JPH01108220A - Flame-retarding resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can be rendered flame-retarding without detriment to the properties of the resin, by reacting, a specified halogenated aromatic diglycidyl ether with an alpha,omega-polybutadienedicarboxylic acid by heating in the presence of a catalyst. CONSTITUTION:A flame-retarding resin composition is obtained by reacting following materials in the presence of a catalyst 1mol of an at least one compound (A) of formula I [wherein X is a halogen, Y is formula II (wherein k and j are each 0-4, and k+j>=1), formula III, SO2, S, O, formula IV or formula V (wherein W is 0-10), l and m are each 0-4, and l+m>=1] or formula VI (wherein X is a halogen, and n is 1-4) with 0.1-1mol of an alpha,omega- polybutadienedicarboxylic acid (B) of formula VII (wherein Z is a repeating unit of formula VIII, Q is a repeating unit of formula IX, t and p are each an integer >=1, and the arrangement of Z and Q may be random, alternate or block). This composition can impart excellent flame retardancy to a thermosetting resin, especially, a phenolic resin, and can retain or improve its heat resistance, solvent resistance and processability.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a flame-retardant resin composition, and more specifically to the field of flame-retardant resins such as phenolic resins, particularly for electrical component resins such as laminates. The present invention relates to a flame-retardant resin composition suitable for use in the field of flame-retardant materials.

[Conventional technology]

In recent years, there has been an increasing demand for flame retardant properties for various synthetic resin materials used in large quantities in electrical parts, building materials, miscellaneous goods, etc. from the viewpoint of safety. A known method for achieving this flame retardancy is to add a flame retardant to the resin. Various flame retardants have been studied for flame retardant thermosetting resins, especially phenolic resins, for example, Japanese Patent Application Laid-Open No. 60-1
As shown in No. 92732, etc., methods using halogen compounds such as halogenated epoxy resins, and JP-A No. 5
There is a method of using a halogen compound and a phosphorus compound in combination, as shown in Japanese Patent No. 8-8749.

[Problem that the invention seeks to solve]

However, when additive flame retardants such as these halogen compounds and phosphorus compounds are used, which do not react with phenolic resins, there is a problem that the heat resistance and solvent resistance of the resins are inferior. When a reactive halogenated epoxy resin is used, the storage stability of the face is poor, and when this face is used for a laminate, the punching workability of the laminate and the storage stability of the prepreg are affected. The problem was that it was inferior.

The present invention has been made based on the above circumstances, and its purpose is to be able to impart excellent flame retardancy to resins such as phenolic resins, while maintaining heat resistance, solvent resistance, and processability. It is an object of the present invention to provide a flame retardant resin composition which is practically excellent and can improve flame retardancy.

[Means for solving problems]

As a result of intensive research to solve the above problems, the present inventors have discovered that halogen-containing aromatic diglycidyl ethers having a specific structure and α,ω-polybutadiene dicarboxylic acid having a specific composition have been developed. The present inventors discovered that a composition obtained by a heating reaction in the presence of a catalyst satisfies the object of the present invention, and based on this knowledge, the present invention was completed.

That is, the present invention provides [A] general formula (I a) [wherein, X represents a halogen atom, and YCk
H2k+1 is -C- (where k and j are respectively CjH2j
*1 represents an integer from O to 4, and +j≧1), CF
i CFi O (where W represents an integer from O to 10), L and m are
Each represents an integer from 0 to 4, and L0m≧1.

Note that X may be of the same type or different types.

] Or general formula (Ib) [However, in the formula, X represents a halogen atom, and n represents an integer from 1 to 4. Note that X may be of the same type or of different types. ] per mole of one or more compounds represented by (B) general formula (II) HOOC-4Zh-IkuQ? rCOOH(II) [In the formula, Z represents the following repeating unit -CHl-C
l = CH-CHt-, Q represents the following repeating unit = CIl-CI+□- CH=CI(Z, t and p represent integers of 0 or more, and t
+p≧1, and the arrangement of Z and Q is random,
It may be alternate or block. ] α, ω-polybutadiene dicarboxylic acid represented by 0.1
The present invention provides a flame-retardant resin composition obtained by subjecting ~1 mol of the compound to a heating reaction in the presence of a catalyst.

General formula (I a) and (
As the halogen atom X in Ib), mention may be made of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a bromine atom is particularly preferred.

Among the compounds of the general formula (I a), 1 and m in the liquid formula are l + m = 2 to 4, especially l = m = 1 or,
One in which l=m=2 can be suitably used.

Among the compounds represented by the general formula (Ia), specific examples of compounds that can be normally used preferably include, for example, the hydrogen atom of each phenol hydroxyl group of bisphenols in which the benzene nucleus is substituted with a halogen atom. But, CH
Examples include \1 compounds substituted with a z-C1l-Cll□- group. That is, the halogen-substituted bisphenols include tetrahalobisphenol A such as tetrabromobisphenol A, tetrahalobisphenol AF such as tetrabromobisphenol AF, tetrahalobisphenol B such as tetrabromobisphenol B, tetrahalobisphenol B such as tetrabromobisphenol E, etc. Bisphenol B1 Tetrahalobisphenol F such as tetrabromobisphenol F, Tetrahalobisphenol S such as tetrabromobisphenol S1 Dihalobisphenol A such as dibromobisphenol A1 Dihalobisphenol AF such as dibromobisphenol AF, dihalobisphenol AF such as dibromobisphenol B, etc. Examples include dihalobisphenol E such as halobisphenol A1 dibromobisphenol E, dihalobisphenol F such as dibromobisphenol F1, dihalobisphenol S such as dibromobisphenol S, and among these, bromo-substituted products are preferred; In particular, tetrabromobisphenol A and the like are preferred.

Among the compounds represented by the general formula (I b>), specific examples of compounds that are usually preferably used include, for example, the hydrogen of each phenolic hydroxyl group of the halogen-substituted 1,4-dihydroxybenzenes listed below. atoms in Hz
A compound substituted with a -CH-CIlz- group. ´ I can list hardware. That is, the halogen-substituted 1,4-dihydroxybenzenes include, for example,
2,5-dihalo-1,4-dihydroxybenzene, such as 2,5-dibromo-1,4-dihydroxybenzene, 2
．． Examples include 2,3゜5.6-tetrahalo-1,4-dihydroxybenzene such as 3.5.6-tetrabromo-1,4-dihydroxybenzene, among which bromo-substituted compounds are particularly preferred. It is.

Among the compounds exemplified above, diglycidyl ether of tetrabromobisphenol A is particularly preferred.

In addition, as the component [A], one type of compound selected from the compound represented by the general formula (■a) and the compound represented by the general formula (Ib) may be used alone; More than one type of compound may be used in combination.

As the α,ω-polybutadiene dicarboxylic acid represented by the general formula (II) used as the component CB), those having a number average molecular weight of about 300 to 2000 can be suitably used.

If the number average molecular weight is less than 300, the resulting resin may not have a sufficient softening effect when used in resins such as phenolic resins, while if it is greater than 2000, the viscosity will be low. It may become expensive and difficult to use.

Moreover, the repeating unit Z in general formula (II),,! :
Although the ratio of Q, that is, the ratio of t and p, is not particularly limited, a ratio of t:p=5 to 100:95 to O can be preferably used. If this ratio of L is too small, a sufficient flexibility effect may not be obtained. Generally, as the proportion of t increases, the flexibility effect increases, while as the proportion of p increases, the intermolecular reactivity due to the vinyl group in the side chain increases.

The flame-retardant resin composition of the present invention can be obtained by carrying out a heating reaction in the presence of a catalyst at a ratio of 0.5 to 1 mole of the component (CB) per 1 mole of the component [A].

If the proportion of component (B) used is less than 0.5 mol per mol of component [A] used, the storage stability of the resulting composition will decrease; If the amount exceeds the molar amount, the amount of unreacted CB) component increases, which is not preferable.

The heating reaction is usually preferably carried out in the presence of a solvent. The catalyst to be used is not particularly limited as long as it has excellent solubility, such as uniformly dissolving the reaction product, and does not interfere with the catalytic activity.

Specific examples include aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene.

Examples of the catalyst include organic amines, imidazoles, quaternary onium salts such as quaternary ammonium salts and quaternary phosphonium salts, and alkali metal alcoholates.

Examples of the organic amines include tertiary alkylamines such as triethylamine, tripropylamine, and tributylamine; secondary alkylamines such as diethylamine and dibutylamine; and ethylamine, propylamine, butylamine, pentylamine, and cyclohexylamine. Primary alkylamines; aromatic amines such as aniline, N-methylaniline, and N,N-dimethylamine; heterocyclic amines such as pyridine, lutidine, and picoline; among these, for example, Tertiary amines, heterocyclic amines, etc. can be suitably used.

Examples of the imidazole include imidazole, 2-ethylimidazole, 2-methylimidazole,
Alkylimidazoles such as 4-ethylimidazole, 2,4-dimethylimidazole, and 2-ethyl-4-methylimidazole can be mentioned, and among these, for example, alkylimidazoles such as 2-ethyl-4-methylimidazole are preferred. It can be used suitably.

As the quaternary ammonium salt, for example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraethylammonium chloride, etc. can be suitably used.

Examples of the quaternary phosphonium salt include tetraalkylphosphonium halides such as tetraethylphosphonium chloride. Examples of the alkali metal alcoholate B include alcohols such as methanol, ethanol, propatool, butanol, pentanol, hexanol, cyclohexanol, and ofthanol, or alkali metal salts of phenols such as phenol and cresol. . In addition, examples of alkali metals include lithium, sodium, potassium, etc.
Preferred are lium, potassium, and the like.

The conditions for the heating reaction cannot be uniformly defined because they vary depending on other conditions such as the type of catalyst used, the amount used, and the type and usage ratio of the [A] component and (B) component.
For example, it is preferable that the reaction temperature is usually about 50 to 200°C, preferably about 80 to 150°C, the reaction pressure is normal pressure, and the reaction time is about 2 to 5 hours.

The proportion of the catalyst to be used cannot be uniformly defined as it varies depending on the type of catalyst used, the reaction conditions, the type and proportion of the [A] component and CB) component used, etc., but, for example,
Usually 0.1 to 1 per 100 parts by weight of component [A] used
The amount is preferably about 0.1 to 0.5 parts by weight.

After carrying out the heating reaction as described above, the solvent and catalyst used can be distilled off to a necessary extent to obtain the combustible resin composition of the present invention.

The combustible resin composition of the present invention thus obtained is
For example, it is suitably used as a combustion agent for various flammable polymer resin materials such as phenol resin, epoxy resin, polyester resin, polyethylene resin, polystyrene resin, polypropylene resin, ABS resin, methacrylic resin, acrylic resin, polyamide resin, etc. can do.

In addition, the flammable resin composition of the present invention not only combusts the resin, but also has the effect of increasing the stiffness of the resin, and is particularly effective for phenolic resins, which are required to be flammable and flexible at the same time. It can be suitably used for

〔Example〕

(Example 1) 550 g of a 60% toluene solution of Kasudkan tetrabromobisphenol A diglycidyl ether, 390 g of α,ω-polybutadiene dicarboxylic acid (number average molecular weight 1300.1,2-polybutadiene component 85%), 2-ethyl- 0.55 g of 4-methylimitazole was introduced into a No. 21 4-day flask and reacted at 110° C. for 3 hours. After the reaction was cooled, a yellow transparent viscous liquid was obtained.

The HLC chart of the reaction product is shown in Figure 1.
The R chart is shown in FIG.

Production example of phenolic resin base varnish: 3000 g of metacresol, 2000 g of tung oil.

2 g of para-toluenesulfonic acid was mixed and 100 g was reacted for 1 hour. Next, 750 g of phenol was added to this reaction solution.
, 1400 g of 80% paraformaldehyde, and 100 g of 25% aqueous ammonia were added, and the mixture was reacted at 80° C. for 3 hours. The condensed water was distilled off, and the end point was the point at which the gel time of the reaction solution on a hot plate at 160° C. reached 3 minutes, and a base varnish was obtained.

Preparation of varnish containing flame retardant resin composition To 1500 g of the base varnish obtained in the above production example, 600 g of the reaction product obtained in the above synthesis example was added and uniformly mixed and dissolved to obtain a flame retardant compound face.

160% of the above base varnish and blended varnish.
It was cured to a B-stage state on a hot plate at .degree. After pulverizing these resins, they were heat-molded at 170° C. for 100 minutes under a pressure of 100 kg/cni using stainless steel plates with 1.6 mm spacers in between to obtain resin plates. The properties of the obtained resin plate were measured according to JIs-6911. The results are shown in Table 1.

(Comparative Example 1) 300 g of tetrabromobisphenol A digucidyl ether was added to 1500 g of the base varnish produced in Example 1.
In addition, the mixture was uniformly mixed and dissolved to obtain a blended face.

Using this blending face, a resin plate was obtained in the same manner as in the production example of Example 1, and the same tests as in Example 1 were conducted. The results are shown in Table 1.

(Comparative Example 2) 200 g of hexabromodiphenyl ether and 100 g of triphenyl phosphate were added to 1500 g of the base varnish produced in Example 1 and mixed and dissolved uniformly to obtain a blended varnish. The following was carried out in the same manner as the production example and test example of Example 1. The results are shown in Table 1.

(The following is a blank space) [Effects of the Invention] As is clear from the results in Table 1, the flame-retardant resin composition of the present invention can be made flame-retardant without deteriorating the resin properties, and in particular, phenol For resins that require flexibility, such as resins, it is possible to provide a flame-retardant resin composition that is extremely advantageous in practice and can significantly improve flexibility as well as flame retardancy.

[Brief explanation of the drawing]

Figure 1 shows HLC (
Liquid chromatography) chart is shown. FIG. 2 shows an IR (infrared absorption spectrum) chart of the flame-retardant resin composition (after solvent removal) synthesized in the synthesis example of Example 1. Explanation of symbols 1 Toluene 2 Tetrabromobisphenol A diglycidyl ether (TBBG) 3 α, ω-polybutadiene dicarboxylic acid 4 7BBG
and PB reactant otoe shogi (Gaupt) No. 111 Return of clothing (C-1) Figure 2 Procedure amendment (Shark)

Claims (1)

[Claims] 1. [A] General formula (Ia) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(Ia) [However, in the formula, X represents a halogen atom, ▲Mathematical formula,
There are chemical formulas, tables, etc.▼ (Here, k and j each represent an integer from 0 to 4, and k+j≧1.), ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2,
-S-, -O-, ▲Mathematical formulas, chemical formulas, tables, etc.▼ or ■CH_2■_w (however, w represents an integer from 0 to 10), l and m are each 0 to 4 represents an integer, and l+m≧1. Note that X may be of the same type or different types. ] Or general formula (I b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I b) [However, in the formula, X represents a halogen atom, and n represents an integer from 1 to 4. Note that X may be of the same type or of different types. [B] General formula (II) HOOC■Z■_t■Q■_p-COOH (II) [However, in the formula, Z is Repeating unit -CH_2-CH
=CH-CH_2-, Q represents the following repeating unit ▲There are mathematical formulas, chemical formulas, tables, etc.▼, t and p represent integers greater than or equal to 0, and t
+p≧1, and the arrangement of Z and Q is random,
It may be alternate or block. ] α,ω-polybutadiene dicarboxylic acid represented by 0.1
1. A flame-retardant resin composition obtained by subjecting 1 mol of mol of mol of chloride to a heating reaction in the presence of a catalyst. 2. The flame-retardant resin composition according to claim 1, wherein the catalyst is an organic amine, an imidazole, a quaternary onium salt, or an alkali metal alcoholate. 3. The flame-retardant resin composition according to claim 1 or 2, wherein the compound used as the component (A) is diglycidyl ether of tetrabromobisphal A. 4. The number average molecular weight of the compound represented by the general formula (II) is within the range of 300 to 2000, and the ratio of repeating units Z and Q is t:p = 5 to 100:95 to 0. A flame-retardant resin composition according to claim 1, 2, or 3.