JP2001311011A - Flame-retarded thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retarded thermoplastic resin composition comprising a flame-retarded thermoplastic resin composed of a thermoplastic resin and a bromine-based flame retardant and excellent in thermal stability. SOLUTION: This flame-retarded thermoplastic resin composition excellent in thermal stability is obtained by adding a specific amount of a dolomite-based compound or further adding a specified amount of hydrotalcite, a zinc-substituted hydrotalcite compounds or a zeolite compound to the flame-retarded thermoplastic resin composed of the thermoplastic resin and a specific amount of the bromine-based flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a stabilized flame-retardant thermoplastic resin obtained by adding a specific additive to a flame-retardant thermoplastic resin comprising a thermoplastic resin and a bromo-based flame retardant. It relates to a composition and can be widely used in fields where flame retardancy is required.

2. Description of the Related Art In general, a method of adding a flame retardant or a flame retardant such as a halogen compound, a phosphorus compound, and antimony trioxide to a flame retardant thermoplastic resin has been conventionally performed. Among flame retardants, halogen compounds, particularly bromo compounds, are frequently used. However, in general, when a bromo flame retardant is added to a thermoplastic resin,
During molding, there is a problem that the thermal stability of the flame-retardant thermoplastic resin is significantly reduced, and the commercial value of the molded product is significantly reduced. In order to solve these problems, the following techniques have already been disclosed. (1) A method of adding a halogen-containing organic flame retardant, a hydrotalcite stabilizer and a flame retardant auxiliary to a thermoplastic or thermosetting resin (JP-A-60-1241). Corrosion during molding, yellowing of molded products,
Technology to improve heat resistance and weather resistance. The hydrotalcite stabilizer used in the present technology is the same as the hydrotalcite of the component (b) used in the present invention, but the technology includes, of course, the dolomite-based compound used in the present invention, There is no description or suggestion of a combination with a dolomite compound. (2) A method of adding a hydrotalcite-based solid solution to a synthetic resin containing a halogen and / or an acidic substance (Japanese Patent Application Laid-Open No. Sho 61)
No. 174270) to improve the rust resistance or coloring resistance of the resin composition. The hydrotalcite-based solid solution used in the technique is the same as the zinc-substituted hydrotalcite compound of the component (c) used in the present invention. There is no description or suggestion about the combination with a dolomite compound. (3) A method of adding an A-type zeolite to a flame retardant resin comprising a resin selected from a polyolefin resin, a styrene resin, a polyester resin, and a nylon resin and a halogen flame retardant (Japanese Patent Laid-Open No. 62-199654). Technology to improve the thermal stability of flame-retardant thermoplastics. The type A zeolite and the zeolite containing a metal belonging to Group II or IV of the Periodic Table used in this technique are the same as the zeolite compound of the component (d) used in the present invention. There is no description or suggestion of the dolomite compound used in the present invention or the combined use with the dolomite compound.

SUMMARY OF THE INVENTION A flame-retardant thermoplastic resin comprising a thermoplastic resin and a bromo-based flame retardant is disclosed in
No. 1241, hydrotalcite-type stabilizers described in JP-A-61-174270, and hydrotalcite-based solid solutions described in JP-A-61-270270.
In the prior art of adding type A zeolite alone as described in JP-A-199654, sufficient heat stability cannot be obtained, so that the heat of flame retardation comprising a thermoplastic resin and a bromo flame retardant is not obtained. It is desired to provide a flame-retardant thermoplastic resin composition having excellent thermal stability of the thermoplastic resin.

In view of the above, the present inventors have conducted intensive studies on an additive having excellent heat stabilizing effect on a flame-retarded thermoplastic resin comprising a thermoplastic resin and a bromo-based flame retardant. As a result of the superposition, 0.01 to 5.0 parts by weight of the component (a) dolomite compound is added to the flame retarded thermoplastic resin composed of 100 parts by weight of the thermoplastic resin and 1 to 50 parts by weight of the bromo flame retardant The flame-retardant thermoplastic resin composition is found to have excellent thermal stability, and further comprises a flame-retardant thermoplastic resin comprising 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a bromo-based flame retardant. Component (a) 0.01 to 5.0 parts by weight of dolomite compound and (b)
Component Hydrotalcite, Component (c), Zinc-substituted hydrotalcite compounds, Component (d) At least one compound selected from zeolite compounds in a total amount of 0.1%.
The present inventors have found that a flame-retardant thermoplastic resin composition added in an amount of from 0.01 to 5.0 parts by weight has extremely excellent thermal stability, and have completed the present invention. Specific examples of the thermoplastic resin used in the present invention include polyolefins such as polyethylene and polypropylene, polystyrene (PS), high-impact polystyrene (HIPS), syndiotactic polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin). ), Acrylonitrile-butadiene-styrene- (α-methyl) styrene copolymer, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-ethylene-styrene copolymer (AES resin), acrylonitrile-acrylic rubber-styrene copolymer Merging (AA
Styrene resins such as S resin), polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyarylate, nylon 6, nylon 12, nylon 46, nylon 66, nylon 610, nylon 61
2. Polyamide such as nylon MXD6, polycarbonate, polyacetal, vinyl acetate resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, polyphenylene oxide, polysulfone,
Examples thereof include polyether sulfone, polyphenylene sulfide, and a blend resin (polymer alloy) of these resins. As the bromo flame retardant used in the present invention, bromo flame retardants usually used in this field can be used without limitation. Among them, brominated bisphenol A or brominated bisphenol is widely used. S, brominated phenyl ethers, brominated bisphenol A-based carbonate oligomers, brominated bisphenol A-based epoxy resins, brominated styrene-based, brominated phthalimide-based, brominated benzenes, and brominated cycloalkane flame retardants. be able to. Examples of the brominated bisphenol A or the brominated bisphenol S include compounds in which 1 to 8 bromine atoms are bonded to the benzene ring of a bisphenol A residue or a bisphenol S residue. Bisphenol A, dibromobisphenol A, tribromobisphenol A, tetrabromobisphenol A, pentabromobisphenol A, hexabromobisphenol A, octabromobisphenol A, tetrabromobisphenol A bis (2-hydroxyethyl ether), tetrabromobisphenol A Screw (2-
(Bromoethyl ether), tetrabromobisphenol A bis (1,2-dibromoethyl ether), tetrabromobisphenol A bis (propyl ether), tetrabromobisphenol A bis (3-bromopropyl ether), tetrabromobisphenol A bis ( Two, three
-Dibromopropyl ether), monobromobisphenol S, dibromobisphenol S, tribromobisphenol S, tetrabromobisphenol S, pentabromobisphenol S, hexabromobisphenol S, octabromobisphenol S, tetrabromobisphenol Sbis (2- Hydroxyethyl ether),
Tetrabromobisphenol S bis (2-bromoethyl ether), tetrabromobisphenol S bis (1,
2-dibromoethyl ether), tetrabromobisphenol S bis (propyl ether), tetrabromobisphenol S bis (3-bromopropyl ether), tetrabromobisphenol S bis (2,3-dibromopropyl ether) and the like. Can be. Examples of commercially available brominated bisphenol A or brominated bisphenol S include “FR-1524” manufactured by Bromochem Far East Co., Ltd. and “Great Lakes BA-5” manufactured by Great Lakes Chemical Co., Ltd.
0 "," Great Lakes BA-50P ",
"Great Lakes BA-59", "Great
t Lakes BA-59P "and" Great L
akes PE-68 "and Albemarle's" Sa "
ytex RB-100 ", Teijin Chemicals Limited" Fireguard 2000 "," Fireguard 3000 ",
"Fireguard 3100" and "Fireguard 36"
00 "and" Nonnen PR-2 "manufactured by Marubishi Yuka Kogyo Co., Ltd. Brominated phenyl ethers are compounds in which one or more bromine atoms are bonded to a phenyl ether group, such as 2,3-dibromopropylpentabromphenyl ether, bis (tribromophenoxy) ethane, and pentabromophenylpropane. And ether bromide, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether and polydibromophenylene oxide. Commercially available brominated phenyl ether flame retardants include Bromochem Far East Co., Ltd.'s "F.
“R-1210” and “FR-1208”, “Great Lakes” of Great Lakes Chemical Co., Ltd.
FF-680 "," Great Lakes DE-8 "
3, "Great Lakes DE-83R" and "Great Lakes DE-79", "Saytex 102E" and "Sayt" of Albemarle Co., Ltd.
ex 111 "and the like. The brominated bisphenol A-based carbonate oligomer has the following formula

Embedded image Wherein the oligomer is a polymer having a degree of polymerization (n) of 1 to 10. For example, a flame retardant represented by the following formula can be given.

Embedded image Examples of commercially available flame retardants of the above formula include "Fireguard 7000" and "Fireguard 7500" manufactured by Teijin Chemicals Limited.

Embedded image The commercially available flame retardants of the above formula include Great Lakes Chemical Co., Ltd.'s "Great Lak".
es BC-52 "and" Great Lakes B "
C-58 "and the like. Examples of the brominated bisphenol A-based epoxy resin include compounds represented by the following formula.

Embedded image Commercially available flame retardants of the above formula include polymerization degree (n)
There are various products depending on the product, such as "F-2300", "F-2300H",
"F-2400" and "F-2400H", "Prasam EP-16", "Prasam EP-30", "Prasam EP-100" and "Prasam EP-500" of Dainippon Ink and Chemicals, Sakamoto "SR-T1000", "SR-T2000", "SR
-T5000 "and" SR-T20000 ". Examples of the brominated bisphenol A-based epoxy resin include compounds in which the epoxy groups at both ends of the above formula are blocked with a blocking agent and compounds in which one terminal epoxy group is blocked with a blocking agent. . The blocking agent is not limited as long as it is a compound capable of ring-opening addition of an epoxy group.
Alcohols, carboxylic acids, amines and isocyanates containing a bromine atom can be mentioned, among which brominated phenols are preferable in terms of improving the flame retardant effect, dibromophenol, tribromophenol, Examples thereof include pentabromophenol, ethyldibromophenol, propyldibromophenol, butyldibromophenol, and dibromocresol. Examples of the flame retardant in which the epoxy groups at both ends of the polymer are blocked with a blocking agent include a flame retardant represented by the following formula.

Embedded image Commercially available flame retardants of the above formula include “Prasam EC-14”, “Prasam EC-20” and “Prasam EC-30” of Dainippon Ink and Chemicals, Inc., and “TB” of Toto Kasei Co., Ltd. -60 "and" TB-62 "," SR-T3040 "and" SR-T "of Sakamoto Pharmaceutical Co., Ltd.
7040 "and the like. Examples of the flame retardant in which the terminal epoxy group on one side of the polymer is blocked with a blocking agent include a flame retardant represented by the following formula.

Embedded image Examples of commercially available flame retardants of the above formula include "Prasam EPC-15F" manufactured by Dainippon Ink and Chemicals, Inc., and "E5354" manufactured by Yuka Shell Epoxy Co., Ltd. Brominated styrene-based flame retardants are brominated styrene monomers of the following formula in which 1 to 5 bromine atoms are bonded to a benzene ring of a styrene skeleton.

Embedded image And its polymer of the formula

Embedded image And preferably a polymer. For example, bromostyrene and brominated polystyrene can be mentioned,
Commercially available brominated polystyrene-based flame retardants include Great Lakes Chemical Co., Ltd.'s "Grea
t Lakes PDBS-10 "and" Great
Lakes PDBS-80 "and the like. Further, although the manufacturing method is different from the above-mentioned flame retardant, "Pyrocheck 68PB" of Ferro Co., Ltd. can also be mentioned as an example of a brominated polystyrene-based flame retardant. The brominated phthalimide-based flame retardant is a compound in which 1 to 4 bromo atoms are bonded to a benzene ring of a phthalimide group,
For example, monobromophthalimide, dibromophthalimide, tribromophthalimide, tetrabromophthalimide, ethylenebis (monobromophthalimide), ethylenebis (dibromophthalimide), ethylenebis (tribromophthalimide) and ethylene bis (tetrabromophthalimide) of the following formula Phthalimide)

Embedded image Examples of commercially available flame retardants include:
Albemarle's "Saytex BT-93" and "Saytex BT-93W" can be mentioned. Brominated benzenes are compounds consisting of a group in which one or more bromine atoms are bonded to a benzene ring, and include monobromobenzene, dibromobenzene, tribromobenzene, tetrabromobenzene, pentabromobenzene, hexabromobenzene, Bromophenyl allyl ether,
Pentabromotoluene, bis (pentabromophenyl)
Ethane and poly (pentabromobenzyl acrylate)
Examples of commercially available flame retardants include “Saytex 8010” manufactured by Albemarle Co., Ltd. Brominated cycloalkanes are
Brominated hydrocarbons in which 1 to 6 bromine atoms are bonded to a cycloalkane (cycloaliphatic hydrocarbon) having 6 to 12 carbon atoms. Examples of the cycloalkane include cyclohexane and cyclododecane, and examples of the brominated cycloalkane include monobromocyclohexane, dibromocyclohexane, tribromocyclohexane, tetrabromocyclohexane, pentabromocyclohexane, and hexabromocyclohexane. , Monobromocyclododecane, dibromocyclododecane, tribromocyclododecane, tetrabromocyclododecane, pentabromocyclododecane and hexabromocyclododecane. Examples of commercially available hexabromocyclododecane include "FR-1206" of Bromochem Far East Co., Ltd., "Saytex HBCD" of Albemarle Co., Ltd., and "Great Lakes CD-75" of Great Lakes Chemical Co., Ltd.
P "and" Pirogard SR-1 "by Daiichi Kogyo Seiyaku Co., Ltd.
03 "and the like. In Examples, although a typical bromo-based flame retardant widely used among them is used, it is expected that similar effects can be exhibited even when other bromo-based flame retardants are used. . In addition to the bromo-based flame retardants widely used as described above, those described in the literature and in catalogs of bromo-based flame retardant manufacturers and the like can of course be used, and these bromo-based flame retardants can be used. It is fully expected that the effects of the present invention can be equally achieved with the flame-retardant thermoplastic resin composition. As the brominated flame retardants, brominated phenols,
Brominated phenoxytriazines, brominated alkanes, brominated isocyanurates, brominated maleimides, and brominated phthalic acids can be mentioned. Brominated phenols are compounds in which 1 to 5 bromine atoms are bonded to a phenol group, and include, for example, monobromophenol, dibromophenol, tribromophenol, tetrabromophenol and pentabromophenol. it can. The brominated phenoxytriazine system is a compound in which 1 to 5 bromine atoms are bonded to a phenoxy group, and 1 to 3 of the brominated phenoxy groups are bonded to a triazine ring. For example, mono (monobromophenoxy) Triazine, mono (dibromophenoxy) triazine, mono (tribromophenoxy) triazine, mono (pentabromophenoxy) triazine, bis (monobromophenoxy) triazine, bis (dibromophenoxy) triazine, bis (tribromophenoxy) triazine, Bis (pentabromophenoxy) triazine, tris (monobromophenoxy) triazine,
Tris (dibromophenoxy) triazine, tris (pentabromophenoxy) triazine and tris (tribromophenoxy) triazine of the following formula

Embedded imageAnd the like, and a commercially available flame retardant of the above formula
As the “Pirogard SR-
245 ". Brominated alkanes
Is an alkane having 2 to 6 carbon atoms (chain aliphatic hydrocarbon)
A compound to which a bromo atom is bonded. Examples of the alkane
Ethane, propane, butane, pentane and hex
Sun can be mentioned as an example of a brominated alkane
Is monobromoethane, dibromoethane, tetrabromo
Ethane, monobromopropane, dibromopropane, bird
Brompropane, pentabromopropane, hexabromo
Propane, octabromopropane, monobromobutane,
Dibromobutane, tetrabromobutane, hexabromobutane
Tan, octabromobutane, monobromopentane, jib
Lom pentane, tribrom pentane, penta bromo pen
Tan, octabromopentane, monobromohexane, di
Bromohexane, tribromohexane, tetrabromo
Xan, pentabromohexane, hexabromohexane
And octabromohexane. B
The brominated isocyanurates are the brominated alkanes described above.
Compound in which an alkyl residue and isocyanuric acid residue are combined
And 1 to 5 bromine atoms attached to the phenoxy group
Brominated phenoxy group and isocyanuric acid residue bonded
Compounds can be mentioned. Specific examples include
Lis (monobromoethyl) isocyanurate, tris
(Dibromoethyl) isocyanurate, tris (tetra
Bromoethyl) isocyanurate, tris (monobrom
Propyl) isocyanurate, tris (2,3-dibro
Propyl) isocyanurate, tris (tribromop)
Ropyl) isocyanurate, tris (tetrabrompro
Pill) isocyanurate, tris (pentabromoprop
Le) isocyanurate, tris (heptabromoprop
L) Isocyanurate, tris (monobromobutyl) i
Socyanurate, tris (dibromobutyl) isocyanu
Rate, tris (pentabromobutyl) isocyanurate
G, tris (octabromobutyl) isocyanurate,
Tris (monobromopentyl) isocyanurate, tri
(Dibromopentyl) isocyanurate, tris (pe
Ntabrompentyl) isocyanurate, tris (oct
Tablom pentyl) isocyanurate, tris (monobu)
Romhexyl) isocyanurate, Tris (dibromohe)
Xyl) isocyanurate, tris (tribromohexyl)
Le) isocyanurate, tris (pentabromohexyl)
Le) isocyanurate, tris (monobromophenoki)
B) Isocyanurate, tris (dibromophenoxy)
Isocyanurate, tris (tribromophenoxy) i
Socyanurate, tris (pentabromophenoxy) i
Socyanurate, tris (ethyl monobromophenoki
B) isocyanurate, tris (ethyldibromopheno)
Xy) isocyanurate, tris (ethyltetrabromo
Phenoxy) isocyanurate, tris (propylmono)
Bromphenoxy) isocyanurate, tris (propi
Rudibromophenoxy) isocyanurate and tris
(Propyltetrabromophenoxy) isocyanurate
And the like. The brominated maleimide system has 1
~ 5 bromine atoms attached to phenylmaleimide group
A compound, for example, monobromophenylmaleimi
, Dibromophenylmaleimide, tribromophenyl
Maleimide and pentabromophenylmaleimide
I can do it. Brominated phthalic acids are from 1 to 4
Compounds having a bromo atom bonded to phthalic anhydride
Examples include monobromophthalic anhydride,
Dibromophthalic anhydride, tribromophthalic anhydride and
Trabromophthalic anhydride and the like can be mentioned. Departure
The amount of bromo flame retardant used in Ming
Various depending on the degree of flame retardancy required for fats and physical properties
And usually 100% by weight of thermoplastic resin
1 to 50 parts by weight per part is used. Less than 1 part by weight
Cannot provide the desired flame retardancy, and if it exceeds 50 parts by weight,
Thus, even if the flame retardancy is sufficient, the composition of the resin composition
It is not preferable because the physical properties of the mold are impaired. However,
From the balance between flame retardancy and physical properties, practically 3 to 30
Used in parts by weight. Also, depending on the purpose,
Two or more ROM-based flame retardants can be used in combination. Flame retardant
In order to further enhance the effect, flame retardant aids such as antimony trioxide
It is common practice to use drugs together,
The addition of the flame retardant aid has no effect on the effects of the present invention.
It is not something you can get. Usually, the amount of the flame retardant additive
0.5 to 20 parts by weight based on 100 parts by weight of the plastic resin
Although it is used, a preferable amount is 1 in relation to physical properties.
７7 parts by weight. Component (a) used in the present invention
There are no special restrictions on romite compounds and they are widely used in nature.
Used for production, wall materials, refractories for steelmaking, etc.
Mite (ie, dolomite) can be used. Change
In addition, dolomite compounds have a chemical composition of calcium carbonate.
Dolomite composed of double salt of uranium and magnesium carbonate
Can also be used. Natural mud used in the present invention
The composition of mite and / or synthetic dolomite is
And magnesium in a certain ratio.
The weight ratio of calcium to magnesium is CaO to Mg
The ratio is preferably 5:95 to 95: 5 in terms of O. This
Natural dolomite and / or synthetic
When romite is used, sufficient thermal stability cannot be obtained.
No. In the present invention, these natural and / or synthetic
The dolomite is fired, slaked, etc., and the metal element composition
Of metamorphosed dolomite without major changes
The body can also be used. A specific example is Droma
Dolomite obtained by heating a unit at 700-800 ° C
Cement, light burning obtained by heating at 900-1000 ° C
Dolomite, hard-baked at a high temperature of 1600-1800 ° C
Digested dead burnt dolomite, light burnt dolomite with water
Slaked lime, synthetic mud clinker, etc.
You. Furthermore, Akermanite (Ca_Two MgSi_Two O₇ ) And
Diopside [CaMg (SiO_Three )_Two ], Like various slags
In addition, the ratio of calcium and magnesium is
Natural minerals and double salts in the same range as
Modified derivatives can also be used. In addition, these
Any mixture may be used. These dolomite and
The derivative is referred to herein as a “dolomite compound”.
Collectively, these dolomite compounds are industrially broad
Widely produced in large quantities, from steelmaking to pottery, building materials, agriculture
It is used in an extremely wide range of industries, such as
It is of good quality, easily and cheaply available. Among them,
Flame retardant thermoplastics obtained with lightly burned dolomite
The thermal stability of the conductive resin composition is the best. The present invention
Between the dolomite compound and the flame-retardant thermoplastic resin
In order to improve compatibility, dispersibility, etc., the dolomite-based
Use compounds that have been surface-treated with a surface treatment agent
Can be. Surface used for surface treatment of dolomite compounds
Examples of the treating agent include organic acids and organic acid metal salts.
You. Each of these compounds may be used alone, and
It may be used as a mixture. Used as a surface treatment agent
Organic acids include saturated aliphatic monocarboxylic acids and saturated fatty acids.
Aliphatic dicarboxylic acid, unsaturated aliphatic carboxylic acid, carbocyclic
Carboxylic acids, heterocyclic carboxylic acids, hydroxy acids,
Carboxylic acids and amino acid derivatives. Saturation
Specific examples of the aliphatic monocarboxylic acid include acetic acid and propylene.
Ononic acid, butyric acid, valeric acid, hexanoic acid, octanoic acid, lau
Phosphoric acid, stearic acid, behenic acid, etc.
Wear. Specific examples of the saturated aliphatic dicarboxylic acid include
Uric, malonic, succinic, adipic and sebacic acids
And the like. Ingredients for unsaturated aliphatic carboxylic acids
Examples include acrylic acid, oleic acid, crotonic acid and
And fumaric acid. Carbocyclic carboxyl
Specific examples of the acid include benzoic acid, camphoric acid, and phthalic acid.
Acid, toluic acid, hydroatronic acid, cinnamic acid, etc.
I can do it. Specific examples of heterocyclic carboxylic acids
Are furic acid, tenic acid, pyrrolidone carboxylic acid and nicotine
Acid and the like. Specific examples of hydroxy acids and
Lactic acid, malic acid, benzylic acid, salicylic acid,
Varnish, vanillic acid, protocatechuic acid and gallic acid
Can be mentioned. Tools for amino acids and amino acid derivatives
Examples of the body include alkoxy acid, glutamic acid, lysine,
Aspartic acid, glycine, N-stearoyl glyci
, N-acetylglutamic acid, N-lauroylleucine
And γ-methylglutamic acid.
You. As organic acid metal salts used as surface treatment agents
Is a metal salt of the aforementioned organic acid. The
Specific examples of the metal of the metal salt include zinc, calcium, and magnesium.
Gnesium, potassium, sodium, lithium, aluminum
And nickel and nickel. Furthermore, this
The metal salt of an organic acid is a mixture or a double salt of two or more kinds;
Is also good. It is also necessary that the effects of the present invention are not impaired.
Depending on the other surface treatment agent used industrially
Can be used together. Specific examples include high-grade fats
Fatty acid esters, silane type, aluminum type, phosphorus type, etc.
Coupling agents, anionic, cationic, nonionic
Surfactants, higher fatty acid esters, polymer
And the like. Amount of surface treatment agent used
Indicates the type of dolomite compound and the specific surface of the powder particles
Depends on the product and the amount of water bound to the surface
Is, for dolomite compounds to be surface-treated,
0.05 to 40% by weight, preferably 0.1 to 20% by weight
%. When the amount of surface treatment agent used is less than 0.05% by weight
Has little effect on surface treatment, while 40% by weight
The surface of the dolomite compound powder particles is
Is saturated with the treating agent, and the effect of the surface treatment is more
Does not improve. There are no special restrictions on the surface treatment method.
For example, (1) a surface treatment agent is added to the dolomite compound powder.
Henschel mixer, colloid mill,
Co-milling using a mill such as a mill or an atomizer
Method, (2) toluene, xylene, methyl ethyl keto
, Acetonitrile, chloroform, diethyl ether
In an appropriate solvent such as water, ethanol, methanol, etc.
After adding a surface treatment agent and a dolomite compound, stirring and mixing,
A method of removing the solvent can be used. In the present invention
The hydrotalcite of the component (b) used is
A compound consisting of calcium and aluminum, for example
For example, the following general formula (1)_1-XAl_X(OH)_Two(A^q-)_{X / q}・ AH_TwoThe compound represented by O (1) can be mentioned. (C)
The component zinc-substituted hydrotalcite compounds are, for example,
For example, a compound in which a part of Mg in the general formula (1) is substituted with Zn.
A material having the following general formula (2)_y1Zn_y2Al_X(OH)_Two(A^q-)_{X / q}・ AH_TwoThe compound of O (2) can be mentioned. As the substitution rate of Zn
Is from 1 mol% to 50 mol% with respect to Mg,
More preferably, it is 15 mol% to 30 mol%. [Formula (1) and
And q in (2) is 1 or 2,^q-Is q-valent ani
ON, ie (CO_Three )^2-Or (ClO_Four )^- And X
 , Y1, y2, and a are real numbers that satisfy the following conditions, respectively.
Is shown. 0 <X ≦ 0.5, y1 + y2 = 1−X, y1 ≧ y2, 0 ≦
a <1] A typical example of the hydrotalcite represented by the general formula (1)
For example, the following may be mentioned. No. 1: Mg_0.750 Al_0.250 (OH)_Two (CO
_Three )_0.125 ・ 0.5 H_Two O No. 2: Mg_0.692 Al_0.308 (OH)_Two (CO
_Three )_0.154 ・ 0.1 H_Two O No. 3: Mg_0.683 Al_0.317 (OH)_Two (CO
_Three )_0.159 ・ 0.5 H_Two O No. 4: Mg_0.667 Al_0.333 (OH)_Two (CO
_Three )_0.167 ・ 0.1 H_Two O No. 5: Mg_0.750 Al_0.250 (OH)_Two (ClO
_Four )_0.250 ・ 0.5 H_Two O No. 6: Mg_0.692 Al_0.308 (OH)_Two (ClO
_Four )_0.308 ・ 0.1 H_Two O No. 7: Mg_0.667 Al_0.333 (OH)_Two (ClO
_Four )_0.333 ・ 0.1 H_Two O Zinc-substituted hydrotalcites represented by the general formula (2)
The following are typical examples of the compounds. No. 8: Mg_0.625 Zn_0.125 Al_0.250 (OH)
_Two (CO_Three )_0.125 ・ 0.45H_Two O No. 9: Mg_0.538 Zn_0.154 Al_0.308 (OH)
_Two (CO_Three )_0.154 No. 10: Mg_0.500 Zn_0.167 Al_0.333 (OH)
_Two (CO_Three )_0.167 ・ 0.54H_Two O No. 11: Mg_0.625 Zn_0.125 Al_0.250 (OH)
_Two (ClO_Four )_0.250 ・ 0.3 H_Two O No. 12: Mg_0.538 Zn_0.154 Al_0.308 (OH)
_Two (ClO_Four )_0.308 ・ 0.5 H_Two O No. 13: Mg_0.500 Zn_0.167 Al_0.333 (OH)
_Two (ClO_Four )_0.333 ・ 0.1 H_Two O In the present invention, the hydrotalcite and zinc-substituted
Phases of idrotalcite compounds and flame-retardant thermoplastics
In order to improve solubility, dispersibility, etc., the hydrotalsa
And zinc-substituted hydrotalcite compounds
Also use surface treatment agents such as higher fatty acids
can do. Of surface treated hydrotalcite
An example of a specific product is Kyowa Chemical Industry Co., Ltd.
Mizer 2, Alkamizer 3, DHT-4A and DH
T-4A-2 and the like can be mentioned. Also, surface treatment
Of zinc-substituted hydrotalcite compounds
An example of the product is Alkamizer from Kyowa Chemical Industry Co., Ltd.
4, Alkamizer 4-2 and Alkamizer 7 etc.
I can do it. Such a surface treatment agent has the above-mentioned high
Other than the lower fatty acids, known literature, for example, JP-A-60-1
No. 241, page 4 and the like.
You. Examples of the surface treatment agent described in the known document include:
Commonly used in, for example, anionic surfactant
Agents, silane coupling agents, titanium coupling
Agents, higher fatty acid esters and the like.
Specific examples include, for example, sodium stearate, oley
Acid sodium, sodium laurylbenzenesulfonate, etc.
Nionic surfactants, vinyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, isopropyl
Liisostearoyl titanate, isopropyl trideci
Silane or titan such as benzenesulfonyl titanate
Coupling agents, glycerin monostearate,
Higher fatty acid esters such as glycerin monooleate
Have been. Zeorai of component (d) used in the present invention
Compounds of the following general formula (3):₁₂Al₁₂Si₁₂O₄₈・ BH_Two O (3) [In the formula (3), b represents a real number satisfying 0 ≦ b ≦ 36. ]
4A zeolite compound represented by the formula:
3A-type enzyme in which sodium is replaced with potassium
Olite compound, sodium of 4A type zeolite compound
5A zeolite compound in which is replaced by calcium, Na
₈₆Al₈₆Si₁₀₆O₃₈₄ ・ 264H_Two 1 having the composition of O
3X type zeolite compound, 13X type zeolite compound
10X zeolite in which sodium is replaced by calcium
Compound and sodium 4A zeolite compound
Nesium, zinc, strontium, barium, zirconi
Group II or IV of the periodic table, such as um or tin
Zeolite compounds partially substituted with group III metals (hereinafter referred to as “gold
Genus-substituted zeolite compound ". )
Wear. The metal-substituted zeolite compound is a 4A-type zeolite.
Periodic Table No. that replaces part of sodium in light compounds
There is no particular limitation on Group II or Group IV metals.
However, in terms of efficacy, toxicity, and availability, magnetic
Cium, zinc, strontium, barium, zirconium
Metal-substituted zeolite compounds substituted with
Specific of the metal-substituted zeolite compound.
Examples include, for example, magnesium-substituted zeolite compounds.
Material, zinc-substituted zeolite compound, strontium-substituted zeolite
Olyte compound, barium-substituted zeolite compound, jill
Conium-substituted zeolite compounds and tin-substituted zeolites
Synthetic zeolite compounds such as compounds can be mentioned,
Preferred are magnesium, zinc and barium.
-Substituted magnesium-substituted zeolite compound, zinc
Substituted zeolite compounds and barium substituted zeolite compounds
Things can be mentioned. In addition, 3A type zeolite compound
, 5A zeolite compound, 10X zeolite compound
Products and metal-substituted zeolite compounds are usually industrially
The resulting product is a 4A zeolite compound
Is the metal substitution rate of sodium in the 13X type zeolite compound
Is from 10 mol% to 70 mol%. Used in the present invention
(D) the most preferred of the zeolite compounds
As the zeolite compound, a 4A type zeolite compound
And 5A type zeolite compounds. 4
Specific examples of the A-type zeolite compound include, for example, Na
₁₂Al₁₂Si₁₂O₄₈, Na₁₂Al₁₂Si₁₂O₄₈・ 6H_Two 
O, Na₁₂Al₁₂Si₁₂O₄₈・ 12H_Two O, Na₁₂Al
₁₂Si₁₂O₄₈・ 21H_Two O, Na₁₂Al₁₂Si₁₂O₄₈・
27H_Two O, Na₁₂Al₁₂Si₁₂O₄₈・ 36H_Two O etc.
Can be mentioned. Commercially available type 4A zeolite
Specific examples of the compound include “Zero” manufactured by Nippon Chemical Industry Co., Ltd.
Oster NA-100P "," ZEOSTAR NA-1
10P "and" Toyo Builder "manufactured by Tosoh Corporation
Can be Commercially available 3A type zeolite compound
As a specific example of the product, "ZEOS" manufactured by Nippon Chemical Industry Co., Ltd.
Tar KA-100P "," Zeostar KA-110 "
P "can be used as a tool for the 5A type zeolite compound.
As an example, "Zeostar" manufactured by Nippon Chemical Industry Co., Ltd.
CA-100P "and" ZEOSTAR CA-110P "
Can be mentioned. In addition, commercially available 13X type zeo
Specific examples of light compounds include those manufactured by Nippon Chemical Industry Co., Ltd.
"ZEOSTAR NX-100P", "ZEOSTAR NX
-110P "and 10X zeolite.
Specific examples of the compound include “Zero” manufactured by Nippon Chemical Industry Co., Ltd.
Oster CX-100P "," ZEOSTAR CX-1
10P ". Also used in the present invention
The zeolite compound used is a higher fatty acid such as stearic acid.
High-grade fats such as alkali metal salts such as phosphoric acid and oleic acid
Alkali metal salts of fatty acids and organic sulfonic acids such as dode
Yes, such as alkali metal salts such as silbenzene sulfonic acid
Surface treatment with an alkali metal salt of sulfonic acid
Good. Regarding the production method of the synthetic zeolite, known methods
Method, for example, as described in JP-A-57-28145.
The above-mentioned manufacturing method is mentioned. Component (a) used in the present invention
The amount of the dolomite-based compound of the thermoplastic resin 100
Parts by weight, 0.01 to 5.0 parts by weight, preferably
Is 0.05 to 3.0 parts by weight. (A) Dro of the component
When the added amount of the mite compound is less than 0.01 parts by weight
Has insufficient thermal stability and exceeds 5.0 parts by weight
In some cases, the expected thermal stability cannot be obtained by increasing the amount.
No. Further, the hydrota of the component (b) used in the present invention
Lucite, zinc-substituted hydrotalcites of component (c)
Selected from the compounds and zeolite compounds of component (d).
The sum of the amounts of at least one compound added is
0.01 to 5.0 parts by weight based on 100 parts by weight of resin
And preferably 0.05 to 3.0 parts by weight.
In addition, select from component (b), component (c) and component (d).
The total amount of at least one compound added is 0.0
If the amount is less than 1 part by weight, remarkable thermal stability cannot be obtained,
If it exceeds 5.0 parts by weight, the expected heat
Stability cannot be obtained. Component (a) used in the present invention
Each of the components (b), (c) and (d)
Combination discount when using at least one compound
The combination is not particularly limited, and may be any ratio. Ma
And component (b), component (c) and component (d).
The combined ratio when two or more of the above compounds are used in combination
Is not particularly limited, and may be any ratio. Difficulties of the present invention
Glass fiber, carbon fiber,
What is the thermal stability of the present invention even if fillers such as
Unaffected. Further, if necessary, antioxidants, purple
External ray absorbents, lubricants, pigments and the like can be added. Book
The flame-retardant thermoplastic resin composition of the present invention comprises a calender
Extruder, Banbury mixer, kneader, etc.
By kneading the components. Also kneading
When kneading each component at once, separate
May be added and kneaded. In practicing the present invention
Can include the following embodiments. (1) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 1
To 50 parts by weight of a flame-retardant thermoplastic resin,
A flame-retardant thermoplastic resin composition comprising 0.01 to 5.0 parts by weight of a dolomite compound. (2) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 1
To 50 parts by weight of a flame-retardant thermoplastic resin,
Min Natural dolomite and / or calcium carbonate-carbonate
0.01 g of synthetic dolomite consisting of magnesium double salt
To 5.0 parts by weight of a flame-retardant thermoplastic resin composition. (3) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 1
To 50 parts by weight of a flame-retardant thermoplastic resin,
The weight ratio of calcium and magnesium is CaO to M
5 to 95 to 95: 5 natural dolomite and / or in terms of gO
Or calcium carbonate-magnesium carbonate double salt
Flame retardant thermoplastic resin composition comprising 0.01 to 5.0 parts by weight of synthetic dolomite. (4) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 1
To 50 parts by weight of a flame-retardant thermoplastic resin,
The weight ratio of calcium and magnesium is CaO to M
5 to 95 to 95: 5 natural dolomite and / or in terms of gO
Or calcium carbonate-magnesium carbonate double salt
Lightly-baked dolomite obtained by lightly burning synthetic dolomite
A flame-retardant thermoplastic resin composition obtained by adding 0.01 to 5.0 parts by weight. (5) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 3
To 30 parts by weight of a flame-retardant thermoplastic resin,
The weight ratio of calcium and magnesium is CaO to M
5 to 95 to 95: 5 natural dolomite and / or in terms of gO
Or calcium carbonate-magnesium carbonate double salt
Lightly-baked dolomite obtained by lightly burning synthetic dolomite
A flame retardant thermoplastic resin composition obtained by adding 0.05 to 3.0 parts by weight. (6) 100 parts by weight of thermoplastic resin and bromo-based flame retardant 3
To 30 parts by weight of a flame-retardant thermoplastic resin,
The weight ratio of calcium and magnesium is CaO to M
5 to 95 to 95: 5 natural dolomite and / or in terms of gO
Or calcium carbonate-magnesium carbonate double salt
Lightly-baked dolomite obtained by lightly burning synthetic dolomite
At least one selected from organic acids and organic acid metal salts
Dolomite compound obtained by surface treatment with the compound of
A flame retardant thermoplastic resin composition obtained by adding 0.05 to 3.0 parts by weight. (7) Polyolefin, styrene resin, polyester
And 100 parts by weight of thermoplastic resin selected from polyamide
Flame retardant heat of 1 to 50 parts by weight
The dolomite compound (a) is added to the plastic resin in an amount of 0.0
A flame-retardant thermoplastic resin composition obtained by adding 1 to 5.0 parts by weight. (8) Polyolefin, styrene resin, polyester
And 100 parts by weight of thermoplastic resin selected from polyamide
Flame retardant heat of 1 to 50 parts by weight
(A) component natural dolomite and / or
Synthesis of double salt of calcium carbonate and magnesium carbonate
A flame-retardant thermoplastic resin composition comprising dolomite in an amount of 0.01 to 5.0 parts by weight. (9) Polyolefin, styrene resin, polyester
And 100 parts by weight of thermoplastic resin selected from polyamide
Flame retardant heat of 1 to 50 parts by weight
In plastic resin, (a) component of calcium and magnesium
The weight ratio is from 5:95 to 95: 5 in terms of CaO: MgO.
Natural dolomite and / or calcium carbonate-carbonate mug
Synthetic dolomite consisting of a double salt of nesium
A flame-retardant thermoplastic resin composition obtained by adding 5.0 parts by weight. (10) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 1 part by weight and 1 to 50 parts by weight of bromo flame retardant
(A) component calcium and magnesium in plastic resin
Is 5:95 to 95: 5 in terms of CaO to MgO.
Natural dolomite and / or calcium carbonate-carbonate
Light calcination of synthetic dolomite composed of double salts of gnesium
A flame-retardant thermoplastic resin composition obtained by adding 0.01 to 5.0 parts by weight of the lightly burned dolomite obtained. (11) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 3 parts by weight and 3 to 30 parts by weight of a bromo flame retardant
(A) component calcium and magnesium in plastic resin
Is 5:95 to 95: 5 in terms of CaO to MgO.
Natural dolomite and / or calcium carbonate-carbonate
Light calcination of synthetic dolomite composed of double salts of gnesium
A flame-retardant thermoplastic resin composition obtained by adding 0.05 to 3.0 parts by weight of the lightly burned dolomite obtained. (12) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 3 parts by weight and 3 to 30 parts by weight of a bromo flame retardant
(A) component calcium and magnesium in plastic resin
Is 5:95 to 95: 5 in terms of CaO to MgO.
Natural dolomite and / or calcium carbonate-carbonate
Light calcination of synthetic dolomite composed of double salts of gnesium
Of lightly burned dolomite from organic acids or metal salts of organic acids
Surface-treated with at least one selected compound
A flame retardant thermoplastic resin composition comprising 0.05 to 3.0 parts by weight of a dolomite compound. (13) 100 parts by weight of styrene-based resin and bromo-based flame retardant
1 to 50 parts by weight of a flame retardant styrenic resin
(A) Component Dolomite compound is used in an amount of 0.01 to 5.0 times.
A flame-retardant styrenic resin composition obtained by adding a part by weight. (14) 100 parts by weight of styrene-based resin and bromo-based flame retardant
1 to 50 parts by weight of a flame retardant styrenic resin
(A) Component Natural dolomite and / or calcium carbonate
-Synthetic dolomite consisting of double salt of magnesium carbonate
A flame-retardant thermoplastic resin composition obtained by adding 0.01 to 5.0 parts by weight. (15) 100 parts by weight of styrene-based resin and bromo-based flame retardant
1 to 50 parts by weight of a flame retardant styrenic resin
(A) Component The weight ratio of calcium to magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
A flame-retardant styrene resin composition obtained by adding 0.01 to 5.0 parts by weight of a synthetic dolomite composed of a salt. (16) 100 parts by weight of styrene-based resin and bromo-based flame retardant
1 to 50 parts by weight of a flame retardant styrenic resin
(A) Component The weight ratio of calcium to magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
A flame-retardant styrene resin composition obtained by adding 0.01 to 5.0 parts by weight of mite. (17) 100 parts by weight of styrene-based resin and bromo-based flame retardant
3 to 30 parts by weight of a flame retardant styrenic resin
(A) Component The weight ratio of calcium to magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
A flame-retardant styrenic resin composition obtained by adding 0.05 to 3.0 parts by weight of mite. (18) 100 parts by weight of styrene-based resin and bromo-based flame retardant
3 to 30 parts by weight of a flame retardant styrenic resin
(A) Component The weight ratio of calcium to magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
Mite is selected from organic acids or organic acid metal salts.
Dolomite obtained by surface treatment with one kind of compound
A flame-retardant styrenic resin composition obtained by adding 0.05 to 3.0 parts by weight of a compound. (19) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
(A) Component dolomite compound is added to a flame retardant thermoplastic resin of 1 to 50 parts by weight in an amount of 0.01 to 5.0 parts by weight.
Parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component a small amount selected from zeolite compounds
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (20) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
1 to 50 parts by weight of a flame-retardant thermoplastic resin containing (a) component natural dolomite and / or calcium carbonate
-Synthetic dolomite consisting of double salt of magnesium carbonate
0.01 to 5.0 parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (21) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
1 to 50 parts by weight of a flame-retardant thermoplastic resin, wherein the weight ratio of component (a) calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
0.01 to 5.0 parts by weight of a synthetic dolomite composed of a salt; and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (22) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
1 to 50 parts by weight of a flame-retardant thermoplastic resin, wherein the weight ratio of component (a) calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.01 to 5.0 parts by weight of mite and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (23) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
In the flame retardant thermoplastic resin consisting of 3 to 30 parts by weight, the weight ratio of component (a) calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.05 to 3.0 parts by weight of mite, and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding together at least one compound in a total amount of 0.05 to 3.0 parts by weight. (24) 100 parts by weight of thermoplastic resin and bromo-based flame retardant
In the flame retardant thermoplastic resin consisting of 3 to 30 parts by weight, the weight ratio of component (a) calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
Mite is selected from organic acids or organic acid metal salts.
Dolomite obtained by surface treatment with one kind of compound
0.05 to 3.0 parts by weight of the compound and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component
A flame-retardant thermoplastic resin composition obtained by adding together at least one compound in a total amount of 0.05 to 3.0 parts by weight. (25) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 1 part by weight and 1 to 50 parts by weight of bromo flame retardant
(A) Component Dolomite-based compound is added to a plastic resin in an amount of 0.01 to 5.0 times.
Parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component a small amount selected from zeolite compounds
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (26) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 1 part by weight and 1 to 50 parts by weight of bromo flame retardant
(A) component natural dolomite and / or calcium carbonate
-Synthetic dolomite consisting of double salt of magnesium carbonate
0.01 to 5.0 parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.01 to 5.0 parts by weight of a single compound. (27) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 1 part by weight and 1 to 50 parts by weight of bromo flame retardant
(A) Component The weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
0.01 to 5.0 parts by weight of a synthetic dolomite composed of a salt;
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (28) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 1 part by weight and 1 to 50 parts by weight of bromo flame retardant
(A) Component The weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.01 to 5.0 parts by weight of mite and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition comprising a total of 0.01 to 5.0 parts by weight of a single compound. (29) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 3 parts by weight and 3 to 30 parts by weight of a bromo flame retardant
(A) Component The weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.05 to 3.0 parts by weight of mite, and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.05 to 3.0 parts by weight of a single compound. (30) Polyolefin, styrene resin, polyester
100% thermoplastic resin selected from polyester and polyamide
Flame retardant heat consisting of 3 parts by weight and 3 to 30 parts by weight of a bromo flame retardant
(A) Component The weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
Mite is selected from organic acids or organic acid metal salts.
Dolomite obtained by surface treatment with one kind of compound
0.05 to 3.0 parts by weight of the compound and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.05 to 3.0 parts by weight of a single compound. (31) 100 parts by weight of styrene-based resin and bromo-based flame retardant
(A) Component dolomite compound is added to a flame retardant styrene resin composed of 1 to 50 parts by weight of a dolomite compound in an amount of 0.01 to 5.0 parts
Parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component a small amount selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.01 to 5.0 parts by weight of a single compound. (32) 100 parts by weight of styrene-based resin and bromo-based flame retardant
(A) component natural dolomite and / or calcium carbonate
-Synthetic dolomite consisting of double salt of magnesium carbonate
0.01 to 5.0 parts by weight and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.01 to 5.0 parts by weight of a single compound. (33) 100 parts by weight of styrene-based resin and bromo-based flame retardant
The flame-retardant styrenic resin consisting of 1 to 50 parts by weight of the agent has a component (a) in which the weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
0.01 to 5.0 parts by weight of a synthetic dolomite composed of a salt;
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.01 to 5.0 parts by weight of a single compound. (34) 100 parts by weight of styrene-based resin and bromo-based flame retardant
The flame-retardant styrenic resin consisting of 1 to 50 parts by weight of the agent has a component (a) in which the weight ratio of calcium and magnesium is C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.01 to 5.0 parts by weight of mite and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.01 to 5.0 parts by weight of a single compound. (35) 100 parts by weight of styrene resin and bromide flame retardant
The flame retardant styrenic resin consisting of 3 to 30 parts by weight of the agent contains (a) the weight ratio of calcium and magnesium to C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
0.05 to 3.0 parts by weight of mite, and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least selected from zeolite compounds
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.05 to 3.0 parts by weight of a single compound. (36) 100 parts by weight of styrene-based resin and bromo-based flame retardant
The flame retardant styrenic resin consisting of 3 to 30 parts by weight of the agent contains (a) the weight ratio of calcium and magnesium to C
5 to 95 to 95: 5 natural dolomite in terms of aO to MgO
And / or a mixture of calcium carbonate and magnesium carbonate
Light fired mud obtained by light firing of synthetic dolomite made of salt
Mite is selected from organic acids or organic acid metal salts.
Dolomite obtained by surface treatment with one kind of compound
0.05 to 3.0 parts by weight of the compound and (b) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component
A flame-retardant thermoplastic resin composition obtained by adding a total of 0.05 to 3.0 parts by weight of a single compound.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As preferred embodiments of the present invention, the above embodiments (2) to (6), (8) to (1)
2), (14) to (18), (20) to (24), (2)
6) to (30) and (32) to (36). More preferred embodiments are the embodiments (4) to (4).
(6), (10) to (12), (16) to (18),
(22)-(24), (28)-(30), (34)-
(36), and the most preferred embodiments are the embodiments (5), (6), (11), (12),
(17), (18), (23), (24), (29),
(30), (35) and (36).

[Additive used in the present invention: component (a)]

A-1: Dolomite [manufactured by Tagen Lime Industry Co., Ltd.] surface untreated / ground product A-2: Light burnt dolomite [manufactured by Tagen Lime Industry Co., Ltd.] surface untreated / ground product A-3: Soiled lime [ Tagen Lime Industry Co., Ltd.] Untreated surface / crushed product A-4: Synthetic dolomite described in (Synthesis Example 1) Untreated surface / crushed product A-5: Light fired dolomite described in (Synthesis Example 2)
Surface-untreated / crushed product A-6: Light-burned synthetic dolomite described in (Synthesis Example 3)
Surface treated / crushed product A-7: Lightly burned dolomite described in (Synthesis Example 4) Surface treatment / crushed product A-8: Lightly burned dolomite described in (Synthesis Example 5)
Surface treated / crushed product A-9: Lightly fired synthetic dolomite described in (Synthesis Example 6)
Surface treatment / crushed product [Additive used in the present invention: component (b)] B-1: No. 1 in the description. Hydrotalcite B-2: No. 1 in the description. Hydrotalcite B-3: No. 3 in the description Hydrotalcite represented by No. 6 [Additive used in the present invention: component (c)] C-1: No. 6 in the specification. Zinc-substituted hydrotalcite compound represented by No. 10 [Additive used in the present invention: component (d)] D-1: 4A type zeolite compound [Na ₁₂ Al ₁₂ Si
₁₂ O ₄₈ · 27H ₂ O, manufactured by Tosoh Corporation Toyo Builder] D-2: 5A zeolite compound [Nippon Chemical Industrial Co., Ltd. Zeosuta CA-100P] D-3: Zinc-substituted zeolite compounds (D-3 of (The zinc substitution rate is 70 mol%.) [Additives other than the present invention: component (e)] E-1: magnesium oxide E-2: calcium oxide E-3: magnesium carbonate E-4: calcium carbonate E -5: Magnesium hydroxide E-6: Calcium hydroxide E-7: Magnesium stearate E-8: Calcium stearate [Example 1] HIPS resin [Stylon 492 manufactured by Asahi Kasei Kogyo Co., Ltd.] 100 parts, bis (pentabrom) Phenyl) ethane [Saytex 8 manufactured by Albemarle Co., Ltd.
010] 15 parts, antimony trioxide 2 parts, polyethylene wax [HI-WAX manufactured by Mitsui Petrochemical Industries, Ltd.]
400PF] 0.5 parts of the additives shown in Tables 1 to 3 were blended, mixed with a Henschel mixer, and then mixed with an extruder.
Pellets were obtained by melt-kneading at 00 ° C. The pellet was injection molded at 230 ° C. to obtain a flat plate of 52 mm × 40 mm × 3 mm. Wrap the obtained plate twice with aluminum foil,
The sample was placed in a gear oven set at 55 ° C., and the time (minutes) until the product turned blackish brown was measured. The results are shown in Tables 1 to 3. The longer the time, the better the thermal stability.

[Table 1]

[Table 2]

[Table 3] Sample numbers 1 to 27 are examples, and sample numbers 28 to 45 are comparative examples. As is clear from comparing the results of Tables 1 to 3,
It is understood that the flame retardant thermoplastic resin composition of the present invention has extremely excellent thermal stability. As shown in Sample Nos. 19 to 27, component (a) and component (b), component (c) and component (d)
It can be seen that when at least one compound selected from the components is added in combination, the thermal stability is further improved as compared with the case where only the component (a) like Nos. 1 to 18 is added. . Further, as shown in sample numbers 28 to 30, (a)
When only the component (b), the component (c) or the component (d) is added without adding the component, and when only the component (e), which is an additive other than the present invention, is added as in the same reference numerals 31 to 41 When the addition amount of the component (a) is smaller than the range of the addition amount of the present invention as in the case of the same number 42, the same numbers 43 and 44 are used.
As described above, when the component (a) is used in combination with at least one compound selected from the component (b), the component (c) and the component (d), the addition amount is within the range of the addition amount of the present invention. When the amount is small or when no additive is added as in the case of the same number 45, sufficient thermal stability cannot be obtained in any case. Example 2 100 parts of HIPS resin [Stylon 492 manufactured by Asahi Kasei Kogyo Co., Ltd.], hexabromocyclododecane [Great manufactured by Great Lakes Chemical Co., Ltd.]
Lakes CD-75P], 3 parts, polyethylene wax [HI-WAX 40 manufactured by Mitsui Petrochemical Industries, Ltd.]
0PF] was mixed with 0.5 part of the additives shown in Tables 4 and 5, and mixed with a Henschel mixer.
Pellets were obtained by melting and kneading at 0 ° C. This pellet is
Injection molding was performed at 85 ° C. to obtain a flat plate of 52 mm × 40 mm × 3 mm. Wrap the obtained plate twice with aluminum foil,
It was placed in a gear oven set at 0 ° C., and the time (minutes) until it turned dark brown was measured. The results are shown in Tables 4 and 5. The longer the time, the better the thermal stability.

[Table 4]

[Table 5] Sample numbers 1 to 18 are working examples, and sample numbers 19 to 35 are comparative examples. As is clear from comparison of the results in Tables 4 and 5, it can be seen that the flame-retardant thermoplastic resin composition of the present invention has extremely excellent thermal stability. In addition, sample number 9-18
When component (a) and at least one compound selected from component (b), component (c) and component (d) are added in combination, (a) It can be seen that the thermal stability is much better than when only the components were added. Also, as in sample numbers 19 to 23,
When at least one compound selected from the component (b), the component (c) and the component (d) is added without adding the component (a), as in the case of the same reference numerals 24 to 34, other than the present invention, When only the component (e), which is an additive, is added, or when no additive is added as in the case of No. 35, sufficient thermal stability cannot be obtained. Example 3 100 parts of HIPS resin (Stylon 492, manufactured by Asahi Kasei Corporation), hexabromocyclododecane [Great, manufactured by Great Lakes Chemical Co., Ltd.]
Lakes CD-75P], 1 part, polyethylene wax [HI-WAX 40 manufactured by Mitsui Petrochemical Industries, Ltd.]
0PF] was mixed with 0.5 part of the additives shown in Table 6, mixed with a Henschel mixer, and melt-kneaded at 180 ° C. using an extruder to obtain pellets. The pellet was injection molded at 185 ° C. to obtain a flat plate of 52 mm × 40 mm × 3 mm. The obtained flat plate was wrapped twice with aluminum foil, placed in a gear oven set at 240 ° C., and the time (minutes) until it was deteriorated to blackish brown was measured. Table 6 shows the results. The longer the time, the better the thermal stability.

[Table 6] Sample numbers 1 to 8 are working examples, and sample numbers 9 to 16 are comparative examples. As is clear from comparison of the results in Table 6, it can be seen that the flame-retarded thermoplastic resin composition of the present invention has extremely excellent thermal stability. When the components (a) and (b), at least one compound selected from the components (c) and (d) are added together as in sample Nos. 4 to 8, It can be seen that the thermal stability is much better than when only the component (a) is added as in No. 3. When at least one compound selected from the component (b), the component (c) and the component (d) is added without adding the component (a) as in Sample Nos. 9 to 12, the same number is used. 1
In cases where only the component (e), which is an additive other than the present invention, is added as in Nos. 3 to 15, and where no additive is added as in No. 16, no sufficient thermal stability is obtained. [Example 4] ABS resin [Technopolymer Co., Ltd. T
ECHNO ABS 130NP] 100 parts, bis (pentabromophenyl) ethane [Albemarle Co., Ltd.
Saytex 8010] 15 parts, brominated bisphenol A-based epoxy resin [Platherm EC-14 manufactured by Dainippon Ink and Chemicals, Inc.] 15 parts, antimony trioxide 3
Parts to 0.5 parts of polyethylene wax [HI-WAX 400PF manufactured by Mitsui Petrochemical Industry Co., Ltd.]
After mixing the additives shown in the above and mixing with a Henschel mixer,
The mixture was melt-kneaded at 200 ° C. using an extruder to obtain pellets. The pellets were injection molded at 240 ° C.
A flat plate of 40 mm × 3 mm was obtained. The obtained flat plate was wrapped twice with aluminum foil, put in a gear oven set at 260 ° C., and the time (minute) until the black plate was deteriorated was measured.
Tables 7 to 9 show the results. The longer the time, the better the thermal stability.

[Table 7]

[Table 8]

[Table 9] Sample Nos. 1 to 21 are Examples, and Sample Nos. 22 to 42 are Comparative Examples. As is clear from comparing the results of Tables 7 to 9,
It is understood that the flame retardant thermoplastic resin composition of the present invention has extremely excellent thermal stability. As shown in Sample Nos. 10 to 21, components (a) and (b), components (c) and (d)
It can be seen that when at least one compound selected from the components is added in combination, the thermal stability is much better than when only the component (a) as in the same numbers 1 to 9 is added. . When at least one compound selected from component (b), component (c) and component (d) is added without adding component (a) as in sample numbers 22 to 27, the same number is used. In cases where only the component (e), which is an additive other than the present invention, is added as in Nos. 28 to 38, and where no additive is added as in No. 42, sufficient thermal stability cannot be obtained. In addition, when the addition amount of the component (a) is larger than the range of the addition amount of the present invention as in the same number 39, and as in the same number 40 and 41, the components (a) and (b)
When the amount of addition in combination with at least one compound selected from the components (c) and (d) is larger than the range of the addition amount of the present invention, the expected thermal stability by increasing the amount is obtained. I can't. [Example 5] ABS resin [Technopolymer Co., Ltd. T
80 parts of ECHNO ABS 130NP], 20 parts of polyamide [Nylon 6 Novamid 1020CA2 manufactured by Mitsubishi Engineering-Plastics Corporation], 20 parts of bis (pentabromophenyl) ethane [manufactured by Albemarle Co., Ltd.]
Saytex 8010], 30 parts, brominated bisphenol A-based epoxy resin [Platherm EC-20, manufactured by Dainippon Ink and Chemicals, Inc.], 20 parts, antimony trioxide 4
Parts, polyethylene wax [HI-WAX 400PF, manufactured by Mitsui Petrochemical Industry Co., Ltd.], 0.5 part, and the additives shown in Table 10 were blended, mixed with a Henschel mixer, and then melt-kneaded at 210 ° C. using an extruder. Thus, a pellet was obtained. This pellet is injection molded at 250 ° C., and is 52 mm × 40 m
An mx 3 mm flat plate was obtained. The obtained flat plate is made of aluminum foil 2
Wrap and place in a gear oven set at 260 ° C.
The time (minutes) until the black-brown color deteriorated was measured. Table 10 shows the results. The longer the time, the better the thermal stability.

[Table 10] Sample Nos. 1 to 9 are Examples, and Sample Nos. 10 to 16 are Comparative Examples. As is clear from the comparison of the results in Table 10, it can be seen that the flame-retarded thermoplastic resin composition of the present invention has extremely excellent thermal stability. In addition, like sample numbers 4 to 9,
When the component (a) and at least one compound selected from the component (b), the component (c) and the component (d) are added in combination, only the component (a) like the same number 1 to 3 is added. It can be seen that the thermal stability is much better than in the case where it is added. Further, as in Sample Nos. 10 to 12, when at least one compound selected from the components (b), (c) and (d) is added without adding the component (a),
In the case where only the component (e), which is an additive other than the present invention, is added as in Nos. 13 to 15, and in the case where no additive is added as in No. 16, sufficient thermal stability is obtained. Absent. [Example 6] Polypropylene resin [Idemitsu Petrochemical Co., Ltd.
100 parts of Idemitsu Polypro J-2000G], tetrabromobisphenol A bis (2,3-dibromopropyl ether [Fireguard 310 manufactured by Teijin Chemicals Ltd.]
0] 7 parts, antimony trioxide 5 parts, polyethylene wax [HI-WAX 400 manufactured by Mitsui Petrochemical Industry Co., Ltd.]
PF] was added to 0.5 part of the additives shown in Tables 11 and 12, and mixed with a Henschel mixer.
Pellets were obtained by melting and kneading at 10 ° C. The pellet was injection molded at 220 ° C. to obtain a flat plate of 52 mm × 40 mm × 3 mm. Wrap the obtained plate twice with aluminum foil,
The sample was placed in a gear oven set at 55 ° C., and the time (minutes) until the product turned blackish brown was measured. The results are shown in Tables 11 and 12. The longer the time, the better the thermal stability.

[Table 11]

[Table 12] Sample numbers 1 to 16 are working examples, and sample numbers 17 to 33 are comparative examples. As is clear from comparison of the results in Tables 11 and 12, it can be seen that the flame-retarded thermoplastic resin composition of the present invention has extremely excellent thermal stability. In addition, sample numbers 9-1
As shown in No. 6, when component (a) and at least one compound selected from components (b), (c) and (d) are added together, (a) ) It can be seen that the thermal stability is much better than when only the component is added. Also, as in sample numbers 17 to 21,
When at least one compound selected from the component (b), the component (c) and the component (d) is added without adding the component (a), as in the case of the same reference numerals 22 to 32, other than the present invention, When only the component (e), which is an additive, is added, and when no additive is added, as in the case of No. 33, sufficient thermal stability cannot be obtained. [Example 7] PBT resin [Teijin PBT manufactured by Teijin Limited]
C-700] 100 parts, brominated bisphenol A-based epoxy resin [Platherm EP-100 manufactured by Dainippon Ink and Chemicals, Inc.] 15 parts, antimony trioxide 5 parts, polyethylene wax [HI manufactured by Mitsui Petrochemical Industries, Ltd.] −
[WAX 400PF] 0.5 part was mixed with the additives shown in Tables 13 and 14, mixed with a Henschel mixer, and melt-kneaded at 240 ° C using an extruder to obtain pellets.
This pellet was injection molded at 260 ° C.
A flat plate of mm × 3 mm was obtained. The obtained flat plate was wrapped twice with an aluminum foil, placed in a gear oven set at 265 ° C., and the time (minutes) required until the plate became blackish brown was measured. The results are shown in Tables 13 and 14. The longer the time, the better the thermal stability.

[Table 13]

[Table 14] Sample numbers 1 to 15 are working examples, and sample numbers 16 to 32 are comparative examples. As is clear from the comparison of the results in Tables 13 and 14, the flame retardant thermoplastic resin composition of the present invention has extremely excellent thermal stability. In addition, sample number 9-15
When component (a) and at least one compound selected from component (b), component (c) and component (d) are added in combination, (a) It can be seen that the thermal stability is much better than when only the components were added. Also, as in sample numbers 16 to 20,
When at least one compound selected from the component (b), the component (c) and the component (d) is added without adding the component (a), as in the case of the same numbers 21 to 31, other than the present invention, When only the component (e), which is an additive, is added, or when no additive is added as in the case of No. 32, sufficient thermal stability cannot be obtained.

The flame-retarded thermoplastic resin composition of the present invention comprises:
It has remarkably excellent thermal stability.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kuji Ihara 788 Kuji, Takatsu-ku, Kawasaki City, Kanagawa Prefecture Inside Sankyo Organic Synthesis Co., Ltd. (72) Inventor Takeo Tanaka 1-2 Suzukicho, Kawasaki-ku, Kawasaki City, Kanagawa Prefecture Ajino (72) Inventor Masaharu Akitsu 788 Kuji, Takatsu-ku, Kawasaki-shi, Kanagawa F-term (reference) 4J002 AA011 BB011 BB121 BC021 BC041 BC112 BN151 CF001 CF071 CG032 CL001 DE077 DE147 DJ008 EB046 EJ056 EU026 EU186 EU196 FB087 FD067 FD132 FD136 FD208

Claims (7)

[Claims] 1. A dolomite compound (a) in an amount of 0.01 to 5.0 parts by weight is added to a flame retarded thermoplastic resin comprising 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a bromo flame retardant. A flame-retardant thermoplastic resin composition comprising: 2. A flame-retardant thermoplastic resin comprising 100 parts by weight of a thermoplastic resin and 1 to 50 parts by weight of a bromo-based flame retardant, wherein (a) a dolomite compound is contained in an amount of 0.01 to 5.0 parts by weight; (B) component hydrotalcite (c) component zinc-substituted hydrotalcite compound (d) component at least one compound selected from zeolite compounds in a total amount of 0.0
1 to 5.0 parts by weight A flame-retardant thermoplastic resin composition added in combination. 3. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin, a styrene resin, a polyester or a polyamide. 4. The flame retardant according to claim 1, wherein the dolomite compound is natural dolomite and / or synthetic dolomite comprising a double salt of calcium carbonate and magnesium carbonate. Thermoplastic resin composition. 5. A dolomite compound having a calcium to magnesium weight ratio of 5 to 9 in terms of CaO to MgO.
The flame retardant thermoplastic resin composition according to any one of claims 1 to 4, wherein the ratio is 5 to 95: 5. 6. A dolomite compound having a calcium to magnesium weight ratio of 5 to 9 in terms of CaO to MgO.
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 5, comprising light-burned dolomite obtained by light-burning a 5-95 to 5 double salt compound. object. 7. The method according to claim 1, wherein the dolomite compound is surface-treated with at least one compound selected from organic acids and organic acid metal salts. Flamed thermoplastic resin composition.