JP2019089967A - Allyl group-containing carbonate resin, method for producing the same, resin varnish, and method for producing laminated plate - Google Patents

Abstract

To provide an allyl group-containing carbonate resin which can be used as an epoxy resin curing agent and can provide a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing the allyl group-containing carbonate resin, a resin varnish capable of providing a cured product having a low dielectric constant and a low dielectric loss tangent, and a method for producing a laminated plate using the resin varnish.SOLUTION: The allyl group-containing carbonate resin is provided that contains a compound represented by the following formula (1) as a main component. In formula (1), Rrepresents a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, n represents an integer of 0 or more, Rrepresents a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, at least a part of 2 pieces of Rand n pieces of Rcontain an allyl group, and X represents a hydrogen atom or an allyl group.SELECTED DRAWING: None

Description

  The present invention relates to an allyl group-containing carbonate resin, a method for producing the same, a resin varnish, and a method for producing a laminate.

  BACKGROUND ART Epoxy resins are conventionally used for members used in electronic products, such as insulating laminates and laminates (copper-clad laminates) in which copper foil is laminated on one side or both sides thereof. For example, a resin varnish in which an epoxy resin, a curing agent, etc. is dissolved in a solvent is impregnated into a fibrous base material such as glass cloth and dried to form a prepreg, which is heat-pressed singly or in combination. Manufactured by As a curing agent for epoxy resin, phenol novolac resin using phenol and formaldehyde is widely used.

  In recent years, while higher performance of electronic products has been achieved, lower dielectric constants and lower dielectric loss tangents are required of resins constituting laminates. The electrical properties (low dielectric constant, low dielectric loss tangent) of the cured product of epoxy resin cured with phenol novolac resin can meet the level required for general purpose electronic products, but it is a high performance electronic product (smartphone, It is difficult to meet the level required for tablets etc.).

It has been proposed to use a bifunctional phenylene ether oligomer as an epoxy resin curing agent (Patent Document 1). According to such an epoxy resin curing agent, it is said that an epoxy resin cured product having excellent electrical properties can be obtained.
However, the dielectric loss tangent of the cured product using the epoxy resin curing agent of Patent Document 1 is not yet sufficiently low.

Unexamined-Japanese-Patent No. 2004-224860

  The present invention is an allyl group-containing carbonate resin which can be used as a maleimide curing agent and provides a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing the same, and a resin varnish capable of obtaining a cured product having a low dielectric constant and a low dielectric loss tangent. And it aims at providing the manufacturing method of the laminated board using this.

［式中、Ｒ^１は、ビスフェノール化合物由来の残基、ビフェノール化合物由来の残基または脂環式ジメタノール化合物由来の残基を示し、２個のＲ^１はそれぞれ同一であっても異なっていてもよく、ｎは０以上の整数を示し、Ｒ^２は、ビスフェノール化合物由来の残基、ビフェノール化合物由来の残基または脂環式ジメタノール化合物由来の残基を示し、ｎが２以上である場合、ｎ個のＲ^２はそれぞれ同一であっても異なっていてもよく、２個のＲ^１およびｎ個のＲ^２の少なくとも一部はアリル基を含有し、Ｘは水素原子またはアリル基を示し、２個のＸはそれぞれ同一であっても異なっていてもよい。］
〔２〕前記式（１）中のＲ^１が、アリル基含有ビスフェノール化合物由来の残基またはアリル基含有ビフェノール化合物由来の残基である、〔１〕のアリル基含有カーボネート樹脂。
〔３〕前記式（１）中のＲ^１が、下記式（ｒ１）、下記式（ｒ２）または下記式（ｒ３）で表される基である、〔２〕のアリル基含有カーボネート樹脂。

［式中、ｐは１または２を示し、ｑは０〜２の整数を示す。］
〔４〕前記式（１）中のｎ個のＲ^２の少なくとも一部が、脂環式ジメタノール化合物由来の残基である、〔１〕〜〔３〕のいずれかのアリル基含有カーボネート樹脂。
〔５〕炭酸ジエステルと、ビスフェノール化合物、ビフェノール化合物および脂環式ジメタノール化合物からなる群から選ばれる少なくとも１種のジオール化合物とを反応させる工程を有し、前記ジオール化合物の少なくとも一部がアリル基を含有する、アリル基含有カーボネート樹脂の製造方法。
〔６〕前記炭酸エステルと前記ジオール化合物とを反応させる工程が、
炭酸ジエステルと、脂環式ジメタノール化合物とを反応させ、または、炭酸ジエステルと、脂環式ジメタノール化合物と、ビスフェノール化合物およびビフェノール化合物からなる群から選ばれる少なくとも１種の芳香族ジオール化合物とを反応させ、一次反応生成物を得て、前記一次反応生成物と、ビスフェノール化合物およびビフェノール化合物からなる群から選ばれる少なくとも１種の芳香族ジオール化合物とを反応させる工程、または
炭酸ジエステルと、ビスフェノール化合物およびビフェノール化合物からなる群から選ばれる少なくとも１種の芳香族ジオール化合物とを反応させる工程である、〔５〕のアリル基含有カーボネート樹脂の製造方法。
〔７〕前記一次反応生成物を得る際の、前記脂環式ジメタノール化合物と前記芳香族ジオール化合物との合計量に対する前記炭酸ジエステルのモル比が、１．０５〜３．００である、〔６〕のアリル基含有カーボネート樹脂の製造方法。
〔８〕前記炭酸エステルと前記ジオール化合物との反応により生成した、末端が水酸基であるアリル基含有カーボネート樹脂と、ハロゲン化アリルとを反応させ、前記水酸基をアリルエーテル化する工程をさらに有する、〔６〕または〔７〕のアリル基含有カーボネート樹脂の製造方法。
〔９〕前記〔１〕〜〔４〕のいずれかのアリル基含有カーボネート樹脂と、マレイミド基を２以上有するマレイミド化合物と、溶剤とを含む樹脂ワニス。
〔１０〕前記アリル基含有カーボネート樹脂が、前記式（１）中の２個のＸの少なくとも一方が水素原子である化合物を含み、
エポキシ樹脂をさらに含む〔９〕の樹脂ワニス。
〔１１〕前記〔９〕または〔１０〕の樹脂ワニスを繊維質基材に含浸させ、前記樹脂ワニスが含浸した繊維質基材を加熱加圧し、硬化させて積層板を得る、積層板の製造方法。 The present invention has the following aspects.
[1] An allyl group-containing carbonate resin containing a compound represented by the following formula (1) as a main component.

[Wherein, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and two R ^{1 s} are identical to or different from each other] N is an integer of 0 or more, R ² is a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and n is 2 or more And n R ^{2 s} may be the same or different, and at least a portion of ^two R ^{1 s} and n R ^{2 s} contain an allyl group, and X represents a hydrogen atom or an allyl group And two X's may be the same or different. ]
[2] The allyl group-containing carbonate resin of [1], wherein R ¹ in the formula (1) is a residue derived from an allyl group-containing bisphenol compound or a residue derived from an allyl group-containing biphenol compound.
[3] The allyl group-containing carbonate resin of [2], wherein R ¹ in the formula (1) is a group represented by the following formula (r1), the following formula (r2) or the following formula (r3).

[In formula, p shows 1 or 2 and q shows the integer of 0-2. ]
[4] The allyl group-containing carbonate resin according to any one of [1] to [3], wherein at least a part of n R ^{2 in} the formula (1) is a residue derived from an alicyclic dimethanol compound .
[5] A step of reacting carbonic acid diester with at least one diol compound selected from the group consisting of a bisphenol compound, a biphenol compound and an alicyclic dimethanol compound, wherein at least a part of the diol compound is an allyl group A method for producing an allyl group-containing carbonate resin, comprising
[6] The step of reacting the carbonic ester with the diol compound
A carbonic acid diester is reacted with an alicyclic dimethanol compound, or a carbonic acid diester, an alicyclic dimethanol compound, and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound Reacting to obtain a primary reaction product, and reacting the primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound, or a carbonic diester with a bisphenol compound And a process for producing the allyl group-containing carbonate resin of [5], which is a step of reacting with at least one aromatic diol compound selected from the group consisting of biphenol compounds.
[7] The molar ratio of the carbonic diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound when obtaining the primary reaction product is 1.05 to 3.00, [ 6] The manufacturing method of allyl group containing carbonate resin.
[8] The method further comprising the step of reacting the allyl group-containing carbonate resin having a hydroxyl group at a terminal with an allyl halide, which is produced by the reaction of the carbonic ester with the diol compound, and allyletherifying the hydroxyl group [ 6] Or the manufacturing method of allyl group containing carbonate resin of [7].
[9] A resin varnish comprising the allyl group-containing carbonate resin of any one of the above [1] to [4], a maleimide compound having two or more maleimide groups, and a solvent.
[10] The allyl group-containing carbonate resin contains a compound in which at least one of two X in the formula (1) is a hydrogen atom,
The resin varnish of [9] which further contains an epoxy resin.
[11] A laminate obtained by impregnating a fibrous base material with the resin varnish of the above [9] or [10] and heating and pressing the fibrous base material impregnated with the resin varnish to obtain a laminate. Method.

  According to the present invention, an allyl group-containing carbonate resin which can be used as a maleimide curing agent and can obtain a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing the same, and a cured product having a low dielectric constant and a low dielectric loss tangent The resin varnish and the manufacturing method of the laminated board using the same can be provided.

«Allyl group-containing carbonate resin»
The allyl group-containing carbonate resin of the present invention (hereinafter, also referred to as "the present carbonate resin") contains a compound represented by the following formula (1) as a main component. The "main component" refers to the component having the largest content among the components constituting the present carbonate resin.
The carbonate resin may be a mixture of a plurality of compounds having different values of n.
The present carbonate resin contains components other than the compound represented by the formula (1) (for example, a compound represented by the formula (2) described later, a bisphenol compound, a biphenol compound, or an allyletherified compound thereof) It may be These components may be the raw materials used for the production of the present carbonate resin or by-products by-produced during the production.
80 mass% or more is preferable, and, as for content of the compound represented by Formula (1) in this carbonate resin, 90 mass% or more is more preferable. The upper limit of the content is not particularly limited, and may be 100% by mass. The content of the compound represented by formula (1) is measured by gel permeation chromatography (GPC).

［式中、Ｒ^１は、ビスフェノール化合物由来の残基、ビフェノール化合物由来の残基または脂環式ジメタノール化合物由来の残基を示し、２個のＲ^１はそれぞれ同一であっても異なっていてもよく、ｎは０以上の整数を示し、Ｒ^２は、ビスフェノール化合物由来の残基、ビフェノール化合物由来の残基または脂環式ジメタノール化合物由来の残基を示し、ｎが２以上である場合、ｎ個のＲ^２はそれぞれ同一であっても異なっていてもよく、２個のＲ^１およびｎ個のＲ^２の少なくとも一部はアリル基を含有し、Ｘは水素原子またはアリル基を示し、２個のＸはそれぞれ同一であっても異なっていてもよい。］

[Wherein, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and two R ^{1 s} are identical to or different from each other] N is an integer of 0 or more, R ² is a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and n is 2 or more And n R ^{2 s} may be the same or different, and at least a portion of ^two R ^{1 s} and n R ^{2 s} contain an allyl group, and X represents a hydrogen atom or an allyl group And two X's may be the same or different. ]

n is preferably an integer of 0 to 50, more preferably an integer of 0 to 40, and still more preferably an integer of 0 to 35.
The average value of n is preferably a value such that the weight average molecular weight (Mw) of the carbonate resin is in the range of 3000 to 12000. More preferable Mw is as described later. As the average value of n is larger, Mw tends to be larger.

The bisphenol compound is a compound having two hydroxyphenyl groups linked via a linking group. The hydroxyphenyl group may have a substituent.
The residue derived from the bisphenol compound is a group having a structure in which two phenolic hydroxyl groups are removed from the bisphenol compound. That is, it is a group having a structure in which two phenylene groups which may have a substituent are linked via a linking group.
Examples of the substituent include an allyl group and an alkyl group. The number of substituents may be one or two or more.
Specific examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol C, bisphenol C, bisphenol E, bisphenol S, bisphenol Z, and allyl having an allyl group bonded to at least one of the hydroxyphenyl groups of these bisphenol compounds. Group-containing bisphenol compounds and the like can be mentioned.

A biphenol compound is a compound having two hydroxyphenyl groups directly bonded. The hydroxyphenyl group may have a substituent.
The residue derived from a biphenol compound is a group having a structure in which two phenolic hydroxyl groups are removed from a biphenol compound. That is, it is a biphenylene group which may have a substituent.
Examples of the substituent include an allyl group, a halogen atom and an alkyl group. The number of substituents may be one or two or more.
Specific examples of biphenol compounds include biphenols, halogenated biphenols, alkyl biphenols, and allyl group-containing biphenol compounds in which an allyl group is bonded to at least one of the hydroxyphenyl groups of these biphenol compounds.

An alicyclic dimethanol compound is a compound which has an alicyclic group and two methanol groups (-CH2OH) _couple | bonded with the alicyclic group.
The residue derived from the alicyclic dimethanol compound is a group having a structure in which two hydroxyl groups are removed from the alicyclic dimethanol compound. Specifically, a group represented by the following formula (r4) can be mentioned.

［式中、Ｒ^３は、脂環式基を示す。］

[Wherein, R ³ represents an alicyclic group. ]

The alicyclic group may have a single ring structure or a multiple ring structure. The alicyclic group preferably has no unsaturated bond. 6-20 are preferable and, as for carbon number of an alicyclic group, 8-15 are more preferable. Specific examples of the alicyclic group include cyclohexylene group, tricyclodecanediyl group, perhydro-1,4; 5,8-naphthylene-2,3-diyl group, bicyclo [2.2.1] heptane-2 And 3-diyl groups.
The alicyclic group may have a substituent such as an allyl group, an alkyl group or a halogen atom.
Specific examples of the alicyclic dimethanol compound include cyclohexane dimethanol, tricyclodecane dimethanol, trans-2,3-di (hydroxymethyl) -perhydro-1,4; 5,8-dimethanonaphthalene, trans- 2,3-di (hydroxymethyl) bicyclo [2.2.1] heptane and the like can be mentioned. Each isomer may be mixed.

In the formula (1), at least a part of ^two R ¹ and n R ² contains an allyl group. That is, at least a part of ^two R ¹ and n R ² are derived from an allyl group-containing bisphenol compound (for example, the above-mentioned allyl bisphenol) -derived residue, an allyl group-containing biphenol compound (for example, the above-mentioned allylbiphenol) It is a residue or a residue derived from an allyl group-containing alicyclic dimethanol compound. Thereby, this carbonate resin can be used as a maleimide curing agent.
Some of two R ¹ and n R ² may not contain an allyl group.
Among all R ¹ and R ^{2 in} the present carbonate resin, the ratio of the sum of R ¹ containing an allyl group and R ² containing an allyl group is preferably 2 to 80 mol%, and 5 to 50 mol% More preferable.

Two R ¹ in the formula (1) may be the same or different.
As R ¹ , a residue derived from an allyl group-containing bisphenol compound or a residue derived from an allyl group-containing biphenol compound is preferable. In this case, OX is a phenolic hydroxyl group when X in the formula (1) is a hydrogen atom. The phenolic hydroxyl group is excellent in the reactivity with the epoxy resin. Moreover, phenolic hydroxyl group is excellent also in the reactivity (reactivity with allyl halide) in the case of allyl etherification.
As the residue derived from the allyl group-containing bisphenol compound or the residue derived from the allyl group-containing biphenol compound, the following formula (r1), the following formula (r2) or the following formula The group represented by r3) is preferred. These groups are residues derived from allyl group-containing bisphenol A, allyl group-containing bisphenol F or allyl group-containing biphenol.

In formula, p shows 1 or 2 and q shows the integer of 0-2.
1 is preferable as p. 1 is preferable as q.

When n in Formula (1) is 2 or more, n R ^{2 s} may be the same or different.
At least a part of n R ^{2 in} the formula (1) is a residue derived from an alicyclic dimethanol compound, that is, a group represented by the formula (r ⁴ ) in that the cured product has a lower dielectric loss tangent. Is preferred. When n is 1, R ² is preferably a residue derived from a cycloaliphatic dimethanol compound, and when n is 2 or more, at least one of n R ^{2 s} is a cycloaliphatic dimethanol compound. It is preferably a residue derived from a methanol compound.
A part of n R ² may be a residue derived from a bisphenol compound or a residue derived from a biphenol compound. The residue derived from the bisphenol compound or the residue derived from the biphenol compound may or may not have an allyl group.

Of all the ^{R 2} of the carbonate in the resin, the ratio of ^{R 2} is a residue derived from a cycloaliphatic di-methanol compound is preferably 20 to 100 mol%, more preferably 50 to 90 mol%. When the ratio of R ² which is a residue derived from an alicyclic dimethanol compound is equal to or more than the lower limit, a cured product having a lower dielectric loss tangent can be obtained.

In the formula (1), each of two X's may be a hydrogen atom or an allyl group.
The present carbonate resin may contain a compound in which at least one of two X's in the formula (1) is a hydrogen atom. In this case, the present carbonate resin can also be used as an epoxy resin curing agent.
When using this carbonate resin as an epoxy resin hardening | curing agent, 50-100 mol% is preferable and, as for the ratio of X which is a hydrogen atom among all X in this carbonate resin, 80-100 mol% is more preferable. The reactivity with an epoxy resin and heat resistance of hardened | cured material are more excellent in the ratio of X which is a hydrogen atom being more than the said lower limit.

70-130 degreeC is preferable and, as for the softening point of this carbonate resin, 90-120 degreeC is more preferable. When the softening point is at least the lower limit value, the blocking resistance of the resin is more excellent. If a softening point is below the said upper limit, fluidity | liquidity is more excellent.
The softening point is measured in accordance with JIS K 6910.

10P-100P are preferable and, as for melt viscosity at 150 degrees C of this carbonate resin, 30P-80P are more preferable. The blocking resistance of resin is more excellent in melt viscosity being more than the above-mentioned lower limit. It is excellent in fluidity | liquidity that melt viscosity is below the said upper limit.
Melt viscosity is measured by the measuring method as described in the Example mentioned later.

3000-12000 are preferable and, as for the weight average molecular weight (Mw) of this carbonate resin, 5000-10000 are more preferable. The blocking resistance of resin is more excellent in Mw being more than the above-mentioned lower limit. Fluidity is more excellent in it being Mw below the above-mentioned upper limit.
Mw and Mn of the carbonate resin are values measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

500-3000 g / eq is preferable and, as for the allyl group equivalent of this carbonate resin, 800-2000 g / eq is more preferable. A dielectric characteristic is more excellent in the allyl group equivalent being more than the said lower limit. The reactivity with a maleimide compound is more excellent in an allyl group equivalent being below the above-mentioned upper limit.
The allyl group equivalent of the present carbonate resin is a value obtained by dividing the number average molecular weight (Mn) of the present carbonate resin by the number of allyl groups.

<Method of producing the present carbonate resin>
The present carbonate resin can be produced, for example, by the production method having the following step 1. After step 1, step 2 may be performed as necessary.
Step 1: A step of reacting carbonic diester with at least one diol compound selected from the group consisting of a bisphenol compound, a biphenol compound and an alicyclic dimethanol compound.
Step 2: A step of reacting the allyl group-containing carbonate resin having a hydroxyl group at the terminal, which is produced in Step 1, with allyl halide to allyletherify the hydroxyl group.

(Diol compound)
The bisphenol compound, the biphenol compound and the alicyclic dimethanol compound are the same as described above.
At least a portion of the diol compound used in step 1 contains an allyl group. That is, at least a part of the diol compound contains at least one selected from the group consisting of an allyl group-containing bisphenol compound, an allyl group-containing biphenol compound and an allyl group-containing alicyclic dimethanol compound.

The allyl group-containing bisphenol compound can be produced, for example, by allyletherifying the phenolic hydroxyl group of the bisphenol compound and then rearranging the allyl group.
Allyl etherification can be carried out by reacting a bisphenol compound with an allyl halide. In this reaction, the phenolic hydroxyl group of the bisphenol compound (-OH) is converted into an allyl ether group _{(-O-CH 2 -CH = CH} 2).

Examples of the allyl halide include allyl chloride, allyl bromide, allyl fluoride, allyl iodide and the like. Allyl chloride is preferred from the viewpoint of low cost.
The reaction of the bisphenol compound with the allyl halide (allyl etherification) is preferably carried out in the presence of a catalyst. As the catalyst, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amine compounds such as diazabicyclononene, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide, lithium diisopropyl Amides, silicon-basic amines, lithium tetramethylpiperidine and the like can be mentioned.

  The reaction of the bisphenol compound with the allyl halide may be carried out in the presence of a solvent. The solvent is only required to be capable of dissolving the bisphenol compound and the allyl halide, and examples thereof include the solvents in the resin varnish described later.

In the reaction of the bisphenol compound and the allyl halide, the amount of allyl halide to be reacted with the bisphenol compound is such that the molar ratio of allyl halide to phenolic hydroxyl group of the bisphenol compound (aryl halide / phenolic hydroxyl group) is 0.3 An amount of ̃2.0 is preferred. The molar ratio of halogenated allyl / phenolic hydroxyl group is more preferably 1.0 to 1.5.
The amount of the catalyst used is preferably 0.7 to 1.3 times the molar amount of the allyl halide used.
The reaction temperature may be, for example, 10 to 150 ° C. The reaction time may be, for example, 1 to 30 hours.
After completion of the reaction, the reaction product may be subjected to treatment such as washing with water, concentration, etc., if necessary.

Rearrangement of the allyl group of the allyl etherified bisphenol compound produces an allyl group-containing bisphenol compound in which an allyl group is bonded to the benzene ring of the hydroxyphenyl group of the bisphenol compound.
The rearrangement reaction of the allyl group can be carried out, for example, by heating the allyl etherified bisphenol compound. So-called Claisen rearrangement in which the allyl group of the allyl ether group (—O—CH ₂ —CH = CH ₂ ) bonded to the benzene ring is rearranged to the ortho or para position of the benzene ring when the allyl etherified bisphenol compound is heated. A reaction occurs. The heating conditions can be set, for example, at 160 to 200 ° C. for 1 to 24 hours.
Heating may be performed in the presence of a solvent. The solvent is only required to be capable of dissolving the allyletherified bisphenol compound, and includes, for example, methanol.
After the reaction, if necessary, the reaction product may be subjected to treatments such as removal of the solvent and washing with water.
The allyl group-containing biphenol compound can also be produced in the same manner as described above.

(Carbon diester)
Examples of carbonic diesters include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate (preferably having an alkyl group having 1 to 4 carbon atoms), alkylene carbonates having 1 to 4 carbon atoms (for example, ethylene carbonate), diphenyl carbonate and the like Be One of these carbonic acid diesters may be used alone, or two or more thereof may be used in combination. Diphenyl carbonate is preferred because it has good reactivity with diols (alicyclic dimethanol compounds and aromatic diol compounds), is relatively inexpensive, and is easy to handle.

(Step 1)
A preferred embodiment of step 1 is a reaction (first reaction) of a carbonic diester, an alicyclic dimethanol compound, and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound as required. A step of reacting (secondarily reacting) the obtained primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound to obtain a primary reaction product , “Step 1A”).
The primary and secondary reactions are each transesterification reactions. By reacting the aromatic diol compound in the secondary reaction, a carbonate resin in which the terminal hydroxyl group is a phenolic hydroxyl group is obtained.

The primary reaction is carried out, for example, by melt-mixing a diester of carbonic acid, an alicyclic dimethanol compound, and, if necessary, an aromatic diol compound, adding a catalyst, and maintaining a predetermined reaction temperature for a predetermined time. it can.
The carbonic diester, the alicyclic dimethanol compound and the aromatic diol compound may be used alone or in combination of two or more.

  In the primary reaction, the molar ratio of carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound (the amount of the alicyclic dimethanol compound alone when the aromatic diol compound is not reacted) (carbonic diester / ( 1.05 to 3.00 is preferable, and 1.20 to 2.50 is more preferable for the alicyclic dimethanol compound + aromatic diol compound). If the ratio of carbonic diester is too low, many hydroxyl groups of the alicyclic dimethanol compound remain in the primary reaction product, and in secondary reaction, a compound whose terminal hydroxyl group is not a phenolic hydroxyl group is by-produced. There is a risk of When the ratio of carbonic diester is too high, the amount of use of the aromatic diol compound used in the secondary reaction increases, and the effect of reducing the dielectric loss tangent due to the structure derived from the alicyclic dimethanol compound may be insufficient.

  In the primary reaction, the proportion of the alicyclic dimethanol compound is preferably 20 to 100 mol%, and 50 to 90 mol% of the total amount (100 mol%) of the alicyclic dimethanol compound and the aromatic diol compound. Is more preferred.

  The catalyst is not particularly limited as long as the reaction (transesterification) proceeds. Specific examples include sodium hydroxide, potassium hydroxide, magnesium metal, alkyl zinc compounds (eg, di-n-butyl zinc), lithium hydroxide, lithium acetate, titanium esters (eg, tetra-n-butyl titanate), zinc oxide , Lead oxide, manganese dioxide, tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, various alkoxides (eg, potassium-t-butoxide, sodium methoxide), alkali metals (eg, lithium, sodium), hydrogens of alkali metals Hydrides (eg, lithium hydride, sodium hydride), alkali metal hydroxides (eg, lithium hydroxide and sodium hydroxide), metal halides and the like.

  The amount of the catalyst used is preferably 1.0 to 0.00001% by mass, and more preferably 0.1 to 0.0001% by mass, with respect to the diester carbonate. If the amount of the catalyst used is larger than this range, turbidity may occur in the formed resin, and if smaller than this range, the polymerization rate becomes slow and a resin having a high degree of polymerization can not be obtained. Sometimes.

130-250 degreeC is preferable and, as for the reaction temperature of primary reaction, 150-200 degreeC is more preferable. If the reaction temperature is too low, the reaction does not proceed, and if it is too high, it may be difficult to control the reaction, and the resin may not be stably obtained. The reaction time may be, for example, 0.5 to 10 hours.
The primary reaction may be carried out under normal pressure or under reduced pressure.
The primary reaction may be performed while removing alcohols and phenols by-produced in the reaction (transesterification) under reduced pressure.

The secondary reaction can be carried out, for example, by adding an aromatic diol compound to the primary reaction product generated in the primary reaction, and maintaining a predetermined reaction temperature for a predetermined time.
The aromatic diol compound used in the secondary reaction may be the same as or different from the aromatic diol compound used in the primary reaction. The aromatic diol compounds may be used alone or in combination of two or more.
The amount of the aromatic diol compound to be reacted in the second reaction is preferably 5 to 80 mol%, more preferably 15 to 60 mol%, with respect to the carbonic diester (100 mol%) used in the first reaction.

130-250 degreeC is preferable and, as for the reaction temperature of secondary reaction, 170-230 degreeC is more preferable. If the reaction temperature is too low, the reaction does not proceed, and if it is too high, it may be difficult to control the reaction, and the resin may not be stably obtained. The reaction time may be, for example, 0.5 to 10 hours.
The secondary reaction is preferably performed while removing alcohols and phenols by-produced in the reaction (transesterification) under reduced pressure.
The degree of reduced pressure in the secondary reaction is not particularly limited as long as alcohols and phenols by-produced in the reaction can be removed under reduced pressure. For example, it may be 80-5 mmHg and may be 20-5 mmHg.
After completion of the secondary reaction, the reaction product may be subjected to treatment such as washing with water, concentration, etc., if necessary.

  Another preferable embodiment of step 1 is a step of reacting carbonic diester with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound (hereinafter, also referred to as "step 1B"). is there. This reaction is a transesterification reaction.

0.40-0.99 are preferable, and, as for the molar ratio (carbonic diester / aromatic diol compound) of carbonic diester with respect to aromatic diol compound, 0.50-0.95 are more preferable.
The reaction of the carbonic diester with the aromatic diol compound is preferably carried out in the presence of a catalyst. As the catalyst, the same as those described above can be mentioned. The preferred range of the amount of catalyst used is the same as above.

The reaction between the carbonic diester and the aromatic diol compound can be carried out, for example, by melt-mixing the carbonic diester and the aromatic diol compound, adding a catalyst, and maintaining a predetermined reaction temperature for a predetermined time.
130-250 degreeC is preferable and, as for reaction temperature, 170-230 degreeC is more preferable. If the reaction temperature is too low, the reaction does not proceed, and if it is too high, it may be difficult to control the reaction, and the resin may not be stably obtained. The reaction time may be, for example, 0.5 to 10 hours.
The reaction is preferably carried out while removing by-produced alcohols and phenols under reduced pressure. At the start of the reaction, the reaction may be carried out under normal pressure, and the pressure may be reduced after a predetermined time has elapsed.
The degree of reduced pressure in the reaction is not particularly limited as long as alcohols and phenols by-produced in the reaction can be removed under reduced pressure. For example, it may be 80-5 mmHg and may be 20-5 mmHg.
After completion of the reaction, the reaction product may be subjected to treatment such as washing with water, concentration, etc., if necessary.

  In step 1, an allyl group-containing carbonate resin in which the terminal is a hydroxyl group is obtained. The allyl group-containing carbonate resin contains, as a main component, a compound in which X in the formula (1) is a hydrogen atom, that is, a compound represented by the following formula (2).

［式中、Ｒ^１、ｎ、Ｒ^２はそれぞれ前記と同義であり、好ましい態様も同様である。］

[In the Formula, R ¹ , n and R ² are as defined above, and preferred embodiments are also the same. ]

When step 1 is step 1A, R ¹ in the formula (2) is a residue derived from an allyl group-containing bisphenol compound or a residue derived from an allyl group-containing biphenol compound, and at least a part of R ² is alicyclic An allyl group-containing carbonate resin containing as a main component a compound which is a residue derived from a dimethanol compound is obtained.
When step 1 is step 1B, an allyl containing, as a main component, a compound in which R ¹ and R ² in the formula (2) are each a residue derived from an allyl group-containing bisphenol compound or a residue derived from an allyl group-containing biphenol compound A group-containing carbonate resin is obtained.
These allyl group-containing carbonate resins may be used in combination.
It is preferable to include the allyl group-containing carbonate resin obtained in step 1A in that the cured product has a lower dielectric loss tangent.

(Step 2)
In step 2, the allyl group-containing carbonate resin produced in step 1 and having a hydroxyl group at the end is reacted with allyl halide. Allyl containing Thereby, terminal hydroxyl group (-OH) is converted into an allyl ether group _{(-O-CH 2 -CH = CH} 2), the formula (1) compounds wherein X is an allyl group in a main component A group-containing carbonate resin is obtained.
Examples of the allyl halide include the same as described above.
The allylic etherification can be carried out as described above.

  The amount of allyl halide to be reacted with the allyl group-containing carbonate resin in the reaction of the allyl group-containing carbonate resin whose end is a hydroxyl group with the allyl halide is the molar ratio of allyl halide to hydroxyl group of the allyl group-containing carbonate resin The amount of the halogenated allyl / phenolic hydroxyl group) is preferably 0.3 to 2.0. The molar ratio of halogenated allyl / phenolic hydroxyl group is more preferably 1.0 to 1.5.

Since this carbonate resin has an allyl group, it can be used as a curing agent (maleimide curing agent) for curing a maleimide compound. Curing of the maleimide compound can be carried out by heating.
Moreover, since the hardened | cured material which hardened the maleimide compound using this carbonate resin is using a maleimide compound, it shows high glass transition temperature, high thermal decomposition temperature, and a low thermal expansion coefficient. In addition, since this carbonate resin is used, it has a lower dielectric constant and a lower dielectric loss tangent than a cured product obtained by curing a maleimide compound with an allylphenol resin or a cured product obtained by curing an epoxy resin with a phenol novolac resin. is there.

When hardening a maleimide compound using this carbonate resin, it is thought that reaction of the following (1)-(3) arises and it hardens | cures.
(1) Reaction of maleimide group with allyl group.
(2) Reaction between maleimide groups.
(3) Reaction between allyl groups.

When the carbonate resin has a hydroxyl group (when X is a hydrogen atom), the carbonate resin can be used as a curing agent (epoxy resin curing agent) for curing the epoxy resin. Curing of the epoxy resin can be carried out by heating.
When the epoxy resin is cured using the present carbonate resin, it is considered that the reaction of (3) described above and the reactions of (4) to (5) below occur to cure.
(4) Reaction of epoxy group and hydroxyl group.
(5) Reaction between epoxy groups.

Furthermore, this carbonate resin is excellent in the solubility with respect to the solvent generally used in order to dissolve a maleimide compound and an epoxy resin. Therefore, it is possible to obtain a resin varnish in which both the present carbonate resin and maleimide compound and, if necessary, epoxy resin are dissolved in a solvent.
As the above-mentioned solvent, solvents having polarity such as methyl ethyl ketone are generally used.

  In addition, even if this carbonate resin is not combined with a maleimide compound or an epoxy resin, it can be independently cured by reaction of said (3). However, by combining with a maleimide compound or an epoxy resin, the curing temperature can be lowered and the thermal characteristics such as the glass transition temperature can be enhanced as compared with the case of curing alone. Therefore, it is preferable to use in combination with a maleimide compound or an epoxy resin for a curing reaction.

  There is no restriction | limiting in particular as a use of this carbonate resin. For example, it may be the same as the application of a known thermosetting molding material, and examples thereof include a sealing material, a film material, a laminated material and the like. Examples of more specific applications include semiconductor encapsulation materials, resin materials for encapsulation of electronic components, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, for liquid crystal color filters Resin materials, paints, various coating agents, adhesives, fiber reinforced plastic (FRP) materials, etc. may be mentioned.

«Resin varnish»
The resin varnish of the present invention (hereinafter, also referred to as "the present resin varnish") contains the present carbonate resin, a maleimide compound having two or more maleimide groups, and a solvent.
The carbonate resin functions as a maleimide curing agent. The "maleimide curing agent" means a curing agent for curing the maleimide compound.
In the resin varnish, a part of the allyl group of the carbonate resin and a part of the maleimide group of the maleimide compound may be in a reacted state.

When the present carbonate resin contains a compound in which at least one of two X in the formula (1) is a hydrogen atom, that is, when the present carbonate resin contains a hydroxyl group, the present carbonate resin also functions as an epoxy resin curing agent Do. "Epoxy resin curing agent" means a curing agent for curing an epoxy resin.
Therefore, a preferred embodiment of the present resin varnish comprises the present carbonate resin, a maleimide compound having two or more maleimide groups, an epoxy resin, and a solvent, and the present carbonate resin comprises two in the formula (1). It is a resin varnish containing a compound in which at least one of X is a hydrogen atom. The resin varnish of this aspect is more excellent in dielectric properties as compared to the case where it does not contain an epoxy resin.

The resin varnish can further include a curing reaction catalyst.
The resin varnish can further contain other components other than the present carbonate resin, maleimide compound, solvent, epoxy resin and curing reaction catalyst.

<Maleimide compound>
The maleimide compound is not particularly limited as long as it is a compound having two or more maleimide groups, and examples thereof include a bismaleimide compound and polyphenylmethane maleimide.
Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide (for example, BMI-1100 manufactured by Daiwa Kasei Kogyo Co., Ltd.), alkyl bismaleimide, diphenylmethane bismaleimide, phenylene bismaleimide, bisphenol A diphenylether bismaleimide (for example, Daiwa Kasei Corp. BMI-4000), manufactured by Kogyo Co., Ltd., 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (eg, BMI-5100 manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4-methyl- 1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3- Bis (3-maleimidophenoki And c) benzene, 1,3-bis (4-maleimidophenoxy) benzene and the like.
Polyphenylmethane maleimide is a polymer in which three or more benzene rings substituted with a maleimide group are bonded via a methylene group, and examples thereof include BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd.
These maleimide compounds may be used alone or in combination of two or more.

  10-300 mass parts is preferable with respect to 100 mass parts of this carbonate resin, as for content of the maleimide compound in this resin varnish, 15-200 mass parts is more preferable, and 20-150 mass parts is more preferable. If the content of the maleimide compound is at least the lower limit value of the above range, the gelling temperature of the resin varnish can be lowered, for example, to 200 ° C. or less. If the content of the maleimide compound is at least the lower limit of the above range, the cured product of the resin varnish exhibits a higher glass transition temperature, a higher thermal decomposition temperature, a lower linear expansion coefficient, a lower dielectric constant, and a lower dielectric loss tangent. Become.

<Solvent>
The solvent is not particularly limited as long as it dissolves the components (the present carbonate resin, maleimide compound, curing reaction catalyst, etc., if necessary) contained in the present resin varnish.
As a solvent, a polar solvent is typically used. Examples of polar solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, ketone solvents such as diacetone alcohol and cyclohexanone, N, N-dimethylformamide, N- Examples include methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran and the like. One of these solvents may be used alone, or two or more thereof may be used in combination. Among the above, ketone solvents are preferable, and methyl ethyl ketone is particularly preferable.

The content of the solvent in the present resin varnish is appropriately set according to the solid content concentration of the present resin varnish.
Although solid content concentration of this resin varnish changes also with uses, 20-80 mass% is preferable, and 50-70 mass% is more preferable.
The solid content concentration of the present resin varnish is the ratio of the mass of the present resin varnish excluding the solvent to the total mass of the present resin varnish.

<Epoxy resin>
The epoxy resin is not particularly limited and may be a known epoxy resin, such as phenol novolac epoxy resin, ortho cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenol 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, A phosphorus atom containing epoxy resin etc. are mentioned. One of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination.

<Curing reaction catalyst>
As the curing reaction catalyst (curing accelerator), it is preferable to include a catalyst (hereinafter, also referred to as “catalyst (1)”) having an action of promoting the reaction between an allyl group and a maleimide group. Examples of the catalyst (1) include imidazole compounds and organic peroxides. Examples of imidazole compounds 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-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1- Anoechiru 2-phenyl imidazole, and the like. Examples of organic peroxides include ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxy dicarbonates, and peroxy esters. In the dialkyl peroxide, the alkyl group may be substituted by a phenyl group or the like. Examples of such dialkyl peroxides include dicumyl peroxide.

  When the present carbonate resin has a hydroxyl group and the present resin varnish contains an epoxy resin, it is also referred to as a catalyst having a function of promoting the reaction between the hydroxyl group and the epoxy group as a curing reaction catalyst (hereinafter referred to as "catalyst (2)"). ) May be included. Examples of the catalyst (2) include phosphorus compounds, tertiary amines, imidazole compounds, organic acid metal salts, Lewis acids, amine complex salts and the like. Examples of phosphorus compounds include triphenylphosphine, tris-2, 6-dimethoxyphenyl phosphine, tri-p-tolyl phosphine, triphenyl phosphite and the like. Examples of tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, and 1,8-diazabicyclo [5.4.0] undecene-7. As an imidazole compound, the thing similar to the above is mentioned.

One of these curing reaction catalysts may be used alone, or two or more thereof may be used in combination.
The content of the catalyst (1) in the present resin varnish is preferably 0.1 to 5.0% by mass with respect to the maleimide compound.
The content of the catalyst (2) in the present resin varnish is preferably 0.1 to 5.0% by mass with respect to the epoxy resin.
The total content of the catalyst (1) and the catalyst (2) in the resin varnish is preferably 0.1 to 5.0% by mass with respect to the total amount of the maleimide compound and the epoxy resin.

<Other ingredients>
As other components, for example, inorganic fillers (for example, carbon black, glass cloth, silica, etc.), waxes, flame retardants, coupling agents, etc., curing agents other than the present carbonate resin (hereinafter, also referred to as other curing agents). And fillers, mold release agents, surface treatment agents, colorants, flexibility imparting agents and the like. Examples of other curing agents include maleimide curing agents, epoxy resin curing agents and the like, and conventionally known ones can be used. For example, as the maleimide curing agent, novolac resins such as allyl novolac phenol resins and the like can be mentioned.
From the viewpoint of the effect of the present invention, the content of the other curing agent in the present resin varnish is preferably 10% by mass or less, and particularly preferably 0% by mass, with respect to the solid content (100% by mass) of the present resin varnish.
The solid content of the present resin varnish is a portion obtained by removing the solvent from the present resin varnish.

Examples of fillers include carbon black, crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder, etc. Silica powder and fusible silica powder are preferred.
As a mold release agent, various waxes, such as carnauba wax, etc. are mentioned, for example.
As a surface treating agent, a well-known silane coupling agent etc. are mentioned.
As a coloring agent, carbon black etc. are mentioned.
As the flexibility imparting agent, silicone resin, butadiene-acrylonitrile rubber and the like can be mentioned.

<Method of producing resin varnish>
The present resin varnish can be produced, for example, by mixing the present carbonate resin, a maleimide compound and a solvent. When or after mixing the present carbonate resin, maleimide compound and solvent, if necessary, an epoxy resin, a curing reaction catalyst, and other components may be further mixed.
This carbonate resin can be manufactured by the above-mentioned manufacturing method. A maleimide compound, an epoxy resin, a curing reaction catalyst, and another component can use a commercial item, respectively. Mixing of each component can be performed by a conventional method.

After mixing the present carbonate resin, the maleimide compound and the solvent, the present carbonate resin and the maleimide compound may be prereacted. By pre-reacting the mixture in the varnish state obtained by the above mixing, it is possible to suppress the precipitation of the maleimide compound having high crystallinity from the resin varnish.
50-150 degreeC is preferable, as for the reaction temperature at the time of pre-reacting, 70-130 degreeC is more preferable, and 80-120 degreeC is further more preferable. If the reaction temperature is too low, the reaction does not proceed, and if it is too high, it becomes difficult to control the reaction and it becomes difficult to stably obtain the desired present resin varnish.

Since the present resin varnish contains the present carbonate resin and the maleimide compound, it can be cured by heating to form a cured product.
As for the heating temperature (hardening temperature) at the time of hardening this resin varnish, 60-250 degreeC is preferable.
As an example of the curing operation, there is a method of performing pre-curing for 30 seconds to 1 hour at the above-mentioned suitable temperature, removing the solvent, and then performing post-curing for 1 to 20 hours at the above-mentioned suitable temperature. It can be mentioned.

  In the present resin varnish, since the maleimide compound is used, the cured product of the present resin varnish exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion coefficient. Moreover, since this hardened | cured material is using this carbonate resin as a hardening | curing agent of a maleimide compound, compared with the hardened | cured material which hardened the maleimide compound by allylphenol resin and the hardened | cured material which hardened epoxy resin by phenol novolak resin. Low dielectric constant and low dielectric loss tangent.

There is no restriction | limiting in particular as a use of this resin varnish. For example, it may be the same as the application of a known thermosetting molding material, and examples thereof include a sealing material, a film material, a laminated material and the like. Examples of more specific applications include semiconductor encapsulation materials, resin materials for encapsulation of electronic components, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, for liquid crystal color filters Resin materials, paints, various coating agents, adhesives, fiber reinforced plastic (FRP) materials, etc. may be mentioned.
The cured product of the resin varnish has a low dielectric constant and a low dielectric loss tangent, and is excellent in insulation. In addition, this cured product has a high glass transition temperature, a high thermal decomposition temperature, a low thermal expansion coefficient, and is also excellent in heat resistance. Therefore, this resin varnish is useful as a material for manufacture of the laminated board used for an electronic component.

The relative dielectric constant of the cured product of the resin varnish is preferably 3.50 or less.
The dielectric loss tangent of the cured product of the resin varnish is preferably 0.008 or less.
As for the glass transition temperature of the hardened | cured material of this resin varnish, 150 degreeC or more is preferable.
The 5% thermal decomposition temperature of the cured product of the resin varnish is preferably 300 ° C. or higher.
The normal temperature linear expansion coefficient of the cured product of the resin varnish is preferably 100 ppm or less.
The relative dielectric constant, the dielectric loss tangent, the glass transition temperature, the 5% thermal decomposition temperature, and the room-temperature linear expansion coefficient are each measured by the method described in the examples described later.

«Method of manufacturing laminates»
In the method for producing a laminate of the present invention, the present resin varnish is impregnated into a fibrous base material, the fibrous base material impregnated with the present resin varnish is heated and pressed, and cured to obtain a laminated board.

The laminated board manufactured by the manufacturing method of the laminated board of this invention is equipped with the fiber reinforced resin layer containing a fibrous base material and the hardened | cured material of this resin varnish. The number of fiber reinforced resin layers included in the laminate may be one or two or more.
The laminate may further include another layer other than the fiber reinforced resin layer. As another layer, metal foil layers, such as copper foil, are mentioned, for example.

Examples of the fibrous base material include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers and stainless steel fibers; natural fibers such as cotton, hemp and paper; and synthetic organic fibers such as polyester resin and polyamide resin. One of these may be used alone, or two or more of these may be used in combination.
The shape of the fibrous base material is not particularly limited, and examples thereof include staple fibers, yarns, mats, sheets and the like.

  As one embodiment of the method for producing a laminate of the present invention, the present resin varnish is impregnated into a fibrous base material, dried (solvent is removed) to obtain a prepreg, and a plurality of the prepregs are laminated as required. If necessary, a metal foil may be further laminated on one side or both sides of the above prepreg or a laminate thereof, and a method of heating and pressing may be used.

It does not specifically limit as a quantity of this resin varnish with which a fibrous base material is impregnated. For example, the solid content of the present resin varnish is about 30 to 50% by mass with respect to the fibrous base material (100% by mass).
The heating temperature when heating and pressing the fibrous base material impregnated with the resin varnish is preferably the above-mentioned curing temperature. As pressurization conditions, 2-20 kN / m < ² > is preferable.

  The laminate obtained by the method for producing a laminate of the present invention comprises a fiber-reinforced resin layer containing a fibrous base material and a cured product of the present resin varnish, and the fiber-reinforced resin layer is low in the cured product. Since the dielectric constant and the low dielectric loss tangent are excellent in insulation. Further, the fiber reinforced resin layer is excellent in heat resistance because the cured product has a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion coefficient.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.
In each of the following examples, "%" indicates "% by mass" unless otherwise specified.
The measuring method used in each of the following examples is shown below.

[Weight average molecular weight of resin (Mw), number average molecular weight (Mn), dispersion degree (Mw / Mn)]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using polystyrene as the standard substance using the following GPC apparatus and column, and the degree of dispersion (Mw / Mn) was determined.
GPC apparatus: HLC 8120 GPC manufactured by Tosoh Corporation.
Column: TSKgel (registered trademark) G3000H + G2000H + G2000H manufactured by Tosoh Corporation.

[Softening point of resin]
The softening point (° C.) was measured according to JIS K 6910.

[Melt viscosity of resin]
The melt viscosity (P) at 150 ° C. was measured by a melt viscometer set at 150 ° C. (CAP2000 VISCOMETER manufactured by Brookfield).

[Glass-transition temperature]
The obtained molded product was processed into a size of width 10.0 mm × length 5.5 mm × thickness 1.5 mm as a measurement sample. About this measurement sample, tan δ is measured in the range of 30 ° C. to 400 ° C. at a temperature rising rate of 2 ° C./min using a viscoelasticity measuring apparatus (DMA7100 manufactured by Hitachi High-Tech Science Co., Ltd.) to determine the glass transition temperature (° C.) The

[5% thermal decomposition temperature]
The obtained molded product was pulverized and used as a measurement sample. For this measurement sample, the thermal weight loss is measured in the range of 30 to 800 ° C. at a heating rate of 10 ° C./min in an air atmosphere using a differential thermal thermal gravimetric simultaneous measurement device (TG / DTA 6300 manufactured by Seiko Instruments Inc.), The 5% thermal decomposition temperature (° C.) was determined.

[Room temperature linear expansion coefficient]
The obtained molded product was processed into a size of width 5.0 mm × length 5.0 mm × thickness 1.5 mm as a measurement sample. For this measurement sample, the thermal expansion of the cured product is measured in the range of 30 ° C. to 400 ° C. at a temperature rise rate of 2 ° C./min using a thermomechanical analyzer (TMA 7100 manufactured by Hitachi High-Tech Science Co., Ltd.) (Ppm) was determined. The normal temperature linear expansion coefficient indicates a linear expansion coefficient at 30 ° C.

[Permittivity, dielectric loss tangent]
The obtained molded product was processed into a size of width 50.0 mm × length 50.0 mm × thickness 1.5 mm as a measurement sample. The dielectric constant (ε _r ) and the dielectric loss tangent (tan δ) at a frequency of 1 GHz were determined for this measurement sample by the cavity resonance perturbation method.

Synthesis Example 1: Synthesis of diallyl bisphenol F
In a 3-liter reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 1000.0 g of bisphenol F (BPF-SG manufactured by Gun-ei Chemical Co., Ltd.) and 800.0 g of methanol are charged, and 480 g of sodium hydroxide while paying attention to heat generation Separately added. Then, 995.0 g of allyl chloride is added dropwise over 2 hours while paying attention to heat generation at 35 ° C. or lower, reacted at the same temperature for 2 hours, heated to 65 ° C., reacted for 5 hours, Allyl etherification was performed. Next, after removing methanol from the obtained reaction solution under reduced pressure, a large amount of salt was removed by water washing. The reaction solution after washing with water was heated up to 190 ° C. under a nitrogen atmosphere, and reacted for 5 hours to transfer an allyl group to obtain the desired diallyl bisphenol F. The obtained diallyl bisphenol F was liquid at normal temperature, and the viscosity at 25 ° C. was 0.8 Pa · s by an E-type viscometer.

Synthesis Example 2 Synthesis of Diallyl Bisphenol A
In Synthetic Example 1, diallyl bisphenol A is obtained in the same manner as in Synthetic Example 1 except that 1140.0 g of bisphenol A is used instead of 1000.0 g of bisphenol F and the amount of methanol is changed to 912.0 g. The The obtained diallyl bisphenol A was liquid at normal temperature, and the viscosity at 25 ° C. was 21.2 Pa · s with an E-type viscometer.

Synthesis Example 3: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, diallyl bisphenol F
214.2 g (1.00 mol) of diphenyl carbonate and 98.1 g (0.50 mol) of tricyclodecanedimethanol are charged into a 1 L reaction vessel equipped with a thermometer, a stirrer, and a cooling pipe, and melted at 100 ° C. Mixed. Thereafter, 0.02 g of a 48% aqueous solution of KOH was added, and the temperature was raised to 180 ° C., taking care of heat generation, and the reaction was conducted under normal pressure for 1 hour. Then, the reaction solution was cooled to 130 ° C., 183.0 g (0.61 mol) of diallyl bisphenol F obtained in Synthesis Example 1 was added, the temperature was raised to 180 ° C., and reaction was conducted under normal pressure for 1 hour. Thereafter, the pressure was slowly reduced to 10 mmHg while maintaining the system at 180 ° C. Then, the temperature was raised to 220 ° C. while under reduced pressure, and reaction was performed under reduced pressure for 2 hours. Thereafter, the reaction product was washed with water and concentrated to obtain an allyl group-containing carbonate resin. The softening point of this resin was 93.5 ° C. and the melt viscosity at 150 ° C. was 45.6 P. The Mw is 9153, the Mn is 3139, the Mw / Mn is 2.916, and the content of the compound represented by the formula (1) is 97.2 according to gel permeation chromatography analysis (hereinafter sometimes abbreviated as GPC). %Met.

Synthesis Example 4: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, diallyl bisphenol F
In Synthesis Example 3 except that 98.1 g of tricyclodecanedimethanol was changed to 157.0 g (0.80 mol) and 183.0 g of diallyl bisphenol F was changed to 93.0 g (0.31 mol) Carried out the same operation as in Synthesis Example 3 to obtain an allyl group-containing carbonate resin. The softening point of this resin was 98.4 ° C. and the melt viscosity at 150 ° C. was 69.6 P. The Mw by GPC was 6774, the Mn was 2506, the Mw / Mn was 2.703, and the content of the compound represented by the formula (1) was 97.3%.

Synthesis Example 5 Synthesis of Carbonate Resin Using Diphenyl Carbonate, Tricyclodecane Dimethanol, and Diallyl Bisphenol A>
The same procedure as in Synthesis Example 3 is performed except that 183.0 g of diallyl bisphenol F is changed to 208.6 g (0.61 mol) of diallyl bisphenol A obtained in Synthesis Example 2 in Synthesis Example 3. A group-containing carbonate resin was obtained. The softening point of this resin was 108.4 ° C. and the melt viscosity at 200 ° C. was 26.1 P. The Mw by GPC was 9711, the Mn was 3309, the Mw / Mn was 2.935, and the content of the compound represented by the formula (1) was 96.5%.

Example 1
100 g of the allyl group-containing carbonate resin synthesized in Synthesis Example 3 and 23.7 g of BMI-2300 (polyphenylmethane maleimide, maleimide equivalent: 186.0 g / eq) manufactured by Daiwa Chemical Industries, Ltd. as a maleimide compound, and a curing reaction As a catalyst, 1.2 g of dicumyl peroxide (1% relative to the total resin amount) was dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish.
The obtained resin varnish was impregnated into a glass cloth (E glass) to a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six pieces of this prepreg were stacked, press-molded at 180 ° C., and then after-baked at 230 ° C. for 5 hours to obtain a molded product (laminated plate) having a thickness of 1.5 mm. The resin content indicates the ratio of the resin (cured product) to the total mass of the molded product.

Example 2
A resin varnish was prepared in the same manner as in Example 1 except that 23.7 g of BMI-2300 in Example 1 was replaced by 47.4 g, to obtain a molded product.

Example 3
Example except replacing 23.7 g of BMI-2300 in Example 1 with 72.7 g of BMI-4000 (bisphenol A diphenyl ether bismaleimide, maleimide equivalent: 285.1 g / eq) manufactured by Daiwa Kasei Kogyo Co., Ltd. A resin varnish was prepared in the same manner as 1 to obtain a molded product.

Example 4
100 g of the allyl group-containing carbonate resin synthesized in Synthesis Example 4, 91.0 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound, and 1.9 g of dicumyl peroxide as a curing reaction catalyst (total resin amount Then, 1% of the solution was dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish.
The obtained resin varnish was impregnated into a glass cloth (E glass) to a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six pieces of this prepreg were stacked, press-molded at 180 ° C., and then after-baked at 230 ° C. for 5 hours to obtain a molded product (laminated plate) having a thickness of 1.5 mm.

Example 5
A resin varnish was prepared in the same manner as in Example 4 except that 91.0 g of BMI-4000 was changed to 136.3 g in Example 4, to obtain a molded product.

Example 6
100 g of the allyl group-containing carbonate resin synthesized in Synthesis Example 5, 22.5 g of BMI-2300 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound, and 1.2 g of dicumyl peroxide as a curing reaction catalyst (total resin amount Then, 1% of the solution was dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish.
The obtained resin varnish was impregnated into a glass cloth (E glass) to a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six pieces of this prepreg were stacked, press-molded at 180 ° C., and then after-baked at 230 ° C. for 5 hours to obtain a molded product (laminated plate) having a thickness of 1.5 mm.

Example 7
A resin varnish was prepared in the same manner as in Example 1 except that 22.5 g of BMI-2300 in Example 6 was changed to 45.0 g, to obtain a molded product.

Comparative Example 1
50.0 g of phenol novolac resin (PSM-4261 manufactured by Gunei Chemical Industry Co., Ltd., softening point: 80 ° C., hydroxyl group equivalent: 106 g / eq) and ortho cresol novolac epoxy resin (Nippon Kayaku Co., Ltd .: EOCN 1020, as epoxy resin) A resin varnish is obtained by dissolving 93.9 g of epoxy equivalent: 199 g / eq) and 1.9 g (2% with respect to epoxy resin) of triphenylphosphine as a catalyst in methyl ethyl ketone so as to have a solid content of 60%. The
The obtained resin varnish was impregnated into a glass cloth (E glass) to a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six pieces of this prepreg were stacked, press-molded at 180 ° C., and after-baked at 180 ° C. for 5 hours to obtain a molded product (laminated plate) having a thickness of 1.5 mm.

Comparative Example 2
100 g of allylphenol novolac resin (XPL-4437E manufactured by Gunei Chemical Industry, allyl equivalent: 145 g / eq, liquid at normal temperature, viscosity at 25 ° C. measured with an E-type viscometer: 31 Pa · s), maleimide compound As 196.6 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. and 3.0 g of dicumyl peroxide as a curing reaction catalyst (1% relative to the total amount of resin) to give a solid content of 60% in methyl ethyl ketone The resin varnish was obtained by
The obtained resin varnish was impregnated into a glass cloth (E glass) to a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six pieces of this prepreg were stacked, press-molded at 180 ° C., and then after-baked at 230 ° C. for 5 hours to obtain a molded product (laminated plate) having a thickness of 1.5 mm.

The glass transition temperature, the 5% thermal decomposition temperature, the room temperature linear expansion coefficient, the relative dielectric constant, and the dielectric loss tangent were measured for the molded products obtained in Examples 1 to 7 and Comparative Examples 1 and 2. The results are shown in Tables 1-2. The measured glass transition temperature, 5% thermal decomposition temperature, room temperature linear expansion coefficient, relative dielectric constant, and dielectric loss tangent are respectively the glass transition temperature of the cured product of the resin varnish used for the molded product, 5% thermal decomposition temperature, It can be regarded as a normal temperature linear expansion coefficient, a relative dielectric constant, and a dielectric loss tangent.
The types of the curing agent (allyl group-containing carbonate resin, phenol novolac resin or allyl phenol novolac resin), maleimide compound and epoxy resin used in each example are shown in Tables 1 and 2.

The moldings of Examples 1 to 7 had low dielectric constants, low dielectric loss tangents, and excellent electrical characteristics. In addition, thermal characteristics such as glass transition temperature, 5% thermal decomposition temperature and normal temperature linear expansion coefficient were also sufficiently excellent.
The molded product of Comparative Example 1 in which the epoxy resin was cured with a phenol novolac resin had higher dielectric constant and dielectric loss tangent as compared with Examples 1 to 7. In addition, the room temperature linear expansion coefficient was large.
The molded product of Comparative Example 2 using allylphenol novolac resin as a curing agent had a dielectric constant and a dielectric loss tangent higher than those of Comparative Example 1.

According to the resin varnish, a cured product having excellent electrical characteristics, which has a low dielectric constant and a low dielectric loss tangent, can be obtained. Moreover, according to this resin varnish, the hardened | cured material excellent also in the thermal characteristic which is a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion coefficient is obtained.
Therefore, the present resin varnish and a laminate using the same are extremely useful as a high functional polymer material, and as an electrically and thermally excellent material, a semiconductor sealing material, an electric insulating material, a copper-clad laminate It can be used in a wide range of applications such as resins for resins, resists, resins for sealing electronic parts, resins for color filters for liquid crystals, paints, various coating agents, adhesives, build-up laminate materials, FRP and the like.

Claims (11)

An allyl group-containing carbonate resin containing a compound represented by the following formula (1) as a main component.

[Wherein, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and two R ^{1 s} are identical to or different from each other] N is an integer of 0 or more, R ² is a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and n is 2 or more And n R ^{2 s} may be the same or different, and at least a portion of ^two R ^{1 s} and n R ^{2 s} contain an allyl group, and X represents a hydrogen atom or an allyl group And two X's may be the same or different. ] The allyl group-containing carbonate resin according to claim 1, wherein R ¹ in the formula (1) is a residue derived from an allyl group-containing bisphenol compound or a residue derived from an allyl group-containing biphenol compound. The allyl group-containing carbonate resin according to claim 2, wherein R ¹ in the formula (1) is a group represented by the following formula (r1), the following formula (r2) or the following formula (r3).

[In formula, p shows 1 or 2 and q shows the integer of 0-2. ] The allyl group-containing carbonate resin according to any one of claims 1 to 3, wherein at least a part of n R ² in the formula (1) is a residue derived from an alicyclic dimethanol compound.   A step of reacting carbonic diester with at least one diol compound selected from the group consisting of a bisphenol compound, a biphenol compound and an alicyclic dimethanol compound, wherein at least a part of the diol compound contains an allyl group And a method for producing an allyl group-containing carbonate resin. Reacting the carbonic ester with the diol compound;
A carbonic acid diester is reacted with an alicyclic dimethanol compound, or a carbonic acid diester, an alicyclic dimethanol compound, and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound Reacting to obtain a primary reaction product, and reacting the primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound, or a carbonic diester with a bisphenol compound The process for producing an allyl group-containing carbonate resin according to claim 5, which is a step of reacting with at least one aromatic diol compound selected from the group consisting of and biphenol compounds.   The molar ratio of the carbonic diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound when obtaining the first reaction product is 1.05 to 3.00. The manufacturing method of the allyl group containing carbonate resin as described.   The method according to any one of claims 5 to 10, further comprising the step of reacting an allyl group-containing carbonate resin having a hydroxyl group at a terminal with an allyl halide, generated by the reaction of the carbonic ester and the diol compound. The manufacturing method of allyl group containing carbonate resin as described in any one of 7.   The resin varnish containing the allyl group containing carbonate resin as described in any one of Claims 1-4, the maleimide compound which has 2 or more of maleimide groups, and a solvent. The allyl group-containing carbonate resin includes a compound in which at least one of two X in the formula (1) is a hydrogen atom,
The resin varnish according to claim 9, further comprising an epoxy resin.   A method for producing a laminate, comprising impregnating a fibrous base material with the resin varnish according to claim 9 or 10, heating and pressing the fibrous base material impregnated with the resin varnish, and curing to obtain a laminate.