JPH07173355A - Vinyl chloride-based resin composition and composite material of metal and the same - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in discoloration resistance, heat resistance and metal corrosion resistance and useful, e.g. for wire coating of the inside of a motorcar engine room by blending a specified lead silicate and a specified antioxidant with a vinyl chloride-based resin. CONSTITUTION:This resin composition contains (A) 100 pts.wt. vinyl chloride- based resin, (B) 0.5 to 50 pts.wt. lead silicate prepared by melting a mixture of lead oxide and silicon dioxide, cooling the mixture and subsequently grinding it and (C) 0.1 to 5 pts.wt. polymer type phenol-based antioxidant such as 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane or 1,3,5-trimethyl-2,4,5-tris (3,5-di-t- butyl-4-hydroxybenzyl)benzene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not generate rust on a metal such as copper, aluminum or the like, even if it is kept at a high temperature for a long time after being coated on an electrically conductive plate-like or linear metal, and it is also heat-resistant. The present invention relates to a vinyl chloride-based resin composition that is less likely to deteriorate, and a composite in which an electrically conductive metal is coated with the composition.

[0002]

2. Description of the Related Art As electric appliances, automobile parts, etc. are becoming more compact and lighter, the coated electric wires used in the equipment, automobile engine room, etc. are required to be thinned and have higher heat resistance. Has reached. Usually, a vinyl chloride resin-coated electric wire has a limit of about 105 ° C. in use temperature. If the covered electric wire is thinned to make it compact and lightweight, it is necessary to make the covering material thinner, and in the case of making it thinner, it is necessary to give the covering material sufficient physical properties to withstand temperatures higher than 105 ° C. Is becoming. In addition, in particular, the conventional vinyl chloride resin-coated electric wire has a relatively good heat aging property if only the covering material from which the core wire is pulled out is used, but the vinyl chloride resin-coated electric wire is heated when the covered electric wire is heated as it is. It has been a practical problem that the material discolors easily and the elongation residual rate is remarkably reduced.

The applicant of the present invention has previously disclosed an invention (Japanese Patent Publication No. 28619/1990) of a composition in which an alkyl ester of biphenyltetracarboxylic acid was added as a plasticizer for the purpose of obtaining a vinyl chloride resin composition having heat resistance and melting. Invention of a composition containing lead silicate produced by the method (Japanese Patent Publication No. 5-16461)
However, it was found that the rustproof effect at high temperature is still insufficient.

[0004]

The present inventor has found that even if a vinyl chloride resin composition is compounded with an electrically conductive metal such as copper or aluminum and kept at a high temperature for a long time, the metal does not rust. And as a result of diligent study on a method for producing a vinyl chloride resin composition which does not cause thermal deterioration in the resin composition, a vinyl chloride resin composition obtained by adding a polymer type phenolic antioxidant together with lead silicate has the above-mentioned object. The present invention has been completed and the present invention has been completed. The object of the present invention is to provide a vinyl chloride resin composition and a metal composite coated with the composition, which does not undergo thermal deterioration even at high temperatures and does not generate rust even when composited with a metal such as copper. To provide.

[0005]

The gist of the present invention is to provide a lead silicate obtained by melting a mixture of lead oxide and silicon dioxide with respect to 100 parts by weight of a vinyl chloride resin, cooling and pulverizing. A vinyl chloride resin composition containing 0.5 to 50 parts by weight and a polymer type phenolic antioxidant of 0.1 to 5 parts by weight, and a composite obtained by coating the above composition on an electrically conductive metal. .

To explain the present invention in detail, the vinyl chloride resin used in the composition of the present invention comprises a suspension polymerization method, a bulk polymerization method, a vinyl chloride or a mixture of vinyl chloride and a comonomer copolymerizable therewith. Any of those produced by a usual method such as a fine suspension polymerization method or an emulsion polymerization method can be used. And the average degree of polymerization is 700 to 10,000.
Is preferably in the range of 1100 to 6000. Thus, as the comonomer copolymerizable with vinyl chloride, for example, vinyl acetates such as vinyl acetate, vinyl propionate and vinyl laurate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate and ethyl are used. Methacrylates such as methacrylate, maleates such as dibutyl maleate and diethyl maleate, fumarates such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether. , Vinyl cyanides such as acrylonitrile and methacrylonitrile, α-olefins such as ethylene, propylene and styrene, halogenated other than vinyl chloride such as vinylidene chloride and vinyl bromide Vinylidene or vinyl halides. These comonomers are, 30 wt% in the constituents of the vinyl chloride resin or less, preferably 2
It is used in the range of 0% by weight or less. Of course, the comonomers are not limited to those mentioned above.

The vinyl chloride resin of the present invention exhibits excellent heat resistance when combined with a specific lead silicate. The lead silicate used in the composition of the present invention is obtained by melting a mixture of lead oxide and silicon dioxide, cooling and pulverizing the mixture.
Those mixed in a weight ratio of 3:40 to 7 are particularly preferable.
The crushed particle size is preferably 0.1 to 10 μm.
Furthermore, the lead silicate used in the present invention gives better results if unreacted silicon dioxide is contained rather than that obtained by total reaction of lead oxide and silicon dioxide, although the reason is not clear. It seems The lead silicate is used in an amount of 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the amount used is 0.5 parts by weight or less, the thermal stability effect cannot be expected, and when it is 50 parts by weight or more, the thermal stability does not further improve, and other physical properties such as tensile strength and elongation are deteriorated. cause.

It is essential to add a polymeric phenolic antioxidant to the composition of the present invention. In the present invention, any commercially available polymer phenolic antioxidant can be used, but it is usually preferable to use one having a molecular weight of 500 or more (hereinafter referred to as MW).
Those of about 00 to 1500 are particularly preferable. Specifically, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (MW544.
8), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene (MW775.2), tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (MW1177.
7), bis [3,3'-bis- (4'-hydroxy-
3'-t-butylphenyl) butyric acid] glycol ester (MW794.4), 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine -2,4,6- (1H, 3
H, 5H) trione (MW783) and the like, and at least one of them is used. Of course, the polymeric phenolic antioxidant is not limited to the above.

The mixing ratio of the antioxidant is 0.1 to 5 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the blending ratio is less than 0.1 parts by weight, the effect of suppressing the discoloration of the composition and the rust of the metal due to heating when the metal such as copper and the composition are combined and kept at high temperature for a long time is insufficient. If more than 5 parts by weight is blended, the effect of discoloration and rust does not improve in proportion to the blending ratio, but rather it will be economically disadvantageous.

The vinyl chloride resin composition of the present invention is usually used after adding a plasticizer. It is desirable that the plasticizer is less likely to volatilize when heated, and one having a molecular weight of 400 or more is used. It is particularly preferably a biphenyl tetracarboxylic acid alkyl ester represented by the following general formula [I].

[0011]

[Chemical 1]

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group having 4 to 13 carbon atoms which may have a branched chain, and may be different from each other.)

Specific examples of such an alkyl biphenyltetracarboxylic acid ester include 2,3,3 ', 4'.
-Or 3,4,3 ', 4'-biphenyltetracarboxylic acid tetrabutyl ester, 2,3,3', 4'- or 3,4,3 ', 4'-biphenyltetracarboxylic acid tetrapentyl ester, 2 , 3,3 ', 4'- or 3,4,3', 4'-biphenyltetracarboxylic acid tetrahexyl ester, 2,3,3 ', 4'- or 3,
4,3 ', 4'-biphenyltetracarboxylic acid tetraheptyl ester, 2,3,3', 4'- or 3,4
3 ', 4'-biphenyltetracarboxylic acid tetra (2-
Methylhexyl) ester, 2,3,3 ′, 4′- or 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetra (n-octyl) ester, 2,3,3 ′, 4′-
Or 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetra (2-ethylhexyl) ester, 2,3,3
3 ', 4'- or 3,4,3', 4'-biphenyltetracarboxylic acid tetraisooctyl ester, 2,3,3
3 ', 4'- or 3,4,3', 4'-biphenyltetracarboxylic acid tetranonyl ester, 2,3,3 ',
4'- or 3,4,3 ', 4'-biphenyltetracarboxylic acid tetradecyl ester, 2,3,3', 4'-
Or 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetraundecyl ester, 2,3,3 ′, 4′- or 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetradodecyl ester, 2 , 3,3 ′, 4′- or 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetra (mixed oxo alcohol) ester and the like.

Among these plasticizers, the 2,3,3 ', 4'-form is 2,3,3', 4'-biphenyltetracarboxylic acid, and the 3,4,3 ', 4'-form is 3,4,3 ', 4'-
Biphenyltetracarboxylic acid is produced by an ordinary esterification method in the presence or absence of a solvent, an alcohol having 4 to 13 carbon atoms, and an ester catalyst. The alcohol used for the esterification reaction of biphenyltetracarboxylic acid is, for example, butanol, pentanol, hexanol, heptanol, 2-methylhexanol, octanol, 2-ethylhexanol, isooctanol, nonanol, decanol, isodecanol, undecanol, dodecanol, or the like. C ₇ ~ ₈ obtained by oxo reaction mixtures or α- olefins alcohol as main _{components, C 7 ~ 9, C 9} ~ mixture oxo alcohol having ₁₁ and the like. Of course, a monoester, a diester, or a triester is produced depending on the amount of alcohol added and the esterification conditions, but the plasticizer used in the composition of the present invention may contain these.

Other plasticizers that can be used include, for example, diisononyl phthalate, octyldecyl phthalate,
Phthalic acid plasticizers such as diisodecyl phthalate or phthalic acid esters of higher alcohols having about 11 to 13 carbon atoms, n-octyl-n-decyl trimellitate, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate. , Trimellitic acid-based plasticizers such as tri-n-octyl trimellitate, and fatty acid ester-based plasticizers such as di-2-ethylhexyl azelate and di-2-ethylhexyl sebacate. When oil resistance is required in addition to heat aging resistance, it is preferable to use a polyester plasticizer.

As the polyester-based plasticizer, any conventionally known polyester-based plasticizer (also called polymeric) can be used. That is, succinic acid,
Polycarboxylic acids such as adipic acid, azelaic acid, sebacic acid, phthalic acid, trimellitic acid and ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4 −
Butylene glycol, 1,5-pentanediol, 1,
Polycondensates with polyhydric alcohols such as 6-hexanediol and neopentyl glycol (for example, average molecular weight 40
0-8000) is terminated with a monohydric alcohol such as butanol, pentanol, hexanol, heptanol, n-
Octanol, 2-ethylhexanol, nonanol,
One or more of decanol, undecanol, dodecanol, tridecanol, etc., or a monovalent carboxylic acid such as acetic acid, propanoic acid, butanoic acid, 2-methylpropanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonane Acid, decanoic acid, undecanoic acid, dodecanoic acid,
It is blocked with one or more of tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, cyclohexanoic acid, benzoic acid and the like.

The above plasticizers may be used alone or in combination of two or more. The amount of the plasticizer used is 10 to 200 parts by weight, preferably 20 to 200 parts by weight based on 100 parts by weight of the vinyl chloride resin, from the viewpoint of heat resistance, aging resistance and processability. In the vinyl chloride resin composition of the present invention, together with the lead silicate as a stabilizer, tribasic lead sulfate, dibasic lead phthalate, lead orthosilicate-silica gel coprecipitate, dibasic lead stearate, cadmium- A barium-based stabilizer, a barium-zinc-based stabilizer, a calcium-zinc-based stabilizer, a tin-based stabilizer, and a stabilizer containing a metal salt such as magnesium, aluminum, or silicon as a main component are used in combination as necessary.

The vinyl chloride resin composition of the present invention contains, in addition to the above-mentioned essential components, additives usually used for vinyl chloride resins, such as stabilizers, lubricants, flame retardants, antioxidants (the above-mentioned antioxidants). (Excluding agents), ultraviolet absorbers, fillers, coloring agents, release agents, etc. are often used together. Moreover, you may add a chelator, a crosslinking agent, and a crosslinking aid as needed.
As the lubricant, higher fatty acid or metal salt thereof, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid ester, fatty acid amide and the like are used. As the filler, calcium carbonate, clay,
Talc, fine silica powder, aluminum hydroxide, etc. are used. As the flame retardant, antimony trioxide, barium borate, zinc borate, zinc oxide, chlorinated polyethylene and other halogen-based flame retardants are used.

The vinyl chloride resin composition of the present invention is produced by uniformly mixing a vinyl chloride resin, lead silicate, a polymer type phenolic antioxidant and, if necessary, a plasticizer or the above-mentioned other additives. To be done. For example, the components are uniformly dispersed by a ribbon blender, a cake mixer, a grinder, a high speed mixer, etc. to obtain a composition. Further, this composition may be kneaded using a mill roll, a Banbury mixer, a pressure kneader, a single-screw kneading extruder, a twin-screw extruder, a plastifier, a cokneader or the like. The sheet or strand obtained by kneading may be cooled and then pelletized to obtain a pelletized composition.

The vinyl chloride resin composition produced in this way is usually used as a coating material for a complex with an electrically conductive metal such as an electric wire. Examples of the electrically conductive metal include metals such as aluminum and copper, which may be subjected to surface treatment such as tin plating, and are usually strip-shaped or linear. Particularly, copper strips and linear strips are often used.

In order to compound the above vinyl chloride resin composition with these metals, for example, (1) a method of extrusion coating the composition on a strip-shaped or linear metal with an extruder, (2) a strip-shaped method A method of extrusion laminating the composition on one or both sides of the metal of the composition through an adhesive or directly with an extruder,
(3) First, the composition is formed into a film or sheet shape by a method such as extrusion or calendering, a strip-shaped or linear metal is arranged between the films or sheets, and then the laminated films or sheets are heat-welded to each other. Various methods such as the method of doing are adopted. Applications of the metal and composition composites are vinyl chloride resin coated wires or cables. The electric wire is usually manufactured by the method (1) described above.

[0022]

The vinyl chloride resin composition of the present invention has little discoloration even when exposed to high temperatures and is excellent in so-called heat resistance, as well as being in contact with a metal such as copper. Even if the composition is kept at a high temperature for a long period of time, there is little discoloration of the composition and the effect of suppressing the generation of rust on the metal is exhibited. Further, the composition in which a biphenyl tetracarboxylic acid alkyl ester is used as a plasticizer has particularly good heat resistance.
Therefore, the vinyl chloride resin composition of the present invention has a very high utility value as a thin wall coating material for a coated electric wire arranged in an automobile engine room or a coated electric wire for electric devices.

[0023]

EXAMPLES Next, the composition of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

Examples 1 to 4 and Comparative Examples 1 to 5 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 2900, biphenyl tetracarboxylic acid tetraheptyl ester 60
Parts by weight, 10 parts by weight of lead silicate, 1 part by weight of lead stearate,
A composition was prepared by mixing 1 weight of the epoxy resin and a predetermined amount of the antioxidant shown in Table 1. The composition was coated on a copper wire having a diameter of 0.4 mm to a thickness of 0.38 mm using an electric wire coating molding extruder.

The coated electric wire thus obtained was placed in a constant temperature heater at 158 ° C. (heat resistance test temperature of UL standard) for 1 week, 2 weeks and 4 hours.
After holding for a week, the coating composition was taken out, the degree of discoloration of each coating composition and the rust condition of the copper wire after removing the coating composition were visually evaluated, and are also shown in Table 1. The evaluation criteria are as follows. (1) Discoloration of vinyl chloride resin composition ○: No discoloration, △: Discoloration to brown, ×: Discoloration to black-brown (2) Rust condition of copper wire ○: No discoloration, △: Discoloration to black-brown, ×: Green Discoloration (generation of patina)

The lead silicate described above is manufactured as follows. Lead oxide (PbO, purity 99.8
%) And silica powder for crystal glass (SiO ₂ , purity 9
9.9%) and the weight ratio of PbO: SiO ₂ is 85: 1.
After blending so as to be 5 and melting in an electric furnace maintained at a temperature of 900 to 950 ° C., the melt is poured directly into water. A large number of cracked particles were taken out from water, dried, and pulverized to an average particle size of 3 μm.

[0027]

[Table 1]

* A (polymeric phenolic antioxidant) tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (MW 1177.7) B ( Phenol type antioxidant) Bisphenol A (MW882.3) C (phosphite type antioxidant) Cyclic neopentane tetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite (M
W633) D (phosphite antioxidant) 1,1,3-butanetriyltris (5-methyl-2-)
t-Butyl-4-phenylene) tris (bistridecyl phosphite) (MW1831) E (thioether antioxidant) pentaerythritol tetrakis (3-dodecylthiopropionate) (MW1162)

As is clear from Table 1, when a low molecular weight phenolic antioxidant such as bisphenol A was used in combination with a specific lead silicate, the composition was treated at a high temperature of 158 ° C. for a long time. It is not possible to suppress not only the discoloration and deterioration of the above, but also the occurrence of rust. It was possible to suppress discoloration deterioration and rust generation of the composition for the first time by using the polymer type phenolic antioxidant in combination with the specific lead silicate.

Further, even when a high molecular weight phosphite antioxidant or a thioether antioxidant is used in combination, only the effect of bisphenol A is exerted, and the effect of the polymer type phenol antioxidant is not reached. I understand.

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[Procedure amendment]

[Submission date] November 11, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

Examples 1 to 7, Comparative Examples 1 to 6 100 parts by weight of vinyl chloride resin having an average degree of polymerization of 2900, biphenyl tetracarboxylic acid tetraheptyl ester 60
Parts by weight, 10 parts by weight of lead silicate, 1 part by weight of lead stearate,
A composition was prepared by mixing 1 part by weight of an epoxy resin and a predetermined amount of the antioxidant shown in Table-1. The composition was applied to an electric wire coating molding extruder to form a 0.38 mm copper wire having a diameter of 0.4 mm.
To a thickness of.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

[0027]

[Table 1]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

* A (polymeric phenolic antioxidant) tetrakis (methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate) methane (MW 1177.7) B ( Polymeric phenolic antioxidant) 1,1,3-tris (2-methyl-4-hydroxy-5)
-T-Butylphenyl) butane (MW 544.8) C (polymeric phenolic antioxidant) 1,3,5-trimethyl-2,4,6-tris (3,5)
-Di-t-butyl-4-hydroxybenzyl) benzene (MW775.2) D (polymeric phenolic antioxidant) 1,3,5-tris (3 ', 5'-di-t-butyl-
4'-hydroxybenzyl) -5-triazine-2,
4,6- (1H, 3H, 5H) trione (MW783) E (phenolic antioxidant) 1,1-bis (2′-methyl-4′-hydroxy-5 ′)
-T-butylphenyl) butane (MW383) F (phenolic antioxidant) bisphenol A (MW228) G (phosphite antioxidant) cyclic neopentanetetraylbis (2,6-di-t-butyl-) 4-methylphenyl) phosphite (M
W633) H (phosphite antioxidant) 1,1,3-butanetriyltris (5-methyl-2-)
t-Butyl-4-phenylene) tris (bistridecyl phosphite) (MW1831) I (thioether antioxidant) pentaerythritol tetrakis (3-dodecylthiopropionate) (MW1162)

Claims (9)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
Vinyl chloride containing 0.5 to 50 parts by weight of lead silicate obtained by melting and pulverizing a mixture of lead oxide and silicon dioxide and 0.1 to 5 parts by weight of a polymeric phenolic antioxidant -Based resin composition. 2. The vinyl chloride resin composition according to claim 1, wherein the high molecular weight phenolic antioxidant has a molecular weight of 500 or more. 3. The polymer type phenolic antioxidant is 1,
1,3-tris (2-methyl-4-hydroxy-5-t
-Butylphenyl) butane, 1,3,5-trimethyl-
2,4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-
Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester or 1,3,5-tris (3 ', 5'-di-t-butyl-
4'-hydroxybenzyl) -S-triazine-2,
The vinyl chloride resin composition according to claim 1 or 2, which is at least one selected from 4,6- (1H, 3H, 5H) trione. 4. The chloride according to claim 1, wherein the lead silicate is obtained from a mixture of lead oxide and silicon dioxide in a weight ratio of 60 to 93:40 to 7. Vinyl resin composition. 5. The vinyl chloride resin composition according to claim 1, which contains 10 to 200 parts by weight of a plasticizer having a molecular weight of 400 or more with respect to 100 parts by weight of the vinyl chloride resin. . 6. The vinyl chloride resin composition according to claim 5, wherein the plasticizer is a biphenyl tetracarboxylic acid alkyl ester. 7. A composite obtained by coating an electrically conductive metal with the vinyl chloride resin composition according to any one of claims 1 to 6. 8. The composite according to claim 7, wherein the electrically conductive metal is extrusion-coated with a vinyl chloride resin. 9. The composite according to claim 7, wherein the composite is an electric wire.