WO2018139115A1 - Chlorine-containing resin composition and joint molded body obtained using same - Google Patents

Abstract

The present invention provides a chlorine-containing resin composition which makes it possible to simply and conveniently provide a molded body which exhibits excellent heat resistance and various excellent physical properties, without causing a decline in said physical properties or the appearance thereof. The present invention also provides a molded body such as a joint or the like which is obtained using such a chlorine-containing resin composition. The present invention is a chlorine-containing resin composition which contains a chlorine-containing resin and a lead stabilizer, wherein the resin composition also contains perchloric acid-treated hydrotalcite, and the content of the perchloric acid-treated hydrotalcite content is 0.01-1 parts by mass relative to 100 parts by mass of the chlorine-containing resin.

Description

Chlorine-containing resin composition and joint molded body using the same

The present invention relates to a chlorine-containing resin composition and a joint molded body using the same.

Chlorine-containing resins typified by polyvinyl chloride are flexible and easy to process, and have physical properties such as mechanical strength. Therefore, they are widely used in various applications in addition to pipe materials. On the other hand, chlorine-containing resins have problems in heat resistance (also called thermal stability), and are unstable to heat during processing and use, and decompose due to heating. From the viewpoint of improving heat resistance and workability Usually, a stabilizer is used in combination with the chlorine-containing resin.

Typical stabilizers for chlorine-containing resins are lead-based stabilizers, but various other stabilizers have also been developed (see, for example, Patent Documents 1 to 3).

Japanese Patent Laid-Open No. 9-292063 JP 2001-302862 A JP 2002-179615 A

As described above, from the viewpoint of improving heat resistance and workability, a stabilizer is usually used in combination with a chlorine-containing resin, and as a stabilizer, a pipe for sewage is mainly used because high heat resistance can be imparted. Lead-based stabilizers are used in molding and joints. However, as the inventors proceeded with the study, it was found that the use of a lead-based stabilizer affects the physical properties and appearance of the molded body. That is, for example, since the molding temperature becomes higher as the shape of the molded body becomes larger or complicated, there is a tendency to use a lot of lead-based stabilizers in anticipation of higher stability performance and moldability, but the amount added is large. Then, problems such as deterioration of impact physical properties and weathering discoloration tend to occur.

Here, a method of reducing the amount of the lead-based stabilizer used and adding a tin-based compound, hydrotalcite, or polyhydric alcohol compound instead is also conceivable (see Patent Documents 1 to 3, etc.). However, there is a problem in this point because the heat resistance is not sufficient. In addition, since the processability also changes, it is necessary to adjust the processability by separately adjusting additives such as a lubricant, and there is a concern about the influence on the molded product. This appears more prominently as the molded product becomes larger. In the case of a tin-based compound, although heat resistance is good, it is expensive and adjustment of workability becomes more difficult.

The present invention has been made in view of the above-described present situation, and is a chlorine-containing resin composition that can easily and easily give a molded article having excellent heat resistance and various physical properties without deteriorating its physical properties and appearance. The purpose is to provide. Another object of the present invention is to provide a molded article such as a joint using such a chlorine-containing resin composition.

The present inventors have found that the above-described problems occur due to the use of a chlorine-containing resin and a lead-based stabilizer while intensively studying a chlorine-containing resin composition useful for joint molding and the like. Therefore, when a certain amount of perchloric acid-based hydrotalcite is used in combination with a chlorine-containing resin and a lead-based stabilizer, the amount of lead-based stabilizer is not increased, and while the adjustment of processability is unnecessary or simplified, it is peculiar. In particular, it was found that it can exhibit excellent heat resistance and can be expected to reduce lead-based stabilizers, and it has been found to be a composition useful for forming a joint having a particularly high molding temperature. When such a chlorine-containing resin composition is used, a molded product (also referred to as a molded product or a molded product) can be easily and easily produced without deteriorating the appearance and physical properties. It is extremely advantageous. Thus, the inventors have conceived that the above problems can be solved brilliantly, and have completed the present invention.

That is, the present invention is a chlorine-containing resin composition comprising a chlorine-containing resin and a lead-based stabilizer, the resin composition further comprising a perchloric acid-based hydrotalcite, the perchloric acid-based hydrotalcite The chlorine-containing resin composition has a content of 0.01 to 1 part by mass with respect to 100 parts by mass of the chlorine-containing resin.

The lead-based stabilizer is preferably at least one selected from the group consisting of tribasic lead sulfate, dibasic lead sulfite, and dibasic lead stearate.
The perchloric acid-based hydrotalcite is one obtained by treating hydrotalcite with at least one compound selected from the group consisting of perchloric acid, sodium perchlorate, calcium perchlorate and magnesium perchlorate. Is preferred.
The resin composition is preferably a resin composition for joint molding.

This invention is also a molded object using the said resin composition.
The molded body is preferably a joint.
The joint is preferably a large joint.

The chlorine-containing resin composition of the present invention has the above-described configuration and is extremely excellent in heat resistance. Moreover, if this is used, since it can provide easily and simply the molded object which is excellent in various physical properties, without reducing the physical property and external appearance, it is very advantageous industrially. Furthermore, when a lead-based stabilizer has already been used, the workability adjustment operation can be omitted or simplified, and a reduction in the lead-based stabilizer can be expected. Such a resin composition is particularly useful for molding a joint having a high molding temperature. In recent years, molding of chlorine-containing resin compositions has been accelerated for cost reduction. In order to cope with higher speeds, the amount of additive added is decreasing, while the proportion of lead stabilizer in the additive tends to be reduced and the proportion of lubricant is increased, but in the present invention the amount of lead stabilizer is also reduced. Since this is possible, there is a lot of room for increasing the ratio of lubricant.

It is an infrared absorption spectrum of STABACE HT-1NC (manufactured by Sakai Chemical Industry Co., Ltd., hydrotalcite). Incidentally, the peak near 1100 cm ^-1, was marked on the peak of 1350 ~ 1400 cm ^-1 (Fig. 2 and 3 are also the same). 2 is an infrared absorption spectrum of perchloric acid hydrotalcite (Preparation 1) obtained in Preparation Example 1. It is an infrared absorption spectrum of Alkamizer 5 (Kyowa Chemical Industry Co., Ltd., perchloric acid hydrotalcite).

Hereinafter, although the preferable form of this invention is demonstrated concretely, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply.

1. Chlorine-containing resin composition The chlorine-containing resin composition of the present invention (also simply referred to as “resin composition”) contains a chlorine-containing resin, a lead-based stabilizer, and a perchloric acid-based hydrotalcite. If necessary, one or more other components may be further contained, and one or two or more of each component may be used. Hereinafter, each component will be described.

1) Chlorine-containing resin The chlorine-containing resin is not particularly limited as long as it is a resin (polymer) containing chlorine atoms, but a vinyl chloride resin is preferable. Thereby, the molded object which is excellent in a softness | flexibility and a flame retardance is obtained.

Examples of the vinyl chloride resin include homopolymers such as polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, and chlorinated polyethylene; vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate copolymer Polymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer , Vinyl chloride-acrylic acid ester copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, chloride Vinyl-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate Polymers, vinyl chloride - maleic acid ester copolymer, vinyl chloride - methacrylic acid ester copolymers, vinyl chloride - acrylonitrile copolymer, vinyl chloride - copolymers such as maleimide copolymer; and the like.
A blend of a chlorine-containing resin and a chlorine-free resin may be used, and the polymerization method for obtaining a vinyl chloride resin is not particularly limited.

2) Lead-based stabilizer The lead-based stabilizer is not particularly limited as long as it is appropriately set according to the use of the molded product. For example, lead white, basic lead sulfite, dibasic lead sulfite, tribasic lead sulfate, dibasic lead phosphite, silica gel co-precipitated succinate, lead stearate, lead benzoate, dibasic lead stearate And lead naphthenate. Among them, it is preferable to use at least one selected from the group consisting of tribasic lead sulfate, dibasic lead sulfite, and dibasic lead stearate, and it is more preferable to include all three. Thereby, it becomes a useful resin composition by joint molding.

In the resin composition of the present invention, the content of the lead-based stabilizer (when two or more types are included, the total amount is meant) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the chlorine-containing resin. It is preferable. When the amount is 0.1 part by mass or more, the heat resistance becomes more sufficient, for example, the possibility of appearance defects such as burnt on the molded product is further reduced, and the long run performance is improved. Moreover, the fall of the impact physical property of a molded article and a weather resistance are more suppressed as it is 10 mass parts or less. The amount is more preferably 0.2 to 8 parts by mass, still more preferably 0.3 to 5 parts by mass. The most preferred combination is that each contains 0.3 parts by mass or more of tribasic lead sulfate, dibasic lead sulfite and dibasic lead stearate, and the total of these three is 5 parts by mass or less.

3) Perchloric acid-based hydrotalcite The perchloric acid-based hydrotalcite is not particularly limited as long as it is a powder having a hydrotalcite-type structure and has been treated with perchloric acid. As the above, those containing magnesium element (Mg) and / or zinc element (Zn) and aluminum element (Al) are suitable. Thereby, the heat resistance of a molded object further improves.

More preferably, the perchloric acid hydrotalcite is represented by the following general formula (1):
{(Mg) _x (Zn) _y } (Al) _z (OH) ₂ (A ⁿ⁻ ) _{z / n} · mH ₂ O (1)
(In the formula, A ⁿ⁻ represents one or more n-valent interlayer anions, and includes at least a perchlorate ion (ClO ₄ ⁻ ). X, y, and z are 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, and x + y + z = 1. N and m are numbers satisfying 1 ≦ n ≦ 4 and 0 ≦ m, respectively. It is expressed.

In the general formula (1), the n-valent interlayer anion contains at least a perchlorate ion (ClO ₄ ⁻ ). Although it may be perchlorate ion alone, it may have other interlayer anions together with perchlorate ion. The other interlayer anion is not particularly limited, but from the viewpoint of reactivity and environmental load reduction, a group consisting of hydroxide ion (OH ⁻ ), carbonate ion (CO ₃ ²⁻ ), and sulfate ion (SO ₄ ²⁻ ). At least one selected from the above is preferred. Of these, carbonate ions are preferred.
Note that n in the formula may be appropriately adjusted depending on the valence of the interlayer anion. 1 for perchlorate ions.

x, y, and z are numbers satisfying 0 <x <1, 0 ≦ y <1, 0.2 ≦ z ≦ 0.4, and x + y + z = 1. When y = 0, it is called Mg / Al-based hydrotalcite, and when 0 <y, it is also called zinc-modified hydrotalcite. In the present invention, any of these can be suitably used.

The perchloric acid-based hydrotalcite is also treated with at least one compound selected from the group consisting of perchloric acid, sodium perchlorate, calcium perchlorate and magnesium perchlorate to obtain perchloric acid. It is preferable that ions are incorporated into the hydrotalcite structure. Especially, it is preferable to treat with perchloric acid from the viewpoint of emphasizing press heat resistance, which is considered to reflect the degree of coloring in the molding machine. The perchloric acid hydrotalcite preferably contains a certain amount of perchloric acid radicals. The perchloric acid radical (ClO ⁴⁻ ) contained in the perchloric acid hydrotalcite can be confirmed by a peak appearing in the vicinity of 1100 cm ^{−1 as} measured by an infrared absorption spectrophotometer. At this time, the intensity of the peak A appearing near 1100 cm ^-1, the ratio of the intensity of the carbonic acid radical _(CO ^{3 2-)} Peak B appearing at ^{1350 ~ 1400cm -1 (A / B} ) , the lower limit is 1 or more It is more preferable. More preferably, it is 30 or more. The upper limit is preferably less than 1000. More preferably, it is less than 100.

The shape of the particles in the perchloric acid hydrotalcite is not particularly limited, and examples thereof include a plate shape, a spherical shape, and a disk shape. The particle shape can be observed with a scanning electron microscope or the like.

The average particle size of the perchloric acid hydrotalcite is not particularly limited, but is preferably 0.1 to 20 μm, for example. Thereby, the dispersibility to chlorine containing resin is improved, and the effect of this invention improves more. More preferably, it is 0.1 to 10 μm.

In this specification, an average particle diameter can be measured as D50, for example using a laser diffraction particle size distribution measuring apparatus (LA950 by HORIBA). D50 means a 50% cumulative particle size on a volume basis, and when the powder is divided into two from a certain particle size, it means a diameter in which the larger side and the smaller side are equivalent. Specifically, it is determined according to the following method.
[Measurement method of D50]
Add 0.025 wt% (mass%) aqueous solution of sodium hexametaphosphate to 0.1 g of sample (sample powder), and use ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Seisakusho Co., Ltd.) to adjust the strength to V-LEVEL3. Prepare a sample suspension by setting up and dispersing for 2 minutes. Thereafter, an aqueous 0.025 wt% sodium hexametaphosphate solution is circulated through the sample circulator, and the suspension is added dropwise so that the transmittance is 80 to 95%. Measurement is performed after ultrasonic dispersion for 2 seconds.

The specific surface area (also referred to as SSA) of perchloric acid-based hydrotalcite is not particularly limited, but is preferably 0.1 to 100 m ² / g, for example. Thereby, the dispersibility to chlorine containing resin is improved, and the effect of this invention improves more. More preferably, it is 0.5 to 50 m ² / g, and still more preferably 1 to 30 m ² / g.

In the present specification, the specific surface area means a BET specific surface area (also referred to as SSA) obtained by the BET method. The BET method is a gas adsorption method in which gas particles such as nitrogen are adsorbed on solid particles, and the specific surface area is measured from the adsorbed amount. From the relationship between the pressure P and the adsorption amount V, the monomolecular adsorption amount VM is determined by the BET equation. By determining, the specific surface area is determined. Specifically, the BET specific surface area is determined under the following conditions.
[Specific surface area measurement conditions]
Used machine: Macsorb Model HM-1220, manufactured by Mountec
Atmosphere: Nitrogen gas (N ₂ )
Degassing condition of external degassing device: 105 ° C-15 minutes Degassing condition of specific surface area measuring device body: 105 ° C-5 minutes

In the perchloric acid-based hydrotalcite, particles in the powder may have a coating layer. In this case, it is preferable that the physical properties of the hydrotalcite including the particles having the coating layer satisfy the above-described physical properties (average particle diameter, specific surface area, etc.). Although it does not specifically limit as particle | grains which have a coating layer, It is preferable that it coats by performing a surface treatment using a surface treating agent.

In the resin composition of the present invention, the content of perchloric acid hydrotalcite (meaning the total amount when two or more are included) is 0.01 to 1 mass relative to 100 mass parts of the chlorine-containing resin. Part. As a result, the heat resistance that is specifically excellent can be exhibited without increasing the amount of the lead-based stabilizer, and the workability adjustment work can be unnecessary or simplified. Therefore, reduction of lead-based stabilizers can be expected. If the content exceeds 1 part by mass, a defective phenomenon due to foaming may occur and the appearance of the product may be impaired. Therefore, a molded body that requires high-temperature molding (for example, a molded body having a complicated shape such as a joint) ) Is not suitable for production. From the viewpoint of further suppressing foaming and preventing appearance deterioration, the content is preferably less than 0.5 parts by mass. More preferably, it is 0.4 mass part or less, More preferably, it is 0.3 mass part or less, Especially preferably, it is 0.2 mass part or less, Most preferably, it is 0.1 mass part or less.

There is no limitation on the method for producing the perchloric acid-based hydrotalcite used in the present invention. For example, hydrotalcite powder or a slurry containing hydrotalcite may be added with a perchloric acid aqueous solution having a concentration of 5 to 80%. can get.

4) Other components The resin composition of this invention may contain another component as needed. For example, various additives such as metal soap heat stabilizers, processing aids, reinforcing agents, lubricants, antioxidants, colorants, heat aids and the like can be mentioned.

Each additive is not particularly limited, and examples of the metal soap heat stabilizer include fatty acid metal salts such as calcium stearate, barium stearate, and zinc stearate.

Examples of the processing aid include acrylic processing aids such as (meth) acrylic acid ester polymers. Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and the like. Examples of the methacrylate ester include methyl methacrylate, methacrylic acid. Examples include ethyl, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. The acrylic processing aid may be a single polymer or a copolymer of two or more of the above acrylic acid and / or its ester, methacrylic acid and / or its ester. The weight average molecular weight of the polymer is preferably 200,000 to 7 million.
Examples of commercially available acrylic processing aids include, for example, Metablene P type manufactured by Mitsubishi Rayon Co., Kaneace PA series manufactured by Kaneka, Paraloid K series manufactured by Rohm and Haas, and the like.

Examples of the reinforcing agent include butadiene-based reinforcing agents such as MBS (methyl methacrylate-butadiene styrene copolymer), chlorinated polyethylene, and the like.

Examples of the lubricant include liquid paraffin, industrial white mineral oil, synthetic paraffin, petroleum wax, petrolatum; odorless light hydrocarbon, silicone organopolysiloxane, fatty acid, fatty alcohol obtained from higher fatty acid animal or vegetable fat and oil, and Hydrogenated from these fatty acids and having 8 to 22 carbon atoms; linear hydroxy fatty acids such as hydroxystearic acid; obtained by reducing animal, vegetable oils or their fatty acid esters or cracking and distilling natural waxes Tridecyl alcohol, polyethylene glycol molecular weight 200 to 9500; polypropylene glycol molecular weight 1000 or more; polyoxypropylene-polyoxyethylene-block polymer molecular weight 1900 to 9000; and oleyl palmito Mido, stearyl elcaamide, 2 stearamide ethyl stearate, ethylene bis fatty acid amide, N, N'-oleoyl stearyl ethylenediamine, N, N'-bis (2hydroxyethyl) alkyl (C12-C18) amide, NN ' Bis (hydroxyethyl) lauroamide, oleic acid fatty acid diethanolamine reacted with N-alkyl (C16-C18) trimethylenediamine, distearic acid ester of di (hydroxyethyl) diethylenetriamine monoacetate, stearic acid n-butyl hydrogenated rosin methyl ester, Dibutyl sebacate <both n-butyl and isobutyl>, dioctyl sebacate <both ethylhexyl and n-octyl>, glycerin fatty acid ester glycerin lactstearyl pentaerythritol Stearic acid ester <mono, di, tri, tetra>, sorbitan fatty acid ester, polyethylene glycol monostearate, polyethylene glycol dilaurate, polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol palm fatty acid ester, polyethylene glycol tol Oil fatty acid ester, ethanediol montanic acid ester, 1,3 butanediol montanic acid ester, diethylene glycol stearic acid ester, propylene glycol fatty acid ester, triglyceride, linseed oil, palm oil, glycerin ester of 12-hydroxystearic acid, hydrogenated fish oil , Beef tallow, spal acetyl wax, montan wax, carnauba wax, beeswax, wood wax, hardened whale oil lauryl stew Aliphatic saturated acid esters of monohydric aliphatic alcohols such as allate and stearyl stearate, alkali metals of higher fatty acids such as lanolin, zinc stearate and calcium stearate, salts of alkaline earth metals, low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide , Fluororesin, polytetrafluoroethylene, tetrafluoroethylene / 6-fluoropropylene copolymer, polychloroethylene trifluoride, polyvinyl fluoride, other propylene glycol alginate, dialkyl ketone, acrylic copolymer (for example, manufactured by Monsanto) Modaflow etc.).

Examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, and phosphite antioxidants.
Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6- Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butyl) Ruphenol), 2,2-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4 '-Butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6- Tributylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3- Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3 5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6- Trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-ditert-butyl-4 -Hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl -2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}] ethyl-2,4,8,10-tetraoxaspiro [5,5] unde Emissions, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include mercaptopropionic acid esters.

Examples of the phosphite antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4) -Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonylphenyl) bis (Nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C12- 15 mixed alkyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5- Tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylenediphosphonite, 2,2′-methylenebis (4,6-ditert-butylphenyl) (octyl) phosphite, etc. Can be mentioned.

Examples of the colorant include TiO ₂ , zirconium oxide, BaSO ₄ , zinc oxide (zinc white) lithopone (a mixture of zinc sulfide and barium sulfate), carbon black, a mixture of carbon black and titanium dioxide, iron oxide, and Sb _2. Organic pigments such as inorganic pigments such as spinel such as O ₃ , Cr ₂ O ₃ , cobalt blue and cobalt green, ultramarine blue, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, anthraquinone pigments Is mentioned. Furthermore, the composite pigment which compounded the said pigment is also mentioned.

Examples of the heat-resistant auxiliary agent include hydrotalcite other than perchloric acid-based hydrotalcite, zeolite, partial ester of dipentaerythritol and adipic acid, polyols, and tris (2-hydroxyethyl) isocyanurate. Can be mentioned.

The method for obtaining the resin composition of the present invention is not particularly limited, and a chlorine-containing resin, a lead-based stabilizer, a perchloric acid-based hydrotalcite, and optional components used as necessary may be mixed. In particular, when a large amount is mixed at a time, it is preferable to add the lead-based stabilizer and the perchloric acid-based hydrotalcite in advance to the chlorine-containing resin. More preferably, perchloric acid-based hydrotalcite is premixed with at least one of tribasic lead sulfate, dibasic lead sulfite and dibasic lead stearate at 40 ° C. or lower, and then other additives are added. It is mixing at 40 degrees C or less to make a lead-type stabilizer composition, and adding to chlorine-containing resin after that. When the perchloric acid hydrotalcite and the fatty acid or free fatty acid contained in the lubricant contact at high temperature, the performance of the perchloric acid hydrotalcite may not be exhibited. Here, “mixing in large quantities” generally refers to the case of mixing several hundred kg to several tons as a lead-based stabilizer composition.
The mixing method is not particularly limited, and for example, it is preferable to mix with a Henschel mixer or a super mixer and knead the obtained mixture uniformly using a roll, a Banbury mixer, an extruder, or the like.

2. Molded Product The present invention is also a molded product using the above-described resin composition of the present invention, that is, a molded product formed from the resin composition of the present invention. Such a molded body is useful for various applications because of its good appearance and excellent physical properties.

The molding method (molding method) for obtaining the molded body is not particularly limited, and examples thereof include extrusion molding, injection molding, roll molding, dip molding, and blow molding. As described above, since the resin composition of the present invention is particularly excellent in heat resistance, it is particularly useful for high temperature molding. In particular, it can be particularly preferably used when the molding temperature is 200 ° C. or higher.

A joint is particularly preferable as the molded body. Since the joint usually has a complicated shape, it is usually formed at a high temperature. In general, an injection molding machine is used as a processing molding machine. Since injection molding is a method of injecting a molten chlorine-containing resin composition into a mold at a high pressure from a nozzle at a stretch, the resin composition and Due to the friction with the nozzle or the friction between the resin compositions, the temperature of the resin composition rises several tens of degrees from the processing temperature. Therefore, an extremely high level of heat resistance is required, but the resin composition of the present invention can sufficiently meet such a requirement. Thus, the form in which the molded body is a joint is one of the preferred forms of the present invention, and is also suitable for the form in which the molded body is a large joint.
Here, the large joint refers to a joint for connecting pipes having a diameter of 30 mm or more. Large joints are quite heavy and are buried deep in the soil, and therefore require much greater strength, especially impact strength, than small joints. Therefore, the strength is usually improved by adding a reinforcing agent. However, since the reinforcing agent increases the melt viscosity of the resin composition, the heat resistance during processing and molding is further required.

In order to describe the present invention in detail, specific examples are given below, but the present invention is not limited to these examples.

Preparation Examples 1 to 4
A slurry was prepared by adding 10 g of STABIACE HT-1NC (hydrotalcite manufactured by Sakai Chemical Industry Co., Ltd.) to 100 ml of ion-exchanged water. Perchloric acid in the same mole as hydrotalcite is added to this slurry, stirred at 80 ° C. for 2 hours, filtered, dried (120 ° C., 10 hours), pulverized in a mortar, and then perchloric acid hydrotalcite (preparation) 1) was prepared. Replace perchloric acid with sodium perchlorate (Preparation 2), calcium perchlorate (Preparation 3) and magnesium perchlorate (Preparation 4), respectively. Each was prepared.

For each perchloric acid hydrotalcite obtained in Preparation Examples 1 to 4, spectral characteristics were evaluated using an infrared absorption spectrophotometer (manufactured by Thermo Fisher Scientific, NICOLET 4700), and a peak appearing in the vicinity of 1100 cm ^−1. The ratio (A / B) between the intensity of A and the intensity of peak B appearing at 1350 to 1400 cm ⁻¹ was determined. The results are shown in Table 1. For reference, the peak intensity ratio (A / B) for Alkamizer 5 (Kyowa Chemical Industry Co., Ltd., perchloric acid hydrotalcite) is also shown in Table 1. In addition, FIG. 1 to FIG. 3 show spectral spectra of STABACE HT-1NC, perchloric acid hydrotalcite obtained in Preparation Example 1 (Preparation 1), and Alkamizer 5.

Production Example 1 (Production of standard color sheet)
Additives shown in Table 3 were blended and mixed in 100 g of vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-700) in the proportions shown in Table 3 to obtain a vinyl chloride resin composition. The obtained vinyl chloride resin composition was kneaded for 5 minutes with an 8-inch roll machine (manufactured by Kansai Roll Co., Ltd.) adjusted to a roll surface temperature of 170 ° C. to produce a roll sheet having a thickness of 0.3 mm. Using a press machine with a press surface temperature of 220 ° C (manufactured by Toyo Seiki Seisakusho Co., Ltd., MINI TEST PRESESS-10), 4 sheets are stacked at 100 kg / cm ^{2 for} 4 minutes so that the 7 sheets prepared above are stacked to a thickness of 2 mm. And a reference color sheet (also referred to as a hue reference sheet) was obtained.

Test example 1
Additives shown in Table 2 were blended and mixed in 100 g of vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-700) in the proportions shown in Table 2 to obtain a vinyl chloride resin composition. The obtained vinyl chloride resin composition was kneaded for 5 minutes with an 8-inch roll machine (manufactured by Kansai Roll Co., Ltd.) adjusted to a roll surface temperature of 170 ° C. to produce a roll sheet having a thickness of 0.3 mm. The following evaluation tests were conducted using this sheet. The results are shown in Table 2.

1) Press hue (color difference)
Using a press machine with a press surface temperature of 220 ° C. (MINI TEST PRES-10, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at 100 kg / cm ² so that seven sheets prepared in Test Example 1 are stacked to a thickness of 2 mm. Hold for 4 minutes. About the sheet after holding, the color difference (ΔE) based on the hue reference sheet obtained in Preparation Example 1 was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., simultaneous photometric spectroscopic color difference meter SQ-2000). .
Since a hue reference sheet is formed by adding a large amount of mercaptotin stabilizer, which is considered to have high heat resistance, it is considered that the smaller the ΔE, the better the appearance and color tone of the molded product.

2) Press heat resistant press Using a press machine with a surface temperature of 220 ° C. (MINI TEST PRESS-10, manufactured by Toyo Seiki Seisakusho Co., Ltd.), 100 kg / kg so that seven sheets prepared in Test Example 1 are stacked to a thickness of 2 mm. Hold at cm ^{2 for} 8 minutes. About the sheet | seat after holding | maintenance, the color difference ((DELTA) E) was measured by the method similar to the above-mentioned.
When ΔE is 10 or less, the heat resistance is high and the color tone is good, and the possibility of occurrence of defects in the appearance is low. On the other hand, if it exceeds 10, the heat resistance is judged to be low, and there is a trouble such as a failure of the molding machine. It is thought that it may occur.

3) Foaming property The foaming property of the surface of the sheet | seat after hold | maintaining for 8 minutes of said 2) was evaluated visually by the following reference | standard.
○: There is no firing on or in the sheet surface. It was good with no risk of poor appearance.
Δ: 1 to 5 foams on or in the sheet surface.
X: There are more than 5 foams on or in the sheet surface. This is a level that results in poor appearance.

Test Examples 2 to 13
A vinyl chloride resin composition and a roll sheet were prepared in the same manner as in Test Example 1 except that the additives listed in Table 2 were used at the ratios listed in Table 2. Using this sheet, an evaluation test was conducted in the same manner as in Test Example 1. The results are shown in Table 2.

The symbols and abbreviations in Tables 1 to 3 are as follows.
TK-700: Vinyl chloride resin, TL-5000 manufactured by Shin-Etsu Chemical Co., Ltd., tribasic lead sulfate, NB-2000 manufactured by Sakai Chemical Industry Co., Ltd., DSL manufactured by Sakai Chemical Industry Co., Ltd. DSL: Dibasic stearic acid Lead, Alkamizer 5 manufactured by Sakai Chemical Industry Co., Ltd .: Perchloric acid hydrotalcite, Kyowa Chemical Industry Co., Ltd. Preparation 1-4: Each perchloric acid hydrotalcite SB obtained in Preparation Examples 1-4: Barium stearate METABRENE P-551A manufactured by Sakai Chemical Industry Co., Ltd .: acrylic processing aid, Kane Ace B-564 manufactured by Mitsubishi Rayon Co., Ltd., butadiene type reinforcing agent, LBT-123 manufactured by Kaneka Corporation -1010: Phenol antioxidant, Songwon pigment: Gray pigment, Resin color industrial composite pigment MK-2: Mercapto tin stabilizer, Sakai Chemical Made by Kogyo

From Table 2, the following was confirmed.
Test Examples 1 to 9 differ only in the content of perchloric acid hydrotalcite. Of these, in Test Examples 7 to 9, in which the content of perchloric acid hydrotalcite relative to 100 parts by mass of the chlorine-containing resin exceeded 1 part by mass, a large amount of foaming was confirmed in the molded sheet, so that it was practical in terms of appearance. Not suitable for conversion. In Test Example 1 in which the content was 0 parts by mass, ie, no perchloric acid hydrotalcite, foaming did not occur in the sheet, but the press heat resistance was insufficient, and troubles such as failure of the molding machine were caused. There is concern about the occurrence. In contrast, in Test Examples 2 to 6 having a content of 0.01 to 1 part by mass, it can be seen that the hue and heat resistance are good and the foaming is small. In particular, in Test Examples 2 to 4 in which the content is 0.01 parts by mass or more and less than 0.5 parts by mass, foaming is sufficiently suppressed. In Test Examples 10 to 13 in which the perchloric acid hydrotalcite was changed, foaming was sufficiently suppressed and the hue and heat resistance were also good. Accordingly, in the resin composition of the present invention, in addition to the chlorine-containing resin and the lead-based stabilizer, the perchloric acid-based hydrotalcite is 0.01 to 1 part by mass (preferably 0.00. (01 part by mass or more and less than 0.5 part by mass), it is excellent in heat resistance and gives a molded article easily and easily without deteriorating physical properties and appearance at the time of molding. I understood.

Claims (7)

1. A chlorine-containing resin composition comprising a chlorine-containing resin and a lead-based stabilizer,
   The resin composition further contains perchloric acid-based hydrotalcite,
   A chlorine-containing resin composition, wherein the content of the perchloric acid-based hydrotalcite is 0.01 to 1 part by mass with respect to 100 parts by mass of the chlorine-containing resin.
2. The chlorine-containing resin according to claim 1, wherein the lead-based stabilizer is at least one selected from the group consisting of tribasic lead sulfate, dibasic lead sulfite, and dibasic lead stearate. Composition.
3. The perchloric acid-based hydrotalcite is obtained by treating hydrotalcite with at least one compound selected from the group consisting of perchloric acid, sodium perchlorate, calcium perchlorate and magnesium perchlorate. The chlorine-containing resin composition according to claim 1 or 2.
4. 4. The chlorine-containing resin composition according to claim 1, wherein the chlorine-containing resin composition is a resin composition for forming a joint.
5. A molded article comprising the chlorine-containing resin composition according to any one of claims 1 to 4.
6. The molded body according to claim 5, wherein the molded body is a joint.
7. The molded body according to claim 6, wherein the joint is a large joint.

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