JP6947611B2 - Phenolic carbonate resin, epoxy resin curing agent, phenol carbonate resin manufacturing method, resin varnish, and laminated board manufacturing method - Google Patents

Description

The present invention relates to a phenol 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 or the like is dissolved in a solvent, drying the prepreg, and heat-pressing the prepreg alone or in combination of two or more. 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 provides a phenol carbonate resin that can be used as an epoxy resin 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 and a resin varnish that can obtain a cured product having a low dielectric constant and a low dielectric loss tangent. It is an object of the present invention to provide a method for manufacturing a laminated board using this.

［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、ｎは１以上の整数を示し、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個のＲの少なくとも一部は前記脂環式ジメタノール化合物由来の残基であり、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い。］
〔２〕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）で表される基を示し、ｎ個のＲの少なくとも一部は前記式（ｒ４）で表される基である、〔１〕のフェノールカーボネート樹脂。

［式中、Ｒ^１は、脂環式基を示す。］
〔３〕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、フェノールカーボネート樹脂の製造方法。
〔４〕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、〔３〕のフェノールカーボネート樹脂の製造方法。
〔５〕前記〔１〕または〔２〕のフェノールカーボネート樹脂と、エポキシ樹脂と、溶剤とを含む樹脂ワニス。
〔６〕前記〔５〕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] A phenol carbonate resin containing a compound represented by the following formula (1) as a main component.

[In the formula, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, the two Ars may be the same or different, and n represents an integer of 1 or more. R 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 at least a part of n R is a residue derived from the alicyclic dimethanol compound. When n is 2 or more, the n Rs may be the same or different. ]
[2] 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 is the above formula (r1) and the above formula (r1). r2), the phenol carbonate of [1] showing the group represented by the above formula (r3) or the following formula (r4), and at least a part of n R is the group represented by the above formula (r4). resin.

[In the formula, R ¹ represents an alicyclic group. ]
[3] At least one aromatic diol selected from the group consisting of a carbon dioxide diester and an alicyclic dimethanol compound, or a carbonic acid diester, an alicyclic dimethanol compound, a bisphenol compound and a biphenol compound. React with the compound to obtain the primary reaction product,
A method for producing a phenol carbonate resin, wherein the primary reaction product is reacted with at least one aromatic diol compound selected from the group consisting of bisphenol compounds and biphenol compounds.
[4] The molar ratio of the carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound when obtaining the primary reaction product is 1.05 to 3.00. 3] Method for producing phenol carbonate resin.
[5] A resin varnish containing the phenol carbonate resin of the above [1] or [2], an epoxy resin, and a solvent.
[6] A method for producing a laminated board, wherein the fibrous base material is impregnated with the resin varnish of the above [5], and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board.

According to the present invention, a phenol carbonate resin that can be used as an epoxy resin 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 that can obtain a cured product having a low dielectric constant and a low dielectric loss tangent. A varnish and a method for producing a laminated board using the varnish can be provided.

≪Phenol carbonate resin≫
The phenolic 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 carbonate resin.
The carbonate resin may be a mixture of a plurality of compounds having different values of n.
The carbonate resin contains components other than the compound represented by the formula (1) (for example, a compound represented by the formula (2) described later, a bisphenol compound, a biphenol compound, or an 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、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、ｎは１以上の整数を示し、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個のＲの少なくとも一部は前記脂環式ジメタノール化合物由来の残基であり、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い。］

[In the formula, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, the two Ars may be the same or different, and n represents an integer of 1 or more. R 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 at least a part of n R is a residue derived from the alicyclic dimethanol compound. When n is 2 or more, the n Rs may be the same or different. ]

n is preferably an integer of 1 to 50, more preferably an integer of 1 to 40, and even more preferably an integer of 1 to 35.
The average value of n is preferably a value in which the weight average molecular weight (Mw) of the carbonate resin is in the range of 3000 to 12000. More preferable Mw is as described later. 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.
A residue derived from a 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.
A residue derived from a biphenol compound is a group having a structure in which two phenolic hydroxyl groups are removed 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^１は、脂環式基を示す。］

[In the formula, R ¹ 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, tricyclodecanediyl 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] methanol. The isomers may be mixed with each other.

The two Ars in the formula (1) may be the same or different.
As Ar, a group represented by the following formula (r1), the following formula (r2), or the following formula (r3) is preferable because it is inexpensive and easily available. These groups are residues derived from bisphenol A, bisphenol F or biphenol.

At least a part of n R in the formula (1) is a residue derived from an alicyclic dimethanol compound. That is, when n is 1, R is a residue derived from an alicyclic dimethanol compound, and when n is 2 or more, part or all of n R are residues derived from an alicyclic dimethanol compound. Is. By including a residue derived from an alicyclic dimethanol compound as R, the cured product has a lower dielectric loss tangent.
When n in the formula (1) is 2 or more, the n Rs may be the same or different. For example, a part of R may be a residue derived from a bisphenol compound or a residue derived from a biphenol compound.

As R, a group represented by the above formula (r1), the above formula (r2), the above formula (r3) or the above formula (r4) is preferable because it is inexpensive and easily available. However, at least a part of n R is a group represented by the formula (r4).

The proportion of R, which is a residue derived from the alicyclic dimethanol compound (for example, a group represented by the formula (r4)), is preferably 20 to 100 mol% among all R in the carbonate resin (1). More preferably 50-90 mol%. When the proportion of R, 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.

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 equal to or less 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 hydroxyl group equivalent of this carbonate resin is preferably 500 to 3000 g / eq, more preferably 800 to 2000 g / eq. When the hydroxyl group equivalent is at least the above lower limit value, the dielectric property is more excellent. When the hydroxyl group equivalent is not more than the above upper limit value, the reactivity with the epoxy resin is more excellent.
The hydroxyl group equivalent of the carbonate resin is a value obtained by dividing the number average molecular weight (Mn) of the carbonate resin by the number of hydroxyl groups.

<Manufacturing method of this carbonate resin>
This carbonate resin is obtained by reacting a carbon dioxide diester with an alicyclic dimethanol compound, or at least one fragrance selected from the group consisting of a carbonic acid diester, an alicyclic dimethanol compound, a bisphenol compound and a biphenol compound. A primary reaction product is obtained by reacting with a group diol compound (primary reaction), and the obtained primary reaction product and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound are combined. It can be produced by reacting (secondary reaction).
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 terminal hydroxyl group bonded to Ar (phenolic hydroxyl group) can be obtained.

The alicyclic dimethanol compound, bisphenol compound, and biphenol compound are the same as described above.
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.

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 carbon dioxide 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 / ( 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), hydrogen alkali metals Examples thereof include products (for example, lithium hydride and sodium hydride), alkali metal hydroxides (for example, lithium hydroxide and sodium hydroxide), and metal halides.

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, the produced resin may become turbid, 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 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. One type of aromatic diol compound may be used alone, or two or more types may be used in combination.
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 completion of the secondary reaction, the reaction product may be washed with water, concentrated, or the like, if necessary.

Since this carbonate resin is a hydroxyl group (phenolic hydroxyl group) in which the terminal hydroxyl group is bonded to Ar, it has excellent reactivity with an epoxy group and can be used as a curing agent (epoxy resin curing agent) for curing the epoxy resin. can. The epoxy resin can be cured by heating.
Further, the cured product obtained by curing the epoxy resin using the present carbonate resin has a lower dielectric constant and a lower dielectric loss tangent than the cured product obtained by curing the epoxy resin with a phenol novolac resin. Further, the thermal characteristics such as the glass transition temperature, the thermal decomposition temperature, and the coefficient of linear thermal expansion are also sufficiently good.

When the epoxy resin is cured using this carbonate resin, it is considered that the following reactions (1) and (2) occur and the epoxy resin is cured.
(1) Reaction of epoxy group and hydroxyl group.
(2) Reaction between epoxy groups.

Further, the present carbonate resin has excellent solubility in a solvent generally used for dissolving an epoxy resin. Therefore, a resin varnish in which both the carbonate resin and the epoxy resin are dissolved in a solvent can be obtained.
As the solvent, a polar solvent such as methyl ethyl ketone is generally used.

The use of this carbonate resin is not particularly limited. For example, it may be similar to the use of 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 encapsulation of electronic parts, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, and liquid crystal color filters. Examples 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, an epoxy resin, and a solvent.
This carbonate resin functions as an epoxy resin curing agent. The "epoxy resin curing agent" means a curing agent for curing the epoxy resin.
The resin varnish may further contain a curing reaction catalyst.
The resin varnish may further contain components other than the carbonate resin, epoxy resin, solvent and curing reaction catalyst.

<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, etc. 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 include a phosphorus atom-containing epoxy resin. Any one of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination.

The content of the epoxy resin in the resin varnish is preferably such that the molar ratio (epoxy group / hydroxyl group) of the epoxy group of the epoxy resin to the hydroxyl group of the carbonate resin is 0.8 to 1.2. The epoxy group / hydroxyl group is more preferably 0.9 to 1.1, and even more preferably 0.95 to 1.05. When the epoxy group / hydroxyl group is at least the lower limit of the above range, the gelation temperature of the resin varnish can be lowered, for example, 200 ° C. or less. When the epoxy group / hydroxyl group 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 lower linear expansion coefficient, a lower dielectric constant, and a lower dielectric loss tangent. ..

<Solvent>
The solvent is not particularly limited as long as it dissolves the components contained in the resin varnish (the carbonate resin, the epoxy resin, 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, tetrahydrofuran and the like. Any one of these solvents may be used alone, or two or more of these solvents 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 the resin varnish is the ratio of the mass of the resin varnish excluding the solvent to the total mass of the resin varnish.

<Curing reaction catalyst>
The curing reaction catalyst may be any catalyst having an action of accelerating the reaction between the hydroxyl group and the epoxy group, and for example, a phosphorus compound, a tertiary amine, an imidazole compound, an organic acid metal salt, a Lewis acid, an amine complex salt and the like. Can be mentioned. 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 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.

Any one of these curing reaction catalysts may be used alone, or two or more of them may be used in combination.
The content of the curing reaction catalyst in the present resin varnish is preferably 0.1 to 5.0% by mass with respect to the epoxy resin.

<Other ingredients>
Examples of other components include inorganic fillers (for example, carbon black, glass cloth, silica, etc.), waxes, flame retardants, coupling agents, and other epoxy resin curing agents other than the present carbonate resin (hereinafter, also referred to as other curing agents). ), Filler, mold release agent, surface treatment agent, colorant, flexibility imparting agent and the like.
As the other curing agent, conventionally known epoxy resin curing agents can be used, and examples thereof include novolac type resins such as phenol novolac resin.
The content of the other curing agent in the 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 the resin varnish is the portion of the 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 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, an epoxy resin, and a solvent. When or after mixing the carbonate resin, the epoxy resin, and the solvent, a curing reaction catalyst or 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 as the epoxy resin, the curing reaction catalyst, and other components. Mixing of each component can be carried out by a conventional method.

Since the resin varnish contains the carbonate resin and the epoxy resin, it can be cured by heating to obtain a cured product.
The heating temperature (curing temperature) when curing the resin varnish is preferably 60 to 250 ° C.
As an example of the curing operation, a method of 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 performed. Can be mentioned.

The use of this resin varnish is not particularly limited. For example, it may be similar to the use of 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 encapsulation of electronic parts, electrical insulation materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, and liquid crystal color filters. Examples include resin materials, paints, various coating agents, adhesives, fiber reinforced plastic (FRP) materials and the like.

Since the cured product of this resin varnish uses this carbonate resin as an epoxy resin curing agent, it has a low dielectric constant, a low dielectric loss tangent, and is excellent in insulating properties. In addition, this cured product has a high glass transition temperature, a high thermal decomposition temperature, a low coefficient of thermal expansion, 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 the present 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 normal temperature linear expansion coefficient of the cured product of this resin varnish is preferably 100 ppm or less.
The relative permittivity, dielectric loss tangent, glass transition temperature, 5% thermal decomposition temperature, and 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 resin varnish, and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board.

The laminated board produced 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. 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 fibers, carbon fibers, ceramic fibers and stainless fibers; natural fibers such as cotton, linen and paper; synthetic organic fibers 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 producing a laminated board of the present invention, the fibrous base material is impregnated with the resin varnish and dried (removing the solvent) 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 prepreg or a laminate thereof to cure the prepreg.

The amount of the 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 heating temperature at the time of heating and pressurizing the fibrous base material impregnated with the resin varnish is preferably the above-mentioned curing temperature. 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 insulating properties. 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 coefficient of thermal expansion.

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 methods used in each of the following examples are 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: HLC8120 GPC manufactured by Tosoh Corporation.
Column: TSKgel (registered trademark) G3000H + G2000H + G2000H manufactured by Tosoh Corporation.

[Resin 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 to prepare a measurement sample. For this measurement sample, tan δ was measured in the range of 30 ° C. to 400 ° C. at a heating 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 thermogravimetric weight loss was measured in the range of 30 to 800 ° C. at a heating rate of 10 ° C./min in an air atmosphere using a differential thermogravimetric simultaneous measuring device (TG / DTA6300 manufactured by Seiko Instruments Inc.). The 5% thermal decomposition temperature (° C.) was determined.

[Normal 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 to prepare 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 Co., Ltd.), and the coefficient of linear thermal expansion was measured. (Ppm) was determined. The coefficient of linear expansion at room temperature indicates the coefficient of linear expansion 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 to prepare 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 carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and bisphenol F>
375.0 g (1.75 mol) of diphenyl carbonate and 171.8 g (0.88 mol) of tricyclodecanedimethanol were charged into a 1 L reaction vessel equipped with a thermometer, a stirrer and a cooling tube, and melted at 100 ° C. Mixed. Then, 0.04 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., 213.6 g (1.07 mol) of bisphenol F (BPF-SG manufactured by Gun Ei Chemical Industry Co., Ltd.) 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 a carbonate resin containing an alicyclic skeleton. The softening point of this resin was 101.9 ° C., and the melt viscosity at 150 ° C. was 37.6P. According to gel permeation chromatography analysis (hereinafter, may be abbreviated as GPC), Mw is 4751, Mn is 2419, Mw / Mn is 1.964, and the content of the compound represented by the formula (1) is 96.3. %Met. The hydroxyl group equivalent (g / eq) of this resin was 1209.5, which is half of Mn.

<Synthesis Example 2: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and bisphenol F>
A 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 63.2P. According to GPC, Mw was 5617, Mn was 2973, Mw / Mn was 1.890, and the content of the compound represented by the formula (1) was 97.1%. The hydroxyl group equivalent of this resin was 1486.5, which is half of Mn.

<Example 1>
16. 100 g of the carbonate resin (hydroxyl equivalent: 1209.5 g / eq) synthesized in Synthesis Example 1 and orthocresol novolac type epoxy resin (EOCN1020 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 199 g / eq) as the epoxy resin. 5 g and 2.3 g of triphenylphosphine as a curing reaction catalyst (2% with respect to the total amount of resin) were 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 and 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. The resin content indicates the ratio of the resin (cured product) to the total mass of the molded product.

<Example 2>
Except that 24.0 g of phenol biphenylene type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 290 g / eq) was used instead of 16.5 g of orthocresol novolac type epoxy resin in Example 1. A resin varnish was prepared in the same manner as in Example 1 to obtain a molded product.

<Example 3>
In Example 1, instead of 16.5 g of orthocresol novolac type epoxy resin, 16. A resin varnish was prepared in the same manner as in Example 1 except that 7 g was used, and a molded product was obtained.

<Example 4>
100 g of the carbonate resin (hydroxyl equivalent: 1486.5 g / eq) synthesized in Synthesis Example 2 and 13.4 g of the orthocresol novolac type epoxy resin (EOCN1020 manufactured by Nippon Kayakusha, epoxy equivalent: 199 g / eq). 2.3 g (2% with respect to the total amount of resin) of triphenylphosphine as a curing reaction catalyst 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 and 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.

<Example 5>
Except that 19.5 g of phenol biphenylene type epoxy resin (NC-3000H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 290 g / eq) was used instead of 13.4 g of orthocresol novolac type epoxy resin in Example 4. A resin varnish was prepared in the same manner as in Example 4 to obtain a molded product.

<Example 6>
Example 4 except that 13.6 g of an alicyclic epoxy resin (CEL2021P manufactured by Daicel Co., Ltd., epoxy equivalent: 201.7 g / eq) was used instead of 16.5 g of the orthocresol novolac type epoxy resin. A resin varnish was prepared in the same manner as in No. 4 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, 93.9 g of epoxy equivalent (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 and 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.

The glass transition temperature, 5% thermal decomposition temperature, room temperature linear expansion coefficient, relative permittivity, and dielectric loss tangent were measured for the molded products obtained in Examples 1 to 6 and Comparative Example 1. The results are shown in Tables 1-2. 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 (carbonate resin or phenol novolac resin) and epoxy resin used in each example are also shown in Tables 1 and 2.

The molded products of Examples 1 to 6 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 coefficient of linear expansion at room temperature 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 6.

According to this resin varnish, a cured product having a low dielectric constant and a low dielectric loss tangent and 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 the same 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 laminate. It can be used in a wide range of applications such as resin for resin, resist, resin for encapsulating electronic parts, resin for liquid crystal color filter, paint, various coating agents, adhesive, build-up laminated board material, FRP and the like.

Claims (7)

Look-containing compound represented by the following formula (1) as a main component, a phenolic carbonate resin weight average molecular weight of from 3,000 to 12,000.

[In the formula, Ar represents a residue derived from a bisphenol compound or a residue derived from a biphenol compound, the two Ars may be the same or different, and n represents an integer of 1 or more. R 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 at least a part of n R is a residue derived from the alicyclic dimethanol compound. When n is 2 or more, the n Rs may be the same or different. ] 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 is the above formula (r1), the above formula (r2), and the like. The phenolic carbonate resin according to claim 1, which represents a group represented by the formula (r3) or the following formula (r4), and at least a part of n Rs is a group represented by the formula (r4). ..

[In the formula, R ¹ represents an alicyclic group. ] An epoxy resin curing agent containing the phenolic carbonate resin according to claim 1 or 2. A carbonic acid diester is reacted with an alicyclic dimethanol compound, or at least one aromatic diol compound selected from the group consisting of a carbonic acid diester, an alicyclic dimethanol compound, and a bisphenol compound and a biphenol compound. React to obtain the primary reaction product,
And said primary reaction product is reacted with at least one aromatic diol compound selected from the group consisting of bisphenol compounds and biphenol compounds, the weight average molecular weight of Ru to obtain a phenolic carbonate resin is from 3000 to 12000, phenolic carbonate resin Manufacturing method. According to claim 4 , the molar ratio of the carbonic acid diester to the total amount of the alicyclic dimethanol compound and the aromatic diol compound when obtaining the primary reaction product is 1.05 to 3.00. The method for producing a phenol carbonate resin according to the above. A resin varnish containing the phenol carbonate resin according to claim 1 or 2, an epoxy resin, and a solvent. A method for producing a laminated board, wherein the fibrous base material is impregnated with the resin varnish according to claim 6 , and the fibrous base material impregnated with the resin varnish is heated and pressed to be cured to obtain a laminated board.