TW201922841A - Allyl group-containing carbonate resin, manufacturing method thereof, resin varnish, and manufacturing method of laminated sheet - Google Patents

Abstract

An allyl group-containing carbonate resin includes a compound represented by the following formula (1) as the major component. In the formula, R1 represents a residual group derived from a bisphenol compound, a residual group derived from a biphenol compound or a residual group derived from an alicyclic dimethanol compound, n represents an integer of 0 or more, R2 represents a residual group derived from a bisphenol compound, a residual group derived from a biphenol compound or a residual group derived from an alicyclic dimethanol compound, at least a part of the two R1s and n R2(s) contain an allyl group, and X represents a hydrogen atom or an allyl group.

Description

Allyl carbonate-containing resin, manufacturing method thereof, resin varnish, and manufacturing method of laminated board

FIELD OF THE INVENTION The present invention relates to an allyl carbonate-containing resin, a method for producing the same, a resin varnish, and a method for producing a laminated board.

BACKGROUND OF THE INVENTION Conventionally, epoxy resin is used for components used in electronic products, such as insulating laminated boards or laminated boards (copper-clad laminated boards) with copper foil laminated on one or both sides. Laminated boards are manufactured, for example, by impregnating resinous varnishes, such as epoxy resins and hardeners, which have been dissolved in a solvent, into a fibrous substrate such as glass cloth, drying them to make prepregs, and separately or overlapping them Tablets are manufactured by hot pressing. In terms of hardeners for epoxy resins, phenol novolac resins of phenol and formaldehyde are widely used.

In recent years, in the pursuit of high performance of electronic products, resins constituting laminated boards have been sought for further low dielectric constant and low dielectric tangent. Although the electrical properties (low dielectric constant, low dielectric tangent) of hardened epoxy resin hardened by phenol novolac resin can meet the grade required for general-purpose electronic products, it is difficult to meet the requirements for high-performance electronic products (wisdom Mobile phones, tablets, etc.).

A conventional proposal uses a difunctional phenylene ether oligomer as an epoxy resin hardener (Patent Document 1). It is said that by using this epoxy resin hardener, an epoxy resin hardened | cured material excellent in electrical characteristics can be obtained.
However, the hardened | cured material using the epoxy resin hardening | curing agent of patent document 1 is still not sufficiently low.
Prior technical literature Patent literature

[Patent Document 1] Japanese Patent Laid-Open No. 2004-224860

SUMMARY OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to provide an allyl carbonate-containing resin which can be used as a cis-butene diimide hardener, and which can obtain a hardened product having a low dielectric constant and a low dielectric tangent, and an A manufacturing method and a resin varnish capable of obtaining a hardened product having a low dielectric constant and a low dielectric tangent, and a manufacturing method of a laminated board using the same.

Means for Solving the Problems The present invention has the following aspects.
[1] An allyl carbonate-containing resin containing, as a main component, a compound represented by the following formula (1):
[Chemical Formula 1]

[In the formula, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound, or a residue derived from an alicyclic dimethanol compound, and two R ¹ may be the same or different from each other, and n represents An integer of 0 or more, 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. When n is 2 or more, n R ² may be each The same or different from each other, at least a part of the two R ¹ and n R ² contains an allyl group, X represents a hydrogen atom or an allyl group, and the two Xs may be the same or different from each other].
[2] The allyl carbonate-containing resin according to [1], wherein R ¹ in the aforementioned formula (1) is a residue derived from an allyl-containing bisphenol compound or an allyl-containing biphenol Compound residues.
[3] The allyl carbonate-containing resin according to [2], wherein R ¹ in the foregoing formula (1) is a group represented by the following formula (r1), the following formula (r2), or the following formula (r3):
[Chemical Formula 2]

[In the formula, p represents 1 or 2 and q represents an integer of 0 to 2].
[4] The allyl carbonate-containing resin according to any one of [1] to [3], wherein at least a part of the n R ² in the aforementioned formula (1) is a residue derived from an alicyclic dimethanol compound base.
[5] A method for producing an allyl carbonate-containing resin, comprising: making a carbonic acid diester and at least one kind selected from the group consisting of a bisphenol compound, a biphenol compound, and an alicyclic dimethanol compound; A step of reacting an alcohol compound, and at least a part of the aforementioned diol compound contains an allyl group.
[6] The method for producing an allyl carbonate-containing resin according to [5], wherein the aforementioned step of reacting the carbonate with the aforementioned diol compound is:
Reacting a carbonic acid diester with an alicyclic dimethanol compound or reacting a carbonic acid diester, an alicyclic dimethanol compound, and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound Reacting to obtain a primary reaction product, and reacting the aforementioned primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound;
Or department:
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.
[7] The method for producing an allyl carbonate-containing resin according to [6], in which, when the aforementioned primary reaction product is obtained, the total of the carbonic acid diester to the alicyclic dimethanol compound and the aromatic diol compound The molar ratio is 1.05 ~ 3.00.
[8] The method for producing an allyl carbonate-containing resin as described in [6] or [7], further comprising the step of: making a terminal end which has been generated by the reaction of the aforementioned carbonate and the aforementioned diol compound a hydroxyl group A step of reacting the allyl carbonate-containing resin with halogenated propylene to allyl etherify the aforementioned hydroxyl group.
[9] A resin varnish comprising: an allyl carbonate-containing resin according to any one of [1] to [4], and maleimide diimide having two or more maleimide diimide groups Compounds and solvents.
[10] The resin varnish according to [9], wherein the allyl carbonate-containing resin includes a compound in which at least one of two X in the formula (1) is a hydrogen atom, and the resin varnish further includes an epoxy resin. .
[11] A method for manufacturing a laminated board, in which a resin varnish such as [9] or [10] is impregnated into a fibrous base material, and the fibrous base material impregnated with the resin varnish is heated and pressurized to make it Hardened to obtain a laminated board.
Invention effect

According to the present invention, an allyl carbonate-containing resin and a method for manufacturing the same can be provided. The allyl carbonate-containing resin can be used as a maleimide diimide hardener, and a low dielectric constant, low Dielectric tangent hardened product, and resin varnish which can provide hardened product with low dielectric constant and low dielectric tangent, and method for manufacturing laminated board using the same.

Detailed description of the preferred embodiment (allyl carbonate resin)
The allyl carbonate-containing 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" means a component having the highest content among the components constituting the present carbonate resin.
The compound represented by formula (1) may be a mixture of a plurality of compounds having different n values.
The carbonate resin may contain 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). These components may be raw materials used in the production of this carbonate resin or by-products produced during production.
The content of the compound represented by formula (1) in the present carbonate resin is preferably 80% by mass or more, and more preferably 90% by mass or more relative to the total mass of the carbonate resin. The upper limit of the content is not particularly limited, and may be 100% by mass. The content of the compound represented by the formula (1) can be measured by gel permeation chromatography (GPC).

[Chemical Formula 3]

[In the formula, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound, or a residue derived from an alicyclic dimethanol compound, and two R ¹ may be the same or different from each other, and n represents An integer of 0 or more, 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. When n is 2 or more, n R ² may be each The same or different from each other, at least a part of the two R ¹ and n R ² contains an allyl group, X represents a hydrogen atom or an allyl group, and two X's may be the same or different from each other. ]

n is preferably an integer from 0 to 50, an integer from 0 to 40 is preferred, and an integer from 0 to 35 is more preferred.
The average value of n is preferably a value that allows the weight average molecular weight (Mw) of the carbonate resin to be in the range of 3000 to 12000. The preferred Mw is described later. The larger the average value of n, the higher the Mw.

The bisphenol compound is a compound having two hydroxyphenyl groups bonded through a linking group. The hydroxyphenyl group may have a substituent.
The residue derived from the bisphenol compound is a structure in which two phenolic hydroxyl groups are removed from the bisphenol compound. That is, it is a structure in which two phenyl groups which may have a substituent are bonded through a linking group.
Examples of the substituent include allyl, alkyl, and the like. The number of substituents may be 1 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 hydroxyphenyl of these bisphenol compounds. An allyl-containing bisphenol compound or the like is bonded (substituted) to at least one of the allyl groups. Allyl is bonded to the benzene ring of hydroxyphenyl.

A biphenol compound is a compound having two hydroxyphenyl groups directly bonded. The hydroxyphenyl group may have a substituent.
The residue derived from the biphenol compound is a structure in which two phenolic hydroxyl groups are removed from the biphenol compound. That is, a biphenyl group having a substituent.
Examples of the substituent include an allyl group, a halogen atom, and an alkyl group. The number of substituents may be 1 or may be 2 or more.
Specific examples of the biphenol compound include biphenol, halogenated biphenol, alkyl biphenol, and allyl (substituted) allyl-containing biphenol in which at least one of the hydroxyphenyl groups of the biphenol compound is bonded. Compounds etc. Allyl is bonded to the benzene ring of hydroxyphenyl.

An alicyclic dimethanol compound is a compound which has an alicyclic group and two methanol groups (-CH ₂ OH) bonded to an 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 base represented by the following formula (r4) can be given.

[Chemical Formula 4]

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

The alicyclic group may be a monocyclic structure or a polycyclic structure. The alicyclic group is preferably not unsaturated. The carbon number of the alicyclic group is preferably 6 to 20, and more preferably 8 to 15.
Specific examples of the alicyclic group include cyclohexyl, tricyclodecanediyl, perhydro-1,4; 5,8-naphthyl-2,3-diyl, and bicyclic [2.2.1] heptane- 2,3-diyl 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-bis (hydroxymethyl) -perhydro-1,4: 5,8-di Methylnaphthalene, trans-2,3-bis (hydroxymethyl) bicyclo [2.2.1] heptane, alicyclic groups of these alicyclic dimethanol compounds are bonded (substituted) with allyl groups Allyl-containing alicyclic dimethanol compounds and the like. It is also possible to mix the individual isomers.

In formula (1), at least a part of two R ¹ and n R ² contains an allyl group. That is, at least a part of the two R ¹ and n R ² is a residue derived from an allyl-containing bisphenol compound, a residue derived from an allyl-containing biphenol compound, or an allyl-containing compound Residues of alicyclic dimethanol compounds. Thereby, this carbonate resin can be used as a maleimide hardening | curing agent.
One of the two R ¹ and n R ² portions may also be free of allyl groups.
Relative to the total amount of all R ¹ and R ^{2 in} the carbonate resin, the total ratio of allyl-containing R ¹ and allyl-containing R ² is preferably 2 to 80 mole%, and 5 to 50 moles. Ear% is better.

The two R ¹ in formula (1) may be the same or different from each other.
R ^{1 is} preferably a residue derived from an allyl-containing bisphenol compound or a residue derived from an allyl-containing biphenol compound. In this case, when X in the formula (1) is a hydrogen atom, OX is a phenolic hydroxyl group. The phenolic hydroxyl group has excellent reactivity with epoxy resin. In addition, the reactivity (reactivity with halogenated propylene) of the phenolic hydroxyl group during allyl etherification is also good.
In terms of residues derived from the allyl-containing bisphenol compound or residues derived from the allyl-containing biphenol compound, the following formula (r1), (r2) or a group represented by the following formula (r3) is preferred. These groups are residues derived from allyl-containing bisphenol A, residues derived from allyl-containing bisphenol F, or residues derived from allyl-containing biphenol compounds.

[Chemical Formula 5]

In the formula, p represents 1 or 2, and q represents an integer of 0 to 2.
In terms of p, 1 is preferred. In terms of q, 1 is preferred.

When n in Formula (1) is 2 or more, n R ² may be the same or different from each other.
To the point that the hardened material can be a lower dielectric tangent, at least a part of the n R ² in formula (1) is a residue derived from an alicyclic dimethanol compound, that is, a group represented by formula (r4) Better. When n is 1, R ² is preferably a residue derived from an alicyclic dimethanol compound. When n is 2 or more, at least one of n R ² is an alicyclic dimethanol compound. Residues are preferred.
A part of the n R ² may also be a residue derived from a bisphenol compound or a residue derived from a biphenol compound. The residue derived from the bisphenol compound or the residue derived from the biphenol compound may be used with or without the allyl group.

Relative to the total amount of all R ^{2 in} the carbonate resin, the ratio of R ² of the residue derived from the alicyclic dimethanol compound is preferably 20 to 100 mole%, and more preferably 50 to 90 mole%. If the ratio of R ² of the residue derived from the alicyclic dimethanol compound is above the aforementioned lower limit value, a hardened product having a lower dielectric tangent can be obtained.

In the formula (1), two X's may each be a hydrogen atom or an allyl group.
The carbonate resin may include a compound in which at least one of two X in the formula (1) is a hydrogen atom. In this case, this carbonate resin can also be used as an epoxy resin hardener.
When this carbonate resin is used as an epoxy resin hardener, the ratio of the hydrogen atom X is preferably 50 to 100 mole%, and more preferably 80 to 100 mole% relative to the total amount of all X in the carbonate resin. . When the ratio of the hydrogen atom X is at least the aforementioned lower limit value, the reactivity with the epoxy resin and the heat resistance of the cured product are more excellent.

The softening point of this carbonate resin is preferably 70 to 130 ° C, and more preferably 90 to 120 ° C. If the softening point is above the aforementioned lower limit value, the blocking resistance of the resin is better. If the softening point is below the aforementioned upper limit, the fluidity will be better.
The softening point can be measured in accordance with JIS K 6910.

The melting viscosity of this carbonate resin at 150 ° C is preferably 10P ~ 100P, and 30P ~ 80P is more preferable. If the melt viscosity is above the aforementioned lower limit value, the blocking resistance of the resin is better. When melt viscosity is below the said upper limit, it will be excellent in fluidity | liquidity.
The melt viscosity can be measured according to the measurement method described in the examples described later.

The weight average molecular weight (Mw) of the carbonate resin is preferably from 3000 to 12,000, and more preferably from 5,000 to 10,000. If Mw is above the aforementioned lower limit value, the blocking resistance of the resin will be better. When Mw is below the above-mentioned upper limit, the fluidity is better.
The Mw of this carbonate resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The allyl equivalent of the carbonate resin is preferably 500 to 3000 g / eq, and more preferably 800 to 2000 g / eq. When the allyl equivalent is more than the aforementioned lower limit value, the dielectric characteristics are better. If the allyl equivalent is below the aforementioned upper limit value, the reactivity with the maleimide compound is better.
The allyl equivalent of this carbonate resin is the number average molecular weight (Mn) of this carbonate resin divided by the number of allyl groups. The Mn of this carbonate resin is a value measured by GPC using polystyrene as a standard substance.

＜ Manufacturing method of this carbonate resin ＞
This carbonate resin can be manufactured according to the manufacturing method which has the following process 1, for example. After step 1, step 2 can also be performed as needed.
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 carbonate-containing resin having a hydroxyl group at the end generated in step 1 with a halogenated propylene to etherify the aforementioned hydroxyallyl group.

(Diol compound)
The bisphenol compound, biphenol compound, and alicyclic dimethanol compound are the same as those 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 includes at least one selected from the group consisting of an allyl-containing bisphenol compound, an allyl-containing biphenol compound, and an allyl-containing alicyclic dimethanol compound. One.

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

Examples of the halogenated propylene include chlorinated propylene, brominated propylene, fluorinated propylene, and iodized propylene. From a cheap point of view, chlorinated propylene is preferred.
The reaction of the bisphenol compound with the halogenated propylene (allyl etherification) is preferably performed 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 azobicyclononene, azobicycloundecene, and triethylamine, sodium tertiary butoxide, potassium tertiary butoxide, Lithium diisopropylamine, silicon-basic amine, lithium tertiary butoxide, etc.

The reaction of the bisphenol compound and the halogenated propylene can also be performed in the presence of a solvent.
The solvent may be any solvent that can dissolve a bisphenol compound and a halogenated propylene, and examples thereof include solvents in a resin varnish described later.

In the reaction between a bisphenol compound and a halogenated propylene, the amount of the halogenated propylene reacted with the bisphenol compound makes the molar ratio of the halogenated propylene to the phenolic hydroxyl group in the bisphenol compound (halogenated propylene / phenolic hydroxyl group) be 0.3 to 2.0 Better. The molar ratio of the halogenated propylene / phenolic hydroxyl group is preferably 1.0 to 1.5.
The amount of the catalyst used is preferably 0.7 to 1.3 times the mole compared to the mole of the halogenated propylene.
The reaction temperature may be, for example, 10 to 150 ° C. The reaction time may be, for example, 1 to 30 hours.
After completion of the reaction, the reaction product may be subjected to treatment such as washing with water, concentration, etc., as necessary.

Once the allyl groups of the allyl etherified bisphenol compound are rearranged, an allyl-containing bisphenol compound having an allyl group bonded to a hydroxyphenylbenzene ring in the bisphenol compound is formed.
The rearrangement reaction of allyl groups can be carried out, for example, by heating the bisphenol compound etherified with allyl groups. Upon heating the allyl etherified bisphenol compound, the allyl ether group (-O-CH ₂ -CH = CH ₂ ) bonded to the phenyl ring will be rearranged to the phenyl ring. Ortho or para is the so-called Clesen rearrangement reaction. The heating condition may be, for example, 160 to 200 ° C. for 1 to 24 hours.
Heating can also be performed in the presence of a solvent. The solvent may be any bisphenol compound capable of dissolving allyl etherification, and examples thereof include methanol.
After the reaction, the reaction product may be subjected to solvent removal, water washing and other treatments as required.
The allyl-containing biphenol compound can also be produced 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), and alkylene carbonates having a carbon number of 1 to 4 (e.g., carbonic acid Ethylene glycol), diphenyl carbonate, and the like. These carbonic acid diesters may be used singly or in combination of two or more kinds. From the viewpoint of good reactivity with diols (alicyclic dimethanol compound, aromatic dimethanol compound), relatively low cost, and easy handling, diphenyl carbonate is preferred.

(step 1)
A suitable aspect of step 1 is: reacting a carbonic acid diester with an alicyclic dimethanol compound and optionally at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound (one reaction) ) A step of obtaining a primary reaction product, reacting the obtained primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound (secondary reaction) (hereinafter referred to as "Step 1A").
Each of the primary reaction and the secondary reaction is a transesterification reaction. By reacting the aromatic diol compound by a secondary reaction, a carbonate resin having a terminal hydroxy group as a phenolic hydroxy group can be obtained.

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

Mole of carbonic acid diester relative to the total amount of alicyclic dimethanol compound and aromatic diol compound in a single reaction (only the amount of alicyclic dimethanol compound if aromatic diol compound is not reacted) The ratio (carbonate diester / (alicyclic dimethanol compound + aromatic diol compound)) is preferably 1.05 to 3.00, and more preferably 1.20 to 2.50. If the ratio of the carbonic acid diester is too low, the hydroxyl groups of the alicyclic dimethanol compound or a large amount remain in the primary reaction product, and the secondary hydroxyl non-phenolic hydroxyl compound may be by-produced during the secondary reaction. If the ratio of the carbonic acid diester is too high, the amount of the aromatic diol compound used in the secondary reaction will increase, and the dielectric tangent reduction effect obtained from the residue structure of the alicyclic dimethanol compound may be insufficient.

In one reaction, the ratio of the alicyclic dimethanol compound to the total amount of the alicyclic dimethanol compound and the aromatic diol compound (100 mol%) is preferably 20 to 100 mol%, more preferably 50 ~ 90 Mol%.

The catalyst is not particularly limited as long as the reaction (transesterification reaction) can proceed. Specific examples include sodium hydroxide, potassium hydroxide, magnesium metal, alkyl zinc compounds (such as di-n-butyl zinc), lithium hydroxide, lithium acetate, titanium esters (such as tetra-n-butyl titanium), zinc oxide, and oxide. Lead, manganese dioxide, Tetra-alkyl-orthotitanate, zinc acetate, antimony oxide, germanium oxide, various alkoxides (e.g. potassium tertiary butoxide, sodium methoxide), alkali metals (e.g. Lithium, sodium), alkali metal hydrides (such as lithium hydride, sodium hydride), alkali metal hydroxides (such as lithium hydroxide or sodium hydroxide), metal halides, and the like.

The amount of the catalyst used is preferably 1.0 to 0.00001% by mass, and more preferably 0.1 to 0.0001% by mass relative to the carbonic acid diester. If the amount of the catalyst used is more than this range, the resulting resin will be turbid. If it is less than this range, the polymerization rate will be slow, and a resin with a high degree of polymerization may not be obtained.

The reaction temperature of the primary reaction is preferably 130 to 250 ° C, and more preferably 150 to 200 ° C. If the reaction temperature is too low, the reaction cannot progress, and if it is too high, it is difficult to control the reaction, and the resin may not be customizable. The reaction time may be, for example, 0.5 to 10 hours.
The primary reaction can be carried out under normal pressure or under reduced pressure. The primary reaction may be performed while removing alcohols or phenols produced as a by-product in the reaction (transesterification reaction) under reduced pressure.

The secondary reaction can be performed, for example, by adding an aromatic diol compound to the primary reaction product generated in the primary reaction and maintaining the predetermined reaction temperature for a predetermined time.
The aromatic diol compound used in the secondary reaction may be the same as or different from the aromatic diol compound used in the primary reaction. The aromatic diol compounds may be used singly or in combination of two or more kinds.
The amount of the aromatic diol compound used in the secondary reaction is preferably 5 to 80 mol% relative to the carbonic acid diester (100 mol%) used in the primary reaction. good.

The reaction temperature of the secondary reaction is preferably 130 to 250 ° C, and more preferably 170 to 230 ° C. If the reaction temperature is too low, the reaction cannot progress, and if it is too high, it is difficult to control the reaction, and the resin may not be customizable. The reaction time may be, for example, 0.5 to 10 hours.
The secondary reaction may be performed while removing alcohols or phenols produced as a by-product in the reaction (transesterification reaction) under reduced pressure, and at the same time.
The degree of reduced pressure in the secondary reaction is not particularly limited as long as it can remove alcohols or phenols produced as a by-product in the reaction under reduced pressure. For example, it may be 80 to 5 mmHg or 20 to 5 mmHg.
After the secondary reaction is completed, the reaction product may be washed and concentrated according to needs.

Another suitable aspect 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"). 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, and more preferably 0.50 to 0.95.
The reaction of the carbonic acid diester and the aromatic diol compound is preferably performed in the presence of a catalyst. The catalyst may be the same as described above. The appropriate range of the amount of the catalyst used is also the same as described above.

The reaction of the carbonic acid diester and the aromatic diol compound can be performed, for example, by melt-mixing the carbonic acid diester and the aromatic diol compound, adding a catalyst, and maintaining the predetermined reaction temperature for a predetermined time.
The reaction temperature is preferably 130 to 250 ° C, and more preferably 170 to 230 ° C. If the reaction temperature is too low, the reaction cannot progress, and if it is too high, it is difficult to control the reaction, and the resin may not be customizable. The reaction time may be, for example, 0.5 to 10 hours.
The reaction is preferably carried out while removing by-produced alcohols or phenols under reduced pressure. It is also possible to carry out the reaction under normal pressure at the beginning of the reaction and reduce the pressure after a certain period of time.
The degree of reduced pressure in the reaction is not particularly limited as long as alcohols or phenols produced as by-products in the reaction can be removed under reduced pressure. For example, it may be 80 to 5 mmHg or 20 to 5 mmHg.
After the reaction is completed, the reaction product may be washed, and concentrated, if necessary.

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

[Chemical Formula 6]

[In the formula, the definitions of R ¹ , n, and R ² are the same as those described above, and preferred embodiments are also the same. ]

In the case where Step 1 is Step 1A, R ¹ in the formula (2) can be prepared to include a residue derived from an allyl-containing bisphenol compound or a residue derived from an allyl-containing biphenol compound and Allyl carbonate-containing resin having at least a part of R ² as a main component of a compound derived from a residue of an alicyclic dimethanol compound.
In the case where Step 1 is Step 1B, R ¹ and R ² in Formula (2) can be prepared each containing a residue derived from an allyl-containing bisphenol compound or an allyl-containing biphenol compound. Allyl carbonate-containing resin as a main component of the residue compound.
These allyl carbonate-containing resins may be used in combination.
From the point that the hardened product can have a lower dielectric tangent, it is preferable to include the allyl carbonate-containing resin prepared in step 1A.

(Step 2)
In step 2, the allyl carbonate-containing resin having a hydroxyl group at the end generated in step 1 is reacted with a halogenated propylene. Thereby, a terminal hydroxyl group (-OH) can be converted into an allyl ether group (-O-CH ₂ -CH = CH ₂ ), and a compound containing X as an allyl group in the aforementioned formula (1) can be obtained as a main component Allyl carbonate resin.
The halogenated propylene may be the same as described above.
Allyl etherification can be performed in the same manner as described above.

The amount of halogenated propylene reacted with the allyl carbonate-containing resin in the reaction of the allyl carbonate-containing resin with a hydroxyl group at the end,
The molar ratio (halogenated propylene / phenolic hydroxyl group) of the halogenated propylene containing the terminal hydroxyl group of the allyl carbonate resin is preferably 0.3 to 2.0. The mole of the halogenated propylene / phenolic hydroxyl group is preferably 1.0 to 1.5.

Since this carbonate resin has an allyl group, it can be used as a hardener (maleimide hardener) for hardening a maleimide compound. The hardening of the maleimide compound can be performed by heating.
In addition, the cured product obtained by curing the maleimide compound using this carbonate resin exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion coefficient because a maleimide compound is used. .
In addition, since this carbonate resin is used, compared with a hardened product obtained by hardening a maleimide compound with an allylphenol resin or a hardened product obtained by hardening an epoxy resin with a novolac resin, Low dielectric constant, low dielectric tangent.

When the maleic acid compound is used to harden the maleimide compound, the following reactions (1) to (3) occur and harden.
(1) Reaction of cis-butenylimino group and allyl group.
(2) Reaction of the cis-butene diamidino groups with each other.
(3) Allyl groups react with each other.

When this carbonate resin has a hydroxyl group (when X is a hydrogen atom), this carbonate resin can be used as a hardener (epoxy resin hardener) for hardening an epoxy resin. The hardening of the epoxy resin can be performed by heating.
When the present epoxy resin is used to harden an epoxy resin, it is estimated that the reaction in the above (3) and the following reactions (4) to (5) will occur to harden.
(4) Reaction of epoxy group and hydroxyl group.
(5) Reaction of epoxy groups with each other.

Furthermore, the carbonate resin has good solubility in a solvent generally used for dissolving a maleimide compound or an epoxy resin. Therefore, a resin varnish in which the carbonate resin and the maleimide compound are dissolved together with the epoxy resin, if necessary, can be obtained.
The aforementioned solvent is generally a polar substance such as methyl ethyl ketone.

In addition, even if the present carbonate resin is not combined with a cis butane diimide compound and an epoxy resin, it can still be hardened by the reaction of (3) above. However, by combining a maleimide compound or an epoxy resin, it is possible to reduce the curing temperature and improve thermal characteristics such as glass transition temperature, as compared with the case of curing alone. Therefore, it is suitable to be combined with a maleimide compound or an epoxy resin and supplied to a curing reaction.

The use of the carbonate resin is not particularly limited. For example, it can be used for the same purpose as a well-known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. Examples of more specific applications include semiconductor sealing materials, resin materials for electronic component sealing, electrical insulation materials, resin materials for copper clad laminates, build-up laminate materials, resist materials, and color filters for liquid crystals. Resin materials, coatings, various coating agents, adhesives, fiber reinforced plastic (FRP) materials, etc.

≪Resin varnish≫
The resin varnish (hereinafter also referred to as "the resin varnish") of the present invention includes the carbonate resin, a maleimide compound having two or more maleimide groups, and a solvent.
This carbonate resin can function as a maleimide diimide hardener. The "cis butadiene diimide hardener" means a hardener for hardening the aforementioned cis butane diimine compound.
In this resin varnish, a part of the allyl carbonate resin and a part of the maleimide compound of the maleimide compound may be in a state in which they react.

When this carbonate resin contains a compound in which at least one of two X in the above formula (1) is a hydrogen atom, that is, when this carbonate resin contains a hydroxyl group, this carbonate resin can also be hardened as an epoxy resin. Agent function. The "epoxy resin hardener" means a hardener used to harden an epoxy resin.
Therefore, a preferred aspect of the resin varnish includes the present carbonate resin, a maleimide compound having two or more maleimide groups, an epoxy resin, and a solvent. A resin varnish containing a compound in which at least one of two X in the aforementioned formula (1) is a hydrogen atom. Compared with the case without epoxy resin, the resin varnish of this aspect has better dielectric properties.

The resin varnish may further include a hardening reaction catalyst.
This resin varnish may further contain other components than this carbonate resin, a maleimide compound, a solvent, an epoxy resin, and a hardening reaction catalyst.

<Cis-butene diamidine 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 dimaleimide compound and a polyphenylmethane maleimide醯 imine and so on.
Examples of the dicis-butene difluorene imine compound include 4,4'-diphenylmethane biscis-butene diimine (e.g., Daiwa Kasei Industry Co., Ltd. product BMI-1100), alkylbiscis-butene Diamidine, diphenylmethane biscis-butenediamidine, phenylene biscisbutenedifluorene, bisphenol A diphenyl ether biscisene difluorene (e.g. Daiwa Kasei Industry Co., Ltd product BMI-4000), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane biscis-butene diamidine imide (e.g. Daiwa Kasei Industry Co., Ltd product BMI-5100), 4-methyl-1,3-phenylene biscis- butylene diimide, 1,6'-bis-cis-butene diimide- (2,2, 4-trimethyl) hexane, 4,4'-diphenyl ether biscis butylene diimide, 4,4'-diphenyl bis-bis-cis butylene diimide, 1,3-bis (3-cis-butenediamidophenoxy) benzene, 1,3-bis (4-cis-butenediamidophenoxy) benzene, and the like.
Polyphenylmethane cis-butene diimide is a polymer in which three or more benzene rings substituted with a cis-butene diimide group pass through a methylene bond, and examples thereof include BMI from Daiwa Kasei Industry Co., Ltd. -2300.
These maleimide compounds may be used singly or in combination of two or more kinds.

The content of the maleimide compound in the resin varnish,
With respect to 100 parts by mass of the carbonate resin, 10 to 300 parts by mass is preferred, 15 to 200 parts by mass is more preferred, and 20 to 150 parts by mass is more preferred. If the content of the maleimide compound is above the lower limit of the aforementioned range, the gelation temperature of the resin varnish can be lowered, and it can be, for example, 200 ° C or lower. If the content of the maleimide compound is above the lower limit of the foregoing range, the cured product of the resin varnish can exhibit higher glass transition temperature, high thermal decomposition temperature, low coefficient of linear expansion, low dielectric constant, Low dielectric tangent.

<Solvent>
The solvent is not particularly limited as long as it can dissolve the components contained in the resin varnish (this carbonate resin, maleimide compound, optional curing reaction catalyst, etc.).
The solvent is typically a polar solvent. Examples of the polar solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, diacetone alcohol, and cyclohexanone. Ketone solvents such as ketones, N, N-dimethylformamidine, N-methyl-2-pyrrolidone, methanol, ethanol, butanol, ethyl acetate, butyl acetate, methyl cyrusthion, diethyl Glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, and the like.
These solvents may be used singly or in combination of two or more kinds.
Among the foregoing, ketone solvents are preferred, and methyl ethyl ketone is particularly preferred.

The content of the solvent in the resin varnish can be appropriately set according to the solid content concentration of the resin varnish.
The solid content concentration of this resin varnish varies depending on the application, but it is preferably 20 to 80% by mass, and more preferably 50 to 70% by mass.
The solid content concentration of the resin varnish is a ratio of the mass after the solvent is removed from the resin varnish to the total mass of the resin varnish.

＜ Epoxy resin ＞
The epoxy resin is not particularly limited, and may be a well-known epoxy resin, and examples thereof include phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol A epoxy resin, and bisphenol F-ring. Oxygen resin, biphenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, naphthol type epoxy resin, xylene type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin , Dicyclopentadiene type epoxy resin, fluorene type epoxy resin, sulfur atom-containing epoxy resin, phosphorus atom-containing epoxy resin, and the like. These epoxy resins may be used either alone or in combination of two or more.

＜ Hardening reaction catalyst ＞
The hardening reaction catalyst (hardening accelerator) should preferably include a catalyst (hereinafter also referred to as "catalyst (1)") which can promote the reaction between the allyl group and the maleimide group. Examples of the catalyst (1) include imidazole compounds and organic peroxides. Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, and 2-heptadecane Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dimethylol imidazole, 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 Wait. Examples of the organic peroxide include ketone peroxide, hydroperoxide, dialkyl peroxide, difluorenyl peroxide, peroxydicarbonate, and peroxyester. In the dialkyl peroxide, the alkyl group may be substituted with a phenyl group or the like. Such a dialkyl peroxide may be, for example, dicumyl peroxide.

When the present carbonate resin has a hydroxyl group and the resin varnish contains an epoxy resin, the curing reaction catalyst may include a catalyst (hereinafter also referred to as "catalyst (2)") having a function of promoting the reaction between the hydroxyl group and the epoxy group. Examples of the catalyst (2) include a phosphorus compound, a tertiary amine, an imidazole compound, a metal salt of an organic acid, a Lewis acid, and an amine complex. Examples of the phosphorus-based compound include triphenylphosphine, ginseng-2,6-dimethoxyphenylphosphine, ginsyl-p-tolylphosphine, and triphenylphosphite. Examples of tertiary amines include 2-dimethylaminomethylphenol, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazinebicyclo [5.4.0] 11-7 -Ene and the like. The imidazole compound may be the same as described above.

These hardening reaction catalysts may be used singly or in combination of two or more kinds.
The content of the catalyst (1) in the resin varnish is preferably 0.1 to 5.0% by mass based on the maleimide compound.
The content of the catalyst (2) in the resin varnish is preferably 0.1 to 5.0% by mass relative to the epoxy resin.
The total content of the catalyst (1) and the catalyst (2) in the resin varnish is preferably 0.1 to 5.0% by mass relative to the total amount of the maleimide compound and the epoxy resin.

＜ Other ingredients ＞
In terms of other ingredients, examples include inorganic fillers (e.g. carbon black, glass cloth, silicon dioxide, etc.), waxes, flame retardants, coupling agents, etc., hardeners other than this carbonate resin (hereinafter also referred to as other hardeners), Fillers (fillers), release agents, surface treatment agents, colorants, flexibility imparting agents, and the like. Other curing agents include cis-butene diimide curing agent, epoxy resin curing agent, and the like, and known ones can be used. For example, as a maleimide hardening | curing agent, a novolak-type resin, such as an allyl novolak-type phenol resin, etc. are mentioned.
The content of other hardeners in the resin varnish is, in terms of the effect of the present invention, preferably 10% by mass or less, more preferably 0% by mass, relative to the solid content (100% by mass) of the resin varnish.
The solid content of this resin varnish is a part after removing the solvent from this resin varnish.

Examples of filling materials (fillers) include carbon black, crystalline silica powder, fusible silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, calcium carbonate powder, etc. It is better to use crystalline silica powder and fusible silica powder.
Examples of the release agent include various waxes such as palm wax.
Examples of the surface treatment agent include known silane coupling agents.
Examples of the colorant include carbon black.
Examples of the flexibility imparting agent include silicone resin, butadiene-acrylonitrile rubber, and the like.

＜ Manufacturing method of resin varnish ＞
The resin varnish can be produced, for example, by mixing the carbonate resin, a maleimide compound, and a solvent. When the carbonate resin, the maleimide compound and the solvent are mixed, or after mixing, an epoxy resin, a curing reaction catalyst, or other components may be further added as necessary.
This carbonate resin can be manufactured by the said manufacturing method. As the maleimide compound, epoxy resin, curing reaction catalyst, and other components, commercially available products can be used. Mixing of each component can be performed according to a conventional method.

After the carbonate resin, the maleimide compound and the solvent are mixed, the carbonate resin and the maleimide compound may be pre-reacted. By performing a pre-reaction on the varnish-state mixture obtained by the aforementioned mixing, it is possible to suppress precipitation of a cis-butene diamidine compound having high crystallinity from the resin varnish.
The reaction temperature during the pre-reaction is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and even more preferably 80 to 120 ° C. If the reaction temperature is too low, the reaction cannot progress, and if it is too high, it is difficult to control the reaction. I am afraid that it is difficult to customize the resin varnish for the purpose.

Since this resin varnish contains this carbonate resin and a maleimide compound, it can be hardened by heating to form a cured product.
The heating temperature (hardening temperature) for curing the resin varnish is preferably 60 to 250 ° C.
An example of the hardening operation is a method of curing at the aforementioned suitable temperature for 30 seconds to 1 hour, removing the solvent, and then further curing at the aforementioned suitable temperature for 1 to 20 hours.

As for the resin varnish, since a maleimide compound is used, the cured product of the resin varnish exhibits a high glass transition temperature, a high thermal decomposition temperature, and a low thermal expansion coefficient. In addition, since this hardened product uses the carbonate resin as a hardening agent of the maleimide compound, it is a hardened product compared with a hardened product of a maleimide compound using an allylphenol resin. Or the hardened product of epoxy resin hardened by phenol novolac resin is low dielectric constant and low dielectric tangent.

The use of the resin varnish is not particularly limited. For example, it can be used for the same purpose as a well-known thermosetting molding material, and examples thereof include a sealing material, a film material, and a laminated material. Examples of more specific applications include semiconductor sealing materials, resin materials for electronic component sealing, electrical insulation materials, resin materials for copper clad laminates, build-up laminate materials, resist materials, and color filters for liquid crystals. Resin materials, coatings, various coating agents, adhesives, fiber reinforced plastic (FRP) materials, etc.
The hardened material of this resin varnish is low dielectric constant, low dielectric tangent, and good insulation. Moreover, this hardened | cured material has a high glass transition temperature, a high thermal decomposition temperature, a low thermal expansion rate, and heat resistance is also excellent. Therefore, this resin varnish can be used as a material for manufacturing laminated boards for electronic parts.

The specific dielectric constant of the hardened product of the resin varnish is preferably 3.50 or less. The lower limit of the specific dielectric constant is, for example, 2.00.
The dielectric tangent of the hardened material of this resin varnish is preferably 0.008 or less. The lower limit of the dielectric tangent is, for example, 0.0001.
The glass transition temperature of the hardened product of this resin varnish is preferably 150 ° C or higher. The upper limit of the glass transition temperature is, for example, 500 ° C.
The 5% thermal decomposition temperature of the cured product of this resin varnish is preferably 300 ° C or higher. The upper limit of the 5% thermal decomposition temperature is, for example, 600 ° C.
The linear expansion coefficient of the hardened material of this resin varnish at room temperature is preferably 100 ppm or less. The lower limit of the normal-temperature linear expansion coefficient is, for example, 5 ppm.
Specific permittivity, dielectric tangent, glass transition temperature, 5% thermal decomposition temperature, and room temperature linear expansion coefficient can be measured in accordance with the methods described in Examples described later.

制造 Manufacturing method of laminated board≫
In the manufacturing method of the laminated board of the present invention, the resin varnish is impregnated into the fibrous base material, and the fibrous base material which has been impregnated with the resin varnish is heated and pressurized to harden the laminated base plate.

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

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

As one embodiment of the manufacturing method of the laminated board of the present invention, the following methods can be mentioned: impregnate the resin varnish to the fibrous substrate, and then dry (remove the solvent) to obtain a prepreg. As needed, a method of further laminating a metal foil on one or both sides of the aforementioned prepreg or its laminate, and applying heat and pressure to harden it.

The amount of the resin varnish impregnated into the fibrous substrate is not particularly limited. For example, the solid content of the resin varnish is an amount of about 30 to 50% by mass based on the fibrous substrate (100% by mass).
The heating temperature when the fibrous substrate impregnated with the resin varnish is heated and pressed is preferably the aforementioned hardening temperature. The pressing condition is preferably 2 to 20 kN / m ² .

The laminated board prepared by the method for manufacturing a laminated board of the present invention includes a fiber-reinforced resin layer including a fibrous substrate and a cured product of the resin varnish. The fiber-reinforced resin layer has a low dielectric constant because the cured product 5, low dielectric tangent and good insulation. 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 coefficient.
Examples

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 the following examples, "%" means "mass%" when it is not particularly limited.
The measurement methods used in the following examples are shown below.

[Resin weight average molecular weight (Mw), number average molecular weight (Mn), dispersion (Mw / Mn)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using polystyrene as a standard substance using the following GPC apparatus and column, and the degree of dispersion (Mw / Mn) was determined.
GPC device: HLC8120GPC manufactured by TOSOH CORPORATION.
Column: TSKgel (registered trademark) G3000H + G2000H + G2000H manufactured by TOSOH CORPORATION.

[Softening point of resin]
The softening point (° C) was measured in accordance with JIS K 6910.

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

[Glass transition temperature]
The obtained molded article 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 using a viscoelasticity measuring device (DMA7100 manufactured by Hitachi High-Tech Science Corporation) at a temperature rise rate of 2 ° C / min in the range of 30 ° C to 400 ° C, and the glass transition temperature (° C) was determined.

[5% thermal decomposition temperature]
The obtained molded article was pulverized to prepare a measurement sample. For this measurement sample, a differential thermal-thermogravimetric simultaneous measurement device (TG / DTA6300 manufactured by Seiko Instruments Inc.) was used to measure the thermal weight loss in the range of 30 to 800 ° C at a temperature increase rate of 10 ° C / min in the atmospheric environment, and obtained 5% thermal decomposition temperature (° C).

[Linear expansion coefficient at room temperature]
The obtained molded article was processed into a size of 5.0 mm in width × 5.0 mm in length × 1.5 mm in thickness to prepare a measurement sample. For this measurement sample, the thermal expansion of the hardened material was measured using a thermomechanical analysis device (TMA7100 manufactured by Hitachi High-Tech Science Corporation) at a temperature rise rate of 2 ° C / min in the range of 30 ° C to 400 ° C, and the linear expansion coefficient (ppm) at room temperature was determined. . The coefficient of linear expansion at room temperature shows the coefficient of linear expansion at 30 ° C.

[Specific permittivity, dielectric tangent]
The obtained molded article was processed into a size of 50.0 mm in width × 50.0 mm in length × 1.5 mm in thickness to prepare a measurement sample. For this measurement sample, the specific permittivity (ε _r ) and the dielectric tangent (tan δ) at a frequency of 1 GHz were obtained using a resonant cavity perturbation method.

<Synthesis Example 1: Synthesis of diallyl bisphenol F>
In a reaction vessel having a content of 3 L including a thermometer, a stirrer, and a cooling tube, 1000.0 g of bisphenol F (BPF-SG manufactured by Gunei Chemical Industry Co., Ltd.) and 800.0 g of methanol were fed. 480 g of sodium oxide was split addition. Next, 995.0 g of chloropropene was dripped over 2 hours while paying attention to heat generation below 35 ° C. After the reaction was allowed to proceed at the same temperature for 2 hours, the temperature was raised to 65 ° C and the reaction was allowed to proceed for 5 hours to carry out the allyl ether of bisphenol F. Into. Next, methanol was removed from the obtained reaction solution under reduced pressure, and then a large amount of salt was removed by washing with water. The reaction solution after washing with water was heated to 190 ° C. under a nitrogen gas atmosphere, and the reaction was allowed to proceed for 5 hours, thereby rearranging the allyl groups to obtain the desired diallyl bisphenol F. The obtained diallyl bisphenol F was liquid at normal temperature, and the viscosity at 25 ° C was 0.8 Pa · s in terms of E-type viscosity.

<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 amount of methanol was changed to 912.0 g. The same operation as in Synthesis Example 1 was performed to obtain diallyl bisphenol A. The obtained diallyl bisphenol A was liquid at normal temperature, and the viscosity at 25 ° C was 21.2 Pa · s in terms of E-type viscosity.

<Synthesis Example 3: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and diallyl bisphenol F>
Into a reaction container having a content of 1L with a thermometer, a stirrer, and a cooling tube, 214.2 g (1.00 mol) of diphenyl carbonate and 98.1 g (0.50 mol) of tricyclodecanedimethanol were fed, and melted and mixed at 100 ° C. . Then, 0.02 g of a 48% KOH aqueous solution was added, and the temperature was raised to 180 ° C. while paying attention to heat generation, and the reaction was allowed to proceed at normal pressure for 1 hour. Next, it cooled to 130 degreeC, and 183.0 g (0.61 mol) of diallyl bisphenol F obtained in the synthesis example 1 were added, it heated up to 180 degreeC, and reaction was performed at normal pressure for 1 hour. Thereafter, the system was gradually depressurized to 10 mmHg while maintaining the system at 180 ° C. Next, the temperature was raised to 220 ° C. under reduced pressure, and the reaction was allowed to proceed for 2 hours under reduced pressure. Thereafter, the reaction product was washed with water and concentrated to obtain an allyl carbonate-containing resin. The softening point of the resin was 93.5 ° C, and the melt viscosity at 150 ° C was 45.6P. Mw obtained by gel permeation chromatography (hereinafter also abbreviated as GPC) was 9153, Mn was 3139, Mw / Mn was 2.916, and the content of the compound represented by formula (1) was 97.2%.

<Synthesis Example 4: Synthesis of carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and diallyl bisphenol F>
In Synthesis Example 3, 98.1 g of tricyclodecane dimethanol 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). In the same manner as in Example 3, an allyl carbonate-containing resin was obtained. The resin had a softening point of 98.4 ° C and a melt viscosity of 69.6P at 150 ° C. Mw obtained by GPC was 6774, Mn was 2506, Mw / Mn was 2.703, and the content of the compound represented by 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 mole) of diallyl bisphenol A obtained in Synthesis Example 2, and the same operation as in Synthesis Example 3 was performed. An allyl carbonate-containing resin was obtained. The softening point of the resin was 108.4 ° C, and the melt viscosity at 200 ° C was 26.1P. The Mw obtained by GPC was 9711, Mn was 3309, Mw / Mn was 2.935, and the content of the compound represented by formula (1) was 96.5%.

<Example 1>
100 g of an allyl carbonate-containing resin synthesized in Synthesis Example 3 and BMI-2300 (polyphenylmethanecis butadiene diimide) produced by Daiwa Kasei Industry Co., Ltd. as a cis butene diimide compound 2, maleimide equivalent: 186.0 g / eq) 23.7 g, 1.2 g of dicumene peroxide as a curing reaction catalyst (1% of the total resin content) was dissolved in methyl ethyl ketone to make it a solid component 60 % To obtain a resin varnish.
The obtained resin varnish was impregnated with glass cloth (E glass) so that the resin content was 40%, and it was dried at 100 ° C for 10 minutes, and the solvent was removed to obtain a prepreg. Six sheets of this prepreg were stacked and press-molded at 180 ° C, and then post-baked at 230 ° C for 5 hours to obtain a molded product (laminated sheet) having a thickness of 1.5 mm. The resin classification refers to the ratio of the resin (cured material) to the total mass of the molded product.

<Example 2>
In Example 1, 23.7 g of BMI-2300 was changed to 47.4 g, and a resin varnish was prepared in the same manner as in Example 1 to obtain a molded article.

<Example 3>
In Example 1, 23.7 g of BMI-2300 was replaced with BMI-4000 (bisphenol A diphenyl ether bis-cis-butene-diimide, cis-butene-diimide) manufactured by Daiwa Kasei Industry Co., Ltd. Equivalent weight: 72.7 g of 285.1 g / eq). A resin varnish was prepared in the same manner as in Example 1 to obtain a molded product.

<Example 4>
100 g of the allyl carbonate-containing resin synthesized in Synthesis Example 4, 91.0 g of BMI-4000 manufactured by Daiwa Kasei Industry Co., Ltd. as a maleimide compound, and peroxide peroxide as a hardening reaction catalyst 1.9 g of cumene (1% of the total resin content) was dissolved in methyl ethyl ketone to make it a solid content of 60%, and a resin varnish was obtained.
The obtained resin varnish was impregnated with glass cloth (E glass) so that the resin content was 40%, and it was dried at 100 ° C for 10 minutes, and the solvent was removed to obtain a prepreg. Six sheets of this prepreg were stacked and press-molded at 180 ° C, and then post-baked at 230 ° C for 5 hours to obtain a molded product (laminated sheet) having a thickness of 1.5 mm.

<Example 5>
In Example 4, 91.0 g of BMI-4000 was replaced with 136.3 g, and a resin varnish was prepared in the same manner as in Example 4 to obtain a molded product.

<Example 6>
100 g of the allyl carbonate-containing resin synthesized in Synthesis Example 5 and 22.5 g of BMI-2300 manufactured by Daiwa Kasei Industry Co., Ltd. as a maleimide compound were used as a curing reaction catalyst. 1.2 g of cumene (1% of the total resin content) was dissolved in methyl ethyl ketone to make it a solid content of 60%, and a resin varnish was obtained.
The obtained resin varnish was impregnated with glass cloth (E glass) so that the resin content was 40%, and it was dried at 100 ° C for 10 minutes, and the solvent was removed to obtain a prepreg. Six sheets of this prepreg were stacked and press-molded at 180 ° C, and then post-baked at 230 ° C for 5 hours to obtain a molded product (laminated sheet) having a thickness of 1.5 mm.

<Example 7>
In Example 6, 22.5 g of BMI-2300 was replaced with 45.0 g, and a resin varnish was prepared in the same manner as in Example 1 to obtain a molded product.

〈Comparative example 1〉
50.0 g of a phenol novolac resin (PSM-4261, manufactured by Gunei Chemical Industry Co., Ltd., softening point: 80 ° C, hydroxyl equivalent: 106 g / eq), and o-cresol novolac-type epoxy resin ( Manufactured by Nippon Kayaku Co., Ltd .: EOCN1020, epoxy equivalent: 199 g / eq) 93.9 g, 1.9 g of triphenylphosphine as a catalyst (2% relative to epoxy resin) dissolved in methyl ethyl ketone to make it a solid content of 60% To obtain a resin varnish.
The obtained resin varnish was impregnated with glass cloth (E glass) so that the resin content was 40%, and it was dried at 100 ° C for 10 minutes, and the solvent was removed to obtain a prepreg. Six sheets of this prepreg were stacked and press-molded at 180 ° C, and then post-baked at 180 ° C for 5 hours to obtain a molded product (laminated sheet) having a thickness of 1.5 mm.

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

For the formed articles obtained in Examples 1 to 7 and Comparative Examples 1 to 2, the glass transition temperature, the thermal decomposition temperature of 5%, the linear expansion coefficient at room temperature, the specific permittivity, and the dielectric tangent were measured. The results are shown in Tables 1-2. In addition, the measured glass transition temperature, 5% thermal decomposition temperature, room temperature linear expansion coefficient, specific permittivity, and dielectric tangent can each be regarded as the glass transition temperature of the hardened product of the resin varnish for the molded product, 5%. Thermal decomposition temperature, room temperature linear expansion coefficient, specific permittivity, and dielectric tangent.
The types of hardeners (including allyl carbonate resin, phenol novolac resin, or allylphenol novolac resin), maleimide compounds, and epoxy resins used in each example are listed together. Table 1 ~ 2.

[Table 1]

[Table 2]

The molded articles of Examples 1 to 7 have low dielectric constant, low dielectric tangent, and good electrical characteristics. In addition, thermal characteristics such as glass transition temperature, 5% thermal decomposition temperature, and room temperature linear expansion coefficient are also very excellent.
The molded product of Comparative Example 1 in which the epoxy resin was hardened with phenol novolac resin had a higher dielectric constant and dielectric tangent than those of Examples 1 to 7. The coefficient of linear expansion at room temperature is large.
The molded product of Comparative Example 2 using an allylphenol novolak resin as a hardener has a higher dielectric constant and dielectric tangent than those of Comparative Example 1.
Industrial availability

With this resin varnish, a hardened product with low dielectric constant, low dielectric tangent, and excellent electrical characteristics can be obtained. In addition, by using this resin varnish, a hardened product having high glass transition temperature, high thermal decomposition temperature, low thermal expansion rate, and excellent thermal characteristics can be obtained.
Therefore, this resin varnish and its laminated board are extremely useful as high-performance polymer materials.
Can be used as a material with excellent electrical and thermal properties in semiconductor sealing materials, electrical insulation materials, resins for copper clad laminates, resists, resins for sealing electronic components, resins for color filters for liquid crystals, coatings, various Coatings, adhesives, build-up laminated board materials, FRP, etc. are widely used.

Claims (11)

An allyl carbonate-containing resin containing a compound represented by the following formula (1) as a main component: [Chemical Formula 1] [In the formula, R ¹ represents a residue derived from a bisphenol compound, a residue derived from a biphenol compound, or a residue derived from an alicyclic dimethanol compound, and two R ¹ may be the same or different from each other, and n represents An integer of 0 or more, 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. When n is 2 or more, n R ² may be each The same or different from each other, at least a part of the two R ¹ and n R ² contains an allyl group, X represents a hydrogen atom or an allyl group, and the two Xs may be the same or different from each other]. The allyl carbonate-containing resin according to claim 1, wherein R ¹ in the aforementioned formula (1) is a residue derived from an allyl-containing bisphenol compound or a residue derived from an allyl-containing biphenol compound base. For example, the allyl carbonate-containing resin of claim 2, wherein R ¹ in the aforementioned formula (1) is a group represented by the following formula (r1), (r2), or (r3): [Chemical formula 2] [In the formula, p represents 1 or 2 and q represents an integer of 0 to 2]. The allyl carbonate-containing resin according to any one of claims 1 to 3, wherein at least a part of the n R ² in the aforementioned formula (1) is a residue derived from an alicyclic dimethanol compound. A method for producing an allyl carbonate-containing resin, comprising 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, and at least a part of the diol compound contains an allyl group. The method for producing an allyl carbonate-containing resin according to claim 5, wherein the aforementioned step of reacting the carbonate with the aforementioned diol compound is: Reacting a carbonic acid diester with an alicyclic dimethanol compound or reacting a carbonic acid diester, an alicyclic dimethanol compound, and at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound Reacting to obtain a primary reaction product, and reacting the aforementioned primary reaction product with at least one aromatic diol compound selected from the group consisting of a bisphenol compound and a biphenol compound; Or it 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. For example, in the method for producing an allyl carbonate-containing resin according to claim 6, when the aforementioned primary reaction product is obtained, the total amount of the carbonic acid diester to the alicyclic dimethanol compound and the aromatic diol compound is not equal. The ear ratio is 1.05 ~ 3.00. According to the method for producing an allyl carbonate-containing resin according to any one of claims 5 to 7, it further has the following steps: the end of the hydroxyl group produced by the reaction between the carbonate and the diol compound is a hydroxyl group containing The step of reacting allyl carbonate resin with halogenated propylene to allyl etherify the aforementioned hydroxyl group. A resin varnish comprising the allyl carbonate-containing resin according to any one of claims 1 to 4, a maleimide compound having two or more maleimide groups, and a solvent. The resin varnish according to claim 9, wherein the allyl carbonate-containing resin includes a compound in which at least one of two X in the aforementioned formula (1) is a hydrogen atom, The resin varnish further contains epoxy resin. A method for manufacturing a laminated board is to impregnate a resinous varnish such as the item 9 or 10 to a fibrous substrate, and heat and press the fibrous substrate impregnated with the resin varnish to harden to obtain a laminated board. .