JPH1036607A - Method for controlling processibility of vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate the control of processibility of a vinyl chloride resin compsn. comprising a vinyl chloride resin, an org. metal salt, and an impact modifier and/or a process aid by adjusting the amt. of a water-soluble inorg. salt added to the compsn. SOLUTION: 0.008-1.6wt.% water-soluble inorg. salt is incorporated into a vinyl chloride resin compsn. comprising 100 pts.wt. vinyl chloride resin, 0.1-10 pts.wt. org. metal salt, and 0.1-20 pts.wt. impact modifier and/or process aid. The content of the inorg. salt in the compsn, may be adjusted by adding the salt in the form of a powder or an aq. soln. or by adjusting the content of a water-soluble inorg. salt present on the impact modifier and/or the process aid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention belongs to the technical field of controlling the processability of a vinyl chloride resin composition.
More specifically, a vinyl chloride resin composition containing an organic metal salt as a stabilizer so that molding can be performed in an optimum state without impairing the excellent physical and chemical properties inherent in the vinyl chloride resin composition. It belongs to the technical field of controlling the processability of a vinyl chloride resin composition by adjusting the amount of a water-soluble inorganic salt contained in a product.

[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 in which molding can be performed and a long time until the molten state.

[0003] In addition, when vinyl chloride resin is exposed to heat and light, it tends to undergo thermal decomposition due to dehydrochlorination in its molecules, which causes deterioration in the color tone and mechanical properties of processed products. A significant disadvantage.

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

[0005]

However, if the workability is changed by adding a new additive, for example, an impact-resistant reinforcing agent, the quality of the molded product such as dimensional stability is adversely affected. Since the physical properties of the molded product are adversely affected, such as the inability to express the impact strength as described above, it is necessary to newly adjust the compounding amount of the stabilizer and / or the lubricant and to set the molding processing conditions again. There is a need.

[0006] When a compounding maker mixes a stabilizer and / or a lubricant,
There is a problem that a molding manufacturer 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 an ester thereof as a main component are used in a specific ratio, and the amount in a specific range is adjusted. A method has been proposed which enables the lubrication during molding to be adjusted by blending it with a vinyl chloride resin (JP-A-55-69643). Enables the use of stabilizers.

However, according to this method, the amount of the compound added is relatively large, about 2 parts per 100 parts (parts by weight, hereinafter the same) of the vinyl chloride resin, which increases the burden on molding manufacturers and the like in terms of cost. It is not an easy method.

[0009] As described above, a method capable of easily adjusting the moldability of a vinyl chloride resin composition has not yet been proposed, and development of such a method has been awaited.

[0010]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that vinyl chloride resins, organometallic salts, impact-resistant reinforcing agents and / or processing aids are used. It has been found that the processability can be controlled by a simple method of adjusting the amount of the water-soluble inorganic salt contained in the resulting vinyl chloride resin composition, and the present invention has been completed.

That is, according to the present invention, 100 parts of a vinyl chloride resin (A), 0.1 to 10 parts of an organic metal salt (B), an impact-resistant reinforcing agent and / or a processing aid (C) 0.1 part.
For a vinyl chloride resin composition comprising 1 to 20 parts,
0.008 to 1.6% of water-soluble inorganic salt (D) (% by weight,
The same applies hereinafter). A method for controlling the processability of a vinyl chloride resin composition (Claim 1), wherein the organometallic salt (B) is an organic lead salt (B-1) and / or an organozinc. The method according to claim 1 which is a salt (B-2), wherein the organic lead salt (B-1) has 6 to 22 carbon atoms.
The method according to claim 2, wherein the organic zinc salt (B-2) is at least one of a lead salt of an organic saturated fatty acid and a lead salt of an organic unsaturated fatty acid having 6 to 22 carbon atoms,
3. The method according to claim 2, wherein the salt is at least one of zinc salts of organic saturated fatty acids having 6 to 22 carbon atoms and zinc salts of organic unsaturated fatty acids having 6 to 22 carbon atoms. ) Is at least one of a water-soluble inorganic hydrochloride and a water-soluble inorganic sulfate (claim 5). The method according to claim 1, wherein the water-soluble inorganic salt (D) is treated with an impact modifier and / or The method according to claim 1 or 5, wherein the water-soluble inorganic salt (D) contained in the processing aid (C) is contained as the water-soluble inorganic salt (D), the impact-resistant reinforcing agent and / or the processing aid (C). The content of the water-soluble inorganic salt (D) contained in the water-soluble inorganic salt (D) used as a salting-out agent for a polymer emulsion synthesized as an impact resistance enhancer and / or a processing aid (C) 7. The method according to claim 6, wherein the amount is adjusted by adjusting the amount of use. Claim 7), the content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C) is as the impact-resistant reinforcing agent and / or the processing aid (C). The synthesized polymer emulsion is adjusted by adjusting the degree of dehydration and / or washing of the impact-resistant and / or processing aid (C) slurry obtained using the water-soluble inorganic salt (D) as a salting-out agent. Claim 6
Or the method according to claim 7 (claim 8), wherein the content of the water-soluble inorganic salt (D) contained in the impact strengthening agent and / or the processing aid (C) is less than or equal to the impact strengthening agent and / or the processing aid. 8. The water-soluble inorganic salt (D) is added to the dewatered cake of the impact-resistant reinforcing agent and / or the processing aid (C) in the production process of the auxiliary (C) by adding a powder or an aqueous solution thereof. 8. The method according to claim 8, wherein the content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C) is different from the impact-resistant reinforcing agent and / or the processing aid. The method according to claim 6, 7, 8 or 9, which is prepared by adding a powder or aqueous solution of a water-soluble inorganic salt (D) to the agent (C).

[0012]

DETAILED DESCRIPTION OF THE INVENTION In the present invention, a vinyl chloride resin composition comprising a vinyl chloride resin (A), an organic metal salt (B), an impact modifier and / or a processing aid (C). The processability of the vinyl chloride resin composition (I) is controlled by adjusting the amount of the water-soluble inorganic salt (D) contained in I). This phenomenon is a phenomenon first discovered by the present inventors. When discussing the amount of the water-soluble inorganic salt (D) with respect to the vinyl chloride-based resin composition, the vinyl chloride-based resin composition (I) does not substantially contain the water-soluble inorganic salt (D). The amount of the water-soluble inorganic salt (D) as determined by ICP emission spectrometry, atomic absorption spectrometry or ion chromatography is 0.001.
%. Here, in ICP emission spectrometry, Na,
Metals other than K, Na and K in atomic absorption spectrometry, Cl ion, sulfate ion, nitrate ion, and phosphate ion in ion chromatography are quantified and the content of water-soluble inorganic salt (D) is calculated. ing. Such a vinyl chloride resin composition (I) is sufficiently washed with the vinyl chloride resin composition (I) or each component contained therein (for example, about 1 to 5 times with 5 to 10 times the volume of water). This can be easily obtained. When the water-soluble inorganic salt (D) is originally contained in the vinyl chloride resin composition, the amount of the water-soluble inorganic salt (D) contained is contained in the vinyl chloride resin composition (I). It is handled as a part of the water-soluble inorganic salt (D).

The vinyl chloride resin (A) is not particularly limited, and any conventionally used vinyl chloride resin may be used. As a specific example of such a vinyl chloride resin, for example, polyvinyl chloride, preferably 80
% Or more of a copolymer of vinyl chloride and a monomer copolymerizable therewith (for example, vinyl acetate, propylene, styrene, acrylate, etc.). These may be used alone or in combination of two or more. Among them, polyvinyl chloride is preferred because it is widely used and low in cost.

The vinyl chloride resin (A) is produced by a method such as a suspension polymerization method or an emulsion polymerization method, and contains a water-soluble inorganic salt (D) contained in the resin (solubility in water at 20 ° C. (water The amount of the inorganic salt (g number of solutes) or 5 or more in 100 g is at most 0.001% or less, usually 0 to
0.0005%. When the water-soluble inorganic salt (D) is contained in the vinyl chloride resin (A) and the amount of the water-soluble inorganic salt (D) contained is substantially zero, As described above, washing with water may be sufficiently performed.

The organic metal salt (B) is a component used as a stabilizer and a lubricant. Specific examples thereof include an organic lead salt (B-1), an organic zinc salt (B-2), and an organic calcium salt. Salt and the like. Of these, organic lead salts (B
-1) and a water-soluble inorganic salt (D) whose content is controlled to control the processability of the organic zinc salt (B-2)
Is preferred because it has a large interaction with and a large control effect on workability.

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.
And organic unsaturated fatty acids such as oleic acid, octanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, ricinoleic acid, and ricinoleic acid. Of these, lead stearate is the most common and is 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. (Specific examples are the same as in the case of organic lead salts) and zinc. Of these, zinc stearate is the most common and is preferred because it is a general purpose product.

Further, specific examples of the organic calcium salt include organic saturated fatty acids having 6 to 22 carbon atoms and organic unsaturated fatty acids having 6 to 22 carbon atoms (specific examples are the same as in the case of the organic lead salt). (Similar to the case of organic lead salts) and calcium. Of these, calcium stearate is the most common and is preferred because it is a general purpose product.

The organic metal salt (B) may be used alone or in combination of two or more. In the present invention, a combined system of lead stearate and calcium stearate is the most common among lead-based stabilizers, and is preferred because it is widely used.

The amount of the water-soluble inorganic salt (D) contained in the organometallic salt (B) is at most 0.001% or less, usually 0 to 0.0005%. When the water-soluble inorganic salt (D) is contained in the organic metal salt (B) and the amount of the water-soluble inorganic salt (D) contained is substantially zero, As described above, the washing may be sufficiently performed.

There is no particular limitation on the impact modifier and / or processing aid (C), and any impact modifier and / or processing aid conventionally used can be used.

Examples of the impact modifier 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 (for example, styrene, α-
Methylstyrene, etc.), unsaturated nitrile compounds (eg, acrylonitrile, methacrylonitrile, etc.), organosiloxanes (eg, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, dimethoxydimethylsilane, diethoxydimethylsilane, etc.), conjugated diene-based monomers (Eg, butadiene, isoprene, chloroprene, etc.) and copolymerizable with them, maleic anhydride, (meth) acrylic acid, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. If necessary, another vinyl monomer having a reactive functional group such as an acid anhydride group, a carboxyl group, an amino group, or a hydroxy group may be added to a polymerization initiator (for example, methyl ethyl ketone peroxide, t-butyl One or more of the monomers may be polymerized or copolymerized using peroxyisopropyl carbonate, t-butyl hydroperoxide, etc.) and a crosslinking agent (eg, diallyl phthalate, divinylbenzene, allyl methacrylate, etc.). A copolymer obtained by graft-polymerizing one or more of the above monomers to one or more of the obtained rubber components (a core-shell type modifier obtained by graft-copolymerizing the rubber component) is used. 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. Legit is preferred.

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

The processing aids include, for example, alkyl (meth) acrylates (eg, methyl (meth) acrylate, ethyl (meth) acrylate,
N-butyl (meth) acrylate, i (meth) acrylate
-Butyl, 2-ethylhexyl (meth) acrylate), an unsaturated nitrile compound (eg, acrylonitrile, methacrylonitrile, etc.), a vinyl ester (vinyl acetate, vinyl propionate, etc.), if necessary, a polymerization initiator ( (For example, the same as in the case of impact modifier)
And copolymers obtained by using the above. For such copolymers, an 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. Coalescent, methyl methacrylate-n-butyl methacrylate copolymer, and methyl methacrylate-n-butyl acrylate copolymer. These may be used alone or in combination of two or more. Among them, a methyl methacrylate-n-butyl acrylate copolymer is a general-purpose product, and is also preferable in that it has excellent effects as a processing aid.

The amount of the water-soluble inorganic salt contained in each of the impact modifier and the processing aid is usually 0 to 0.1%. Water-soluble inorganic salts (D) as impact modifiers and processing aids
Is contained, and when it is desired to reduce the amount of the water-soluble inorganic salt (D) contained to substantially 0, washing may be sufficiently performed as described above.

In the present invention, the water-soluble inorganic salt (D) whose content is controlled to control the processability of the vinyl chloride resin composition (I) has a solubility in water at 20 ° C. of 5 or more, and Is an inorganic salt such as a metal salt of 10 or more, especially 50 or more. As described above, since the solubility of the inorganic salt is relatively high, the interaction with the organometallic salt (B) increases, and when the content of the water-soluble inorganic salt (D) increases, the processability (especially, (Gelling property) can be improved.

Specific examples of the water-soluble inorganic salt (D) include, for example, alkaline earth metal hydrochlorides such as magnesium chloride and calcium chloride, alkaline earth metal perchlorates such as magnesium perchlorate, and sulfuric acid. magnesium,
Alkali metals such as potassium sulfate and aluminum sulfate,
Sulfates of alkaline earth metals or III _A group elements, magnesium nitrate, alkaline earth metal nitrates such as calcium nitrate, ammonium phosphate, phosphoric acid salts of alkali metals or ammonia such as sodium phosphate and the like. These may be used alone or in combination of two or more. Among these, those belonging to the water-soluble inorganic hydrochloride are preferred because they are general-purpose products and have a large effect of improving workability, and particularly preferred are magnesium chloride and calcium chloride.

Improving the processability means that during the forming process,
This refers to improving the processability in accordance with the desired values of resin temperature, resin pressure, and degree of gelation at the vent, and without changing the molding conditions (for example, temperature conditions, screw rotation speed, feed amount, etc.), This can be achieved by incorporating a relatively small amount of a water-soluble inorganic salt (D) in the presence of a metal salt.

The method of the present invention not only improves the workability but also includes the case where the workability is reduced. In that sense, it is a method of controlling workability. If the processability of the molding machine is set to a certain condition (this condition is set so as to match the molding material obtained so far), the case where the processability is reduced is included. If the conditions are not satisfied, problems may occur even if the workability is improved or deteriorated. When the processability is reduced, the components may be selected and blended so as to reduce the amount of the water-soluble inorganic salt (D) contained in the molding material, or the molding material may be washed with water.

The amount of the organic metal salt (B) to be added to 100 parts of the vinyl chloride resin (A) in the vinyl chloride resin composition (I) of the present invention is determined by the amount in the usual vinyl chloride resin composition for molding. The amount is 0.1 to 10 parts, preferably 0.2 to 5 parts. If the amount of the organic metal salt (B) is less than the above range, sufficient thermal stability cannot be obtained, and if the amount is too large, the lubricity is increased and the processability such as insufficient gelation is caused.

The compounding amount of the impact modifier and / or the processing aid (C) to 100 parts of the vinyl chloride resin (A) is 0.1 to 20 parts, preferably 1 to 10 parts. In addition, an impact resistance enhancer and a 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 enhancer and / or the processing aid (C) is less than the above range, the strength of the molded article is lowered and the workability is lowered. It is not economical because it does not increase.

In the present invention, the vinyl chloride resin composition (I) comprising the vinyl chloride resin (A), the organometallic salt (B), the impact modifier and / or the processing aid (C) as described above. ), A water-soluble inorganic salt to be contained (D)
Of 0.008 to 1.6%, more preferably 0.015 to 1%
By adjusting the percentage, the moldability can be adjusted. 0.008 of water-soluble inorganic salt (D)
If it is less than 1.6%, it is not sufficient to control the workability, and if it exceeds 1.6%, the thermal stability at the time of molding may be impaired. Also, 1.6
Even if it is used in excess of%, it is not economical because the effect is not increased by increasing the amount used.

The content of the water-soluble inorganic salt (D) is adjusted by adjusting the content of the vinyl chloride resin (A), the organic metal salt (B), the impact-resistant reinforcing agent and / or the processing aid (C), and other additives. The compounding ingredients used if necessary (the other compounding ingredients used if necessary hardly contain the component (D), but if so, the component (D) is deducted accordingly. May be added as a powder or may be added as an aqueous solution to a composition prepared by mixing two or more of these. Since the addition amount of the water-soluble inorganic salt (D) is relatively small, it is preferable to add the water-soluble inorganic salt as an aqueous solution in order to enhance the dispersion efficiency.

Further, the adjustment of the water-soluble inorganic salt (D) is as follows:
It may be carried out by adjusting the content of the water-soluble inorganic salt (D) present in the impact modifier and / or the processing aid (C). As a method for adjusting the content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C), for example, as the impact-resistant reinforcing agent and / or the 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 so that the impact-resistant reinforcing agent and / or the processing aid (C) are finally obtained. 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 impact modifier and / or processing aid (C) is approximately 25 to 60%, and when the polymer is recovered from this solution, for example, calcium chloride, An electrolyte such as magnesium chloride is added in an amount of 1 to 2 with respect to the solid content of the component (C).
%. 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 a dehydration method and a washing method. The concentration of the electrolyte is 5 to the solid content of the component (C).
When added to 10% to 10%, the resulting polymer usually contains 0.4 to 0.8% of a water-soluble inorganic salt.
It is preferable to add the water-soluble inorganic salt (D) by this method, since the water-soluble inorganic salt can be added uniformly.

When the polymer is obtained from the slurry, by controlling the degree of dehydration and / or washing,
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 dewatering efficiency. When a 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.

Further, when the polymer obtained by the salting out is separated by filtration and washed with fresh water several times, the washing is controlled or completely carried out, and the impact resistance obtained after dehydration is obtained. The powder or aqueous solution of the water-soluble inorganic salt (D) is added to the dewatered cake of the agent and / or the processing aid (C) to remain in the impact-resistant reinforcing agent and / or the processing aid (C). By adjusting the content of the water-soluble inorganic salt (D), the content of the water-soluble inorganic salt (D) finally remaining in the impact modifier and / or the processing aid (C) is adjusted. There is also a method. This method is suitable for completely removing impurities remaining in the polymer or for precisely controlling the amount of the water-soluble inorganic salt (D) to be added.

Further, 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 modifier and / or
By mixing a powder or an aqueous solution of the water-soluble inorganic salt (D) with the processing aid (C) using a mixer such as a Henschel mixer, the impact-resistant reinforcing agent and / or the processing aid (C) are finally mixed. )), There is a method of adjusting the content of the water-soluble inorganic salt (D) remaining in the above. This method is suitable for finely adjusting the amount of the water-soluble inorganic salt (D) to be added.

The vinyl chloride resin composition (I) of the present invention may contain a stabilizer, a lubricant, a plasticizer, a coloring agent, a filler, a foaming agent and the like other than the organic metal salt (B). Although these additives hardly contain the water-soluble inorganic salt (D), if they do, they contain the water-soluble inorganic salt (D) contained in the vinyl chloride resin composition (I). )
Considering that a part of the amount is separately added, the amount to be contained may be adjusted.

The vinyl chloride resin composition (I) comprising the vinyl chloride resin (A), the organometallic salt (B), the impact modifier and / or the processing aid (C) as described above was commercially available. When manufactured using a general component, the amount of the water-soluble inorganic salt (D) originally contained is usually 0 to 0.005% in the vinyl chloride resin composition (when substantially 0%, Is a vinyl chloride resin composition (I), and substantially 0
%, The water-soluble inorganic salt (D) is added to the vinyl chloride resin composition (I). At this time, the added amount of the water-soluble inorganic salt (D) is the total amount of the originally contained and the later added). This amount is a value determined as a ratio of the total of the water-soluble inorganic salt (D) contained in each component of the generally used vinyl chloride resin composition to the vinyl chloride resin composition (I).

The method for molding the vinyl chloride resin composition (II) in which the water-soluble inorganic salt (D) is added to the vinyl chloride resin composition (I) in the present invention includes, for example, a calender molding method and an extrusion molding method. Method, thermoforming method, injection molding method, vacuum forming method, pressure forming method, vacuum pressure forming method, solid-state pressure forming method, blow molding method, foaming method and the like. When molding by these methods, molding conditions (eg, temperature conditions, screw rotation speed, feed amount, etc.)
By adjusting the content of the water-soluble inorganic salt (D) without changing the content, the processability, for example, the resin temperature can be adjusted to 175.
It can be controlled in the range of -210 ° C.

In a preferred embodiment of the present invention, the amount of lead stearate and / or zinc stearate (component (B)) is from 0.2 to 100 parts of the vinyl chloride resin (A).
5 parts, impact modifier and / or processing aid (C) 1
A method in which calcium chloride and / or magnesium chloride (component (D)) is contained in an amount of 0.015 to 1% based on 10 to 10 parts of the vinyl chloride resin composition (I). In addition to these, inorganic metal salts such as stabilizers and lubricants other than the component (B) (eg, dibasic lead phosphite, dibasic lead sulfate, lead white, zinc white, lead carbonate, dibasic lead phosphate, etc.) And fatty acid esters) 0.2 to 10 parts, coloring agent TiO ₂ 0.5 to 10 parts, filler CaCO ₃ 0.5 to 2
0 parts may be blended. In the case of the above aspect, the thermal stability at the time of molding is high, high-temperature molding is possible, and molding can be carried out in a gelled state necessary for developing strength. Further, the content of the component (D) The effect that molding can be performed under optimum conditions can be obtained by adjusting the value of.

[0044]

Next, the method of 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 In 100 parts of polyvinyl chloride, 0.5 part of lead stearate, 0.5 part of calcium stearate, and an impact modifier (C) (n-butyl acrylate 80) produced by an emulsion polymerization method. And a rubber component obtained by polymerization using 1 part of allyl methacrylate as a cross-linking agent and 5 parts of a copolymer obtained by graft-polymerizing 20 parts of methyl methacrylate. D) -free (by ICP emission spectrometry, ion chromatography and atomic absorption spectrometry), a vinyl chloride resin composition (I-1) containing calcium chloride (water at 20 ° C.) as a water-soluble inorganic salt (D). The vinyl chloride resin compositions (II-1) to (II-7) to which the solubility shown in Table 1 was added to 74.5) or magnesium chloride (the solubility in water at 20 ° C was 64.5) were added. It was manufactured and subjected to the following processability evaluation. Table 1 shows the results.

(Workability) Labo plast mill (manufactured by Toyo Seiki Co., Ltd.) was charged with 65 g of a vinyl chloride resin composition,
Kneading was carried out while increasing the temperature from 100 ° C. to 200 ° C. at 5 ° C. per minute at a rotation speed of 24 rpm, and the temperature at which the maximum torque was reached (gelation temperature) was measured. The lower the gelation temperature, the better the workability.

Comparative Examples 1 to 5 The amount of calcium chloride added in Example 1 was changed to the amount shown in Table 1 or calcium sulfate (at 20 ° C.) which was a poorly soluble inorganic salt instead of the water-soluble inorganic salt in Examples 2 and 4. Workability was evaluated in the same manner as in Example 1 except that the solubility in water was 0.298). Table 1 shows the results.

[0048]

[Table 1]

As shown in Table 1, Comparative Examples 2 and 5 in which the amount of the water-soluble inorganic salt (D) was small and Comparative Examples 4 and 5 in which the hardly soluble inorganic salt was added were used. ) Is the same as that of Comparative Example 1 in which no water-soluble inorganic salt (D) is added, but in Examples 1 to 5 in which the water-soluble inorganic salt (D) is added within the scope of the present invention, the amount of the water-soluble inorganic salt (D) added is It can be seen that the processability improves as the amount increases, and that the processability can be controlled by adjusting the amount of the water-soluble inorganic salt (D) added. Also, it can be seen that the same effects can be obtained in Examples 6 and 7 using magnesium chloride.

Examples 8 to 9 Workability was evaluated in the same manner as in Example 2 except that 0.5 part of zinc stearate was used instead of 0.5 part of lead stearate in Examples 2 and 4. . Table 2 shows the results.

Comparative Example 6 The processability was evaluated in the same manner as in Example 8, except that the amount of calcium chloride added was changed to 0. Table 2 shows the results.

[0052]

[Table 2]

As shown in Table 2, even when zinc stearate was used as the organometallic salt (B), the water-soluble inorganic salt (D) was not added. It can be seen that the workability of Example 8 to which D) was added was improved. Further, as in Examples 8 and 9, when the amount of the water-soluble inorganic salt (D) added was increased, the effect of improving the processability was increased. By adjusting the amount of the water-soluble inorganic salt (D), the processability was improved. It can be seen that can be controlled.

Examples 10 to 14 0.5 part of lead stearate and 0.5 part of calcium stearate were added to 100 parts of polyvinyl chloride, and an impact modifier (C) (n-butyl acrylate 80) produced by an emulsion polymerization method was used. And a rubber component obtained by polymerization using 1 part of allyl methacrylate as a cross-linking agent and 5 parts of a copolymer obtained by graft-polymerizing 20 parts of methyl methacrylate. D) -free vinyl chloride resin composition (I-1), 2 parts of dibasic lead phosphite substantially free of water-soluble inorganic salt (D), and fatty acid ester (Henkel Shirasu (Roxyol G-32, manufactured by Co., Ltd.)
1 part and 10 parts of CaCO ₃ were blended, and as a water-soluble inorganic salt (D), calcium chloride (solubility in water at 20 ° C. 74.5) or magnesium chloride (solubility in water at 20 ° C. 64.5) was used. The vinyl chloride-based resin composition added in the amount described in Example 1 was produced, and the processability was evaluated in the same manner as in Example 1. Table 3 shows the results.

Comparative Examples 7 to 9 The amount of calcium chloride added in Example 10 was 0 or the water-soluble inorganic salt in Examples 10 and 12 was replaced with calcium sulfate (a solubility in water at 20 ° C. 298), except that the workability was evaluated in the same manner as in Example 10. Table 3 shows the results.

[0056]

[Table 3]

From the results shown in Table 3, the content of the water-soluble inorganic salt (D) can be reduced even if other additives are added to the vinyl chloride resin composition (II) containing the water-soluble inorganic salt (D). It can be seen that the workability can be controlled by adjusting.

Examples 15-16 Workability was evaluated in the same manner as in Example 10 except that 0.5 part of zinc stearate was used instead of 0.5 part of lead stearate in Examples 10 and 12. . Table 4 shows the results.

Comparative Example 10 The processability was evaluated in the same manner as in Example 15 except that the amount of calcium chloride added was set to 0. Table 4 shows the results.

[0060]

[Table 4]

As shown in Table 4, zinc stearate was used as the organic metal salt (B), and the amount of the water-soluble inorganic salt (D) was adjusted even when other additives were added. This shows that the workability can be controlled.

Example 17 Impact Resistant (C) (same as used in Example 1)
At the time of production, 5 parts of calcium chloride was added as a 30% aqueous solution to 100 parts (solid content) of the impact strengthening agent (C) as a salting-out agent, and coagulation was performed. After washing with water about 5 times the amount of the solid content of the impact strengthening agent (C), the powder is dried and dried to obtain a powdered impact strengthening agent (C).
-1 was obtained. The amount of calcium chloride contained in the obtained impact modifier (C) -1 was 0.4% (by ion chromatography, the same applies hereinafter).

5 parts of the obtained impact modifier (C) -1 was mixed with 100 parts of polyvinyl chloride and 0.5 part of lead stearate.
, A vinyl chloride resin composition containing 0.5 part of calcium stearate, 2 parts of dibasic lead phosphite, and 1 part of a fatty acid ester (Roxyl G-32, manufactured by Henkel Hakusui Co., Ltd.) was prepared and implemented. The workability was evaluated in the same manner as in Example 1. Table 5 shows the results.

Example 18: The amount of the salting-out agent (calcium chloride) used in Example 17 was changed to 10 parts with respect to the impact-resistant reinforcing agent (C).
An impact modifier (C) -2 was obtained in the same manner as in Example 17.
The workability was evaluated. Table 5 shows the results.

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

Example 19 The same procedure as in Example 17 was repeated except that the amount of washing water in Example 17 was doubled with respect to the weight of the solid content of the impact modifier (C). -3 and evaluated for workability. Table 5 shows the results.

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

COMPARATIVE EXAMPLE 11 The same procedure as in Example 17 was repeated except that the amount of washing water in Example 17 was changed to 50 times the weight of the solid content of the impact modifier (C). -4 for evaluation of workability. Table 5 shows the results.

The amount of calcium chloride in the impact modifier (C) -4 was substantially 0.

Example 20 To the dehydrated cake of the impact modifier before drying in Comparative Example 11, a 0.5% aqueous solution of 0.5% calcium chloride based on the weight of the solid content was added while dehydrating. Thereafter, the resultant was dried to obtain an impact-resistant reinforcing agent (C) -5.
The workability was evaluated in the same manner as described above. Table 5 shows the results.

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

Example 21 0.4 parts of calcium chloride was added as a 30% aqueous solution while stirring 100 parts of the impact modifier (C) -4 obtained in Comparative Example 11 with a Henschel mixer. Thereafter, the resultant was dried to obtain an impact-resistant reinforcing agent (C) -6, and the workability was evaluated in the same manner as in Example 17. Table 5 shows the results
Shown in

The amount of calcium chloride contained in the impact modifier (C) -6 was 0.4%.

[0074]

[Table 5]

As shown in Table 5, by adjusting the amount of the salting-out agent (calcium chloride) and the amount of the washing water as in Examples 17, 18 and 19, the impact strengthening agent (C ) Can be adjusted in the amount of the water-soluble inorganic salt (D). As a result, it can be seen that the content of the water-soluble inorganic salt (D) with respect to the vinyl chloride resin composition (I) can be adjusted, and the processability of the vinyl chloride resin composition can be controlled. Example 2
By adding an aqueous solution of the water-soluble inorganic salt (D) to the dehydrated cake or dried powder of the impact-reinforcement agent (C) that has been completely washed as shown in 0 and 21, the impact-reinforcement agent (C) It can be seen that a water-soluble inorganic salt (D) can be contained in the powder, and the processability can be improved. On the other hand, in the case of Comparative Example 11, it was found that calcium chloride did not remain by completely washing, and no effect of improving workability was observed.

Examples 22 to 26 and Comparative Examples 12 to 14 Examples 10, 11, 17, 20 and 21, Comparative Example 7,
With respect to the vinyl chloride resin compositions obtained in 9 and 11, workability was evaluated by molding on an actual machine. The evaluation of the processability was performed by measuring the resin temperature and the resin pressure in the adapter portion and visually determining the degree of gelation of the resin in the vent portion. Table 6 shows the results. Here, the higher the resin temperature, the better the processability, and as a result, gelation proceeds, the fluidity becomes better, and the resin pressure decreases.

The degree of gelation at the vent portion was evaluated in the order of goodness as ◎, ○, Δ, ×. Here, ◎: The resin is wrapped around the screw in a clean belt shape. ：: The resin is wrapped around the screw without cutting. △: There is a portion where the resin is cut, and some of the resin is not gelled and powdered. X: indicates that the resin is hardly gelled and is in a powder state.

The molding conditions are shown below.

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 Number of rotations: 25 rpm Feeder amount: 60 kg / hr

[0080]

[Table 6]

As shown in Table 6, in Examples 22 to 26 containing calcium chloride, the behavior and processability of Labo Plastomill were higher than those in Comparative Examples 12 to 14 not containing calcium chloride. Similarly, it can be seen that the workability is also improved in actual machine molding, that is, the degree of gelation of the vent portion is improved and the resin pressure is also reduced as the resin temperature is increased. Also, as in Examples 22, 24, 25 and 26, even if the method of containing calcium chloride is different, if the calcium chloride content is the same,
It can be seen that the same workability improving effect is exhibited. Also,
As in Examples 22 and 23, when the content of calcium chloride is increased, the effect of improving the processability is increased, and it can be seen that the processability can be controlled by adjusting the content of calcium chloride.

[0082]

According to the present invention, a vinyl chloride resin composition (I) comprising a vinyl chloride resin (A), an organic metal salt (B), an impact modifier and / or a processing aid (C). To 0.008 to 0.008 of the water-soluble inorganic salt (D).
By containing 1.6%, the workability can be easily controlled.

Claims (10)

[Claims] 1. A vinyl chloride resin (A) 100 parts by weight,
A water-soluble inorganic compound is used with respect to a vinyl chloride resin composition comprising 0.1 to 10 parts by weight of an organic metal salt (B) and 0.1 to 20 parts by weight of an impact modifier and / or processing aid (C) A method for controlling the processability of a vinyl chloride resin composition, wherein the salt (D) is contained in an amount of 0.008 to 1.6% by weight. 2. The method according to claim 1, wherein the organic metal salt (B) is an organic lead salt (B-
The method according to claim 1, which is 1) and / or an organic zinc salt (B-2). 3. The organic lead salt (B-1) has 6 to 22 carbon atoms.
The method according to claim 2, which is at least one of lead organic saturated fatty acid salts and organic unsaturated fatty acid lead salts having 6 to 22 carbon atoms. 4. The organic zinc salt (B-2) has 6 to 2 carbon atoms.
The method according to claim 2, which is at least one of zinc salt of an organic saturated fatty acid 2 and zinc salt of an organic unsaturated fatty acid having 6 to 22 carbon atoms. 5. The method according to claim 1, wherein the water-soluble inorganic salt (D) is at least one of a water-soluble inorganic hydrochloride and a water-soluble inorganic sulfate. 6. The method according to claim 1, wherein the water-soluble inorganic salt (D) is contained as a water-soluble inorganic salt (D) contained in an impact-resistant reinforcing agent and / or a processing aid (C). . 7. The content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C) as the impact-resistant reinforcing agent and / or the processing aid (C). The method according to claim 6, which is adjusted by adjusting the amount of the water-soluble inorganic salt (D) used as a salting-out agent of the synthesized polymer emulsion. 8. The content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C) as the impact-resistant reinforcing agent and / or the processing aid (C). The synthesized polymer emulsion is adjusted by adjusting the degree of dehydration and / or washing of the impact-resistant and / or processing aid (C) slurry obtained using the water-soluble inorganic salt (D) as a salting-out agent. A method according to claim 6 or claim 7. 9. The content of the water-soluble inorganic salt (D) contained in the impact-resistant reinforcing agent and / or the processing aid (C) is not more than that of the impact-resistant reinforcing agent and / or the processing aid (C). Impact modifier and / or processing aid (C) in the manufacturing process
9. The method according to claim 6, 7 or 8, wherein the method is adjusted by adding a powder or an aqueous solution of a water-soluble inorganic salt (D) to the dehydrated cake. 10. The water-soluble inorganic salt (D) contained in the impact modifier and / or the processing aid (C) has a content of:
10. The method according to claim 6, 7, 8 or 9, wherein the method is adjusted by adding a powder or an aqueous solution of a water-soluble inorganic salt (D) to the impact resistance enhancer and / or the processing aid (C).