JPH08165393A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE: To provide a vinyl chloride resin compsn. which is less likely to migrate to PS resin and ABS resin. CONSTITUTION: This vinyl chloride resin compsn. comprises 100 pts.wt. a vinyl chloride resin and 10 to 200 pts.wt. polyester. The polyester is represented by the formula I or II (wherein, D represents a dibasic acid residue; G represents a 4-9C dihydric alcohol residue; A represents a 10-15C monohydric alcohol residue; L represents a 10-18C monobasic acid residue; and n is an integer of 1 or more). The polyester has a viscosity at 25 deg.C of 1,500 to 10,000cP.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition having a good non-migrating property to polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin and the like, and a molded article comprising the composition. .

[0002]

2. Description of the Related Art Plasticizers are added to various plastics such as vinyl chloride resins to lower their melting temperature to facilitate molding and to make plastics flexible, elastic and cold resistant. It is widely used for imparting properties such as sex to suit various uses of plastics.

As a plasticizer used for such a purpose, a monomeric plasticizer such as di-2-ethylhexyl phthalate or di-2-ethylhexyl adipate is generally used, but oil resistance and resistance Polyester-based plasticizers are widely used in applications requiring durability such as migration, for example, wire coating materials, gaskets for electric appliances, covers and the like.

Polyester plasticizers include polyhydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-butanediol or 1,4-butanediol and phthalic acid, adipic acid, sebacic acid, or It is manufactured by polycondensation with polyvalent carboxylic acid such as trimellitic acid and terminal treatment with monohydric alcohol or monobasic acid, and has durability and polystyrene resin (hereinafter, referred to as “PS Non-migratory property to acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as "ABS resin") is not sufficient with conventional polyester plasticizers. It was

[0005]

DISCLOSURE OF THE INVENTION The present inventor has made diligent studies to solve the above-mentioned problems of the prior art.
The inventors have found that the above problems can be solved by using a specific polyester as a plasticizer, and have completed the present invention. That is, an object of the present invention is to provide a vinyl chloride resin composition excellent in non-migrating property to PS resin and ABS resin, and a molded article made of the composition.

[0006]

SUMMARY OF THE INVENTION The gist of the present invention is, therefore, 1 part per 100 parts by weight of a vinyl chloride resin and the resin.
In the vinyl chloride resin composition consisting of 0 to 200 parts by weight of polyester, the general formula for the polyester is

[0007]

Embedded image

(Wherein D is a dibasic acid residue, G is a dihydric alcohol residue, A is a monohydric alcohol residue, L is a monobasic acid residue, and n is an integer of 1 or more. ),
And G is a dihydric alcohol residue having 4 to 9 carbon atoms,
A is a monohydric alcohol residue having 10 to 15 carbon atoms or L is a monobasic acid residue having 10 to 18 carbon atoms, and the temperature is 25 ° C.
A vinyl chloride resin composition and a molded article comprising the composition, characterized in that a polyester having a viscosity of 1,500 to 10,000 centipoise is used.

The vinyl chloride resin used in the vinyl chloride resin composition of the present invention is not particularly limited, and vinyl chloride alone or a mixture thereof with a copolymerizable monomer is subjected to suspension polymerization or emulsion polymerization. Obtained by polymerizing by a polymerization method such as bulk polymerization, for example, a degree of polymerization of about 600 to about 3,
The vinyl chloride resin of about 000 can be exemplified. As the monomer copolymerizable with vinyl chloride, vinylidene chloride, ethylene, propylene, acrylonitrile,
Mention may be made of vinyl acetate, maleic acid, acrylic acid, methacrylic acid or esters of maleic acid, acrylic acid or methacrylic acid.

The polyester used in the vinyl chloride resin composition of the present invention is represented by the above-mentioned general formula, wherein the dihydric alcohol residue has 4 to 9 carbon atoms and the monohydric alcohol residue has carbon number. 10 to 15 or 10 to 18 carbon atoms of the residue of a monobasic acid, n is an integer of 1 or more and 25 ° C.
Has a viscosity of 1,500 to 10,000 centipoise (cps), preferably 2,000 to 10,000 cp.
It is in the range of s. If the number of carbon atoms in the residue of the dihydric alcohol is less than 4, cold resistance is insufficient, and if it is greater than 9, it is industrially difficult to obtain. If the residue of the monohydric alcohol or the residue of the monobasic acid has a carbon number of less than 10, the non-migration property to the ABS resin is insufficient, and the residue of the monohydric alcohol has a carbon number of more than 15 or If the carbon number of the residue of the monobasic acid is greater than 18, the affinity with the vinyl chloride resin will deteriorate. Also, the viscosity of polyester is 1,500 cp
If it is less than s, the non-migration property to PS resin and ABS resin is insufficient, and if it is more than 10,000 cps, flexibility and processability are impaired.

Examples of the dihydric alcohol having 4 to 9 carbon atoms include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propane. Examples thereof include diols and 1,6-hexanediol. Among them, the average number of branched chains (branched chains when the main chain is a carbon chain formed by connecting carbons connected to OH groups) is on a molar basis. It is preferable that a dihydric alcohol having a ratio of less than 2, especially 1 or less is more excellent in flexibility and cold resistance. These can be used alone or as a mixture thereof.

Examples of the monohydric alcohol having 10 to 15 carbon atoms include decanol, undecanol, tridecanol and the like, and these can be used alone or as a mixture thereof. Above all, carbon number is 10
-12 monohydric alcohols are preferable because they are liquid at room temperature and easy to handle. Examples of the monobasic acid having 10 to 18 carbon atoms include lauric acid, myristic acid, palmitic acid and stearic acid, which can be used alone or as a mixture thereof.

In the present invention, a monohydric alcohol or a monobasic acid is used as an endcapping agent for polyester.
Monohydric alcohols are preferable from the viewpoint of easy removal of excess during the production of polyester. Also,
As the dibasic acid, various types generally used in the production of polyester plasticizers, aliphatic, aromatic, or alicyclic dibasic acids or anhydrides thereof are used, specifically,
Examples thereof include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and phthalic anhydride, and one or a mixture of two or more thereof can be used. Group dibasic acids are preferred, especially adipic acid.

The conventional polyester production method can be applied to the production of the above polyester as it is. That is, it can be produced by either a method of directly condensing a dibasic acid and a dihydric alcohol or a method of reacting a lower alkyl ester of a dibasic acid with a dihydric alcohol. For example, at the initial stage of the reaction, only the dibasic acid and the dihydric alcohol are reacted in the presence or absence of a solvent such as toluene and xylene which can azeotropically dissolve with water but is hardly compatible with each other, and the appropriate acid is reacted. When the valency or hydroxyl number is obtained, the endcapping agent is added, and when the distillation of water is completed or essentially completed, the pressure is reduced to remove excess dihydric alcohol and endcapping agent. A method for carrying out the reaction can be exemplified. At the end of the normal reaction, the temperature is around 200 ° C. and the pressure is 1 to 10 mmHg.

Various kinds of catalysts can be used for the production of polyester, and acid catalysts such as sulfuric acid, phosphoric acid, zinc chloride and p-toluenesulfonic acid, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate and tetraisopropyl. Titanate, organic titanium compounds such as tetrabutyl titanate, tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, etc., and combinations of acetate salts such as magnesium, calcium and zinc with antimony oxide or the above titanium compounds. be able to. In addition, additives such as anti-coloring agent and weather resistance improver can be added if necessary.

The obtained polyester is hydrolyzed with an alkali and then quantified by gas chromatography to confirm various components constituting the polyester, whereby the number of branched chains of the dihydric alcohol can be measured. The polyester used in the vinyl chloride resin composition of the present invention is 10 to 20 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
It is mixed in an amount of 0 part by weight, preferably 30 to 150 parts by weight. If this amount is less than 10 parts by weight, the flexibility of the vinyl chloride resin composition will be impaired, and if it is more than 200 parts by weight, bleed-out will occur and other resin moldings that come into contact with the resin will be contaminated and the commercial value may be impaired. There is. In the vinyl chloride resin composition of the present invention, as the plasticizer, a plasticizer usually used for vinyl chloride resins can be used together with the above polyester within a range not impairing the object of the present invention.

The plasticizer which can be used in combination is, for example, a dihydric alcohol having a residue of less than 4 carbon atoms or 25 ° C.
Viscosity less than 1,500 cps or 10,0
Polyester plasticizers larger than 00 cps; dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, phthalic acid Phthalic acid plasticizers such as diisooctyl, octyldecyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, phthalate esters of higher alcohols having about 11 to 13 carbon atoms; dimethyl isophthalate, Diethyl isophthalate, di-n-butyl isophthalate, diisobutyl isophthalate, diheptyl isophthalate, di-n-octyl isophthalate, di-2-ethylhexyl isophthalate, diisooctyl isophthalate, octyldecyl isophthalate, i Isophthalic acid-based plasticizers such as diisodecyl phthalate, diundecyl isophthalate, ditridecyl isophthalate, butylbenzyl isophthalate, isophthalic acid esters of higher alcohols having about 11 to 13 carbon atoms; trimellitic acid di-n-octyl-n- Decyl, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate, tri-n- trimellitate
Trimellitic acid plasticizers such as octyl; adipic acid di-
Fatty acid ester plasticizers such as 2-ethylhexyl, di-n-decyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate; tributyl phosphate, triphosphate Phosphoric acid plasticizers such as 2-ethylhexyl, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate; epoxidized soybean oil, epoxidized linseed oil,
Examples thereof include epoxy plasticizers such as epoxidized tall oil fatty acid-2-ethylhexyl and liquid epoxy resins.

The vinyl chloride resin composition of the present invention contains the above-mentioned essential components and other additives which are usually added to the vinyl chloride resin composition, such as stabilizers, lubricants, flame retardants, antioxidants and ultraviolet rays. Absorbents, fillers, colorants, mold release agents and the like can be added. Moreover, you may add a chelator, a crosslinking agent, and a crosslinking auxiliary as needed in the range which does not impair the objective of this invention.

As the stabilizer, tribasic lead sulfate, dibasic lead phthalate, lead orthosilicate-silica gel coprecipitate, dibasic lead stearate cadmium-barium stabilizer,
Examples thereof include barium-zinc-based stabilizers, calcium-zinc-based stabilizers, tin-based stabilizers and the like, and further, stabilizers containing a silicate of a metal such as magnesium or aluminum as a main component. Stabilizers are usually added in vinyl chloride resin 1
0.1 to 10 parts by weight, preferably 1 to 100 parts by weight
It is in the range of 5 parts by weight.

Examples of the lubricant include higher fatty acids or metal salts thereof, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid esters and fatty acid amides. The addition amount of the lubricant is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.

Examples of flame retardants include phosphoric acid esters such as tributyl phosphate and diphenyloctyl phosphate; halogen-containing phosphoric acid esters such as tri-2,3-dibromopropylpropyl phosphate and tribromochloropropyl phosphate; chlorinated diphenyl and tetra Halides such as bromobenzene; antimony-based flame retardants such as antimony trioxide and triphenylstibine; zinc borate and the like are used. The amount of flame retardant added is preferably in the range of 0.1 to 20 parts by weight per 100 parts by weight of vinyl chloride resin.

As the antioxidant, di-t-butyl-p is used.
-Phenol derivatives such as cresol, benzimidazoles, amines such as N-phenyl-N'-cyclohexylparaphenylenediamine and phenylalphanaphthylamine and derivatives thereof are used. The amount of the antioxidant added is 0.1 per 100 parts by weight of the vinyl chloride resin.
The range of 10 to 10 parts by weight is preferable. As the UV absorber, hydroquinone-based, salicylic acid-based, benzophenone-based, benzotriazole-based UV absorbers and the like are used. The amount of UV absorber added is 100% vinyl chloride resin.
A range of 0.1 to 10 parts by weight per part by weight is preferred.

Examples of the filler include calcium carbonate, clay, talc, fine silica powder and aluminum hydroxide. The amount of filler added is 1 vinyl chloride resin
A range of 0.5 to 100 parts by weight is preferable per 00 parts by weight. As the colorant, inorganic pigments such as titanium oxide, zinc white, lead white, calcium carbonate, gypsum, precipitated silica, carbon black, red iron oxide, molybdenum red, cadmium yellow, yellow lead, titanium yellow, chromium oxide green, and ultramarine blue; Organic pigments such as Permanent Red 4R, Hansa Yellow 10G, Benzidine Yellow GR, Permanent Carmine FB, Phthalocyanine Blue B and Phthalocyanine Green are mentioned. The amount of the colorant added is preferably in the range of 0.5 to 20 parts by weight per 100 parts by weight of the vinyl chloride resin.

Examples of the releasing agent include waxes, higher fatty acids, salts and esters thereof, silicone oil, fluorinated alkyl compounds and polyvinyl alcohol. The amount of the release agent added is preferably in the range of 0.1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin. To blend the above-mentioned plasticizers and additives with the vinyl chloride resin, it is sufficient to use a blender, a super mixer, a mill, a Banbury mixer or the like, which is usually used for processing vinyl chloride resin. The vinyl chloride resin composition of the present invention produced as described above is used as a molded article, for example, by coating a bare wire or the like by a method such as extrusion coating the composition with an extruder, an extrusion molding machine, or a calendar molding. Using a machine
It is used after being molded into gaskets and covers for appliances such as appliances.

[0025]

The vinyl chloride resin composition of the present invention is
It has excellent non-migrating property to S resin and ABS resin, and especially when the number of branched chains of the residue of the dihydric alcohol constituting the polyester in the composition is less than 2 on average, the flexibility and cold resistance are high. More excellent. Therefore, the vinyl chloride resin composition of the present invention can be suitably used for molded articles such as electric wire coating materials, electric appliance gaskets and covers, and has a great industrial utility value.

[0026]

EXAMPLES The embodiments of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. The polyester synthesis method and evaluation method, and the vinyl chloride resin sheet preparation method and evaluation method in Examples and Comparative Examples are as follows.

<Polyester Synthesis Method> 292 g of adipic acid as a dibasic acid and 1,3-as a dihydric alcohol
198 g of butanediol and 100 g of undecanol as a monohydric alcohol were charged into a flask with an internal volume of 1 liter equipped with a thermometer, a nitrogen inlet tube, a stirrer, a water diverter, and a reflux condenser, and heated while stirring under a nitrogen stream to react. The liquid temperature was raised to 220 ° C., 0.024 ml of tetraisopropyl titanate was added as a catalyst, and the reaction was carried out at 220 ° C. During that time, the produced water was continuously removed from the system by a water separator, and the reaction was continued until the acid value of the reaction solution fell below 5 mgKOH / g. Then, this reaction system
A polyester was obtained by carrying out a 3 hrs condensation reaction at 220 ° C. under a reduced pressure of 3 mmHg.

The viscosity of this polyester is 2,300 cp
s, acid value 0.5 mgKOH / g, hydroxyl value 6 mgK
It was OH / g. This polyester is designated as PE-1. Polyesters prepared by changing the raw material composition of polyester in the same manner as shown in Table-1 were designated as PE-2 to PE-9, and two commercially available adipate polyester plasticizers were also shown in Table-1. .

<Evaluation Method of Polyester> (1) Acid Value In accordance with JIS K 6751. (2) Hydroxyl value Based on JIS K 6751. (3) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer (EM type, manufactured by Tokyo Keiki Co., Ltd.).

[0030]

[Table 1]

<Production Method of Vinyl Chloride Resin Sheet> 100 parts by weight of vinyl chloride resin (Vinica 37H, manufactured by Mitsubishi Kagaku MKV Co., Ltd., average degree of polymerization 1,300), 67 parts by weight of polyester of a predetermined type, barium- Zinc-based liquid stabilizer (KV-69G-1, manufactured by Kyodo Pharmaceutical Co., Ltd.) 3
After mixing 1 part by weight and premixing in a beaker, 170
Sufficiently knead on a two-mill roll whose temperature is adjusted to ℃ (5
Min), then press working (temperature: 175 ° C, preheat:
2.96 MPa (20 kg / cm ² ) for 2 minutes, press: 19.6 MPa (200 kg / cm ² ) for 5 minutes)
Then, a vinyl chloride resin sheet having a thickness of 1 mm was obtained.

<Evaluation Method of Vinyl Chloride Resin Sheet> (1) Tensile Test: According to JIS K 6723. (2) Cold resistance (low temperature flexible temperature): ASTM D1043
Compliant with -51. (3) Non-migration to PS resin and ABS resin 1. Inland method A test piece with a length of 40 mm, a width of 2 mm, and a thickness of 1 mm is sandwiched between resin plates made of PS resin or ABS resin, a load of 1 kg is applied, and the mixture is left at a temperature of 70 ° C. for 96 hours. The degree of migration was visually determined. <Evaluation criteria> 5: No trace of migration to the resin plate. 4: A slight mark is left on the resin plate, but it can be wiped off. 3: A slight mark is left on the resin plate and remains slightly even after wiping. 2: A noticeable transfer mark is made on the resin plate. 1: The resin plate has a marked transition mark.

2. Immersion method Resin plate made of PS resin or ABS resin in about 200 g of polyester (length 40 mm, width 20 mm, thickness 1 mm)
Was dipped and left for 4 hours at a temperature of 70 ° C., and the degree of polyester transfer was visually determined from the surface state of the resin plate, and the weight change rate (%) before and after the test was calculated. <Evaluation Criteria> 5: There is no change in the gloss of the resin plate. 4: The resin plate is slightly glossy. 3: The luster of the resin plate remains slightly. 2: The gloss of the resin plate has disappeared. 1: The surface of the resin plate is melted.

[0034]

[Equation 1]

[0035]

[Table 2]

Claims (7)

[Claims] 1. A vinyl chloride resin composition comprising a vinyl chloride resin and 10 to 200 parts by weight of polyester based on 100 parts by weight of the resin, wherein the polyester has the general formula: (However, D is a dibasic acid residue, G is a dihydric alcohol residue, A is a monohydric alcohol residue, L is a monobasic acid residue,
n represents an integer of 1 or more. ), G is a dihydric alcohol residue having 4 to 9 carbon atoms, and A is 1 carbon atom.
0 to 15 monohydric alcohol residues or L has 10 carbon atoms
A vinyl chloride resin composition characterized by using a polyester, which is a residue of a monobasic acid of -18 and has a viscosity at 25 ° C of 1,500 to 10,000 centipoise. 2. The vinyl chloride resin composition according to claim 1, wherein a polyester having a number of branched chains of residues of a dihydric alcohol constituting the polyester is less than 2. 3. The vinyl chloride resin composition according to claim 1, wherein the polyester having a monohydric alcohol residue constituting the polyester having 10 to 12 carbon atoms is used. 4. The vinyl chloride resin composition according to claim 1, wherein a polyester having a dibasic acid residue constituting the polyester having 4 to 10 carbon atoms is used. 5. The vinyl chloride resin composition according to any one of claims 1 to 4, wherein the polyester having a dibasic acid residue constituting the polyester is an adipic acid residue. 6. The vinyl chloride resin composition according to claim 1, wherein a polyester having a viscosity at 25 ° C. of 2,000 to 10,000 centipoise is used as the polyester. 7. A molded product comprising the vinyl chloride resin composition according to claim 1.