TW201309754A - Thermoplastic resin composition - Google Patents

Abstract

The present invention provides a thermoplastic resin composition comprising (A) a thermoplastic resin, (B) a compound represented by the formula (1), and (C) carbon black, wherein the content of (C) is 2 to 250 weight parts per one weight part of (B). Wherein R1, R2, R5, R6 and R7 represent a hydrogen atom, an alkyl group, an aralkyl group or a phenyl group, R3 and R4 represent a hydrogen atom or an alkyl group, X1 represents a single bond, a sulfur atom or a group represented by -CHR9-, R9 represents a hydrogen atom, an alkyl group or a cycloalkyl group, A1 represents an alkanediyl group or a group represented by *-COR10-, R10 represents a single bond or an alkanediyl group, * represents a hand bonding to -O-, one of Y1 and Z1 represents a hydroxyl group, an alkoxy group or an aralkyloxy group, and the other represents a hydrogen atom or an alkyl group.

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition and the like.

JP2001-106832-A describes a thermoplastic resin composition containing a thermoplastic resin, [6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]- 2,4,8,10-tetrakis(t-butyl)dibenzo[d,f][1,3,2] [6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldib enzo[d,f][1 , 3,2]dioxaphosphepin]) and carbon black, and relative to [6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8 , 10-tetra(t-butyl)dibenzo[d,f][1,3,2] The content of carbon black was 1 part by weight, and the content of carbon black was 0.83 parts by weight.

Further, Patent Document 1 describes a thermoplastic resin composition containing a thermoplastic resin, [6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]- 2,4,8,10-tetrakis(t-butyl)dibenzo[d,f][1,3,2] Phosphonium ring and carbon black, and relative to [6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10- Tetrakis(t-butyl)dibenzo[d,f][1,3,2] The content of carbon black was 1.67 parts by weight, based on 1 part by weight of the phosphonium ring.

In the conventional thermoplastic resin composition, there is a case where the amount of glue generated by thermal deterioration is large and the process stability cannot be sufficiently satisfied.

The present invention contains the following invention.

[1] A thermoplastic resin composition comprising (A) a thermoplastic resin, (B) a compound represented by the formula (I), and (C) carbon black, and (B) 1 part by weight, (C) The content is from 2 to 250 parts by weight.

(wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6; An alkylcycloalkyl group of 12, an aralkyl group having 7 to 12 carbon atoms or a phenyl group.

R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

X ¹ represents a single bond, a sulfur atom or a -CHR ⁹ - group, and R ⁹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.

A ¹ represents a C 2 to 8 alkanediyl group or a *-COR ¹⁰ - group, R ¹⁰ represents a single bond or a C 1 to 8 alkanediyl group, and * represents a bond to -O-.

Any of Y ¹ and Z ¹ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

[2] The thermoplastic resin composition according to [1], wherein Y ¹ is a hydroxyl group, and at least one of R ⁷ and R ^{8 is} an alkyl group having 3 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms. An alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group.

[3] The plastic resin composition according to [1] or [2] wherein (A) is polyethylene.

According to the thermoplastic resin composition of the present invention, the amount of glue generated by thermal deterioration is small, and the process stability is excellent.

<(A) Thermoplastic Resin>

The (A) is exemplified by the following.

(1) Polyethylene, such as high density polyethylene (HD-PE), low density polyethylene (LD-PE) or linear low density polyethylene (LLDPE); (2) polypropylene; (3) methyl pentyl Ethene polymer; (4) EEA (ethylene/ethyl acrylate copolymerization) resin; (5) ethylene/vinyl acetate copolymer resin; (6) polystyrene, such as polystyrene, poly(p-methylbenzene) Ethylene) or poly(α-methylstyrene); (7) AS (acrylonitrile/styrene copolymerization) resin; (8) ABS (acrylonitrile/butadiene/styrene copolymerization) resin; (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymerization) resin; (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymerization) resin; (11) chlorinated polyethylene, polychloroprene Or chlorinated rubber; (12) polyvinyl chloride or polydichloroethylene; (13) methacrylic resin; (14) ethylene/vinyl alcohol copolymer resin; (15) fluororesin; (16) polyacetal; (17) grafted polyphenylene ether resin and polyphenylene sulfide resin; (18) polyurethane; (19) polyamine; (20) polyester resin, such as poly(p-phenylene) Ethylene formate or polybutylene terephthalate; (21) polycarbonate; (22) Acrylate; (23) poly sulfone, polyether ether ketone, polyether sulfone; (24) Aromatic polyester resin; (25) diallyl phthalate prepolymer; (26) polyoxyl resin; (27) 1,2-polybutadiene; (28) polyisoprene; 29) styrene/butadiene copolymer; (30) butadiene/acrylonitrile copolymer; (31) ethylene/propylene copolymer; (32) ethylene/MMA (methyl methacrylate) copolymer.

(A) The above-exemplified resin may be used singly or as a mixture of the above-exemplified resins.

(A) is preferably a polyolefin such as polyethylene (for example, HD-PE, LD-PE, LLDPE) or polypropylene, and particularly preferably polyethylene.

The method for producing the thermoplastic resin is not particularly limited, and may be, for example, obtained by radical polymerization, or by using a metal containing Group IVb, Group Vb, Group VIb or Group VIII of the periodic table. Manufacturer of catalyst polymerization.

The related metal-containing catalyst may be any metal having one or more ligands, for example, an oxide, a halogen compound, an alcoholate, an ester, an aryl group or the like coordinated by a π bond or a sigma bond. The complex compound may be used as it is, and the complex may be used as it is, or may be supported on a substrate such as magnesium chloride, titanium chloride, aluminum oxide or cerium oxide.

For example, in the production of a polyolefin, for example, a Ziegler-Natta catalyst, a metallocene catalyst, a Phillips catalyst, or the like is preferably used.

<(B) Compound represented by formula (I)>

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and n-pentyl group. Isoamyl, n-hexyl, n-heptyl, n-octyl and the like.

Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include a methylcyclopentyl group, a methylcyclohexyl group, a methylcycloheptyl group, a methylcyclooctyl group and the like.

Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the alkanediyl group having 1 to 8 carbon atoms include a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropyl group, and an isobutyl group. 2-methyltrimethylene, isopentyl, exohexyl, isooctyl, 2-ethylhexyl and the like.

Examples of the cycloalkanediyl group having 5 to 8 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cycloheptyl group, a cyclooctyl group, and the like.

Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, a third butoxy group, and a n-pentyl group. Oxyl, n-hexyloxy and the like.

Examples of the aralkyloxy group having 7 to 12 carbon atoms include a benzyloxy group, a phenylethoxy group, a phenylpropoxy group, a triphenylmethoxy group, a naphthylmethoxy group, and a naphthylethoxy group.

(B) The best compound is 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra (third Diphenyl[d,f][1,3,2] Phosphonium ring (hereinafter referred to as (B-1)), 6-[3-(3,5-di(t-butyl)-4-hydroxyphenyl)propoxy]-2,4,8, 10-tetra(t-butyl)dibenzo[d,f][1,3,2] Phosphonium, 6-[3-(3,5-di(t-butyl)-4-hydroxyphenyl)propoxy]-4,8-di(t-butyl)-2,10- Dimethyl-12H-dibenzo[d,g][1,3,2] Phosphonium ring, 6-[3-(3,5-di(t-butyl)-4-hydroxyphenyl)propenyloxy]-4,8-di(t-butyl) 2,10- Dimethyl-12H-dibenzo[d,g][1,3,2] Phosphonium ring, etc., the most preferred compound is 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra ( Tertiary butyl)dibenzo[d,f][1,3,2] Phosphorus heptane ring.

The content of (B) is 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, more preferably 0.03 to 0.5 part by weight, particularly preferably 0.03 to 0.3 part by weight, per 100 parts by weight of (A).

<(C) carbon black>

(C) may be exemplified by hot carbon black, furnace black, acetylene black, and Ketjen black.

The content of (C) is from 0.01 to 5 parts by weight, preferably from 0.3 to 5 parts by weight, per 100 parts by weight of (A).

The content of (C) is 2 to 250 parts by weight, more preferably 3 to 250 parts by weight, still more preferably 3 to 60 parts by weight, particularly preferably 15 to 60 parts by weight, based on 1 part by weight of (B).

When the content is 1 part by weight or more based on 1 part by weight of (B), the processing stability can be sufficiently improved by using (B) and (C) in combination, and if it is 250 parts by weight or less, The amount of carbon black is not excessive, making the processing of (A) easy.

The thermoplastic resin composition of the present invention may further comprise an inorganic pigment, an antioxidant, a light stabilizer, a neutralizing agent, a slip aid, an antistatic agent, a flame retardant, Crosslinking agent, etc.

<Inorganic Pigments>

Examples of the inorganic pigment include titanium oxide (titanium white), zinc oxide, iron oxide, calcium carbonate or aluminum hydroxide.

<antioxidant>

Examples of the antioxidant (other than (B)) include (D) a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

<(D) Phosphorus Antioxidants>

(D) may, for example, be a compound represented by the following formulas (II) to (IV).

(In the formula (II), R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, An aralkyl group having a carbon number of 7 to 12 or a phenyl group).

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 5 to 8 carbon atoms, the alkylcycloalkyl group having 6 to 12 carbon atoms, and the aralkyl group having 7 to 12 carbon atoms are given by the formula (I). The examples are the same.

(In the formula (III), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 12; An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group.

m and n each independently represent an integer of 0 to 2, and when m is 2, two R ^{13 's} may be the same or different, and when n is 2, two R ^{15 's} may be the same or different).

The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 5 to 8 carbon atoms, the alkylcycloalkyl group having 6 to 12 carbon atoms, and the aralkyl group having 7 to 12 carbon atoms are given by the formula (I). The examples are the same.

(In the formula (IV), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a methyl group).

Particularly preferred compounds among the compounds represented by the formulae (II) to (IV) are: tris(2,4-di(t-butyl)phenyl)phosphite (hereinafter referred to as D-1), bis (2) ,4-di(t-butyl)phenyl)neopentanol diphosphite, bis(2,6-di(t-butyl)-4-methylphenyl)neopentanol diphosphite Salt, bis(2,4-di(isopropylphenyl)phenyl)neopentanol diphosphite, and tetrakis(2,4-di(t-butyl)phenyl)-4,4'- Extending biphenyl diphosphite.

The content of (D) is preferably 1 part by weight or less, and particularly preferably 0.3 part by weight or less per 100 parts by weight of (A).

<Phenolic antioxidants and sulfur-based antioxidants>

Examples of the phenolic antioxidant and the sulfur-based antioxidant include 2,6-di(t-butyl)-4-methylphenol and 3-(3,5-di(t-butyl)-4-hydroxyphenyl. n-Octadecyl propionate, pentaerythritol tetrakis(3-(3,5-di(t-butyl)-4-hydroxyphenyl)propionate), triethylene glycol bis(3-( 3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate), 1,3,5-trimethyl-2,4,6-tris(3,5-di(third) (4-hydroxybenzyl)benzene, tris(3,5-di(t-butyl)-4-hydroxybenzyl) isocyanate (hereinafter referred to as AO-1), 1,3, 5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three -2,4,6-(1H,3H,5H)-trione (hereinafter referred to as AO-2), 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5) -methylphenyl)propenyloxy)-1,1-dimethylethyl)-2,4,8,10-tetra Spiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylenebis(6-t-butyl-3- Methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-acrylate- 5-methylbenzyl)-4-methylphenyl ester, 2-(1-(2-hydroxy-3,5-tripentylphenyl)ethyl)-4,6-di-third pentyl acrylate Phenylphenyl ester, 3,3'-thiodipropionic acid dialkyl (C _12-18 ) ester, neopentyl alcohol tetrakis(3-laurylthiopropionate), and the like.

<Light stabilizer>

The light stabilizer can be exemplified by bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and dimethyl succinate ‧1-(2-hydroxyethyl)-4-hydroxyl -2,2,6,6-tetramethylpiperidine polycondensate (hereinafter referred to as H-1), poly[{6-(1,1,3,3-tetramethylbutyl)amino-1 , 3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}] (hereinafter referred to as H-2), 2-hydroxy-4-n-octyloxydiphenyl ketone, 2-(2-hydroxy-5-methylphenyl)benzene Triazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 3,5-di(t-butyl)-4-hydroxybenzyl Acid 2,4-di(t-butyl)phenyl ester.

<neutralizer>

The neutralizing agent may, for example, be synthetic hydrotalcite, natural hydrotalcite, calcium hydroxide or the like.

<slip agent>

Examples of the slip agent include paraffin wax, polyethylene wax, stearic acid, butyl stearate, stearyl alcohol, calcium stearate, and hardened castor oil.

<antistatic agent>

Examples of the antistatic agent include cationic antistatic agents such as a first-grade amine salt, a third-order amine salt, a fourth-order amine salt, and a pyridine derivative; a sulfated oil, a soap, a sulfated ester oil, and a sulfated guanamine oil. Sulfated ester salts of olefins, fatty alcohol sulfate salts, alkyl sulfate salts, fatty acid ethyl esters, alkyl naphthalenesulfonates, alkylbenzenesulfonates, succinate sulfonates and Anionic antistatic agent such as phosphate salt; partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol, ethylene oxide adduct of fatty acid, ethylene oxide of fatty amine or fatty decylamine An adduct, an ethylene oxide adduct of an alkylphenol, an ethylene oxide adduct of a partial fatty acid ester of a polyhydric alcohol, and a nonionic antistatic agent such as polyethylene glycol; a carboxylic acid derivative and an imidazole An amphoteric antistatic agent such as a morphine derivative.

<Flame retardant>

Examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, hydrotalcite, bromine-based flame retardant, antimony trioxide, polyphosphoric acid flame retardant, magnesium carbonate, calcium carbonate, cerium oxide, talc, zeolite, and clay. Wait.

<crosslinker>

The crosslinking agent is exemplified by an organic peroxide, and examples thereof include 2,5-dimethylhexane, 2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (by Oxidized tert-butyl)hexane, 3-di(t-butylperoxide); third diisopropylphenyl peroxide, 2,5-dimethyl-2,5-bis (peroxidized third Base) hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, 3,5-dimethyl-2,5-(t-butylperoxide) Alkane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3,4,4'-bis(t-butylperoxy)diisopropylbenzene, peroxidation Diisopropylphenyl, tributyl cumyl peroxide, α,α'-bis(t-butylperoxyisopropyl)benzene, α,α'-bis(tributylbutyl peroxide) Diisopropylbenzene, n-butyl-4,4-bis(t-butylperoxy)butane, 2,2-bis(tributylbutyl peroxide)butane, 1,1-double (peroxidation) Third butyl)cyclohexane, 1,1-bis(t-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxide)- 2-methylcyclohexane, 2,2-bis[4,4-di(t-butylperoxy)cyclohexane]propane, tert-butyl peroxybenzylate, benzalkonium peroxide, Third hexyl isopropyl monocarbonate, tert-butyl peroxy maleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy laurate , butyl tributyl methoxide monoperlate, tert-butyl peroxy-2-ethylhexyl monocarbonate, third hexyl peroxybenzoate, and the like. These may be used singly or in combination of two or more.

<Manufacturing method>

In the method for producing a thermoplastic resin composition of the present invention, for example, a mixer such as a tumbler blender, a Henschel mixer, or a super mixer may be used; and a single shaft or more Shaft extruder, kneader or Bamburi mixer (Banbury) Mixer) and so on.

For example, by uniformly mixing (A), (B), and (C) in a mixer such as a drum mixer, a Henschel mixer, or a super mixer, a single-axis extruder or a multi-axis extruder is used. The method of melt-kneading granulation; or the method of granulating by a kneading machine or a Banbury mixer, followed by granulation using an extruder, etc., can produce the thermoplastic resin composition of the present invention.

<Use>

The thermoplastic resin composition of the present invention has a small amount of glue due to thermal deterioration and is excellent in process stability.

The thermoplastic resin composition of the present invention can be processed, for example, as a sheath for electric wires, automobile parts, marine parts, parts for electric/electronic parts, electrical insulating parts, and the like.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. Unless otherwise stated, the parts represent the weight basis.

(Example 1)

100 parts of polyethylene (LDPEF-218, manufactured by Sumitomo Chemical Co., Ltd.) and (B-1) [6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]- 2,4,8,10-tetrakis(t-butyl)dibenzo[d,f][1,3,2] 0.1 parts of phosphorus and heptane, and 3 parts of carbon black, using a laboratory plastic grinder (Labo plastomill) (trade name "4C-150", manufactured by Toyo Seiki Co., Ltd.) under a nitrogen atmosphere at 180 ° C, a number of revolutions of 50 rpm Conditional kneading, and determining the time until the torque of the laboratory plastic grinder reaches the maximum value as the gel buildup time. The longer the gel growth time is, the less the amount of glue is generated with thermal deterioration, and the processing stability is excellent. The results are shown in Table 1.

In Examples 2 to 4 and Comparative Examples 1 to 3, the gel growth time was measured in the same manner as in Example 1 except that the amount of (B-1) and carbon black was changed as shown in Table 1.

According to the thermoplastic resin composition of the present invention, the amount of glue generated by thermal deterioration is small, and the process stability is excellent.

Claims (3)

A thermoplastic resin composition comprising (A) a thermoplastic resin, (B) a compound represented by the formula (I), and (C) carbon black, and a content of (C) relative to (B) 1 part by weight 2 to 250 parts by weight, (wherein R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6; An alkylcycloalkyl group to 12, an aralkyl group having 7 to 12 carbon atoms or a phenyl group; R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; X ¹ represents a single bond, sulfur Atom or -CHR ⁹ - group, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms; and A ¹ represents an alkanediyl group having 2 to 8 carbon atoms or *-COR ¹⁰ a group, R ¹⁰ represents a single bond or an alkylenediyl group having 1 to 8 carbon atoms, * represents a bond to -O-; and any of Y ¹ and Z ¹ represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or The aralkyloxy group having 7 to 12 carbon atoms, the other of which represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). The thermoplastic resin composition according to claim 1, wherein Y ¹ is a hydroxyl group, and at least one of R ⁷ and R ^{8 is} an alkyl group having 3 to 8 carbon atoms and a cycloalkyl group having 5 to 8 carbon atoms. An alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms or a phenyl group. The plastic resin composition according to claim 1 or 2, wherein (A) is polyethylene.