JPH0649308A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To improve matte effect without detriment to strengths by compounding a vinyl chloride paste resin with a cross-linked blending resin. CONSTITUTION:Vinyl chloride alone or together with a monomer copolymerizable therewith is copolymerized with a monomer having at least two ethylenic double bonds to give a blending resin having a gel content of 30% or higher and a mean particle diameter of 20-60mum 100 pts.wt. compsn. comprising 85-60wt.% vinyl chloride paste resin having a primary-particle diameter of 0.1-2mum and 15-40wt.% the blending resin is compounded with up to 5 pts.wt. blowing agent.

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, and more specifically, (a) a vinyl chloride paste resin and
(b) A vinyl chloride resin composition containing a cross-linked blending resin and having a weight ratio of (a) to (b) of 85/15 to 60/40.

[0002]

2. Description of the Related Art In recent years, in applications such as wall materials, floor materials, interior parts for automobiles, electric wires, and sundries, it has a low surface gloss and has an antiglare property and is dry. There is a demand for a matte product that has a smooth feel and a calm appearance.

Heretofore, as a delustering method for vinyl chloride resins, a method using vinyl chloride resins having different particle diameters, for example, a method using a vinyl chloride paste resin and a blending resin has been known.

However, according to this method, the obtained product does not show a satisfactory matting property, and in the case of molding, the matting property is deteriorated if it is carried out at a high temperature, and if it is carried out at a low temperature for a long time. However, since the matteness is deteriorated, there is a restriction on the processing condition that molding must be performed at a low temperature in a short time, and further, there is a drawback that the strength of the product cannot be sufficiently expressed due to the restriction.

The inventors of the present invention have conducted extensive studies to improve such defects, and as a result, as a blending resin, a specific resin (b) cross-linked blending resin was used.
(a) By using a specific amount with respect to the vinyl chloride-based paste resin, it is found that a vinyl chloride-based resin composition that exhibits excellent matting performance and that can prevent the strength of the product from being reduced, etc. can be obtained. The composition containing the foaming agent,
Despite the use of cross-linked resin, it was found that the surface smoothness is excellent and the foam cells give a uniform foam product,
The present invention has been completed by further conducting various studies.

[0006]

That is, the present invention is
(a) a vinyl chloride paste resin and (b) a cross-linked blending resin are contained, and the weight ratio of (a) and (b) is 85/15 to 60/4.
A vinyl chloride resin composition showing excellent matting performance characterized by being 0, and excellent matting property characterized by further containing a foaming agent in addition to (a) and (b). The present invention provides the expandable vinyl chloride resin composition.

The present invention will be described in detail below. The vinyl chloride paste resin of the component (a) in the present invention,
For example, a homopolymer of vinyl chloride monomer or a monomer copolymerizable with vinyl chloride, for example, vinyl acetate, a copolymer with various (meth) acrylic acid esters, and a mixture thereof, which are primary particles A resin having a diameter of 0.1 to 2 μm is usually used, and a commercially available resin for plastisols or organosols called paste resin can be used.

As the crosslinked blending resin as the component (b), one having a gel content of 30% or more is usually used. The average particle size is usually 20 to 60 μm. Specifically, a vinyl chloride monomer or a vinyl chloride monomer and a copolymerizable monomer copolymerizable therewith, and a polyfunctional monomer having two or more ethylenic double bonds in the molecule. And the like. As the copolymerizable monomer, for example, vinyl acetate, vinylidene chloride and the like, and as the polyfunctional monomer, for example, diallyl phthalate, diallyl isophthalate, diallyl terephthalate and the like, diallyl esters of phthalic acid, diallyl ma , Diallyl fumarate, diallyl itaconate and other ethylenically unsaturated dibasic acid diallyl esters, diallyl ether, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate and ethylene glycol divinyl ether, butanediol di Divinyl ethers such as vinyl ether and octadecane divinyl ether, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Chi trimethylolethane tri (meth)
(Meth) acrylates of polyhydric alcohols such as acrylate and tetramethylolmethane tri (meth) acrylate, bis (meth) acroyloxyethylene phthalate, 1,3,5-tri (meth) acryloyl hexahydrotriazine, etc. Can be mentioned.

The amount used is 15/85 to the component (a)
It is 40/60 wt times, preferably 20/80 to 30/70 wt times. If the amount used is less than 15/85 wt times, a sufficient matting effect is not obtained, and if it exceeds 40/60 wt times, a matting effect is obtained, but the surface smoothness of the foamed product described later However, the uniformity of the foamed cells is deteriorated, which is not preferable.

The composition of the present invention comprises the above components (a) and (b)
It is characterized in that it is contained in a specific ratio, but a foaming agent can also be contained. Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile,
Examples thereof include compounds used as blowing agents for vinyl chloride resins such as dinitrosopentamethylenetetramine, 4,4′-oxybisbenzenesulfonyl hydrazide and paratoluenesulfonyl hydrazide. These may be used as a mixture of two or more. Further, a foaming aid used for the purpose of lowering the decomposition temperature of the foaming agent may be contained. When a cross-linking resin and a foaming agent are used in combination, the foamed cells become coarse and the surface smoothness of the foamed product is generally reduced, but in the present invention, such a phenomenon is hardly recognized. The amount of foaming agent used is the same as the components (a) and (b)
The amount is usually 6 parts by weight or less, preferably 4 parts by weight or less, relative to 100 parts by weight.

The composition of the present invention contains various additives used for vinyl chloride resins, such as phthalate-based, adipate-based, polyester-based, epoxy-based, phosphate-based plasticizers, pigments such as titanium oxide and tin. System, barium
It may contain a stabilizer such as zinc-based, calcium-zinc-based, or zinc-based stabilizer, a filler such as calcium carbonate, talc, clay, aluminum hydroxide, antimony trioxide, or a hollow filler. The coexistence of the filler can further improve the matting property. In this case, the amount used is usually 30 to 90 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).

In producing the composition of the present invention,
The components (a), (b) and (c) are blended so as to have the above composition ratio. Various additives are usually added after the above components are added. For example, a plastisol or an organosol can be obtained by blending the above components, then adding dioctyl phthalate (DOP) and other additives and stirring with a mixer or the like.

Thus, the composition of the present invention is produced, and the composition of the present invention is usually used in the form of plastisol or organosol, which can be molded by, for example, spread molding, dip molding or coating molding. Depending on the method, after being formed into a film, sheet, various products, etc., it is gelled by heat treatment using an oven, a tunnel type heating furnace, etc.,
Matte products can be manufactured.

[0014]

Industrial Applicability The composition of the present invention is industrially advantageous because it exhibits excellent matting performance and can prevent the strength of the product from decreasing.

[0015]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Examples 1-5, Comparative Examples 1-5 Vinyl chloride paste resin (Sumitomo Chemical Co., Ltd., Summit PxQHC) and cross-linked blending resin (VH5 manufactured by Wacker)
02 (Average particle size 42μm, THF insoluble content 93%), C-100V (Average particle size 42μm, THF insoluble content 38%), Borden VC2
60SS (average particle size 37 μm, THF insoluble content 0%)) in the proportions shown in Table 1 100 parts by weight, DOP 60 parts, titanium oxide (R-820 manufactured by Ishihara Sangyo Co., Ltd.) 15 Part, calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., Whiten P-70) 80 parts, foaming agent (manufactured by Otsuka Chemical Co., Ltd., AZS) 2 parts, stabilizer, (manufactured by Kyodo Chemical Co., Ltd., KF-80A -8) 3 parts were added and mixed for 15 minutes with a stirrer mixer to obtain a plastisistol.

Next, this was spread-coated on flame-retardant paper to a thickness of 100 μm using a test knife coater and heat-treated in a tunnel furnace to give a semi-gelled coating surface. After cooling this,
The sample was cut into strips and heat-treated in an oven set at 220 ° C. to cause gelation. The mattness was evaluated by measuring the value of 60 ° reflectance (gloss) (%) with a gloss meter (SM-4, manufactured by Suga Test Instruments Co., Ltd.).
The smaller this value is, the greater the matting effect is. In practice, 5% or less is preferable, 5% or less is ○ (excellent), and 5-10% is Δ.
(Good), 10% or more was marked as × (impossible). The surface smoothness of the foamed sample and the cell size were evaluated, and the results are shown in Table 1.

Table 1Example Comparative example 1 2 3 4 5 1 2 3 4 5 Summit PxQHC 80 75 80 75 60 100 90 70 50 50 blending resin (gel% = 93) 20 25 10 blending resin (gel% = 38) 20 25 40 50 blending resin (gel% = 0 )  30 50 60 ° reflectance (40 second heating) 4.8 3.6 5.0 3.3 3.0 15 7.5 13 11 3.0 60 ° reflectance (50 second heating) 5.1 3.8 5.3 4.0 3.3 16 7.7 13 12 3.0 Matte ○ ○ ○ ○ ○ × △ × × ○ Surface smoothness ○ ○ ○ ○ △ ○ ○ ○ ○ × Cell shape Dense dense dense medium Dense dense dense coarse

Examples 6 to 9 and Comparative Examples 6 to 10 In Example 1, the compounding ratios of the vinyl chloride paste resin and the cross-linked blending resin are shown in Table 2 without using titanium oxide and calcium carbonate. Other than that, it implemented based on Example 1. The results are shown in Table 2.

Table 2Example Comparative example 6 7 8 9 6 7 8 9 10 Summit PxQHC 70 60 70 60 90 90 90 70 60 blending resin (gel% = 93) 30 40 10 blending resin (gel% = 38) 30 40 10blending resin (gel% = 0 )  10 30 40 60 ° reflectance (40 second heating) 4.7 3.6 4.5 3.7 6.6 6.8 7.8 6.4 6.7 60 ° reflectance (50 second heating) 5.3 3.9 5.3 4.38.0 8.5 8.6 7.4 7.7 Matting property 〇 〇 〇 〇 △ △ △ △ △ △ Surface smoothness 〇 △ 〇 △ 〇 〇 〇 〇 〇 〇 Cell shape Denseness denseness Dense dense dense dense

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Susumu Iijima 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd.

Claims (3)

[Claims] 1. A resin containing (a) a vinyl chloride paste resin and (b) a cross-linked blending resin, wherein the weight ratio of (a) and (b) is
A vinyl chloride resin composition, characterized in that it is 85/15 to 60/40. 2. The vinyl chloride resin composition according to claim 1, which contains a foaming agent. 3. A method for producing a matte vinyl chloride product, which comprises molding the vinyl chloride resin composition according to claim 1 or 2.