JPS5938261B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for flame retardant thermoplastic polyester resin, and more specifically, when flame retardant the resin with alkaline earth metal hypophosphite, a specific phosphorus compound and/or Or it relates to a resin composition with enhanced flame retardant effect in which polycarbonate is present.

BACKGROUND ART Conventionally, halogen-containing compounds, organic phosphorus compounds, and the like have been widely used as a method for making flammable resins, such as thermoplastic resins, flame retardant. Furthermore, recently, the use of red phosphorus alone has been proposed. However, there are drawbacks to their use, such as the toxicity of the gas generated during combustion and, in the case of red phosphorus, the risk of spontaneous combustion during storage due to yellow phosphorus present in small amounts as an impurity. As a result of studies to solve this problem, the present inventor found that alkaline earth metal hypophosphite is not only effective as a flame retardant aid, but also works alone as a flame retardant. Flame retardant compositions, either alone or in co-existence with other flame retardants, have previously been proposed.

However, through subsequent studies, it was discovered that the effect is even greater when a specific phosphorus compound and/or polycarbonate is co-present with the alkaline earth metal hypophosphite salt, leading to the present invention.

That is, the present invention provides thermoplastic polyester resin, a captive alkaline earth metal salt of hypophosphite, and (B) the following general formulas (a) to
A flame-retardant resin composition characterized by containing one or more compounds selected from the group consisting of compounds represented by (d). [However, in the formula, R, , R2 and R3 each represent the same or different alkyl, haloalkyl, aryl and... aryl group] [However, in the formula, X. Y is a bromine atom or a chlorine atom, an alkyl group having 1 to 4 carbon atoms, m
and n is an integer of 0 to 2, l is an integer of 2 or more, R is an alkylene group,
1yo・ノ廿 81S-, -SO- -SO2-.

] The thermoplastic polyester resin in the present invention includes, for example, polyethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalene-2,6-dicarboxylate,
Polytetramethylenenaphthalene-2,6-dicarboxylate, Polyhexamethylenenaphthalene-2,6-dicarboxylate, Polytetramethylene diphenyl-4,
4'-dicarboxylate, polyhexamethylene diphenyl-4,47-dicarboxylate, polyethylene diphenoxyethane-4,4'-dicarboxylate, poly-4-β-oxyethoxybenzoate and their copolymers Linear saturated aromatic polyesters such as polyesters; these may be one type or a blend of two or more types, or may be blended with other general-purpose resins such as polyethylene, polystyrene, etc. The alkaline earth metal salts of hypophosphite used in the present invention are salts of metals in group a of the periodic table, namely beryllium, magnesium, calcium,
Among the salts of strontium, barium, and radium, magnesium salts, calcium salts, and barium salts are preferred, and calcium salts are particularly preferred.

The amount of alkali metal hypophosphite to be blended is not strictly limited in the present invention, as long as it is present at least sufficiently to impart self-extinguishing properties to the combustible resin. However, generally the amount is 1 to 50 parts by weight, preferably about 5 to 30 parts by weight, per 100 parts by weight of resin. In the present invention, the compounds allowed to coexist with the alkaline earth metal hypophosphite are compounds represented by the general formulas (a) to (d).

Examples of the compound represented by the general formula (a) include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, diphenyl octyl phosphate, tributyl phosphate, tris( 3-chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(bromochloropropyl) phosphate,
Examples include tris(2-bromoethyl) phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, and the like.

Examples of the compound represented by the general formula (6) include trimethylphosphite, triethylphosphite, tris(2-chloroethyl)phosphite, triphenylphosphite, and the like.

Examples of the compound represented by the general formula (c) include dimethyl phenylphosphonate, diethyl phenylphosphonate, dibutyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, bis(hydroxyethyl)benzylphosphonate, bis(2-bromoethyl)- Examples include 2-bromoethylphosphonate. The compound represented by the general formula (d) is a polycarbonate from the following bisphenols, and the bisphenol is 4,45-dihydroxydiphenyl-1
・1-diethane, 4,4'-dihydroxydiphenyl-1,1-butane, 4,4'-dihydroxydiphenyl-1,1-isobutane, 4,4'-dihydroxydiphenyl-2,2-propane,゛4,4/-dihydroxydiphenyl-2,2-butane, 4,41-dihydroxydiphenyl-2,2-pentane, 4,45-dihydroxydiphenyl-2,2-(4-methylpentane), 4. 4'-
Dihydroxydiphenyl-2,2-hexane, 4,4'
-dihydroxydiphenyl-4,4-heptane, 4,4
1-dihydroxydiphenyl-2,2-nonane, 4,4
-dihydroxydiphenylphenylmethylmethane, 4.
4! -dihydroxydiphenyldiphenylmethane, 4.
4'-dihydroxydiphenyl 1,1-cyclopentane, 4,4'-dihydroxydiphenyl-1,1-cyclohexane, 4,4'dihydroxydiphenyl ether,
4,4'-dihydroxydiphenyl sulfide, 4,4
'-dihydroxydiphenyl sulfoxide, 4.4'
-dihydroxy-3.3/-dichlorodiphenyl-2.
2-propane, 4,45-dihydroxy-3,3'-dibromodiphenyl-2,2-propane, 4,4''dihydroxy-3,3',5,5'-tetrachlorodiphenyl-2,2 -propane, 4,4'-dihydroxy-3,3
',5,5'-tetrapromodiphenyl-2,2-propane, 4,4'-dihydroxy-3,31-dichlorodiphenyl-1,1-cyclohexane, 4,4'-dihydroxy-3,3'- Dibromodiphenyl 1,1-cyclohexane, 4,41-dihydroxy-3,35,5,5'
-tetrachlorodiphenyl 1,1-cyclohexane, 4
・4'-dihydroxy 3,3/・5,51-tetrapromodiphenyl-1,1-cyclohexane, 4,4'-dihydroxy-3,3! -dimethyldiphenyl-2,2-
Examples include propane.

The compound represented by the general formula (d) may be a homopolymer or a copolymer using one or more of the above bisphenols. The compounds represented by the general formulas (a) to (d) may be used alone or in combination of two or more. The amount of the compounds represented by these general formulas (a) to (d) is not strictly regulated, but it is preferably used in an amount of ~5 times the weight of the alkaline earth metal hypophosphite, and ~3% by weight.
Weight times are particularly preferred.

In the present invention, in addition to the alkaline earth metal hypophosphite salts and the compounds represented by formulas (a) to (d), conventionally used general flame retardants can also be used in combination.

When these common flame retardants are used in combination, the amount of alkaline earth metal hypophosphite can be kept to a relatively small amount. Such common flame retardants include, for example, those having the general formula:

In the above formula, R is alkylene, alkylidene or alicyclic bond, such as methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, etc.; ether, carbonyl, amine , a sulfur-containing bond (eg, sulfide, sulfoxide, sulfone), and a phosphorus-containing bond. R also consists of two or more alkylene or alkylidene bonds connected by groups such as aromatic groups, amino groups, ether groups, carbonyl groups, sulfide groups, sulfoxide groups, sulfone groups, phosphorus-containing bonds, etc. You can also do that. Other groups represented by R will be well known to those skilled in the art. Ar and Ar5 are monocyclic or polycyclic carbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like.

Ar and Ar5 may be the same or different. Y is a substituent selected from the group consisting of organic, inorganic or organometallic groups.

The substituents represented by Y include (1)...rogen, such as chlorine, bromine, iodine, or fluorine, or (2) a monovalent organic group of the general formula 0E (Ell'!.X). )
or (3) a monovalent hydrocarbon group represented by R, or (4) other substituents, such as a nitro group, a cyano group, etc., where the substituents include one aryl nucleus, such as one phenyl nucleus. It is preferred that at least one, preferably two, halogen atoms are present. When using one or more Y, they may be the same or different.

X is a monovalent hydrocarbon group as exemplified below. For example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, decyl, etc.; aryl groups such as phenyl, naphthyl, biphenyl, xylyl, tolyl, etc.; aralkyl groups such as benzyl, ethyl phenyl, etc.; alicyclic groups such as cyclopentyl, cyclohexyl, etc. ; and monovalent hydrocarbon groups containing functional groups therein, such as hydroxyethyl, hydroxybutyl, and the like. When using one or more X, they may be the same or different.

d represents an integer ranging from 1 to a maximum value equal to the number of hydrogens that can be substituted on the aromatic ring-containing Ar or Ar'. e is o to R
Represents an integer up to the number of substitutable hydrogens above. A.. b
and c is an integer from O. When b is not O, a is also c
is also not O. Otherwise a or c (but not both) may be O. When b is O, the aromatic group is directly bonded with a carbon-carbon bond. Aromatic group, Ar
The hydroxyl group or Y substituent on and Ar′ can vary in the ortho, meta or para position on the aromatic ring.

Also, the groups can be in any possible geometric relationship to each other. Included within the scope of the above two general formulas is biphenyl, examples of which are shown below.

2,2-bis-(3,5-dichlorophenyl)propane, bis-(2-chlorophenyl)methane, bis-(2-
6-dibromophenyl)methane, 1,1-bis-(4-
iodophenyl)ethane, 1,2-bis-(2,6-dichlorophenyl)ethane, 1,1-bis-(2-chloro-4-iodophenyl)ethane, 1,1-bis-(2-
Chloro-4methylphenyl)ethane, 1,1-bis-(
3,5-dichlorophenyl)ethane, 1,1-bis-(
3-phenyl-4-bromophenyl)ethane, 2,6-
Bis-(4,6-dichloronaphthyl)propane, 2,2
-bis-(2,6-dichlorophenyl)pentane, 2.
2-bis-(3,5-dipromophenyl)hexane, bis-(4-chlorophenyl)phenylmethane, bis-(
3,5-dichlorophenyl)cyclohexylmethane, bis(3-nitro-4-bromophenyl)methane, bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane, 2,2-bis -(3,5-dichloro-
4-hydroxyphenyl)propane, 2,2-bis-(
3-Bromo-4-hydroxyphenyl)propane, 2.
2-bis-(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyethoxyphenyl)propane, 2,2-bis(
3,5-dibromo-4-hydroxyethoxyphenyl)
propane.

Methods for producing these and other biphenyls that may be used are well known.

The divalent aliphatic groups in the above examples may be replaced with sulfur, oxygen, sulfoxy, and the like. For example, decabromodiphenyl ether, octabromodiphenyl ether, 2.
2-bis(3,5-dichloro-4-hydroxyphenyl)sulfone, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)sulfone, 2,2-bis(3,5-
Examples include dichloro-4-hydroxyethoxyphenyl) propane, 2,2-bis(3,5-dibromo-4-hydroxyethoxyphenyl)propane, and the like. Included in the above structural formula are substituted benzenes such as 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, hexachlorobenzene, hexabromobenzene, and biphenyls such as 2
・25-dichlorobiphenyl, 2,4-dipromovir
G-nyl, and 2,4'-dichlorobiphenyl.

Preferred halogen compounds in the present invention include aromatic halogen compounds such as chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl, brominated terphenyl, or divalent alkylene or brominated terphenyl, which is separated by a divalent alkylene or oxygen, and which has a phenyl nucleus. A compound containing two phenyl groups each having at least two chlorine or bromine atoms, such as dipromobisphenol A and its hydroxyethoxylated product, decapromodiphenyl ether, etc., and at least one of the above compounds. be.
Elemental phosphorus also includes red phosphorus. Suitable flame retardants for the present invention include compounds containing a phosphorus-nitrogen bond, such as phosphonitrile chloride, phosphorus esteramide, phosphoric acid amide, bosyl phonamide, phosphinic acid amide, tri(aziridinyl)phosphine oxide or tetrakis (Hydroxymethyl)phosphonium chloride.

Among these flame retardants, particularly preferred flame retardants are polycarbonates containing brominated products of polypromobiphenyl, polypromobiphenyl ether, hexabromobenzene, and bisphenol A, and halogen-substituted cyclopentadiene dimers. etc.

2 The present invention provides an alkaline earth metal salt of hypophosphite with the general formula (a) to
By coexisting with the compound represented by (d), a further enhanced flame retardant effect is exhibited. Although the reason is not clear, by adding compounds a) to (d),
Hypophosphite alkaline earth metal deficiency is more evenly distributed,
It is presumed that this is to enhance the flame retardant effect. A compound proboscis a) ~
Any method can be used to make (d) coexist.

For example, resin, alkaline earth metal penta salt of hypophosphite, and (B) one or more of compounds (a) to (d), and optionally other general flame retardants (0) are mixed in appropriate proportions and extruded. Put it in a mixer to make molded pellets.Resin, (Al
There is also a method of making molded pellets in advance by making molded pellets in advance with one or more of , (0 and (0), and then mixing with one or more of the remaining c In addition, it is also possible to mix the resins (4), (B) and (0) in an appropriate ratio and mold the mixture directly by injection molding or transfer molding.Also, in the final stage of polymerization of the resin, A method of adding and mixing (B) and/or (0,
Alternatively, a method may be used in which each component is made into a solution, mixed, and then reprecipitated with a non-solvent, or the solvent is evaporated. Further, it is preferable to remove as much water as possible from the flame retardant components, resin, and additives during molding.
Furthermore, during mixing, it is preferable to carefully control the temperature and utilize frictional heat to achieve intimate mixing of the resin and additives. The composition of the present invention includes a heat stabilizer, a light stabilizer, a mold release agent,
Optional additives such as blowing agents, crystallization nucleating agents, dyes and pigments, reinforcing agents such as asbestos and glass fibers, and fillers (usually 5 to 80% by weight based on the resin) may be blended.

Flame-retardant resin molded articles, fibers, films, etc. can be easily produced from the composition of the present invention.

The present invention will be explained in more detail with reference to Examples below.

In the examples, all "parts" are "parts by weight", and the limit oxygen concentration index (LOI) is measured based on JISK-7201. Intrinsic viscosity (6) is a value measured at 35° C. in orthochlorophenol for polyester. Examples 1-3 Comparative Examples 1-4 Intrinsic viscosity 0
．． 62 polyethylene terephthalate (PET), decabromodiphenyl ether (DBDE), calcium hypophosphite (Ca(H2PO2)2), triphenyl phosphate (TPP) and polycarbonate (PC, molecular weight approximately 15,000) from bisphenol A. Predetermined amounts were mixed, melted at 280°C, and injection molded.

Claims (1)

[Claims] 1 A thermoplastic polyester resin containing (A) an alkaline earth metal salt of hypophosphite and (B) the following general formulas (a) to (d).
A flame-retardant resin composition characterized by containing one or more compounds selected from the group consisting of the compounds shown below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(a)
▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(b)
▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(c)
[However, in the formula, R_1, R_2 and R_3 each represent the same or different alkyl, haloalkyl, aryl and haloaryl groups. ]▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(d
) [However, in the formula, X and Y are a bromine atom or a chlorine atom, an alkyl group having 1 to 4 carbon atoms, m and n are integers of 0 to 2, and l is 2
or more, R is an alkylene group, an alkylidene group, a cycloalkylidene group, -O-, -S-, -SO-, -SO
Represents _2-. ].