JPH0564966B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a flame retardant for thermosetting resins. (Prior art) Thermosetting resin is a resin that can provide polymeric materials with various excellent properties, and the resulting materials are widely used as electrical insulation materials, mechanical parts materials, household goods materials, construction materials, etc. used in Examples of thermosetting resins include unsaturated polyester resins, melamine resins, epoxy resins, and phenolic resins. In order to impart flame retardancy to such thermosetting resins, flame retardants are usually added and blended. is being carried out. As such flame retardants, phosphorus-based flame retardants, halogen-based flame retardants, and the like are used. (Problem to be solved by the invention) Flame retardants normally used in thermosetting resins are required to have heat resistance that can withstand heat exposure during molding of the resin or when using molded products. be done. Furthermore, thermosetting resins are often made by polymerizing liquid or solution-like low polymers with relatively low viscosity, making it difficult to uniformly disperse or dissolve flame retardants with high specific gravity and store them for long periods of time. ,
Therefore, flame retardants with excellent compatibility are needed. The commonly used phosphorus-based flame retardants have problems such as insufficient compatibility with resins and water resistance, lack of flame retardancy compared to halogen-based flame retardants, and insufficient heat resistance. However, halogen flame retardants have problems with compatibility, heat resistance, moldability, etc., and the reality is that there is no flame retardant that satisfies all requirements as a flame retardant for thermosetting resins. (Means for Solving the Problems) The present inventors have conducted extensive research in order to solve the above problems, and as a result, have provided the present invention. That is, general formula (1) [In the formula, A is -CH ₂ -, -SO ₂ -, -O- or

[Formula] is shown. R ₄ represents H or CH ₃ . Y represents Br, Cl, _CH3 or H. m and n represent numbers from 1 to 4. l represents a number from 0 to 100. ] 1 mol of the epoxy compound represented by (hereinafter referred to as the epoxy compound of general formula (1)), general formula (2) [In the formula, R ₂ represents H, a C ₁ to ₁₃ linear or branched alkyl group, a phenethyl group, a styrenyl group, or a phenyl group. X represents Cl, Br or I. q represents a number from 0 to 4, and p represents a number from 1 to 5. However, p+q≦5. ] 0.2 to 1.3 mol of the compound represented by (hereinafter referred to as the compound of general formula (2)) and general formula (3) [In the formula, R ₃ represents a C ₁ to ₁₃ linear or branched alkyl group, phenethyl group, or styrenyl group. r represents a number from 1 to 3. ] A flame retardant for thermosetting resins, characterized in that it contains as an essential component the reaction product obtained by reacting 1.8 to 0.7 mol of the compound represented by the formula (hereinafter referred to as the compound of general formula (3)). be. As the epoxy compound of general formula (1) used in the present invention, general formula (4) [In the formula, A, Y, m and n are the same as above. ] Examples include compounds obtained by reacting the bifunctional phenol compound represented by the following with epihalogenhydrin or methyl epihalogenhydrin. Bifunctional phenol compounds include, for example, bisphenol A, tetrabromobisphenol A, di(hydroxyphenyl) sulfone, tetrabromodi(hydroxyphenyl)sulfone, di(hydrophenyl) ether, and tetrabromodi(hydroxyphenyl) sulfone. enyl) ether, di(hydroxyphenyl)methane, tetrabromodi(hydroxyphenyl)methane, tetrachlorobisphenol A, tetramethyl-di(hydroxyphenyl)methane, dichlorodi(hydroxyphenyl)methane, and the like. Epihalogenhydrin or methylepihalogenhydrin includes, for example, epichlorohydrin, epibromohydrin, methylepihalochlorohydrin,
These include methylepichlorohydrin and methylepibromohydrin. As the compound of general formula (2) used in the present invention,
Examples include tribromophenol, dibromocresol, dibromophenethylphenol, dibromononylphenol, monobromo-Sec butylphenol, monochlorophenyl, tribromophenylphenol, monochlorophenylphenol, and the like. Next, the compound formula of general formula (3) used in the present invention includes, for example, cresol, phenol, O-Sec
Examples include butylphenol, phenethylphenol, nonylphenol, di(phenethyl)phenol, octylphenol, aminophenol, styrenated phenol, distyrenated phenol, and the like. As the flame retardant for thermosetting resins according to the present invention, the epoxy compound of the general formula (1), the compound of the general formula (2), and the compound of the general formula (3) are catalyzed in the presence or absence of a solvent. as the fourth
A grade ammonium compound or a quaternary phosphonium compound, etc. are added at a temperature of 40 to 150°C, and 0.2 to 1.3 moles of the compound of general formula (2) and general formula (3) are added to 1 mole of the epoxy compound of general formula (1). compound of
Examples include reaction products obtained by reacting at a reaction ratio of 1.8 to 0.7 moles. In the above reaction, 0.2 to 1.3 mol of the compound of general formula (2) is suitable for 1 mol of the epoxy compound of general formula (1); less than 0.2 mol is insufficient in flame retardancy, and more than 1.3 mol In this case, the resulting flame-retardant thermosetting resin is hard and cannot achieve the desired dimensional stability. Furthermore, the compound of general formula (3) is suitably used in an amount of 1.8 to 0.7 mol. If the amount of the compound of general formula (3) is less than 0.7 mol, a flame-retardant thermosetting resin having sufficient plasticity cannot be obtained.
If the amount exceeds 1.8 mol, a flame-retardant thermosetting resin with poor dimensional stability, mechanical properties, flame retardance, etc. will be obtained. Next, examples of the quaternary ammonium compound used as a catalyst include tetrabutylammonium bromide, tetraethylammonium chloride, trimethylbenzylammonium bromide, lauryltrimethylammonium acetate, tetramethylammonium propionate,
Examples of the quaternary phosphonium compound include octylphenoxyethoxyethyltrimethylammonium bromide, and examples of the quaternary phosphonium compound include tetrabutylphosphonium chloride, tetraethylphosphonium chloride, and cyclohexyltrimethylphosphonium chloride. The amount of these catalysts used is 0.01 to 5% by weight based on the amount of the epoxy compound of general formula (1) used. Of course, it is possible to use a larger amount than this, but it is necessary to consider economic efficiency. Next, the reaction proceeds without using a solvent, but
When used, examples of the solvent include toluene, xylene, methyl ethyl ketone, methanol, ethanol, butanol, cyclohexanol, and the like. Next, the appropriate reaction temperature is generally 40 to 150°C; lower temperatures require a longer reaction time.
Further, at temperatures higher than that, there are problems such as significant coloring. Furthermore, neutral phosphates, phosphonates, or other flame retardants may be added to the reaction system. Next, target thermosetting resins to which the flame retardant of the present invention is blended include unsaturated polyester resins,
Melamine resin, epoxy resin, phenolic resin,
Examples include silicone resin, urea resin, diallyl phthalate resin, butadiene resin, and polyurethane resin. The amount of the flame retardant of the present invention added to the thermosetting resin is 2 to 30 parts per 100 parts (parts by weight, hereinafter the same) of the thermosetting resin. Of course, it is possible to add more or less than this amount, but if the amount is less than 2 parts, satisfactory flame retardancy will not be obtained, and if it exceeds 30 parts, it will not be possible to obtain the desired flame retardant properties, and if the amount is more than 30 parts, there will be problems with the physical properties of the resin and economic efficiency. Undesirable. In addition to the flame retardant of the present invention, the flame retardant for thermosetting resins of the present invention includes other brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, halogen-containing phosphorus flame retardants, and brominated epoxy resins. , tung oil, melamine, melamine isocyanate, antioxidants, plasticizers, stabilizers, fillers, dyes, pigments, solvents, inorganic flame retardants such as aluminum hydroxide, antimony trioxide, zinc borate, etc. may be used in combination. do not have. (Effects of the Invention) The flame retardant obtained according to the present invention provides excellent flame retardancy, plasticity, and dimensional stability when used in a thermosetting resin. For example, when used in thermosetting resin for laminates,
As part density increases and hole spacing becomes finer,
Low temperature punching is possible, cracking during drilling,
No smear etc. occurs. Further, the resulting laminate itself has extremely excellent impact resistance, strength, electrical properties, etc. Furthermore, the flame retardant thermosetting resin composition containing the flame retardant of the present invention can be used to produce various molded products, films,
It is possible to produce synthetic resin-coated paper, laminated products, paints, adhesives, etc. (Example) The present invention will be described below with reference to production examples and examples. Production Example 1 As the epoxy compound of general formula (1), 900 g (1.0
A mixture of 330 g (1.0 mol) of tribromophenol as a compound of general formula (2), 220 g (1.0 mol) of nonylphenol as a compound of general formula (3), and 3 g of tetrabutylammonium bromide as a catalyst was heated at 130° C. Allowed time to react. The obtained reaction product contains 0.1% oxirane oxygen,
The acid value was 0.01 and the bromine content was 47.8 (47.59)%. Note that the values in parentheses are calculated values. Production Example 2: Brominated epoxy resin (epoxy equivalent: 380, Br%: 49) 760 g (1.0
mol), tribromophenol 330g (1.0 mol) as a compound of general formula (2), distyrenated phenol (OHV 185.76) 302 as a compound of general formula (3)
(1.0 mol) and 1 g of tetrabutylphosphonium bromide as a catalyst were reacted at 120° C. for 6 hours. The reaction product obtained is oxirane oxygen 0.15
%, acid value 0.03, and bromine content 45.0 (43.99)%. Production Example 3 628g of brominated epoxy compound (epoxy equivalent: 314, bromine%: 52.2) as the epoxy compound of general formula (1)
(1.0 mol), tribromophenol 330 g (1.0 mol) as a compound of general formula (2), O-Sec butylphenol 150 g (1.0 mol) as a compound of general formula (3)
and lauryltrimethylammonium acetate as a catalyst in a mixture of 277 g of toluene as a solvent.
1.1 g was added and reacted at 115°C for 5 hours. The obtained reaction product had an oxirane oxygen content of 0.12%, an acid value of 0.2, and a bromine content of 52.1 (51.25%) in pure analysis. Production example 4 1020 g of brominated epoxy resin (epoxy equivalent 510, Br% 51.0) as the epoxy compound of general formula (1)
(1.0 mol), dibromocresol 266g (1.0 mol) as a compound of general formula (2), distyrenated phenol (OHV 185.76) as a compound of general formula (3)
A mixture of 302 g (1.0 mol), 1.0 g of tetrabutylphosphonium chloride as a catalyst, and 397 g of toluene as a solvent was reacted at 110° C. for 8 hours. The obtained reaction product has an oxirane oxygen content of 0.09%, an acid value of 0.1, and a bromine content of 43.5 (42.8) based on pure analysis values.
It was %. Production Examples 5 to 7 According to Production Example 1, various epoxy compounds of general formula (1), compounds of general formula (2), and compounds of general formula (3) were used and reacted to obtain various reaction products. . The reaction products obtained in each of the above production examples were
Shown in the table.

【table】

【table】

【table】

[Table] Example 1 To 100 parts of a methanol solution of a phenolic resin containing 70 parts of a commercially available phenolic resin containing tung oil, 20 parts of the reaction product obtained in the production example and 10 parts of diphenylresyl phosphate were added and mixed uniformly. It was dissolved in Spread kraft paper (1 mm thick vertically) on the resulting blended varnish.
150m/m, width 100m/m), then 80℃
Pre-dried for 20 minutes. Eight sheets of pre-dried kraft paper were piled up and pressed for 3 minutes at 160° C. x 100 kg/cm ² using a heated press to make a laminate. The obtained laminate with a resin content of 55% by weight was further
Flammability (UL-94) and physical properties were evaluated after treatment at 160°C for 3 hours. The results are shown in Table 2.

【table】

[Table] (1) Storage stability of varnish: The condition was visually judged after being left at -20°C for 48 hours. (2) Flammability: UL-94 (3) Insulation resistance: Tested according to JIS C 6481 after being left for 96 hours at 40°C and 92% RH. (4) Bending strength (normal): Conducted according to JIS C 6481. (5) Tracking resistance: Tested according to UL-746A. Example 2 20 parts of the reaction product of Production Example 2 was mixed with 200 parts of bisphenol epichlorohydrin resin (Epicote # 1001 # 828 1:1 mixture), and 20 parts of m-phenylenediamine was added and thoroughly mixed. The mold was poured into a mold with a length of 150 m/m and a width of 100 m/m, left at room temperature for 20 minutes, cured at 40°C for 2 hours, and at 150°C for 4 hours, and then evaluated for flammability and insulation resistance according to UL-94. did. The results are as follows. Flammability (UL-94); V-O self-extinguishing in 2.0 seconds Normal insulation resistance (JIS C 6481); 5×10 ¹³

Claims (1)

[Claims] 1 General formula (1) [In the formula, A represents -CH ₂ -, -SO ₂ -, -O- or [Formula]. R ₄ represents H or CH ₃ . Y represents Br, Cl, _CH3 or H. m and n represent numbers from 1 to 4. l represents a number from 0 to 100. ] 1 mol of an epoxy compound represented by the general formula (2) [In the formula, _R2 represents H, a _C1-13 linear or branched alkyl group, a phenethyl group, a styrenyl group, or a phenyl group. X represents Cl, Br or I. q represents a number from 0 to 4, and p represents a number from 1 to 5. However, p+q≦5. ] 0.2 to 1.3 mol of the compound represented by and general formula (3) [In the formula, R ₃ is a C _1-13 linear or branched alkyl group,
Indicates a phenethyl group or a styrenyl group. r is 1~
Shows the number 3. ] A flame retardant for thermosetting resins, which contains as an essential component a reaction product obtained by reacting 1.8 to 0.7 moles of the compound shown below.