JP3534942B2 - Vinyl chloride resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention belongs to the technical field of producing and using a vinyl chloride resin composition (I) having improved processability. More specifically, it is used as a stabilizer so that the vinyl chloride resin composition can be molded in an optimal state without deteriorating the excellent physical properties and chemical properties originally possessed by the vinyl chloride resin composition.
Technical Field: A vinyl chloride resin composition (II) containing a specific organic metal salt is added to a water-soluble inorganic salt to produce a vinyl chloride resin composition (I) with improved processability, and the technical field is used. Belong to.

[0002]

2. Description of the Related Art Vinyl chloride resins are widely used in various fields because of their excellent physical and chemical properties. However, since the processing temperature is close to the thermal decomposition temperature, there are various processing problems such as a narrow temperature range where molding can be performed and a long time until a molten state is achieved.

Further, vinyl chloride resins are liable to undergo thermal decomposition due to dehydrochlorination in their molecules when exposed to heat and light, which causes deterioration of color tone and mechanical properties of processed products. It causes serious disadvantages.

In order to avoid such disadvantages, various stabilizers have been conventionally used. In particular, lead compounds such as lead white, lead stearate, 3 basic lead sulfate, and basic lead phosphate are frequently used, and molding processing under optimum conditions is possible by adjusting the lubricity of the vinyl chloride resin composition. I have to.

[0005]

However, when a new additive, for example, an impact resistance enhancer is added, the workability may be different, which may adversely affect the quality of the molded product such as dimensional stability, and the purpose of the product. Since it has a negative effect on the physical properties of the molded product, such as not being able to develop impact strength, it is necessary to newly adjust the compounding amount of the stabilizer and / or lubricant and reset the molding processing conditions. There is a need.

Further, when the compounding maker mixes the stabilizer and / or the lubricant,
There is a problem that a molding maker or the like cannot easily change or adjust the compounding amount.

Therefore, a specific ethylene-vinyl acetate copolymer resin and an acrylic resin containing (meth) acrylic acid and / or its ester as a main component are used in a specific ratio, and an amount in a specific range is adjusted. A method has been proposed in which it is possible to adjust the slipperiness during molding by blending it with a vinyl chloride resin (JP-A-55-69643), and a wide range of stabilizers from weakly slippery to strong stabilizers is proposed. Enables the use of stabilizers.

However, according to this method, the amount of the compound added is relatively large at about 2 parts with respect to 100 parts (parts by weight, hereinafter the same) of the vinyl chloride resin, which increases the burden on molding makers in terms of cost. However, it is not an easy method.

As described above, the fact is that no vinyl chloride resin composition capable of easily adjusting the molding processability has been proposed yet, and the development of such a method has been desired.

[0010]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a vinyl chloride resin, a specific organic metal salt , an impact resistance enhancer and / or a processing aid. By adjusting the content of the water-soluble inorganic salt present in the vinyl chloride resin composition (II) composed of the agent, a method has been found in which the processability can be easily improved, and the present invention has been completed.

That is, according to the present invention, 100 parts of vinyl chloride resin (A), organic lead salt (B-1) and organic zinc salt (B
-2) and an organic calcium salt
At least one organic metal salt (B) 0.1 to 10 parts, the impact reinforcing agent and (or) processing aid (C) 0.02 ~ 1 parts 1 to 10 parts and water-soluble inorganic salt (D) A vinyl chloride resin composition having improved processability characterized by containing (claim 1), Organic lead salt (B-1) has 6 carbon atoms
At least one kind of claim 1 vinyl chloride resin composition according of to 22 of the organic saturated fatty acid lead salts and organic unsaturated fatty acid lead salts having 6 to 22 carbon atoms (Claim 2),
The vinyl chloride resin composition (claim 3 ) or the water-soluble inorganic salt (claim 3 ), wherein the water-soluble inorganic salt (D) is at least one of water-soluble inorganic hydrochloride and water-soluble inorganic sulfate. The vinyl chloride resin composition according to claim 1 or 3 , wherein D) is contained as a water-soluble inorganic salt present in the impact resistance enhancer and / or the processing aid (C).
4 ), a polymer emulsion in which the content of the water-soluble inorganic salt present in the impact resistance enhancer and / or processing aid (C) is synthesized as the impact resistance enhancer and / or processing aid (C). 5. The vinyl chloride resin composition according to claim 4 adjusted by adjusting the amount of the water-soluble inorganic salt (D) used as the salting-out agent of claim 5 , claim 6 for impact resistance and / or processing. The content of the water-soluble inorganic salt present in the auxiliary agent (C) is such that the polymer emulsion synthesized as the impact resistance enhancer and / or the processing auxiliary agent (C) is a salting agent for the water-soluble inorganic salt (D). 6. The vinyl chloride resin according to claim 4 or 5 , which is prepared by controlling the degree of dehydration and / or washing of the impact resistance enhancer and / or processing aid (C) slurry obtained as above. The composition (claim 6), Oyo impact toughener (Or) The content of the water-soluble inorganic salt present in the processing aid (C) is such that the impact resistance enhancer and / or the impact resistance enhancer and / or the processing aid in the manufacturing process of the processing aid (C). agent according to claim 4, 5 or 6 vinyl chloride resin composition according adjusted by the addition of a powder or an aqueous solution of a water-soluble inorganic salt (D) to the dehydrated cake of (C) (claim 7) and impact toughener And / or the content of the water-soluble inorganic salt present in the processing aid (C) is such that the impact resistance enhancer and / or the processing aid (C) is a powder or an aqueous solution of the water-soluble inorganic salt (D). The vinyl chloride resin composition (claim 8 ) according to claim 4 , 5 , 6 or 7 adjusted by addition.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a vinyl chloride resin (A), an organic lead salt (B-1), an organic zinc salt (B-
2) and an organic calcium salt selected from the group consisting of
At least one kind of organometallic salt (B) (hereinafter, simply organometallic salt
Vinyl chloride resin composition (II) comprising a salt (B)) , an impact resistance enhancer and / or a processing aid (C)
The vinyl chloride resin composition (I) having improved processability by further containing a water-soluble inorganic salt (D)
Can be obtained. The production of the vinyl chloride resin composition (I) is not limited to the addition of the component (D) to the vinyl chloride resin composition (II), and the components (A) to (D) may be added in any order. You may manufacture it.

The vinyl chloride resin (A) is not particularly limited, and any conventionally used vinyl chloride resin can be used. As a specific example of such a vinyl chloride resin, for example, polyvinyl chloride, preferably 80
% (Weight%, the same applies hereinafter) and a copolymer of vinyl chloride and a monomer copolymerizable therewith (for example, vinyl acetate, propylene, styrene, acrylic acid ester). These may be used alone or in combination of two or more. Of these, widely used,
Polyvinyl chloride is preferred because of its low cost.

The vinyl chloride resin (A) is produced by a suspension polymerization method, an emulsion polymerization method or the like, and the water-soluble inorganic salt (solubility in water at 20 ° C. (water 10
The amount of the solute (g number of solutes dissolved in 0 g) of 5 or more) is at most 0.001%, usually 0 to 0.000.
5%.

The amount of the water-soluble inorganic salt is a value determined by atomic absorption spectrometry or ion chromatography.

The organometallic salt (B) is a component used as a stabilizer and a lubricant, and specific examples thereof include an organic lead salt (B-1), an organic zinc salt (B-2), and an organic calcium. Salt and the like. Of these, organic lead salts (B
-1) and the organic zinc salt (B-2) are preferable because they have a large interaction with the water-soluble inorganic salt (D) added to improve the processability and have a large effect of improving the processability.

Specific examples of the organic lead salt (B-1) include organic saturated fatty acids having 6 to 22 carbon atoms and 6 to 2 carbon atoms.
Examples thereof include salts of lead with organic unsaturated fatty acids of 2 such as oleic acid, octanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, ricinoleic acid, and ricinoleic acid. These may be used alone or in combination of two or more. Of these, lead stearate is the most common and preferred because it is a general-purpose product.

Specific examples of the organic zinc salt (B-2) include organic saturated fatty acids having 6 to 22 carbon atoms and organic unsaturated fatty acids having 6 to 22 carbon atoms, as in the case of the organic lead salt. Examples thereof include salts of zinc (a specific example is similar to the case of organic lead salt) and zinc. These may be used alone or in combination of two or more. Of these, zinc stearate is the most common and preferred because it is a general-purpose product.

Further, as specific examples of the organic calcium salt, similar to the case of the organic lead salt, organic saturated fatty acids having 6 to 22 carbon atoms and organic unsaturated fatty acids having 6 to 22 carbon atoms (specific examples are Similar to the case of organic lead salts) and calcium salts. These may be used alone or in combination of two or more. Of these, calcium stearate is the most common and preferred because it is a general-purpose product.

The organic metal salt (B) may be used alone or in combination of two or more kinds. In the present invention, the combined use system of lead stearate and calcium stearate is the most common lead stabilizer and is preferable because it is widely used.

The amount of the water-soluble inorganic salt contained in the organometallic salt (B) is at most 0.001%, usually 0 to 0.
It is 0005%.

The impact resistance enhancer and / or the processing aid (C) are not particularly limited, and any conventionally used impact resistance enhancer and / or processing aid may be used.

Examples of the impact-strengthening agent include alkyl (meth) acrylates (eg, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)).
N-butyl acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, etc., aromatic vinyl compounds (eg styrene, α-
Methylstyrene, etc.), unsaturated nitrile compounds (eg, acrylonitrile, methacrylonitrile, etc.), organosiloxanes (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, dimethoxydimethylsilane, diethoxydimethylsilane, etc.), conjugated diene-based single Polymers (eg, butadiene, isoprene, chloroprene, etc.) and copolymerizable with them, such as maleic anhydride, (meth) acrylic acid, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, and hydroxyethyl (meth) acrylate. Other vinyl-based monomers having a reactive functional group such as an acid anhydride group, a carboxyl group, an amino group, a hydroxy group, etc. of the above are used as a polymerization initiator (eg, methyl ethyl ketone peroxide, t-butyl group) if necessary. Peroxyisopropyl carbonate, t-butyl hydroperoxide, etc.), a crosslinking agent (for example, diallyl phthalate, divinylbenzene, allyl methacrylate, etc.) may be used to polymerize or copolymerize one or more of the monomers. A copolymer obtained by graft-polymerizing one or more of the above-mentioned monomers with one or more of the above-mentioned rubber components (core-shell type modifier graft-copolymerized with the rubber component) is obtained. can give. Such a copolymer can be polymerized by a usual radical polymerization method, and a polymerization method such as a suspension polymerization method or an emulsion polymerization method is used. However, the emulsion weight is easily controlled because the particle diameter and the particle structure can be easily controlled. Legal is preferred.

Specific examples of the impact resistance enhancer include methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-n-butyl acrylate-styrene copolymer, n-butyl methacrylate-n-acrylate. Examples thereof include a butyl-methyl methacrylate copolymer, an ethyl acrylate-n-butyl acrylate-methyl methacrylate copolymer, and a methyl methacrylate-n-butyl acrylate copolymer. These may be used alone or in combination of two or more. Among these, the methyl methacrylate-butadiene-styrene copolymer and the methyl methacrylate-n-butyl acrylate copolymer are general-purpose products and are preferable because they have a large effect of improving strength.

Examples of the processing aids include, for example, (meth) acrylic acid alkyl esters (for example, methyl (meth) acrylate, ethyl (meth) acrylate,
N-Butyl (meth) acrylate, i (meth) acrylic acid
-Butyl, 2-ethylhexyl (meth) acrylate, etc., unsaturated nitrile compounds (eg, acrylonitrile, methacrylonitrile, etc.), vinyl esters (vinyl acetate, vinyl propionate, etc.), etc. (For example, similar to the case of impact strengthening agent)
An example is a copolymer obtained by copolymerizing with. For such a copolymer, the emulsion polymerization method is preferable for the same reason as in the case of the impact resistance enhancer.

Specific examples of the processing aid include methyl methacrylate-ethyl acrylate copolymer, methyl methacrylate-ethyl methacrylate copolymer, methyl methacrylate-ethyl methacrylate-n-butyl acrylate copolymer. Examples thereof include a combination, a methyl methacrylate-n-butyl methacrylate copolymer, a methyl methacrylate-n-butyl acrylate copolymer and the like. These may be used alone or in combination of two or more. Among these, a methyl methacrylate-n-butyl acrylate copolymer is a general-purpose product and is preferable in that it is excellent in the effect as a processing aid.

The amount of the water-soluble inorganic salt contained in the impact resistance enhancer and the processing aid is usually 0 to 0.1%.

In the present invention, the water-soluble inorganic salt (D) used for improving the processability of the vinyl chloride resin composition (II) has a solubility in water at 20 ° C. of 5 or more, further 10 or more. In particular, it is an inorganic salt such as a metal salt of 50 or more. Since the inorganic salt has a relatively high solubility as described above, the interaction with the organic metal salt (B) becomes high, and the processability (particularly gelation property) can be improved.

Specific examples of the water-soluble inorganic salt include alkaline earth metal hydrochlorides such as magnesium chloride and calcium chloride, alkaline earth metal perchlorates such as magnesium perchlorate, magnesium sulfate and sulfuric acid. potassium, alkali metals such as aluminum sulfate, sulfates of alkaline earth metals or III _a group elements, magnesium nitrate, alkaline earth metal nitrates such as calcium nitrate,
Examples thereof include ammonium phosphate, alkali metal such as sodium phosphate, or ammonium phosphate. These may be used alone or in combination of two or more. Among these, those belonging to the water-soluble inorganic hydrochloride are preferable because they are general-purpose products and have a large effect of improving workability, and magnesium chloride and calcium chloride are particularly preferable.

Improving the workability means that during the molding process,
It refers to improving the processability by adjusting the resin temperature, resin pressure, and the degree of gelation of the vent part to the target values, and without changing molding conditions (for example, temperature conditions, screw rotation speed, feed amount, etc.), organic This can be achieved by including a relatively small amount of water-soluble inorganic salt in the presence of the metal salt.

In the vinyl chloride resin composition (I) of the present invention, 100 parts by weight of the vinyl chloride resin (A) is mixed with the organometallic salt (B) in a usual molding vinyl chloride resin composition. The amount is 0.1 to 10 parts, preferably 0.2 to 5 parts. If the blending amount of the organometallic salt (B) is less than the above range, sufficient thermal stability cannot be obtained, and conversely, if the blending amount is more than the above range, the slipperiness is increased and the processability such as insufficient gelation is deteriorated.

The compounding amount of the impact resistance enhancer and / or processing aid (C) with respect to 100 parts of the vinyl chloride resin (A) is 1 to 10 parts. In addition, the impact resistance enhancer and the processing aid may be used in combination, but in this case, the total amount is the same as described above. If the compounding amount of the impact resistance-enhancing agent and / or the processing aid (C) is less than the above range, the strength of the molded article may be lowered, and the workability may be lowered. It does not rise any more, so it is not economical.

It is originally included in the vinyl chloride resin composition (II) comprising the vinyl chloride resin (A), the organic metal salt (B), the impact resistance enhancer and / or the processing aid (C) as described above. The amount of the water-soluble inorganic salt is usually 0 to 0.005% in the vinyl chloride resin composition (II). This amount is a value obtained as the total of water-soluble inorganic salts contained in each component of the vinyl chloride resin composition (II) that is generally used.

In the present invention, the vinyl chloride resin composition (II) which originally contains the water-soluble inorganic salt in the above amount.
In addition, the compounding amount of the water-soluble inorganic salt (D) with respect to 100 parts of the vinyl chloride resin (A) was 0 . The water-soluble inorganic salt (D) is blended so as to be from 02 to 1 part. When the amount of the water-soluble inorganic salt (D) is less than 0.02 part, it is insufficient to improve the processability, and when it exceeds 1 part, the thermal stability during molding is high. However, it is not economical because the effect of addition does not increase even if it exceeds 1 part.

The addition of the water-soluble inorganic salt (D) may be carried out by adding a vinyl chloride resin (A), an organic metal salt (B), an impact resistance enhancer and / or a processing aid (C) and other additives. The compounding agent used (the other compounding agent used, if necessary, contains almost no component (D), but if it is contained, the component (D) may be subtracted and added) Alternatively, it may be added as a powder or as an aqueous solution to a composition prepared by mixing two or more kinds. Since the amount of the water-soluble inorganic salt (D) added is relatively small, it is preferable to add it as an aqueous solution in order to enhance the dispersion efficiency.

The addition of the water-soluble inorganic salt (D)
It may be carried out by adjusting the content of the water-soluble inorganic salt (D) present in the impact resistance enhancer and / or the processing aid (C). The content of the water-soluble inorganic salt (D) present in the impact resistance enhancer and / or processing aid (C) may be adjusted, for example, as an impact resistance enhancer and / or processing aid (C). When salting out the synthesized polymer emulsion, the amount of the water-soluble inorganic salt (D) used for salting-out is adjusted to finally obtain an impact resistance enhancer and / or a processing aid (C). There is a method of adjusting the content of the water-soluble inorganic salt (D) remaining therein.

Usually, the concentration of the polymer emulsion synthesized as the impact-strengthening agent and / or the processing aid (C) is about 25-60%, and when recovering the polymer from this solution, for example, calcium chloride, Electrolyte such as magnesium chloride is 1-2 with respect to the solid content of the component (C)
% To be added. At this time, the polymer from the slurry obtained by salting out contains 0 to 0.1% of a water-soluble inorganic salt, depending on the dehydration method and the washing method. The concentration of the electrolyte is 5 with respect to the solid content of the component (C).
When added to be 10%, the obtained polymer usually contains 0.4 to 0.8% of a water-soluble inorganic salt.
In this case, at least 0.3 to 0.7% is added as the water-soluble inorganic salt (D). It is preferable to add the water-soluble inorganic salt (D) by this method because the water-soluble inorganic salt can be added uniformly.

By adjusting the degree of dehydration and / or washing in obtaining the polymer from the slurry,
Specifically, the content of the water-soluble inorganic salt in the obtained polymer can be adjusted to 0.4 to 0.8% by reducing the amount of washing water or reducing the dehydration efficiency. When the water-soluble inorganic salt (D) is added by this method,
It is preferable because it is not necessary to use an excessive amount of electrolyte, and the electrolyte can be uniformly added.

When the polymer obtained by the salting out is separated by filtration and washed several times with fresh water, the washing is adjusted or completely performed, and the impact resistance after dehydration is enhanced. Remain in impact modifier and / or processing aid (C) by adding powder or aqueous solution of water-soluble inorganic salt (D) to the dehydrated cake of agent and / or processing aid (C) By adjusting the content of the water-soluble inorganic salt (D), the content of the water-soluble inorganic salt (D) remaining in the impact resistance enhancer and / or the processing aid (C) is finally adjusted. There is also such a method. This method is suitable for completely removing impurities remaining in the polymer and for grasping the exact amount of the water-soluble inorganic salt (D) added.

Furthermore, the polymer obtained by the salting-out is separated by filtration, washed with fresh water to remove excess electrolyte, and dried to obtain an impact-strengthening agent and / or a processing aid ( C) is mixed with a powder or an aqueous solution of a water-soluble inorganic salt (D) using a mixer such as a Henschel mixer, so that the impact-resisting agent and / or the processing aid (C) finally remain. There is also a method of adjusting the content of the water-soluble inorganic salt (D). This method is suitable for fine adjustment of the addition amount of the water-soluble inorganic salt (D).

Stabilizers other than the organometallic salt (B), lubricants, plasticizers, colorants, fillers, foaming agents and the like may be added to the vinyl chloride resin composition (I) of the present invention. It should be noted that these additives contain almost no water-soluble inorganic salt (D).

Examples of the method for molding the vinyl chloride resin composition (I) of the present invention include calender molding, extrusion molding, thermoforming, injection molding, vacuum molding, pressure molding, vacuum pressure molding. Method, solid-phase pressure molding method, blow molding method, foam molding method and the like. In the case of molding by these methods, processability, for example, by adjusting the content of the water-soluble inorganic salt (D) without changing molding conditions (for example, temperature conditions, screw rotation speed, feed amount, etc.) The resin temperature can be controlled within the range of 175 to 210 ° C.

A preferred embodiment of the vinyl chloride resin composition (I) of the present invention is vinyl chloride resin (A) 100.
0.2 to 5 parts by weight of lead stearate and / or zinc stearate ((B) component), 1 to 10 parts of impact strengthening agent and / or processing aid (C), calcium chloride and (Or) Magnesium chloride ((D) component)
An example is a mixture of 0.02 to 1 part. In addition to these, stabilizers and lubricants other than the component (B) (for example, dibasic lead phosphite, dibasic lead sulfate, white lead, zinc white, lead carbonate,
Inorganic metal salts such as dibasic lead phosphate, fatty acid ester, etc.) 0.2 to 10 parts, colorant TiO ₂ 0.5 to 1
A mixture of 0 part and 0.5 to 20 parts of CaCO _{3 as} a filler may also be used. In the case of the above aspect, the thermal stability at the time of molding is high, high temperature molding is possible, and it can be molded in a gelled state necessary for expressing strength, and further,
By adjusting the content of the component (D), it is possible to obtain an effect that molding can be performed under further optimum conditions.

[0044]

EXAMPLES Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Example 1 Polyvinyl chloride (100 parts), lead stearate (0.5 parts), calcium stearate (0.5 parts), and an impact polymerization strengthening agent (C) produced by emulsion polymerization (n-butyl acrylate (80 parts)). Copolymer obtained by graft-polymerizing 20 parts of methyl methacrylate to a rubber component obtained by polymerizing with 1 part of allyl methacrylate which is a crosslinking agent) 5 parts, 2 parts of basic lead phosphite, fatty acid ester (Henkel Hakusui Co., Ltd., Roxyol G-32) 1 part and CaCO ₃ 10 parts were mixed, and calcium chloride (20) was added as a water-soluble inorganic salt (D).
A vinyl chloride resin composition (I) was produced by adding 0.02 part of 74.5) solubility in water at 0 ° C. and subjected to the following processability evaluation. The results are shown in Table 1.

(Processability) A laboplast mill (manufactured by Toyo Seiki Co., Ltd.) was charged with 65 g of the vinyl chloride resin composition (I), and the temperature was raised from 100 ° C. to 200 ° C. at a rotation speed of 24 rpm at 5 ° C. per minute. The mixture was kneaded while being allowed to run, and the temperature (gelling temperature) when the maximum torque was reached was measured. It indicates that the lower the gelling temperature, the better the processability.

Examples 2 to 5 Workability was evaluated in the same manner as in Example 1 except that the calcium chloride in Example 1 and the addition amount thereof were changed as shown in Table 1. The results are shown in Table 1.

The magnesium chloride in Table 1 was 20 ° C.
Has a water solubility of 64.5.

Comparative Examples 1 to 3 The addition amount of calcium chloride in Example 1 was 0, or instead of the water-soluble inorganic salt in Examples 1 and 3, calcium sulfate (solubility in water at 20 ° C. was 0. 298) was used, and the workability was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0050]

[Table 1]

As shown in Table 1, the processability of Comparative Example 1 in which the water-soluble inorganic salt (D) was not added and Comparative Examples 2 and 3 in which the sparingly soluble inorganic salt was added were not changed. It can be seen that the processability of Example 1 in which the water-soluble inorganic salt (D) was added was improved. Further, when the addition amount of the water-soluble inorganic salt (D) is increased as in Examples 1 and 2 and 3 or 4 and 5, the workability improving effect becomes large, and the addition amount of the water-soluble inorganic salt (D) is increased. It can be seen that workability can be improved by adjusting.

Examples 6 to 7 Workability was evaluated in the same manner as in Example 1 except that 0.5 part of zinc stearate was used instead of 0.5 part of lead stearate in Examples 1 and 3. . The results are shown in Table 2.

Comparative Example 4 The workability was evaluated in the same manner as in Example 6 except that the addition amount of calcium chloride in Example 6 was set to 0. The results are shown in Table 2.

[0054]

[Table 2]

As shown in Table 2, as the organic metal salt (B), zinc stearate and calcium stearate were used.
It can be seen that even when sium was used, the processability was improved in Example 6 in which the water-soluble inorganic salt (D) was added than in Comparative Example 4 in which the water-soluble inorganic salt (D) was not added. Further, as in Examples 6 and 7, increasing the addition amount of the water-soluble inorganic salt (D) has a greater effect of improving the processability, and the processability can be improved by adjusting the addition amount of the water-soluble inorganic salt (D). You can see that you can control.

Example 8 Impact toughening agent (C) (same as used in Example 1)
At the time of production, 5 parts of calcium chloride as a salting-out agent (C) of 100 parts (solid content) was added as a 30% aqueous solution of calcium chloride to effect coagulation, followed by heat treatment at 80 ° C. and filtration. Impact-strengthening agent (C) in powder form after washing with water in an amount of about 5 times the solid content of impact-strengthening agent (C) and then drying
I got -1. The amount of calcium chloride contained in the obtained impact resistance enhancer (C) -1 was 0.4%.

5 parts of the obtained impact resistance enhancer (C) -1 was added to 100 parts of polyvinyl chloride and 0.5 parts of lead stearate.
Part, 0.5 part of calcium stearate, 2 parts of dibasic lead phosphite, and 1 part of a fatty acid ester (Roxyol G-32 manufactured by Henkel Hakusui Co., Ltd.), a vinyl chloride resin composition (I) -1. Was manufactured and subjected to the evaluation of workability in the same manner as in Example 1. The results are shown in Table 3.

Example 9 The amount of salting-out agent (calcium chloride) used in Example 8 was changed to 10 parts with respect to the impact resistance enhancer (C),
The impact toughening agent (C) -2 was prepared in the same manner as in Example 8 and subjected to the evaluation of workability. The results are shown in Table 3.

The amount of calcium chloride contained in the impact resistance enhancer (C) -2 was 0.6%.

Example 10 The impact toughening agent (C) was prepared in the same manner as in Example 8 except that the amount of washing water in Example 8 was doubled with respect to the solid content weight of the impact toughening agent (C). -3 was obtained and the workability was evaluated. The results are shown in Table 3.

The amount of calcium chloride contained in the impact resistance enhancer (C) -3 was 0.8%.

Comparative Example 5 Impact strength enhancer (C) was prepared in the same manner as in Example 8 except that the amount of washing water in Example 8 was 50 times the solid content weight of impact strength enhancer (C). -4 was obtained and the workability was evaluated. The results are shown in Table 3.

The impact resistance enhancer (C) -4 contained almost no calcium chloride.

Example 11 The impact toughening agent dehydrated cake before drying in Comparative Example 5 was
A 0.5% calcium chloride aqueous solution in an amount 5 times the weight of the solid content was added while dehydrating. After that, it was dried to obtain an impact resistance enhancer (C) -5, and the workability was evaluated in the same manner as in Example 8. The results are shown in Table 3.

The amount of calcium chloride contained in the impact resistance enhancer (C) -5 was 0.4%.

Example 12 Impact Reinforcing Agent (C) -4-1 obtained in Comparative Example 5
While stirring 00 parts with a Henschel mixer, 0.4 parts of calcium chloride was added as a 30% aqueous solution and added. After that, it was dried to give an impact toughening agent (C) -6, and Example 8 was obtained.
The workability was evaluated in the same manner as. The results are shown in Table 3.

The amount of calcium chloride contained in the impact resistance enhancer (C) -5 was 0.4%.

[0068]

[Table 3]

As shown in Table 3, Examples 8 and 9
It is possible to adjust the amount of the water-soluble inorganic salt (D) contained in the impact resistance enhancer (C) by adjusting the amount of salting-out agent (calcium chloride) used and the amount of washing water such as 10 and 10. it can. As a result, the content of the water-soluble inorganic salt (D) with respect to the vinyl chloride resin (A) can be adjusted,
It is understood that the processability of the vinyl chloride resin composition can be improved (controlled). In addition, Example 11
And 12, the water-soluble inorganic salt (D) is added to the dehydrated cake or dry powder of the impact-strengthening agent (C) that has been thoroughly washed.
It is understood that the water-soluble inorganic salt (D) can be contained in the impact resistance-enhancing agent (C) by adding the aqueous solution, and the processability can be improved. On the other hand, in the case of Comparative Example 5, calcium chloride does not remain after complete washing, and no improvement in workability is observed.

Examples 13 to 17 and Comparative Examples 6 to 8 The vinyl chloride resin compositions obtained in Examples 1, 2, 8, 11 and 12 and Comparative Examples 1, 3 and 5 were evaluated for workability. It was performed by actual molding. The workability was evaluated by measuring the resin temperature and the resin pressure at the adapter and visually determining the degree of gelation of the resin at the vent. The results are shown in Table 4. Here, the higher the resin temperature, the better the processability, and as a result, the gelation progresses, the fluidity improves, and the resin pressure decreases.

The degree of gelation of the bent portion was evaluated in the order of goodness by ⊚, ◯, Δ and ×. Here, ◎: The resin is wrapped in a clean band around the screw. ○: The resin is wrapped around the screw without being cut. Δ: There is a portion where the resin is cut off, and some of the resin is not gelled and is in a powder state. Remaining at x: The resin is in a powder state with almost no gelation.

The molding conditions are shown below.

[0073]     Molding machine; TEC-55 manufactured by Toshiba Machine Plastic Engineering Co., Ltd.     Molding temperature (° C); C1 / C2 / C3 / C4 / AD / D1 / D2                   180/175/170/165/160/190/200     Screw rotation speed: 25 rpm     Feeder amount: 60kg / hr

[0074]

[Table 4]

As shown in Table 4, in Examples 13 to 17 containing calcium chloride, in comparison with Comparative Examples 6 to 8 not containing calcium chloride, the behavior of workability by Labo Plastomill was improved. Similarly, in actual machine molding, the workability has improved, that is, with the increase in resin temperature,
It can be seen that the degree of gelation at the vent portion is improved and the resin pressure is also reduced. Also, Examples 13, 15, 16 and 1
As shown in No. 7, even if the method of incorporating calcium chloride is different, if the calcium chloride content is the same, the same workability improving effect is exhibited. Further, as in Examples 13 and 14, increasing the calcium chloride content has a greater effect on improving the workability, and it is understood that the workability can be controlled by adjusting the calcium chloride content.

[0076]

The vinyl chloride resin composition (I) of the present invention
Is a water-soluble inorganic salt present in a vinyl chloride resin composition (II) comprising a vinyl chloride resin (A), an organic metal salt (B), an impact resistance enhancer and / or a processing aid (C). By adjusting the content of (D), the workability can be easily improved (controlled).

Continuation of the front page (56) Reference JP 62-277458 (JP, A) JP 59-98151 (JP, A) JP 55-34275 (JP, A) JP 55-9664 (JP , A) JP 7-278391 (JP, A) JP 5-247312 (JP, A) JP 5-194680 (JP, A) JP 4-342751 (JP, A) JP 3-167241 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 27/06

Claims (8)

(57) [Claims] 1. A vinyl chloride resin (A) 100 parts by weight,
Organic lead salt (B-1), organic zinc salt (B-2) and organic
At least one <br/> organometallic salt (B) 0.1 to 10 parts by weight selected from the group consisting of calcium salts, the impact reinforcing agent and (or) processing aid (C) 1 ~ 10 parts by weight And a vinyl chloride resin composition with improved processability, which comprises 0.02 to 1 part by weight of a water-soluble inorganic salt (D). 2. The organic lead salt (B-1) has 6 to 22 carbon atoms.
At least one of the organic saturated fatty acid lead salts and the C6 to C22 organic unsaturated fatty acid lead salts.
1. The vinyl chloride resin composition according to 1. 3. The vinyl chloride resin composition according to claim 1, wherein the water-soluble inorganic salt (D) is at least one of water-soluble inorganic hydrochloride and water-soluble inorganic sulfate. 4. A water-soluble inorganic salt (D) is, the impact reinforcing agent and (or) a vinyl chloride according to claim 1 or 3 wherein is contained as the water-soluble inorganic salt present in the processing aid (C) Resin composition. 5. The content of water-soluble inorganic salt present in the impact toughening agent and / or processing aid (C) was synthesized as impact toughening agent and / or processing aid (C). claim adjusted by adjusting the amount of water-soluble inorganic salt used as the polymer emulsion salting agent (D) 4
The vinyl chloride resin composition described. 6. The content of the water-soluble inorganic salt present in the impact resistance enhancer and / or processing aid (C) was synthesized as the impact resistance enhancer and / or processing aid (C). A polymer emulsion prepared by using a water-soluble inorganic salt (D) as a salting-out agent and / or adjusting the degree of dehydration and / or washing of an impact-resisting agent (or) processing aid (C) slurry. The vinyl chloride resin composition according to 4 or 5 . 7. The content of the water-soluble inorganic salt present in the impact resistance enhancer and / or processing aid (C) is in the process of producing the impact resistance enhancer and / or processing aid (C). impact reinforcing agent and (or) according to claim 4, 5 or 6 vinyl chloride resin composition according adjusted by the addition of a powder or an aqueous solution of a water-soluble inorganic salt (D) to the dehydrated cake of the processing aid (C) . 8. The content of the water-soluble inorganic salt present in the impact resistance enhancer and / or processing aid (C) is such that the impact resistance enhancer and / or processing aid (C) is water soluble inorganic. The vinyl chloride resin composition according to claim 4 , 5 , 6 or 7 , which is prepared by adding a powder or an aqueous solution of salt (D).