JPS6067550A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a lightweight composition of high wear resistance, capable of retaining stable matte effect for a long period, by incorporating specific filler and plasticizer in specific vinyl chloride copolymer. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts.wt. of vinyl chloride copolymer with an average polymerization degree pref. 600-3,000 constituted by 97.0-99.95wt% of vinyl chloride and 3.0-0.05wt% of allyl (meth)acrylate with (B) 5-100pts.wt. of filler with a specific gravity <=0.7, particle size <=300mu and compressive strength >=70kg/cm<2> and (C) 30- 150pts.wt. of plasticizer. In addition, it is recommended that 0.5-5pts.wt. of stabilizer be incorporated in the above composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stone made of a soft vinyl chloride resin composition that is lightweight and has a matte surface.

Soft vinyl chloride resin has excellent physical and chemical properties, is easy to process, and is relatively inexpensive, so it is widely used in the form of customer molded products, lenses, sheets, etc., from daily goods to automobile parts. It has been used. However, the specific gravity of soft vinyl chloride resin is 1.2 to 1.5, and when compared with other general-purpose resins, for example, it is 1.3 to 1.6 times that of polypropylene, and 2 to 2.5 times that of RIM foamed polyurethane. It shows a high value of twice as much. This means that weight reduction is one step in order to save energy.
It has come to be seen as a serious drawback in the automotive parts applications that it refers to.

Foaming using a chemical foaming agent is a common method for reducing the weight of soft vinyl chloride resin, but it requires a long molding cycle, narrow processing conditions, and bubbles tend to rupture on the surface of the molded product, resulting in poor product yield. There are many problems with productivity and economy, such as poor performance and the inability to recycle waste products.

On the other hand, in automotive parts applications, molded products with matte surfaces have come to be preferred. How to obtain a matte molded product.

■A method of applying matte paint to the surface of a molded product, a method of creating unevenness on the surface of a molded product using a mold or roll with a matte textured surface, ■A method of applying a polymer matting agent such as cross-linked acrylic resin Although there are methods such as (1) blending an inorganic filler such as calcium carbonate, etc., these methods are unsatisfactory due to the following drawbacks.

Methods (2) and (2) tend to lose their matte state due to wear and tear. In method (2), the matting effect is small, and if a large amount is added, uneven gloss will occur on the surface of the molded product. In method (2), although a matting effect can be obtained, the specific gravity becomes large, and the mechanical properties, particularly the abrasion resistance, are greatly reduced, and the surface becomes easily damaged. It is conceivable to use methods (1) and (2) in combination to maintain the matte effect for a long time by layering a matte coating on the textured surface, but this increases the cost due to the increase in the number of steps and is not practical.

The present inventors have conducted intensive research to solve the above-mentioned problems with soft vinyl chloride resin, and have found that by blending a specific filler and plasticizer with a specific vinyl chloride copolymer, the weight can be reduced and The present invention was completed based on the knowledge that a soft vinyl chloride resin composition that can maintain a stable matting effect for a long period of time and has good abrasion resistance can be obtained.

That is, the present invention contains 97.0 to 99.95% by weight of vinyl chloride and 3.9% by weight of allyl acrylate or allyl methacrylate.
Vinyl chloride copolymer 1 consisting of 0 to 0.05% by weight
00 parts by weight, (a) specific gravity 0.7 or less 5 particle size 30
Less than 0 micron, compressive strength 70kg/cII! 5 to 100 parts by weight of the above filler, and (b) 30 to 150 parts of a plasticizer.
This is a soft vinyl chloride resin composition that is lightweight, has a matte appearance, and has excellent abrasion resistance.

The vinyl chloride copolymer used in the composition of the present invention is a copolymer of vinyl chloride monomer (hereinafter referred to as VCMR) and allyl acrylate or allyl methacrylate. The vinyl chloride portion in this copolymer is 97.0 to 99.95% by weight, but part of it may be replaced with other vinyl monomers described below as long as it does not impede the purpose of the present invention. In this case, the vinyl chloride in the vinyl chloride portion must remain in an amount of 50% by weight or more, preferably 70% by weight or more of the total copolymer, and the upper limit thereof is the above-mentioned 99.95% by weight. Examples of other vinyl monomers that can be used in place of vinyl chloride include vinylidene chloride, vinyl acetate, methyl vinyl ether, ethylene, and propylene.

The proportion of allyl acrylate or allyl methacrylate in the copolymer used in the composition of the present invention is 3.0 to 0.05% by weight. If this ratio exceeds 3.0% by weight, the surface of the molded product will become rough and the appearance will deteriorate;
If the amount is less than % by weight, the matting effect and abrasion resistance will be insufficient.

The vinyl chloride copolymer used in the composition of the present invention can be obtained by polymerizing VCMR and allyl acrylate or allyl methacrylate in a predetermined weight ratio according to a conventionally known vinyl chloride polymerization method. That is, bulk polymerization,
Any of suspension polymerization, emulsion polymerization and solution polymerization can be used. However, the reproducibility of degree of polymerization, polymerization rate, etc. is good.
Suspension polymerization is preferred because of the ease of process control. The average degree of polymerization of the obtained copolymer is not particularly limited, but is %600.
~3000 is preferably used.

The filler used in the composition of the present invention has a specific gravity of 0.7 or less, a particle size of 300 microns or less, and a compressive strength of 70 and 9/cI!
That's all. If the specific gravity exceeds 0.7, the contribution to weight reduction of the composition of the present invention will be small, and if a large amount is added for the purpose of weight reduction, the mechanical strength of the obtained molded article will decrease, which is not preferable.

If the particle size exceeds 300 microns, it is undesirable because the strainer of the molding machine is clogged, and the particles stand out on the surface of the molded product, impairing its appearance. Also, the compressive strength is 70
If it is less than 11 kg/c, the particles will break in the molding machine and the weight reduction effect will be reduced, which is not preferable.

The fillers that can be used for the compositions of the invention include alumina silicates (fly ash), magnesium silicates, borosilicate glasses.

Examples include micro hollow spheres made of quartz, epoxy resin, etc.

The blending amount of the filler is 5 to 100 parts by weight based on 100 weight of the vinyl chloride copolymer, but the appropriate range varies depending on the blending amount of the plasticizer described later. That is, if (1) the plasticizer added to 100 parts by weight of the copolymer is 30 to 60 parts by weight, the filler is 5 to 60 parts by weight, and (2) if the plasticizer is 60 to 150 parts by weight, The above filler is 5~
Ioo parts by weight are preferred. In the case of (2), if the amount of filler added exceeds 60 parts by weight, the viscosity of the resulting composition will increase, causing roughness on the surface of the molded product or causing wave breakage of filler particles during crosstalk. I don't like it. ■In the case of
Even if the blending amount of the filler exceeds 100 parts by weight, the contribution to weight reduction is relatively small, and disadvantages such as a decrease in workability and a decrease in the strength of the molded product become noticeable, which is not preferable.

In the composition of the present invention, the vinyl chloride copolymer 1
00 parts by weight, 30' to 150 parts by weight of plasticizer is blended. The type of plasticizer used is not particularly limited, and known plasticizers can be used alone or in combination. Examples of such plasticizers include 7-thalic acid plasticizers such as dioctyl phthalate, adipic acid plasticizers such as dioctyl adipate, phosphate ester plasticizers such as tricresyl phosphate, and even 1,3- Examples include polyester plasticizers such as butylene glycol adipate, trimellitic acid plasticizers such as butyl trimellitate, and epoxy plasticizers such as epoxidized soybean oil. If the amount of plasticizer blended is less than 30 parts by weight, the resulting molded product will be hard, and if it exceeds 150 parts by weight, it will ooze out onto the surface of the molded product, both of which are not preferred.

The composition of the present invention is blended with an appropriate amount of a known stabilizer in the same manner as in ordinary vinyl chloride resin compositions. Examples of stabilizers to be mixed include metal soaps such as zinc stearate, organotin stabilizers such as diptyltin laurate, and lead stabilizers such as tribasic lead sulfate.These stabilizers may be used alone or in combination. Can be used in combination with more than one species, and the amount used is usually 0.5
~5 parts by weight. The composition of the present invention can also contain the same ultraviolet absorbers, pigments, lubricants, processing aids, etc. as in general vinyl chloride resin compositions, within a range that does not impede the purpose of the present invention.

The vinyl chloride copolymer, filler, plasticizer, stabilizer, and other additives are mixed to form the flexible vinyl chloride resin composition of the present invention. There are no special restrictions on the mixing method.
Any known device such as a ribbon blender, V-type blender, tumbler mixer, or Henschel mixer (trade name) can be used, and granulation can also be carried out using a single-screw or twin-screw extruder. The composition of the present invention thus obtained can be made into various soft molded products by known processing methods such as calendar molding, injection molding, extrusion molding, and blow molding, and the molded products obtained have a specific gravity of It is small, has a homogeneous matte appearance, and has good surface abrasion resistance.

The present invention will be specifically illustrated below using Examples and Comparative Examples. The methods used for measuring the physical properties and the properties of the fillers used on each side are as follows.

(1) Specific weight: Based on A8TM D lid 2.

(2) Surface matte state: ■ Judgment by visual inspection, good matteness is indicated by O5, slightly good is indicated by Δ, and poor is indicated by ×.

@Measurement of glossiness, JIS Z 8741. ray angle 6
Depends on 0°.

(3) Wear resistance: According to JIS K 7204, however, the load is 1 kg, the number of revolutions is 1000, and the wear ring is manufactured by Taper Company H.
-22 Filler A Nialumina silicate micro hollow body.

Specific gravity 0.7. Average particle size 130 microns, compressive strength 70k
g/ffl Filler B Nialumina silicate micro hollow body.

Specific gravity 0.7. Average particle size 30 microns, compressive strength 70 Yu/
crl Filler C Nialumina silicate micro hollow body, specific gravity 0.
6. Average particle size 150 microns, compressive strength 20 Yu/cd Filler D Nialumina silicate based micro hollow bodies.

Specific gravity 0.7. Average particle size 450 micro/, compressive strength 70k
lI/c! l Example 1 Allyl methacrylate 0.3% by weight and vinyl chloride 99.7%
% by weight was subjected to suspension polymerization at 57° C. to obtain a vinyl chloride copolymer having an average degree of polymerization (hereinafter p) of 1050. This copolymer was mixed with various fillers, plasticizers, stabilizers, and other additives according to the formulation shown in Table 1, and then mixed with a Henschel mixer at a maximum temperature of 13
After mixing at 0° C. for 20 minutes, the mixture was pelletized by a cold cut method using a single screw extruder with a screw diameter of 651 to obtain a soft vinyl chloride resin composition. This composition was molded into a sample piece measuring 90m x 90IW x 1011E by injection molding, and its physical properties were evaluated. The results are shown in Table 1.

Example 2 A soft vinyl chloride resin composition that is exactly the same as Example 1 except for using copolymer B in which the monomer mixing ratio is allyl methacrylate i,o % by weight and vinyl chloride 99.0 % by weight. was obtained, and its physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1 and Example 2.

Example 3 A soft vinyl chloride resin of Example 3 was obtained in exactly the same manner as in Example 2 except that filler B was used instead of filler B, and the physical properties were determined in the same manner as in Examples 1 and 2. The evaluation results are shown in Table 1 and Example 3.

Comparative Examples 1 to 5 Soft vinyl chloride resin composition that is the same as Example 1 except for using copolymer C in which the monomer mixing ratio is 4.0% by weight of allyl methacrylate and 96.0% by weight of vinyl chloride. (Comparative Example 1), and the composition of Example 2 without any filler (Comparative Example 2).

Filler C was used as filler material (Comparative Example 3)
, one using filler (Comparative Example 4), and one using vinyl chloride homopolymer A (ν=1030) in place of the vinyl chloride copolymer in Example 1 or 2 (Comparative Example 5) )
The physical property values of each are also shown in Table 1.

It is clear from Table 1 that the vinyl chloride resin composition of the present application is lightweight, has a matte surface, and has excellent abrasion resistance.

Examples 4-5. Comparative Examples 6-9 Allyl acrylate 1.0% by weight and vinyl chloride 99,50
% by weight was subjected to suspension polymerization at 40°C to obtain a vinyl chloride copolymer having an average degree of polymerization (p) of 2350. Using this copolymer, a soft vinyl chloride resin composition having the formulation shown in Table 2 was obtained by mixing and pelletizing in the same manner as in Example 1.
Width 20. ．． A belt-like product was molded and its physical properties were evaluated. The results are shown in Table 2. When the amount of filler is more than 100 parts by weight (Comparative Example 6) or when no filler is added (Comparative Example 7), vinyl chloride homopolymer B (do=
2500) (Comparative Examples 8 and 9) are also shown.

=14-

Claims (1)

[Claims] (1) 97.0 to 99.95% by weight of vinyl chloride and allyl acrylate or allyl methacrylate3. θ~0.05
(a) specific gravity of 0.7 or less with respect to 100 parts by weight of a vinyl chloride copolymer consisting of: Particle size less than 300 microns, compressive strength 70' and 9/c! 1
5 to 100 parts by weight of the above filler, and (b) 30 parts by weight of plasticizer.
150 parts by weight of a soft vinyl chloride resin composition.