JP6998739B2 - Allyl group-containing carbonate resin, its manufacturing method, resin varnish, and laminated board manufacturing method - Google Patents

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 laminated board.

Conventionally, epoxy resin has been used for members used in electronic products, for example, an insulating laminated board and a laminated board (copper-clad laminated board) in which copper foil is laminated on one side or both sides thereof. The laminated board is made by impregnating a fibrous base material such as glass cloth with a resin varnish in which an epoxy resin, a curing agent, etc. is dissolved in a solvent, drying the prepreg, and heat-pressing the prepreg alone or in layers. It is manufactured by. As a curing agent for the epoxy resin, a phenol novolac resin using phenol and formaldehyde is widely used.

In recent years, as the performance of electronic products has been improved, the resin constituting the laminated board is required to have a lower dielectric constant and a lower dielectric loss tangent. Although the electrical characteristics (low dielectric constant, low dielectric loss tangent) of the cured product obtained by curing the epoxy resin with phenol novolac resin can meet the levels required for general-purpose electronic products, high-performance electronic products (smartphones, smartphones, etc.) 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 characteristics can be obtained.
However, it cannot be said that the dielectric loss tangent of the cured product using the epoxy resin curing agent of Patent Document 1 is still sufficiently low.

Japanese Unexamined Patent Publication No. 2004-224860

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

［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.

[In the formula, R ¹ indicates a residue derived from a bisphenol compound, a residue derived from a biphenol compound, or a residue derived from an alicyclic dimethanol compound, and the two R ^1s are different even if they are the same. Also, n indicates an integer of 0 or more, R ² indicates a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and when n is 2 or more. , N R ^2s may be the same or different, respectively, at least a portion of the ^two R ^1s and n R 2s contains an allyl group, where X represents a hydrogen atom or allyl group. The two Xs may be the same or different. ]
[2] The allyl group-containing carbonate resin according to [1], wherein R1 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 R1 in the formula ( ¹ ) is a group represented by the following formula (r1), the following formula (r2) or the following formula (r3).

[In the formula, p indicates 1 or 2, and q indicates an integer of 0 to 2. ]
[4] The allyl group-containing carbonate resin according to any one of [1] to [3], wherein at least a part of n R ^2s in the formula (1) is a residue derived from an alicyclic dimethanol compound. ..
[5] The present invention comprises a step of reacting a 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, and at least a part of the diol compound is an allyl group. A method for producing an allyl group-containing carbonate resin containing the above.
[6] The step of reacting the carbonic acid ester with the diol compound is
The carbonic acid diester is reacted with the alicyclic dimethanol compound, or the carbonic acid diester is associated with at least one aromatic diol compound selected from the group consisting of the alicyclic dimethanol compound and the bisphenol compound and the biphenol compound. The reaction is carried out to obtain a primary reaction product, and 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, or a carbonic acid diester and a bisphenol compound. The method for producing an allyl group-containing carbonate resin according to [5], which is a step of reacting with at least one aromatic diol compound selected from the group consisting of the biphenol compound and the biphenol compound.
[7] The molar ratio of the carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound in obtaining the primary reaction product is 1.05 to 3.00. 6] A method for producing an allyl group-containing carbonic acid resin.
[8] Further comprising a step of reacting an allyl group-containing carbonate resin having a hydroxyl group at the end, which is produced by the reaction of the carbonic acid ester with the diol compound, with allyl halide to convert the hydroxyl group into an allyl ether. 6] or [7], a method for producing an allyl group-containing carbonate resin.
[9] A resin varnish containing the allyl group-containing carbonate resin according to 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 the two Xs in the formula (1) is a hydrogen atom.
The resin varnish of [9] further containing an epoxy resin.
[11] Manufacture of a laminated board in which the fibrous base material is impregnated with the resin varnish of the above [9] or [10], and the fibrous base material impregnated with the resin varnish is heated and pressed and cured to obtain a laminated board. 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 and a method for producing the same, and a cured product having a low dielectric constant and a low dielectric loss tangent can be obtained. A resin varnish and a method for manufacturing a laminated board using the resin varnish 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 highest 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.
This carbonate resin contains 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 allyl etherified compound thereof, etc.). You may. These components may be a raw material used in the production of the present carbonate resin or a by-product produced as a by-product during the production.
The content of the compound represented by the formula (1) in the carbonate resin is preferably 80% by mass or more, more preferably 90% by mass or more. The upper limit of this content is not particularly limited and may be 100% by mass. The content of the compound represented by the 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。］

[In the formula, R ¹ indicates a residue derived from a bisphenol compound, a residue derived from a biphenol compound, or a residue derived from an alicyclic dimethanol compound, and the two R ^1s are different even if they are the same. Also, n indicates an integer of 0 or more, R ² indicates a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and when n is 2 or more. , N R ^2s may be the same or different, respectively, at least a portion of the ^two R ^1s and n R 2s contains an allyl group, where X represents a hydrogen atom or allyl group. The two Xs may be the same or different. ]

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

A bisphenol compound is a compound having two hydroxyphenyl groups bonded 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 bonded 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 allele in which an allyl group is 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 directly bonded hydroxyphenyl groups. The hydroxyphenyl group may have a substituent.
The residue derived from the biphenol compound is a group having a structure obtained by removing two phenolic hydroxyl groups from the 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, an alkyl group and the like. The number of substituents may be one or two or more.
Specific examples of the biphenol compound include biphenol, halogenated biphenol, alkyl biphenol, and an allyl group-containing biphenol compound in which an allyl group is bonded to at least one of the hydroxyphenyl groups of these biphenol compounds.

The alicyclic dimethanol compound is a compound having an alicyclic group and two methanol groups (-CH ₂ OH) bonded to 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。］

[In the formula, R ³ represents an alicyclic group. ]

The alicyclic group may have a monocyclic structure or a polycyclic structure. The alicyclic group preferably does not have an unsaturated bond. The alicyclic group preferably has 6 to 20 carbon atoms, more preferably 8 to 15 carbon atoms. Specific examples of the alicyclic group include cyclohexylene group, tricyclodecandyl group, perhydro-1,4; 5,8-naphthylene-2,3-diyl group, bicyclo [2.2.1] heptane-2. , 3-Diyl group and the like.
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 cyclohexanedimethanol, tricyclodecanedimethanol, trans-2,3-di (hydroxymethyl) -perhydro-1,4; 5,8-dimethanonaphthalene, and trans-. Examples thereof include 2,3-di (hydroxymethyl) bicyclo [2.2.1] heptane. The isomers may be mixed with each other.

In formula (1), at least a part of ^two R ^1s and n R 2s contains an allyl group. That is, at least a part of the ^two R ^1s and n R 2s is derived from a residue derived from an allyl group-containing bisphenol compound (for example, the above-mentioned allyl bisphenol) and an allyl group-containing biphenol compound (for example, the above-mentioned allyl biphenol). Residues or residues derived from allyl group-containing alicyclic dimethanol compounds. As a result, the carbonate resin can be used as a maleimide curing agent.
Some of the ^{two R1s} and n R2s may not contain an allyl group.
Of all R ¹ and R ² in the carbonate resin, the total ratio of R ¹ containing an allyl group and R ² containing an allyl group is preferably 2 to 80 mol%, preferably 5 to 50 mol%. More preferred.

The two R1s in the equation ( 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, when X in the formula (1) is a hydrogen atom, OX becomes a phenolic hydroxyl group. The phenolic hydroxyl group has excellent reactivity with the epoxy resin. Further, the phenolic hydroxyl group is also excellent in 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 preferable. These groups are residues derived from allyl group-containing bisphenol A, allyl group-containing bisphenol F or allyl group-containing biphenol.

In the formula, p indicates 1 or 2, and q indicates an integer of 0 to 2.
1 is preferable as p. 1 is preferable as q.

When n in the formula (1) is ² or more, the n R2s may be the same or different.
At least a part of the n ^R2s in the formula (1) is a residue derived from the alicyclic dimethanol compound, that is, a group represented by the formula (r4), in that the cured product has a lower dielectric loss tangent. Is preferable. When n is 1, it is preferable that R ² is a residue derived from an alicyclic dimethanol compound, and when n is 2 or more, at least one of n R ² is an alicyclic diethanol. It is preferably a residue derived from a methanol compound.
A part of n R ^2s may be a residue derived from a bisphenol compound or a residue derived from a biphenol compound. Residues derived from bisphenol compounds or residues derived from biphenol compounds may or may not have an allyl group.

The proportion of R ² which is a residue derived from the alicyclic dimethanol compound in all R ² in the present carbonate resin is preferably 20 to 100 mol%, more preferably 50 to 90 mol%. When the ratio of R ² which is a residue derived from the alicyclic dimethanol compound is at least the above lower limit value, a cured product having a lower dielectric loss tangent can be obtained.

In the formula (1), the two Xs may be hydrogen atoms or allyl groups, respectively.
The carbonate resin may contain a compound in which at least one of the two Xs in the formula (1) is a hydrogen atom. In this case, the carbonate resin can also be used as an epoxy resin curing agent.
When the present carbonate resin is used as an epoxy resin curing agent, the ratio of X, which is a hydrogen atom, to all X in the present carbonate resin is preferably 50 to 100 mol%, more preferably 80 to 100 mol%. When the ratio of X, which is a hydrogen atom, is at least the above lower limit value, the reactivity with the epoxy resin and the heat resistance of the cured product are more excellent.

The softening point of the carbonate resin is preferably 70 to 130 ° C, more preferably 90 to 120 ° C. When the softening point is at least the above lower limit value, the blocking resistance of the resin is more excellent. When the softening point is not more than the upper limit value, the fluidity is more excellent.
The softening point is measured according to JIS K 6910.

The melt viscosity of the carbonate resin at 150 ° C. is preferably 10P to 100P, more preferably 30P to 80P. When the melt viscosity is at least the above lower limit value, the blocking resistance of the resin is more excellent. When the melt viscosity is not more than the upper limit value, the fluidity is excellent.
The melt viscosity is measured by the measuring method described in Examples described later.

The weight average molecular weight (Mw) of the carbonate resin is preferably 3000 to 12000, more preferably 5000 to 10000. When Mw is at least the above lower limit value, the blocking resistance of the resin is more excellent. When Mw is not more than the upper limit value, the fluidity is more excellent.
Mw and Mn of the carbonate resin are values measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The allyl group equivalent of this carbonate resin is preferably 500 to 3000 g / eq, more preferably 800 to 2000 g / eq. When the allyl group equivalent is at least the above lower limit value, the dielectric property is more excellent. When the allyl group equivalent is not more than the above upper limit value, the reactivity with the maleimide compound is more excellent.
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.

<Manufacturing method of this carbonate resin>
The carbonate resin can be produced, for example, by a production method having the following step 1. After step 1, step 2 may be performed if necessary.
Step 1: A step of reacting a 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.
Step 2: A step of reacting the allyl group-containing carbonate resin having a hydroxyl group at the end, which was produced in step 1, with allyl halide to convert the hydroxyl group into an allyl ether.

(Glycol compound)
The bisphenol compound, the biphenol compound, and the alicyclic dimethanol compound are the same as described above.
At least a part 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 converting the phenolic hydroxyl group of the bisphenol compound into an allyl ether 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 (-OH) of the bisphenol compound is converted to 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 preferable because of its low cost.
The reaction between the bisphenol compound and the allyl halide (allyl etherification) is preferably carried out in the presence of a catalyst. Examples of the catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amine compounds such as diazabicyclononen, diazabicycloundecene and triethylamine, sodium tert-butoxide, potassium tert-butoxide and lithium diisopropyl. Examples thereof include amide, silicon-basic amine, lithium tetramethylpiperidin and the like.

The reaction between the bisphenol compound and the allyl halide may be carried out in the presence of a solvent. The solvent may be any solvent as long as it can dissolve the bisphenol compound and the allyl halide, and examples thereof include a solvent in a resin varnish described later.

In the reaction between the bisphenol compound and the allyl halide, the amount of the allyl halide to react with the bisphenol compound is such that the molar ratio of the allyl halide to the phenolic hydroxyl group of the bisphenol compound (allyl halide / phenolic hydroxyl group) is 0.3. An amount of up to 2.0 is preferable. The molar ratio of allyl halide / phenolic hydroxyl groups 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 the reaction is completed, the reaction product may be washed with water, concentrated, or the like, if necessary.

When the allyl group of the allyl etherified bisphenol compound is rearranged, an allyl group-containing bisphenol compound in which the allyl group is bonded to the benzene ring of the hydroxyphenyl group of the bisphenol compound is produced.
The rearrangement reaction of the allyl group can be carried out, for example, by heating the allyl etherified bisphenol compound. When the allyl etherified bisphenol compound is heated, 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 this benzene ring, the so-called Claisen rearrangement. A reaction occurs. The heating conditions can be, for example, 160 to 200 ° C. for 1 to 24 hours.
The heating may be carried out in the presence of a solvent. The solvent may be any solvent as long as it can dissolve the allyl etherified bisphenol compound, and examples thereof include methanol.
After the reaction, if necessary, the reaction product may be treated with a solvent, washed with water, or the like.
The allyl group-containing biphenol compound can also be produced in the same manner as described above.

(Carbonate diester)
Examples of the carbonic acid diester include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate (preferably those 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 done. Any one of these carbonic acid diesters may be used alone, or two or more thereof may be used in combination. Diphenyl carbonate is preferable because it has good reactivity with diols (alicyclic dimethanol compound, aromatic diol compound), is relatively inexpensive, and is easy to handle.

(Step 1)
A preferred embodiment of step 1 is a reaction of a carbon dioxide diester, an alicyclic dimethanol compound, and, if necessary, at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound (primary reaction). A step of reacting (secondary reaction) 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 (hereinafter referred to as a secondary reaction). , Also referred to as "step 1A").
The primary reaction and the secondary reaction are transesterification reactions, respectively. By reacting the aromatic diol compound in the secondary reaction, a carbonate resin having a phenolic hydroxyl group at the terminal hydroxyl group can be obtained.

The primary reaction is carried out, for example, by melting and mixing a carbonic acid diester, an alicyclic dimethanol compound, and an aromatic diol compound, if necessary, adding a catalyst, and maintaining a predetermined reaction temperature for a predetermined time. can.
The carbonic acid 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 the carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound (the amount of the alicyclic dimethanol compound only when the aromatic diol compound is not reacted) (carbonic acid diester / (carbonic acid diester / (). The alicyclic dimethanol compound + aromatic diol compound)) is preferably 1.05 to 3.00, more preferably 1.20 to 2.50. If the ratio of the carbonic acid diester is too low, a large amount of hydroxyl groups of the alicyclic dimethanol compound will remain in the primary reaction product, and during the secondary reaction, compounds whose terminal hydroxyl groups are not phenolic hydroxyl groups will be produced as by-products. There is a risk of If the ratio of the carbonic acid diester is too high, the amount 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 ratio of the alicyclic dimethanol compound to the total amount (100 mol%) of the alicyclic dimethanol compound and the aromatic diol compound is preferably 20 to 100 mol%, preferably 50 to 90 mol%. Is more preferable.

The catalyst is not particularly limited as long as the reaction (transesterification reaction) 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 methoxydo), alkali metals (eg lithium, sodium), alkali metal hydrogen Examples thereof include compounds (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, more preferably 0.1 to 0.0001% by mass, based on the carbonic acid diesters. If the amount of the catalyst used is more than this range, turbidity may occur in the produced resin, and if it is less than this range, the polymerization rate becomes slow and a resin with a high degree of polymerization cannot be obtained. Sometimes.

The reaction temperature of the primary reaction is preferably 130 to 250 ° C, more preferably 150 to 200 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and there is a risk that the resin cannot be obtained stably. 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 carried out while removing alcohols and phenols by-produced in the reaction (transesterification reaction) under reduced pressure.

The secondary reaction can be carried out, for example, by adding an aromatic diol compound to the primary reaction product produced by 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 compound may be used alone or in combination of two or more.
The amount of the aromatic diol compound to be reacted in the secondary reaction is preferably 5 to 80 mol%, more preferably 15 to 60 mol%, based on the carbonic acid diester (100 mol%) used in the primary reaction.

The reaction temperature of the secondary reaction is preferably 130 to 250 ° C, more preferably 170 to 230 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and there is a risk that the resin cannot be obtained stably. The reaction time may be, for example, 0.5 to 10 hours.
The secondary reaction is preferably carried out while removing alcohols and phenols by-produced in the reaction (transesterification reaction) under reduced pressure.
The degree of decompression 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 to 5 mmHg and may be 20 to 5 mmHg.
After the completion of the secondary reaction, the reaction product may be washed with water, concentrated, or the like, if necessary.

Another preferred embodiment of step 1 is a step of reacting a carbonic acid 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"). be. This reaction is a transesterification reaction.

The molar ratio of the carbonic acid diester to the aromatic diol compound (carbonic acid diester / aromatic diol compound) is preferably 0.40 to 0.99, more preferably 0.50 to 0.95.
The reaction between the carbonic acid diester and the aromatic diol compound is preferably carried out in the presence of a catalyst. Examples of the catalyst include the same catalysts as described above. The preferable range of the amount of the catalyst used is the same as described above.

The reaction between the carbonic acid diester and the aromatic diol compound can be carried out, for example, by melt-mixing the carbonic acid diester and the aromatic diol compound, adding a catalyst, and maintaining a predetermined reaction temperature for a predetermined time.
The reaction temperature is preferably 130 to 250 ° C, more preferably 170 to 230 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and there is a risk that the resin cannot be obtained stably. 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 lapse of a certain period of time.
The degree of decompression 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 to 5 mmHg and may be 20 to 5 mmHg.
After the reaction is completed, the reaction product may be washed with water, concentrated, or the like, if necessary.

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

［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 have the same meanings as described above, and the 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 an alicyclic type. An allyl group-containing carbonate resin containing a compound which is a residue derived from a dimethanol compound as a main component can be obtained.
When step 1 is step 1B, allyl containing a compound in which R ¹ and R ² in the formula (2) are residues derived from an allyl group-containing bisphenol compound or residues derived from an allyl group-containing biphenol compound as a main component, respectively. A group-containing carbonate resin is obtained.
These allyl group-containing carbonate resins may be used in combination.
It is preferable to contain the allyl group-containing carbonate resin obtained in step 1A from the viewpoint that the cured product has a lower dielectric loss tangent.

(Step 2)
In step 2, the allyl group-containing carbonate resin having a hydroxyl group at the end, which was produced in step 1, is reacted with the allyl halide. As a result, the terminal hydroxyl group (-OH) is converted to an allyl ether group (-O-CH ₂ -CH = CH ₂ ), and the allyl containing the compound in which X in the formula (1) is an allyl group as a main component. A group-containing carbonate resin is obtained.
Examples of the allyl halide include the same as described above.
Allyl etherification can be carried out in the same manner as described above.

In the reaction between an allyl group-containing carbonate resin having a hydroxyl group at the end and allyl halide, the amount of allyl halide to react with the allyl group-containing carbonate resin is the molar ratio of allyl halide to the hydroxyl group at the end of the allyl group-containing carbonate resin (the molar ratio of allyl halide to the hydroxyl group at the end of the allyl group-containing carbonate resin. The amount of allyl halide / phenolic hydroxyl group) is preferably 0.3 to 2.0. The molar ratio of allyl halide / phenolic hydroxyl groups 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 performed by heating.
Further, the cured product obtained by curing the maleimide compound using the present carbonate resin exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low heat ray expansion rate because the maleimide compound is used. In addition, because this carbonate resin is used, it has a lower dielectric constant and lower dielectric 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. be.

When the maleimide compound is cured using this carbonate resin, it is considered that the following reactions (1) to (3) occur and the compound is cured.
(1) Reaction of maleimide group and 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. The epoxy resin can be cured by heating.
When the epoxy resin is cured using the present carbonate resin, it is considered that the above-mentioned reaction (3) and the following reactions (4) to (5) occur and the epoxy resin is cured.
(4) Reaction between epoxy group and hydroxyl group.
(5) Reaction between epoxy groups.

Further, the present carbonate resin has excellent solubility in a solvent generally used for dissolving a maleimide compound or an epoxy resin. Therefore, it is possible to obtain a resin varnish in which the present carbonate resin, the maleimide compound, and, if necessary, the epoxy resin are both dissolved in a solvent.
As the solvent, a polar solvent such as methyl ethyl ketone is generally used.

The carbonate resin can be cured independently by the reaction of (3) above without being combined with a maleimide compound or an epoxy resin. 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 by itself. Therefore, it is preferable to combine it with a maleimide compound or an epoxy resin and subject it to a curing reaction.

The use of this carbonate resin is not particularly limited. For example, it may have the same use as a known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. More specific examples of applications include semiconductor encapsulation materials, resin materials for encapsulating electronic components, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, and liquid crystal color filters. Examples thereof include resin materials, paints, various coating agents, adhesives, fiber reinforced plastic (FRP) materials and the like.

≪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.
This carbonate resin functions as a maleimide curing agent. The "maleimide curing agent" means a curing agent for curing the maleimide compound.
In the present resin varnish, a part of the allyl group of the present carbonate resin and a part of the maleimide group of the maleimide compound may be in a reacted state.

When the carbonate resin contains a compound in which at least one of the two Xs in the formula (1) is a hydrogen atom, that is, when the carbonate resin contains a hydroxyl group, the carbonate resin also functions as an epoxy resin curing agent. do. The "epoxy resin curing agent" means a curing agent for curing an epoxy resin.
Therefore, a preferred embodiment of the present resin varnish contains the present carbonate resin, a maleimide compound having two or more maleimide groups, an epoxy resin, and a solvent, and the present carbonate resin contains two of the above formula (1). A resin varnish containing a compound in which at least one of X is a hydrogen atom. The resin varnish of this embodiment has more excellent dielectric properties than the case where the epoxy resin is not contained.

The present resin varnish may further contain a curing reaction catalyst.
The resin varnish may further contain components other than the 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, and bisphenol A diphenyl ether bismaleimide (for example, Yamato Kasei). BMI-4000) manufactured by Kogyo Co., Ltd., 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide (for example, BMI-5100 manufactured by Daiwa Kasei Kogyo Co., Ltd.), 4-methyl- 1,3-Phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulphon bismaleimide, 1,3- Examples thereof include bis (3-maleimide phenoxy) benzene and 1,3-bis (4-maleimide phenoxy) benzene.
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 resin varnish is preferably 10 to 300 parts by mass, more preferably 15 to 200 parts by mass, still more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the carbonate resin. When the content of the maleimide compound is not less than the lower limit of the above range, the gelation temperature of the present resin varnish can be lowered, for example, 200 ° C. or less. When the content of the maleimide compound is equal to or higher than the lower limit of the above range, the cured product of this resin varnish exhibits a higher glass transition temperature, a higher thermal decomposition temperature, a low linear expansion coefficient, a low dielectric constant, and a low dielectric loss tangent. Become.

<Solvent>
The solvent is not particularly limited as long as it dissolves the components contained in the resin varnish (the carbonate resin, the maleimide compound, the curing reaction catalyst, etc., if necessary).
A polar solvent is typically used as the solvent. Examples of the polar solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, diacetone alcohol, and cyclohexanone, N, N-dimethylformamide, and N-. Examples thereof 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, and tetrahydrofuran. Any one of these solvents may be used alone, or two or more thereof may be used in combination. Among the above, a ketone solvent is preferable, and methyl ethyl ketone is particularly preferable.

The content of the solvent in the resin varnish is appropriately set according to the solid content concentration of the resin varnish.
The solid content concentration of the present resin varnish varies depending on the application, but is preferably 20 to 80% by mass, more preferably 50 to 70% by mass.
The solid content concentration of this resin varnish is the ratio of the mass of this resin varnish excluding the solvent to the total mass of this resin varnish.

<Epoxy resin>
The epoxy resin is not particularly limited and may be a known epoxy resin, for example, a phenol novolac type epoxy resin, an orthocresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenol type epoxy resin, and the like. 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, stilben type epoxy resin, sulfur atom-containing epoxy resin, Examples thereof include a phosphorus atom-containing epoxy resin. Any one of these epoxy resins may be used alone, or two or more thereof may be used in combination.

<Curing reaction catalyst>
The curing reaction catalyst (curing accelerator) preferably contains a catalyst having an action of accelerating the reaction between the allyl group and the maleimide group (hereinafter, also referred to as "catalyst (1)"). Examples of the catalyst (1) include imidazole compounds and organic peroxides. Examples of the imidazole compound 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-cyanoethyl -2-phenylimidazole and the like can be mentioned. Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters and the like. In the dialkyl peroxide, the alkyl group may be substituted with a phenyl group or the like. Examples of such dialkyl peroxide include dicumyl peroxide.

When the carbonate resin has a hydroxyl group and the resin varnish contains an epoxy resin, the curing reaction catalyst is also referred to as a catalyst having an action of promoting the reaction between the hydroxyl group and the epoxy group (hereinafter, also 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 the phosphorus compound include triphenylphosphine, tris-2,6-dimethoxyphenylphosphine, tri-p-tolylphosphine, triphenyl phosphite and the like. Examples of the tertiary amine include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7 and the like. Examples of the imidazole compound include the same compounds as described above.

Any one of these curing reaction catalysts may be used alone or in combination of two or more.
The content of the catalyst (1) in the 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 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 present 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>
Examples of other components include inorganic fillers (for example, carbon black, glass cloth, silica, etc.), waxes, flame retardant agents, coupling agents, and other curing agents other than this carbonate resin (hereinafter, also referred to as other curing agents). , Filler, mold release agent, surface treatment agent, colorant, flexibility-imparting agent and the like. Examples of other curing agents include maleimide curing agents, epoxy resin curing agents, and the like, and conventionally known curing agents can be used. For example, examples of the maleimide curing agent include novolak-type resins such as allyl-novolak-type phenolic resins.
The content of the other curing agent in the present resin varnish is preferably 10% by mass or less, particularly preferably 0% by mass, based on the solid content (100% by mass) of the present resin varnish in terms of the effect of the present invention.
The solid content of this resin varnish is the portion of this resin varnish from which the solvent has been removed.

Examples of the filler include carbon black, crystalline silica powder, molten silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder and the like, and are crystalline. Silica powder and meltable silica powder are preferable.
Examples of the mold release agent include various waxes such as carnauba wax.
Examples of the surface treatment agent include known silane coupling agents and the like.
Examples of the colorant include carbon black and the like.
Examples of the flexibility-imparting agent include silicone resin, butadiene-acrylonitrile rubber, and the like.

<Manufacturing method of 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 carbonate resin, the maleimide compound, and the solvent, an epoxy resin, a curing reaction catalyst, and other components may be further mixed, if necessary.
The carbonate resin can be produced by the above-mentioned production method. Commercially available products can be used for the maleimide compound, the epoxy resin, the curing reaction catalyst, and other components. Mixing of each component can be carried out 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 pre-reacted. By performing a prereaction on the varnished mixture obtained by the above mixing, it is possible to suppress the precipitation of the highly crystalline maleimide compound from the resin varnish.
The reaction temperature at the time of carrying out the pre-reaction is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, still more preferably 80 to 120 ° C. If the reaction temperature is too low, the reaction will not proceed, and if it is too high, it will be difficult to control the reaction, and it will be difficult to stably obtain the desired resin varnish.

Since the present resin varnish contains the present carbonate resin and the maleimide compound, it can be cured by heating to obtain a cured product.
The heating temperature (curing temperature) for curing the resin varnish is preferably 60 to 250 ° C.
As an example of the curing operation, a method of performing pre-curing at the above-mentioned suitable temperature for 30 seconds or more and 1 hour or less, removing the solvent, and then further performing post-curing at the above-mentioned suitable temperature for 1 to 20 hours is used. Can be mentioned.

Since the maleimide compound is used in this resin varnish, the cured product of this resin varnish exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low heat ray expansion rate. In addition, since this carbonate resin is used as a curing agent for the maleimide compound, this cured product is compared with 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. It has a low dielectric constant and a low dielectric tangent.

The use of this resin varnish is not particularly limited. For example, it may have the same use as a known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. More specific examples of applications include semiconductor encapsulation materials, resin materials for encapsulating electronic components, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, and liquid crystal color filters. Examples thereof include resin materials, paints, various coating agents, adhesives, fiber reinforced plastic (FRP) materials and the like.
The cured product of this resin varnish has a low dielectric constant and a low dielectric loss tangent, and has excellent insulating properties. In addition, this cured product has a high glass transition temperature, a high thermal decomposition temperature, a low thermal expansion rate, and is excellent in heat resistance. Therefore, this resin varnish is useful as a material for manufacturing laminated boards used for electronic parts.

The relative permittivity of the cured product of this resin varnish is preferably 3.50 or less.
The dielectric loss tangent of the cured product of this resin varnish is preferably 0.008 or less.
The glass transition temperature of the cured product of this resin varnish is preferably 150 ° C. or higher.
The 5% thermal decomposition temperature of the cured product of the present resin varnish is preferably 300 ° C. or higher.
The room temperature linear expansion coefficient of the cured product of this resin varnish is preferably 100 ppm or less.
The relative permittivity, the dielectric loss tangent, the glass transition temperature, the 5% pyrolysis temperature, and the room temperature linear expansion coefficient are each measured by the methods described in Examples described later.

≪Manufacturing method of laminated board≫
In the method for producing a laminated board of the present invention, the fibrous base material is impregnated with the present resin varnish, and the fibrous base material impregnated with the present resin varnish is heated and pressed to be cured to obtain a laminated board.

The laminated board manufactured by the method for manufacturing a laminated board of the present invention includes a fiber-reinforced resin layer containing a fibrous base material and a cured product of the present resin varnish. The number of fiber-reinforced resin layers included in the laminated board may be one layer or two or more layers.
The laminated board may further include a layer other than the fiber reinforced resin layer. Examples of the other layer include a metal foil layer such as a copper foil.

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

As one embodiment of the method for manufacturing a laminated board of the present invention, the fibrous base material is impregnated with the present resin varnish and dried (solvent is removed) to obtain a prepreg, and a plurality of the prepregs are laminated as needed. If necessary, a method of further laminating a metal foil on one side or both sides of the prepreg or a laminate thereof and heating and pressurizing the metal leaf to cure the prepreg or its laminate can be mentioned.

The amount of the present resin varnish impregnated in the fibrous base material is not particularly limited. 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 above-mentioned curing temperature is preferable as the heating temperature when the fibrous substrate impregnated with the present resin varnish is heated and pressed. The pressurizing condition is preferably 2 to 20 kN / m ² .

The laminated board obtained by the method for producing a laminated board of the present invention includes 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 has a low cured product. Since it has a dielectric constant and a low dielectric loss tangent, it has excellent insulation. Further, the fiber-reinforced resin layer is also excellent in heat resistance because the cured product has a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion rate.

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 "mass%" unless otherwise specified.
The measurement method used in each of the following examples is shown below.

[Weight average molecular weight (Mw), number average molecular weight (Mn), dispersity (Mw / Mn) of resin]
Using the following GPC apparatus and column, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using polystyrene as a standard substance, and the dispersity (Mw / Mn) was determined.
GPC device: HLC8120GPC manufactured by Tosoh Corporation.
Column: TSKgel (registered trademark) G3000H + G2000H + G2000H manufactured by Tosoh Corporation.

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

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

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

[5% pyrolysis temperature]
The obtained molded product was finely pulverized and used as a measurement sample. For this measurement sample, the thermal weight loss was measured in the range of 30 to 800 ° C. at a heating rate of 10 ° C./min under an air atmosphere using a differential thermal thermal weight simultaneous measuring device (TG / DTA6300 manufactured by Seiko Instruments). The 5% thermal decomposition temperature (° C.) was determined.

[Room temperature line expansion coefficient]
The obtained molded product was processed into a size of width 5.0 mm × length 5.0 mm × thickness 1.5 mm and used as a measurement sample. For this measurement sample, the thermal expansion of the cured product was measured in the range of 30 ° C to 400 ° C at a heating rate of 2 ° C / min using a thermomechanical analyzer (TMA7100 manufactured by Hitachi High-Tech Science), and the room temperature linear expansion coefficient. (Ppm) was calculated. The room temperature linear expansion coefficient indicates the linear expansion coefficient at 30 ° C.

[Relative 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 and used as a measurement sample. For this measurement sample, the relative permittivity (ε _r ) and the dielectric loss tangent (tan δ) at a frequency of 1 GHz were determined by the cavity resonance perturbation method.

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

<Synthesis Example 2: Synthesis of diallyl bisphenol A>
In Synthesis Example 1, 1140.0 g of bisphenol A was used instead of 1000.0 g of bisphenol F, and the same operation as in Synthesis Example 1 was carried out except that the amount of methanol was changed to 912.0 g to obtain diallyl bisphenol A. rice field. The obtained diallyl bisphenol A was a liquid at room 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, and diallyl bisphenol F>
214.2 g (1.00 mol) of diphenyl carbonate and 98.1 g (0.50 mol) of tricyclodecanedimethanol were charged into a reaction vessel having a content of 1 L equipped with a thermometer, a stirrer and a cooling tube, and melted at 100 ° C. Mixed. Then, 0.02 g of a 48% KOH aqueous solution was added, the temperature was raised to 180 ° C. while paying attention to heat generation, and the reaction was carried out under normal pressure for 1 hour. Then, the mixture 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 the reaction was carried out under normal pressure for 1 hour. Then, the pressure was slowly reduced to 10 mmHg while maintaining the inside of the system at 180 ° C. Then, the temperature was raised to 220 ° C. under reduced pressure, and the reaction was carried out under reduced pressure for 2 hours. Then, 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. According to gel permeation chromatograph analysis (hereinafter, may be abbreviated as GPC), Mw is 9153, Mn is 3139, Mw / Mn is 2.916, and the content of the compound represented by the formula (1) is 97.2. %Met.

<Synthesis Example 4: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and diallyl bisphenol F>
In Synthesis Example 3, 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). Performed 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 69.6P. According to GPC, Mw was 6774, Mn was 2506, 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, tricyclodecanedimethanol, and diallyl bisphenol A>
In Synthesis Example 3, 183.0 g of diallyl bisphenol F was changed to 208.6 g (0.61 mol) of diallyl bisphenol A obtained in Synthesis Example 2, and the same operation as in Synthesis Example 3 was carried out. 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 26.1P. The GPC Mw was 9711, Mn was 3309, Mw / Mn was 2.935, and the content of the compound represented by the formula (1) was 96.5%.

<Example 1>
Curing reaction with 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 Kasei Kogyo Co., Ltd. as a maleimide compound. As a catalyst, 1.2 g of dicumyl peroxide (1% with respect to the total amount of resin) 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 glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs 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 was replaced with 47.4 g in Example 1 to obtain a molded product.

<Example 3>
Examples except that 23.7 g of BMI-2300 in Example 1 was replaced 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 in No. 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 (to the total amount of resin). 1%) 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 glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs 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 replaced with 136.3 g in Example 4, and a molded product was obtained.

<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 (to the total amount of resin). 1%) 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 glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs 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 was replaced with 45.0 g in Example 6 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 orthocresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd .: EOCN1020) Epoxy equivalent: 93.9 g of 199 g / eq) and 1.9 g of triphenylphosphine as a catalyst (2% with respect to epoxy resin) were dissolved in methyl ethyl ketone so as to have a solid content of 60% to obtain a resin varnish. rice field.
The obtained resin varnish was impregnated into glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs were stacked, press-molded at 180 ° C., and then 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 novolak resin (XPL-4437E manufactured by Gunei Chemical Industry Co., Ltd., allyl group equivalent: 145 g / eq, liquid at room temperature, viscosity at 25 ° C. measured with an E-type viscosity meter: 31 Pa · s) and a maleimide compound. 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% of the total amount of resin) are added to methyl ethyl ketone so that the solid content is 60%. To obtain a resin varnish.
The obtained resin varnish was impregnated into glass cloth (E glass) so as to have a resin content of 40%, dried at 100 ° C. for 10 minutes, and the solvent was removed to obtain a prepreg. Six of these prepregs 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, 5% pyrolysis temperature, room temperature linear expansion coefficient, relative permittivity, and 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 and 2. The measured glass transition temperature, 5% thermal decomposition temperature, room temperature linear expansion coefficient, relative permittivity, and dielectric loss tangent are the glass transition temperature and 5% thermal decomposition temperature of the cured resin varnish used for the molded product, respectively. It can be regarded as the room temperature line expansion coefficient, relative permittivity, and 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 also shown in Tables 1 and 2.

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

According to this resin varnish, a cured product having a low dielectric constant and a low dielectric loss tangent and having excellent electrical characteristics can be obtained. Further, according to the present resin varnish, a cured product having a high glass transition temperature, a high thermal decomposition temperature, a low thermal expansion rate, and excellent thermal characteristics can be obtained.
Therefore, this resin varnish and the laminated board using it are extremely useful as a highly functional polymer material, and as electrically and thermally excellent materials, a semiconductor encapsulant, an electrically insulating material, and a copper-clad laminated board are used. It can be used in a wide range of applications such as resins for varnishes, resists, resins for encapsulating electronic parts, resins for liquid crystal color filters, paints, various coating agents, adhesives, build-up laminated board materials, and FRP.

Claims (10)

An allyl group-containing carbonate resin containing a compound represented by the following formula (1) as a main component and having a weight average molecular weight of 3000 to 12000 .

[In the formula, R ¹ indicates a residue derived from a bisphenol compound, a residue derived from a biphenol compound or a residue derived from an alicyclic dimethanol compound, and the two R ^1s are different even if they are the same. Also, n represents an integer greater than or equal to 0, R ² 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 at least n R ^2s . When a part is a residue derived from the alicyclic dimethanol compound and n is 2 or more, the n R ^2s may be the same or different, respectively, and the two R ^1s and n At least a portion of the R ² contains an allyl group, where X represents a hydrogen atom or an allyl group, and the two Xs 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 R1 in the formula ( ¹ ) is a group represented by the following formula (r1), the following formula (r2) or the following formula (r3).

[In the formula, p indicates 1 or 2, and q indicates an integer of 0 to 2. ] A method for producing an allyl group-containing carbonate resin.
It comprises a step of reacting a 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, and at least a part of the diol compound is the alicyclic diethanol. A method for producing an allyl group-containing carbonate resin , which is a methanol compound, wherein at least a part of the diol compound contains an allyl group, and the weight average molecular weight of the allyl group-containing carbonate resin is 3000 to 12000 . The step of reacting the carbonic acid diester with the diol compound is
The carbonic acid diester is reacted with the alicyclic dimethanol compound, or the carbonic acid diester is associated with at least one aromatic diol compound selected from the group consisting of the alicyclic dimethanol compound and the bisphenol compound and the biphenol compound. The step according to claim 4 , wherein the reaction is carried out to obtain a primary reaction product, and 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. The method for producing an allyl group-containing carbonate resin according to the above. The fifth aspect of the present invention, wherein the molar ratio of the carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound in obtaining the primary reaction product is 1.05 to 3.00. The method for producing an allyl group-containing carbonic acid resin according to the above method. 4. The fourth aspect of the present invention further comprises a step of reacting an allyl group-containing carbonate resin having a hydroxyl group at the terminal, which is produced by the reaction of the carbonic acid diester with the diol compound, with allyl halide to convert the hydroxyl group into allyl ether. The method for producing an allyl group-containing carbonate resin according to any one of 6 to 6 . A resin varnish containing the allyl group-containing carbonate resin according to any one of claims 1 to 3 , a maleimide compound having two or more maleimide groups, and a solvent. The allyl group-containing carbonate resin contains a compound in which at least one of the two Xs in the formula (1) is a hydrogen atom.
The resin varnish according to claim 8 , further comprising an epoxy resin. A method for manufacturing a laminated board, wherein the fibrous base material is impregnated with the resin varnish according to claim 8 or 9 , and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board.