JP2019089966A - Allyl ether group-containing carbonate resin, method for producing the same, resin varnish, and method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an allyl ether 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 and a method for producing the same, and a resin varnish to obtain a cured product having a low dielectric constant and a low dielectric loss tangent. And the provision of a method for manufacturing a laminated board using this. SOLUTION: The allyl ether group-containing carbonate resin in which the phenolic hydroxyl group of a carbonate resin having a phenolic hydroxyl group at the terminal is allyl etherified. A resin varnish containing the allyl ether group-containing resin, a maleimide compound having two or more maleimide groups, and a solvent. A method for manufacturing a laminated board, wherein the fibrous base material is impregnated with the resin varnish, and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board. [Selection diagram] None

Description

  The present invention relates to an allyl ether 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 can be used as a maleimide curing agent, an allyl ether group-containing carbonate resin which can obtain a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing the same, and a resin capable of obtaining a cured product with a low dielectric constant and a low dielectric loss tangent An object of the present invention is to provide a method of producing a varnish and a laminate using the same.

［式中、Ａｒは、ビスフェノール化合物由来の残基またはビフェノール化合物由来の残基を示し、２個のＡｒはそれぞれ同一であってもよく異なっていてもよく、Ｒ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は０以上の整数を示し、ｎが２以上である場合、ｎ個のＲはそれぞれ同一であってもよく異なっていてもよく、Ｘは水素原子またはアリル基を示し、２個のＸのうち少なくとも一方はアリル基である。］
〔５〕前記式（１）中のＡｒが、下記式（ｒ１）、下記式（ｒ２）または下記式（ｒ３）で表される基を示し、Ｒが、前記式（ｒ１）、前記式（ｒ２）、前記式（ｒ３）または下記式（ｒ４）で表される基を示す、〔４〕のアリルエーテル基含有カーボネート樹脂。

［式中、Ｒ^１は、脂環式基を示す。］
〔６〕末端がフェノール性水酸基であるカーボネート樹脂と、ハロゲン化アリルとを反応させ、前記フェノール性水酸基をアリルエーテル化する、アリルエーテル基含有カーボネート樹脂の製造方法。
〔７〕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、末端がフェノール性水酸基であるカーボネート樹脂を得て、
前記カーボネート樹脂とハロゲン化アリルとを反応させ、前記フェノール性水酸基をアリルエーテル化する、アリルエーテル基含有カーボネート樹脂の製造方法。
〔８〕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、〔７〕のアリルエーテル基含有カーボネート樹脂の製造方法。
〔９〕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、末端がフェノール性水酸基であるカーボネート樹脂を得て、
前記カーボネート樹脂と、ハロゲン化アリルとを反応させ、前記フェノール性水酸基をアリルエーテル化する、アリルエーテル基含有カーボネート樹脂の製造方法。
〔１０〕前記芳香族ジオール化合物に対する前記炭酸ジエステルのモル比が、０．６０〜０．９９である、〔９〕のアリルエーテル基含有カーボネート樹脂の製造方法。
〔１１〕前記〔１〕〜〔５〕のいずれかのアリルエーテ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。
〔１２〕前記〔１１〕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 ether group-containing carbonate resin in which the phenolic hydroxyl group of the carbonate resin whose terminal is a phenolic hydroxyl group is allyletherified.
[2] The carbonate resin is a reaction product 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, [1] Allyl ether group-containing carbonate resin.
[3] The allyl ether group-containing carbonate resin of [1], wherein the carbonate resin is a reaction product of a diester of carbonic acid and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound.
[4] An allyl ether group-containing carbonate resin containing a compound represented by the following formula (1) as a main component.

[Wherein, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, and two Ars may be the same or different, and R is a residue derived from a bisphenol compound And a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, n represents an integer of 0 or more, and when n is 2 or more, n Rs may be identical to each other. It may be different, and X represents a hydrogen atom or an allyl group, and at least one of two X's is an allyl group. ]
[5] Ar in the above formula (1) represents a group represented by the following formula (r1), the following formula (r2) or the following formula (r3), and R represents the above formula (r1) or the above formula r2) An allyl ether group-containing carbonate resin of [4] showing a group represented by the above formula (r3) or the following formula (r4).

[Wherein, R ¹ represents an alicyclic group. ]
[6] A method for producing an allyl ether group-containing carbonate resin, which comprises reacting a carbonate resin whose terminal is a phenolic hydroxyl group with allyl halide to allyletherify the phenolic hydroxyl group.
[7] At least one aromatic diol selected from the group consisting of carbonic diester and an alicyclic dimethanol compound, or carbonic diester, an alicyclic dimethanol compound, a bisphenol compound and a biphenol compound The compound is reacted to obtain a primary reaction product,
The primary reaction product is reacted with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound to obtain a carbonate resin whose terminal is a phenolic hydroxyl group,
A method for producing an allyl ether group-containing carbonate resin, which comprises reacting the carbonate resin with an allyl halide to allyletherify the phenolic hydroxyl group.
[8] The molar ratio of the carbonic diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound in obtaining the first-order reaction product is 1.05 to 3.00, [ 7] The manufacturing method of allyl ether group containing carbonate resin.
[9] A carbonic acid diester is reacted with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound to obtain a carbonate resin whose terminal is a phenolic hydroxyl group,
A method for producing an allyl ether group-containing carbonate resin, which comprises reacting the carbonate resin with an allyl halide to allyletherify the phenolic hydroxyl group.
[10] The method for producing an allyl ether group-containing carbonate resin of [9], wherein the molar ratio of the carbonic diester to the aromatic diol compound is 0.60 to 0.99.
[11] A resin varnish comprising the allyl ether group-containing carbonate resin of any one of the above [1] to [5], a maleimide compound having two or more maleimide groups, and a solvent.
[12] A method for producing a laminate, comprising impregnating a fibrous base material with the resin varnish of the above [11], heating and pressing the fibrous base material impregnated with the resin varnish, and curing to obtain a laminate.

  According to the present invention, an allyl ether 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 cured product having a low dielectric constant and a low dielectric loss tangent It is possible to provide a method of producing a resin varnish and a laminate using the same.

«Allyl ether group-containing carbonate resin»
The allyl ether group-containing carbonate resin of the present invention (hereinafter, also referred to as "the present carbonate resin") allyls the phenolic hydroxyl group of a carbonate resin whose terminal is a phenolic hydroxyl group (hereinafter, also referred to as the "phenol carbonate resin"). It is etherified. The phenolic hydroxyl group is a hydroxyl group bonded to an aromatic ring. Thus, the ends of the carbonate resin, an allyl ether group bonded to an aromatic ring _{(-O-CH 2 -CH = CH} 2).

As a preferable embodiment of the present carbonate resin, a carbonate resin containing a compound represented by the following formula (1) as a main component (hereinafter also referred to as "carbonate resin (1)") can be mentioned. The "main component" refers to the component having the largest content among the components constituting the present carbonate resin.
The carbonate resin (1) may be a mixture of a plurality of compounds having different values of n.
The carbonate resin (1) is a component 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) May be included. These components may be the raw materials used for producing the carbonate resin (1) 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 carbonate resin (1), 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、Ａｒは、ビスフェノール化合物由来の残基またはビフェノール化合物由来の残基を示し、２個のＡｒはそれぞれ同一であってもよく異なっていてもよく、Ｒ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は０以上の整数を示し、ｎが２以上である場合、ｎ個のＲはそれぞれ同一であってもよく異なっていてもよく、Ｘは水素原子またはアリル基を示し、２個のＸのうち少なくとも一方はアリル基である。］

[Wherein, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, and two Ars may be the same or different, and R is a residue derived from a bisphenol compound And a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, n represents an integer of 0 or more, and when n is 2 or more, n Rs may be identical to each other. It may be different, and X represents a hydrogen atom or an allyl group, and at least one of two X's is an allyl group. ]

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 (1) 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 E, bisphenol S, bisphenol Z and the like.

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 the biphenol compound include biphenol, halogenated biphenol, alkyl biphenol and the like.

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.
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.

As Ar, a group represented by the following formula (r1), the following formula (r2) or the following formula (r3) is preferable in that it is inexpensive and easily available. These groups are residues derived from bisphenol A, bisphenol F or biphenol.
As R, a group represented by the above-mentioned formula (r1), the above-mentioned formula (r2), the above-mentioned formula (r3) or the following formula (r4) is preferable in that it is inexpensive and easily available. The group represented by the formula (r4) is a residue derived from an alicyclic dimethanol compound. The alicyclic group for R ¹ is as defined above.

［式中、Ｒ^１は、脂環式基を示す。］

[Wherein, R ¹ represents an alicyclic group. ]

Two Ar in Formula (1) may be the same or different.
When n in the formula (1) is 2 or more, n Rs may be identical to or different from each other.
At least a part of R is preferably a residue derived from an alicyclic dimethanol compound, that is, a group represented by the formula (r4) in that the cured product has a lower dielectric loss tangent. When n is 1, R is preferably a residue derived from an alicyclic dimethanol compound, and when n is 2 or more, at least one of n Rs is an alicyclic dimethanol compound It is preferable that it is a residue derived from.

  20-100 mol% is preferable and, as for the ratio of R which is a residue derived from an alicyclic dimethanol compound among all R in carbonate resin (1), 50-90 mol% is more preferable. When the ratio of R, which is a residue derived from an alicyclic dimethanol compound, is equal to or more than the lower limit value, a cured product with a lower dielectric loss tangent can be obtained.

  In formula (1), it is preferable that at least one of the two X's is an allyl group, and both of them are an allyl group.

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 by reacting a phenol carbonate resin with an allyl halide to allyletherify the phenolic hydroxyl group at the terminal of the phenol carbonate resin.

(Phenol carbonate resin)
The phenol carbonate resin has a phenolic hydroxyl group at the end. Thereby, allyl etherification can be performed favorably.
As a phenol carbonate resin, the thing of the structure where the allylether group of the terminal of this carbonate resin became a hydroxyl group is used.
For example, when the present carbonate resin is the above-mentioned carbonate resin (1), as a phenol carbonate resin, a carbonate resin containing a compound represented by the following formula (2) as a main component (hereinafter also referred to as "carbonate resin (2)") Is used.

  In the formula, Ar, R and n are as defined above, and preferred embodiments are also the same.

In a preferred embodiment of the phenol carbonate resin, a carbonate resin (a reaction product 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) Hereinafter, it may be referred to as "resin (I)".
Resin (I) is a resin in which at least a portion of R in the carbonate resin (2) is a residue derived from an alicyclic dimethanol compound.
The alicyclic dimethanol compound, the bisphenol compound and the biphenol compound are the same as described above.

  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.

Resin (I) is obtained by, for example, reacting a carbonic diester, an alicyclic dimethanol compound, and, if necessary, an aromatic diol compound (primary reaction) to obtain a primary reaction product, the obtained primary reaction It is obtained by reacting the product with an aromatic diol compound (secondary reaction).
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.

In another preferred embodiment of the phenol carbonate resin, a carbonate resin (hereinafter referred to as “resin (II), which is a reaction product of a diester of carbonic acid and at least one aromatic diol compound selected from the group consisting of bisphenol compounds and biphenol compounds Also referred to as ").
Resin (II) is a resin in which, in the carbonate resin (2), R is a residue derived from a bisphenol compound or a residue derived from a biphenol compound.
The carbonic diester, the bisphenol compound, and the biphenol compound are the same as described above.

The resin (II) can be obtained, for example, by reacting a carbonic diester with an aromatic diol compound. 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.

70-130 degreeC is preferable and, as for the softening point of phenol carbonate resin, 90-120 degreeC is more preferable.
As for melt viscosity at 150 ° C of phenol carbonate resin, 10P-100P are preferred, and 30P-80P are more preferred.
3000-12000 are preferable and, as for the weight average molecular weight (Mw) of phenol carbonate resin, 5000-10000 are more preferable.

500-3000 g / eq is preferable, and, as for the hydroxyl equivalent of phenol carbonate resin, 800-2000 g / eq is more preferable.
The hydroxyl equivalent of phenol carbonate resin is the value which divided the number average molecular weight (Mn) of phenol carbonate resin by the number of hydroxyl groups.

As a phenol carbonate resin, 1 type may be used independently and 2 or more types may be used together. For example, resin (I) and resin (II) may be used in combination.
It is preferable that phenol carbonate resin contains resin (I) at the point from which the hardened | cured material using the aryl ether group containing carbonate resin obtained becomes a low dielectric loss tangent more.

(Allyl halide)
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.

(Allyl etherification)
Reaction of phenol carbonate resin and the allyl halide, phenol carbonate resin terminal phenolic hydroxyl groups (-OH) is converted into an allyl ether group _{(-O-CH 2 -CH = CH} 2).

  The reaction of the phenol carbonate resin with the allyl halide (allylic 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 phenol carbonate resin with the allyl halide may be carried out in the presence of a solvent. As a solvent, it is sufficient if it is capable of dissolving a phenol carbonate resin and an allyl halide, and examples thereof include a solvent in a resin varnish described later.

The amount of allyl halide to be reacted with the phenol carbonate resin in the reaction between the phenol carbonate resin and the allyl halide is the molar ratio of allyl halide to phenolic hydroxyl group at the terminal of the phenol carbonate resin (aryl halide / phenolic hydroxyl group) Preferably, the amount is 0.3 to 2.0. 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.

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.

Furthermore, this carbonate resin is excellent in the solubility with respect to the solvent generally used in order to dissolve a maleimide compound. Therefore, the resin varnish in which the present carbonate resin and maleimide compound are both dissolved in the solvent can be obtained.
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, it can be independently hardened | cured by reaction of said (3). However, by combining with a maleimide compound, 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 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.
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 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.

  The content of the maleimide compound in the present resin varnish is preferably such that the molar ratio of the maleimide group of the maleimide compound to the allyl group of the present carbonate resin (maleimido group / allyl group) is 0.5 to 8.0. The maleimide group / allyl group is more preferably 1.0 to 6.0, further preferably 1.5 to 5.0. If the maleimide group / allyl group 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. When the maleimide group / allyl group 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.

<Curing reaction catalyst>
As a curing reaction catalyst (curing accelerator), what is necessary is just to have the effect | action which accelerates | stimulates reaction with an allyl group and a maleimide group, for example, an imidazole compound, an organic peroxide, etc. are mentioned. 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.

One of these curing reaction catalysts may be used alone, or two or more thereof may be used in combination.
As for content of the curing reaction catalyst in this resin varnish, 0.1-5.0 mass% is preferable with respect to a maleimide compound.

<Other ingredients>
As other components, for example, inorganic fillers (for example, carbon black, glass cloth, silica, etc.), waxes, flame retardants, coupling agents, etc., and maleimide curing agents other than the present carbonate resin (hereinafter, also referred to as other curing agents). , Fillers, mold release agents, surface treatment agents, colorants, flexibility imparting agents and the like.
As the other curing agent, those conventionally known as a maleimide curing agent can be used, and examples thereof include novolac resins such as allyl novolac phenol resins.
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 the present carbonate resin, maleimide compound and solvent are mixed, a curing reaction catalyst and other components may be further mixed, if necessary.
This carbonate resin can be manufactured by the above-mentioned manufacturing method. As the maleimide compound, the curing reaction catalyst, and other components, commercially available products can be used. 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: Allyl Etherification of Carbonate Resin Using Diphenyl Carbonate, Tricyclodecane Dimethanol, and Bisphenol F>
In a 1-liter reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, 375.0 g (1.75 mol) of diphenyl carbonate and 171.8 g (0.88 mol) of tricyclodecanedimethanol are charged and melted at 100 ° C. Mixed. Then, 0.04 g of a 48% aqueous solution of KOH was added, and the temperature was raised to 180 ° C. while paying attention to heat generation, and the reaction was conducted under normal pressure for 1 hour. Subsequently, it cooled to 130 degreeC and added 213.6 g (1.07 mol) of bisphenol F (BPF-SG by Gun-ei Chemical Co., Ltd.), heated up to 180 degreeC, and was made to react 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 a phenol carbonate resin containing an alicyclic skeleton. The softening point of this resin was 101.9 ° C. and the melt viscosity at 150 ° C. was 37.6 P. Mw was 4751, Mn was 2419, and Mw / Mn was 1.964 according to gel permeation chromatography analysis (hereinafter sometimes abbreviated as GPC). The hydroxyl equivalent (g / eq) of this resin was 1209.5 which is half of Mn.
100 g of the phenol carbonate resin and 9.5 g of allyl chloride were dissolved in methyl ethyl ketone so as to have a solid content of 50%. Next, 11.3 g of diazabicycloundecene was added dropwise at 30 ° C. or less over 2 hours. Thereafter, the temperature was raised to 50 ° C., and reaction was performed for 3 hours, followed by washing with water and concentration to obtain allyl ether group-containing carbonate resin 1. The softening point of this resin was 97.3 ° C. and the melt viscosity at 150 ° C. was 17.0 P. The Mw by GPC was 4888, the Mn was 2530, the Mw / Mn was 1.995, and the content of the compound represented by the formula (1) was 97.1%. The allyl group equivalent (g / eq) of this resin was 1265.0 which is half of Mn.

Synthesis Example 2: Allyl etherification of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and bisphenol F>
Synthesis Example 1 is the same as Synthesis Example 1 except that 171.8 g of tricyclodecanedimethanol is changed to 274.9 g (1.40 mol) and 213.6 g of bisphenol F is changed to 108.6 g (0.54 mol). A phenol carbonate resin was obtained by the method. The softening point of this resin was 98.4 ° C. and the melt viscosity at 150 ° C. was 69.6 P. Mw by GPC was 4577, Mn was 1743, and Mw / Mn was 2.626. The hydroxyl equivalent (g / eq) of this resin was 871.5, which is half of Mn.
100 g of the phenol carbonate resin and 13.2 g (0.17 mol) of allyl chloride were dissolved in methyl ethyl ketone so as to have a solid content of 50%. Then, 15.7 g of diazabicycloundecene was dropped dropwise at 30 ° C. or less over 2 hours. Thereafter, the temperature was raised to 50 ° C., and reaction was performed for 3 hours, followed by washing with water and concentration to obtain allyl etherified carbonate resin 2. The softening point of this resin was 98.6 ° C. and the melt viscosity at 150 ° C. was 56.8 P. The Mw by GPC was 4520, the Mn was 1703, the Mw / Mn was 2.654, and the content of the compound represented by the formula (1) was 95.5%. The allyl group equivalent of this resin was 851.5 which is half of Mn.

Synthesis Example 3: Allyl Etherification of Carbonate Resin Using Diphenyl Carbonate, Tricyclodecane Dimethanol, and Bisphenol A>
A phenol carbonate resin was obtained in the same manner as in Synthesis Example 1 except that 243.8 g (1.07 mol) of bisphenol A was used instead of 213.6 g of bisphenol F in Synthesis Example 1. The softening point of this resin was 109.6 ° C. and the melt viscosity at 150 ° C. was 63.2 P. Mw by GPC was 5617, Mn was 2973, and Mw / Mn was 1.890. The hydroxyl equivalent of this resin was 1486.5 which is half of Mn.
100 g of the phenol carbonate resin and 7.7 g of allyl chloride were dissolved in methyl ethyl ketone so as to have a solid content of 50%. Next, 11.3 g of diazabicycloundecene was added dropwise at 30 ° C. or less over 2 hours. Thereafter, the temperature was raised to 50 ° C., and reaction was performed for 3 hours, followed by washing with water and concentration to obtain allyl etherified carbonate resin 3. The softening point of this resin was 101.7 ° C. and the melt viscosity at 150 ° C. was 37.2 P. The Mw by GPC was 5791, the Mn was 2603, the Mw / Mn was 2.006, and the content of the compound represented by the formula (1) was 95.7%. The allyl group equivalent of this resin was set to 1301.5 which is half of Mn.

Synthesis Example 4: Allyl etherification of carbonate resin using diphenyl carbonate and bisphenol F
375.0 g (1.75 mol) of diphenyl carbonate, 388.9 g (1.94 mol of bisphenol F (BPF-SG manufactured by Gunei Chemical Industry Co., Ltd.) in a 1 L reaction vessel equipped with a thermometer, a stirrer, and a cooling pipe ) Was charged and melt mixed at 100 ° C. Then, 0.04 g of a 48% aqueous solution of KOH was added, and the temperature was raised to 180 ° C. while paying attention to heat generation, and the 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 a phenol carbonate resin. The softening point of this resin was 107.6 ° C., and the melt viscosity at 150 ° C. was 60.3 P. Mw by GPC was 3662, Mn was 1977, and Mw / Mn was 1.852. The hydroxyl equivalent of this resin was 988.5 which is half of the number average molecular weight (Mn).
100 g of the phenol carbonate resin and 11.6 g (0.15 mol) of allyl chloride were dissolved in methyl ethyl ketone so as to have a solid content of 50%. Then, 16.9 g of diazabicycloundecene was added dropwise at 30 ° C. or less over 2 hours. Thereafter, the temperature was raised to 50 ° C., and reaction was performed for 3 hours, followed by washing with water and concentration to obtain allyl etherified carbonate resin 4. The softening point of this resin was 100.9 ° C. and the melt viscosity at 150 ° C. was 29.7 P. The Mw by GPC was 4012, the Mn was 2135, the Mw / Mn was 1.888, and the content of the compound represented by the formula (1) was 96.2%. The allyl group equivalent of this resin was 1067.5 which is half of Mn.

Synthesis Example 5 Allyl Etherification of Carbonate Resin Using Diphenyl Carbonate, Bisphenol F, and Bisphenol A>
The same method as in Synthesis Example 4 except that 388.9 g of bisphenol F was changed to 155.6 g (0.78 mol) in Synthesis Example 4 and 266.0 g (1.17 mol) of bisphenol A was used. Thus, a phenol carbonate resin was obtained. The softening point of this resin was 121.1 ° C. and the melt viscosity at 150 ° C. could not be measured. Mw by GPC was 4478, Mn was 2394, and Mw / Mn was 1.871. The hydroxyl equivalent of this resin was 1197.0, which is half of Mn.
100 g of the phenol carbonate resin and 9.6 g (0.13 mol) of allyl chloride were dissolved in methyl ethyl ketone so as to have a solid content of 50%. Next, 14.0 g of diazabicycloundecene was added dropwise at 30 ° C. or less over 2 hours. Thereafter, the temperature is raised to 50 ° C., and reaction is performed for 3 hours, followed by washing with water and concentration to obtain allyl etherified carbonate resin 5. The softening point of this resin was 113.3 ° C. and the melt viscosity at 150 ° C. was 81.0 P. The Mw by GPC was 4691, the Mn was 2444, the Mw / Mn was 1.908, and the content of the compound represented by the formula (1) was 95.4%. The allyl group equivalent of this resin was 1222.0 which is half of Mn.

Example 1
100 g of allyl ether group-containing carbonate resin 1 (allyl group equivalent: 1265.0 g / eq) synthesized in Synthesis Example 1 and BMI-4000 (bisphenol A diphenyl ether bismaleimide as a maleimide compound, maleimide equivalent: Resin containing 67.6 g of 285.1 g / eq) and 1.7 g of dicumyl peroxide (1% with respect to the total resin amount) as a curing reaction catalyst dissolved in methyl ethyl ketone so as to have a solid content of 60% I got a 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 62.7 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. in Example 1 was replaced with 112.7 g, to obtain a molded product.

Example 3
100 g of allyl ether group-containing carbonate resin 2 (allyl group equivalent: 851.5 g / eq) synthesized in Synthesis Example 2 and 100.3 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound as a curing reaction catalyst A resin varnish was obtained by dissolving 2.0 g (1% relative to the total resin amount) of dicumyl peroxide in methyl ethyl ketone so as to have a solid content of 60%.
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 having a thickness of 1.5 mm.

Example 4
A resin varnish was prepared in the same manner as in Example 3 except that 100.3 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. in Example 3 was changed to 167.3 g, to obtain a molded product.

Example 5
100 g of allyl ether group-containing carbonate resin 3 (allyl group equivalent: 1301.5 g / eq) synthesized in Synthesis Example 3, 65.7 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound, and a curing reaction catalyst A resin varnish was obtained by dissolving 1.7 g (1% relative to the total resin amount) of dicumyl peroxide in methyl ethyl ketone so as to have a solid content of 60%.
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 having a thickness of 1.5 mm.

Example 6
100 g of allyl ether group-containing carbonate resin 4 (allyl group equivalent: 1067.5 g / eq) synthesized in Synthesis Example 4 and 80.1 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound as a curing reaction catalyst A resin varnish was obtained by dissolving 1.8 g (1% relative to the total resin amount) of dicumyl peroxide in methyl ethyl ketone so as to have a solid content of 60%.
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 having a thickness of 1.5 mm.

Example 7
100 g of allyl ether group-containing carbonate resin 5 (allyl group equivalent: 1222.0 g / eq) synthesized in Synthesis Example 5 and 70.0 g of BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. as a maleimide compound as a curing reaction catalyst A resin varnish was obtained by dissolving 1.7 g (1% relative to the total resin amount) of dicumyl peroxide in methyl ethyl ketone so as to have a solid content of 60%.
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 having a thickness of 1.5 mm.

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 then after-baked at 180 ° C. for 5 hours to obtain a molded product 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 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 curing agent (allyl ether group-containing carbonate resin, phenol novolac resin or allyl phenol novolac resin), maleimide compound and epoxy resin used in each example, and molar ratio of maleimide group to allyl group (maleimido group / allyl group) It described together to Tables 1-2.

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 (12)

  An allyl ether group-containing carbonate resin in which the phenolic hydroxyl group of the carbonate resin whose terminal is a phenolic hydroxyl group is allyletherified.   The said carbonate resin is a reaction product of a carbonic diester, an alicyclic dimethanol compound, and at least 1 sort (s) of aromatic diol compound chosen from the group which consists of a bisphenol compound and a biphenol compound. Allyl ether group-containing carbonate resin.   The allyl ether group-containing carbonate resin according to claim 1, wherein the carbonate resin is a reaction product of a carbonic diester and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound. An allyl ether group-containing carbonate resin containing a compound represented by the following formula (1) as a main component.

[Wherein, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, and two Ars may be the same or different, and R is a residue derived from a bisphenol compound And a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, n represents an integer of 0 or more, and when n is 2 or more, n Rs may be identical to each other. It may be different, and X represents a hydrogen atom or an allyl group, and at least one of two X's is an allyl group. ] Ar in the formula (1) represents a group represented by the following formula (r1), the following formula (r2) or the following formula (r3), and R represents the formula (r1), the formula (r2), or The allyl ether group-containing carbonate resin according to claim 4, which represents a group represented by the formula (r3) or the following formula (r4).

[Wherein, R ¹ represents an alicyclic group. ]   A method for producing an allyl ether group-containing carbonate resin, which comprises reacting a carbonate resin whose terminal is a phenolic hydroxyl group with allyl halide to allyletherify the phenolic hydroxyl group. 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 React to obtain the primary reaction product,
The primary reaction product is reacted with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound to obtain a carbonate resin whose terminal is a phenolic hydroxyl group,
A method for producing an allyl ether group-containing carbonate resin, which comprises reacting the carbonate resin with an allyl halide to allyletherify the phenolic hydroxyl group.   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 ether group containing carbonate resin as described. A carbonic acid diester is reacted with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound to obtain a carbonate resin whose terminal is a phenolic hydroxyl group,
A method for producing an allyl ether group-containing carbonate resin, which comprises reacting the carbonate resin with an allyl halide to allyletherify the phenolic hydroxyl group.   The manufacturing method of the allyl ether group containing carbonate resin of Claim 9 whose molar ratio of the said carbonic diester with respect to the said aromatic diol compound is 0.60-0.99.   The resin varnish containing the allylether group containing carbonate resin as described in any one of Claims 1-5, the maleimide compound which has 2 or more of maleimide groups, and a solvent.   A method for producing a laminate, wherein the resin varnish according to claim 11 is impregnated into a fibrous base material, the fibrous base material impregnated with the resin varnish is heated and pressed, and cured to obtain a laminate.