JPS6042444A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent mechanical properties and surface dullness when molded at a high temp., by blending a plasticizer with a vinyl chloride copolymer contg. a diallyl phthalate prepolymer. CONSTITUTION:20-200pts.wt. plasticizer is blended with 100pts.wt. vinyl chloride copolymer contg. 0.5-20wt% diallyl phthalate prepolymer. Examples of monomers for use in preparing the diallyl phthalate prepolymer are diallyl orthophthalate and diallyl isophthalate. When the average MW of the diallyl phthalate prepolymer is too low, the effect of improving mechanical properties and surface dullness, when molded at a high temp., is insufficient, while when it is too high, a remarkable effect can be obtd., but moldability is deteriorated. An average MW of 4,000-30,000 is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition that is excellent in six-time matte properties and mechanical properties during high-temperature molding.

Vinyl chloride resin is widely used in hard applications such as hard boards, corrugated boards, and irregularly shaped products, and in soft applications such as films, resin 1 flooring, hoses, and footwear.

Depending on the purpose of use, for example, special electric wires for home appliances or garden hoses, molded products with excellent texture and no gloss are required on the surface.

Conventionally, various methods have been studied in order to obtain molded articles with excellent matte properties. For example, methods of lowering the resin temperature during the molding process of ordinary vinyl chloride resin, methods of adding inorganic fillers such as calcium carbonate and colloidal silica, methods of adding resins such as acrylic resins, ethylene-vinyl acetate copolymers, etc. There are methods of adding it, but as will be described later, a satisfactory matting effect could not be obtained by any of the methods. For example, methods of lowering the resin temperature during molding may cause the desired mechanical properties of the molded product to deteriorate due to cross-contact and insufficient melting of the resin, or may result in uneven matteness on the surface of the product. I stumbled. In the method of adding inorganic fillers and other resins, if the amount added is small, the matting effect is insufficient, and on the other hand, even when added vertically, the expected good matting properties were not achieved.

Also, Special Publication No. 6-17091, QK Publication No. 38-
The copolymer of vinyl chloride monomer and diallyl hepthalate obtained by the production method described in Publication No. 1494 can be produced by adjusting the conditions of the polymerization temperature and the concentration of diallyl phthalate. It is known that the polymer may contain a branched structure or a crosslinked structure that is insoluble in the flange agent, depending on factors such as the concentration of the chain transfer agent and the polymerization rate. A molded product made of a composition in which a plasticizer, stabilizer, filler, etc. are blended with this copolymer has better surface matteness than that of a typical vinyl chloride homopolymer. However, when the molding temperature is high, this surface matteness begins to become glossy, similar to vinyl chloride homopolymer systems, and specifically when coextruded with resins that require high temperature molding conditions. Moreover, the mechanical properties such as tensile strength during high-temperature molding were poor.

On the other hand, in order to improve the surface matte properties and mechanical properties during high-temperature molding, there is a method of increasing the concentration of σ) phthalate diallyl monomer in the copolymer with diallyl phthalate monomer.

According to this method, the effect is not recognized when the concentration of diallyl phthalate monomer is high, but when the concentration of diallyl phthalate monomer is high, for example, about 0.5% According to the above, the number of crosslinked polymer needles insoluble in the m agent increases significantly, which in turn causes extremely poor moldability.
.

This phenomenon is not limited to monomers of phthalic esters, but also copolymers with polyfunctional monomers such as ethylene glycol dimethacrylate, triallyl trimellitate, triallyl cyanurate, etc., and are of the same type at high temperatures. It was impossible to significantly improve the elubility and mechanical properties of the fir surface during molding.

As a result of intensive studies to improve the above-mentioned drawbacks, the inventors of the present invention have developed a raw material for phthalic diallyl resin that has excellent properties such as side heat resistance, flame resistance, one-sided mulberry quality, and pressure resistance. mouth"
By adding a polyvinyl chloride yarn copolymer containing 0.5 to 20% of diallyl phthalate prepolymer containing aromatic ester bonds in the main chain that are resistant to heat resistance, it is possible to achieve the desired high-temperature molding. The inventors have discovered that it is possible to obtain a vinyl chloride thread resin composition with excellent surface matte properties and mechanical properties, and have arrived at the present invention.

That is, the present invention provides a copolymerized polyhinyl chloride yarn containing 0.5 to 20% of diallyl phthalate prepolymer.
20 to 200 plasticizer in the groin area! This is a vinyl chloride-based resin composition that contains a polyester.

The diallyl phthalate prepolymer used in the present invention is 0
．． The monomer constituting the diallyl phthalate prepolymer in the vinyl chloride-based co-polymer containing 5 to 20 tbsp consists of at least one selected from diallyl orthophthalate and diallyl isophthalate. In addition, diallylchlorendate can also be used in the same manner as phthalated diallyl. The average molecular weight of diallyl phthalate prepolymer is as follows:
The desired effect of improving surface matteness and mechanical properties during high-temperature molding is small, and although the improvement effect is remarkable when the temperature is increased, molding processability deteriorates.
A range of 50,000 is preferred.

More preferably, it is in the range of 7,000 to 25,000.

If the content of sialyl heptatarate prepolymer in the copolymer is less than 0.51% by weight, the improvement of surface gloss heptadility during high temperature molding is insufficient, and if it is more than 20% by weight. Since the melt viscosity becomes extremely high and the molding processability deteriorates, a range of 0.5 to 20 ittit is preferable. A particularly preferred range is 2 to 8% by weight.

In addition, during copolymerization, monomers that can be copolymerized with vinyl chloride monomers such as ethylene, α-olefins such as propylene, vinyl acetate, vinyl esters of vinyl stearate, methyl vinyl ether, lauryl vinyl ether, etc. Vinyl ethers, acrylic acid and methacrylic esters such as methyl acrylate and methyl methacrylate, amides such as methacrylamide and acrylonitrile, nitriles, styrenes such as styrene and α-methylstyrene, phthalate and diallyl monomers, The present invention also includes those containing polyfunctional monomers such as ethylene glycol dimethacrylate, oligomers such as polyethylene glycol dimethacrylate, and 1,2-polybutadiene as constituent components.

The plasticizer of the present invention is not limited in its type, but the amount added can be arbitrarily selected within the range of 20 to 200 folds. If the amount added is less than 20 vertical parts, plasticization will be insufficient and moldability will be significantly poor, making it impossible to obtain a good matte product. If the amount is close to 200 folds, it is suitable for soft applications.

If it exceeds 200 parts by weight, the mechanical strength of the molded article will decrease and the plasticizer will exhibit significant zolid properties, making it impractical. Types of plasticizers include di-2-ethylhexyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, etc.
, adipic acid esters such as di-2-ethylhexyl adipate, sepacic acid esters such as dibutyl sebacate, trimellitic acid esters such as tri-2-ethylhexyl trimellitate, and epoxidized soybean oil.

Further, other polymeric auxiliaries such as ethylene-vinyl acetate copolymer, acrylic thread resin, chlorinated polyethylene, acrylonitrile-butadiene copolymer, etc. may be added.

In addition to the above, heat stabilizers, fillers, lubricants, foaming agents, flame retardants, pigments, and the like may be added to the vinyl chloride resin composition of the present invention, depending on the comfort.

Graft polymerization is employed as the method for producing the vinyl chloride copolymer containing sialyl phthalate prepolymer used in the present invention. Specifically, the most preferred method is to convert diallyl phthalate prepolymer into a vinyl chloride group type dispersion and carry out aqueous suspension polymerization.

Fields of application of the composition of the present invention include hard molded products such as hardboard, pipes, corrugated sheets, irregularly shaped products, etc., which have good general matte properties and mechanical properties during high temperature molding, and films and resin products. -1 It is useful for all vinyl chloride resin products such as flooring materials, hoses, footwear, and soft molded products such as wire coverings. 1k, coextruded products K with hot molding resins are particularly suitable.

In order to make the present invention easier to understand, the present invention will be specifically explained below using experimental examples, examples, and comparative examples, but the present invention is not limited by these.

Experimental Example 1 Contents: In a stainless steel autoclave of 30011, saponification degree of 80 mol.) and homopolymerization degree of 2 were added as suspension stabilizers.
400 partially saponified polyvinyl alcohol 7° revolimer 2.4 to 9, pure water 180kl? After evacuating the autoclave, 57.6 kg of biher chloride monomer was added, and after 4 hours at 55°G without stirring, radical polymerization initiator, di-2-ethylhexyl peroxycabonate was added. 15g of the mixture was added with nitric acid, and the mixture was stirred at 55°C for about 12 hours. After dehydration and drying, the content of diallyl phthalate in the copolymer was measured to be 4.7 parts by weight, and the 'I'HF insoluble matter was 29 parts by weight. In addition, T.H.
Fm was measured by the following method.

Add 2!9 of the vinyl chloride copolymer to a 500 ml glass beaker with 3 D of THF (tetrahydrofuran).
Pour it in with O'F and leave it at room temperature for about 60 hours.
Filter it with a filter to remove the intoxicants, dry it, and then crush it with a pestle. The THF' content was calculated using the following formula.

THF unsaponifiable content (1%) = No. XI D.

Experimental Examples 2 to 4 Using a diallyl phthalate prepolymer having a predetermined average degree of polymerization shown in Table 1, the diallyl phthalate-containing copolymer and THF-insoluble matter in the copolymer produced according to Experimental Example 1 were It was shown on the clothes.

Experimental Examples 5 and 6 A copolymer of a diallyl phthalate monomer and a vinyl chloride monomer, a forging containing diallyl phthalate in the copolymer,
The I'HF vinegar-free content is shown in the first batter.

Examples 1 to 9 Comparative Examples 1 to 7 100 weight bL of copolymers produced in the experimental examples shown in Table 2
Part K, DOP (di-2-ethylhexyl phthalate) of υr fixed size, barium, zinc fatty acid salt complex stabilized 6-layer part, and 3 M parts of epoxidized soybean oil were blended (
In Comparative Examples 6 and 7, the same polymers as in Example 1 were used except that the diallyl phthalate prepolymer was not used (fc).

Steel surface temperature 155℃,'! Or, put the compound into two rolls at 175°C, and after the compound wraps around the rolls,
After 0 minutes of crosstalk, the sheet was taken out.

The matte properties of the coated surfaces of roll sheets kneaded at temperatures of 155°C and 175°C were visually observed.

Evaluation was made based on the following criteria.

0Very good matte property・・・・・・・・・・・・O
Slightly good matteness...
QO Matteness is a little uneven...601M
It's coming out......
The roll sheet kneaded at 175°C was subjected to 18°C molding (at 1°C), and its tensile strength was measured at room temperature according to J-Toku-6723. Results are not shown for the second iK.

Table 2 Table 2 Comparative Example 6.7 using a vinyl chloride polymer containing no diallyl cyphthalate showed no matting properties at either 155°C or 175°C.

When using a copolymer with diallyl phthalate monomer,
In Comparative Example 2.6 using the copolymer of Experimental Example 5, at high temperature (
1759C) and the soft matte properties with a large amount of plasticizer were insufficient, and Comparative Example 4.5 using the copolymer of Experimental Example 6 had a high content of diallyl phthalate. 4.5% by weight
However, it is unsuitable because it cannot be molded. Also, Comparative Example 1
When the DOP is in excess of 220 parts by weight, the tensile strength is significantly inferior, which is not preferable.

It can be seen that the compositions of Examples 1 to 9, which are within the scope of the present invention, all have excellent matting properties at 155° C. and 1175° C., and also have good tensile strength.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment September 16, 1980 Director of the Patent Office Kazuo Wakasugi 2 Name of Invention Vinyl Chloride Resin Composition 6 Relationship with the Person Making the Amendment Case Patent Applicant Address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Contents of the amendment in Column 5 of the detailed description of the invention in the specification 1) "Average degree of polymerization" in line 3 of page 10 was changed to "average molecular weight"
I am corrected.

2) In Table 2 on page 16, "(experiment side number)" is corrected to "(experiment example number)".

3) Correct "soft and flexible" in line 8 of page 14 to "soft type".

Claims (1)

[Scope of Claims] 1) A vinyl chloride resin prepared by blending 20 to 200 parts by weight of a plasticizer with 100 parts by weight of a vinyl chloride copolymer containing 0.5 to 20 parts by weight of diallyl phthalate prepolymer. Composition. 2) Diallyl phthalate prepolymer has an average molecular weight of 400
0 to 30,000, the vinyl chloride thread resin composition according to claim 1).