JP2000159955A - Styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition improving processability such as gelling properties, tackiness, peeling property and fluidity, by blending a stylene- based resin with polyolefin wax and a specific alkali (alkaline earth) metal salt. SOLUTION: This composition is obtained by blending (A) 100 pts.wt. of a stylene-based resin, (B) 0.01-10 pts.wt. of at least one kind of polyolefin wax and (C) 0.01-10 pts.wt. of at least one kind of alkali metal salt and alkaline earth metal salt of an 8-30C aliphatic monocarboxylic acid. For example, a polymer, etc., of a monomer such as stylene is used as the component A, a polyethylene wax, etc., is used as the component B and lithium octylate or magnesium octylate, etc., is used as the component C, and further (D) a phthalate-based plasticizer and (E) an organic phosphite, etc., may be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic resin composition which is remarkably excellent in gelling properties during molding and excellent in metal releasability.

[0002]

2. Description of the Related Art When a styrene resin is processed by a processing machine such as an extruder, there is a step of degassing by venting. The design of the gel time of the resin greatly affects the processability, and if the gel time is too fast, degassing will be insufficient,
Phenomena such as foaming occur. Therefore, in order to delay the gel time, the gelling time is adjusted by the processing temperature and additives, but there are still unsolved parts in the product properties, and a more excellent processability improver is required. Further, in order to obtain a molded product having good surface properties, processing at a high temperature is necessary. At this time, it is required that the mold has good releasability.

[0003] Also, there have been reported many methods for adding a polyolefin wax, metal soap, or the like to a resin composition as an additive. For example, Japanese Patent Application Laid-Open Nos. 63-113057 and 2-182742 are disclosed. However, none of them shows a synergistic effect by the combined use of these additives.

[0004]

SUMMARY OF THE INVENTION In view of the present situation, the present invention has been intensively studied, and as a result, 1) a styrene resin is specified.
Polyolefin wax, 2) Gelling properties, tackiness, releasability, fluidity, etc. by using at least one compound of an alkali metal salt and an alkaline earth metal salt of an aliphatic monocarboxylic acid having 8 to 30 carbon atoms. The present invention provides a styrenic resin composition which improves the processability of styrene.

[0005]

[Means for Solving the Problems] That is, the present invention provides:
1) at least one kind of polyolefin wax is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the styrene resin.
More preferably, 0.01 to 10 parts by weight of at least one of 0.05 to 3.0 parts by weight and 2) at least one of an alkali metal salt and an alkaline earth metal salt of an aliphatic monocarboxylic acid having 8 to 30 carbon atoms.
An object of the present invention is to provide a styrenic resin composition having improved processability, characterized in that the styrenic resin composition contains a heavy part, more preferably 0.05 to 3.0 parts by weight.

In the present invention, the polyolefin wax includes polyethylene wax, polypropylene wax and derivatives thereof, such as copolymers with other monomers such as acrylic acid, vinyl acetate, styrene and maleic acid, and partially oxidized. It is a disassembled type or the like.

In the present invention, the alkali metal salt of an aliphatic monocarboxylic acid having 8 to 30 carbon atoms includes octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, oleic acid, behenic acid,
Metal salts of aliphatic monocarboxylic acids such as montanic acid and lithium, sodium, potassium and the like.

[0008] The alkaline earth metal salts of aliphatic monocarboxylic acids having 8 to 30 carbon atoms include octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, oleic acid, behenic acid, montanic acid and the like. Is a metal salt of an aliphatic monocarboxylic acid with magnesium, calcium and barium.

The styrenic resin used in the present invention includes a resin having a structure derived at least in part from a styrene skeleton, and a blend resin thereof.
Styrene-based compound monomers, for example, polymers of monomers such as styrene, side-chain-substituted styrene such as α-methylstyrene and vinyl-substituted styrene such as o-chlorostyrene, and styrene-based compound monomers And other compound monomers such as a vinyl compound monomer and a conjugated diene compound monomer.
Examples of vinyl compound monomers include cyano-containing vinyl compounds of acrylonitrile, vinyl carboxylic acids such as acrylic acid and methacrylic acid, vinyl carboxylic acid esters such as methyl esters and ethyl esters thereof, and vinyl heterocyclic rings such as vinyl pyridine vinyl carbazole. And the like. Examples of the conjugated diene compound include butadiene, 1-chlorobutadiene, 2-chlorobutadiene, isoprene, and an ethylene / propylene / diene compound. Examples of the styrene-based resin include binary conjugated polymers of a styrene-based compound monomer and the compound monomer described above, such as acrylonitrile-butadiene-styrene copolymer and acrylate-butadiene. -Styrene copolymer, methacrylate-butadiene-styrene copolymer, or a blend of these resins.

Other commonly used stabilizers or additives can be added to the styrenic resin composition of the present invention. For example, plasticizers, organic phosphites,
Organophosphates, organotin compounds, inorganic compounds, antioxidants, ultraviolet absorbers, hindered amine light stabilizers, lubricants, pigments, fillers, processing aids, flame retardants, flame retardant aids, antistatic agents , A foaming agent and the like can also be added.

Specific examples of the plasticizer include a phthalate ester plasticizer, an ester plasticizer of a carboxylic acid other than phthalic acid or a polyester plasticizer, a phosphate ester plasticizer, and a chlorine plasticizer. Can be Specific examples of phthalate plasticizers include dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, and diisononyl. Phthalate,
Didecyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, dibenzyl phthalate and the like. Specific examples of ester plasticizers or polyester plasticizers of carboxylic acids other than phthalic acid include di-n-butyl adipate, di-n-octyl adipate, diisononyl adipate, and diisodecyl adipate. , Polypropylene adipate, polybutylene adipate, diisobutyl azelate, di-2-ethylhexyl azelate,
Dibutyl sebacate, di-2-ethylhexyl sebacate
, Polypropylene sebacate, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate,
Di-2-ethylhexyl fumarate, tributyl citrate, dibutyl maleate, dioctyl maleate, methyl acetyl ricinoleate, polypropylene sebacate and the like. Specific examples of the phosphate ester plasticizer include:
Triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate,
Tricresyl phosphate, trixylenyl phosphate
, Tris (dimethylphenyl) phosphate, diphenyloctyl phosphate, diphenylcresyl phosphate, and the like. Specific examples of chlorine plasticizers include:
Chlorinated paraffin, chlorinated methyl stearate, dioctyl tetrachlorophthalate and the like.

Specific examples of the organic phosphite include:
Tris (2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tri (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tri (2-ethylhexyl) phosphite, tris (Nonylphenyl) phosphite, tri (octylphenyl) phosphite, tri (cyclohexylphenyl) phosphite, tricyclohexylphosphite, tri (decyl) thiophosphite, triisodecylthiophosphite, phenyl di (2-ethylhexyl) ) Phosphite, phenyl diisodecyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite,
Phenyl dicyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl mono (tridecyl)
Thiophosphite, nonylphenyldi (tridecyl) phosphite, phenyl / p-tert-butylphenyl / dodecylphosphite, di (nonylphenyl) phosphite, mono (nonylphenyl) phosphite, diisopropylphosphite, monoisopropylphosphite , Diisodecyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite,
Di (cyclohexylphenyl) phosphite, monocyclohexylphenyl phosphite, di (p-tert
-Butylphenyl) phosphite, tetratridecyl.
4,4'-isopropylidene-diphenyl diphosphite, tetratridecyl-4,4'-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl-4,4'-thio- Bis (2-tert-butyl-5-methylphenol) diphosphite, tetra (nonylphenyl) poly (propyleneoxy) isopropyldiphosphite, tetra (tridecyl) propyleneoxypropyldiphosphite, tetra (tridecyl) 4,4 ' Isopropylidene di (cyclohexyl) diphosphite, penta (nonylphenyl) bis [poly (propyleneoxy) isopropyl] triphosphite, hepta (nonylphenyl) tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, deca (no Butylphenyl) heptakis (propyleneoxy isopropyl) octa phosphite, deca-phenyl-hept (propyleneoxy isopropyl) octa phosphite, di (butoxyethyl carboxymethyl ethyl) 2,2 '
Dimethylene-trimethylenedithiophosphite, di (isooctoxycarbomethyl) 2,2'-dimethylene-trimethylenedithiophosphite, tetra (lauryl) 2,2'-oxydiethylenedithiophosphite,
Tetra (lauryl) ethylenedithiophosphite, tetra (lauryl) hexamethylenedithiophosphite, penta (dodecyl) di (hexamethylene) trithiophosphite, diphenylphosphite, 4,4'-isopropylidene-dicyclohexylphosphite, 4, 4'-
Isopropylidene-diphenylalkyl phosphite, 2-tert-butyl-4- [1- (3-tert
-Butyl-4-hydroxyphenyl) isopropyl] phenyl di (p-nonylphenyl) phosphite, di (tridecyl) 4,4'-butylidene-bis (3-methyl-6-tert-butylphenyl) phosphite, di Stearyl 2,2-dimethylene-trimethylene diphosphite, tri (cyclohexylphenyl) phosphite, tri (dodecyl) thiophosphite, decaphenyl hepta (propyleneoxyisopropyl) octaphosphite, dibutylpenta (2,2- Dimethylene-trimethylene) diphosphite, dioctyl penta (2,
2-dimethylene-trimethylene) diphosphite, didecyl-2,2-dimethylene-trimethylene diphosphite, distearylpentaerythritol diphosphite, 1,1,3-tris (2-methyl-4-di-tritesylphosphite) -5-tert-butylphenyl) butane and a mixture of diphenylphosphite, tetrakis (2,4-di-t, 4,4′-biphenylenediphosphinate)
tert-butylphenyl) and the like.

Specific examples of the organic phosphate include t
tert-butylphenoxypolyethoxyphosphate,
Octyloxy polyethoxy phosphate, octyl phenoxy polyethoxy phosphate, oleyloxy polyethoxy dilauryl phosphate, oleyl oxy polyethoxy phosphate, xyenyl diphenyl phosphate, di (lauryl oxy polyethoxy) phosphate, di-t-butyl phenoxy polyethoxy phosphate , Dioctyl monophenyl phosphate, dicresyl monophenyl phosphate, dinonylphenoxy polyethoxy phosphate, diphenyl-2-ethylhexyl phosphate, stearyloxy polyethoxy phosphate, tris (butoxyethyl) phosphate, tridecyl hydroxy polyethoxy phosphate, tridecyl polyoxy Ethylene phosphate, dodecylphenoxy polyethoxyphos Eto, nonylphenyl polyoxyethylene phosphate, nonyl phenoxy polyethoxy phosphate, monolauryl phosphate, and the like lauryl oxy polyethoxy phosphate.

Specific examples of the organotin compound include mono (or di) butyltin tris (or bis) isooctylmalate, mono (or di) octyltin tris (or bis) isooctylmalate, mono (or di) octyltin tris (or bis) isooctylmalate A) methyltin malate polymer, mono (or di) butyltin tyltin malate polymer, mono (or di) octyltin malate polymer, and the like.

Specific examples of the antioxidant include phenolic antioxidants including phenol derivatives such as hindered phenol, polyalkylphenol bonded via alkylene or alkylidene, and poly (alkylphenol) bonded via sulfur, and sulfur. And alkanoic acid and alkyl esters thereof, for example, sulfur-containing compounds such as distearyl thiodipropionate and dilauryl thiodipropionate, hindered amines, organic phosphites, and those described in the positive list of JHPA. And the like.

Specific examples of the ultraviolet absorber include benzophenone, benzotriazole, and salicylate. Specific examples of benzophenones include 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octylbenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, -Hydroxy-4-methoxy-4'-chlorobenzophenone,
2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-
5-sulfobenzophenone trihydrate, 2,4-dihydroxy-benzophenone, 2,4,5-trihydroxybenzophenone and the like. Specific examples of the benzotriazole type include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3',
5'-di-tert-butylphenyl) -5-chloro-
Benzotriazole, 2- (2'-hydroxy-3'-
tert-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-
3'-tert-butyl-5'-methacryloxyethylphenyl) -5-chloro-benzotriazole. Specific examples of salicylates include phenyl salicylate, 4-tert-butylphenyl salicylate, 4-tert-octylphenyl salicylate, bisphenol A disalicylate, 2-isopropyl-methyl-cyclohexyl salicylate, monoglycol salicylate, and the like.

Specific examples of the hindered amine light stabilizer include 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-1,
2,2,6,6-pentamethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-dodecylsuccinimide-2,2,6,6-tetramethylpiperidine, 1- (3 , 5-di-tert-
Butyl-4-hydroxyphenyl) propionyloxyethyl-4- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy-2,2,6
6-tetramethylpiperidine, tris [2-hydroxy-3- (2,2,6,6-tetramethyl-4-piperidylamino) propyl] isocyanurate, 1,5,8,
12-tetrakis [2,4-bis (butyl (2,2,
6,6-tetramethyl-4-piperidyl) amino) -6
-1,3,5-triazinyl] -1,5,8,12-tetraazadodecane.

Specific examples of the lubricant include higher alcohol esters of adipic acid, higher alcohol esters of azelaic acid, ethylene bisstearamide, higher fatty acid esters of glycerin, higher fatty acid esters of pentaerythritol, methylene bisstearamide, higher alcohols and higher fatty acids. And paraffin waxes derived from petroleum or coal, natural or synthetic polymer ester waxes, lubricating metal salts other than the above-mentioned metallic soaps, and the like.

Specific examples of the filler include metal oxides,
Hydroxide, chloride, sulfide, carbonate, phosphate, phosphite, hypophosphite, sulfate, sulfite, chlorate, perchlorate, borate, silicate, And the like can also be used. Examples thereof include A-type, X-type and Y-type synthetic zeolites, diatomaceous earth, aluminum silicate, calcium silicate, sodium silicate, magnesium silicate, metal silicate, asbestos, alumina, alumina silicate Sodium, alumina site, kaolin, clay, syenite, zeolite, talc, nepheline, nepheline cyenite hydrocalumite, hydrotalcite,
Natural zeolites such as Bengala, bentonite, monazite powder, and mordenite, or metal-substituted zeolites obtained by substituting Group 1a metal of these zeolites with Group 2 metal ions, zinc phosphite, zinc chloride, barium perchlorate , Activated clay, antimony trioxide, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, zinc hydroxide, Otani stone powder, calcium carbonate,
Barium carbonate, magnesium carbonate, zinc carbonate, anhydrous hydrotalcite, zinc sulfide, barium sulfate and the like.

Specific examples of the processing aid include acrylate butadiene styrene copolymer, acrylic resin, acrylonitrile styrene copolymer, acrylonitrile butadiene styrene copolymer, ethylene propylene copolymer, ethylene vinyl acetate copolymer Styrene butadiene copolymer, polystyrene, methacrylate butadiene styrene copolymer, chlorinated polyethylene and the like.

Specific examples of the flame retardant include bromine compounds such as tetrabromobisphenol A (TBA) and derivatives thereof, hexabromobenzene, decabromodiphenyl ether, tetrabromoethane, tetrabromobutane, and hexabromocyclodecane (HBCD). Chlorinated paraffin, diphenyl chloride, perchloropentacyclodecane,
Halogen flame retardant such as chlorinated naphthalene. Tri (β-chloroethyl) phosphate, tri (dichloropropyl) phosphate, tri (dibromopropyl) phosphate,
Phosphorus flame retardants such as phosphoric esters such as 2,3-dibromopropyl-2,3-chloropropyl phosphate or halogenated phosphoric esters. Aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, calcium hydroxide, barium hydroxide, zinc stannate, hydrate of tin oxide, hydrate of inorganic metal compounds such as borax, borane Zinc acid, zinc metaborate,
Inorganic flame retardants such as barium metaborate, zinc carbonate, magnesium-calcium carbonate, calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, and red phosphorus.

Specific examples of the antistatic agent include N, N'-
Dimethyl-N-octyl-N-benzylammonium perchlorate, N-bis (hydroxyethoxyethyl)
-N-octyl-N-methylammonium chloride,
N, N'-bis (hydroxyethoxyethyl) -N-stearyl-N-ethylammonium perchlorate, N
-Hydroxytriethoxyethyl-N-decyl-N,
N′-dimethylammonium perchlorate, N-nonanoylaminopropyl-N-hydroxyethyl-N,
N'-dimethylammonium perchlorate, N-ethylphenoxypentaethoxyethyl-N-lauryl-
N, N'-dimethylammonium perchlorate and the like.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
In these examples, “parts” means “parts by weight”.

Example 1 A blend of 100 parts by weight of ABS resin (Sumitika ABS Latex Co., Ltd. K-2540A) and the additives shown in Table 1 was added using a plastmill tester (Toyo Seiki Labo Plastmill). 170
The mixture was kneaded under conditions of 50 ° C., 50 rpm and 40 g, and the time until gelation was measured. Further, the above composition was kneaded with a 6-inch test roll adjusted to 180 ° C. for 5 minutes, and the roll releasability was evaluated. Evaluation of peelability from roll is 1 to
It is represented by 5, and 1 represents a state where peeling can be performed with almost no resistance, and the peel resistance increases as the numerical value increases. The results are shown in Table 1.

[0025]

[Table 1]

Example 2 A mixture of 100 parts by weight of an AS resin (Mitsui Chemicals Lightac A 120PCF) and the additives shown in Table 2 was used at 170 ° C. and 50 rpm using a plastmill tester (Toyo Seiki Labo Plastmill). 4
The mixture was kneaded under the condition of 0 g, and the time until gelation was measured. Further, the above composition was kneaded with a 6-inch test roll adjusted to 180 ° C. for 5 minutes, and the roll releasability was evaluated. The evaluation of the releasability from the roll is represented by 1 to 5, and 1 represents a state in which the film can be peeled almost without resistance, and the larger the value, the larger the peel resistance. The results are shown in Table 2.

[0027]

[Table 2]

[0028]

The styrenic resin composition of the present invention has excellent releasability and initial lubricity, and provides a composition having remarkably improved workability.

Continued on the front page F term (reference) 4J002 BB032 BB062 BB082 BB092 BB122 BB142 BC031 BC041 BC051 BC061 BC071 BC081 BC091 BN151 BN161 EG026 EG036 FD010 FD020 FD030 FD040 FD050 FD070 FD090 FD100 FD100

Claims (1)

[Claims] 1. A styrene-based resin, relative to 100 parts by weight,
1) At least one kind of polyolefin wax is used in 0.0
1 to 10 parts by weight, and 2) a styrene resin obtained by adding 0.01 to 10 parts by weight of at least one kind of an alkali metal salt or an alkaline earth metal salt of an aliphatic monocarboxylic acid having 8 to 30 carbon atoms. Composition.