JP2001335569A - Polyhydroxyl compound, method for producing the same, epoxy resin composition and its cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new polyhydric hydroxyl resin useful as an epoxy resin curing agent providing a cured product having excellent humidity resistance, heat resistance, heat cycle resistance, electric characteristics and flame retardance, to provide a method for producing the same, to obtain an epoxy resin composition using the resin and a cured product of the composition. SOLUTION: This polyhydric hydroxyl compound of general formula (1) (X is a 1-14C hydrocarbon group; Rs are each independently hydrogen, a 1-10C alkyl group, a phenyl group or a halogen group; m is an integer of 0-2; n is an integer of 0-4) is characterized by having a dendritic repeating unit containing a triazine skeleton and a naphthalene skeleton. This epoxy resin composition comprises the polyhydric hydroxyl compound as an essential component. A cured material of the composition is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to heat resistance, moisture resistance,
Electrical properties, a polyvalent hydroxy resin useful as an epoxy resin curing agent that gives a cured product having excellent flame retardancy and a method for producing the same, and further relates to an epoxy resin composition using the same and a cured product thereof, a semiconductor encapsulant, It is suitably used for laminates, coating materials, composite materials and the like.

[0002]

2. Description of the Related Art In recent years, particularly with the advancement of advanced materials,
There is a demand for higher performance organic materials. For example, in the field of printed circuit boards, there is a demand for epoxy resins or hardeners having characteristics capable of coping with high multilayer, high density mounting, surface mounting, and the like. In particular, there is a strong demand for excellent heat resistance, moisture resistance, and electrical characteristics. Also, due to recent environmental problems, non-halogenation has been strongly called out in the field of flame retardancy.

[0003] Therefore, there is great expectation for a flame-retardant material containing no chlorine or bromine. Many non-halogen flame retardants using phosphorus atoms have been proposed, but from the standpoint of toxicity and moisture resistance reliability, they cannot be said to have sufficiently solved the existing problems and contain both halogen and phosphorus atoms. Not flame retardant materials are required.

However, there is no known epoxy resin or curing agent which sufficiently satisfies these requirements. In the field of curing agents, for example, existing phenol-based curing agents and amine-based curing agents do not have sufficiently satisfactory properties in all of heat resistance, moisture resistance, and electrical properties.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a material having excellent heat resistance, moisture resistance, electrical characteristics, and excellent flame retardancy, such as lamination, molding, casting, and adhesion. It is an object of the present invention to provide a polyvalent hydroxy resin useful as an epoxy resin curing agent useful for applications, a method for producing the same, an epoxy resin composition using them, and a cured product thereof.

[0006]

Means for Solving the Problems As a result of intensive studies on the means for solving the above-mentioned problems, the present inventors have found that a polyvalent hydroxy compound having a dendritic repeating unit containing a triazine skeleton and a naphthalene skeleton is obtained. The present inventors have found that an epoxy resin composition used as a curing agent satisfies the above-mentioned problems regardless of the presence or absence of halogen, and have completed the present invention.

That is, the present invention provides

[0008] 1. A polyvalent hydroxy compound represented by the general formula (1),

Embedded image

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group;
Represents an integer of 0 to 2, and n represents an integer of 0 to 4. )

[0010] 2. X in the general formula (1) is a methylene group, R
Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein the polyvalent hydroxy compound according to the above 1,

3. X in the general formula (1) is a methylene group, R
Is a hydrogen atom, the polyvalent hydroxy compound according to the above 1,

4. It contains a compound represented by the general formula (1) and a derivative having a residue of the polyvalent hydroxy compound represented by the general formula (1) as a central skeleton, and the content of the compound represented by the general formula (1) is 20 to 70% by weight, a polyvalent hydroxy compound,

Embedded image

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group;
Represents an integer of 0 to 2, and n represents an integer of 0 to 4. )

5. The derivative having, as a central skeleton, a residue of the polyvalent hydroxy compound represented by the general formula (1) is a compound having a central skeleton derived from the general formula (2) and a repeating structure represented by the general formula (3). 5. The polyvalent hydroxy compound according to the above 4, wherein

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(In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group.
Represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a structure of the following general formula (3) or a hydrogen atom.

Embedded image

(Wherein X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group;
Represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a hydrogen atom or a general formula (3))

6. A method for producing a polyvalent hydroxy compound, comprising subjecting a cyanuric halide (A) and a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule to a dehydrohalogenation condensation reaction,

[7] The molar ratio (A) / (B) = 1/1. Of a cyanuric halide (A) and a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule.
7. The method for producing a polyvalent hydroxy compound according to the above 6, wherein the reaction is performed at a ratio of 5/5.

8. The method for producing a polyhydroxy compound according to the above item 6 or 7, wherein a hydrogen halide scavenger is present in the reaction system;

9. 9. The method for producing a polyvalent hydroxy compound according to 6, 7, or 8, wherein the naphthalene skeleton-containing compound (B) containing two or more hydroxyl groups in one molecule is a bisnaphthol (b).

10. Bisnaphthols (b) are 1,1 '
10. The method for producing a polyvalent hydroxy compound according to the above item 9, wherein the compound is -bis (2-hydroxy-1-naphthyl) methane.

11. An epoxy resin composition comprising an epoxy resin and a curing agent, characterized in that the polyvalent hydroxy compound according to any one of the above 1 to 5 is blended as an essential component,

12. In an epoxy resin composition comprising an epoxy resin and a curing agent, an epoxy resin composition comprising, as an essential component, a polyvalent hydroxy compound obtained by the production method according to any one of the above 6 to 10,

13. 11. A cured product obtained by curing the epoxy resin composition according to 9 or 10 above.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The polyvalent hydroxy compound according to the present invention includes a compound containing a triazine skeleton and a naphthalene skeleton represented by the general formula (1), and a polyvalent hydroxy compound represented by the general formula (1). Dendritic repetition having a compound and a derivative having a polyvalent hydroxy compound residue represented by the general formula (1) as a central skeleton and containing a triazine skeleton and a naphthalene skeleton represented by the general formula (3) A compound having a unit and containing 20 to 70% by weight of the general formula (1).

A compound having, as a central skeleton, a derivative of the polyvalent hydroxy compound represented by the above general formula (1) and having a dendritic repeating unit containing a triazine skeleton and a naphthalene skeleton represented by the general formula (3) Represents, for example, a compound having a structure represented by the following general formula (2).

Embedded image

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group;
Represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a structure of the following general formula (3) or a hydrogen atom.

In the above general formula (2), the structure represented by the following formula (3) is the above-mentioned repeating structure.

Embedded image

(Wherein, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a halogen group;
Represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a general formula (3) or a hydrogen atom. )

As the polyvalent hydroxy compound according to the present invention, the case where X is a methylene group (= —CH ₂ —) and R is a hydrogen atom in the general formulas (1), (2) and (3) is as described above. It is most preferable to solve the problem.

The polyhydric hydroxy compound is obtained by subjecting a cyanuric halide (A) to a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule by a dehydrohalogenation condensation reaction. Examples of the cyanuric halides include cyanuric chloride, cyanuric bromide, cyanuric iodide and the like. Among them, cyanuric chloride is more preferable in terms of easy control of reactivity and cost. Further, as a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule,
1,1′-bis (2-hydroxy-1-naphthyl) methane (b), 1,1′-bis (2-hydroxy-1-naphthyl-6methyl) methane, 1,1′-bis (2-hydroxy And bisnaphthols having a structure in which naphthols are dimerized with a divalent hydrocarbon group as a linking group, such as -1-naphthyl-7ethyl) butane, but are not limited thereto. Among them, 1,1′-bis (2-hydroxy-1-naphthyl) methane (b) is particularly preferred.

The reaction ratio between the cyanuric halide (A) and the naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule is not particularly limited, but the molar ratio (A) / (B) = 1 / 1.2 to 1/8,
Preferably, the molar ratio (A) / (B) = 1 / 1.5 to 1/5
, The compound having the structure of the formula (1) can be contained in an amount of 20 to 70% by weight, and excellent characteristics of fluidity, curability, heat resistance and flame retardancy can be obtained. .

In the reaction, the presence of a hydrogen halide scavenger in the reaction system allows the reaction to proceed promptly. As the hydrogen halide scavenger, known compounds can be used. Examples thereof include tertiary amines such as triethylamine and trimethylamine, and basic compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Substances can be used. The amount of the hydrogen halide scavenger used is 1 halogen atom.
1.0 to 3.0 mol, preferably 1.0 mol, per mol.
１．５1.5 mol. The halogenated scavenger is added in 0.5 to 3 hours.

In the above reaction, the reaction is preferably performed in the presence of an organic solvent. The organic solvent used at this time is not particularly limited, but a hydrophobic solvent is preferable. As the hydrophobic solvent, for example, aromatic solvents such as benzene, toluene, and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used.

The amount of the organic solvent to be used is usually 30 to 30 parts by weight based on 100 parts by weight of the total of the cyanuric halide (A) and the compound (B) containing two or more hydroxyl groups per molecule. 500 parts by weight, preferably 5
0 to 300 parts by weight. The reaction temperature is usually 20 to 150
C., the reaction time is 1 to 20 hours.

After a halogenated scavenger is added in such a system to carry out the reaction, an appropriate amount of water is added to the reaction solution to dissolve the formed salt. Thereafter, the product salt in the system is removed by repeating washing with water, followed by further purification by dehydration or filtration and removal of the organic solvent by distillation to obtain the target compound.

Hereinafter, the epoxy resin composition of the present invention will be described. The polyhydroxy compound acts as a curing agent for the epoxy resin in the epoxy resin composition of the present invention, and the polyhydroxy compound can be used alone or in combination with another curing agent. When used in combination, the proportion of the polyhydroxy compound of the present invention in the total curing agent is 30
% By weight or more, preferably 40% by weight or more.

As other curing agents that can be used in combination with the polyvalent hydroxy compound of the present invention, any curing agents generally known as epoxy resin curing agents can be used. Examples of such a curing agent include dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like. Specifically, examples of polyhydric phenols include bisphenol A, bisphenol F,
Bisphenol S, fluorene bisphenol, 4,
Divalent phenols such as 4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol; tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ) Trivalent or higher phenols represented by ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc .; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol,
Polyhydric phenols synthesized with dihydric phenols such as 2,2'-biphenol, hydroquinone, resorcinol, naphthalene diol and condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde and p-xylylene glycol of naphthols Compounds. Examples of the acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, nadic anhydride, trimellitic anhydride, and the like. No. Further, as the amines, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone,
Examples thereof include aromatic amines such as m-phenylenediamine and p-xylylenediamine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the epoxy resin composition containing a polyhydroxy compound as an essential component according to the present invention, any ordinary epoxy resin having two or more epoxy groups in the molecule can be used as the epoxy resin component. Specific examples include bisphenol A, bisphenol S, fluorene bisphenol, 4,4′-biphenol,
Divalent phenols such as 2'-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4
-Hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, etc., and trivalent or more phenols, or glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A, or the polyhydric hydroxy compound according to the present invention And epoxy resins derived therefrom. These epoxy resins may be used alone or in combination of two or more in the epoxy resin composition of the present invention.

The amount of the curing agent containing a polyvalent hydroxy compound according to the present invention used in the epoxy resin composition of the present invention is preferably 1 equivalent of the epoxy group of the epoxy resin because a good cured product can be obtained. Hydroxyl group is 0.5 to 2.0
An equivalent amount is preferred. Further, the epoxy resin composition of the present invention may contain various additives such as fillers such as silica, alumina and talc, silane coupling agents, release agents and pigments, if necessary.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the components. The epoxy resin composition of the present invention containing the epoxy resin of the present invention, the curing agent and, if necessary, a curing accelerator can be easily formed into a cured product by a method similar to a conventionally known method. For example, if necessary, an epoxy resin and a compounding agent such as a curing agent and a filler are sufficiently mixed using an extruder, a kneader, a roll, or the like until a uniform mixture is obtained to obtain an epoxy resin composition. After the epoxy resin composition is melted, molded using a casting or transfer molding machine or the like, and further heated at 80 to 200 ° C. for 2 to 10 hours, a cured product can be obtained.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and is used for preparing glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like. A prepreg obtained by impregnating a substrate and drying by heating may be subjected to hot press molding to obtain a cured product. The solvent in this case is usually 10 to 10 parts by weight of the total amount of the mixture of the epoxy resin composition of the present invention and the solvent.
An amount occupying 70 parts by weight, preferably 15 to 65 parts by weight, is used.

[0043]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following, parts are by weight unless otherwise specified. Example 1 In a four-necked flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 92 parts of cyanuric chloride (a), 1,1'-
Bis (2-hydroxy-1-naphthyl) methane (b) 4
50 parts (molar ratio; (a) / (b) = 1/3) and 700 parts of methyl ethyl ketone as a solvent were charged and dissolved by stirring. Next, 60 minutes was required while the temperature was raised from 50 ° C. to 70 ° C., and triethylamine 1 was used as a hydrogen halide scavenger.
54 parts [molar ratio; chlorine / triethylamine in the cyanuric chloride charged = 1 / 1.02] were added dropwise. After completion of the dropwise addition, stirring was further continued at 70 ° C. for 5 hours. Then water 20
0 parts were added to dissolve triethylamine hydrochloride, and the mixture was separated and discarded. Further, after washing twice with the same amount of water, methyl ethyl ketone was recovered by distillation to obtain 441 parts of the objective polyhydric hydroxy compound (I). For the compound (I), 13 C nuclear magnetic resonance absorption spectrum, mass spectrum,
An infrared absorption spectrum is measured, and the structure is a dendritic compound having a repeating structure having at least three hydroxy groups in one molecule, and having a structure represented by the formula (4) at the emission center. It was confirmed that the component of the repeating unit was a polyvalent hydroxy compound represented by the formula (5). Also GPC
From the results, it was confirmed that X in formula (1) contained 45.9% by weight of a component having the structure of formula (6) in which m is a methylene group (—CH ₂ —). The hydroxyl equivalent was 324 g / eq. 13C-NMR, MS, IR and GPC charts are shown in FIGS.

Embedded image (In the formula, T represents a hydrogen atom or formula (5).)

Embedded image (In the formula, T represents a hydrogen atom or formula (5).)

Embedded image

Example 2 and Comparative Example 1 The compositions having the compositions shown in Table 1 were kneaded at 110 ° C. for 10 minutes using two rolls. Crush it after cooling,
After press molding under the condition of 80 ° C. × 10 minutes, it was further post-cured at 180 ° C. for 8 hours to obtain a test piece having a thickness of 1.3 mm. Using this, the glass transition temperature, the moisture absorption, the coefficient of linear expansion, the dielectric constant, and the flame retardancy were tested.

[Table 1]

[0045]

The cured product obtained by curing the polyvalent hydroxy compound of the present invention and an epoxy resin composition containing the same as an essential component has heat resistance, moisture resistance, electrical properties, heat cycle resistance, Excellent electrical characteristics and flame retardancy, laminated board materials such as printed wiring boards, semiconductor sealing materials, adhesives,
It can be suitably used for structural materials, casting materials, and coating materials.

[Brief description of the drawings]

FIG. 1 shows ^{13 of the} compound of the present invention obtained in Example 1.
It is a C nuclear magnetic resonance absorption spectrum.

FIG. 2 is a mass spectrum of the compound according to the present invention obtained in Example 1.

FIG. 3 is an infrared absorption spectrum of the compound according to the present invention obtained in Example 1.

FIG. 4 shows a compound according to the present invention obtained in Example 1,
FIG. 2 is a GPC chart showing that 45.9% by weight of a component having the structure of Formula (5) in which X in Formula (1) is a methylene group (—CH ₂ —) is contained.

Claims (13)

[Claims] 1. A polyvalent hydroxy compound represented by the general formula (1). Embedded image (In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms,
A phenyl group or a halogen group; m represents an integer of 0 to 2; and n represents an integer of 0 to 4; ) 2. In the formula (1), X is a methylene group, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
The polyvalent hydroxy compound according to the above. 3. The polyhydroxy compound according to claim 1, wherein X in the general formula (1) is a methylene group and R is a hydrogen atom. 4. A compound comprising a compound represented by the general formula (1) and a derivative having, as a central skeleton, a residue of a polyvalent hydroxy compound represented by the general formula (1). A polyhydric hydroxy compound having a content of 20 to 70% by weight. Embedded image (In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms,
It represents a phenyl group or a halogen group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4. ) 5. A derivative having, as a central skeleton, a residue of a polyvalent hydroxy compound represented by the general formula (1), comprising a central skeleton derived from the general formula (2) and a repeating structure represented by the general formula (3). The polyhydroxy compound according to claim 4, which is a compound having the following formula: Embedded image (In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms,
A phenyl group or a halogen group, m represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a structure of the following general formula (3) or a hydrogen atom. (In the formula, X represents a hydrocarbon group having 1 to 14 carbon atoms, and R independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms,
A phenyl group or a halogen group, m represents an integer of 0 to 2, n represents an integer of 0 to 4, and T represents a hydrogen atom or a general formula (3)) 6. A polyhydric hydroxy compound characterized by subjecting a cyanuric halide (A) and a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule to a dehydrohalogenation condensation reaction. Production method. 7. A cyanuric halide (A) and a naphthalene skeleton-containing compound (B) containing two or more hydroxyls in one molecule, in a molar ratio (A) / (B) = 1 / 1.5 to
The method according to claim 6, wherein the reaction is performed at a ratio of 1/5. 8. The method for producing a polyvalent hydroxy compound according to claim 6, wherein a hydrogen halide scavenger is present in the reaction system. 9. The naphthalene skeleton-containing compound (B) containing two or more hydroxyl groups in one molecule is a bisnaphthol (b).
A method for producing the polyvalent hydroxy compound as described above. 10. The method for producing a polyvalent hydroxy compound according to claim 9, wherein the bisnaphthol (b) is 1,1′-bis (2-hydroxy-1-naphthyl) methane. 11. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyvalent hydroxy compound according to any one of claims 1 to 5 is blended as an essential component. object. 12. An epoxy resin composition comprising an epoxy resin and a curing agent, characterized in that the polyvalent hydroxy compound obtained by the production method according to any one of claims 6 to 10 is an essential component. Epoxy resin composition. 13. A cured product obtained by curing the epoxy resin composition according to claim 9 or 10.