JP2019019228A - Resin composition, resin varnish, method for producing laminate, thermosetting molding material, sealing material, and method for producing propenyl group-containing resin - Google Patents

Resin composition, resin varnish, method for producing laminate, thermosetting molding material, sealing material, and method for producing propenyl group-containing resin Download PDF

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JP2019019228A
JP2019019228A JP2017139087A JP2017139087A JP2019019228A JP 2019019228 A JP2019019228 A JP 2019019228A JP 2017139087 A JP2017139087 A JP 2017139087A JP 2017139087 A JP2017139087 A JP 2017139087A JP 2019019228 A JP2019019228 A JP 2019019228A
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健児 生山
Kenji Ikuyama
健児 生山
達 天野
Tatsu Amano
達 天野
幸雄 阿部
Yukio Abe
幸雄 阿部
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Gun Ei Chemical Industry Co Ltd
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Abstract

To provide a resin composition that has excellent curability and can form a cured product having excellent heat resistance while suppressing voids from occurring.SOLUTION: A resin composition contains a propenyl group-containing resin, and a maleimide compound having two or more maleimide groups in one molecule. The propenyl group-containing resin has a constitutional unit having a propenyl group at a specific rate, and the content of a component in which the total number of a benzene ring and a naphthalene ring in one molecule is 2 or less, is 3 mass% or less relative to the total mass of the propenyl group-containing resin.SELECTED DRAWING: None

Description

本発明は、樹脂組成物、樹脂ワニス、積層板の製造方法、熱硬化性成型材料、封止材、およびプロペニル基含有樹脂の製造方法に関する。   The present invention relates to a resin composition, a resin varnish, a method for producing a laminate, a thermosetting molding material, a sealing material, and a method for producing a propenyl group-containing resin.

熱硬化性を有する樹脂組成物は、その硬化性を利用し、樹脂ワニスや熱硬化性成型材料等として様々な分野に使用されている。たとえば、電子部品においては、繊維質基材に樹脂ワニスを含浸させたプリプレグと銅箔を積層して硬化させた銅張積層板や、熱硬化性成型材料の硬化物からなる封止材等が挙げられる。   The resin composition having thermosetting property is used in various fields as a resin varnish, a thermosetting molding material, and the like by utilizing its curability. For example, in an electronic component, a copper-clad laminate obtained by laminating and curing a prepreg impregnated with a resin varnish on a fibrous base material and copper foil, a sealing material made of a cured product of a thermosetting molding material, and the like Can be mentioned.

熱硬化性を有する樹脂組成物としては、アリルフェノール樹脂と、１分子中にマレイミド基を２以上有するマレイミド化合物とを含有する樹脂組成物が提案されている（特許文献１、２）。また、アリルフェノール樹脂と、前記アリルフェノール樹脂のアリル基がプロペニル基に変換されたプロペニル基含有樹脂と、マレイミド化合物とを含有する樹脂組成物が提案されている（特許文献３）。また、アリル基含有樹脂と、プロペニル基含有樹脂と、マレイミド化合物と、エポキシ樹脂とを含有する樹脂組成物も提案されている（特許文献４）。   As a resin composition having thermosetting properties, a resin composition containing an allylphenol resin and a maleimide compound having two or more maleimide groups in one molecule has been proposed (Patent Documents 1 and 2). Moreover, a resin composition containing an allylphenol resin, a propenyl group-containing resin in which an allyl group of the allylphenol resin is converted to a propenyl group, and a maleimide compound has been proposed (Patent Document 3). A resin composition containing an allyl group-containing resin, a propenyl group-containing resin, a maleimide compound, and an epoxy resin has also been proposed (Patent Document 4).

特開平６−１３２４２６号公報JP-A-6-132426 特開２０１５−１１７３７５号公報JP2015-117375A 特開２０１３−１９９６２７号公報JP 2013-199627 A 特許第４７９３５６５号公報Japanese Patent No. 4793565

マレイミド化合物を用いた樹脂組成物の硬化物はガラス転移温度が高く耐熱性に優れる。しかし、特許文献１、２のようなアリルフェノール樹脂を用いる樹脂組成物は、硬化速度が遅いうえ、硬化物にボイドが生じて不良率が上がるために電子部品等の生産性が低くなる。また、特許文献３、４のようにプロペニル基含有樹脂を用いれば硬化速度は上がるが、硬化物にボイドが生じて不良率が上がる問題は充分に改善されない。   A cured product of a resin composition using a maleimide compound has a high glass transition temperature and excellent heat resistance. However, resin compositions using allylphenol resins as in Patent Documents 1 and 2 have a low curing rate, and voids are generated in the cured product, resulting in an increased defect rate, resulting in low productivity of electronic components and the like. Moreover, if propenyl group containing resin is used like patent document 3, 4, although a cure rate will raise, the problem that a void will arise in hardened | cured material and a defect rate will raise is not fully improved.

本発明は、硬化性に優れ、かつボイドが生じることを抑制しつつ耐熱性に優れた硬化物を形成できる樹脂組成物、該樹脂組成物を利用した樹脂ワニス、積層板の製造方法、熱硬化性成型材料、封止材、および該樹脂組成物に用いるプロペニル基含有樹脂の製造方法の提供を目的とする。   The present invention provides a resin composition that is excellent in curability and can form a cured product excellent in heat resistance while suppressing generation of voids, a resin varnish using the resin composition, a method for producing a laminate, and thermosetting An object of the present invention is to provide a method for producing a propenyl group-containing resin used in a resin molding material, a sealing material, and the resin composition.

本発明は、以下の態様を有する。
［１］プロペニル基含有樹脂と、１分子中にマレイミド基を２以上有するマレイミド化合物とを含有し、
前記プロペニル基含有樹脂が、下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（３）で表される構成単位（３）からなる群から選ばれる１つ以上と、下記式（４）で表される構成単位（４）、下記式（５）で表される構成単位（５）および下記式（６）で表される構成単位（６）からなる群から選ばれる１つ以上とを有し、
前記構成単位（２）と前記構成単位（３）と前記構成単位（５）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５０〜１００モル％であり、
前記構成単位（３）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５〜１００モル％であり、
１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が、前記プロペニル基含有樹脂の総質量に対して３質量％以下である、樹脂組成物。 The present invention has the following aspects.
[1] containing a propenyl group-containing resin and a maleimide compound having two or more maleimide groups in one molecule;
The propenyl group-containing resin comprises a structural unit (1) represented by the following formula (1), a structural unit (2) represented by the following formula (2), and a structural unit (3 represented by the following formula (3): ), One or more selected from the group consisting of: a structural unit (4) represented by the following formula (4), a structural unit (5) represented by the following formula (5), and a formula (6) One or more selected from the group consisting of structural units (6)
The total content of the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6) is the structural unit (1), the structural unit (2), and the structural unit. 50 to 100 mol% based on the total of the unit (3), the structural unit (4), the structural unit (5) and the structural unit (6),
The total content of the structural unit (3) and the structural unit (6) is the structural unit (1), the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit. 5 to 100 mol% with respect to the total of the unit (5) and the structural unit (6),
The resin composition whose content of the component whose total number of the benzene ring and naphthalene ring in 1 molecule is 2 or less is 3 mass% or less with respect to the total mass of the said propenyl group containing resin.

Figure 2019019228
Figure 2019019228

［式中、Ａｒはメチル基を有していてもよいベンゼン環またはナフタレン環を示し、Ｒは下記式（ｒ１）または（ｒ２）で表される基を示し、ｐおよびｑはそれぞれ独立に０または１を示し、−＊および−＊＊はそれぞれ結合手を示す。−＊は、他の構成単位に結合し、−（Ｒ）ｐ−＊＊の−＊＊は、ｐが０である場合は他の構成単位または水素原子に結合し、ｐが１である場合は他の構成単位に結合し、−（Ｒ）ｑ−＊＊の−＊＊は、ｑが０である場合は他の構成単位または水素原子に結合し、ｑが１である場合は他の構成単位に結合する。］ [In the formula, Ar represents a benzene ring or a naphthalene ring which may have a methyl group, R represents a group represented by the following formula (r1) or (r2), and p and q each independently represents 0; Or 1 is shown,-* and-** show a bond, respectively. -* Is bonded to another structural unit,-** of-(R) p -** is bonded to another structural unit or a hydrogen atom when p is 0, and p is 1 Is bonded to another structural unit, and-** of-(R) q -** is bonded to another structural unit or a hydrogen atom when q is 0, and is bonded to another structural unit when q is 1. Join the building unit. ]

Figure 2019019228
Figure 2019019228

［２］１分子中のベンゼン環とナフタレン環の合計数が３である成分の含有量が、前記プロペニル基含有樹脂の総質量に対して４０質量％以上である、［１］に記載の樹脂組成物。
［３］前記プロペニル基含有樹脂が有するアリル基およびプロペニル基の合計に対する前記マレイミド化合物が有するマレイミド基の合計のモル比が、０．５〜３．０である、［１］または［２］に記載の樹脂組成物。
［４］エポキシ樹脂をさらに含む、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］前記プロペニル基含有樹脂と前記マレイミド化合物との硬化反応を促進する硬化促進剤と、無機フィラーとをさらに含む、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］溶剤をさらに含む、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］［６］に記載の樹脂組成物からなる樹脂ワニス。
［８］繊維質基材に請求項７に記載の樹脂ワニスを含浸させたプリプレグを含む積層物を加熱加圧し、硬化させて積層板を得る、積層板の製造方法。
［９］［５］に記載の樹脂組成物からなる熱硬化性成型材料。
［１０］［９］に記載の熱硬化性成型材料の硬化物からなる封止材。
［１１］前記構成単位（１）、前記構成単位（２）および前記構成単位（３）からなる群から選ばれる１つ以上と、前記構成単位（４）、前記構成単位（５）および前記構成単位（６）からなる群から選ばれる１つ以上とを有し、
前記構成単位（２）と前記構成単位（３）と前記構成単位（５）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５０〜１００モル％であり、
前記構成単位（３）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５〜１００モル％であり、
１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が３質量％以下であるプロペニル基含有樹脂の製造方法であって、
前記構成単位（１）および前記構成単位（４）を有し、前記構成単位（２）、前記構成単位（３）、前記構成単位（５）および前記構成単位（６）を有さず、かつ１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が３質量％以下である多価ヒドロキシ樹脂をアリル化し、前記構成単位（１）および前記構成単位（４）の少なくとも一部を前記構成単位（２）または前記構成単位（５）に変換した後、さらに前記構成単位（２）および前記構成単位（５）のアリル基の少なくとも一部をプロペニル化して前記構成単位（３）または前記構成単位（６）に変換する、プロペニル基含有樹脂の製造方法。 [2] The resin according to [1], wherein the content of the component having a total of 3 benzene rings and naphthalene rings in one molecule is 40% by mass or more based on the total mass of the propenyl group-containing resin. Composition.
[3] In [1] or [2], the molar ratio of the total maleimide group of the maleimide compound to the total of allyl group and propenyl group of the propenyl group-containing resin is 0.5 to 3.0. The resin composition as described.
[4] The resin composition according to any one of [1] to [3], further including an epoxy resin.
[5] The resin composition according to any one of [1] to [4], further including a curing accelerator that accelerates a curing reaction between the propenyl group-containing resin and the maleimide compound, and an inorganic filler.
[6] The resin composition according to any one of [1] to [5], further including a solvent.
[7] A resin varnish comprising the resin composition according to [6].
[8] A method for producing a laminate, wherein a laminate comprising a prepreg impregnated with a resin varnish according to claim 7 is heated and pressed and cured to obtain a laminate.
[9] A thermosetting molding material comprising the resin composition according to [5].
[10] A sealing material comprising a cured product of the thermosetting molding material according to [9].
[11] One or more selected from the group consisting of the structural unit (1), the structural unit (2), and the structural unit (3), the structural unit (4), the structural unit (5), and the structural unit One or more selected from the group consisting of units (6),
The total content of the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6) is the structural unit (1), the structural unit (2), and the structural unit. 50 to 100 mol% based on the total of the unit (3), the structural unit (4), the structural unit (5) and the structural unit (6),
The total content of the structural unit (3) and the structural unit (6) is the structural unit (1), the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit. 5 to 100 mol% with respect to the total of the unit (5) and the structural unit (6),
A method for producing a propenyl group-containing resin in which the content of components having a total number of benzene rings and naphthalene rings in one molecule of 2 or less is 3% by mass or less,
Having the structural unit (1) and the structural unit (4), not having the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6); A polyvalent hydroxy resin having a content of a component having a total number of benzene rings and naphthalene rings of 2 or less in one molecule of 2 or less is allylated, and at least the structural unit (1) and the structural unit (4) After a part is converted into the structural unit (2) or the structural unit (5), at least a part of the allyl groups of the structural unit (2) and the structural unit (5) is further propenylated to form the structural unit ( 3) A method for producing a propenyl group-containing resin, which is converted into the structural unit (6).

本発明によれば、耐熱性に優れた硬化物を、ボイドが生じることを抑制しつつ短時間で形成でき、積層板や封止材等を高い生産性で製造できる。   ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material excellent in heat resistance can be formed in a short time, suppressing generation | occurrence | production of a void, and a laminated board, a sealing material, etc. can be manufactured with high productivity.

＜樹脂組成物＞
本発明の樹脂組成物は、後述のプロペニル基含有樹脂（Ａ）と、１分子中にマレイミド基を２以上有するマレイミド化合物（以下、「マレイミド化合物（Ｉ）」ともいう。）とを含有する。 <Resin composition>
The resin composition of the present invention contains a propenyl group-containing resin (A) described later and a maleimide compound having two or more maleimide groups in one molecule (hereinafter also referred to as “maleimide compound (I)”).

［プロペニル基含有樹脂（Ａ）］
プロペニル基含有樹脂（Ａ）は、下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（３）で表される構成単位（３）からなる群から選ばれる１つ以上と、下記式（４）で表される構成単位（４）、下記式（５）で表される構成単位（５）および下記式（６）で表される構成単位（６）からなる群から選ばれる１つ以上とを有する。プロペニル基含有樹脂（Ａ）は、構成単位（３）および構成単位（６）の少なくとも一方を必須として有する。
なお、「構成単位」は、重合体を構成する単位を示す。また、本発明においては、「プロペニル基」とは１−プロペニル基（−ＣＨ＝ＣＨ−ＣＨ３）を示し、「アリル基」とは２−プロペニル基（−ＣＨ２−ＣＨ＝ＣＨ２）を示す。 [Propenyl group-containing resin (A)]
The propenyl group-containing resin (A) includes a structural unit (1) represented by the following formula (1), a structural unit (2) represented by the following formula (2), and a structural unit represented by the following formula (3). One or more selected from the group consisting of (3), a structural unit (4) represented by the following formula (4), a structural unit (5) represented by the following formula (5), and the following formula (6) And one or more selected from the group consisting of the structural units (6) represented. The propenyl group-containing resin (A) has at least one of the structural unit (3) and the structural unit (6) as an essential component.
“Structural unit” refers to a unit constituting the polymer. In the present invention, “propenyl group” means 1-propenyl group (—CH═CH—CH 3 ), and “allyl group” means 2-propenyl group (—CH 2 —CH═CH 2 ). Show.

Figure 2019019228
Figure 2019019228

［式中、Ａｒはメチル基を有していてもよいベンゼン環またはナフタレン環を示し、Ｒは下記式（ｒ１）または（ｒ２）で表される基を示し、ｐおよびｑはそれぞれ独立に０または１を示し、−＊および−＊＊はそれぞれ結合手を示す。−＊は、他の構成単位に結合し、−（Ｒ）ｐ−＊＊の−＊＊は、ｐが０である場合は他の構成単位または水素原子に結合し、ｐが１である場合は他の構成単位に結合し、−（Ｒ）ｑ−＊＊の−＊＊は、ｑが０である場合は他の構成単位または水素原子に結合し、ｑが１である場合は他の構成単位に結合する。］ [In the formula, Ar represents a benzene ring or a naphthalene ring which may have a methyl group, R represents a group represented by the following formula (r1) or (r2), and p and q each independently represents 0; Or 1 is shown,-* and-** show a bond, respectively. -* Is bonded to another structural unit,-** of-(R) p -** is bonded to another structural unit or a hydrogen atom when p is 0, and p is 1 Is bonded to another structural unit, and-** of-(R) q -** is bonded to another structural unit or a hydrogen atom when q is 0, and is bonded to another structural unit when q is 1. Join the building unit. ]

Figure 2019019228
Figure 2019019228

プロペニル基含有樹脂（Ａ）は、構成単位（１）〜（６）に由来して、複数のＡｒを含む。プロペニル基含有樹脂（Ａ）における複数のＡｒは、１つのＲを介して互いに結合しており、直接結合しない。
以下、プロペニル基含有樹脂（Ａ）において、Ａｒを３つ有するものを「３核体」と記し、Ａｒが３つ以外のものも同様に記す。 The propenyl group-containing resin (A) is derived from the structural units (1) to (6) and contains a plurality of Ar. A plurality of Ar in the propenyl group-containing resin (A) are bonded to each other through one R and are not directly bonded.
Hereinafter, in the propenyl group-containing resin (A), those having three Ars are referred to as “trinuclear bodies”, and those other than three are similarly described.

構成単位（１）〜（３）のＲから伸びる結合手（−＊）は、構成単位（４）〜（６）のいずれかのＡｒから伸びる結合手（−＊）に結合する。
構成単位（４）〜（６）のＡｒから伸びる結合手は、構成単位（１）〜（３）のいずれかのＲから伸びる結合手（−＊）、または、ｐおよびｑの少なくとも一方が１である別の（４）〜（６）のいずれかのＲから伸びる結合手に結合する。
ｐおよびｑの少なくとも一方が１である構成単位（４）〜（６）のＲから伸びる結合手は、別の構成単位（４）〜（６）のいずれかのＡｒから伸びる結合手に結合する。
なお、構成単位（４）〜（６）において、Ａｒから伸びる結合手とは、−＊、ｐが０である（Ｒ）ｐ−＊＊、またはｑが０である（Ｒ）ｑ−＊＊のいずれかである。Ｒから伸びる結合手とは、ｐが１である（Ｒ）ｐ−＊＊、またはｑが１である（Ｒ）ｑ−＊＊のいずれかである。 The bond (-*) extending from R of the structural units (1) to (3) is bonded to the bond (-*) extending from any Ar of the structural units (4) to (6).
The bond extending from Ar in the structural units (4) to (6) is a bond (-*) extending from any R of the structural units (1) to (3), or at least one of p and q is 1. It is bonded to a bond extending from R in any one of (4) to (6).
The bond extending from R of the structural units (4) to (6) in which at least one of p and q is 1 is bonded to the bond extending from any Ar of the other structural units (4) to (6). .
In the structural units (4) to (6), the bond extending from Ar is-*, p is 0 (R) p -**, or q is 0 (R) q -** One of them. The bond extending from R is either (R) p -** where p is 1 or (R) q -** where q is 1.

前記式（１）〜（６）中、Ａｒは、ベンゼン環でもよく、ナフタレン環でもよく、メチル基を有するベンゼン環でもよく、メチル基を有するナフタレン環でもよく、ベンゼン環が好ましい。Ａｒがメチル基を有する場合、メチル基の数は、１つであってもよく、２つ以上であってもよく、１つが好ましい。
Ｒは、前記式（ｒ１）で表される基でもよく、前記式（ｒ２）で表される基でもよい。
前記式（ｒ２）中、ベンゼン環におけるメチン基と水酸基の結合位置は、特に限定されず、原料価格および入手のしやすさの点から、オルソ位またはパラ位が好ましい。
プロペニル基含有樹脂（Ａ）に含まれる複数のＡｒはそれぞれ同じでもよく異なってもよい。プロペニル基含有樹脂（Ａ）がＲを複数含む場合、これらの複数のＲはそれぞれ同じでもよく異なってもよい。
プロペニル基含有樹脂（Ａ）が構成単位（４）〜（６）のうち２つ以上を有する場合、複数の−（Ｒ）ｐ−＊＊のｐは同じであっても異なってもよく、複数の−（Ｒ）ｑ−＊＊のｑは同じであっても異なってもよい。 In the formulas (1) to (6), Ar may be a benzene ring, a naphthalene ring, a benzene ring having a methyl group, a naphthalene ring having a methyl group, or a benzene ring being preferred. When Ar has a methyl group, the number of methyl groups may be one, two or more, and one is preferable.
R may be a group represented by the formula (r1) or a group represented by the formula (r2).
In the formula (r2), the bonding position of the methine group and the hydroxyl group in the benzene ring is not particularly limited, and the ortho-position or para-position is preferable from the viewpoint of the raw material price and availability.
A plurality of Ar contained in the propenyl group-containing resin (A) may be the same or different. When the propenyl group-containing resin (A) includes a plurality of Rs, these Rs may be the same or different.
When the propenyl group-containing resin (A) has two or more of the structural units (4) to (6), p in the plurality of — (R) p — ** may be the same or different. -(R) q -** in q may be the same or different.

構成単位（１）の具体例としては、下記式（１−１）、（１−２）、（１−３）または（１−４）で表される構成単位が挙げられる。これらの中でも式（１−１）で表される構成単位が好ましい。   Specific examples of the structural unit (1) include structural units represented by the following formula (1-1), (1-2), (1-3) or (1-4). Among these, the structural unit represented by Formula (1-1) is preferable.

Figure 2019019228
Figure 2019019228

式（１−１）で表される構成単位のベンゼン環における−Ｒ−＊の結合位置は特に限定されない。
式（１−２）または（１−３）で表される構成単位のナフタレン環における−Ｒ−＊の結合位置は特に限定されない。たとえば式（１−２）中、水酸基が結合した位置を１位とした場合、−Ｒ−＊が結合するのは２〜８位のいずれでもよい。式（１−３）中、水酸基が結合した位置を２位とした場合、−Ｒ−＊が結合するのは１、３〜８位のいずれでもよい。
式（１−４）で表される構成単位のベンゼン環における−ＣＨ３の結合位置は、典型的には、水酸基に対してオルソ位またはパラ位である。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（１）は１種でも２種以上でもよい。 The bonding position of -R- * in the benzene ring of the structural unit represented by formula (1-1) is not particularly limited.
The bonding position of -R- * in the naphthalene ring of the structural unit represented by formula (1-2) or (1-3) is not particularly limited. For example, in the formula (1-2), when the position at which a hydroxyl group is bonded is defined as the 1st position, -R- * may be bonded at any of the 2nd to 8th positions. In Formula (1-3), when the position at which the hydroxyl group is bonded is the 2nd position, -R- * may be bonded at either the 1st or 3rd to 8th positions.
The bonding position of —CH 3 in the benzene ring of the structural unit represented by the formula (1-4) is typically an ortho position or a para position with respect to the hydroxyl group.
The structural unit (1) contained in the propenyl group-containing resin (A) may be one type or two or more types.

構成単位（２）の具体例としては、前記式（１−１）または（１−４）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位、前記式（１−２）または（１−３）におけるナフタレン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位等が挙げられる。−ＣＨ２−ＣＨ＝ＣＨ２の結合位置は、典型的には、水酸基に対してオルソ位またはパラ位である。
構成単位（２）としては、上記の中でも、式（１−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位が好ましい。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（２）は１種でも２種以上でもよい。 Specific examples of the structural unit (2) include a structural unit having a structure in which —CH 2 —CH═CH 2 is bonded to the benzene ring in the formula (1-1) or (1-4), and the formula (1-2). ) Or a structural unit having a structure in which —CH 2 —CH═CH 2 is bonded to the naphthalene ring in (1-3). The bonding position of —CH 2 —CH═CH 2 is typically in the ortho or para position with respect to the hydroxyl group.
Among the above, the structural unit (2) is preferably a structural unit having a structure in which —CH 2 —CH═CH 2 is bonded to the benzene ring in the formula (1-1).
The structural unit (2) contained in the propenyl group-containing resin (A) may be one type or two or more types.

構成単位（３）の具体例としては、前記式（１−１）または（１−４）におけるベンゼン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位、前記式（１−２）または（１−３）におけるナフタレン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位等が挙げられる。−ＣＨ＝ＣＨ−ＣＨ３の結合位置は、典型的には、水酸基に対してオルソ位またはパラ位である。
構成単位（３）としては、上記の中でも、式（１−１）におけるベンゼン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位が好ましい。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（３）は１種でも２種以上でもよい。 Specific examples of the structural unit (3) include structural units having a structure in which —CH═CH—CH 3 is bonded to the benzene ring in the formula (1-1) or (1-4), and the formula (1-2). Alternatively, a structural unit having a structure in which —CH═CH—CH 3 is bonded to the naphthalene ring in (1-3) can be used. The bonding position of —CH═CH—CH 3 is typically in the ortho or para position with respect to the hydroxyl group.
Among the above, the structural unit (3) is preferably a structural unit having a structure in which —CH═CH—CH 3 is bonded to the benzene ring in the formula (1-1).
The structural unit (3) contained in the propenyl group-containing resin (A) may be one type or two or more types.

構成単位（４）の具体例としては、下記式（４−１）、（４−２）、（４−３）または（４−４）で表される構成単位が挙げられる。これらの中でも式（４−１）で表される構成単位が好ましい。   Specific examples of the structural unit (4) include structural units represented by the following formula (4-1), (4-2), (4-3), or (4-4). Among these, the structural unit represented by Formula (4-1) is preferable.

Figure 2019019228
Figure 2019019228

式（４−１）で表される構成単位のベンゼン環における−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊のそれぞれの結合位置は特に限定されない。
式（４−２）または（４−３）で表される構成単位のナフタレン環における−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊のそれぞれの結合位置は特に限定されない。たとえば式（４−２）中、水酸基が結合した位置を１位とした場合、−Ｒ−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊が結合するのは２〜８位のいずれでもよい。式（４−３）中、水酸基が結合した位置を２位とした場合、−Ｒ−＊、−（Ｒ）ｐ−＊＊、−（Ｒ）ｑ−＊＊が結合するのは１、３〜８位のいずれでもよい。
式（４−４）で表される構成単位のベンゼン環における−ＣＨ３の結合位置は、典型的には、水酸基に対してオルソ位またはパラ位である。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（４）は１種でも２種以上でもよい。 The bonding positions of-*,-(R) p -**, and-(R) q -** in the benzene ring of the structural unit represented by the formula (4-1) are not particularly limited.
The bonding positions of-*,-(R) p -**, and-(R) q -** in the naphthalene ring of the structural unit represented by formula (4-2) or (4-3) are particularly limited. Not. For example, in the formula (4-2), when the position at which the hydroxyl group is bonded is the 1-position, -R- *,-(R) p -**, and-(R) q -** are bonded to 2 Any of the 8th place may be sufficient. In formula (4-3), when the position at which the hydroxyl group is bonded is the 2-position, -R- *,-(R) p -**, and-(R) q -** are bonded to 1, 3 Any of -8th position may be sufficient.
The bonding position of —CH 3 in the benzene ring of the structural unit represented by formula (4-4) is typically in the ortho or para position with respect to the hydroxyl group.
The structural unit (4) contained in the propenyl group-containing resin (A) may be one type or two or more types.

構成単位（５）の具体例としては、前記式（４−１）または（４−４）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位、前記式（４−２）または（４−３）におけるナフタレン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位等が挙げられる。
構成単位（５）としては、上記の中でも、式（４−１）におけるベンゼン環に−ＣＨ２−ＣＨ＝ＣＨ２が結合した構造の構成単位が好ましい。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（５）は１種でも２種以上でもよい。 Specific examples of the structural unit (5) include structural units having a structure in which —CH 2 —CH═CH 2 is bonded to the benzene ring in the formula (4-1) or (4-4), and the formula (4-2). ) Or a structural unit having a structure in which —CH 2 —CH═CH 2 is bonded to the naphthalene ring in (4-3).
Among the above, the structural unit (5) is preferably a structural unit having a structure in which —CH 2 —CH═CH 2 is bonded to the benzene ring in the formula (4-1).
The structural unit (5) contained in the propenyl group-containing resin (A) may be one type or two or more types.

構成単位（６）の具体例としては、前記式（４−１）または（４−４）におけるベンゼン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位、前記式（４−２）または（４−３）におけるナフタレン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位等が挙げられる。
構成単位（６）としては、上記の中でも、式（４−１）におけるベンゼン環に−ＣＨ＝ＣＨ−ＣＨ３が結合した構造の構成単位が好ましい。
プロペニル基含有樹脂（Ａ）に含まれる構成単位（６）は１種でも２種以上でもよい。 Specific examples of the structural unit (6) include structural units having a structure in which —CH═CH—CH 3 is bonded to the benzene ring in the formula (4-1) or (4-4), and the formula (4-2). Alternatively, a structural unit having a structure in which —CH═CH—CH 3 is bonded to the naphthalene ring in (4-3) can be used.
Among the above, the structural unit (6) is preferably a structural unit having a structure in which —CH═CH—CH 3 is bonded to the benzene ring in the formula (4-1).
The structural unit (6) contained in the propenyl group-containing resin (A) may be one type or two or more types.

プロペニル基含有樹脂（Ａ）は、必要に応じて、本発明の効果を損なわない範囲で、構成単位（１）、構成単位（２）、構成単位（３）、構成単位（４）、構成単位（５）および構成単位（６）以外の他の構成単位をさらに有していてもよい。
他の構成単位としては、たとえば、構成単位（１）〜（６）におけるＡｒに水酸基が結合している位置に、水酸基の代わりに水素原子が結合している構造の構成単位が挙げられる。 The propenyl group-containing resin (A) is a structural unit (1), a structural unit (2), a structural unit (3), a structural unit (4), or a structural unit as long as it does not impair the effects of the present invention. You may further have other structural units other than (5) and structural unit (6).
As another structural unit, for example, a structural unit having a structure in which a hydrogen atom is bonded instead of a hydroxyl group at a position where a hydroxyl group is bonded to Ar in the structural units (1) to (6).

プロペニル基含有樹脂（Ａ）における構成単位（２）と構成単位（３）と構成単位（５）と構成単位（６）の合計の含有量（以下、「含有量Ｐ１」ともいう。）は、構成単位（１）と構成単位（２）と構成単位（３）と構成単位（４）と構成単位（５）と構成単位（６）の合計に対して、５０〜１００モル％であり、７０〜１００モル％が好ましく、８０〜１００モル％が特に好ましい。含有量Ｐ１が前記範囲の下限値以上であれば、充分な硬化速度が得られる。また、得られる硬化物が、高ガラス転移温度、高熱分解温度を示す。 The total content of the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6) in the propenyl group-containing resin (A) (hereinafter also referred to as “content P 1 ”). , 50 to 100 mol% based on the total of the structural unit (1), the structural unit (2), the structural unit (3), the structural unit (4), the structural unit (5), and the structural unit (6), 70-100 mol% is preferable and 80-100 mol% is especially preferable. When the content P 1 is lower than the lower limit value of the range, a sufficient curing rate can be obtained. Moreover, the hardened | cured material obtained shows a high glass transition temperature and a high thermal decomposition temperature.

プロペニル基含有樹脂（Ａ）における構成単位（３）と構成単位（６）の合計の含有量（以下、「含有量Ｐ２」ともいう。）が、構成単位（１）と構成単位（２）と構成単位（３）と構成単位（４）と構成単位（５）と構成単位（６）の合計に対して、５〜１００モル％であり、１０〜９０モル％が好ましく、１５〜８０モル％がより好ましい。この割合は、プロペニル基含有樹脂（Ａ）中のＡｒの総モル数（１００モル％）に対するプロペニル基の合計のモル数の割合（モル％）に等しい。含有量Ｐ２が前記範囲の下限値以上であれば、充分な硬化速度が得られる。また、得られる硬化物が、高ガラス転移温度、高熱分解温度を示す。 The total content of the structural unit (3) and the structural unit (6) in the propenyl group-containing resin (A) (hereinafter also referred to as “content P 2 ”) is the structural unit (1) and the structural unit (2). And 5 to 100 mol%, preferably 10 to 90 mol%, preferably 15 to 80 mol% based on the total of the structural unit (3), the structural unit (4), the structural unit (5) and the structural unit (6). % Is more preferable. This ratio is equal to the ratio (mol%) of the total number of moles of propenyl groups to the total number of moles of Ar (100 mole%) in the propenyl group-containing resin (A). When the content P 2 is more than the lower limit of the range, a sufficient curing rate can be obtained. Moreover, the hardened | cured material obtained shows a high glass transition temperature and a high thermal decomposition temperature.

プロペニル基含有樹脂（Ａ）は、３核体以上の成分を含む。プロペニル基含有樹脂（Ａ）における３核体以上の成分は、通常はＡｒに結合する水酸基を２以上有しており、全てのＡｒに水酸基が結合し、Ａｒの数と水酸基の数が同じであることが好ましい。
プロペニル基含有樹脂（Ａ）においては、３核体以上の成分の中でも、樹脂組成物が低粘度となり、無機フィラーを配合しやすくなる点から、３核体が好ましい。３核体としては、下記式（ａ１）で表される化合物、および下記式（ａ２）で表される化合物が好ましい。 The propenyl group-containing resin (A) includes a trinuclear or higher component. The trinuclear or higher component in the propenyl group-containing resin (A) usually has two or more hydroxyl groups bonded to Ar, hydroxyl groups are bonded to all Ar, and the number of Ar and the number of hydroxyl groups are the same. Preferably there is.
In the propenyl group-containing resin (A), among the components having three or more nuclei, the trinuclear is preferable because the resin composition has a low viscosity and the inorganic filler can be easily blended. As the trinuclear body, a compound represented by the following formula (a1) and a compound represented by the following formula (a2) are preferable.

Figure 2019019228
Figure 2019019228

［式中、Ｑはプロペニル基、アリル基または水素原子のいずれかであり、３つのＱのうち少なくとも１つはプロペニル基である。］ [Wherein, Q is a propenyl group, an allyl group or a hydrogen atom, and at least one of the three Qs is a propenyl group. ]

前記式（ａ１）および（ａ２）における３つのＱは、互いに同じでもよく、異なってもよい。
Ｑの結合位置は、典型的には、水酸基に対してオルソ位またはパラ位である。 The three Qs in the formulas (a1) and (a2) may be the same or different from each other.
The bonding position of Q is typically an ortho position or a para position with respect to the hydroxyl group.

プロペニル基含有樹脂（Ａ）における１分子中のベンゼン環とナフタレン環の合計数が２以下の成分、すなわち２核体以下の成分の含有量は、プロペニル基含有樹脂（Ａ）の総質量に対して、３質量％以下であり、２質量％以下が好ましく、１質量％以下がより好ましい。２核体以下の成分の含有量が前記上限値以下であれば、プロペニル基含有樹脂（Ａ）の揮発性が低くなり、硬化時に揮発して硬化物にボイドが生じることを抑制できる。   In the propenyl group-containing resin (A), the total number of benzene rings and naphthalene rings in one molecule is 2 or less, that is, the content of the dinuclear or less component is based on the total mass of the propenyl group-containing resin (A). 3 mass% or less, preferably 2 mass% or less, more preferably 1 mass% or less. If content of the component below 2 nucleus is below the said upper limit, the volatility of propenyl group containing resin (A) will become low, and it can suppress that it volatilizes at the time of hardening and a void arises in hardened | cured material.

プロペニル基含有樹脂（Ａ）における１分子中のベンゼン環とナフタレン環の合計数が３である成分、すなわち３核体の含有量は、プロペニル基含有樹脂（Ａ）の総質量に対して、４０質量％以上が好ましく、４５〜９５質量％がより好ましく、５０〜９０質量％がさらに好ましい。３核体の含有量が前記下限値以上であれば、樹脂組成物が低粘度となり、無機フィラーを配合しやすくなる。３核体の含有量が前記上限値以下であれば、樹脂組成物がさらに低粘度かつ原料入手が容易である。   The component in which the total number of benzene rings and naphthalene rings in one molecule in the propenyl group-containing resin (A) is 3, that is, the content of the trinuclear is 40% with respect to the total mass of the propenyl group-containing resin (A). % By mass or more is preferable, 45 to 95% by mass is more preferable, and 50 to 90% by mass is more preferable. If the content of the trinuclear body is equal to or higher than the lower limit, the resin composition has a low viscosity, and the inorganic filler is easily blended. If the content of the trinuclear body is less than or equal to the above upper limit, the resin composition has a lower viscosity and the raw material can be easily obtained.

プロペニル基含有樹脂（Ａ）における１分子中のベンゼン環とナフタレン環の合計数が４以上である成分、すなわち４核体以上の成分の含有量は、プロペニル基含有樹脂（Ａ）の総質量に対して、５〜２５質量％が好ましく、７〜２０質量％がより好ましく、１０〜１５質量％がさらに好ましい。４核体以上の含有量が前記下限値以上であれば、プロペニル基含有樹脂（Ａ）の揮発性がより低くなり、硬化物にボイドが生じることを抑制しやすい。４核体以上の成分の含有量が前記上限値以下であれば、樹脂組成物がさらに低粘度となる。   In the propenyl group-containing resin (A), the total number of benzene rings and naphthalene rings in one molecule is 4 or more, that is, the content of the 4-nuclear or higher component is the total mass of the propenyl group-containing resin (A). On the other hand, 5-25 mass% is preferable, 7-20 mass% is more preferable, and 10-15 mass% is further more preferable. When the content of tetranuclear or more is equal to or more than the lower limit, the volatility of the propenyl group-containing resin (A) becomes lower, and it is easy to suppress the formation of voids in the cured product. If the content of the tetranuclear or higher component is less than or equal to the upper limit, the resin composition will have a lower viscosity.

（プロペニル基含有樹脂（Ａ）の製造方法）
プロペニル基含有樹脂（Ａ）の製造方法としては、例えば、以下の方法が挙げられる。
構成単位（１）および構成単位（４）を有し、構成単位（２）、構成単位（３）、構成単位（５）および構成単位（６）を有さず、かつ２核体以下の成分の含有量が３質量％以下である多価ヒドロキシ樹脂（以下、「多価ヒドロキシ樹脂（Ｃ）」という。）をアリル化し、構成単位（１）および構成単位（４）の少なくとも一部を構成単位（２）または構成単位（５）に変換してアリル基含有樹脂（以下、「アリル基含有樹脂（Ｂ）」という。）を得る。次いで、アリル基含有樹脂（Ｂ）の構成単位（２）および構成単位（５）のアリル基の少なくとも一部をプロペニル化して構成単位（３）または構成単位（６）に変換してプロペニル基含有樹脂（Ａ）を得る。 (Production method of propenyl group-containing resin (A))
As a manufacturing method of propenyl group containing resin (A), the following method is mentioned, for example.
Components having a structural unit (1) and a structural unit (4), having no structural unit (2), a structural unit (3), a structural unit (5) and a structural unit (6), and having two or less nuclei The polyvalent hydroxy resin (hereinafter referred to as “polyvalent hydroxy resin (C)”) having a content of 3% by mass or less is allylated to constitute at least a part of the structural unit (1) and the structural unit (4). Conversion into the unit (2) or the structural unit (5) yields an allyl group-containing resin (hereinafter referred to as “allyl group-containing resin (B)”). Next, at least a part of the allyl groups of the structural unit (2) and the structural unit (5) of the allyl group-containing resin (B) is propenylated to be converted into the structural unit (3) or the structural unit (6) to contain a propenyl group. Resin (A) is obtained.

多価ヒドロキシ樹脂（Ｃ）の製造方法としては、たとえば、以下の方法が挙げられる。
Ｒが前記式（ｒ１）で表される多価ヒドロキシ樹脂（Ｃ）の製造方法としては、酸性触媒の存在下に、フェノール類およびナフトール類からなる群から選ばれる少なくとも１種とホルムアルデヒド源とを縮合反応させた後、２２０〜２５０℃での蒸留により２核体以下の成分の含有量を低減する方法が挙げられる。
また、フェノール類とホルムアルデヒドをアルカリ条件下によりメチロール付加反応を行った後、酸条件下で過剰のフェノール類と縮合反応をさせ、余剰のフェノールを蒸留により除去する方法が挙げられる。
Ｒが前記式（ｒ２）で表される多価ヒドロキシ樹脂（Ｃ）の製造方法としては、酸性触媒の存在下に、フェノール類とヒドロキシベンズアルデヒドとを縮合反応させる方法が挙げられる。 Examples of the method for producing the polyvalent hydroxy resin (C) include the following methods.
In the production method of the polyvalent hydroxy resin (C) in which R is represented by the formula (r1), in the presence of an acidic catalyst, at least one selected from the group consisting of phenols and naphthols and a formaldehyde source are used. After the condensation reaction, a method of reducing the content of the binuclear or lower component by distillation at 220 to 250 ° C. can be mentioned.
Moreover, after performing a methylol addition reaction of phenols and formaldehyde under alkaline conditions, a method of causing a condensation reaction with excess phenols under acid conditions and removing excess phenol by distillation can be mentioned.
Examples of the method for producing the polyvalent hydroxy resin (C) in which R is represented by the formula (r2) include a method in which a phenol and hydroxybenzaldehyde are subjected to a condensation reaction in the presence of an acidic catalyst.

フェノール類としては、フェノール、クレゾール等が挙げられる。
ナフトール類としては、１−ナフトール、２−ナフトール等が挙げられる。
ホルムアルデヒド源としては、ホルマリン、パラホルムアルデヒド等が挙げられる。
酸性触媒としては、塩酸、硫酸等が挙げられる。 Examples of phenols include phenol and cresol.
Examples of naphthols include 1-naphthol and 2-naphthol.
Examples of formaldehyde sources include formalin and paraformaldehyde.
Examples of the acidic catalyst include hydrochloric acid and sulfuric acid.

多価ヒドロキシ樹脂（Ｃ）における２核体以下の成分の含有量は、アリル基含有樹脂（Ｂ）の総質量に対して、３質量％以下であり、２質量％以下が好ましく、１質量％以下がより好ましい。   The content of the binuclear or lower component in the polyvalent hydroxy resin (C) is 3% by mass or less, preferably 2% by mass or less, and preferably 1% by mass with respect to the total mass of the allyl group-containing resin (B). The following is more preferable.

多価ヒドロキシ樹脂（Ｃ）は、市販品を用いてもよく、たとえば、製品名：ＬＶＲ８２１０ＤＬ、ＴＰＭ−１００（群栄化学工業社製）等が挙げられる。
プロペニル基含有樹脂（Ａ）の製造に用いる多価ヒドロキシ樹脂（Ｃ）は、１種でもよく２種以上でもよい。 A commercially available product may be used as the polyvalent hydroxy resin (C), and examples thereof include product names: LVR8210DL, TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.) and the like.
The polyvalent hydroxy resin (C) used for the production of the propenyl group-containing resin (A) may be one type or two or more types.

多価ヒドロキシ樹脂（Ｃ）をアリル化する方法としては、たとえば以下の方法が挙げられる。多価ヒドロキシ樹脂（Ｃ）とハロゲン化アリルとを反応させ、構成単位（１）および構成単位（４）の少なくとも一部の水酸基をアリルエーテル化して−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２に変換する。次いで、クライゼン転移反応により、−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２におけるアリル基を転移させる。
構成単位（１）がアリル化されると構成単位（２）が生成し、構成単位（４）がアリル化されると構成単位（５）が生成する。 Examples of the method for allylating the polyvalent hydroxy resin (C) include the following methods. The polyvalent hydroxy resin (C) is reacted with an allyl halide, and at least a part of the hydroxyl groups of the structural unit (1) and the structural unit (4) is allyl etherified to convert to —O—CH 2 —CH═CH 2 . To do. Next, the allyl group in —O—CH 2 —CH═CH 2 is transferred by Claisen rearrangement reaction.
When the structural unit (1) is allylated, the structural unit (2) is generated, and when the structural unit (4) is allylated, the structural unit (5) is generated.

ハロゲン化アリルとしては、たとえば、塩化アリル、臭化アリル、フッ化アリル、ヨウ化アリル等が挙げられる。コストの点から、塩化アリルが好ましい。
多価ヒドロキシ樹脂（Ｃ）の水酸基の合計量に対するハロゲン化アリルのモル比は、０．３〜２．０が好ましく、０．５〜１．２がより好ましい。前記モル比が前記範囲内であれば、硬化物の耐熱性に優れる。また、余剰のハロゲン化アリルを使用しないため、生産性に優れる。 Examples of the allyl halide include allyl chloride, allyl bromide, allyl fluoride, allyl iodide, and the like. In view of cost, allyl chloride is preferred.
The molar ratio of the allyl halide to the total amount of hydroxyl groups in the polyvalent hydroxy resin (C) is preferably from 0.3 to 2.0, more preferably from 0.5 to 1.2. When the molar ratio is within the above range, the cured product has excellent heat resistance. Further, since no excess allyl halide is used, the productivity is excellent.

多価ヒドロキシ樹脂（Ｃ）とハロゲン化アリルによるアリルエーテル化反応は、触媒の存在下で行うことが好ましい。
アリルエーテル化反応の触媒としては、たとえば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属類、ジアザビシクロノネン、ジアザビシクロウンデセン、トリエチルアミン等のアミン類、ナトリウムｔｅｒｔ−ブトキシド、カリウムｔｅｒｔ−ブトキシド、リチウムジイソプロピルアミド、ケイ素−塩基性アミン、リチウムテトラメチルピペリジン等が挙げられる。これらの中でも、比較的安価であり、副反応が起こりにくい点で、アルカリ金属類、ジアザビシクロノネン、ジアザビシクロウンデセンが好ましい。触媒は１種を単独で用いてもよく、２種以上を併用してもよい。 The allyl etherification reaction between the polyvalent hydroxy resin (C) and the allyl halide is preferably performed in the presence of a catalyst.
Examples of the catalyst for the allyl etherification reaction include alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononene, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide. , Lithium diisopropylamide, silicon-basic amine, lithium tetramethylpiperidine and the like. Among these, alkali metals, diazabicyclononene, and diazabicycloundecene are preferable because they are relatively inexpensive and hardly cause side reactions. A catalyst may be used individually by 1 type and may use 2 or more types together.

アリルエーテル化反応の触媒の使用量は、ハロゲン化アリルの使用モル量に対して、０．７〜１．３倍モルが好ましく、０．８〜１．１倍モルがより好ましい。触媒の使用量が少なすぎると、反応速度が遅く、使用量が多すぎると、余剰のアルカリを除去しなくてはならなくなり、生産性が低下する。   The amount of the catalyst used for the allyl etherification reaction is preferably 0.7 to 1.3 times mol, more preferably 0.8 to 1.1 times mol, based on the amount of allyl halide used. If the amount of the catalyst used is too small, the reaction rate is slow, and if the amount used is too large, excess alkali must be removed and the productivity is lowered.

アリルエーテル化反応の反応温度は、多価ヒドロキシ樹脂（Ｃ）の水酸基とハロゲン化アリルとが反応する温度であれば特に限定されず、１０〜１５０℃が好ましく、３０〜１３０℃が好ましい。
アリルエーテル化反応後には、必要に応じて、反応生成物に対し、蒸留等による未反応の原料の除去、濃縮、精製（洗浄、カラムクロマトグラフィー等）等の処理を行ってもよい。 The reaction temperature of the allyl etherification reaction is not particularly limited as long as it is a temperature at which the hydroxyl group of the polyvalent hydroxy resin (C) reacts with allyl halide, and is preferably 10 to 150 ° C, and preferably 30 to 130 ° C.
After the allyl etherification reaction, the reaction product may be subjected to treatments such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.) as necessary.

アリル基のクライゼン転位反応は、例えば、アリルエーテル化反応後の樹脂を加熱することにより実施できる。クライゼン転位反応により、Ａｒに結合した−Ｏ−ＣＨ２−ＣＨ＝ＣＨ２のアリル基がＡｒのオルソ位またはパラ位に転位する。
加熱温度は、１５０〜２２０℃が好ましく、１７０〜２００℃がより好ましく、窒素等の不活性ガス存在下の転移反応がさらに好ましい。加熱温度が下限値以上であれば、アリル基の転移反応が起こりやすい。加熱温度が上限値以下であれば、アリル基の重合が起きにくい。
反応後、必要に応じて、反応生成物に対し、水洗等の処理を行ってもよい。 The Claisen rearrangement reaction of the allyl group can be carried out, for example, by heating the resin after the allyl etherification reaction. The Claisen rearrangement reaction, the allyl group of -O-CH 2 -CH = CH 2 bonded to Ar is translocated into the ortho or para position of Ar.
The heating temperature is preferably 150 to 220 ° C, more preferably 170 to 200 ° C, and further preferably a transfer reaction in the presence of an inert gas such as nitrogen. If the heating temperature is equal to or higher than the lower limit, an allyl group transfer reaction is likely to occur. If the heating temperature is not more than the upper limit, polymerization of allyl groups is difficult to occur.
After the reaction, if necessary, the reaction product may be subjected to a treatment such as washing with water.

多価ヒドロキシ樹脂（Ｃ）をアリル化して得られるアリル基含有樹脂（Ｂ）は、構成単位（２）および構成単位（５）を必須として含み、構成単位（１）および構成単位（４）を含んでいてもよい。
アリル基含有樹脂（Ｂ）における構成単位（２）と構成単位（５）の合計の含有量は、構成単位（１）と構成単位（２）と構成単位（４）と構成単位（５）の合計に対して、５０〜１００モル％が好ましく、７０〜１００モル％がより好ましく、８０〜１００モル％が特に好ましい。 The allyl group-containing resin (B) obtained by allylation of the polyvalent hydroxy resin (C) contains the structural unit (2) and the structural unit (5) as essential components, and includes the structural unit (1) and the structural unit (4). May be included.
The total content of the structural unit (2) and the structural unit (5) in the allyl group-containing resin (B) is that of the structural unit (1), the structural unit (2), the structural unit (4), and the structural unit (5). 50-100 mol% is preferable with respect to the total, 70-100 mol% is more preferable, and 80-100 mol% is especially preferable.

アリル基含有樹脂（Ｂ）のアリル基をプロペニル化する方法としては、アリル基含有樹脂（Ｂ）を溶剤に溶解させ、プロペニル化反応の触媒下に加熱する方法が挙げられる。   Examples of the method for propenylating the allyl group of the allyl group-containing resin (B) include a method in which the allyl group-containing resin (B) is dissolved in a solvent and heated under a catalyst for the propenylation reaction.

溶媒としては、アリル基含有樹脂（Ｂ）を溶解するものであればよく、典型的には極性溶剤が挙げられる。
極性溶剤としては、たとえば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン、メタノール、エタノール、ブタノール、酢酸エチル、酢酸ブチル、メチルセロソルブ、エチルジグリコールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、テトラヒドロフランが挙げられる。溶剤としては、１種を単独で使用してもよく、２種以上を併用してもよい。 Any solvent may be used as long as it dissolves the allyl group-containing resin (B), and a typical example is a polar solvent.
Examples of polar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N, N-dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol. Examples include acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and tetrahydrofuran. As a solvent, 1 type may be used independently and 2 or more types may be used together.

プロペニル化反応の触媒としては、たとえば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属類、ジアザビシクロノネン、ジアザビシクロウンデセン、トリエチルアミン等のアミン類、ナトリウムｔｅｒｔ−ブトキシド、カリウムｔｅｒｔ−ブトキシド、リチウムジイソプロピルアミド、ケイ素−塩基性アミン、リチウムテトラメチルピペリジン等が挙げられる。なかでも、比較的安価であり、副反応が起こりにくい点から、水酸化カリウム、水酸化ナトリウムが好ましい。触媒は１種を単独で用いてもよく、２種以上を併用してもよい。   Examples of the propenylation catalyst include alkali metals such as sodium hydroxide and potassium hydroxide, amines such as diazabicyclononene, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide, Examples include lithium diisopropylamide, silicon-basic amine, and lithium tetramethylpiperidine. Of these, potassium hydroxide and sodium hydroxide are preferable because they are relatively inexpensive and hardly cause side reactions. A catalyst may be used individually by 1 type and may use 2 or more types together.

プロペニル化反応の触媒の使用量は、アリル基含有樹脂（Ｂ）の水酸基の合計モル量に対して、０．４〜１．５倍モルが好ましく、０．８〜１．２倍モルがより好ましい。触媒の使用量が少なすぎると、プロペニル化反応が進みにくく、使用量が多すぎると、余剰のアルカリを除去しなくてはならなくなり、生産性が低下する。   The amount of the propenylation catalyst used is preferably 0.4 to 1.5 times mol, more preferably 0.8 to 1.2 times mol, based on the total molar amount of hydroxyl groups of the allyl group-containing resin (B). preferable. If the amount of the catalyst used is too small, the propenylation reaction is difficult to proceed. If the amount used is too large, excess alkali must be removed, and the productivity is lowered.

プロペニル化反応の反応温度は、８０〜１４０℃が好ましく、１００〜１２０℃がより好ましい。反応温度が下限値以上であれば、プロペニル化反応が進行しやすい。反応温度が上限値以下であれば、プロペニル基の重合が起きにくい。
プロペニル化反応後には、必要に応じて、反応生成物に対し、蒸留等による未反応の原料の除去、濃縮、精製（洗浄、カラムクロマトグラフィー等）等の処理を行ってもよい。 The reaction temperature of the propenylation reaction is preferably 80 to 140 ° C, more preferably 100 to 120 ° C. If reaction temperature is more than a lower limit, propenylation reaction will advance easily. When the reaction temperature is not more than the upper limit value, polymerization of propenyl group is difficult to occur.
After the propenylation reaction, the reaction product may be subjected to treatment such as removal of unreacted raw materials by distillation or the like, concentration, purification (washing, column chromatography, etc.), etc., as necessary.

本発明では、プロペニル化反応後の樹脂とアリル基含有樹脂（Ｂ）とを配合した配合樹脂をプロペニル基含有樹脂（Ａ）としてもよい。   In this invention, it is good also considering the compounded resin which mix | blended resin after propenylation reaction and allyl group containing resin (B) as propenyl group containing resin (A).

［マレイミド化合物（Ｉ）］
マレイミド化合物（Ｉ）は、１分子中にマレイミド基を２以上有するマレイミド化合物である。マレイミド化合物（Ｉ）としては、たとえば、１分子中にマレイミド基を２つ有するビスマレイミド類、ポリフェニルメタンマレイミド等が挙げられる。 [Maleimide compound (I)]
The maleimide compound (I) is a maleimide compound having two or more maleimide groups in one molecule. Examples of the maleimide compound (I) include bismaleimides having two maleimide groups in one molecule, polyphenylmethane maleimide, and the like.

ビスマレイミド類としては、たとえば、アルキルビスマレイミド、ジフェニルメタンビスマレイミド、フェニレンビスマレイミド、ビスフェノールＡジフェニルエーテルビスマレイミド、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジフェニルメタンビスマレイミド、４−メチル−１，３−フェニレンビスマレイミド、１，６’−ビスマレイミド−（２，２，４−トリメチル）ヘキサン、４，４’−ジフェニルエーテルビスマレイミド、４，４’−ジフェニルスルフォンビスマレイミド、１，３−ビス（３−マレイミドフェノキシ）ベンゼン、１，３−ビス（４−マレイミドフェノキシ）ベンゼンが挙げられる。
ポリフェニルメタンマレイミドは、マレイミド基が置換した３以上のベンゼン環がメチレン基を介して結合した重合体である。 Examples of the bismaleimides include alkyl bismaleimide, diphenylmethane bismaleimide, phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4 -Methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1 , 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with maleimide groups are bonded via a methylene group.

マレイミド化合物（Ｉ）としては、プロペニル基含有樹脂（Ａ）との相溶性に優れる点、および比較的安価である点から、４，４’−ジフェニルメタンビスマレイミド、ポリフェニルメタンマレイミドが好ましい。
マレイミド化合物（Ｉ）は、市販品を用いてもよい。具体的には、たとえば、大和化成工業社製の製品名「ＢＭＩ−１１００」（４，４’−ジフェニルメタンビスマレイミド）、製品名「ＢＭＩ−２３００」（ポリフェニルメタンマレイミド）が挙げられる。
マレイミド化合物（Ｉ）としては、１種を単独で使用してもよく、２種以上を併用してもよい。 As the maleimide compound (I), 4,4′-diphenylmethane bismaleimide and polyphenylmethane maleimide are preferable because they are excellent in compatibility with the propenyl group-containing resin (A) and relatively inexpensive.
As the maleimide compound (I), a commercially available product may be used. Specific examples include the product name “BMI-1100” (4,4′-diphenylmethane bismaleimide) and the product name “BMI-2300” (polyphenylmethane maleimide) manufactured by Daiwa Kasei Kogyo Co., Ltd.
As maleimide compound (I), 1 type may be used independently and 2 or more types may be used together.

本発明の樹脂組成物では、プロペニル基含有樹脂（Ａ）が有するプロペニル基やアリル基と、マレイミド化合物（Ｉ）のマレイミド基とが反応することで硬化が進行する。このように、本発明では、プロペニル基含有樹脂（Ａ）がマレイミド化合物（Ｉ）に対する硬化剤として機能する。   In the resin composition of the present invention, curing proceeds by the reaction of the propenyl group or allyl group of the propenyl group-containing resin (A) with the maleimide group of the maleimide compound (I). Thus, in the present invention, the propenyl group-containing resin (A) functions as a curing agent for the maleimide compound (I).

樹脂組成物中のプロペニル基含有樹脂（Ａ）が有するアリル基およびプロペニル基の合計に対するマレイミド化合物（Ｉ）が有するマレイミド基の合計のモル比は、０．５〜３．０が好ましく、０．８〜２．０がより好ましく、０．９〜１．５がさらに好ましい。前記モル比が前記下限値以上であれば、得られる硬化物に耐熱性が良好かつ低弾性率の物性が付与できる。前記モル比が前記上限値以下であれば、耐熱性が良好である。   The molar ratio of the maleimide group of the maleimide compound (I) to the total of allyl groups and propenyl groups of the propenyl group-containing resin (A) in the resin composition is preferably 0.5 to 3.0, and preferably 8-2.0 are more preferable and 0.9-1.5 are more preferable. When the molar ratio is equal to or higher than the lower limit, the resulting cured product can be imparted with good heat resistance and low elastic properties. When the molar ratio is not more than the upper limit, heat resistance is good.

［他の成分］
本発明の樹脂組成物は、プロペニル基含有樹脂（Ａ）およびマレイミド化合物（Ｉ）に加えて、プロペニル基含有樹脂（Ａ）およびマレイミド化合物（Ｉ）以外の他の成分を含んでいてもよい。他の成分としては、エポキシ樹脂、プロペニル基含有樹脂（Ａ）以外の他のマレイミド硬化剤、硬化促進剤、無機フィラー、溶剤、離型剤、表面処理剤、着色剤、可撓性付与剤等が挙げられる。 [Other ingredients]
The resin composition of the present invention may contain components other than the propenyl group-containing resin (A) and the maleimide compound (I) in addition to the propenyl group-containing resin (A) and the maleimide compound (I). Other components include epoxy resins, maleimide curing agents other than propenyl group-containing resins (A), curing accelerators, inorganic fillers, solvents, mold release agents, surface treatment agents, colorants, flexibility imparting agents, and the like. Is mentioned.

本発明の樹脂組成物は、硬化物の密着性に優れる点、および硬化反応が進行しやすく硬化物の分子量が大きくなりやすい点から、エポキシ樹脂を含むことが好ましい。プロペニル基含有樹脂（Ａ）とエポキシ樹脂は、プロペニル基含有樹脂（Ａ）の水酸基とエポキシ樹脂のエポキシ基が反応することにより硬化反応が進行する。   The resin composition of the present invention preferably contains an epoxy resin from the viewpoint of excellent adhesion of the cured product and the point that the curing reaction easily proceeds and the molecular weight of the cured product tends to increase. In the propenyl group-containing resin (A) and the epoxy resin, the curing reaction proceeds by the reaction between the hydroxyl group of the propenyl group-containing resin (A) and the epoxy group of the epoxy resin.

エポキシ樹脂としては、特に限定されず、たとえば、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂、ナフトール型エポキシ樹脂、キシリレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、スチルベン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、リン原子含有エポキシ樹脂等が挙げられる。   The epoxy resin is not particularly limited. For example, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy Resin, naphthol type epoxy resin, xylylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, stilbene type epoxy resin, sulfur atom containing epoxy resin, phosphorus atom containing epoxy resin, etc. It is done.

エポキシ樹脂として、プロペニル基含有樹脂（Ａ）の水酸基の少なくとも一部がエポキシ化されたエポキシ樹脂を用いてもよい。水酸基のエポキシ化は、公知の方法により実施できる。たとえばプロペニル基含有樹脂（Ａ）とエピクロロヒドリンとを反応させることで、プロペニル基含有樹脂（Ａ）の水酸基の一部または全部が−ＯＺ（ここで、Ｚはグリシジル基である。）となった構造のエポキシ樹脂を得ることができる。
エポキシ樹脂は、いずれか１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 As the epoxy resin, an epoxy resin in which at least a part of the hydroxyl groups of the propenyl group-containing resin (A) is epoxidized may be used. Epoxidation of the hydroxyl group can be carried out by a known method. For example, by reacting the propenyl group-containing resin (A) with epichlorohydrin, part or all of the hydroxyl groups of the propenyl group-containing resin (A) are —OZ (where Z is a glycidyl group). An epoxy resin having a different structure can be obtained.
Any one epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

樹脂組成物中のプロペニル基含有樹脂（Ａ）の水酸基当量に対するエポキシ樹脂のエポキシ基当量の当量比は、０．７〜１．５が好ましく、０．９〜１．１がより好ましい。当量比が前記範囲内であれば、得られる硬化物がより低弾性率なものになる。   The equivalent ratio of the epoxy group equivalent of the epoxy resin to the hydroxyl equivalent of the propenyl group-containing resin (A) in the resin composition is preferably 0.7 to 1.5, more preferably 0.9 to 1.1. When the equivalent ratio is within the above range, the resulting cured product has a lower elastic modulus.

他のマレイミド硬化剤としては、例えば、アリルノボラック型フェノール樹脂等のノボラック型樹脂が挙げられる。   Examples of other maleimide curing agents include novolac resins such as allyl novolac phenol resins.

硬化促進剤としては、プロペニル基含有樹脂（Ａ）とマレイミド化合物（Ｉ）との硬化反応を促進する硬化促進剤（以下、硬化促進剤（Ｐ）ともいう。）、硬化促進剤（Ｐ）以外の、プロペニル基含有樹脂（Ａ）とエポキシ樹脂との硬化反応を促進する硬化促進剤（以下、硬化促進剤（Ｑ）ともいう。）が挙げられる。   As the curing accelerator, a curing accelerator (hereinafter, also referred to as a curing accelerator (P)) that accelerates the curing reaction between the propenyl group-containing resin (A) and the maleimide compound (I), other than the curing accelerator (P). And a curing accelerator that accelerates the curing reaction between the propenyl group-containing resin (A) and the epoxy resin (hereinafter also referred to as a curing accelerator (Q)).

硬化促進剤（Ｐ）としては、たとえば、イミダゾール類、有機過酸化物類が挙げられる。樹脂組成物がエポキシ樹脂を含む場合、硬化促進剤（Ｐ）としてイミダゾール類を用いれば、プロペニル基含有樹脂（Ａ）とエポキシ樹脂との硬化反応も促進される。   Examples of the curing accelerator (P) include imidazoles and organic peroxides. When the resin composition contains an epoxy resin, if an imidazole is used as the curing accelerator (P), the curing reaction between the propenyl group-containing resin (A) and the epoxy resin is also accelerated.

イミダゾール類としては、たとえば、２−エチル−４−メチルイミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２，４−ジメチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、１−ビニル−２−メチルイミダゾール、１−プロピル−２−メチルイミダゾール、２−イソプロピルイミダゾール、１−シアノメチル−２−メチル−イミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−フェニルイミダゾールが挙げられる。   Examples of imidazoles include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2- Methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole Include 1-cyanoethyl-2-phenylimidazole.

有機過酸化物類としては、たとえば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステルが挙げられる。   Examples of organic peroxides include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester.

硬化促進剤（Ｐ）としては、高温で比較的安定で、溶剤溶解性が良好で、取り扱いが容易なものが好ましく、イミダゾール類では２−エチル−４−メチルイミダゾール、有機過酸化物類ではジアルキルパーオキサイドのジクミルパーオキサイドが好ましい。
硬化促進剤（Ｐ）としては、１種を単独で使用してもよく、２種以上を併用してもよい。
硬化促進剤（Ｐ）の含有量は、マレイミド化合物（Ｉ）に対し、０．１〜５．０質量％が好ましい。 As the curing accelerator (P), those which are relatively stable at high temperature, have good solvent solubility and are easy to handle are preferable. 2-ethyl-4-methylimidazole is used for imidazoles, and dialkyl is used for organic peroxides. Peroxide dicumyl peroxide is preferred.
As a hardening accelerator (P), 1 type may be used independently and 2 or more types may be used together.
The content of the curing accelerator (P) is preferably 0.1 to 5.0% by mass with respect to the maleimide compound (I).

硬化促進剤（Ｑ）としては、特に限定されず、たとえば、リン系化合物、第３級アミン、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。
リン系化合物としては、トリフェニルホスフィン、トリス−２，６−ジメトキシフェニルホスフィン、トリ−ｐ−トリルホスフィン、亜リン酸トリフェニル等が挙げられる。第３級アミンとしては、２−ジメチルアミノメチルフェノール、ベンジルジメチルアミン、α−メチルベンジルジメチルアミン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７等が挙げられる。これらの硬化促進剤は、いずれか１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
硬化促進剤（Ｑ）としては、硬化性、耐熱性、電気特性がより優れる点、耐湿信頼性が低下しにくい点で、リン系化合物（特にトリフェニルホスフィン）が好ましい。
硬化促進剤（Ｑ）の含有量は、エポキシ樹脂に対し、０．１〜５質量％が好ましい。 The curing accelerator (Q) is not particularly limited, and examples thereof include phosphorus compounds, tertiary amines, organic acid metal salts, Lewis acids, and amine complex salts.
Examples of the phosphorus compound include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, and triphenyl phosphite. Examples of the tertiary amine include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7, and the like. Any one of these curing accelerators may be used alone, or two or more thereof may be used in combination.
As the curing accelerator (Q), a phosphorus compound (particularly triphenylphosphine) is preferable in that it is more excellent in curability, heat resistance, and electrical characteristics, and is less likely to deteriorate moisture resistance reliability.
As for content of a hardening accelerator (Q), 0.1-5 mass% is preferable with respect to an epoxy resin.

無機フィラーとしては、結晶性シリカ粉、溶融性シリカ粉、石英ガラス粉、タルク、ケイ酸カルシウム粉、ケイ酸ジルコニウム粉、アルミナ粉、炭酸カルシウム粉等が挙げられ、結晶性シリカ粉、溶融性シリカ粉が好ましい。   Examples of the inorganic filler include crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder, and the like. Powder is preferred.

本発明の樹脂組成物中の無機フィラーの含有量は、樹脂組成物全体に対して、３０〜９０質量％が好ましい。
本発明の樹脂組成物を、封止材を形成する熱硬化性成型材料として用いる場合、本発明の樹脂組成物には硬化促進剤（Ｐ）と無機フィラーを配合することが好ましい。 As for content of the inorganic filler in the resin composition of this invention, 30-90 mass% is preferable with respect to the whole resin composition.
When using the resin composition of this invention as a thermosetting molding material which forms a sealing material, it is preferable to mix | blend a hardening accelerator (P) and an inorganic filler with the resin composition of this invention.

本発明の樹脂組成物に溶剤を配合し、プロペニル基含有樹脂（Ａ）、マレイミド化合物（Ｉ）等を溶剤に溶解させることで樹脂ワニスとすることができる。溶剤としては、プロペニル基含有樹脂（Ａ）、マレイミド化合物（Ｉ）等を溶解するものであれば特に制限はなく、典型的には、極性溶剤が用いられる。極性溶剤としては、プロペニル化反応の説明で挙げたものと同じものが挙げられる。溶剤としては、１種を単独で使用してもよく、２種以上を併用してもよい。   A resin varnish can be obtained by blending the solvent in the resin composition of the present invention and dissolving the propenyl group-containing resin (A), maleimide compound (I) and the like in the solvent. The solvent is not particularly limited as long as it can dissolve the propenyl group-containing resin (A), maleimide compound (I) and the like, and a polar solvent is typically used. Examples of the polar solvent are the same as those mentioned in the description of the propenylation reaction. As a solvent, 1 type may be used independently and 2 or more types may be used together.

離型剤としては、たとえばカルナバワックス等の各種ワックス類等が挙げられる。
表面処理剤としては、公知のシランカップリング剤等が挙げられる。
着色剤としては、カーボンブラック等が挙げられる。
可撓性付与剤としては、シリコーン樹脂、ブタジエン−アクリロニトリルゴム等が挙げられる。 Examples of the release agent include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents.
Examples of the colorant include carbon black.
Examples of the flexibility imparting agent include silicone resin and butadiene-acrylonitrile rubber.

本発明の樹脂組成物の硬化は、硬化温度を２００〜２５０℃に制御して行うことが好ましい。硬化操作の一例としては、一旦前記の好適な硬化温度で３０秒間以上３時間以下の硬化を行った後、さらに、前記の好適な硬化温度で１〜２０時間の後硬化を行う方法が挙げられる。   The resin composition of the present invention is preferably cured by controlling the curing temperature at 200 to 250 ° C. As an example of the curing operation, there may be mentioned a method in which after the curing is performed at the suitable curing temperature for 30 seconds to 3 hours, the post-curing is further performed at the suitable curing temperature for 1 to 20 hours. .

以上説明したように、本発明の樹脂組成物は、特定の条件を満たすプロペニル基含有樹脂（Ａ）と、マレイミド化合物（Ｉ）とを含んでいる。構成単位（３）および構成単位（６）のプロペニル基は、構成単位（２）および構成単位（５）のアリル基に比べてマレイミド基と反応しやすい。プロペニル基含有樹脂（Ａ）はプロペニル基を有するため、本発明の樹脂組成物は硬化速度が速く、硬化性に優れている。また、本発明の樹脂組成物は、硬化速度が速いため、有機過酸化物類等の慎重な取り扱いが求められる硬化促進剤を必ずしも使用しなくてもよい。本発明の樹脂組成物に硬化促進剤を配合しないことで、取り扱い性が向上する。   As described above, the resin composition of the present invention includes the propenyl group-containing resin (A) satisfying specific conditions and the maleimide compound (I). The propenyl group of the structural unit (3) and the structural unit (6) is more likely to react with the maleimide group than the allyl group of the structural unit (2) and the structural unit (5). Since the propenyl group-containing resin (A) has a propenyl group, the resin composition of the present invention has a high curing rate and excellent curability. Further, since the resin composition of the present invention has a high curing rate, it is not always necessary to use a curing accelerator that requires careful handling such as organic peroxides. Handling property improves by not mix | blending a hardening accelerator with the resin composition of this invention.

マレイミド化合物（Ｉ）を含む樹脂組成物の硬化は、通常２００〜２５０℃の高温で加熱する必要がある。本発明者等が検討したところ、このような高温の硬化時において、プロペニル基含有樹脂（Ａ）における２核体以下の成分は揮発するが、３核体以上は揮発しにくいことを見出した。本発明の樹脂組成物では、プロペニル基含有樹脂（Ａ）の２核体以下の成分の含有量が３質量％以下であるため、硬化時に揮発しにくい。そのため、硬化物にボイドが生じにくく、電子部品等の製造において不良率が低くなるため、生産性が高くなる。
本発明の樹脂組成物は、硬化物の耐熱性にも優れている。このように、本発明の樹脂組成物を用いることで、耐熱性に優れた硬化物を、ボイドが生じることを抑制しつつ短時間で形成でき、積層板や封止材等を高い生産性で製造できる。 Curing of the resin composition containing the maleimide compound (I) usually requires heating at a high temperature of 200 to 250 ° C. As a result of studies by the present inventors, it has been found that at the time of curing at such a high temperature, the component of the dinuclear body or lower in the propenyl group-containing resin (A) volatilizes, but that of the trinuclear body or higher is difficult to volatilize. In the resin composition of the present invention, the propenyl group-containing resin (A) has a binuclear or lower component content of 3% by mass or less, and thus hardly evaporates during curing. For this reason, voids are hardly generated in the cured product, and the defect rate is reduced in the manufacture of electronic components and the like, and thus productivity is increased.
The resin composition of this invention is excellent also in the heat resistance of hardened | cured material. Thus, by using the resin composition of the present invention, a cured product excellent in heat resistance can be formed in a short time while suppressing the generation of voids, and a laminate, a sealing material, etc. can be produced with high productivity. Can be manufactured.

本発明の樹脂組成物の用途としては、たとえば、半導体等の電子部品の封止材、電気絶縁材料、銅張り積層板用樹脂、レジスト、液晶のカラーフィルター用樹脂、各種コーティング剤、接着剤、ビルドアップ積層板材料、繊維強化プラスチック（ＦＲＰ）等が挙げられる。   Applications of the resin composition of the present invention include, for example, encapsulants for electronic components such as semiconductors, electrical insulating materials, resins for copper-clad laminates, resists, resin for liquid crystal color filters, various coating agents, adhesives, Examples include build-up laminate materials and fiber reinforced plastic (FRP).

＜樹脂ワニス＞
本発明の樹脂ワニスは、プロペニル基含有樹脂（Ａ）と、マレイミド化合物（Ｉ）と、溶剤とを必須成分とする本発明の樹脂組成物からなる。本発明の樹脂組成物を用いることで、銅張り積層板等の積層板を製造できる。 <Resin varnish>
The resin varnish of the present invention is composed of the resin composition of the present invention containing propenyl group-containing resin (A), maleimide compound (I), and a solvent as essential components. By using the resin composition of the present invention, a laminate such as a copper-clad laminate can be produced.

樹脂ワニス中の溶剤の含有量は、樹脂ワニスの固形分濃度に応じて適宜設定される。樹脂ワニスの固形分濃度は、用途によっても異なるが、３０〜８０質量％が好ましく、５０〜７０質量％がより好ましい。
なお、樹脂ワニスの固形分濃度は、樹脂ワニスの総質量に対する、樹脂ワニスから溶剤を除いた質量の割合である。 The content of the solvent in the resin varnish is appropriately set according to the solid content concentration of the resin varnish. The solid content concentration of the resin varnish varies depending on the use, but is preferably 30 to 80% by mass, and more preferably 50 to 70% by mass.
The solid content concentration of the resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.

本発明の樹脂ワニスは、マレイミド化合物（Ｉ）とプロペニル基含有樹脂（Ａ）と溶剤とを混合することで製造できる。各成分の混合は、常法により行うことができる。マレイミド化合物（Ｉ）とプロペニル基含有樹脂（Ａ）と溶剤とを混合する際、または混合した後に、必要に応じて、硬化促進剤や他の成分をさらに混合してもよい。   The resin varnish of the present invention can be produced by mixing the maleimide compound (I), the propenyl group-containing resin (A) and a solvent. Mixing of each component can be performed by a conventional method. When mixing the maleimide compound (I), the propenyl group-containing resin (A) and the solvent, or after mixing, a curing accelerator and other components may be further mixed as necessary.

本発明の樹脂ワニスは、マレイミド化合物（Ｉ）とプロペニル基含有樹脂（Ａ）と溶剤とを混合した後、マレイミド化合物（Ｉ）とプロペニル基含有樹脂（Ａ）とを前反応させてもよい。ワニス状態で前反応を行うことで、結晶性が高いマレイミド化合物（Ｉ）が樹脂ワニスから析出することを抑制できる。   In the resin varnish of the present invention, the maleimide compound (I), the propenyl group-containing resin (A), and the solvent may be mixed, and then the maleimide compound (I) and the propenyl group-containing resin (A) may be prereacted. By performing the pre-reaction in the varnish state, it is possible to suppress precipitation of the maleimide compound (I) having high crystallinity from the resin varnish.

前反応を行う際の反応温度は、５０〜１５０℃が好ましく、７０〜１３０℃がより好ましく、８０〜１２０℃がさらに好ましい。反応温度があまりに低いと反応は進まない。また、反応温度があまりに高すぎると反応をコントロールすることが難しくなり、樹脂ワニスを安定的に得ることが難しくなる。   50-150 degreeC is preferable, as for the reaction temperature at the time of performing pre-reaction, 70-130 degreeC is more preferable, and 80-120 degreeC is further more preferable. If the reaction temperature is too low, the reaction will not proceed. If the reaction temperature is too high, it becomes difficult to control the reaction, and it becomes difficult to stably obtain the resin varnish.

＜積層板の製造方法＞
本発明の積層板の製造方法は、繊維質基材に本発明の樹脂ワニスを含浸させたプリプレグを含む積層物を加熱加圧し、硬化させて積層板を得る方法である。
積層物におけるプリプレグの積層数は、１層であってもよく、２層以上であってもよい。積層物においては、プリプレグ以外の他の基材を積層してもよい。他の基材としては、たとえば、銅箔等の金属箔が挙げられる。 <Manufacturing method of laminated board>
The method for producing a laminate of the present invention is a method for obtaining a laminate by heating and pressurizing and curing a laminate containing a prepreg obtained by impregnating a fibrous base material with the resin varnish of the present invention.
The number of prepregs laminated in the laminate may be one layer or two or more layers. In the laminate, a substrate other than the prepreg may be laminated. As another base material, metal foil, such as copper foil, is mentioned, for example.

繊維質基材を構成する繊維としては、たとえば、ガラス繊維、炭素繊維、セラミック繊維、ステンレス繊維等の無機繊維；綿、麻、紙等の天然繊維；ポリエステル樹脂、ポリアミド樹脂等の合成有機繊維が挙げられる。これらの繊維は、いずれか１種を単独で使用してもよく、２種以上を併用してもよい。
繊維質基材の形状は、特に限定されず、たとえば、短繊維、ヤーン、マット、シート等が挙げられる。 Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and stainless fibers; natural fibers such as cotton, hemp, and paper; synthetic organic fibers such as polyester resins and polyamide resins. Can be mentioned. Any one of these fibers may be used alone, or two or more thereof may be used in combination.
The shape of the fibrous base material is not particularly limited, and examples thereof include short fibers, yarns, mats, and sheets.

本発明の積層板の製造方法で製造される積層板は、繊維質基材と樹脂ワニスの硬化物とを含む繊維強化樹脂層を備える。積層板が備える繊維強化樹脂層の数は１層でもよく２層以上でもよい。積層板は、銅箔等の金属箔層を有していてもよい。   The laminated board manufactured with the manufacturing method of the laminated board of this invention is equipped with the fiber reinforced resin layer containing the fibrous base material and the hardened | cured material of resin varnish. The number of fiber reinforced resin layers provided in the laminate may be one or two or more. The laminated board may have metal foil layers, such as copper foil.

本発明の積層板の製造方法の一例としては、たとえば、以下の方法が挙げられる。樹脂ワニスを繊維質基材に含浸させ、乾燥し、溶剤を除去してプリプレグとする。プリプレグと、必要に応じて使用する他の基材とを積層して積層物を形成し、該積層物を加熱加圧して硬化させ、積層板を得る。   As an example of the manufacturing method of the laminated board of this invention, the following method is mentioned, for example. A fibrous base material is impregnated with a resin varnish, dried, and the solvent is removed to obtain a prepreg. A prepreg and another base material used as needed are laminated to form a laminate, and the laminate is heated and pressurized to be cured to obtain a laminate.

繊維質基材に含浸させる本樹脂ワニスの量としては、特に限定されず、たとえば、含浸される樹脂ワニスの固形分量が、繊維質基材（１００質量％）に対して３０〜５０質量％程度となるようにする。
積層物を加熱加圧する際の加熱温度は、前述の硬化温度が好ましい。加圧条件としては、２〜２０ｋＮ／ｍ２が好ましい。 The amount of the resin varnish to be impregnated into the fibrous base material is not particularly limited. For example, the solid content of the resin varnish to be impregnated is about 30 to 50% by mass with respect to the fibrous base material (100% by mass). To be.
The heating temperature for heating and pressurizing the laminate is preferably the aforementioned curing temperature. As a pressurizing condition, 2 to 20 kN / m 2 is preferable.

＜熱硬化性成型材料＞
本発明の熱硬化性成型材料は、本発明の樹脂組成物からなる。本発明の熱硬化性成型材料は、溶剤を含まないことが好ましい。 <Thermosetting molding material>
The thermosetting molding material of the present invention comprises the resin composition of the present invention. The thermosetting molding material of the present invention preferably contains no solvent.

＜封止材＞
本発明の封止材は、本発明の熱硬化性成型材料の硬化物からなる。
封止材の形状は、特に限定されず、たとえば、公知の半導体等で採用される形状と同様の形状を採用できる。
本発明の熱硬化性成型材料を用いて封止材を形成する方法としては、たとえばトランスファー成型法、圧縮成型法等を用いて半導体を封止する方法が挙げられる。 <Encapsulant>
The sealing material of the present invention is composed of a cured product of the thermosetting molding material of the present invention.
The shape of the sealing material is not particularly limited, and for example, the same shape as that employed in a known semiconductor or the like can be employed.
Examples of a method for forming a sealing material using the thermosetting molding material of the present invention include a method for sealing a semiconductor using a transfer molding method, a compression molding method, or the like.

以下、実施例によって本発明を具体的に説明するが、本発明は以下の記載によっては限定されない。
［水酸基当量］
自動滴定装置（平沼産業製ＣＯＭ−１７００Ｓ）を用い、無水酢酸によるアセチル化法で水酸基当量を測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following description.
[Hydroxyl equivalent]
The hydroxyl equivalent was measured by an acetylation method with acetic anhydride using an automatic titrator (COM-1700S manufactured by Hiranuma Sangyo).

［不飽和基当量］
１３Ｃ−ＮＭＲにより、不飽和基当量を測定した。
なお、不飽和基当量における不飽和基には、アリル基とプロペニル基の両方が含まれる。アリル基を有し、プロペニル基を有しない樹脂の不飽和基当量はアリル基当量であり、プロペニル基を有し、アリル基を有しない樹脂の不飽和基当量はプロペニル基当量であり、アリル基とプロペニル基の両方を有する樹脂の不飽和基当量はそれら両方の基を加味した当量である。 [Unsaturated group equivalent]
The unsaturated group equivalent was measured by 13 C-NMR.
The unsaturated group in the unsaturated group equivalent includes both allyl group and propenyl group. An unsaturated group equivalent of a resin having an allyl group and having no propenyl group is an allyl group equivalent, and an unsaturated group equivalent of a resin having a propenyl group and having no allyl group is a propenyl group equivalent, The unsaturated group equivalent of a resin having both a propenyl group and a propenyl group is an equivalent taking into account both of these groups.

［軟化点］
ＪＩＳ Ｋ ６９１０に従って軟化点を測定した。 [Softening point]
The softening point was measured according to JIS K 6910.

［溶融粘度］
１５０℃に設定した粘度計（ブルックフィールド社製ＣＡＰ２０００ ＶＩＳＣＯＭＥＴＥＲ）により１５０℃における溶融粘度を測定した。 [Melt viscosity]
The melt viscosity at 150 ° C. was measured with a viscometer (CAP2000 VISCOMETER manufactured by Brookfield) set at 150 ° C.

［粘度］
２５℃に設定したＥ型粘度計（ＴＯＫＩＭＥＣ製）により、２５℃における粘度を測定した。 [viscosity]
The viscosity at 25 ° C. was measured with an E-type viscometer (manufactured by TOKIMEC) set at 25 ° C.

［アリル化率、変性率、プロペニル化率］
樹脂のベンゼン骨格のアリル化率、アリル基およびプロペニル基の変性率、プロペニル化率は、１３Ｃ−ＮＭＲにより測定した。
アリル化率は、樹脂中のＡｒ（ただし、式（ｒ１）で表される基のベンゼン環は除く。）の総モル数に対するアリル基のモル数の割合である。アリル基およびプロペニル基の変性率は、樹脂中のＡｒ（ただし、式（ｒ１）で表される基のベンゼン環は除く。）の総モル数に対する、アリル基およびプロペニル基の合計のモル数の割合である。プロペニル化率は、アリル基およびプロペニル基の合計のモル数の割合に対するプロペニル基のモル数の割合である。
なお、アリル基およびプロペニル基の変性率は前記した含有量Ｐ１と一致する。アリル基率が１００％の場合、プロペニル化率は、前記した含有量Ｐ２と一致する。 [Allylation rate, modification rate, propenylation rate]
The allylation rate of the benzene skeleton of the resin, the modification rate of the allyl group and the propenyl group, and the propenylation rate were measured by 13 C-NMR.
The allylation rate is the ratio of the number of moles of allyl groups to the total number of moles of Ar in the resin (excluding the benzene ring of the group represented by the formula (r1)). The modification rate of allyl group and propenyl group is the total number of moles of allyl group and propenyl group relative to the total number of moles of Ar in the resin (excluding the benzene ring of the group represented by formula (r1)). It is a ratio. The propenylation rate is the ratio of the number of moles of propenyl group to the ratio of the total number of moles of allyl group and propenyl group.
Incidentally, the modification rate of the allyl group and propenyl group are consistent with the content of P 1 described above. If an allyl group ratio is 100%, propenyl Karitsu is consistent with the content P 2 described above.

［２核体以下の成分、３核体、４核体以上の成分の含有量］
樹脂中の２核体以下の成分、３核体、４核体以上の成分の含有量は、ゲル浸透クロマトグラフ分析（ＧＰＣ）により、標準物質をポリスチレンとして測定した。
測定装置：東ソー社製 ＨＬＣ８１２０ＧＰＣ、
カラム：ＴＳＫｇｅｌ Ｇ３０００Ｈ＋Ｇ２０００Ｈ＋Ｇ２０００Ｈ。 [Content of binuclear or lower component, trinuclear or tetranuclear or higher component]
The content of the binuclear or lower component, trinuclear or tetranuclear component in the resin was measured by gel permeation chromatographic analysis (GPC), using polystyrene as the standard substance.
Measuring device: HLC8120GPC manufactured by Tosoh Corporation
Column: TSKgel G3000H + G2000H + G2000H.

［ゲル化時間］
ゲル化時間は、１７５℃にて、ＪＩＳ Ｋ ６９１０：２００７に準じた方法により測定した。 [Gelification time]
The gelation time was measured at 175 ° C. by a method according to JIS K 6910: 2007.

［揮発性］
アルミシャーレに樹脂組成物を１ｇ図りとり、２３０℃に設定したオーブンにて１０時間静置し、静置前後の質量減少率を測定した。 [volatility]
1 g of the resin composition was taken on an aluminum petri dish and allowed to stand in an oven set at 230 ° C. for 10 hours, and the mass reduction rate before and after the standing was measured.

［ガラス転移温度（Ｔｇ）］
得られた成型物を幅１０．０ｍｍ×長さ５．５ｍｍ×厚さ１．０ｍに加工し、粘弾性測定装置（日立ハイテクサイエンス社製 ＤＭＡ７１００）を用いて、２℃／分の昇温速度で３０℃〜４００℃の範囲でＴｇを測定した。 [Glass transition temperature (Tg)]
The obtained molding was processed into a width of 10.0 mm, a length of 5.5 mm, and a thickness of 1.0 m, and a temperature increase rate of 2 ° C./min using a viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.). Tg was measured in the range of 30 ° C to 400 ° C.

［５％熱分解温度］
得られた成型物を微粉砕し、示差熱熱重量同時測定装置（セイコーインスツルメンツ社製 ＴＧ／ＤＴＡ６３００）により、エアー雰囲気下で１０℃／分の昇温速度で３０℃〜８００℃の範囲で熱質量減量を測定し、熱分解開始温度を求めた。 [5% thermal decomposition temperature]
The obtained molded product is finely pulverized and heated in a temperature range of 30 ° C. to 800 ° C. at a temperature increase rate of 10 ° C./min under an air atmosphere by a differential thermothermogravimetric simultaneous measurement apparatus (TG / DTA6300 manufactured by Seiko Instruments Inc.). The weight loss was measured and the thermal decomposition start temperature was determined.

＜製造例１＞
温度計、撹拌機、冷却管を備えた内容量１Ｌの反応容器に、メタノール２１０ｇ、水酸化ナトリウム４８．０ｇ、低分子カットフェノールホルムアルデヒド樹脂（群栄化学工業社製、製品名：ＬＶＲ８２１０ＤＬ、軟化点：６９．０℃、溶融粘度：０．５Ｐ、水酸基当量：１０５ｇ／ｅｑ）１０５．０ｇを仕込み、４０℃で塩化アリル９１．８ｇを発熱に注意しながら３時間かけて滴下した。その後、メタノールが還流する温度（約６０℃）まで昇温し、アリルエーテル化反応を４時間行った。次いで、水洗により塩を除去した後、１８０℃まで昇温し、１０時間転移反応を行い、アリル基含有樹脂（Ｂ−１）を得た。
アリル基含有樹脂（Ｂ−１）は、アリル基を有するフェノールノボラック型多価ヒドロキシ樹脂（低分子カットフェノールホルムアルデヒド樹脂のアリル化品）であり、半固形状態で、１５０℃における溶融粘度は０．１Ｐ、アリル化率は９９．９％、２核体以下の成分の含有量は０．９質量％であった。 <Production Example 1>
In a reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a cooling tube, 210 g of methanol, 48.0 g of sodium hydroxide, low molecular weight cut phenol formaldehyde resin (manufactured by Gunei Chemical Industry Co., Ltd., product name: LVR8210DL, softening point) : 69.0 ° C., melt viscosity: 0.5 P, hydroxyl group equivalent: 105 g / eq) 105.0 g was charged, and 91.8 g of allyl chloride was added dropwise at 40 ° C. over 3 hours while paying attention to heat generation. Thereafter, the temperature was raised to a temperature at which methanol refluxed (about 60 ° C.), and an allyl etherification reaction was carried out for 4 hours. Next, after removing the salt by washing with water, the temperature was raised to 180 ° C. and a transfer reaction was carried out for 10 hours to obtain an allyl group-containing resin (B-1).
The allyl group-containing resin (B-1) is a phenol novolac-type polyvalent hydroxy resin having an allyl group (an allylated product of a low-molecular cut phenol formaldehyde resin), and has a melt viscosity of 0.1 at 150 ° C. in a semi-solid state. 1P, the allylation rate was 99.9%, and the content of dinuclear or lower components was 0.9% by mass.

＜製造例２＞
製造例１と同様にしてアリル基含有樹脂（Ｂ−１）を得た後、１００℃まで温度を下げ、ブタノールを１０５．０ｇ添加して樹脂を溶解させ、さらに水酸化カリウムを７０．５ｇ添加し、１１５℃で６時間プロペニル化反応を行った。その後、水洗し、濃縮してプロペニル基含有樹脂（Ａ−１）を得た。
プロペニル基含有樹脂（Ａ−１）は、プロペニル基を有するフェノールノボラック型多価ヒドロキシ樹脂（低分子カットフェノールホルムアルデヒド樹脂のプロペニル化品）であり、軟化点は６８．０℃、１５０℃における溶融粘度は０．８Ｐ、アリル基およびプロペニル基の変性率は９９．９％、プロペニル化率は８６．６％、２核体以下の成分の含有量は０．７質量％であった。 <Production Example 2>
After obtaining the allyl group-containing resin (B-1) in the same manner as in Production Example 1, the temperature was lowered to 100 ° C., 105.0 g of butanol was added to dissolve the resin, and 70.5 g of potassium hydroxide was further added. Then, the propenylation reaction was performed at 115 ° C. for 6 hours. Then, it washed with water and concentrated and obtained propenyl group containing resin (A-1).
The propenyl group-containing resin (A-1) is a phenol novolac type polyvalent hydroxy resin having a propenyl group (propenylated product of a low-molecular cut phenol formaldehyde resin), and has a softening point of 68.0 ° C. and a melt viscosity at 150 ° C. Was 0.8P, the modification rate of allyl group and propenyl group was 99.9%, the propenylation rate was 86.6%, and the content of dinuclear and lower components was 0.7% by mass.

＜製造例３＞
温度計、撹拌機、冷却管を備えた内容量１Ｌの反応容器に、メタノール１９６．０ｇ、水酸化ナトリウム４８．０ｇ、フェノールサリチルアルデヒド樹脂（群栄化学工業社製、製品名：ＴＰＭ−１００、軟化点：１０８．２℃、溶融粘度：４．３Ｐ、水酸基当量：９８ｇ／ｅｑ）を９８．０ｇ仕込み、４０℃で塩化アリル９１．８ｇを発熱に注意しながら３時間かけて滴下した。その後、メタノールが還流する温度（約６０℃）まで昇温し、アリルエーテル化反応を４時間行った。次いで、水洗により塩を除去した後、１８０℃まで昇温し、１０時間転移反応を行い、アリル基含有樹脂（Ｂ−２）を得た。
アリル基含有樹脂（Ｂ−２）は、アリル基を有するトリフェノールメタン型多価ヒドロキシ樹脂（フェノールサリチルアルデヒド樹脂のアリル化品）であり、半固形状態で、１５０℃における溶融粘度は０．１Ｐ、アリル化率は９９．９％、２核体以下の成分の含有量は０．０質量％であった。 <Production Example 3>
In a reaction vessel having an internal volume of 1 L equipped with a thermometer, a stirrer, and a condenser tube, 196.0 g of methanol, 48.0 g of sodium hydroxide, phenol salicylaldehyde resin (manufactured by Gunei Chemical Industry Co., Ltd., product name: TPM-100, 98.0 g of softening point: 108.2 ° C., melt viscosity: 4.3P, hydroxyl group equivalent: 98 g / eq) was added, and 91.8 g of allyl chloride was added dropwise at 40 ° C. over 3 hours while paying attention to heat generation. Thereafter, the temperature was raised to a temperature at which methanol refluxed (about 60 ° C.), and an allyl etherification reaction was performed for 4 hours. Next, after removing the salt by washing with water, the temperature was raised to 180 ° C. and a transfer reaction was performed for 10 hours to obtain an allyl group-containing resin (B-2).
The allyl group-containing resin (B-2) is a triphenolmethane type polyvalent hydroxy resin having an allyl group (allylated product of phenol salicylaldehyde resin), and has a melt viscosity of 0.1 P at 150 ° C. in a semi-solid state. The allylation rate was 99.9%, and the content of dinuclear or lower components was 0.0% by mass.

＜製造例４＞
製造例３と同様にしてアリル基含有樹脂（Ｂ−２）を得た後、１２０℃まで温度を下げ、ブタノールを９８．０ｇ添加して樹脂を溶解させ、さらに水酸化カリウムを７０．５ｇ添加し、１１５℃で６時間プロペニル化反応を行った。その後、水洗し、濃縮して、プロペニル基含有樹脂（Ａ−２）を得た。
プロペニル基含有樹脂（Ａ−２）は、プロペニル基を有するトリフェノールメタン型多価ヒドロキシ樹脂（フェノールサリチルアルデヒド樹脂のプロペニル化品）であり、軟化点は９６．２℃、１５０℃における溶融粘度は４．０Ｐ、アリル基およびプロペニル基の変性率は９９．９％、プロペニル化率は８４．１％、２核体以下の成分の含有量は０．０質量％であった。 <Production Example 4>
After obtaining an allyl group-containing resin (B-2) in the same manner as in Production Example 3, the temperature was lowered to 120 ° C., 98.0 g of butanol was added to dissolve the resin, and 70.5 g of potassium hydroxide was further added. Then, the propenylation reaction was performed at 115 ° C. for 6 hours. Then, it washed with water and concentrated and obtained propenyl group containing resin (A-2).
Propenyl group-containing resin (A-2) is a triphenolmethane type polyvalent hydroxy resin having a propenyl group (propenylated product of phenol salicylaldehyde resin), the softening point is 96.2 ° C, and the melt viscosity at 150 ° C is The modification rate of 4.0P, allyl group and propenyl group was 99.9%, the propenylation rate was 84.1%, and the content of dinuclear and lower components was 0.0% by mass.

＜製造例５＞
アリルフェノールホルムアルデヒド樹脂（群栄化学工業社製、製品名：ＸＰＬ−４４３７Ｅ）をアリル基含有樹脂（Ｘ−１）とした。
アリル基含有樹脂（Ｘ−１）は常温で液状であり、２５℃での粘度は３１Ｐａ・ｓ、アリル化率は１００％、２核体以下の成分の含有量は３７．０質量％であった。 <Production Example 5>
Allylphenol formaldehyde resin (manufactured by Gunei Chemical Industry Co., Ltd., product name: XPL-4437E) was used as the allyl group-containing resin (X-1).
The allyl group-containing resin (X-1) is liquid at room temperature, the viscosity at 25 ° C. is 31 Pa · s, the allylation rate is 100%, and the content of the binuclear or lower component is 37.0% by mass. It was.

＜製造例６＞
アリルフェノールホルムアルデヒド樹脂のプロペニル化品（群栄化学工業社製、製品名：１ＰＰ−１）をプロペニル基含有樹脂（Ｘ−２）とした。
プロペニル基含有樹脂（Ｘ−２）の軟化点は８１．２℃、１５０℃における溶融粘度は１．５Ｐ、アリル基およびプロペニル基の変性率は１００％、プロペニル化率は９５．４％、２核体以下の成分の含有量は３６．２質量％であった。 <Production Example 6>
A propenylated product of an allylphenol formaldehyde resin (manufactured by Gunei Chemical Industry Co., Ltd., product name: 1PP-1) was used as a propenyl group-containing resin (X-2).
The softening point of the propenyl group-containing resin (X-2) is 81.2 ° C., the melt viscosity at 150 ° C. is 1.5 P, the modification rate of allyl and propenyl groups is 100%, the propenylation rate is 95.4%, 2 The content of components below the nucleus was 36.2% by mass.

各製造例で得た樹脂のアリル化率、アリル基およびプロペニル基の変性率、プロペニル化率、および２核体以下の成分、３核体、４核体以上の成分のそれぞれの含有量を表１に示す。   The allylation rate of the resin obtained in each production example, the modification rate of the allyl group and the propenyl group, the propenylation rate, and the content of each of the component of 2 nuclei or less, the component of 3 nuclei, and the component of 4 nuclei or more are shown. It is shown in 1.

Figure 2019019228
Figure 2019019228

＜実施例１＞
プロペニル基含有樹脂（Ａ−１）の６ｇとアリル基含有樹脂（Ｂ−１）の２０ｇとを１２０℃にて配合してプロペニル基含有樹脂（Ａ−３）とした。さらにマレイミド化合物（Ｉ）としてポリフェニルメタンマレイミド（大和化成工業社製、製品名：ＢＭＩ−２３００、マレイミド当量：１８６ｇ／ｅｑ）の３１．４ｇを混合して樹脂組成物を得た。樹脂組成物においては、プロペニル基含有樹脂（Ａ−１）およびアリル基含有樹脂（Ｂ−１）が有するプロペニル基とアリル基の合計に対する、マレイミド化合物（Ｉ）が有するマレイミド基の合計のモル比を１とした。
前記樹脂組成物を１３５℃で溶融させ、幅１００ｍｍ×長さ１００ｍｍ×厚さ１ｍｍのキャビティを有する金型に流し込み、２００℃でプレス成型した後、２３０℃で５時間加熱して後硬化反応を行い、幅１００ｍｍ×長さ１００ｍｍ×厚さ１ｍｍの成型物を得た。 <Example 1>
6 g of the propenyl group-containing resin (A-1) and 20 g of the allyl group-containing resin (B-1) were blended at 120 ° C. to obtain a propenyl group-containing resin (A-3). Furthermore, 31.4 g of polyphenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-2300, maleimide equivalent: 186 g / eq) was mixed as maleimide compound (I) to obtain a resin composition. In the resin composition, the molar ratio of the total maleimide group of maleimide compound (I) to the total of propenyl group and allyl group of propenyl group-containing resin (A-1) and allyl group-containing resin (B-1) Was set to 1.
The resin composition is melted at 135 ° C., poured into a mold having a cavity of width 100 mm × length 100 mm × thickness 1 mm, press molded at 200 ° C., and then heated at 230 ° C. for 5 hours for post-curing reaction. A molded product having a width of 100 mm, a length of 100 mm and a thickness of 1 mm was obtained.

＜実施例２、４、５＞
プロペニル基含有樹脂（Ａ−３）の代わりに、表２に示す組成のプロペニル基含有樹脂（Ａ−４）、（Ａ−５）または（Ａ−６）を調製する以外は、実施例１と同様にして樹脂組成物を調製し、成型物を作製した。なお、各樹脂組成物におけるプロペニル基とアリル基の合計に対するマレイミド基の合計のモル比はいずれも１とした。 <Examples 2, 4, and 5>
Example 1 except that the propenyl group-containing resin (A-4), (A-5) or (A-6) having the composition shown in Table 2 was prepared instead of the propenyl group-containing resin (A-3). Similarly, a resin composition was prepared and a molded product was produced. The molar ratio of the total maleimide group to the total of propenyl group and allyl group in each resin composition was 1.

＜実施例３、６、比較例１〜４＞
プロペニル基含有樹脂（Ａ−３）の代わりに表２および表３に示す樹脂を用いる以外は、実施例１と同様にして樹脂組成物を調製し、成型物を作製した。なお、各樹脂組成物におけるプロペニル基とアリル基の合計に対するマレイミド基の合計のモル比はいずれも１とした。
各例で得た成型物の評価結果を表２および表３に示す。 <Examples 3 and 6, Comparative Examples 1 to 4>
A resin composition was prepared in the same manner as in Example 1 except that the resins shown in Table 2 and Table 3 were used instead of the propenyl group-containing resin (A-3), and a molded product was produced. The molar ratio of the total maleimide group to the total of propenyl group and allyl group in each resin composition was 1.
Tables 2 and 3 show the evaluation results of the molded products obtained in each example.

Figure 2019019228
Figure 2019019228

Figure 2019019228
Figure 2019019228

なお、表２および表３における略号は以下の意味を示す。
ＢＭＩ−２３００：ポリフェニルメタンマレイミド（大和化成工業社製、製品名：ＢＭＩ−２３００）。 In addition, the symbol in Table 2 and Table 3 shows the following meaning.
BMI-2300: Polyphenylmethane maleimide (manufactured by Daiwa Kasei Kogyo Co., Ltd., product name: BMI-2300).

表２および表３に示すように、プロペニル基含有樹脂（Ａ）を含む樹脂組成物を用いた実施例１〜６では、ゲル化時間が短く硬化性に優れるうえ、樹脂組成物の揮発性が低かった。また、成型体はガラス転移温度が３００℃以上であり、５％熱分解温度も高く、耐熱性に優れていた。
一方、２核体以下の成分の含有量が３質量％を超えるアリル基含有樹脂（Ｘ−１）を用いた比較例１の樹脂組成物は、ゲル化時間が長く硬化性が劣っているうえ、揮発性が高かった。２核体以下の成分の含有量が３質量％を超えるプロペニル基含有樹脂（Ｘ−２）を用いた比較例２の樹脂組成物は、硬化性は優れるものの、揮発性が高かった。プロペニル基含有樹脂（Ａ）を用いずにアリル基含有樹脂（Ｂ）を用いた比較例３、４の樹脂組成物は、ゲル化時間が長く、硬化性が劣っていた。 As shown in Tables 2 and 3, in Examples 1 to 6 using the resin composition containing the propenyl group-containing resin (A), the gelation time is short and the curability is excellent, and the volatility of the resin composition is high. It was low. The molded body had a glass transition temperature of 300 ° C. or higher, a high 5% thermal decomposition temperature, and excellent heat resistance.
On the other hand, the resin composition of Comparative Example 1 using the allyl group-containing resin (X-1) in which the content of the binuclear component or less exceeds 3% by mass is long in gelation time and inferior in curability. It was highly volatile. Although the resin composition of Comparative Example 2 using the propenyl group-containing resin (X-2) in which the content of the binuclear component or less exceeds 3 mass%, the curability was excellent, but the volatility was high. The resin compositions of Comparative Examples 3 and 4 using the allyl group-containing resin (B) without using the propenyl group-containing resin (A) had a long gel time and poor curability.

Claims (11)

プロペニル基含有樹脂と、１分子中にマレイミド基を２以上有するマレイミド化合物とを含有し、
前記プロペニル基含有樹脂が、下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（３）で表される構成単位（３）からなる群から選ばれる１つ以上と、下記式（４）で表される構成単位（４）、下記式（５）で表される構成単位（５）および下記式（６）で表される構成単位（６）からなる群から選ばれる１つ以上とを有し、
前記構成単位（２）と前記構成単位（３）と前記構成単位（５）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５０〜１００モル％であり、
前記構成単位（３）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５〜１００モル％であり、
１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が、前記プロペニル基含有樹脂の総質量に対して３質量％以下である、樹脂組成物。
Figure 2019019228
 ［式中、Ａｒはメチル基を有していてもよいベンゼン環またはナフタレン環を示し、Ｒは下記式（ｒ１）または（ｒ２）で表される基を示し、ｐおよびｑはそれぞれ独立に０または１を示し、−＊および−＊＊はそれぞれ結合手を示す。−＊は、他の構成単位に結合し、−（Ｒ）ｐ−＊＊の−＊＊は、ｐが０である場合は他の構成単位または水素原子に結合し、ｐが１である場合は他の構成単位に結合し、−（Ｒ）ｑ−＊＊の−＊＊は、ｑが０である場合は他の構成単位または水素原子に結合し、ｑが１である場合は他の構成単位に結合する。］
Figure 2019019228
 Containing a propenyl group-containing resin and a maleimide compound having two or more maleimide groups in one molecule;
The propenyl group-containing resin comprises a structural unit (1) represented by the following formula (1), a structural unit (2) represented by the following formula (2), and a structural unit (3 represented by the following formula (3): ), One or more selected from the group consisting of: a structural unit (4) represented by the following formula (4), a structural unit (5) represented by the following formula (5), and a formula (6) One or more selected from the group consisting of structural units (6)
The total content of the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6) is the structural unit (1), the structural unit (2), and the structural unit. 50 to 100 mol% based on the total of the unit (3), the structural unit (4), the structural unit (5) and the structural unit (6),
The total content of the structural unit (3) and the structural unit (6) is the structural unit (1), the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit. 5 to 100 mol% with respect to the total of the unit (5) and the structural unit (6),
The resin composition whose content of the component whose total number of the benzene ring and naphthalene ring in 1 molecule is 2 or less is 3 mass% or less with respect to the total mass of the said propenyl group containing resin.
Figure 2019019228
 [In the formula, Ar represents a benzene ring or a naphthalene ring which may have a methyl group, R represents a group represented by the following formula (r1) or (r2), and p and q each independently represents 0; Or 1 is shown,-* and-** show a bond, respectively. -* Is bonded to another structural unit,-** of-(R) p -** is bonded to another structural unit or a hydrogen atom when p is 0, and p is 1 Is bonded to another structural unit, and-** of-(R) q -** is bonded to another structural unit or a hydrogen atom when q is 0, and is bonded to another structural unit when q is 1. Join the building unit. ]
Figure 2019019228
 １分子中のベンゼン環とナフタレン環の合計数が３である成分の含有量が、前記プロペニル基含有樹脂の総質量に対して４０質量％以上である、請求項１に記載の樹脂組成物。   2. The resin composition according to claim 1, wherein the content of a component having a total of 3 benzene rings and naphthalene rings in one molecule is 40% by mass or more based on the total mass of the propenyl group-containing resin. 前記プロペニル基含有樹脂が有するアリル基およびプロペニル基の合計に対する前記マレイミド化合物が有するマレイミド基の合計のモル比が、０．５〜３．０である、請求項１または２に記載の樹脂組成物。   The resin composition according to claim 1 or 2, wherein a molar ratio of a total maleimide group of the maleimide compound to a total of allyl groups and propenyl groups of the propenyl group-containing resin is 0.5 to 3.0. . エポキシ樹脂をさらに含む、請求項１〜３のいずれか一項に記載の樹脂組成物。   The resin composition according to any one of claims 1 to 3, further comprising an epoxy resin. 前記プロペニル基含有樹脂と前記マレイミド化合物との硬化反応を促進する硬化促進剤と、無機フィラーとをさらに含む、請求項１〜４のいずれか一項に記載の樹脂組成物。   The resin composition according to any one of claims 1 to 4, further comprising a curing accelerator that promotes a curing reaction between the propenyl group-containing resin and the maleimide compound, and an inorganic filler. 溶剤をさらに含む、請求項１〜５のいずれか一項に記載の樹脂組成物。   The resin composition according to any one of claims 1 to 5, further comprising a solvent. 請求項６に記載の樹脂組成物からなる樹脂ワニス。   A resin varnish comprising the resin composition according to claim 6. 繊維質基材に請求項７に記載の樹脂ワニスを含浸させたプリプレグを含む積層物を加熱加圧し、硬化させて積層板を得る、積層板の製造方法。   The manufacturing method of a laminated board which heat-presses and hardens the laminated body containing the prepreg which impregnated the resin varnish of Claim 7 to the fibrous base material, and obtains a laminated board. 請求項５に記載の樹脂組成物からなる熱硬化性成型材料。   A thermosetting molding material comprising the resin composition according to claim 5. 請求項９に記載の熱硬化性成型材料の硬化物からなる封止材。   A sealing material comprising a cured product of the thermosetting molding material according to claim 9. 下記式（１）で表される構成単位（１）、下記式（２）で表される構成単位（２）および下記式（３）で表される構成単位（３）からなる群から選ばれる１つ以上と、下記式（４）で表される構成単位（４）、下記式（５）で表される構成単位（５）および下記式（６）で表される構成単位（６）からなる群から選ばれる１つ以上とを有し、
前記構成単位（２）と前記構成単位（３）と前記構成単位（５）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５０〜１００モル％であり、
前記構成単位（３）と前記構成単位（６）の合計の含有量が、前記構成単位（１）と前記構成単位（２）と前記構成単位（３）と前記構成単位（４）と前記構成単位（５）と前記構成単位（６）の合計に対して５〜１００モル％であり、
１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が３質量％以下であるプロペニル基含有樹脂の製造方法であって、
前記構成単位（１）および前記構成単位（４）を有し、前記構成単位（２）、前記構成単位（３）、前記構成単位（５）および前記構成単位（６）を有さず、かつ１分子中のベンゼン環とナフタレン環の合計数が２以下の成分の含有量が３質量％以下である多価ヒドロキシ樹脂をアリル化し、前記構成単位（１）および前記構成単位（４）の少なくとも一部を前記構成単位（２）または前記構成単位（５）に変換した後、さらに前記構成単位（２）および前記構成単位（５）のアリル基の少なくとも一部をプロペニル化して前記構成単位（３）または前記構成単位（６）に変換する、プロペニル基含有樹脂の製造方法。
Figure 2019019228
 ［式中、Ａｒはメチル基を有していてもよいベンゼン環またはナフタレン環を示し、Ｒは下記式（ｒ１）または（ｒ２）で表される基を示し、ｐおよびｑはそれぞれ独立に０または１を示し、−＊および−＊＊はそれぞれ結合手を示す。−＊は、他の構成単位に結合し、−（Ｒ）ｐ−＊＊の−＊＊は、ｐが０である場合は他の構成単位または水素原子に結合し、ｐが１である場合は他の構成単位に結合し、−（Ｒ）ｑ−＊＊の−＊＊は、ｑが０である場合は他の構成単位または水素原子に結合し、ｑが１である場合は他の構成単位に結合する。］
Figure 2019019228
 The structural unit (1) represented by the following formula (1), the structural unit (2) represented by the following formula (2), and the structural unit (3) represented by the following formula (3) are selected. From one or more, a structural unit (4) represented by the following formula (4), a structural unit (5) represented by the following formula (5), and a structural unit (6) represented by the following formula (6) One or more selected from the group consisting of:
The total content of the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6) is the structural unit (1), the structural unit (2), and the structural unit. 50 to 100 mol% based on the total of the unit (3), the structural unit (4), the structural unit (5) and the structural unit (6),
The total content of the structural unit (3) and the structural unit (6) is the structural unit (1), the structural unit (2), the structural unit (3), the structural unit (4), and the structural unit. 5 to 100 mol% with respect to the total of the unit (5) and the structural unit (6),
A method for producing a propenyl group-containing resin in which the content of components having a total number of benzene rings and naphthalene rings in one molecule of 2 or less is 3% by mass or less,
Having the structural unit (1) and the structural unit (4), not having the structural unit (2), the structural unit (3), the structural unit (5), and the structural unit (6); A polyvalent hydroxy resin having a content of a component having a total number of benzene rings and naphthalene rings of 2 or less in one molecule of 2 or less is allylated, and at least the structural unit (1) and the structural unit (4) After a part is converted into the structural unit (2) or the structural unit (5), at least a part of the allyl groups of the structural unit (2) and the structural unit (5) is further propenylated to form the structural unit ( 3) A method for producing a propenyl group-containing resin, which is converted into the structural unit (6).
Figure 2019019228
 [In the formula, Ar represents a benzene ring or a naphthalene ring which may have a methyl group, R represents a group represented by the following formula (r1) or (r2), and p and q each independently represents 0; Or 1 is shown,-* and-** show a bond, respectively. -* Is bonded to another structural unit,-** of-(R) p -** is bonded to another structural unit or a hydrogen atom when p is 0, and p is 1 Is bonded to another structural unit, and-** of-(R) q -** is bonded to another structural unit or a hydrogen atom when q is 0, and is bonded to another structural unit when q is 1. Join the building unit. ]
Figure 2019019228
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03229717A (en) * 1990-02-02 1991-10-11 Shin Etsu Chem Co Ltd Phenolic resin containing propenyl group
JPH07206949A (en) * 1994-01-12 1995-08-08 Shin Etsu Chem Co Ltd Thermosetting resin composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03229717A (en) * 1990-02-02 1991-10-11 Shin Etsu Chem Co Ltd Phenolic resin containing propenyl group
JPH07206949A (en) * 1994-01-12 1995-08-08 Shin Etsu Chem Co Ltd Thermosetting resin composition

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