JP3321476B2 - Thermoplastic elastomer composition with improved processability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer having improved processability. More specifically, the present invention relates to an olefin-based thermoplastic elastomer containing at least one organic phosphate compound and a hindered phenol compound containing an ester group. The present invention relates to a thermoplastic elastomer composition having at least one added material and improved processability.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers have intermediate performances between ordinary resins and elastomers, and have excellent weather resistance, ozone resistance, cold resistance and heat resistance. Is also excellent,
In addition to having the same elasticity as ordinary synthetic rubber, it can shorten the multi-stage synthetic rubber processing process such as kneading, molding, and vulcanization into one process, so that it can be used for automobile parts, civil engineering materials, and building materials. It can be used for a wide range of applications such as home electric parts and sports equipment.

[0003] On the other hand, olefin-based thermoplastic elastomers have the disadvantage that they have a higher viscosity during processing and are inferior in processability as compared with ordinary resins and the like, and improve the processability of ordinary resins or elastomers. When various lubricants such as fatty acids or metal salts thereof, amide compounds, and olefin waxes are used for the olefin thermoplastic elastomer, the effect is insufficient, and when the roll is kneaded. In order to improve the processability of olefin-based thermoplastic elastomers, simply diverting the technology of ordinary resins and elastomers is completely inadequate. there were.

[0004] Also, Japanese Patent Application Laid-Open No. 53-398338,
JP-A-63-168462 proposes to improve processability by adding a metal salt of an organic phosphate to a thermoplastic resin such as polyolefin, and JP-A-54-111541. It has been proposed to improve mold contamination by adding a metal salt of an organic phosphate to rubber, but when these are used alone in olefin-based thermoplastic elastomers having different properties, The effect was insufficient and not practically satisfactory. Also, Japanese Patent Application Laid-Open No. Sho 62-43
Japanese Patent No. 442 proposes to improve gas pollution resistance by adding a metal alkyl phosphate and a hindered phenolic antioxidant having a molecular weight of 500 or more to a polyolefin resin. There is no suggestion about improving the processability of the steel.

[0005]

Means for Solving the Problems In view of this situation, the present inventors have made intensive studies, and as a result, by adding an organic phosphate compound to an olefin-based thermoplastic elastomer, the processability has been improved. The present inventors have found that a thermoplastic elastomer composition can be obtained, and have reached the present invention.

That is, the present invention relates to the following general formula (I) based on 100 parts by weight of an olefinic thermoplastic elastomer.
Alternatively, 0.001 to 5 parts by weight of at least one kind of an organic phosphate compound represented by the general formula (II) and 0.001 to 5 parts by weight of a hindered phenol compound represented by the following general formula (III) are added. And a thermoplastic elastomer composition having improved processability.

[0007]

Embedded image (Wherein, R ₁ , R ₂ and R ₃ each independently represent an alkyl group or an alkylaryl group having 8 to 30 carbon atoms, and Me represents two hydrogen atoms, alkaline earth metal atoms or zinc atoms. Is shown.)

Embedded image (Wherein, R ₄ represents a methyl group or a tertiary butyl group;
Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 1 to 4 valences, and n represents an integer of 1 to 4. )

The present invention also relates to an olefin-based thermoplastic elastomer.
The following general formula (I ′) or
Less of the organic phosphate compound represented by (II ')
At least 0.001 parts by weight of the same type, and the following general formula (I ")
Or an organic phosphate compound represented by the general formula (II ")
0.001 part by weight or more of at least one kind of product (however,
Represented by (I ′), (II ′), (I ″) and (II ″)
(Total of organic phosphate compound is 5 parts by weight or less) and
And a hindered phenol represented by the following general formula (III)
Processability by adding 0.001 to 5 parts by weight of compound
An improved thermoplastic elastomer composition is provided .

Embedded image (Wherein, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 8 to 30 carbon atoms or an alkylaryl group, and Me represents an alkaline earth metal atom or a zinc atom.
Show . )

Embedded image (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 8 to 30 carbon atoms or an alkylaryl group, and Me represents two hydrogen atoms .)

Embedded image (Wherein, R ₄ represents a methyl group or a tertiary butyl group;
Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 1 to 4 valences, and n represents an integer of 1 to 4. )

Hereinafter, the composition of the present invention will be described in detail.

The olefin-based thermoplastic elastomer of the present invention comprises a crystalline olefin-based resin as a hard segment and an olefin-based copolymer elastomer as a soft segment. Alternatively, it may be completely crosslinked.

The crystalline olefin resin constituting the olefin thermoplastic elastomer in the present invention includes:
For example, low density, high density or linear low density ethylene polymer, propylene homopolymer, or propylene and ethylene, 1-butene, 1-pentene, 1-hexene,
And copolymers with -methyl-1-pentene, 1-heptene, 1-octene, 1-butene and the like.

The olefin elastomer constituting the olefin thermoplastic elastomer in the present invention includes, for example, ethylene-propylene copolymer elastomer, ethylene-propylene-dicyclopentadiene copolymer elastomer, ethylene-propylene-1, 4
-Hexadiene copolymer elastomer, ethylene-propylene-cyclooctadiene copolymer elastomer, ethylene-propylene-methylenenorbornene copolymer elastomer, ethylene-propylene-ethylidene norbornene copolymer elastomer, ethylene-butadiene copolymer elastomer, etc. can give.

The organic peroxide used as a crosslinking agent includes dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-dimethyl-2,5
-Di- (tert-butylperoxy) hexyne-3,1,3
-Bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) 3,3,5
-Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, dibenzoyl peroxide, p-chlorobenzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, tert-butylperoxybenzene, tertiary Butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl peroxy cumene and the like can be mentioned.

When the thermoplastic elastomer is heat-treated with the above-mentioned organic peroxide, sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene ,
Diphenylguanidine, trimethylolpropane, N,
Cross-linking aids such as N ', m-phenylenedimaleimide; polyfunctional vinyls such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate Monomers and the like can be blended.

In the general formula (I) or (II) used in the present invention, examples of the alkyl group represented by R ₁ , R ₂ or R ₃ include octyl, 2-ethylhexyl, Octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, stearyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and the like. Examples of the alkylaryl group represented by R ₁ , R ₂ or R ₃ include an alkyl group having 8 to 30 carbon atoms such as octylphenyl, nonylphenyl, dinonylphenyl, decylphenyl and dodecylphenyl. Things can give. Examples of the alkaline earth metal atom represented by Me include magnesium, calcium, barium, and strontium.
In addition, the general formulas (I ′) and (II ′) are represented by the general formulas
In (I) and (II), Me is an alkaline earth metal
Represents a compound that is an atom or a zinc atom and has the general formula
(I ″) and (II ″) are those represented by the general formulas (I) and
In (II), a compound in which Me is two hydrogen atoms is
Represent.

The metal salt of the organic phosphate represented by the general formula (I) or (II) used in the present invention includes, for example, those represented by the following formulas.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The amount of the organic phosphoric acid ester compound is 0.000.00 parts by weight per 100 parts by weight of the thermoplastic elastomer.
It is 1 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

These organophosphate compounds can be used alone, or several kinds can be used in combination or in advance. In this case,
The effect can be further improved by using a compound in which Me represents a metal atom and a compound in which hydrogen represents a hydrogen atom in combination or in advance. Hydrogen source with two Me
In the case of representing a compound, the compound represented by the general formula (I) is
This formula represents a molecule, which is represented by the following formula.
Is the main purpose.

The hindered phenol compound represented by the general formula (III) used in the present invention includes, for example, the following compounds.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The amount of the hindered phenol compound added is 0.0 to 100 parts by weight of the thermoplastic elastomer.
The amount is from 0.01 to 5 parts by weight, preferably from 0.005 to 3 parts by weight.

The processability of the thermoplastic elastomer composition of the present invention can be further improved by using an acrylic or methacrylic acid alkyl ester polymer in combination.

Examples of the alkyl group constituting the polymer of the acrylic acid or methacrylic acid alkyl ester include methyl, ethyl, propyl, n-butyl and the like.
Isobutyl, tert-butyl, pentyl, cyclohexyl, benzyl, n-octyl, isooctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl,
Hexadecyl, octadecyl, methoxyethyl, ethoxyethyl, butoxyethyl, 2-hydroxyethyl,
Alkyl groups and substituted alkyl groups such as -hydroxypropyl, 2-hydroxy-3-chloropropyl, dimethylaminoethyl , diethylaminoethyl, glycidyl or tetrahydrofurfuryl.

A part of the above alkyl group may be a metal salt such as lithium, sodium, potassium, magnesium, calcium, zinc, aluminum, tin, and organotin.

The acrylic acid or methacrylic acid alkyl ester polymer is an oligomer having an average degree of polymerization of 50 or less, preferably 3 to 30 and an average degree of polymerization exceeding 50. Is not preferred because the lubricating effect is lost and the mechanical properties are reduced.

The above-mentioned polymer of acrylic acid or methacrylic acid alkyl ester is a vinyl monomer, for example, α-olefin such as ethylene, propylene, butene-1, styrene, acrylonitrile, vinyl acetate, butadiene, vinyl It may contain monomer units such as alcohol, maleic acid, fumaric acid, itaconic acid or esters thereof.

These acrylic acid or methacrylic acid alkyl ester polymers are described, for example, in
No. 778, JP-B-53-15302, and the like.

The addition amount of the acrylic acid or methacrylic acid alkyl ester polymer is 0.05 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer.
Preferably it is 0.1 to 5 parts by weight.

In the composition of the present invention, the compound
Additives such as phosphite-based, sulfur-based antioxidants, hindered amine-based light stabilizers, and ultraviolet absorbers can be used in combination.

The phosphite antioxidants include:
For example, tris nonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonyl phenyl) bis (nonyl phenyl) phosphite, di ( Tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-me Butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C _12-15 mixed alkyl)-4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2 4
-Di-tert-butylphenyl) biphenylenediphosphonite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (octyl) phosphite and the like.

Examples of the sulfur-based antioxidants include thiodipropionic acid dilauryl, dimyristyl,
Examples include dialkylthiodipropionates such as distearyl and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

The hindered amine light stabilizers include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl laurate, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-
Pentamethyl-4-piperidylbenzoate, N-
(2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6 6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4
-Hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butane Tetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4
-Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2 -{Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, 3,9-bis [1,1-dimethyl-2
-Tris (1,2,2,6,6-pentamethyl-4-
Piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis} N- (2 , 2,6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-
Triazin-2-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6 -Pentamethylpiperidin-4-yl) amino) 1,3,5-triazin-2-yl {amino] undecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-
Piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine /
N, N'-bis (2,2,6,6-tetramethyl-4-
Piperidyl) hexamethylenediamine condensate, N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

Examples of the ultraviolet absorber include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
2-hydroxybenzophenones such as 4-octoxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- ( 2- (2 ′) such as 2′-hydroxy-3′.5′-dicumylphenyl) benzotriazole and 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol
-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate,
2,4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α -Cyano-β, β-
And cyanoacrylates such as diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

If necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metallic soap, an organotin compound, a plasticizer, an epoxy compound, a hydrotalcite compound, a filler, a foaming agent, An antistatic agent, a flame retardant, a lubricant, a processing aid, and the like can be included.

[0049]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples.

Example 1 The following composition was mixed at 185 ° C. for 30 r using a two-roll mill.
A kneading test was performed at pm to measure roll dirt and peelability.

At this time, the roll dirt was evaluated on a 10-point scale. 1 indicates that there was no abnormality, the following indicates that the dirt becomes more severe as the numerical value increases, and 5 indicates that a bluish thin coating was formed on the whole. And 10 indicate that a thick coating of glare was formed. In addition, the releasability is expressed in 10 stages, 1 indicates that the film is easily peeled, and the larger the value, the more difficult the peeling becomes.

The composition is shown in Table 1 and the results are shown in Table 2.

[0053]

[Table 1]

[0054]

[Table 2]

Example 2 The same test as in Example 1 was conducted with the composition shown in Table 3 below. The results are shown in Table-4.

[0056]

[Table 3]

[0057]

[Table 4]

Example 3 The same test as in Example 1 was conducted with the composition shown in Table 5 below. The results are shown in Table-6.

[0059]

[Table 5]

[0060]

[Table 6]

As is clear from the examples, even if a metal salt of a fatty acid or an amide compound is added to the olefin-based thermoplastic elastomer, the improvement in the releasability is small, the stain on the mold is increased, and the short chain length is increased. When an organic phosphoric acid ester compound is added, the effect is extremely small with respect to both the releasability and the mold contamination performance. Further, even when the organic phosphate ester compound of the present invention is added to an olefin-based thermoplastic elastomer, the effect is insufficient when combined with a hindered phenol compound having no ester group.

On the other hand, when the hindered phenol compound having an ester group and the organic phosphate compound having a long chain length of the present invention are added to the olefin-based thermoplastic elastomer, the peelability is excellent and The effect of suppressing mold contamination is shown.

[0063]

According to the present invention, by adding an organic phosphate compound and a hindered phenol compound containing an ester group to an olefin-based thermoplastic elastomer, a thermoplastic elastomer composition having excellent processability can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-43442 (JP, A) JP-A-62-20538 (JP, A) JP-A-53-84919 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08K 3/00-13/08

Claims (2)

(57) [Claims] 1. An olefinic thermoplastic elastomer 100
0.001 to 5 parts by weight of at least one organic phosphate compound represented by the following general formula (I) or (II) and hindered phenol represented by the following general formula (III) A thermoplastic elastomer composition having improved processability, comprising 0.001 to 5 parts by weight of a compound. Embedded image (Wherein, R ₁ , R ₂ and R ₃ each independently represent an alkyl group or an alkylaryl group having 8 to 30 carbon atoms, and Me represents two hydrogen atoms, alkaline earth metal atoms or zinc atoms. Is shown.) (Wherein, R ₄ represents a methyl group or a tertiary butyl group;
Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 1 to 4 valences, and n represents an integer of 1 to 4. ) 2. An olefinic thermoplastic elastomer 100
With respect to parts by weight, represented by the following general formula (I ′) or (II ′)
At least one of the organic phosphoric ester compounds
01 parts by weight or more, the following general formula (I ") or general formula (I
At least the organic phosphate compound represented by I ”)
0.001 parts by weight or more (however, (I '), (I
Organophosphoric acids represented by I '), (I ") and (II")
The total of the ester compounds is 5 parts by weight or less) and the following general
Hindered phenol compound represented by the formula (III)
Improved workability by adding 001 to 5 parts by weight
Thermoplastic elastomer composition . Embedded image (Wherein, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 8 to 30 carbon atoms or an alkylaryl group, and Me represents an alkaline earth metal atom or a zinc atom.
Show . ) (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 8 to 30 carbon atoms or an alkylaryl group, and Me represents two hydrogen atoms .) (Wherein, R ₄ represents a methyl group or a tertiary butyl group;
Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having 1 to 4 valences, and n represents an integer of 1 to 4. )