JPS5911618B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant composition of thermoplastic polyester resin, and more specifically, when flame-retardant thermoplastic polyester resin is made with an alkaline earth metal salt of hypophosphite, The present invention relates to a resin composition with enhanced flame retardant effect in which a specific phosphorus compound is coexisted.

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 coexistence with other flame retardants, were previously proposed.

[In the formula, R4, R5, and R6 may be the same or different and each represents an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, and a metal, and n represents O or the number of 1 (However, if the general formula ( R in d) does not contain a hydrogen atom, and R4 and R6 in general formula (e) do not contain a hydrogen atom)] [In the formula, R4, R5
, R6 each may be the same or different and is an alkyl group,
It represents a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, and a metal, and n represents 0 or the number of l (however, in the case of n=0, three types of R4, R, and R6 are hydrogen atoms at the same time). Some compounds are not included, and in the case of n-1, R4
, R, , R6 do not contain a hydrogen atom)] The phosphorus compounds represented by these general formulas (a) to (f) have a boiling point that is 10° C. or more higher than the melting point of the thermoplastic polyester resin used. is preferably used.

Therefore, suitable phosphorus compounds may vary depending on the type of thermoplastic polyester resin used. Thermoplastic polyester resin and umbrella in the present invention However, through subsequent studies, it was discovered that the effect is even greater when a specific phosphorus compound is co-existed with the alkaline earth metal salt of hypophosphite, and the present invention has been achieved. It is.

That is, the present invention provides thermoplastic polyester resin with (4) hypophosphorous acid ano-earth metal salt and (B) the following general formula (a
1 selected from the group consisting of compounds shown in ) to (f)
A flame-retardant resin composition characterized by containing at least one kind of compound.

[However, in the formula, Rl, R2 and R3 may be the same or different and each represents an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, or a metal atom (provided that at least one of R1 and R3 is a hydrogen atom) or a metal atom, and R2 of the compound shown in general formula (c)
iCj contains a hydrogen atom and Tljj. ))] are also sufficiently present, there are no strict restrictions on the present invention.

However, in general, 1 to 100 parts by weight of resin
50 parts by weight, preferably about 5 to 30 parts by weight. In the present invention, the compounds allowed to coexist with the alkaline earth metal hypophosphite are compounds represented by the general formulas (a) to (f).

Preferred examples of the phosphoric acid or its partial ester or metal salt represented by the general formula (a) include the following.

Preferred examples of the phosphorous acid or its partial ester or metal salt represented by the general formula (b) include the following.

Preferred examples of the phosphonic acid represented by the general formula (c) or its partial stillyl or metal salt include the following.

Preferred examples of the phosphorous acid or its ester or metal salt represented by the general formula (d) include the following.

Preferred examples of the phosphinic acid, phosphinic acid, or ester or metal salt thereof represented by the general formula (e) include the following.

Preferred examples of the phosphine and phosphine oxide represented by the general formula (f) include the following.

The compounds represented by the general formulas (a) to (f) may be used alone or in combination of two or more.

The amount of the compounds represented by these general formulas (a) to (f) is not strictly regulated, but it is preferably used in an amount of 1/10 to 5 times the weight of the alkaline earth metal hypophosphite; /
Particularly preferred is 5 to 3 times the weight.

In the present invention, in addition to the alkaline earth metal hypophosphite salts and compounds represented by formulas (a) to (f), 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. Examples of such general flame retardants (c) include 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 Ar' are monocyclic or polycyclic carbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene and the like.

Ar<15Ar' may be the same or different.
Y is a substituent selected from the group consisting of organic, inorganic or organometallic groups.

The substituent represented by Y includes (1) a halogen such as chlorine, bromine, iodine, or fluorine, or (2) an ether of the general formula 0E (E is the same monovalent organic group as X). or (3) a monovalent hydrocarbon group represented by R, or (4) other substituents, such as nitro groups, cyano groups, etc., which substituents include at least one aryl nucleus, such as a phenyl nucleus. Preferably 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 pentyl, cyclohexyl, etc.; and functional groups therein. The monovalent hydrocarbon groups contained therein include, for example, 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 c to R
Represents an integer up to the number of substitutable hydrogens above. A, b and c are O to integers. When b is not 0, neither a nor c is 0. Otherwise a or c (but not both) may be 0. When b is 0, the aromatic group is directly bonded through a carbon-carbon bond. The hydroxyl group or Y substituent on the aromatic group, Ar and Ar', may vary in the orthogonal 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 general formula 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-4-methylphenyl)ethane, 1,1-bis-
(3,5-dichlorophenyl)ethane, 1,1-bis-
(3-phenyl-4-promophenyl)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-promophenyl)methane, bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane, 2,2-bis-(3.5-dichloro-4-hydroxy phenyl)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, decapromodiphenyl ether, octapromodiphenyl ether, 2,
2-bis-(3,5-dichloro-4-hydroxyphenyl)sulfone, 2,2-bis-(3,5-dibromo-4
-Hydroxypheno(ha)sulfone, 2,2-bis-
(3,5-cyclo-4-hydroxyethoxyphenyl)propane, 2,2-bis-(3,5-dibromo-4-
Examples include hydroxyethoxyphenyl)propane. Substituted benzenes included in the above structural formula include, for example, 1
, 3-dichlorobenzene, 1,4-dibromobenzene,
1,3-dichloro-4-hydroxybenzene, hexachlorobenzene, hexabromobenzene, and biphenyl such as 2,Z-dichlorobiphenyl, 2,4-dipromobiphenyl, and 2,4'-dichloro There is biphenyl.

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 oxygen-separated; Compounds containing two phenyl groups having at least two chlorine or bromine atoms per phenyl nucleus, such as dipromobisphenol A and its hydroxyethoxylated products, decapromodiphenyl ether, and at least one of the above compounds. That's all.
Elemental phosphorus also includes red phosphorus. Flame retardants suitable for the present invention include compounds containing a phosphorus-nitrogen bond, such as phosphonitrile chloride, phosphorus esteramide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide,
These include tri(aziridinyl)phosphine oxide or tetrakiz(hydroxymethyl)phosphonium chloride.

Among these flame retardants, particularly preferred flame retardants include polypromobiphenyl, polypromobiphenyl ether, hexabromobenzene, polycarbonates containing brominated bisphenol A, and halogen-substituted cyclopentadiene dimers. It is.

The present invention exhibits a further enhanced flame retardant effect by allowing the compounds represented by the general formulas (a) to (f) to coexist in the alkaline earth metal hypophosphite salt.

The reason for this is not clear, but it is presumed that by adding compounds (a) to (f), the alkaline earth metal hypophosphite is more uniformly dispersed and the flame retardant effect is enhanced. Any method may be used to cause the compounds (a) to (f) to coexist in the thermoplastic polyester resin containing an alkaline earth metal salt of hypophosphite.

For example, resin, (4) alkaline earth metal hypophosphite salt, and (B) one or more of compounds (a) to (f), optionally further mixed with other general flame retardants (O) in appropriate proportions. Put into an extrusion mixer to make molded pellets.Resin, (4)
There is also a method in which molded pellets are made in advance from one or more of , (3) and (C), and then further mixed with the remaining one or more. 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, ( Examples include a method of adding and mixing 4), (B) and/or (O), or a method of making each component into a solution, mixing them, and then reprecipitating with a non-solvent or evaporating the solvent. In addition, it is preferable to remove as much water as possible from flame retardant components, resins, and additives during molding.Furthermore, when mixing, carefully adjust the temperature and use frictional heat to combine the resin and additives. It is preferred to obtain intimate mixing of the additives.
The composition of the present invention may contain optional additives such as heat stabilizers, light stabilizers, mold release agents, blowing agents, crystallization nucleating agents, dyes, pigments, reinforcing agents such as asbestos and glass fibers, 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 [η] is a value measured at 35° C. in orthochlorophenol for polyester. Examples 1-2 Comparative Examples 1-2 Intrinsic viscosity 0.
Polyethylene terephthalate (62) with a melting point of 262°C (
PET), decabromodiphenyl ether (DBDE)
, calcium hypophosphite (Ca(H2PO2)2), and 4-methylbenzylphosphonic acid (MBP), which has a melting point of 185°C and a boiling point of 300°C or higher, are mixed in predetermined amounts,
Melting and injection molding were performed at ℃.

The flame retardancy (L.O.l.) of the obtained test piece was as shown in Table 1. As is clear from the above table, it can be seen that the flame retardant effect is improved when 4-methylbenzylphosphonic acid and Ca(H2PO2)2 coexist.

Examples 3-8 Comparative Example 3 Intrinsic Viscosity}. Example 2 shows an example in which polytetramethylene terephthalate (PBT) having a melting point of 225°C and an alkaline earth metal salt of hypophosphite and a phosphorus compound shown below coexist.
Shown in the table.

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 (f).
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), ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼...(c) [However, R_ in the formula
1, R_2 and R_3 may be the same or different and represent an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, and a metal atom (however, R_1
At least one of R_3 and R_3 is a hydrogen atom or a metal atom, and R_2 of the compound represented by general formula (c)
does not contain a hydrogen atom)] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (d), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (e) [In the formula, R_4, R_5, R_6 may be the same or different and each represents an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, or a metal, and n represents a number of 0 or 1 (however, if the general formula (
R_5 in d) does not contain a hydrogen atom, and R_4 and R_6 in general formula (e) do not contain a hydrogen atom)] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(
f) [In the formula, R_4, R_5, and R_6 may be the same or different and represent an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, a hydrogen atom, and a metal, and n represents the number of 0 or 1 (however, n = If 0, R_4, R
Compounds in which three types of _5 and R_6 are hydrogen atoms at the same time are not included, and when n = 1, none of R_4, R_5, and R_6 contain hydrogen atoms)]