JP2914856B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hardly chargeable vinyl chloride resin composition suitable as an injection molding material.

[0002]

2. Description of the Related Art In general, synthetic resin has a high electric insulation property and is easily charged with static electricity, so that it is easy to absorb dust.
In factories and the like that manufacture synthetic resin molded products, static electricity is generated and accumulated, which hinders work, and there is a risk of causing a fire due to spark discharge.

[0003] Under such circumstances, in order to prevent the human body from being charged and coming into contact with the grounded body to receive an electric shock and to feel uncomfortable, a hard-to-charge article made of a vinyl chloride resin is often used.

Various countermeasures have been studied for hard-to-charge articles, for example, a method of blending dibutyl phthalate and magnesium carbonate with a vinyl chloride resin (Japanese Patent Laid-Open No. 55-31).
No. 856), and a method of blending a general-purpose plasticizer, an antistatic agent or a surfactant with a vinyl chloride resin, etc., but these methods do not provide sufficient antistatic performance. In addition, the durability of antistatic performance is also lacking.

[0005] Also, ammonium chloride,
A method for improving the antistatic performance of a vinyl chloride resin by blending a perchlorate and a plasticizer having an ether bond has also been proposed (JP-A-64-90242). In order to improve the processability during molding and to impart flexibility to the molded product, a large amount of plasticizer must be used, and as a result, bleeding out of the plasticizer occurs and the quality of the molded product is reduced. There are drawbacks such as lowering.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a hard-to-charge vinyl chloride resin composition having excellent antistatic performance and injection moldability in order to solve the above-mentioned conventional problems. And

[0007]

The vinyl chloride resin composition according to the present invention comprises the following component (a) in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin. )) And the following component (c) in an amount of 30 to 150 parts by weight, and the weight ratio of the component (b) to the component (c) is 1: 5 to 5: 1. Thus, the above object is achieved.

Component (a): an ammonium salt represented by the following general formula (1)

Embedded image (In the formula, _one of R ₁ , R ₂ and R ₃ has 5 to 5 carbon atoms.
24 alkyl groups, the other two are alkyl groups having 1 to 5 carbon atoms, R ₄ is an alkylene group having 2 to 4 carbon atoms, and n is 1 to
X represents an anion of hydrochloric acid, chloric acid or perchloric acid) (b) Component: ester having an ether bond in the molecule (c) Component: phthalic acid represented by the following general formula (2) Diester

Embedded image (Wherein, R ₅ and R ₆ are the same or different and have 6 to 10 carbon atoms.
Represents a linear or branched alkyl group)

As the vinyl chloride resin in the present invention, polyvinyl chloride or a copolymer of vinyl chloride with other monomers, for example, ethylene, vinyl acetate, (meth) acrylic acid, (meth) acrylic ester and the like can be used. No.

The average degree of polymerization of the vinyl chloride resin is 7
It is preferably about 00 to 1800, especially 1000 to 1
About 500 is more preferable.

When the average degree of polymerization of the vinyl chloride resin is less than about 700, the fluidity and the moldability are excellent.
The mechanical strength, abrasion resistance, shape retention at the time of high temperature use, etc. of the molded product are reduced. On the other hand, when the average degree of polymerization of the vinyl chloride resin exceeds about 1800, problems such as a decrease in fluidity and molding processability, an increase in molding distortion, and shrinkage of the molded product occur.

The ammonium salt as the component (a) in the present invention is represented by the formula (1), wherein R ₁ , R
_One of R ₂ and R ₃ needs to be an alkyl group having 5 to 24 carbon atoms.
18 alkyl groups are preferably used. The other two are required to be an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 or 2 carbon atoms is preferably used. R ₄ needs to be an alkylene group having 2 to ₄ carbon atoms, and among them, an alkylene group having 2 or 3 carbon atoms is preferably used. n needs to be an integer of 1 to 15, but is preferably an integer of 1 to 5. X must be an anion of hydrochloric acid, chloric acid or perchloric acid.

The above ammonium salt needs to be used in a range of 0.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin, and a particularly preferred range is 1 to 3 parts by weight. If the amount of the ammonium salt is less than 0.5 parts by weight based on 100 parts by weight of the vinyl chloride resin, a sufficient antistatic effect cannot be obtained, and if the amount exceeds 5 parts by weight, the compatibility of the ammonium salt and the vinyl chloride resin is exceeded. Of the molded product, heat resistance and water resistance of the molded product are reduced, and ammonium salts are leached on the surface to deteriorate the appearance of the product.

The ester having an ether bond as the component (b) in the present invention generally has a higher antistatic property than the ester having no ether bond, which is known as a general-purpose plasticizer.

Examples of the ester having an ether bond include esters of aliphatic or aromatic mono-, di-, tricarboxylic acids and phosphoric acids with alkoxyalkyl alcohols, polyoxyalkylene monoalkyl ethers and alkylene glycol monoalkyl ethers. And diesters of polyalkylene glycol and fatty acid.

Specific examples of the aliphatic monocarboxylic acid include butyric acid, n-octylic acid, 2-ethylhexylic acid, lauric acid, palmitic acid and oleic acid. Specific examples of the aliphatic dicarboxylic acid include glutaric acid. Acids, adipic acid, azelaic acid, sebacic acid, etc., as specific examples of the aromatic mono-, di-, and tricarboxylic acids, benzoic acid,
(Anhydrous) phthalic acid, (anhydrous) trimellitic acid and the like.

Specific examples of the polyoxyalkylene monoalkyl ether include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, diethylene glycol monohexyl ether, propylene glycol monobutyl ether, and dipropylene glycol monoethyl ether. However, specific examples of the polyalkylene glycol include diethylene glycol, triethylene glycol, hexaethylene glycol, dipropylene glycol, and butylene glycol.

These esters can be easily synthesized under ordinary esterification conditions of an acid and an alcohol.

The phthalic diester as the component (c) in the present invention is represented by the formula (2).
₅ and R ₆ are required to be the same or different linear or branched alkyl groups having 6 to 10 carbon atoms.

Specific examples of the phthalic acid-based diester include dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, and their mixed esters and mixed esters.

In the present invention, the vinyl chloride resin 10
The total amount of the components (b) and (c) with respect to 0 parts by weight needs to be in the range of 30 to 150 parts by weight, but is more preferably in the range of 60 to 130 parts by weight.

If the total amount of the component (b) and the component (c) is less than 30 parts by weight based on 100 parts by weight of the vinyl chloride resin, the fluidity and moldability at the time of injection molding are reduced and the molded product is reduced. Lacks flexibility and has a markedly reduced impact resistance. Conversely, if the total amount of the components (b) and (c) exceeds 150 parts by weight, the mechanical strength, abrasion resistance, shape retention at high temperatures, and the like of the molded product are reduced.

In the present invention, the weight ratio of component (b) to component (c) must be in the range of 1: 5 to 5: 1.

The weight ratio of component (b) to component (c) is 1:
If it is less than 5, sufficient antistatic performance cannot be obtained. Conversely, if it exceeds 5: 1, the bleed out of the ester having an ether bond, which is the component (b), becomes remarkable with time and the quality of the molded product becomes poor. descend.

The vinyl chloride resin composition of the present invention may optionally contain commonly used additives such as stabilizers, foaming agents, fillers, coloring agents and lubricants.

As the above stabilizer, zinc stearate,
One or more kinds of metal soap-based stabilizers such as calcium stearate, organic tin-based stabilizers such as dibutyltin laurate, and ultraviolet absorbers are used. The amount of the stabilizer used is based on 100 parts by weight of the vinyl chloride resin.
Usually about 0.5 to 5.0 parts by weight, preferably 1.0 to 5.0 parts by weight.
It is about 3.0 parts by weight. When the amount of the stabilizer is less than about 0.5 part by weight based on 100 parts by weight of the vinyl chloride resin, the thermal stability is poor, and the thermal decomposition of the vinyl chloride resin composition during molding cannot be suppressed. 4. The amount of stabilizer used is 5.
If the amount exceeds about 0 parts by weight, bleed out of the stabilizer occurs or the cost increases.

As the foaming agent, a pyrolytic foaming agent is preferable, and particularly, an azo foaming agent such as azodicarbonamide, azobisformamide and azobisisobutyronitrile is preferable. The amount of the foaming agent used is 100 vinyl chloride resin.
Usually, about 0.5 to 5.0 parts by weight based on parts by weight is preferable. If the amount of the foaming agent used is less than about 0.5 part by weight based on 100 parts by weight of the vinyl chloride resin, the foaming effect is poor. Conversely, if the amount of the foaming agent exceeds about 5.0 parts by weight, molding processing is performed. The mechanical strength and abrasion resistance of the product decrease.

As the filler, for example, calcium carbonate, magnesium carbonate, talc, clay, aluminum hydroxide, magnesium hydroxide and the like are used in necessary amounts.

As the coloring agent, for example, titanium oxide,
Carbon black, phthalocyanine green, chrome yellow and the like are used as needed. The amount of colorant used is
Usually 1.0 to 100 parts by weight of vinyl chloride resin
It is preferably about 6.0 parts by weight. Vinyl chloride resin 100
When the amount of the coloring agent is less than about 1.0 part by weight, the coloring effect is poor. Conversely, when the amount of the coloring agent exceeds about 6.0 parts by weight, the coloring effect is proportionally increased. Without doing so, the cost increases.

As the above lubricant, for example, higher fatty acid esters, low molecular weight polyethylene and the like are appropriately used.

The vinyl chloride resin composition of the present invention is uniformly mixed and kneaded with a Banbury mixer, a Henschel mixer, a mixing roll, a kneader, an extruder, etc., as in the case of the conventional vinyl chloride resin composition. Then, it is granulated and used as a vinyl chloride resin composition for injection molding.

[0032]

The vinyl chloride resin composition of the present invention uses three components of an ammonium salt, an ester having an ether bond and a phthalic acid diester as essential components.
It has good compatibility of each component and exhibits excellent injection molding processability, antistatic performance and its durability.

[0033]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” means “parts by weight”.

(Examples 1 to 9, Comparative Examples 1 to 6)

(A ) Preparation of Vinyl Chloride Resin Composition The following formulations are referred to as basic formulations A and B, and the amounts of ammonium salt, ester having an ether bond, and phthalic acid diester relative to 100 parts of the vinyl chloride resin are shown in Table 1. 1
The vinyl chloride resin composition was obtained by variously changing as shown in Table 1.

Basic Formulation A: Vinyl chloride resin (average degree of polymerization: 1300) 100.0 parts Stabilizer (Ba / Zn type) 2.5 parts Stabilizer (epoxy type) 2.0 parts Antioxidant (hindered phenol type) 0.5 part Coloring agent (titanium oxide) 5.0 parts Filler (calcium carbonate) 25.0 parts Basic formulation B: Vinyl chloride resin (average degree of polymerization 1300) 100.0 parts Stabilizer (Ba / Zn system) 2.0 copies

[0037]

[Table 1] (Note) -1 Ammonium salt: Shown in the following formula (3).

Embedded image (Note) -2 Ester A: Shown in the following formula (4).

Embedded image (Note) -3 Ester B: Shown in the following formula (5).

Embedded image (Note) -4 DHP: Diheptyl phthalate (Note) -5 DOP: Di-2-ethylhexyl phthalate

( B) Evaluation The obtained vinyl chloride resin composition was subjected to injection molding, and the workability, adhesive strength, surface resistivity and volume resistivity were evaluated by the following methods. The results are shown in Table 2. Met.

The workability: the basic formulation and the resulting vinyl chloride resin composition as A, were uniformly mixed in a kneader, 1
After forming a sheet with a mixing roll at 60 ° C., the mixture was granulated with a pelletizer to prepare 15 types of pellets. Next, the obtained 15 types of pellets were placed in an injection mold having a 1 mm thick shoe upper cover sheet coated with a vinyl chloride-acrylic copolymer resin, and an injection nozzle temperature of 1%.
Injection was performed under the conditions of 60 ° C. and an injection pressure of 20 kg / cm ² , and the vinyl chloride resin composition was adhesively molded to a shoe upper cover sheet to obtain an adhesive molded sheet having a thickness of 3 mm. The appearance of the shape of the obtained adhesive molded sheet was visually observed, and the filling property of the vinyl chloride resin composition in the mold was determined, and the workability was determined.

Adhesive strength: 15 types of injection molded sheets obtained by bonding the vinyl chloride resin composition to the shoe upper covering sheet obtained above were cut into a width of 30 mm and a length of 150 mm (measurement length of 90 mm). And left in a gear oven at 70 ° C. for 10 days, and then taken out.
After leaving for 1 day in the atmosphere of JIS K-
According to 6772 "Vinyl Leather Cloth", 180-degree angle peel strength (kgf / cm) was measured at a tensile speed of 200 mm / min using a Tensilon tester.

Surface resistivity : The vinyl chloride resin composition obtained with the basic composition B was uniformly mixed with a kneader,
160 ° C mixing roll and 170 ° C x 150kg
/ Cm ² into a sheet by hot pressing, 0.8mm thick
Were obtained. Then, at 20 ° C.-65% R
In an atmosphere of H, a voltage of 250 V × is applied in accordance with JIS K-6911 “General Test Method for Thermosetting Plastics”.
Under the condition of 60 seconds, the surface resistivity (Ω /
□) was measured.

Volume specific resistance : 15 kinds of sheets were obtained in the same manner as in the measurement of the surface resistivity.
According to JIS K-6911, voltage application 250V × 6
Under the condition of 0 seconds, the volume resistivity (Ω) of the above 15 types of sheets
Cm).

[0043]

[Table 2]

[0044]

As described above, the vinyl chloride resin composition according to the present invention has excellent injection moldability, antistatic performance, durability of antistatic performance, and adhesiveness. Therefore, it is very suitable as a molding material for, for example, injection molded shoes.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ identification code FI C08K 5:19) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 1/00-101/14 C08K 3 / 00-13/08

Claims (1)

(57) [Claims] 1. 0.5 to 5 parts by weight of the following component (a) is added to 100 parts by weight of a vinyl chloride resin, and the total amount of the following components (b) and (c) is 30 to 150 parts by weight. A vinyl chloride resin composition which is blended by weight and has a weight ratio of the component (b) to the component (c) of 1: 5 to 5: 1. Component (a): an ammonium salt represented by the following general formula (1) (In the formula, _one of R ₁ , R ₂ and R ₃ has 5 to 5 carbon atoms.
24 alkyl groups, the other two are alkyl groups having 1 to 5 carbon atoms, R ₄ is an alkylene group having 2 to 4 carbon atoms, and n is 1 to
X represents an anion of hydrochloric acid, chloric acid or perchloric acid) (b) Component: ester having an ether bond in the molecule (c) Component: phthalic acid represented by the following general formula (2) Diester (Wherein, R ₅ and R ₆ are the same or different and have 6 to 10 carbon atoms.
Represents a linear or branched alkyl group)