JPH0940879A - Aqueous flame retardant resin composition, method for producing electric laminate, and flame retardant for aqueous resin - Google Patents

Abstract

(57) [Summary] [Structure] A water-soluble thermosetting resin typified by a resole resin, a water-soluble flame retardant neutralized by reacting a dialkanolamine with a tetrabromobisphenol A type epoxy resin, and an aqueous solution. Contains medium and. [Effect] It can be used as a water-soluble varnish and can
It can be used as a secondary impregnating varnish or as a main varnish for a paper substrate, and the flame retardant effect can be improved.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-soluble flame-retardant resin composition useful in adhesives, paints, fiber treatment agents, castings, molding powders, building materials, paper processing, etc., which require water solubility, and the composition. The present invention relates to an aqueous flame retardant used for materials.

The aqueous flame-retardant resin composition of the present invention is particularly useful as a flame-retardant phenolic resin laminated board (printed wiring board) having a paper as a base material.

[0003]

2. Description of the Related Art Generally, a method for producing a flame-retardant resin laminate using paper as a base material is such that a paper base material is pretreated (undercoating with a varnish) with a hydrophilic varnish in consideration of impregnation of the base material. Then, impregnate a lipophilic varnish mixed with phenol resin and flame-retardant resin and optionally tung oil etc. and dry it 2
A general method is to obtain a prepreg by a stepwise impregnation method and then heat-laminate the prepreg to form a laminated plate.

Conventionally, in order to obtain flame retardancy of a laminated board using a paper base material, for example, a halide or a phosphoric acid ester is used as a flame retardant in a lipophilic varnish. Especially as the halide, mainly brominated bisphenol A
Type epoxy resin is widely used.

[0005]

However, none of the flame retardants, including the above-mentioned brominated bisphenol A type epoxy resin, have sufficient flame retardant effect, and further, due to their lipophilic nature, hydrophilic varnish cannot be used. Since it is difficult to use, a flame retardant can be compounded and used as a lipophilic varnish after being pretreated with a hydrophilic varnish, so that there is a problem that a more sufficient flame retardant effect is not exhibited.

[0006] The problem to be solved by the present invention is that it has an unprecedentedly excellent flame retardant effect, and is used as a hydrophilic varnish, for example, as a varnish for pretreatment in the production of a laminated board using a paper substrate. As a result, the flame retardant can be brought closer to the paper, so that the flame retardant effect can be further improved, and the prepreg can be produced by using the main varnish as the main varnish without the above-mentioned two-step impregnation. Therefore, it is an object of the present invention to provide a water-soluble flame-retardant resin composition capable of improving the productivity of a laminate, a flame retardant used in the composition, and a method for producing a laminate having good flame retardancy.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned conventional circumstances, and as a result, by using a halogenated aromatic compound having an amino group in the molecular structure as a flame retardant, It has been found that a water-soluble flame-retardant varnish having a high flame-retardant effect and water-solubility can be prepared, and the present invention has been completed.

That is, the present invention comprises a water-soluble thermosetting resin (A), a halogen atom-containing water-soluble aromatic compound (B) having an amino group in its molecular structure, and an aqueous medium (C) as essential components. A water-based flame-retardant resin composition characterized by
An inorganic laminate is impregnated with the water-soluble flame-retardant resin composition to form a prepreg, and then a plurality of prepregs are laminated and heat-molded, and a method for producing an electric laminate,
The present invention relates to a flame retardant for an aqueous resin, which comprises a halogen atom-containing water-soluble aromatic compound having an amino group in its molecular structure as an essential component.

The water-soluble thermosetting resin (A) used in the present invention is liquefied to show fluidity when heated to a high temperature or softened to show plasticity, and at the same time, it is intermolecularly reacted by a chemical reaction. Three-dimensional cross-linking occurs, refers to a water-soluble resin that can be insoluble and infusible by curing, specifically, for example, considering the purpose of use and the importance of compatibility of the resin,
Water-soluble melamine resin such as methylated melamine resin, phenol resin such as melamine-modified phenol resin, urea resin,
Resol resin, water-soluble blocked isocyanate resin such as tolylene diisocyanate, methylenebis- (4-
Phenyl isocyanate), isophorone diisocyanate, hexamethylene diisocyanate, and other polyalkylene glycol adducts. Among these, the resole resin is preferable for the paper base laminate from the practical point of view.

The molecular weight range of the water-soluble thermosetting resin (A) is not particularly limited, but if it is a resole resin that can be preferably used, it is 100 to 4 in terms of compatibility.
A relatively low molecular weight of 00 is preferred.

The water-soluble thermosetting resin (A) is
There is no problem even if they are used partially or in combination.

Next, the halogen atom-containing water-soluble aromatic compound having an amino group in the molecular structure, which is used as the component (B) in the composition of the present invention or the flame retardant of the present invention, is particularly limited. Instead, for example, it is obtained by a method of reacting a halogenated epoxy resin with an amine or an amine salt. When reacting with an amine, it may be neutralized with an acid in order to further improve the compatibility with water. In the case where the halogenated epoxy resin and the amine are neutralized after the reaction, or when the amine is neutralized to form an amine salt and reacted with the halogenated epoxy resin, all of the amino groups or amines are acidified. It is not necessary to neutralize with, and it is important to use the acid within the range considering other practical properties.

The epoxy resin used here is not particularly limited, and examples thereof include halogenated bisphenol A type epoxy resin and halogenated bisphenol F.
Type epoxy resin, halogenated bisphenol type epoxy resin such as halogenated bisphenol S type epoxy resin,
Examples thereof include novolac type epoxy resins such as halogenated biphenol type epoxy resin, halogenated phenol novolac type epoxy resin, and halogenated naphthol type novolac type epoxy resin, but particularly excellent compatibility with the water-soluble thermosetting resin (A). From the viewpoint, halogenated bisphenol type epoxy resin is preferable.

Further, particularly preferable examples of the halogenated bisphenol type epoxy resin include tetrabromobisphenol A type epoxy resin and tetrabromobisphenol F type epoxy resin.

Particularly, the tetrabromobisphenol A type epoxy resin is preferably a bisphenol A type epoxy resin in which four hydrogens of phenyl groups are replaced with bromine from the viewpoint of the flame retardant effect.

The halogenated bisphenol type epoxy resin has an epoxy equivalent of 300 to 300 from the viewpoint of compatibility.
The thing of 1000 is preferable and the thing of 330-700 is especially more preferable.

In the halogenated epoxy resin described in detail, the halogen content is not particularly limited, but from the viewpoint of the resin characteristic value obtained, a halogen atom content of 35 to 55% is preferable. That is, when the content is 35% or more, the halogen content of the obtained resin is increased, and the flame retarding effect becomes more remarkable, and when the content is 55% or less, a higher molecular weight of the obtained resin can be prevented and the impregnation property can be enhanced. .

The amine or amine salt used in the reaction with the halogenated epoxy resin may be any of primary, secondary and tertiary, and there is no particular limitation. For example, as amine, specifically, Diethylenetriamine, triethylenetetramine, tetraethylpentamine, dipropylenetriamine, bis (hexamethylene) triamine, polyamines such as 1,3,6-trisaminomethylhexane, polyamines such as trimethylhexamethylenediamine, polyetherdiamine and diethylaminopropylamine. Aliphatic polyamines such as ethylenediamine, menthenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, and aliphatic amines containing aromatic rings such as metaxylylenediamine. Aromatic primary amines such as primary amines, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, eutectic mixtures of aromatic diamines, other aromatic diamines, 3,9-bis (3-aminopropyl) -2,4 , 8,10-Tetraspiro [5,5] undecane and other diamines containing a spiro ring, diamines having a hydanto ring, diamines having an imide ring, diamines having an ether bond in the main chain, triamines,
Polyoxyethylene chain diamine, diamine whose main chain is silicone, polyamine epoxy resin adduct, polyamine-ethylene oxide adduct, polyamine-propylene oxide adduct, cyanoethylated polyamine,
Ketimine, modified amines such as melamine, long-chain diamines, trimethylguanidine, tetramethylguanidine,
Examples thereof include guanidine derivatives, benzoguanamine, polyamide resins, polyamide adducts, dicyandiamide and its derivatives, organic acid hydrazides, diaminomaleonitrile and its derivatives, melamine and its derivatives, and amino alcohols such as monoalkanolamines and dialkanolamines. As the amine salt, any of the above amines neutralized with an acid can be used.

Of these, a secondary amine or a salt thereof is particularly preferable, and an amino alcohol or a salt thereof is particularly preferable, since the water-solubility of the finally obtained compound is remarkably good and the reaction is easily controlled. Examples of such amino alcohols or salts thereof include diethanolamine, diisopropanolamine, N,
Examples thereof include N-methyldiethanolamine and salts thereof. Of these, dialkanolamines and salts thereof are particularly preferable.

The above-mentioned amine or amine salt is
It goes without saying that they may be used alone or in combination of two or more.

The acid for forming the amine salt or the acid for reacting the halogenated epoxy resin with the amine and then neutralizing the acid is not particularly limited as long as it has an anion group. However, specifically, acetic acid, sulfonic acid, sulfuric acid ester, phosphoric acid ester, phosphoric acid and the like can be mentioned. Among them, acetic acid having a carboxylic acid, particularly acetic acid, lactic acid, propionic acid, butyric acid and the like are preferable from the viewpoint of those that decompose and volatilize during heat curing.

The reaction ratio between the halogenated epoxy resin and the amine or amine salt is not particularly limited and may be set in an appropriate range according to each.
For example, the reaction ratio of the halogenated bisphenol type epoxy resin and the amine or amine salt is not particularly limited as long as the compatibility with water is not problematic, but the epoxy group /
The molar ratio of amino groups (including neutralized ones) is 0.
The ratio of 1 to 20 is preferable from the viewpoint of suppressing the molecular weight to be low and improving the impregnation property.

This reaction can be obtained, for example, by heating and melting a halogenated bisphenol type epoxy resin and an amine or an amine salt and reacting them at a temperature of 50 to 150 ° C. When carrying out the reaction, an organic solvent may be used if necessary.

The halogen atom-containing water-soluble aromatic compound having an amino group in the molecular structure thus obtained is dissociated from the halogen due to the influence of the basicity of the adjacent amino group as compared with the conventional halogen compound. Happens easily,
Pyrolysis occurs at low temperature, resulting in excellent flame retardancy.
Further, by changing the amount of amine, it is possible to adjust the degree of thermal decomposition to some extent, and there is an advantage that the degree of freedom in resin design can be widened.

Further, since the above compound becomes a halogenated flame retardant having a hydrophilic property, it can be used as a varnish for paper base materials, for example.
It is possible to reduce the number of processes and shorten the process. Further, in the paper base material, the pretreatment step with the hydrophilic varnish can be omitted, or since the flame retardant can be blended with the hydrophilic varnish used in the pretreatment step, the halogen source should be arranged in a portion closer to the paper base material. The flame retardancy can be further improved.

The specific structure of such a halogen atom-containing water-soluble aromatic compound (B) having an amino group in its molecular structure is not particularly specified, but its average molecular weight is, for example, the fluidity of the composition, especially paper. From the viewpoint of impregnating the base material with the varnish, it is preferably from 300 to 1,000. Further, specifically, when a halogenated bisphenol A type epoxy resin is used as the halogenated epoxy resin and amino alcohols are used as the amine, those represented by the following general formula can be mentioned.

[0027]

Embedded image

(In the formula, X is a bromine atom, a chlorine atom or a fluorine atom, R is a methylol group, an ethylol group or a butyrol group, and n is an integer of 0 to 4.)

The use ratio of the halogen atom-containing water-soluble aromatic compound having an amino group in the detailed molecular structure is not particularly limited, but from the viewpoint of the flame retardant effect, it is 5 to 2 as a solid content.
It is preferably 0% by weight.

In the present invention, in addition to the above compounds, other flame retardants may be used in combination as long as the effects of the present invention are not impaired. Other flame retardants that can be used include, for example, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, phosphorus compounds such as triphenyl phosphite, brominated epoxy resin,
Examples thereof include halogenated compounds such as brominated epoxy oligomers and metal oxides such as aluminum hydroxide, and one or a mixture of two or more of these is used.

Next, as the aqueous medium (C) used in the present invention, an alcoholic solvent is useful in view of compatibility with the components (A) and (B) other than water. Examples of the alcoholic solvent used here include methanol, ethanol, n-butanol, methoxypropanol and the like, but it is usually preferable to use it as an aqueous alcohol solution.

Further, in the composition of the present invention, (A)
In order to adjust the compatibility with the component as well as the component (B),
Other organic solvents of the aqueous medium (C) may be used in combination, and examples thereof include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, and the like. You may use it as 2 or more types of mixed solvent.

The proportion of the aqueous medium (C) used is not particularly limited, but, for example, as a matrix resin composition for a printed wiring board, for example, when another organic solvent of the aqueous medium (C) is used in combination. The total amount of solvents including them is preferably 10 to 90% by weight in the composition, and in particular 40 to 80 in terms of varnish formation.
It is preferably used in the range of weight%.

The water-soluble flame-retardant resin composition of the present invention is extremely useful for laminates as described above, but it can be used in combination with a curing agent such as adhesives, paints, fiber treatment agents, castings, molding powders. It can be used for various purposes such as building materials and paper manufacturing.

The method for producing a laminated board from the water-soluble flame-retardant resin composition of the present invention is not particularly limited, and it can be produced by a known and commonly used method. Generally, a method for producing a flame-retardant resin laminate using paper as a base material is
First, as a pretreatment (undercoating of varnish), the above (A)
To (C) a hydrophilic varnish composed of a composition containing each component is impregnated into a paper base material such as kraft paper and dried to prepare a treated base material having a constant resin amount, preferably 5 to 20% by weight, Then, a pretreated base material is impregnated with a lipophilic varnish prepared by adding and mixing a phenol resin, a flame-retardant resin, and optionally tung oil, and dried at 100 ° C to 200 ° C to obtain a prepreg having a resin amount of 20 to 70% by weight. Or, (A) above
To (C) are impregnated into a paper base material such as kraft paper with a hydrophilic varnish made of a composition containing 100 to 200 ° C.
A method may be mentioned in which a prepreg having a resin amount of 20 to 70% by weight is dried at 0 ° C., then the prepreg is set to about 1 to 10 sheets of copper foil with an adhesive and heated and pressed to obtain a laminated plate. .

In the method (1), the paper substrate can be effectively flame-retarded by pre-treating the paper base material with the water-soluble flame retardant, and further, the amino group in the flame retardant can be further added. Due to the basicity, the dissociation of the adjacent halogen easily occurs, and the flame retardant effect can be improved. By reducing the amount of additives, it also has the effect of preventing deterioration of mechanical strength.

Further, in the above method, the pretreatment and the secondary impregnation step are performed in one step, and the effect of further shortening the steps can be obtained.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION A paper base is impregnated with a resin varnish containing a water-soluble thermosetting resin typified by a resole resin, a compound represented by the above general formula, and water or an aqueous alcohol solution as essential components. Then, a prepreg is obtained, and then about 1 to 10 sheets of the prepreg are set with an adhesive-attached copper foil and heated and pressed to form a laminated plate.

[0039]

EXAMPLES Next, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples. In the examples, "parts" and "%" are based on weight unless otherwise specified.

Synthesis Example 1 <Synthesis of thermosetting resin (A) [water-soluble varnish]> 1000 parts of phenol, 9800 parts of 37% formalin,
20 parts of triethylamine were mixed and reacted at 60 ° C. for 3 hours, and then concentrated under reduced pressure.
It was diluted with a mixed solvent of 80/20 to obtain a water-soluble phenol resin (A-1) having a resin amount of 50%.

Synthesis Example 2 <Synthesis of thermosetting resin (A) [lipophilic varnish]> A mixture of 600 parts of phenol resin, 400 parts of tung oil and 2.5 parts of paratoluenesulfonic acid was reacted at 80 ° C. for 4 hours. . Then, 400 parts of toluene and 10 parts of triethanolamine are added to this to dilute and neutralize, and then 250 parts of paraformaldehyde and 15 g of 25% ammonia water are added,
React at 90 ° C to 100 ° C for 3 hours, then under reduced pressure,
After dehydration and detoluene, 500 parts of toluene and 500 parts of methanol were added for dilution to obtain a tung oil-modified phenol resin (A-2) having a resin content of 50%.

Synthesis Example 3 <Synthesis of Reaction Product (B) of Halogen-Containing Epoxy Resin and Amine> Brominated epoxy resin having epoxy equivalent of 400 and bromine content of 48% (manufactured by Dainippon Ink and Chemicals; EPICLON 153) 1
After 000 parts were dissolved in 1000 parts of methoxypropanol, 260 parts of diethanolamine (1 mol of amine to 1 mol of epoxy group) was added and reacted at 120 ° C. for 2 hours. Next, the temperature was lowered to 100 ° C., 150 parts of acetic acid and 110 parts of water were added and reacted for 2 hours to obtain a resin having a solid content of 50% (hereinafter referred to as reference resin B-1). The average molecular weight of the solid resin was 1,000 and the bromine content was 38%.

Synthesis Example 4 <Synthesis of Reaction Product (B) of Halogen-Containing Epoxy Resin and Amine> The procedure of Reference Example 1 was repeated except that the amount of acetic acid was 75 parts and the amount of water was 185 parts. A resin having a solid content of 50% (hereinafter referred to as reference resin B-2) was obtained. The average molecular weight of the solid resin is
And the bromine content was 38%.

Synthesis Example 5 <Synthesis of Reaction Product (B) of Halogen-Containing Epoxy Resin and Amine> Brominated epoxy resin having epoxy equivalent of 360 and bromine content of 46% (manufactured by Dainippon Ink and Chemicals; EPICLON 152) 1
After dissolving 000 parts in 700 parts of methoxypropanol and 300 parts of n-butanol, 230 parts of diethanolamine (0.8 mol of amine per 1 mol of epoxy group) and 130 parts of acetic acid were heated and mixed at 80 ° C. for 2 hours. What was added was added, and the mixture was further reacted at 100 ° C. for 2 hours. Then, the temperature was lowered, and 100 parts of water was added to obtain a resin having a solid content of 50% (hereinafter referred to as reference resin B-3). The solid content resin had an average molecular weight of 850 and a bromine content of 39%.

Examples 1 to 3 and Comparative Example 1 Using the resin (A-1) obtained in Synthesis Example 1, a varnish was prepared according to the formulation shown in Table 1 and the compatibility was examined.

[0046]

[Table 1] [Criteria] O: Compatible. … Transparent.

X: Not compatible … Muddy.

Examples 4 to 6 Resin varnishes were prepared on kraft paper as shown in Table 2, and the varnishes prepared separately were impregnated and dried to obtain prepregs having a total resin content of 56%. 8 sheets of this are laminated, 35 μm on one side
Of copper foil on top of each other, 6 at 160 ℃, 50kg / cm ²
It was heated and pressed for 0 minutes to produce a phenol single-sided copper-clad resin laminate having a thickness of 1.6 mm.

Each of the obtained single-sided copper-clad laminates was tested for workability, flame retardancy, water absorption, and physical properties. The results are shown in Table 2.

Comparative Example 3 As a pretreatment, kraft paper was first impregnated with the water-soluble resin (A-1) prepared in <Synthesis Example 1> and dried to give a resin content of 10%.
A treated substrate of

Thereafter, this treated substrate was impregnated with a resin varnish prepared according to Table 2 and dried to obtain a prepreg having a total resin content of 56%. Hereinafter, a phenol single-sided copper-clad resin laminate having a thickness of 1.6 mm was produced in the same manner as in Examples 4 to 6.

The one-sided copper-clad laminate thus obtained was tested for workability, flame retardancy, water absorption and various physical properties. The results are shown in Table 2.

[0053]

[Table 2] * 1: Comparative Example 3 uses 17 parts of (A-1) resin for pretreatment * 2: Brominated epoxy resin (epoxy equivalent 400; bromine content: 48%) 60% non-volatile toluene solution

[0054]

EFFECTS OF THE INVENTION According to the present invention, an excellent flame retarding effect is exhibited as compared with the conventional one, and further, it can be used as a hydrophilic varnish, for example, as a pretreatment varnish in the production of a laminated board using a paper substrate. As a result, the flame retardant can be brought closer to the paper, so that the flame retardant effect can be further improved. Further, since the prepreg can be manufactured by using the main varnish as the main varnish without performing the above-mentioned two-step impregnation and only by one-step impregnation, the productivity of the laminated plate can be improved.

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Claims (15)

[Claims] 1. A water-soluble thermosetting resin (A), a halogen atom-containing water-soluble aromatic compound (B) having an amino group in its molecular structure, and an aqueous medium (C) as essential components. A characteristic aqueous flame-retardant resin composition. 2. A halogen atom-containing aromatic compound (B)
Is a halogen atom-containing bisphenol-based compound having an amino group in its molecular structure. 3. A halogen atom-containing aromatic compound (B)
The aqueous flame-retardant resin composition according to claim 2, wherein is a bisphenol type epoxy resin containing a halogen atom and an amine or an amine salt reacted with each other. 4. The aqueous flame-retardant resin composition according to claim 3, which is a halogen atom-containing bisphenol type epoxy resin having an epoxy equivalent of 300 to 1000. 5. The water-based flame-retardant resin composition according to claim 3, wherein the amine or amine salt is an amino alcohol or a salt thereof. 6. A halogen atom-containing water-soluble aromatic compound (B) having an amino group in its molecular structure has a number average molecular weight of 3
The water-based flame-retardant resin composition according to any one of claims 1 to 5, which is from 00 to 2000. 7. The water-based flame-retardant resin composition according to claim 1, wherein the thermosetting resin (A) is a resole resin. 8. The aqueous flame-retardant resin composition according to any one of claims 1 to 7, wherein the aqueous medium (C) is an aqueous alcohol solution. 9. A prepreg obtained by impregnating an inorganic base material with the water-soluble flame-retardant resin composition according to any one of claims 1 to 8, and then laminating a plurality of prepregs and thermoforming. A method for manufacturing an electric laminate, comprising: 10. A flame retardant for an aqueous resin, comprising a halogen atom-containing water-soluble aromatic compound having an amino group in its molecular structure as an essential component. 11. The flame retardant for an aqueous resin according to claim 10, wherein the halogen atom-containing water-soluble aromatic compound is a halogen atom-containing bisphenol compound having an amino group in its molecular structure. 12. The halogen atom-containing aromatic compound is obtained by reacting a halogen atom-containing bisphenol epoxy resin with an amine or an amine salt.
The flame retardant for water-based resin described. 13. The flame retardant for an aqueous resin according to claim 12, which is a halogen atom-containing bisphenol type epoxy resin and has an epoxy equivalent of 300 to 1000. 14. The flame retardant for an aqueous resin according to claim 12, wherein the amine or amine salt is an amino alcohol or a salt thereof. 15. A halogen atom-containing water-soluble aromatic compound having an amino group in its molecular structure has a number average molecular weight of 300.
The flame retardant for aqueous resins according to any one of claims 10 to 14, wherein the flame retardant is for water-based resin.