JPS58189219A - Flame retardant for thermosetting resin - Google Patents

Abstract

PURPOSE:A flame retardant suitable for use in thermosetting resins especially for laminated sheets, comprising a phosphorus-containing melamine-modified phenol/ formaldehyde condensate prepared by reacting a specified melamine-modified phenolic resin with an organic phosphoromonohalodate. CONSTITUTION:A phenol is condensed with formaldehyde in a formaldehyde/ phenol molar ratio of 0.6-2.5/1. To the produced condensate are added 0.1- 3.0mol%, per mol of phenol, of melamine and 0.1-10.5mol, per mol of phenol, of formaldehyde, and the mixture is cocondensed. The obtained melamine- modified phenolic resin is reacted with an organic phosphoromonohalodate of formula I , wherein X is Cl or Br, R1 and R2 are each a 1-5C alkyl or a group of formula II, wherein R3 is a 1-12C alkyl Cl or Br. The titled flame retardant is prepared from the obtained phosphorus-containing melamine-modified phenol/ formaldehyde condensate having a gelation time of 40-600sec (at 150 deg.C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame retardant for thermosetting resins, particularly a flame retardant suitable for thermosetting resins for laminates.

Thermosetting resins have traditionally been used mainly in electrical and electronic equipment, and their demand is extremely high. In recent years, various regulations have been set regarding the flammability of the materials used in these materials from the standpoint of fire safety measures, and various studies have been made to make thermosetting resins flame retardant. However, when thermosetting resin is made into a laminate, it satisfies not only flame retardancy but also various other properties such as heat resistance, dimensional stability, electrical properties, punching workability, and bleedability. need to be kept.

Therefore, Japanese Patent Application Laid-Open No. 104682,
Although inventions such as Publication No. 108180 have also been proposed,
None of these methods can satisfactorily solve the problems encountered in laminated plates, and there has been a great need for improvements.

The present invention makes this improvement 1-1, and provides excellent flame retardancy while maintaining practical properties such as heat resistance and dimensional stability. To provide a flame retardant for thermosetting resins that exhibits properties.

The %F refractor of the present invention is a phenol-formaldehyde condensate condensed at a ratio of 0.6 to 2.5 moles of formaldehyde per mole of phenols, and 0.1 to 3.0 of melamine per mole of phenols. Melamine and formaldehyde are added at a ratio of 0.1 to 10.5 moles, formaldehyde is added, and a melamine-modified phenol resin obtained by co-condensation is mixed with a melamine-modified phenol resin of the general formula (where, X represents C1 or Br, R1 and R2 are carbon Alkyl group of numbers 1 to 5, haloalkyl group, 7''-/
'! , 1RId:<F””&i L, R3U/fft
Jik 1 to 12 alkyl groups, 1 □ 11 or more substituents selected from C1 and Br) obtained by reacting organic phosphoric acid monohalode l- represented by 1 to 12 alkyl groups, C1 and Br, with a gelation time of 40 to 600 seconds at 1500C It is characterized by a certain phosphorus-containing melamine-modified phenol formaldehyde condensate.

The above phenols include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenylphenol ether,
Phenoxyphenol, styrenated phenol, motuprominated styrenated phenol, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenylene/L/)pentane, dihydroxydiphenylmethane, bis(hydroxyphenyl)propane, methylenebis(ethyl tertiary butyl fresi/ Formalin and paraformaldehyde may be used as the aldehyde component.

In the ff production of phenol formaldehyde condensate,
If the molar ratio of formaldehyde to phenol is less than 0.6, co-condensation is difficult and the stability of the product is also poor. On the other hand, when it exceeds 2.5, the amount of free formalin increases, causing problems in workability.

Furthermore, melamine and formaldehyde added to the phenol-formaldehyde condensate have no effect when used at a molar ratio of less than 0.1 to the phenol, and when the molar ratio exceeds 3.0, the product cannot be stored. Since the stability is poor, gelation tends to occur in the next phosphoric acid esterification step, making it less practical. The amount of formaldehyde is
If the molar ratio to the phenol exceeds 10.5, a problem will arise in the amount of free formalin, and if the molar ratio is less than 0.1, a problem will arise in the co-condensation property.

The condensation reaction between phenols and formaldehyde and the subsequent co-condensation reaction with melamine/formaldehyde are generally carried out in an alkaline range of pH 8-12 at a temperature of 50-100'C1.
Preferably, it is carried out at 60 to 800C.

Next, the organic phosphoric acid 7-8 rodate represented by the general formula (1) to be reacted with the melamine-modified phenol resin includes, for example, dimethyl phosphate monochlororesort, diethyl phosphate monochlororesort, dipropyl phosphate monochlororeso-1-, diptyl phosphate Monochrome Resort, Cyamyl Phosphate Monochrome Resort, Di(chloroethyl)phosphate Monochrome Resort, Di(
Gromoech tv) Phosphate monochrome resort, di(chloropropyl) phosphate monochrome resort, di(bromopropyl) phosphate monochrome resort, bis(dibromo 10 p/L)
/) Phosphoric acid monochrome resort, bis(dichloropropyl/I)
/) Phosphoric acid monochlore resort, diphenyl phosphate monochlore resort, dipropyl phosphate monochlore resort!・, dixylenyl phosphate monochrome resort, bis(propylphenyl)
Phosphoric acid monochrome resort, bis (butylphenyl) phosphoric acid monochrome resort, bis (amil pheni tv) phosphorus f
p monochrome resort, bis(chlorophenyl) phosphate monochrome resort, bis(dibromophenyl/I/) phosphate monochrome resort, cyamyl phosphate monopromizo-1゛, di(bromoethyl) phosphate monopromidate, bis(dibromopropyl) phosphate monopromidate, diphenyl Included are phosphate monochlororesort, dicresyl phosphate monopromidate, and mixtures thereof.

The reaction between the organic phosphoric acid monohalide 1- and the melamine-modified phenol resin can be carried out by a conventionally known method.

Thermosetting resins to which the flame retardant of the present invention is applied are not particularly limited, but are useful as resins for manufacturing laminates, such as unsaturated polyvarnish resins, epoxy resins, phenol resins, and melamine resins.

The flame retardant of the present invention is 3 parts by weight per 100 parts by weight of the thermosetting resin.
It is preferable to use it in a proportion of 150 parts by weight. Although it is possible to mix more than this amount, it is not economical.

Further, the compounding method can be either by adding it at an appropriate stage during the production of the thermosetting resin or by adding and mixing it into a previously produced or commercially available thermosetting resin. Furthermore, in the present invention, in order to improve flame retardancy, it is also possible to use an organic halogen-containing compound, aretimone trioxide, etc. in combination. Examples of the organic halogen-containing compound include halogenated phenol, halogenated aniline, halogenated hisphenol, halogenated diphenyl ether, halogenated phenylhydroxyethyl ether, and halogenated phenyl glycidyl ether.

Next, examples of the present invention will be shown. In the examples, parts and % indicate parts by weight and % by weight unless otherwise specified.

Example (1) First, in the first stage, 1.0 mol of phenol and 42% phenol
Lemarin 1. OmoA/10% Na OT-1 (catalyst)
was adjusted to pIIh, o, and reacted at 80°C for 2 hours.

This reaction product was then heated at 600C with 0.8 mol of melamine and 1 L of 16 mol of 42% formalin.
After the reaction was completed, the reaction was carried out at 40-50°C for 3 hours.
%Na0T was added and stirred at this temperature for 60 minutes to form a homogeneous liquid. To this liquid were added 30 l of toluene and 65 p of methylene chloride, cooled, and then 1 mol of di(chloroethyl/L/)phosphoric acid monochlororesort, which had been synthesized separately, was added dropwise at 20 to 300C. After completion of the dropwise addition, continue stirring for 60 minutes, then add pLI 5 to 6 with 10%) 11Cl.
and washed three times with water.

Separate the oily layer, adjust the pH to 7-8 with triethylamine, and distill off the solvent and water at 60-8oC under reduced pressure.
A phosphorus-containing melamine-modified phenol formaldehyde condensate, that is, a flame retardant, was obtained. Let this be A.

Hereinafter, flame retardants B-H were synthesized in the same manner as A using the reaction components shown in Table 1.

Table 1 shows the gelation time at 15 o'C of each flame retardant.

Example (2) Commercially available phenolic resin varnish with a solid content of 60%], O0
A refueling agent in the proportion shown in Table 2 was added to the portion, and the mixture was heated to a thickness of 0.
A 25+++π cotton linter paper was impregnated with a resin content of 45% and dried.

Seven sheets of the obtained resin-impregnated paper were laminated and heated at 160°C and 180%.
Pressure was applied for 50 minutes under these conditions to obtain a laminate with a thickness of 1.6 wings.

The properties of each laminate are shown in Table 2, and it can be seen that all products using the flame retardant of the present invention have excellent flame retardancy and insulation, and also have good product stability and processability.

Example (3) 94 parts of phenol, 108 parts of cresol, 60 parts of the product of Example H, 240 parts of 37% formalin, and 5 parts of triethylamine were mixed and stirred at 90-100°C for 2 hours.
I reacted while doing so. Thereafter, it was dehydrated under reduced pressure, and methanol was added to adjust the resin content to 60% to obtain a resol varnish. This varnish or a varnish prepared by adding anti-flammability to 100 parts of this varnish in the proportions shown in Table 3 was applied to a thickness of 0°25.
It was impregnated with linter paper containing 45% resin and dried. Seven sheets of the resulting resin-impregnated paper were laminated and pressed for 50 minutes under the conditions of 1-5]-600C180 to obtain a laminate of Ir7 and 1.6 degrees.

Table 3 shows the properties of each laminate.

Example (4) Epoxy resin (trademark Epu) 828) 50% MEK solution], 0 parts of O, 3 parts of dianediamide, and the flame retardant shown in Table 4 were mixed and dissolved.

Soak a piece of cotton linter paper with a thickness of 0.25 part m, and
% resin content and dried. Seven sheets of the resulting resin-impregnated paper were stacked, a copper foil was placed on one side, and pressure was applied for 60 minutes under the conditions of 1600C180''XJ to obtain a 19-1.6#Iff laminate.

Table 4 shows the properties of each laminate.

Table 4 *1), E, and G are products T of Example jl) 131)
P f6 is tetrabromophenyl ether *Comparative Example The properties of the laminates shown in Tables 2 to 4 were measured by the following test method.

Flame retardancy: U■, -94 (]/8 inches) Insulation: JIS
C-6481 Heat resistance: JIS C-6481 Dimensional stability: Measurement of shrinkage rate after 150' Cl2O heat treatment Punching workability: ASi'Ml) -617 board surface condition: Visually determined Bleedability: Judging the oozing state of oily substances with the naked eye after storage at 120°C for 148 hours Soldering heat resistance: JIS C-5034 Special ♂1゛Applicant No. 1-Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] 0.6 phor J2 aldehyde per mole of phenols
For a phenol-formaldehyde condensate condensed at a ratio of ~2.5 moles, 0.1 to 3.0 moles of melamine and 0.1 to 0.1 moles of melamine and 0.1 to 3.0 moles of formaldehyde per mole of phenols.
The product is obtained by adding melamine and formaldehyde in a ratio of 1O15 mol and co-condensing (where X represents C1 or Br, and one or more substituents selected from the alkyl group, Ci and Br of R1 and R212) A phosphorus-containing melamine-modified phenol-formaldehyde condensate obtained by reacting an organic phosphoric acid monohalodate represented by ) with a gelation time of 40 to 600 seconds at 500C. fuel.