(上述式(c1-1)中，R²⁰ 及R²¹ 分別獨立表示取代或非取代之烯丙基，R²² 表示q價之基。q表示1～10之整數，p1分別獨立表示0～4之整數，p2分別獨立表示0～2之整數)。(C) The first example of the component is a benzoxazine compound containing a first allyl group represented by the following formula (C1-1).

(In the above formula (c1-1), R ²⁰ and R ²¹ each independently represent a substituted or unsubstituted allyl group, R ²² represents a q-valent group. q represents an integer of 1-10, and p1 each independently represents 0-4 P2 represents an integer from 0 to 2 independently).

The q-valent group represented by R ²² is preferably selected from the group consisting of substituted or unsubstituted allyl groups, q-valent aromatic hydrocarbon groups, q-valent aliphatic hydrocarbon groups, oxygen atoms, and combinations thereof The basis of the q price in the. At least one of the hydrogen atoms of the q-valent aromatic hydrocarbon group and the q-valent aliphatic hydrocarbon group may be substituted with a halogen atom. When R ²² is a substituted or unsubstituted allyl group, q=1. In this case, both p1 and p2 may be 0. When R ²² has a substituted or unsubstituted 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 comprising an arylene group, an alkylene group, an oxygen atom, or a combination of two or more of these divalent groups, and more preferably an aryl group or two or more kinds of divalent groups. A base formed by a combination of divalent groups, and more preferably a base formed by a combination of two or more kinds of divalent groups.

The arylene group at R ²² is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms base. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, and biphenylene, and phenylene is preferred.

The alkylene group at R ²² is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms base. As a specific example of an alkylene group, a methylene group, an ethylene group, a propylene group, etc. are mentioned, for example, Preferably it is a methylene group.

As a group formed by a combination of two or more divalent groups included in R ²² , for example, a group bonded with one or more arylalkylene groups and one or more oxygen atoms; having an arylalkylene group-alkylene group -The base of the arylene structure, etc., which bond more than one aryl group and one or more alkylene groups; a group that bonds more than one alkylene group and more than one oxygen atom; bonding One or more arylalkylene groups, one or more alkylene groups, and one or more oxygen atom groups, etc., preferably a group that bonds more than one arylalkylene group and more than one oxygen atom, bonding More than one aryl group and more than one alkyl group.

q represents an integer of 1-10, preferably represents an integer of 1-4, more preferably represents an integer of 1-3, and still more preferably represents 1 or 2.

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

The benzoxazine compound represented by the general formula (C1-1) is preferably an allyl-containing benzoxazine compound represented by the following general formula (C1-1a) from the viewpoint of obtaining the expected effects of the present invention Oxazine compounds.

(上述式(c1-1a)中，R²⁰ 、R²¹ 及R²³ 分別獨立表示取代或非取代之烯丙基，p1’分別獨立表示0～4之整數，p2’分別獨立表示0～2之整數，p3’分別獨立表示0～4之整數。惟，複數個p1’、p2’及p3’當中之至少一個係表示1以上之整數)。

(In the above formula (c1-1a), R ²⁰ , R ²¹ and R ²³ each independently represent a substituted or unsubstituted allyl group, p1' each independently represents an integer from 0 to 4, and p2' each independently represents an integer from 0 to 2 Integer, p3' each independently represents an integer from 0 to 4. However, at least one of plural p1', p2', and p3' represents an integer of 1 or more).

The allyl group-containing benzoxazine compound represented by the general formula (C1-1a) is preferably the benzoxazine compound represented by the formula (C1-1b).

(上述式(c1-1b)中，R²⁰ 、R²¹ 、p1’及p2’分別與前述式(c1-1a)中之R²⁰ 、R²¹ 、p1’及p2’相同)。

(In the above formula ^{(c1-1b), R 20, R} 21, p1 ' and p2' respectively ^20, R ^21, p1 'and p2' of the same as in the formula (c1-1a) R).

As the first allyl group-containing benzoxazine compound, a commercially available product can be used. As a commercially available product, for example, "ALP-d" (P-d type benzoxazine compound containing an allyl group having the structure of the above formula (C1-1a)) manufactured by Shikoku Kasei Kogyo Co., Ltd., and the like can be cited. In addition, as the first allyl group-containing benzoxazine compound, the benzoxazine compound disclosed in JP 2016-074871 A or a derivative thereof can be used. In addition, the first allyl group-containing benzoxazine compound can be produced, for example, according to the method described in JP 2016-074871 A.

(上述式(C2-1)中，R^20a 、R^21a 及R^22a 分別獨立表示取代或非取代之烯丙基，R^22’ 表示與苯并並噁嗪環所具有之碳原子鍵結的q’價之基。q’表示1～10之整數，p1a分別獨立表示0～4之整數，p2a分別獨立表示0～2之整數。關於與R^22’ 鍵結之各苯並噁嗪構造，p1a與p2a之和的最大值為5)。The second example of the component (C) is the second allyl group-containing benzoxazine compound represented by the following formula (C2-1).

(In the above formula (C2-1), R ^20a , R ^21a and R ^22a each independently represent a substituted or unsubstituted allyl group, and R ^22' represents q bonded to a carbon atom of the benzoxazine ring 'Valency base. q'represents an integer from 1 to 10, p1a each independently represents an integer from 0 to 4, and p2a each independently represents an integer from 0 to 2. Regarding each benzoxazine structure bonded ^{to R 22', p1a} The maximum sum of p2a is 5).

Preferred is when R ^20a, R ^21a and R ^22a which at least one of a substituted or unsubstituted allyl group, R ^20a, R ^21a and R ^22a are not all of the substituted or unsubstituted allyl group, R ^{22 'at} least Has a substituted or unsubstituted allyl group.

The q'-valent group represented by R ^22' is preferably a q'-valent aromatic hydrocarbon group, a q'-valent aliphatic hydrocarbon group selected from the group consisting of an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and combinations thereof The basis of q'price in the group. At least one of the hydrogen atoms of the q'-valent aromatic hydrocarbon group and the q'-valent aliphatic hydrocarbon group may be substituted by a halogen atom or a substituted or unsubstituted allyl group. For example, when q'is 2, R ^{22' is} preferably selected from the group consisting of an arylene group, an alkylene group, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, and a combination of two or more of these divalent groups. The base of the group.

The arylene group at R ^22' is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and still more preferably an arylene group having 6 to 12 carbon atoms. Aryl. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, and biphenylene, and phenylene is preferred.

The alkylene group at R ^22' is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. alkyl. As a specific example of an alkylene group, a methylene group, an ethylene group, a propylene group, etc. are mentioned, for example, Preferably it is a methylene group.

Examples of the group formed by the combination of two or more divalent groups included in R ^22' include a group that bonds at least one aryl group and one or more oxygen atoms; for example, a group having an aryl group -Alkylene-arylene structure base, etc., a group that binds more than one arylene group and more than one alkylene group; a group that binds more than one alkylene group and more than one oxygen atom Group; bonding more than one aryl group and more than one alkyl group and more than one oxygen atom group, etc., preferably bonding more than one aryl group and more than one oxygen atom A group, a group bonding more than one aryl group and more than one alkyl group.

q'represents an integer of 1-10, preferably an integer of 1-4, more preferably an integer of 1-3, and still more preferably 1 or 2. When q'is an integer of 2 or more, the structure of q'benzoxazine ^{bonded to R 22'} and its substituents may be the same or different from each other.

p1a each independently represents an integer of 0-4, preferably represents an integer of 0-2, more preferably represents 0 or 1, and still more preferably 1. p2a each independently represents an integer of 0-2, represents 0 or 1, preferably 0. However, regarding ^{each benzoxazine structure bonded to R 22'} , the maximum value of the sum of p1a and p2a is 5.

As the second allyl group-containing benzoxazine compound, the benzoxazine compound disclosed in JP 2016-074871 A or a derivative thereof can be used. In addition, the second allyl group-containing benzoxazine compound can be produced according to the method described in JP 2016-074871 A.

The third example of component (C) is the third allyl-containing benzoxazine compound that does not belong to the above-mentioned first allyl-containing benzoxazine compound and the second allyl-containing benzoxazine compound Azine compounds. As the third allyl group-containing benzoxazine compound, an allyl group-containing benzoxazine containing a 1,2-benzoxazine structure or a 1,4-benzoxazine structure capable of ring-opening reaction can be cited Azine compounds.

As the molecular weight of (C) component, from the viewpoint of improving adhesion, it is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, preferably 1000 or less, more preferably 800 or less, and More preferably, it is 500 or less.

(C) The equivalent of the benzoxazine structure of the component (hereinafter, also referred to as the "ring-opening reaction participating group equivalent"), from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably 100g/eq. ～1000g/eq., more preferably 150g/eq.～500g/eq., still more preferably 200g/eq.～300g/eq. The ring-opening reaction participant group equivalent is the mass of the allyl group-containing benzoxazine compound containing 1 equivalent of the ring-opening reaction participant group (benzoxazine structure).

(C) The allyl equivalent of the component is preferably 100 g/eq. to 1000 g/eq., more preferably 150 g/eq. to 500 g/eq., from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 200g/eq.～300g/eq. The allyl equivalent is the mass containing 1 equivalent of the allyl-containing benzoxazine compound.

The content of (C) component is preferably the amount of (C) component between (C) component or other components, which can constitute a cross-linked structure that can exhibit the desired effect of the present invention, and the resin composition When the non-volatile content is set to 100% by mass, for example, it can be set to 0.01% by mass or more, 0.02% by mass or more, 0.03% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more. Although the upper limit is not particularly limited, it is, for example, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less. From the viewpoint of obtaining a cured product with excellent flexibility, it is preferable that when the non-volatile content in the resin composition is 100% by mass, the content of component (C) is 20% by mass or less, more preferably 15% by mass Hereinafter, it is more preferably 10% by mass or less. In addition, the content of the (C) component is preferably set in accordance with the ring-opening reaction participating group equivalent and the allyl equivalent of the (C) component.

In addition, the content of the component (C) is preferably smaller than the total content of the component (A) and the component (B) from the viewpoint of exhibiting the desired effect of the present invention. The mass ratio (mass%) of the amount (parts by mass) of the (C) component of the resin composition to the sum of the amount (parts by mass) of the (A) component and the amount (parts by mass) of the (B) component (below, Also called "C/(A+B) ratio"), from the viewpoint of exerting the desired effect of the present invention, for example, it can be set to 1% by mass or more, 2% by mass or more, 3% by mass or more, or 4% by mass Or more or more than 5 mass%. Here, the C/(A+B) ratio refers to the ratio (percentage) of the content of the (C) component when the total of the content of the (A) component and the content of the (B) component is 100% by mass. From the viewpoint of obtaining a cured product with excellent flexibility, heat resistance, and moisture resistance, the C/(A+B) ratio is usually 100% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less , And more preferably 20% by mass or less.

＜(D) Thermosetting resin＞ The resin composition of the present invention may further contain (D) thermosetting resin. (D) The thermosetting resin does not contain what corresponds to the (A) component and (C) component. As the (D) thermosetting resin, any resin selected from thermosetting resin (hereinafter, also referred to as "(D-1) component") and resin used as a curing agent (hereinafter, also referred to as "( D-2) One or more resins in "Component").

(D-1) Although the component is not particularly limited, for example, epoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic (Arcyl) Resins, cyanate ester resins, silicone resins, oxetane resins, melamine resins, maleimide resins, etc., among them, epoxy resins are preferred. In addition, in an embodiment, the component (D-1) is selected from epoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic (Arcyl) One or more resins among resins, cyanate ester resins, silicone resins, oxetane resins, and melamine resins. That is, in this embodiment, by excluding the maleimide resin from the component (D-1), a varnish with excellent compatibility can be obtained.

Examples of epoxy resins include Bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. , Dicyclopentadiene type epoxy resin, ginseng phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type 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 epoxy resin Resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, Naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

As the epoxy resin, the resin composition is preferably an epoxy resin having two or more epoxy groups in one molecule. From the standpoint of remarkably obtaining the expected effect of the present invention, the ratio of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile content of epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more.

Among epoxy resins, 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"). Although the resin composition of the present invention may include only a liquid epoxy resin, or may include only a solid epoxy resin as the epoxy resin, it is preferably included in a combination of a liquid epoxy resin and a solid epoxy resin.

As a liquid epoxy resin, the liquid epoxy resin which has 2 or more epoxy groups in 1 molecule is preferable.

The liquid epoxy resin is preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl ester type epoxy resin. Glyceryl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin and glycidyl amine type Epoxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", and "jER828EL manufactured by Mitsubishi Chemical Corporation" ", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" manufactured by Mitsubishi Chemical Corporation (Phenolic novolac epoxy resin); "630" and "630LSD" (glycidylamine epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A ring Oxygen resin and bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" manufactured by Daicel (resin with ester skeleton) Cyclic epoxy resin); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. These can be used in one type alone, or in combination of two or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid having 3 or more epoxy groups in one molecule状 epoxy resin.

The solid epoxy resin is preferably Bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, and dicyclopentadiene type epoxy resin. Epoxy resin, ginseng phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC ); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP-7200" made by DIC ", "HP-7200HH", "HP-7200H" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation , "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (ginseng phenol type epoxy resin) manufactured by Nippon Kayaku Corporation; "Nippon Kayaku Corporation" NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Corporation; manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin); "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Corporation "(Biphenyl type epoxy resin); "YX4000HK" (Bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YX7700" (novolac epoxy resin containing xylene structure); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Company; "YL7760" (bisphenol AF -Type epoxy resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (茀-type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (Tetraphenylethane type epoxy resin) and so on. These can be used in one type alone, or in combination of two or more types.

As the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio of these (liquid epoxy resin: solid epoxy resin) is preferably 1:1 to 1:50 , More preferably 1:3～1:30, particularly preferably 1:5～1:20. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin within this range, the expected effect of the present invention can be significantly obtained.

The epoxy equivalent of the epoxy resin is preferably 50g/eq.～5000g/eq., more preferably 50g/eq.～3000g/eq., still more preferably 80g/eq.～2000g/eq., and still more Preferably, it is 110g/eq.～1000g/eq. By setting it in this range, the crosslinking density of the cured product of the resin composition becomes sufficient, and an insulating layer with a small surface roughness can be provided. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene conversion value by gel permeation chromatography (GPC).

(D-1) Although the content of the component is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, it is more important from the viewpoint of obtaining a cured product with excellent heat resistance and moisture resistance. It is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. (D-1) Although the upper limit of the content of the component is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, a cured product with excellent flexibility, heat resistance, and moisture resistance can be obtained. From a viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

The resin used as the (D-2) hardener (except for the (D-1) component) preferably has a function of hardening at least one of the (C) component and (D-1) component. Although the component (D-2) is not particularly limited, when the component (D-1) is an epoxy resin, it is preferably used, for example, as a phenol-based hardener, a naphthol-based hardener, an acid anhydride-based hardener, Any of active ester hardeners, benzoxazine hardeners, cyanate ester hardeners, and carbodiimide hardeners, phenol hardeners, naphthol hardeners, and active ester hardeners One resin (hereinafter, also simply referred to as "hardener"). The component (D-2) preferably contains a resin used as an active ester curing agent. (D-2) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

As the phenol-based curing agent and naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. In addition, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol hardener or a nitrogen-containing naphthol hardener is preferable, and a phenol hardener containing a triazine skeleton or a triazine is more preferable The naphthol of the skeleton is a hardener. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a phenol novolak resin containing a triazine skeleton is preferred. Specific examples of phenol-based hardeners and naphthol-based 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", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN- 495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356" manufactured by DIC , "TD2090", "TD-2090-60M", etc.

As an acid anhydride hardener, the hardener which has 1 or more acid anhydride groups in 1 molecule is mentioned. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Formic anhydride, methyl nadi acid anhydride, hydrogenated methyl nadi acid anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furan) Base)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic acid Acid dianhydride, oxydiphthalic 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(anhydro trimellitate), Copolymerization of styrene and maleic acid styrene, maleic acid resin and other polymeric acid anhydrides. Examples of commercially available products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

The active ester curing agent is not particularly limited, but in general, it is preferable to use phenol esters, thiophenol esters, N-hydroxyamine esters, heterocyclic hydroxy compound esters, etc., in one molecule Compounds with more than two ester groups with high reactivity. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent derived from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound 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, phenolphthalein, methylated bisphenol A, methylated bisphenol F, Methylated 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 type two Phenolic compounds, phenol novolacs, etc. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a phenol novolak, and a benzyl containing a phenol novolak. Among the active ester compounds of the acyl compounds, the active ester compounds containing the naphthalene structure and the active ester compounds containing the dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" refers to a bivalent structural unit composed of phenylene-bicyclopentylene-phenylene.

As a commercially available product of an active ester curing agent, as an active ester compound containing a dicyclopentadiene-type diphenol structure, examples include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "HPC- 8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", (manufactured by DIC Corporation); as containing naphthalene The active ester compound of the structure includes "EXB9416-70BK" and "EXB-8150-65T" (manufactured by DIC Corporation); as the active ester compound containing the acetate of phenol novolak, "DC808" (Mitsubishi Chemical Corporation) As the active ester compound containing the benzoate of phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; as the active ester hardener of the acetate of phenol novolak, "DC808" can be cited (Manufactured by Mitsubishi Chemical Corporation); as the active ester hardener of the benzoate of phenol novolac, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation) Chemical Company); etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Corporation, and "Pd" manufactured by Shikoku Kasei Kogyo Co., Ltd. ", "Fa", etc.

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate ester)phenyl propane, 1,1-bis(4-cyanate ester phenylmethane), bis(4-cyanate ester-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl) Difunctional cyanate resins such as ethers, polyfunctional cyanate resins such as phenol novolac and cresol novolac, and prepolymers in which a part of these cyanate resins are triazineized, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (bisphenol A part or all of the A dicyanate becomes the prepolymer of the triazine-treated trimer) and the like.

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

When the resin composition contains the (D-2) component, the ratio of the (D-1) component to the (D-2) component is based on [the total number of reactive groups of the (D-1) component]: [(D-2 ) The ratio of the total number of reactive groups of the components] is preferably in the range of 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and still more preferably 1:0.4 to 1:1.2. Here, the reactive group of the (D-1) component is an epoxy group, etc., and it varies depending on the type of the (D-1) component. The reactive group of the (D-2) component is an active hydroxyl group, an active ester group, etc., depending on the type of the (D-2) component.

When the resin composition contains component (D-2), its content is not particularly limited, but when the non-volatile content in the resin composition is set to 100% by mass, for example, it can be set to 0.1% by mass or more and 1% by mass. % Or more or 3% by mass or more. (D-2) Although the upper limit of the content of the component is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, it can be set to 30% by mass or less, 25% by mass or less, or 20% by mass. the following.

Although the content of the component (D) is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, from the viewpoint of obtaining a cured product having excellent heat resistance and moisture resistance, it is preferably 5.1% by mass or more, more preferably 11% by mass or more, still more preferably 18% by mass or more. (D) Although the upper limit of the content of the component is not particularly limited, when the non-volatile content in the resin composition is set to 100% by mass, from the viewpoint of obtaining a cured product excellent in flexibility, heat resistance, and moisture resistance In terms of view, it is preferably 80% by mass or less, more preferably 65% by mass or less, and still more preferably 55% by mass or less.

＜(E) Hardening accelerator＞ The resin composition of the present invention may include (E) a hardening accelerator as an optional component. (E) The hardening accelerator has a function of accelerating the hardening speed of the resin component (for example, the (C) component and (D) component).

Although the (E) hardening accelerator is not particularly limited, when the component (D-1) is an epoxy resin, for example, phosphorus hardening accelerator, amine hardening accelerator, imidazole hardening accelerator, guanidine Hardening accelerator, metal hardening accelerator, peroxide hardening accelerator, etc. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, peroxide-based curing accelerators are preferred, and amine-based curing accelerators and peroxide-based curing accelerators are more preferred. Hardening accelerator. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of phosphorus-based hardening accelerators include triphenyl phosphine, phosphonium borate compounds, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, and tetrabutyl phosphonium decanoic acid. Salt, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc.

As an amine-based hardening accelerator (hereinafter, also referred to as "(E-1) component"), for example, trialkylamines such as triethylamine and tributylamine, and 4-dimethylaminopyridine ( DMAP), benzyldimethylamine, 2,4,6,-ginseng (dimethylaminomethyl)phenol, 1,8-diaza ring (5,4,0)-undecene, etc. , Preferably 4-dimethylaminopyridine.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium 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 isocyanurate Acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2 -Imidazole compounds such as phenylimidazoline and adducts of imidazole compounds and epoxy resins.

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, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of the metal-based hardening accelerator 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 acetyl acetate (II) and cobalt acetyl acetate (III), organic copper complexes such as copper acetyl acetate (II), Organic zinc complexes such as zinc (II) acetyl acetate, organic iron complexes such as iron (III) acetyl acetate, organic nickel complexes such as nickel (II) acetyl acetate, manganese acetyl acetate ( II) Organic manganese complexes and so on. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

As a peroxide-based curing accelerator (hereinafter also referred to as "(E-2) component"), for example, t-butylperoxycumene, t-butylperoxyacetate, α,α '-Bis(t-butylperoxy)diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecyl Peroxides such as acid ester, t-butylperoxybenzoate, and di-t-peroxyhexyl.

As commercially available products of peroxide-based hardening accelerators, for example, "PERBUTYL (registered trademark) C", "PERBUTYL (registered trademark) A", "PERBUTYL (registered trademark) P", "PERBUTYL" manufactured by NOF Corporation (Registered trademark) L", "PERBUTYL (registered trademark) O", "PERBUTYL (registered trademark) ND", "PERBUTYL (registered trademark) Z", "PERBUTYL (registered trademark) I", "PERCUMYL P", "PERCUMYL D", "PERHEXYL (registered trademark) D", "PERHEXYL (registered trademark) A", "PERHEXYL (registered trademark) I", "PERHEXYL (registered trademark) Z", "PERHEXYL (registered trademark) ND", "PERHEXYL (Registered trademark) O", "PERHEXYL (registered trademark) PV", "PERHEXYL (registered trademark) O", etc.

When the resin composition contains (E) a hardening accelerator, its content is not particularly limited, but when the non-volatile content in the resin composition is 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, more preferably 0.02% by mass or more. (E) Although the upper limit of the content of the hardening accelerator is not particularly limited, when the non-volatile content in the resin composition is 100% by mass, it is preferably 2% by mass or less, more preferably 1% by mass or less, More preferably, it is 0.5 mass% or less.

＜(F) Other additives＞ The resin composition of the present invention may further contain optional additives as a non-volatile component. Examples of such additives include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polyvinyl acetal resins, polyether crumb resins, polyphenylene ether resins, polycarbonate resins, and polyether ether ketones. Thermoplastic resins such as resins and polyester resins; organic copper compounds, organic zinc compounds, organic cobalt compounds and other organic metal compounds; phthalocyanine blue, phthalocyanine green, iodo green, diazo yellow, crystal violet, titanium oxide, carbon Coloring agents such as black; polymerization inhibitors for hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents for silicone, etc.; Benton, montmorillonite, etc. Tackifier; defoamer of polysilicone defoamer, acrylic (Arcyl) defoamer, fluorine defoamer, vinyl resin defoamer; defoamer of benzotriazole-based ultraviolet absorber, etc. Absorbent; Adhesion enhancer such as urea silane; Adhesion imparting agent such as silane coupling agent, triazole-based adhesiveness imparting agent, tetrazole-based adhesiveness imparting agent, and triazine-based adhesiveness imparting agent; Hindered phenol-based antioxidants, hindered amine-based antioxidants, etc.; fluorescent whitening agents such as stilbene derivatives; phosphorus-based flame retardants (such as phosphate ester compounds, Phosphazene compounds) , Hypophosphorous acid compounds, red phosphorus), nitrogen-based flame retardants (for example, melamine sulfate), halogen-based flame retardants, inorganic flame retardants (for example, antimony trioxide) and other flame retardants. Additives may be used alone or in combination of two or more at any ratio. (F) The content of other additives can be appropriately set by a person with ordinary knowledge in the field of the present invention.

＜(G)Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As (G) the organic solvent, as long as it can dissolve at least a part of non-volatile components, a well-known one can be used suitably, and its kind is not specifically limited. (G) Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate , Isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl Ether solvents such as methyl ether, dibutyl ether, diphenyl ether, etc.; alcohol solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, Ester alcohol solvents such as ethyl lactate and methyl 2-hydroxyisobutyrate; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylenedi Alcohol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Amine-based solvents; dimethyl sulfide and other sulfide-based solvents; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbons such as hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. Solvents: aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. An organic solvent may be used individually by 1 type, and may be used combining 2 or more types at arbitrary ratios.

(G) The content of the organic solvent, the mass ratio of the non-volatile components relative to the total mass of the resin composition, that is, the solid content ratio, from the viewpoint of efficiently drying the resin composition, it can be preferably 30 mass % Or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Although the upper limit of the solid content rate is not particularly limited, from the viewpoint of the handleability of the resin composition, it is preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass % Or less, particularly preferably 90% by mass or less.

＜Manufacturing method of resin composition＞ The resin composition of the present invention can be prepared by, for example, adding (A) component, (B) component and (C) component at the same time to any reaction vessel in any order, and/or part or all of them, if necessary ( D) component, (E) component if necessary, (G) component if necessary, and (H) component if necessary, and mixed to manufacture. In addition, in the process of adding and mixing each component, the temperature can be appropriately set, and heating and/or cooling can be performed temporarily or from beginning to end. In addition, in the process of adding and mixing each component, stirring or shaking may be performed. In addition, during or after the addition and mixing, the resin composition may be stirred using a stirring device such as a stirrer to uniformly disperse it.

＜Physical properties and application of resin composition＞ The resin composition of the present invention includes (A) a polymer containing a butadiene skeleton, (B) an inorganic filler, and (C) a resin composition containing a substituted or unsubstituted allyl group-containing benzoxazine compound, It is characterized in that when the non-volatile content in the resin composition is set to 100% by mass, the content of (B) the inorganic filler is 60% by mass or less and more than 0% by mass. By combining these ingredients, as demonstrated in the examples, a cured product with excellent heat resistance and moisture resistance can be obtained. In addition, since this cured product contains (A) a polymer containing a butadiene skeleton, it has flexibility. As the reason for exerting such an effect, it is considered that the resin composition contains the component (C) to form an appropriate cross-linked structure, and the cross-linked structure incorporates the (A) component and (B) component.

The cured product obtained by thermally curing the resin composition of the present embodiment at 180°C for 30 minutes showed a characteristic of less peeling after the heat resistance test. The heat resistance test can be implemented by the method described in the examples described later. Therefore, the cured product of the resin composition of the present invention is excellent in heat resistance.

The cured product obtained by thermally curing the resin composition of this embodiment at 200°C for 90 minutes exhibits a characteristic that the value of water absorption is small. The value of water absorption can be measured by the method described in the examples described later. Specifically, the water absorption value of the cured product of the resin composition of the present invention is preferably less than 0.20%, more preferably less than 0.19%. Therefore, the cured product of the resin composition of the present invention is excellent in moisture resistance.

In addition, the resin composition of the present invention can provide an insulating layer formed of a cured product having excellent heat resistance and moisture resistance. Accordingly, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer, and a resin composition for a printed wiring board including an insulating layer. The cured product of the resin composition of the present invention has flexibility. Accordingly, the resin composition of the present invention can be suitably used as a resin composition for a flexible substrate including an insulating layer. In addition, the resin composition of the present invention can also be suitably used as a resin composition other than insulation applications.

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

In addition to the resin composition of the present invention, the resin composition layer may include any material without significantly impairing the effect of the present invention, for example, may include a sheet-like reinforcing member such as glass cloth. However, when the resin composition layer is a sheet-like reinforcement member, since the thickness of the resin composition layer tends to increase, from the viewpoint of reducing the thickness, the resin composition layer preferably does not include the sheet-like reinforcement The member, for example, the resin composition layer is composed of only the resin composition. The characteristics of the cured product described earlier are those of a cured product obtained by curing a resin composition layer of a resin composition that does not include a sheet-like reinforcing member.

The thickness of the resin composition layer is preferably 70 μm or less from the viewpoint of providing a cured product with excellent insulation even when the printed wiring board is thinned and the cured product of the resin composition is a thin film. It is 50 μm or less, more preferably 45 μm, and still more preferably 40 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can usually be 1 μm or more, 1.5 μm or more, 2 μm or more, or 5 μm or more.

As the support, for example, a film made of a plastic material, a metal foil, and release paper can be cited, and a film made of a plastic material, and a metal foil are preferred.

In the case of using a film containing a plastic material as a support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter Sometimes abbreviated as "PEN") such as polyester, polycarbonate (hereinafter sometimes referred to as "PC"), polymethylmethacrylate (PMMA) and other acryl, cyclic polyolefin, triacetin Base cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil made of a single metal containing copper can be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. As a specific example of the polyethylene terephthalate film, "Lumirror R80" manufactured by Toray Corporation can be cited.

The support may be subjected to matting treatment, corona treatment, and antistatic treatment on the surface joined to the resin composition layer.

In addition, as the support, a support with a mold release layer having a mold release layer on the surface to be bonded to the resin composition layer can be used. As the mold release agent used in the mold release layer of the support with the mold release layer, for example, one may be selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. More than one release agent. As an alkyd resin-based mold release agent, "AL-5" manufactured by Lindek Co., Ltd. can be cited. Commercial products can be used for the support with a release layer. Examples include PET films with a release layer based on an alkyd resin-based release agent, namely "SK-1" and "AL -5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipiel" manufactured by Unitika, etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is in the above-mentioned range.

In one embodiment, the resin sheet may further include other layers if necessary. As the other layer, for example, it is provided on the surface not joined to the support of the resin composition layer (that is, the surface on the opposite side to the support), the protective film according to the support, and the like. 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 dust and the like on the surface of the resin composition layer.

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

Drying can be performed by a well-known method such as heating and hot air blowing. Although the drying conditions are not particularly limited, the drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies with the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% to 60% by mass of an organic solvent is used, it can be dried at 50°C to 150°C for 3 minutes to 10 minutes to form a resin Composition layer.

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

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The printed wiring board may be a flexible substrate or a rigid substrate. Since the cured product of the resin composition of the present invention has flexibility, it is suitable for the case where the printed wiring board is a flexible substrate.

[Laminated Sheet] The resin composition or resin sheet of the present invention can be used to produce a laminated sheet. The so-called laminated sheet is a sheet made by laminating and hardening a plurality of resin composition layers. The laminated sheet is a plurality of insulating layers including a cured product of the resin composition layer. Generally, the number of resin composition layers laminated in order to manufacture the laminated sheet is the same as the number of insulating layers included in the laminated sheet. The number of specific insulating layers per laminated sheet is usually 2 or more, preferably 3 or more, particularly preferably 5 or more, preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The laminated sheet can be used by bending so that one side of the sheet faces each other. The minimum bending radius of the laminated sheet is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.3 mm or more, preferably 5 mm or less, more preferably 4 mm or less, Particularly preferred is 3mm or less.

Holes can be formed in each insulating layer included in the laminated sheet. This hole can be used as a through hole or a through hole in a multilayer flexible substrate.

In addition to the insulating layer, the laminated sheet may further contain any elements. For example, the laminated sheet may be provided with a conductor layer as an optional element. The conductor layer is usually partially formed on the surface of the insulating layer or between the insulating layers. This conductor layer is usually used as wiring in a multilayer flexible substrate system.

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductive layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Above the metal. The conductor material can be a single metal or an alloy. As the alloy, for example, an alloy of two or more metals selected from the above-mentioned group (for example, nickel･chromium alloy, copper･nickel alloy, and copper･titanium alloy). Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as a single metal is preferred; And nickel･chromium alloy, copper･nickel alloy, copper･titanium alloy and other alloys. Among them, more preferred are single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel and chromium alloys; and even more preferred are single metals of copper.

The conductor layer can be a single-layer structure or a multi-layer structure. The multi-layer structure includes two or more single metal layers or alloy layers composed of different types of metals or alloys. 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.

The conductor layer can be patterned in order to be used as wiring.

Although the thickness of the conductor layer varies depending on the design of the multilayer flexible substrate, it is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.

The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, preferably 2,000 μm or less, more preferably 1,000 μm or less, particularly preferably 500 μm or less.

＜Manufacturing method of laminated sheet＞ The laminated sheet can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet, and (b) a step of using a resin sheet, laminating a plurality of layers, and curing the resin composition layer. The order of lamination and curing of the resin composition layer is arbitrary as long as the desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the plural resin composition layers are laminated, the laminated plural resin composition layers can be cured at one time. In addition, for example, when a certain resin composition layer is laminated with another resin composition layer, the resin composition layer to be laminated can be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, for the sake of distinction, it is appropriate for the resin composition layer, such as the "first resin composition layer" and the "second resin composition layer", with numbers attached to indicate that, in turn, the resin composition The insulating layer obtained by curing the composition layer is also the same as the resin composition layer, and is indicated by numbers like "first insulating layer" and "second insulating layer".

In a preferred embodiment, step (b) includes: (II) The step of hardening the first resin composition layer to form the first insulating layer, and (VI) the step of laminating the second resin composition layer on the first insulating layer, and (VII) A step of hardening the second resin composition layer to form a second insulating layer. Furthermore, step (b) may include if necessary: (I) The step of laminating the first resin composition layer on the sheet supporting substrate, (III) The step of drilling holes in the first insulating layer, (IV) The step of roughening the first insulating layer, (V) Step of forming a conductor layer on the first insulating layer And so on any steps. The following describes each step.

Step (I) is a step of laminating the first resin composition layer on the sheet supporting substrate before step (II). The sheet supporting substrate is a peelable member, for example, a plate-shaped, sheet-shaped or film-shaped member is used.

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

The lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressurized laminator manufactured by Meiji Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko & Material Co., Ltd., a batch vacuum pressurized laminator, etc. can be cited.

When using a resin sheet, the sheet supports the lamination of the base material and the first resin composition layer. For example, by pressing the resin sheet from the support side, the first resin composition layer of the resin sheet can be heated and pressed on the sheet support base材进行。 Material progress. As a member for heating and pressing the resin sheet on the sheet supporting substrate (hereinafter, sometimes referred to as "heating and pressing member" as appropriate), for example, a heated metal plate (SUS mirror plate, etc.) or metal roller (SUS Roller) and so on. It is preferable not to press the heating and pressing member directly on the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the unevenness of the surface of the sheet support substrate is sufficiently followed by the first resin composition layer.

After lamination, the first resin composition layer can be smoothed by pressing under normal pressure (under atmospheric pressure), for example, by heating and pressing the member. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet from the support side with a heating and pressing member. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be carried out by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

Step (II) is a step of hardening the first resin composition layer to form a first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of the printed wiring board can be arbitrarily applied. Although the first resin composition layer can be cured by drying, it can be cured by thermal curing in addition to drying when it contains a thermosetting resin such as epoxy resin.

When an epoxy resin is generally contained, the specific thermosetting conditions vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and still more preferably 170°C to 210°C. In addition, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and still more preferably 20 minutes to 100 minutes.

When the epoxy resin is included, before the first resin composition layer is thermally cured, the first resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the first resin composition layer is thermally cured, the temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less) can be A resin composition layer is preheated for more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes).

Step (III) is a step of drilling the first insulating layer. Through this step (III), holes such as through holes and through holes can be formed in the first insulating layer. Drilling can be performed according to the composition of the resin composition, for example, using a drilling machine, laser, plasma, etc. The size and shape of the hole can be appropriately set according to the design of the multilayer flexible substrate.

Step (IV) is a step of roughening the first insulating layer. Usually in this step (IV), the removal of scum is also carried out. Therefore, roughening treatment is sometimes referred to as desmear treatment. As an example of the roughening treatment, a method of performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a method of neutralizing treatment with a neutralization liquid can be cited.

Although it does not specifically limit as a swelling liquid, alkali aqueous solutions, such as a sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, are mentioned. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment of the swelling liquid can be performed, for example, by immersing the hardened body in the swelling liquid at 30 to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

Although it does not specifically limit as an oxidizing agent, for example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, the alkaline permanganic acid solution which melt|dissolved permanganate is mentioned. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate･Compact P", "Concentrate･Compact CP", and "Dosing solution･Securiganth P" manufactured by Atotech Japan. The roughening treatment by the oxidizing agent can be performed by immersing the hardened body in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

In addition, as the neutralizing liquid, an acidic aqueous solution was used. As a commercially available product, for example, "Reduction solution･Securigant P" manufactured by Atotech Japan can be cited. The treatment by the neutralization solution can be performed by immersing the hardened body in the neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the hardened body in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

The arithmetic average roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. Although the lower limit is not particularly limited, it may be 30 nm or more, 40 nm or more, or 50 nm or more.

Step (V) is a step of forming a conductor layer on the first insulating layer if necessary. The method of forming the conductor layer includes, for example, a plating method, a sputtering method, and a vapor deposition method. Among them, the plating method is preferred. As a suitable example, a suitable method such as a semi-additive method and a full additive method may be used to plate the surface of the first insulating layer to form a conductor layer with a desired wiring pattern. Methods. Among them, from the viewpoint of 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, on the surface of the first insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, corresponding to the desired wiring pattern, a mask pattern is formed that exposes a part of the plating seed layer. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by processing such as etching, and a conductor layer having a desired wiring pattern can be formed.

After the first insulating layer is obtained in step (II), if necessary, after performing step (III), step (IV), and step (V), perform step (VI). Step (VI) is a step of laminating the second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed in the same manner as the lamination of the sheet support substrate and the first resin composition layer in step (I).

However, when a resin sheet is used to form the first resin composition layer, the support of the resin sheet is removed earlier than step (VI). The removal of the support can be performed between step (I) and step (II), between step (II) and step (III), or between step (III) and step (IV) It can also be carried out between step (IV) and step (V).

After step (VI), proceed to step (VII). Step (VII) is a step of hardening the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed in the same way as the curing of the first resin composition layer in step (II). Thereby, a laminated sheet including a plurality of insulating layers including the first insulating layer and the second insulating layer can be obtained.

In addition, in the method related to the foregoing embodiment, if necessary, (VIII) the step of drilling the second insulating layer, (IX) the step of roughening the second insulating layer, and (X) The step of forming a conductor layer on the second insulating layer. The drilling of the second insulating layer in step (VIII) can be performed in the same way as the drilling of the first insulating layer in step (III). In addition, the roughening treatment of the second insulating layer in step (IX) can be performed in the same way as the roughening treatment of the first insulating layer in step (IV). Furthermore, the formation of the conductor layer on the second insulating layer in step (X) can be performed in the same way as the formation of the conductor layer on the first insulating layer in step (V).

In the foregoing embodiment, although the first resin composition layer and the second resin composition layer are laminated and hardened so-called two-layer resin composition layer to produce a laminated sheet, it can also be made by Lamination and curing of three or more resin composition layers to produce a laminated sheet. For example, in the method related to the aforementioned embodiment, the laminating and curing of the resin composition layer by step (VI) to step (VII) and, if necessary, by step (VIII) to step (X ) The insulating layer is drilled, the insulating layer is roughened, and the conductor layer on the insulating layer is formed to produce a laminated sheet. Thereby, a laminated sheet including three or more insulating layers is obtained.

Furthermore, the method of the aforementioned embodiment may include any steps other than the above-mentioned steps. For example, in the case of performing step (I), a step of removing the sheet supporting substrate may be performed.

＜Flexible substrate＞ The flexible substrate includes an insulating layer formed of a cured product of the resin composition of the present invention. When the flexible substrate includes the aforementioned laminated sheet, a multilayer flexible substrate can be formed. Can be combined in insulating layer or laminated sheet, including any components. As optional members, for example, electronic parts, cover films, etc. can be cited.

The multilayer flexible substrate can be manufactured by a manufacturing method including the method of manufacturing the above-mentioned laminated sheet. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet, and (b) a step of using a resin sheet, laminating a plurality of layers, and curing the resin composition layer.

The manufacturing method of the multilayer flexible substrate can be combined with the aforementioned steps, and further includes any steps. For example, a method of manufacturing a multilayer flexible substrate with electronic components may include the step of bonding the electronic components with the laminated sheet. The bonding conditions of the laminate sheet and the electronic component can be any conditions of the terminal electrode of the electronic component that can be connected by a conductor and the conductor layer as the wiring provided on the laminate sheet. In addition, for example, a method for manufacturing a multilayer flexible substrate provided with a cover film may include a step of laminating a laminate sheet and a cover film.

The aforementioned flexible substrate is generally used by bending one side of the laminated sheet included in the flexible substrate so as to face each other. For example, the flexible substrate is housed in the housing of the semiconductor device in a state of being bent and reduced in size. In addition, for example, a flexible substrate is provided in a semiconductor device having a movable portion that can be bent.

[Semiconductor device] The semiconductor device includes the aforementioned printed wiring board. The semiconductor device includes, for example, a printed wiring board and a semiconductor chip mounted on the printed wiring board. In most semiconductor devices, the printed wiring board can be placed in the housing of the semiconductor device, and the printed wiring board can be bent and housed in such a way that one side of the printed wiring board can face each other. The printed wiring board may be the aforementioned flexible substrate or a multilayer flexible substrate.

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

The aforementioned semiconductor device, for example, may include a step of preparing a flexible substrate, a step of bending the flexible substrate so that one side of the flexible substrate faces each other, and storing the bent flexible substrate in The frame is manufactured by the manufacturing method of the steps. [Example]

Hereinafter, the present invention will be specifically described with examples. However, the present invention is not limited to the following examples. In the following descriptions, the "parts" and "%" of the quantity, unless otherwise specified, mean "parts by mass" and "% by mass" respectively. In addition, unless otherwise specified, the operations described below are performed in an environment of normal temperature and pressure.

<Synthesis example 1: Preparation of varnish A containing Bu polymer a> Put the bifunctional hydroxyl-terminated polybutadiene "G-3000" (number average molecular weight: 5047 (GPC method), hydroxyl equivalent: 1798 g/eq., non-volatile content: 100% by mass) manufactured by Soda Corporation in the reaction vessel ) (Hereinafter, also referred to as "PBu material") 50.0g, 23.5g of aromatic hydrocarbon mixed solvent (Idemitsu Petrochemical Co., Ltd. "Ipsol150"), and 0.005g of dibutyltin dilaurate, and mix them to make All ingredients dissolve uniformly. When it becomes uniform, the temperature is increased to 50°C, and while stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08g/eq.) (hereinafter, also referred to as "TDI") is added, and the process is carried out for about 3 Hour response. In this way, the first reactant is obtained. Next, this first reactant was cooled to room temperature.

Add 3,3',4,4'-benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1g/eq.) (hereinafter, also referred to as "BTDA") 8.96g, With 0.07 g of triethylenediamine (Triethylenediamine) and 40.4 g of ethyl diethylene glycol acetate (manufactured by Daicel), the temperature was raised to 130° C. while stirring, and the reaction was performed for about 4 hours.

Confirm the disappearance of the NCO peak ^{at 2250 cm -1} by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end of the reaction, and the obtained second reactant was cooled to room temperature. Furthermore, the second reactant was filtered with a 100-mesh filter cloth to filter out solids. Thereby, as a filtrate, a varnish containing Bu polymer a (hereinafter, also referred to as "varnish A") is obtained.

From the above reaction steps, it is inferred that this Bu polymer a, as a butadiene backbone, has a PBu structure derived from PBu materials, has a urethane bond derived from PBu materials and TDI, and has acetone derived from TDI and BTDA A polymer resin having an imine structure and containing a divalent aromatic group derived from TDI and a trivalent aromatic group derived from BTDA.

The properties of Bu polymer a and varnish A are as follows. Viscosity of varnish A: 7.5Pa･s (25℃, E-type viscometer) The content of non-volatile components (Bu polymer a) in varnish A: 50% by mass Acid value of Bu polymer a: 16.9mgKOH/g Number average molecular weight of Bu polymer a: 13723 Glass transition temperature of Bu polymer a: -10℃ The content ratio of the butadiene skeleton in the Bu polymer a: 78.4% by mass Here, the content ratio (percentage) of the butadiene skeleton is calculated by the following formula using the mass parts of each material used. {50.0/(50.0+4.8+8.96)}×100

<Synthesis example 2: Preparation of varnish B containing Bu polymer b> Put the bifunctional hydroxyl-terminated polybutadiene "G-3000" (number average molecular weight: 5047 (GPC method), hydroxyl equivalent: 1798 g/eq., non-volatile content: 100% by mass) manufactured by Soda Corporation in the reaction vessel ) ("PBu material") 69.0g, 40.0g of aromatic hydrocarbon mixed solvent (Idemitsu Petrochemical Co., Ltd. product "Ipsol150") 40.0g, and 0.005g of dibutyltin laurate, and mixed to uniformly dissolve each component. When it becomes uniform, the temperature is raised to 60°C, and while stirring, 8.0 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, isocyanate group equivalent: 113 g/eq.) (hereinafter, also referred to as "IPDI") is added, and carried out. It takes about 3 hours to react. In this way, the first reactant is obtained.

Next, 23.0 g of cresol novolac resin "KA-1160" (hydroxyl equivalent: 117 g/eq.) (hereinafter, also referred to as "PO framework material") manufactured by DIC Corporation, and ethyl two 60.0 g of glycol acetate (manufactured by Daicel Chemical Industry Co., Ltd.) was heated to 150°C while stirring, and the reaction was performed for about 10 hours.

Confirm the disappearance of the NCO peak ^{at 2250 cm -1} by FT-IR. Confirmation of the disappearance of the NCO peak was regarded as the end of the reaction, and the obtained second reactant was cooled to room temperature. Furthermore, the second reactant was filtered with a 100-mesh filter cloth to filter out solids. Thereby, as a filtrate, a varnish containing Bu polymer b (hereinafter, also referred to as "varnish B") was obtained.

From the above reaction steps, it is inferred that this Bu polymer b, as a butadiene skeleton, has a PBu structure derived from PBu materials, and has a urethane bond derived from PBu materials and IPDI and a combination of IPDI and PO skeleton materials. A polymer resin having a urethane bond and having a cresol novolak skeleton containing a divalent aromatic group derived from a PO skeleton material and a phenolic hydroxyl group.

The properties of Bu polymer b and varnish B are as follows. The content of non-volatile components (Bu polymer b) in varnish B: 50% by mass Number average molecular weight of Bu polymer b: 5900 Glass transition temperature of Bu polymer b: -7℃ The content of the butadiene skeleton in the Bu polymer b: 69.0% by mass Here, the content ratio (percentage) of the butadiene skeleton is calculated by the following formula using the mass parts of each material used. {69.0/(69.0+8.0+23.0)}×100

<Example 1> [Preparation of resin composition E1] 5 parts of the second phenol epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent approximately 185) as the (D-1) component, and the naphthalene-based epoxy resin (Nippon "ESN475V" manufactured by Tetsusumijin Chemical Co., Ltd., epoxy equivalent: about 332) 5 parts, bisphenol AF type epoxy resin as component (D-1) ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238) 10 parts, 2 parts of cyclohexane type epoxy resin (Mitsubishi Chemical Corporation "ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 135) as component (D-1), and varnish A (non-volatile component) as component (A-1) : 50% by mass) 40 parts, and 10 parts of cyclohexanone as a solvent, while heating and stirring, each component is dissolved to obtain a solution. The resulting solution was cooled to room temperature.

Then, add 5 parts of the allyl-containing benzoxazine compound "ALP-d" manufactured by Shikoku Chemical Co., Ltd. as the component (C), and the active ester system as the component (D-2) for curing (DIC company "EXB-8000L-65TM", active base equivalent: about 220, non-volatile content 65% by mass toluene: MEK 1:1 solution) 7.7 parts, containing triazine as component (D-2) Frame cresol novolac hardener (LA-3018-50P, manufactured by DIC Corporation, hydroxyl equivalent: about 151, solid content 50% 2-methoxypropanol solution) 4 parts, as component (B) Inorganic filler F (relative to 100 parts of spherical silica "SC2500SQ" manufactured by Admatechs, with 1 part of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.)) Treater (average particle size: 0.5μm, specific surface area measured by the measurement method described later: 11.2m ² /g)) 35 parts, amine hardening accelerator (4-dimethyl) as component (E-1) 0.2 parts of aminopyridine (DMAP)), and 0.03 parts of peroxide-based hardening accelerator ("PERBUTYLC" manufactured by NOF Corporation) as the component (E-2), mixed the components, and then uniformly dispersed them with a high-speed rotary mixer. In this way, a dispersion liquid is obtained.

Then, the dispersion was filtered with a cartridge filter ("SHP020" manufactured by ROKITECHNO) to filter out solids of 2.0 μm or more. Thereby, as a filtrate, the resin composition E1 containing (A) component, (B) component, (C) component, (D) component, and (E) component was prepared.

[Production of cured film (A)] The cured product film (A) used for the evaluation of moisture resistance was produced as follows. First, as a support, a polyethylene terephthalate film ("PET501010" manufactured by Lindeco Co., Ltd.) provided with a mold release layer formed by performing mold release treatment on one surface was prepared.

Next, on the release layer of the support, the resin composition E1 obtained in Example 1 was uniformly coated with a die coater so that the thickness of the resin composition layer after drying became 50 μm. Then, the resin composition E1 was dried at 80 to 110°C (average 95°C) for 6 minutes. Thereby, a resin sheet (a) including a support and a resin composition layer including a resin composition provided on the support is obtained.

Then, the resin composition layer of the resin sheet (a) was heat-treated at 200°C for 90 minutes to cure it. Then, the support is peeled off from the resin sheet. Thereby, a cured product film formed of a cured product of the resin composition is obtained (hereinafter, the cured product film produced in this manner is also referred to as "cured product film (A)").

[Production of Resin Sheet (B)] The resin sheet (B) used for the evaluation of heat resistance was produced in the following manner. First, as a support, prepare a parylene with a mold release layer formed by a mold release process on one side with an alkyd resin mold release agent ("AL-5" manufactured by Lindeco) Ethylene dicarboxylate film ("Lumirror R80" manufactured by Toray, thickness 38μm, softening point 130°C).

Next, on the release layer of the support, the resin composition E1 obtained in Example 1 was uniformly coated with a die coater so that the thickness of the resin composition layer after drying became 40 μm. Then, the resin composition E1 was dried from 70°C to 110°C for 5 minutes. Thereby, a resin sheet including a support and a resin composition layer including a resin composition provided on the support is obtained. Next, the rough surface of a polypropylene film ("ALPHAN MA-411" manufactured by Oji F-TEX Co., Ltd., thickness 15 μm) was attached as a protective film to the surface not bonded to the support of the resin composition layer. Thereby, a resin sheet having the support, the resin composition layer, and the protective film in this order is obtained (hereinafter, the resin sheet produced in this manner is also referred to as "resin sheet (B)"). And the obtained resin sheet (B) was used for the evaluation of heat resistance mentioned later.

[Evaluate] The prepared cured film (A) and resin sheet (B) are respectively used for the evaluation of moisture resistance and the evaluation of heat resistance described later.

<Example 2> In Example 1, 35 parts of the inorganic filler F which is the component (B) was changed to 25 parts of the inorganic filler F. Except for the above matters, the others were carried out in the same manner as in Example 1, and the resin composition E2 containing the (A) component, (B) component, (C) component, (D) component, and (E) component was prepared. And instead of resin composition E1, resin composition E2 was used instead, and it carried out similarly to Example 1, and produced hardened|cured material film (A) and resin sheet (B). The produced cured product film (A) and resin sheet (B) were carried out in the same manner as in Example 1, and were used for the evaluation of moisture resistance and the evaluation of heat resistance, respectively.

<Example 3> In Example 1, 40 parts of varnish A as the component (A-1) was changed to 40 parts of varnish B. Except for the above matters, the others were carried out in the same manner as in Example 1, and the resin composition E3 containing the (A) component, (B) component, (C) component, (D) component, and (E) component was prepared. And instead of the resin composition E1, the resin composition E3 was used instead, and the same procedure as in Example 1 was carried out to produce a cured product film (A) and a resin sheet (B). The produced cured product film (A) and resin sheet (B) were carried out in the same manner as in Example 1, and were used for the evaluation of moisture resistance and the evaluation of heat resistance, respectively.

<Example 4> In Example 1, 40 parts of varnish A as the component (A-1) was changed to "BX-360" made by Nippon Kayaku Co., Ltd. (a toluene solution of 50% by mass of non-volatile content; here, "BX-360" contains PBu structure as a butadiene structure, and p-PPE structure as a phenoxy structure, a polymer containing butadiene structure) 40 parts. Except for the above matters, the others were carried out in the same manner as in Example 1, and the resin composition E4 containing the (A) component, (B) component, (C) component, (D) component, and (E) component was prepared. And instead of resin composition E1, resin composition E4 was used instead, and it carried out similarly to Example 1, and produced the hardened|cured material film (A) and the resin sheet (B). The produced cured product film (A) and resin sheet (B) were carried out in the same manner as in Example 1, and were used for the evaluation of moisture resistance and the evaluation of heat resistance, respectively.

<Comparative example 1> Not used in Example 1. As the component (C), 5 parts of the allyl-containing benzoxazine compound "ALP-d" manufactured by Shikoku Chemical Co., Ltd., and the peroxide system as the component (E-2) Hardening accelerator ("PERBUTYLC" manufactured by NOF Corporation) 0.03 parts. In addition, in Example 1, 35 parts of the inorganic filler F as the component (B) was changed to 32 parts of the inorganic filler F. Except for the above matters, the others are the same as in Example 1 to prepare a resin composition CE1 containing (A) component, (B) component, (D) component and (E) component (that is, resin not containing (C) component) Composition). And instead of the resin composition E1, the resin composition CE1 was used instead, and the same procedure as in Example 1 was carried out to produce a cured product film (A) and a resin sheet (B). The produced cured product film (A) and resin sheet (B) were carried out in the same manner as in Example 1, and were used for the evaluation of moisture resistance and the evaluation of heat resistance, respectively.

＜Comparative example 2＞ In Example 1, 5 parts of the allyl-containing benzoxazine compound "ALP-d" manufactured by Shikoku Chemical Co., Ltd. as the component (C) was changed to the one manufactured by Shikoku Chemical Co., Ltd. as the component (C') 5 parts of allyl-free benzoxazine compound "Pd". In addition, 0.03 parts of peroxide-based hardening accelerator ("PERBUTYL C" manufactured by NOF Corporation) as the component (E-2) was not used in Example 1. Except for the above matters, the others were the same as in Example 1. The resin composition CE2 containing (A) component, (C') component, (D) component, and (E) component was prepared (that is, component (C) was replaced, and changed Resin composition containing component (C')). And instead of the resin composition E1, the resin composition CE2 was used instead, and the same procedure as in Example 1 was carried out to produce a cured product film (A) and a resin sheet (B). The produced cured product film (A) and resin sheet (B) were carried out in the same manner as in Example 1, and were used for the evaluation of moisture resistance and the evaluation of heat resistance, respectively.

[Evaluation method and measurement method] The measurement method and evaluation method are shown below.

＜Measurement of specific surface area＞ The specific surface area of the inorganic filler F used in the above-mentioned Examples and Comparative Examples was measured in the following manner.

By using a BET automatic specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech), nitrogen gas is adsorbed on the surface of the inorganic filler F. Using the BET multipoint method, the specific surface area is calculated and the ratio of the inorganic filler F is measured Surface area.

＜Evaluation of moisture resistance＞ Using the cured film (A) obtained in the Examples and Comparative Examples, the moisture resistance was evaluated in the following manner. Roughly measure the water absorption rate and evaluate the value of the water absorption rate.

(Measurement of Water Absorption) First, by cutting the cured film (A) produced in the Examples and Comparative Examples into 40 mm square, a plurality of test pieces were prepared respectively. Next, one test piece of Example 1 was dried at 130°C for 30 minutes and then weighed to obtain the first weighing result. The first measurement value obtained from this weighing result (that is, the mass of the test piece before moisture absorption) is defined as W ₀ (g). In addition, each test piece was placed in a constant temperature and humidity tank (manufactured by ETAC), and after 96 hours under the conditions of 60°C and 60% humidity, it was taken out from the constant temperature and humidity tank, and the second weighing result was obtained immediately thereafter. The second measurement value (mass of the test piece after moisture absorption) obtained from this weighing result is defined as W ₁ (g).

Next, the test piece W _A water absorption was calculated according to the following formula. W _A (%)=((W ₁ -W ₀ )/W ₀ }×100

In the same manner, with respect to the other four test pieces of Example 1, the first weighing result and the second weighing result were obtained, and the water absorption rate W _{A was} calculated. And calculates an average of about 1 of total water absorption of Example 5 W _A of the test pieces. Examples and Comparative Examples for other embodiments, a total of five test pieces of the average value W _A water absorption also calculated similarly.

(Evaluation standard) Furthermore, the average value W _A of the water absorption as assessed following manner. "○": the average value of water absorption W _A is less than 0.2%, showing excellent moisture resistance. "×": the average value W _A water absorption of 0.2% or more, the moisture resistance of the display is deteriorated.

＜Evaluation of heat resistance＞ Using the resin sheet (B) obtained in Examples and Comparative Examples, the heat resistance was evaluated in the following manner. Roughly fabricate the evaluation substrate (C), expose the evaluation substrate (C) to high temperature according to the reflow temperature profile that can be used in the manufacture of the printed wiring board, and then, whether the obtained evaluation substrate (C) peels off As a heat resistance test evaluation.

[Production of evaluation board (C)] (1) Preparation of copper clad laminate First, as a copper-clad laminate, a glass cloth base epoxy resin double-sided copper-clad laminate prepared by laminating copper foil layers on both sides (copper foil thickness 3μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Corporation "HL832NSF LCA ”, 255×340mm size).

(2) Laminating of resin sheet (B) From each resin sheet (B) produced in the Examples and Comparative Examples, the protective film was peeled off to expose the resin composition layer. Next, using a batch vacuum pressure laminator (two-stage stacking laminator "CVP700" manufactured by Nikko & Materials Co., Ltd.), the resin sheet (B) from which the protective film is peeled off is brought into contact with the copper-clad laminate with the resin composition layer The way, laminated on both sides of the copper clad laminate. The lamination was carried out by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, and then pressing at 130°C and a pressure of 0.74 MPa for 45 seconds. Next, hot stamping was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of resin composition layer Put the copper clad laminate on both sides laminated with resin sheet (B) into the first oven and expose it for 30 minutes in an environment with a temperature of 100°C, then transfer to the second oven and pass in an environment with a temperature of 180°C Exposure and heat curing is performed for 30 minutes, and the resin composition layer of the resin sheet (B) forms an insulating layer. Then, take out the copper clad laminate with insulating layers formed on both sides from the second oven. Then, the support is peeled from the resin sheet (B) to expose the resin composition layer. Thereby, a copper clad laminate (hereinafter, also referred to as "hardened substrate (c1)") with insulating layers exposed on both sides is obtained.

(4) Steps for roughening treatment The hardened substrate (c1) is subjected to a desmear treatment as a roughening treatment. Still, as a desmear treatment, the following wet desmear treatment is implemented.

Wet slag removal treatment: The hardened substrate c1 was first 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 10 minutes, and then in an oxidizing agent solution (Atotech Japan "Concentrate･Compact CP", potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4% aqueous solution) was immersed at 80 ℃ for 20 minutes, and finally in the neutralization solution (Atotech Japan company "Reduction solution･ Securigant P", sulfuric acid aqueous solution) was immersed at 40°C for 5 minutes. Then, the hardened substrate c1 was taken out from the neutralized liquid and dried at 80°C for 15 minutes. Thereby, a copper clad laminate (hereinafter, also referred to as "roughened substrate (c2)") in which the surface of the insulating layer is roughened is obtained.

(5) Steps to form conductor layer [prepare in advance] First, as a preliminary preparation for forming a conductor layer on the surface of the roughened substrate (c2), the following steps (5-1) to (5-5) are implemented in this order.

(5-1) Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer) The surface of the roughened substrate (c2) was washed with a cleaning solution (trade name "Cleaning Cleaner Securiganth 902" manufactured by Atotech Japan) at 60°C for 5 minutes.

(5-2) Soft etching (cleaning) The surface of the roughened substrate (c2) was treated with a sulfuric acid acid sodium peroxodisulfate aqueous solution at 30°C for 1 minute.

(5-3) Pre-dip (adjustment of the charge on the surface of the insulating layer before Pd is imparted) The surface of the roughened substrate (c2) was treated with a chemical solution (trade name "Pre. Dip Neoganth B" manufactured by Atotech Japan) at room temperature for 1 minute. In this way, the charge adjustment on the surface of the insulating layer is performed.

(5-4) Application of activator (application of Pd to the surface of the insulating layer) The surface of the roughened substrate (c2) was treated with a chemical solution (trade name "Activator Neoganth 834" manufactured by Atotech Japan) at 35°C for 5 minutes. In this way, Pd is provided on the surface of the insulating layer.

(5-5) Reduction (reduction of Pd imparted by the insulating layer) The surface of the roughened substrate (c2) was treated at 30°C for 5 minutes using a mixed chemical solution (a mixed solution of the product name "Reducer Neoganth WA" and the product name "Reducer Acceralator 810 mod." manufactured by Atotech Japan)). Thereby, reduction of Pd imparted to the surface of the insulating layer is performed. Proceed as described above to complete the pre-preparation for forming a conductor layer on the surface of the roughened substrate (c2).

[Step of electroless copper plating (Cu precipitation on the surface of the insulating layer (Pd surface))] Next, the surface of the roughened substrate (c2) was mixed with a chemical solution (trade name "Basic Solution Printganth MSK-DK" manufactured by Atotech Japan, "Copper solution Printganth MSK (trade name)" and trade name "Stabilizer Printganth". A mixed solution of "MSK-DK" and a brand name of "Reducer Cu"), treated at 35°C for 15 minutes. Thereby, by depositing Cu on the surface of the insulating layer (Pd surface), the first copper plating layer (hereinafter, also referred to as "electroless copper plating layer") is formed. The thickness of the formed electroless copper plating layer was 1 μm.

[Electrolytic copper plating step (a further copper plating layer is formed on the surface of the electroless copper plating layer)] Then, by forming the roughened substrate (c2) of the electroless copper plating layer, electrolytic copper plating is performed, and a second copper plating layer (hereinafter, also referred to as "electrolytic copper plating layer") is further formed on the surface of the electroless copper plating layer. ). Thereby, a conductor layer including an electroless copper plating layer and an electrolytic copper plating layer is formed. The thickness of the conductor layer (that is, the total thickness of the electroless copper plating layer and the electrolytic copper plating layer) is approximately 15 μm. In this way, a substrate on which a conductor layer is formed (hereinafter also referred to as "evaluation substrate (C)") is obtained.

(Heat resistance test) The evaluation substrate (C) was cut into test pieces of 100 mm×100 mm. A heat resistance test was performed on the obtained test piece. Specifically, the test piece is placed in the reflow device ("HAS6116" manufactured by Anton), and the test piece will be tested according to IPC/JEDEC J-STD-020C ("Moisture/Reflow Sensitivity Classification For Nonhermetic Solid State Surface Mount Devices", July 2004) The reflow step of the reflow temperature profile (peak temperature: 260°C) for lead-free assembly, without taking it out of the reflow device, was carried out 20 times to conduct a simulated heat resistance test.

(observe) In addition, after the heat resistance test, the surface of the test piece taken out from the reflow device was visually observed to confirm the presence or absence of peeling between the insulating layer and the conductor layer, and if peeling occurred, the location was counted.

The observation results are evaluated based on the following evaluation criteria. (Assessment criteria) "○": The peeling between the insulating layer and the conductor layer is 2 or less, indicating excellent heat resistance. "×": There are three or more peelings between the insulating layer and the conductor layer, indicating that the heat resistance has deteriorated.

[result] The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1 below, the amount of each component is a non-volatile component conversion amount. The content of the (A) component, the content of the (B) component, and the content of the (C) component in Table 1 indicate the percentage [mass%] when the non-volatile content in the resin composition is set to 100% by mass.

＜Conclusion＞ As is clear from Table 1, from the comparison between the examples and the comparative examples, the examples can provide a resin composition that can obtain a cured product having excellent heat resistance and moisture resistance. In addition, it is also known to provide a cured product of the resin composition of the related embodiment; a resin sheet including the resin composition; a printed wiring board including an insulating layer formed by the cured product of the resin composition; The semiconductor device of the wiring board becomes possible.

In addition, when the evaluation substrate (C) of Examples 1 to 4 was bent, no cracks were observed in the bent portion. Therefore, it is understood that it is possible to provide a resin composition that can obtain a cured product having excellent flexibility. Furthermore, it is understood that there is provided a cured product of the resin composition of the related embodiment; a resin sheet including the resin composition; a flexible substrate including an insulating layer formed by the cured product of the resin composition, and includes the Semiconductor devices with flexible substrates are also possible.

Furthermore, in Examples 1 to 4, even if one or both of the (D) component and (E) component were not contained, although there was a difference in the degree, it was confirmed that they all returned to the same results as the above-mentioned examples. In addition, in Examples 1 to 4, even if the component (C') is contained in an amount that does not significantly inhibit the expected effect of the present invention, although the degree is different, it was confirmed that all returned to the same results as the above-mentioned examples.

Claims (19)

A resin composition comprising (A) a polymer containing a butadiene skeleton, (B) an inorganic filler, and (C) a benzoxazine compound containing substituted or unsubstituted allyl groups, It is characterized by When the non-volatile content in the resin composition is 100% by mass, the content of (B) inorganic filler is 60% by mass or less and more than 0% by mass. The resin composition of claim 1, wherein the component (A) is a butadiene skeleton-containing polymer containing one or two or more aromatic groups in the molecule. The resin composition according to claim 2, wherein at least one of the aforementioned aromatic groups constitutes a part of the phenoxy structure. The resin composition of claim 3, wherein the aforementioned phenoxy structure includes a phenoxy structure represented by the following formula (A2-2),

(In the above formula (A2-2), A ^a1 and A ^a2 are bonding parts, and A ^a3 to A ^a6 are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted linear alkane with 1 to 5 carbon atoms base). The resin composition of claim 2, wherein the component (A) is a polymer containing a butadiene skeleton in which an aromatic group is interposed between two butadiene skeletons. The resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (A) is 15% by mass or more. The resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (A) is 50% by mass or less. Such as the resin composition of claim 1, wherein, when the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is less than 50% by mass. The resin composition of claim 1, wherein, when the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is 10% by mass or more. The resin composition of claim 1, wherein the component (C) is a benzoxazine compound containing two or more benzoxazine structures in the molecule. The resin composition of claim 1, wherein the component (C) is a benzoxazine compound containing two or more allyl groups in the molecule. The resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (C) is 0.01% by mass or more. Such as the resin composition of claim 1, wherein the water absorption rate of the hardened product is less than 0.2%. The resin composition of claim 1, which is used for forming an insulating layer. A cured product of the resin composition according to any one of claims 1-14. A resin sheet comprising a support and a resin composition layer including the resin composition according to any one of claims 1 to 14 provided on the support. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 14 or a cured product according to claim 15. A flexible substrate comprising an insulating layer formed by a hardened resin composition according to any one of claims 1 to 14 or a hardened material according to claim 15. A semiconductor device including a printed wiring board as claimed in claim 17 or a flexible substrate as claimed in claim 18.