JPH11172066A - Chlorinated vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chlorinated vinyl chloride resin compsn. excellent in moldability by incorporating a chlorinated vinyl chloride resin having a specified chlorine content or a mixture thereof with a vinyl chloride resin, a stabilizer (e.g. a silicate of a metal of the group II or III, a composite of a metal oxide with silicic acid, a composite of a metal hydroxide with silicic acid, a composite of a metal carbonate with silicic acid, or hydrotalcite) and talc into the same. SOLUTION: This compsn. comprises 100 pts.wt. chlorinated vinyl chloride resin having an average chlorine content of 60-75 wt.% or its mixture with a vinyl chloride resin, 0.5-6 pts.wt. at least one stabilizer selected from among silcates of metals of the groups II and II (e.g. MgSiO3 or ZnSiO3 ), composites of metal oxides (e.g. CaO or ZnO) with silicic acid, composites of metal hydroxides [e.g. Ca(OH)2 or Zn (OH)2 ] with silicic acid, and composites of metal carbonates (e.g. MgCO3 or CaCO3 ) with silicic acid, 1-30 pts.wt. talc having an average particle size of 0.05-5 μm, 0.2-5 pts.wt. polyethylene wax, and 1-30 pts.wt. methacrylate-styrene-butadiene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorinated vinyl chloride resin composition having impact resistance and heat resistance and capable of obtaining a molded article having a small shrinkage.

[0002]

2. Description of the Related Art A roof molding for an automobile is mounted on an upper portion of a roof of an automobile body and is used for preventing corrosion of a welded portion between the automobile body and the body or for design. The cross-sectional shape is as shown in FIG. 1, and 1 is made of stainless steel or vinyl chloride resin, and 2 is made of soft vinyl chloride resin. 3 is an automobile body.

A chlorinated vinyl chloride resin (hereinafter referred to as CPVC)
Is generally made by chlorinating a vinyl chloride resin (hereinafter, referred to as PVC). CPVC retains the flame retardant and chemical resistance properties that are said to be the advantages of PVC,
It is expected to be widely used because it improves the low heat resistance point, which is said to be a drawback. On the other hand, PVC has a major drawback that it cannot be used at temperatures of 60 to 70 ° C. or higher because of its low heat deformation temperature. On the other hand, the heat deformation temperature of CPVC is higher by 20 to 40 ° C. than that of PVC, and the heat resistance, which is a drawback of PVC, is improved. Therefore, it is widely used for automobiles, and is often used for roof moldings, weather strips and the like.

Conventionally, a roof molding has been used in which a metal such as stainless steel is combined with a soft PVC resin or rubber. However, recently, there have been problems with lighter vehicles and recyclability due to environmental issues, and it has been difficult to meet cost reduction requirements with conventional stainless steel and the like, and there has been a demand for resinization that can replace stainless steel. Was.

At present, as a roof molding made of resin, C
PVC products are preferably used. CPVC for this application
In general, lead-based stabilizers are often used, but due to environmental issues, automobile manufacturers have requested CPVC products that do not contain lead-based stabilizers. However, when a tin-based stabilizer is used instead of the lead-based stabilizer, for example, CP
Heat resistance, which is the greatest feature of VC, is greatly impaired, molding is difficult, long run properties are poor, and there is also a problem in fusing property with soft PVC.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, and uses CPVC, does not use a lead-based stabilizer, has good moldability, and has a good fusion property with flexible PVC. CPV suitable for automotive applications, such as roof moldings and weather strips, with the aim of providing an excellent CPVC
It is intended to provide a C composition.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a single CPVC or PVC having an average chlorine content of 60 to 75% by weight.
At least one of a silicate of a metal of Group II or Group III of the periodic table, a composite of silicic acid and an oxide of the metal, a hydrotalcite, or a zeolite Characterized by comprising 0.5 to 6 parts by weight of a stabilizer and 1 to 30 parts by weight of talc having an average particle size of 0.05 to 5 μm.

The average degree of polymerization of CPVC used in the present invention is 500 to 14 as the average degree of polymerization of PVC before chlorination.
00 is preferred. If the average degree of polymerization is less than 500, the impact resistance decreases, and if it exceeds 1,400, the melt fluidity decreases, and molding becomes difficult.

The average chlorine content of CPVC is 60 to
Limited to 75% by weight. 60% by weight average chlorine content
If it is less than 30, heat resistance is reduced and deformation is liable to occur, and 75
If the content exceeds% by weight, the fluidity is greatly reduced, and molding becomes difficult. Similarly, when used in combination with PVC, it is limited to the range of 60 to 75% by weight.

The metal used in the present invention may be a metal selected from the group II or III of the periodic table.
l, Ca, or Zn is preferred.

Examples of the silicate include alkaline earth metal silicates such as magnesium silicate, calcium silicate, barium silicate and strontium silicate; Group IIb metal salts of silicic acid such as zinc silicate; Group IIIb metal salts of silicic acid, such as aluminum silicate, may be used alone or in combination of two or more. Among these silicates, magnesium silicate, calcium silicate, zinc silicate and aluminum silicate are preferably used as a non-lead-based non-toxic stabilizer.

Examples of the composite of silicic acid and the oxide, hydroxide, or carbonate of the metal include, but are not limited to, the following.

Group II or III of the periodic table
Examples of the oxide and hydroxide with a group metal include calcium oxide, calcium hydroxide, magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide and the like.

Group II or III of the periodic table
Examples of the carbonate with a group metal include basic calcium carbonate, calcium carbonate, basic magnesium carbonate, magnesium carbonate, basic zinc carbonate, and bicarbonates such as calcium bicarbonate and magnesium bicarbonate.

The amount of the stabilizer is limited to 0.5 to 6 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 0.5 part by weight, the thermal stability of the CPVC composition is poor, and if it exceeds 6 parts by weight, the melt fluidity of the CPVC is reduced and molding becomes difficult.

The talc used in the present invention is limited to an average particle size of 0.05 to 5 μm. If the thickness is less than 0.05 μm, the bulk specific gravity increases, the handling properties deteriorate, and the kneading becomes insufficient. If it exceeds 5 μm, the surface state of the obtained molded article will deteriorate.

The amount of the talc used is limited to 1 to 30 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 1 part by weight, the effect for increasing the elastic modulus is insufficient, and
If the amount exceeds 0 parts by weight, the impact resistance is reduced.

The wax used in the present invention is preferably, for example, natural waxes such as carnauba wax and candela wax; petroleum waxes such as paraffin wax; polyethylene wax and montanic acid wax. The above wax may be used alone,
Two or more kinds may be used in combination.

Almost any polyethylene wax can be used, but preferably the weight average molecular weight is 10%.
It is in the range of 00 to 4000. There is no restriction on the weight average molecular weight and the like of the montanic acid-based wax, and any can be suitably used.

The amount of the wax used is as follows:
0.2 to 5 parts by weight per 100 parts by weight is preferred. 0.
If the amount is less than 2 parts by weight, the effect of improving the moldability is insufficient, and
When the amount exceeds the weight part, the elastic modulus and the heat resistance temperature decrease. When a polyethylene wax and a montanic acid wax are used, the amount of the montanic acid wax used is 10%.
0.1 to 1.5 parts by weight per 0 parts by weight is preferred.

The methyl methacrylate / butadiene / styrene copolymer resin (hereinafter referred to as MBS) used in the present invention is obtained by graft polymerization of an acrylic compound such as methyl acrylate and a styrene compound to a rubber resin such as polybutadiene. Resin, rubber component 50-80
% By weight is preferred. If the rubber component is less than 50% by weight, the effect of improving the impact properties is small, and if it exceeds 80% by weight, the elastic modulus and the heat resistance temperature decrease. The amount of MBS used is preferably 1 to 30 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 1 part by weight, the purpose of improving the impact resistance cannot be achieved, and 3
When the amount exceeds 0 parts by weight, the elastic modulus and the heat resistance temperature decrease.

Other impact modifiers include chlorinated polyethylene and ABS resin. However, chlorinated polyethylene tends to orient at the time of molding and thus hardly exhibits impact resistance. And the addition of a large amount is required, and the solvent resistance is inferior to that of CPVC resin, which is not suitable for this use.

The composition of the present invention is particularly preferably used for roof moldings, but is used for other automobiles, for example, weather strips, side moldings, center pillars, front pillars and the like attached to windowpanes. May be used.

The CPVC composition of the present invention can be obtained by an extrusion method,
Although injection molding is possible, extrusion molding is more suitable. In order to extrude the CPVC composition of the present invention, for example, a mixture obtained by uniformly dispersing the composition by a supermixer, or a pellet obtained by supplying the mixture to an extruder and cutting the mixture with a pelletizer, is used. What is necessary is just to shape | mold.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Examples 1 to 7, Comparative Examples 1 to 6) A resin composition obtained by uniformly mixing the components having the amounts shown in Tables 1 and 2 with a super mixer was measured at a cylinder temperature of (C
1: 150 ° C, C2: 160 ° C, C3: 170 ° C, C
4: 175 ° C.), and the mixture was fed to a 30 mm biaxial extruder set at an adapter temperature of 170 ° C. and a die temperature of 170 ° C., and cut with a pelletizer to obtain pellets. The pellets were then extruded into a 65 mm single extruder (L / D = 22,
The barrel temperature was set to (B1: 150 ° C, B2: 160 ° C, B: full flight screw, compression ratio = 3.0), respectively.
3: 170 ° C.), and the die temperature is set to (DH:
(175 ° C, D1: 175 ° C, D2: 185 ° C) to obtain a flat molded body.

The following raw materials shown in Tables 1 and 2 were used. * 1 CPVC: manufactured by Tokuyama Sekisui Industry Co., Ltd. (raw material PVC polymerization degree 8
00, chlorine content 64% by weight) * 2 CPVC: manufactured by Tokuyama Sekisui Industry Co., Ltd. (raw material PVC polymerization degree 8
PVC: TS-800E manufactured by Tokuyama Sekisui Kogyo Co., Ltd. (degree of polymerization: 80, chlorine content: 60% by weight)
0) Calcium silicate: manufactured by Mizusawa Chemical Co., Ltd. Magnesium silicate: manufactured by Mizusawa Chemical Co., Ltd. Tribasic lead sulfate: manufactured by Sakai Chemical Co., Ltd. Talc: manufactured by Nippon Talc (average particle size: 3.2 μm) * 3 Talc: manufactured by Fuji Talc MBS: BTA-751 manufactured by Kureha Chemical Industry Co., Ltd. (butadiene content: 75% by weight) Polyethylene wax: Mitsui High Wax 200P manufactured by Mitsui Petrochemical Industry Co., Ltd. (weight average molecular weight: 2000) Montanic acid wax: Hoechst Japan Hoechst Wax OP

The following performance evaluations were carried out using the molded articles obtained in the above Examples and Comparative Examples, and the results are shown in Tables 1 and 2.

(1) Charpy impact test The above resin composition was kneaded with a roll at 200 ° C. for 3 minutes, and then preheated with a 200 ° C. press for 4 minutes, pressurized for 5 minutes, and surface pressure of 7 minutes.
Prepare a 3 mm thick plate at 5 kg / cm ^{2 and} follow JIS
According to K 7111, measurement was performed at 23 ° C. with a notch on a No. 5 test piece. Practical impact strength 8kg / c
m ² or more is required. (2) Heat deformation temperature A test piece was prepared in the same manner as in (1) above, and was subjected to JIS K
It was measured according to 7207. In practice, the heating deformation temperature must be 80 ° C. or higher.

(3) Shrinkage ratio The distance (a ₁ ) between the marked lines before heating in the length direction of a flat molded product (width 20 mm, thickness 3 mm, length 500 mm) obtained by a 65 mm single extruder was measured. Measure. The molded body is heated at 90 ° C. for 72 hours, and further cooled at room temperature for 2 hours, and then the distance between marked lines (a ₂ ) is measured. Shrinkage = {(a ₁ −a ₂ ) / a ₁ } × 100. Those having a shrinkage of 0.15% or less are good. (4) Surface properties The surface condition of the molded body obtained in the same manner as in (3) above was visually observed and ranked according to the following criteria. ◎: very smooth and good surface ○: good △: slightly wavy × large wavy XX: very bad

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

The CPVC composition of the present invention is constituted as described above. By using a silicate of Group II or Group III of the periodic table as a stabilizer, it is comparable to a lead-based stabilizer. Talc, MBS
Impact resistance by adding resin and wax together,
Shrinkage and surface properties are also excellent.

[0034]

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a shape of a roof molding.

[Explanation of symbols]

 1 stainless steel or PVC 2 soft PVC 3 car body

Claims (8)

[Claims] 1. A chlorinated vinyl chloride resin having an average chlorine content of 60 to 75% by weight or 100 parts by weight of a mixture with a vinyl chloride resin, Group II or II of the periodic table
Group I metal silicates, composites of silicic acid and said metal oxides, composites of silicic acid and said metal hydroxides, composites of silicic acid and said metal carbonates, hydrotals 0.5 to 6 parts by weight of at least one stabilizer among sites or zeolites, and an average particle size of 0.05 to 5 μm
A chlorinated vinyl chloride resin composition comprising 1 to 30 parts by weight of talc. 2. The group II or III of the periodic table
The chlorinated vinyl chloride resin composition according to claim 1, wherein the group metal is Mg, Al, Ca or Zn. 3. The chlorinated vinyl chloride resin composition according to claim 1, further comprising 0.2 to 5 parts by weight of a wax. 4. The chlorinated vinyl chloride resin composition according to claim 3, wherein the wax is a polyethylene wax. 5. The method according to claim 1, wherein the wax is montanic acid wax.
The chlorinated vinyl chloride resin composition according to claim 4, which is a polyethylene wax containing 1 to 1.5 parts by weight. 6. The chlorinated vinyl chloride resin composition according to claim 1, further comprising 1 to 30 parts by weight of a methyl methacrylate / butadiene / styrene copolymer resin. 7. The chlorinated vinyl chloride resin composition according to claim 1, which is used for automobiles. 8. The chlorinated vinyl chloride resin composition according to claim 1, which is used for roof molding.