JP2005097492A - Stabilized chlorinated vinyl chloride resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stabilized chlorinated vinyl chloride resin composition, more specifically the chlorinated vinyl chloride resin composition containing a tribasic salt of phosphoric acid and an organotin-based stabilizer, having synergistically improved heat stability, providing a compounded resin having improved processability and properties, reducing the tendency of corrosion of a mold, and utilizable for a hot-water supply tube, a joint, a cable protective tube for an underground line or the like. <P>SOLUTION: The stabilized chlorinated vinyl chloride resin composition contains (A) 0.1-10 pts. wt. tribasic salt of the phosphoric acid and (B) 0.01-10 pts. wt. organotin-based stabilizer based on 100 pts. wt. chlorinated vinyl chloride resin. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a stabilized chlorinated vinyl chloride resin composition, and more specifically, it contains a tertiary phosphate and an organotin stabilizer, and the thermal stability is synergistically improved and blended. The present invention relates to a chlorinated vinyl chloride resin composition that is improved in resin processability and physical properties, has a reduced tendency to mold corrosion, and is used in hot water pipes, joints, underground cable protection pipes, and the like.

The chlorinated vinyl chloride resin composition (CPVC), like the vinyl chloride resin (PVC), undergoes dehydrochlorination within its molecular chain when exposed to heat and light, resulting in decomposition, discoloration, deterioration of physical properties, etc. . It is also known that the cause of this discoloration and physical property degradation is the formation of a polyene structure. In order to stabilize the chlorinated vinyl chloride resin composition against this thermal decomposition, various stabilizers or stabilizer compositions have been proposed and widely used.

The use of organotin stabilizers for the thermal stabilization of chlorinated vinyl chloride resin compositions has long been known, and it is also well known that combinations of organotin stabilizers with other inorganic stabilizers are used. It has been.

For example, a post-chlorinated vinyl chloride resin composition having excellent processability and heat resistance by adding a specific organotin carboxylate and A-type zeolite in combination to the post-chlorinated vinyl chloride resin has been described (Patent Documents) 1).

A chlorinated vinyl chloride resin composition comprising a chlorinated vinyl chloride resin and a polyvalent metal hydroxide is also described (Patent Document 2).

Furthermore, post-chlorinated polyvinyl chloride is described which comprises adding a combination of an organotin stabilizer and an alkali metal or alkaline earth metal oxide or hydroxide to post-chlorinated polyvinyl chloride (patent) Reference 3).

JP-A-1-221447 (Claims) JP-A-3-179049 (Claims) JP-A-8-311286 (Claims)

Organotin-based stabilizers are certainly excellent in thermal stability, but tend to lower the softening point of blended chlorinated vinyl chloride resins, and are used for molding blended chlorinated vinyl chloride resins. There is a tendency to corrode the mold.
On the other hand, the use of an organic tin stabilizer causes generation of odor, sulfur contamination, an increase in cost, etc., and therefore a reduction in the blending amount is desired. ,
There are disadvantages of increased initial coloration and reduced thermal stability.

The combined use of the alkaline earth metal compounds described above has helped to improve these defects to some extent, but there is still a limit to the improvement of thermal stability, and there is a limit to the reduction of organotin stabilizers. There is a need for further improvement.

The present inventors have succeeded in synergistically improving the thermal stability of the chlorinated vinyl chloride resin composition by selecting a tertiary phosphate and combining it with an organotin stabilizer. The invention has been completed.

According to the present invention, (A) 0.1 to 10 parts by weight of a tertiary phosphate and (B) 0.01 to 10 parts by weight of an organic tin stabilizer are added to 100 parts by weight of a chlorinated vinyl chloride resin. There is provided a stabilized chlorinated vinyl chloride resin composition comprising.

In the chlorinated vinyl chloride resin composition of the present invention,
1. (A) the triphosphate is tricalcium phosphate,
2. (B) The organotin stabilizer (B) is an alkylmercaptotin stabilizer,
3. Further containing at least one selected from magnesium-aluminum composite oxide, dawsonite, and zeolite (C);
4). Magnesium-aluminum composite oxide, dosonite, and zeolite (C) are present in an amount of 0.1 to 10 parts by weight per 100 parts by weight of chlorinated vinyl chloride resin,
5). The magnesium-aluminum composite oxide is a hydrotalcite compound,
Is preferred.

According to the present invention, it was possible to synergistically improve the thermal stability of the chlorinated vinyl chloride resin composition by selecting a tertiary phosphate and combining it with an organotin stabilizer.
By using the above-mentioned tertiary phosphate in combination with an organic tin-based stabilizer, not only the organic tin-based stabilizer can be reduced, but also the thermal stability can be improved as compared with the case where the organic tin is blended alone.
In addition, by reducing the distribution of organotin stabilizers, the processability and physical properties of the compounded resin were improved, and the tendency of mold corrosion was also reduced.

In the present invention, the thermal stability of the chlorinated vinyl chloride resin composition is remarkably improved by blending the tertiary phosphate (A) in a form replacing the part of the organotin stabilizer (B). be able to.

See the examples below.
According to the result of the gear oven heat test at 185 ° C., the blackening time is 45 minutes for a resin composition containing 2 parts by weight of an organotin stabilizer (B) per 100 parts by weight of the chlorinated vinyl chloride resin composition. In contrast to the order (Comparative Example 2), when 1 part by weight of the organotin stabilizer (B) is replaced with tricalcium phosphate (A), the blackening time is improved to 80 minutes (implementation) Example 2) According to the present invention, it can be seen that the amount of the organotin stabilizer (B) can be reduced and the thermal stability can be significantly improved.

Furthermore, as a result of measuring the Vicat softening point of the sample, the softening point of the comparative resin composition is 116.4 ° C. (Comparative Example 2), whereas the softening point of the resin composition (present invention) is 1
It is 19.3 ° C. (Example 2), and it is clear that the drawback of lowering the softening point due to the organotin stabilizer is also improved.

In the present invention, it is important to use a tertiary phosphate as the phosphate. As described below,
When 1 part by weight of 2 parts by weight of the organic tin stabilizer (B) is replaced with monobasic calcium phosphate (Ca (H ₂ PO ₄ )), the blackening time is 30 minutes (Comparative Example 4). In the case of substitution with dicalcium phosphate (CaHPO ₄ ), it is more possible to use tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) than when the blackening time is improved only by 55 minutes (Comparative Example 5). It turns out that it is excellent in improving heat resistance.

In the present invention, (A) 0.1 to 10 parts by weight of a tertiary phosphate and (B) 0.01 to 10 parts by weight of an organotin stabilizer are contained with respect to 100 parts by weight of a chlorinated vinyl chloride resin. It is preferable. When there are few compounding parts of a tertiary phosphate, heat resistance will not fully improve and a softening point will not be improved. On the other hand, when the amount is more than the above-mentioned blending parts, the initial coloring becomes strong, which is not preferable.

In the present invention, (C) magnesium / aluminum composite oxide, dosonite,
It is preferable to further contain at least one selected from zeolites. That is, the softening point of the stabilizer-blended resin composition can be improved by blending the component (C) (see Example 5).

(C) Magnesium / aluminum composite oxide, dawsonite and zeolite are preferably present in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the chlorinated vinyl chloride resin.

[Tertiary phosphate]
Examples of the tertiary phosphate used in the present invention include tricalcium phosphate, tribasic sodium phosphate, tribasic ammonium phosphate, tribasic potassium phosphate, and tertiary barium phosphate.
Among these, tricalcium phosphate is preferable in terms of performance and the like.

[Organic tin stabilizer]
As the organotin stabilizer, an alkyl mercaptotin stabilizer is used, and organotin mercaptides, organotin mercaptides / sulfides, and organotin mercaptocarboxylates in which an alkyl group is bonded to a tin atom are included.

Examples of the organic tin mercaptides include dibutyltin bis (lauryl mercaptide), dimethyltin bis (stearyl mercaptide), dioctyltin bis (mercaptoethyl tall oil fatty acid ester), dioctyltin bis (2-mercaptoethyl caprylate). ), Dibutyltin bis (mercaptoethyl tall oil fatty acid ester), dimethyltin bis (mercaptoethyl stearate), dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexylthioglycolate), dioctyltin Bis (dodecylthioglycolate), dioctyltin bis (tetradecylthioglycolate), dioctyltin bis (hexadecylthioglycolate), dioctyltin bis (octadecylthioglycolate), dioctyltin bis ( _12-16 mixed alkyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dimethyltin bis (isooctyl mercaptopropionate), bis (2-mercaptoethyl carbonyl ethyl) tin bis (isooctyl thioglycolate), Diorganotin mercaptides such as bis (2-butoxycarbonylethyl) tin bis (butylthioglycolate) and monobutyltin tris (lauryl mercaptide), monobutyl monochlorotin bis (lauryl mercaptide), monooctyltin tris ( 2-mercaptoethyl caprylate), monobutyltin tris (mercaptoethyl tall oil fatty acid ester), monomethyltin tris (mercaptoethyl tall oil fatty acid ester), monomethyltin tris (mercaptoethyl laurate), monomethyltin Lith (mercaptoethyl stearate), monomethyltin tris (mercaptoethyl oleate), monooctyl tin tris (isooctyl thioglycolate) monooctyl tin tris (2-ethylhexyl thioglycolate), monooctyl tin tris (dodecyl thioglycolate) ), Monooctyltin tris (dodecylthioglycolate), monooctyltin tris (tetradecylthioglycolate), monooctyltin tris (hexadecylthioglycolate), monooctyltin tris (C _12-16 mixed alkylthioglycolate) ), Monooctyltin tris (octadecylthioglycolate), monobutyltin tris (isooctylthioglycolate), monobutyltin tris (isooctyl mercaptopropionate), monomethyltin tris (isooctylchi) Monoorganotin such as olglycolate), monomethyltin tris (tetradecylthioglycolate), 2-methoxycarbonylethyltin tris (isooctylthioglycolate), 2-butoxycarbonylethyltin tris (2-ethylhexylthioglycolate) Mercaptides.

  Examples of organotin mercaptide sulfides include bis [monobutyl di (isooctoxycarbonylmethylenethio) tin] sulfide, bis [dibutylmono (isooctoxycarbonylmethylenethio) tin] sulfide, and bis [bis (2-methoxycarbonylethyl). ) Tin isooctylthioglycolate] sulfide, bis (methyltin diisooctylthioglycolate) disulfide, bis (methyl / dimethyltin mono / diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthio) Glycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide, bis [methyltin di (2-methylcaptoethylcaprylate) sulfide, bis [methyltin di (2-mercaptoethylcapri) Over door)] disulfide, and the like.

  Examples of organotin mercaptocarboxylates include dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, bis (2-methoxycarbonylethyl) tin thioglycolate) tin thioglycol Rate, bis (2-methoxycarbonylethyl) tin mercaptopropionate, and the like.

These alkyl mercaptotin stabilizers can be used alone or in combination of two or more, and other organotin stabilizers such as organotin carboxylates, mono- or dimethyltin, mono- or dibutyltin, Mono- or dioctyltin or mono- or bis (butoxycarbonylethyl) tin octoate, laurate, myristate, palmitate, stearate, isostearate and other aliphatic monovalent carboxylates: malate polymer,
Malates such as butyl malate, benzyl malate, oleyl malate, stearyl malate; and these can also be used in combination with mixed salts or basic salts.

[Magnesium-aluminum composite oxide]
Examples of the magnesium / aluminum composite oxide include hydrotalcite compounds. Hydrotalcite is a synthetic mineral belonging to aluminum magnesium magnesium hydroxide. The general chemical composition of aluminum magnesium carbonate hydroxide is represented by the following formula (2)
,
M ² _x M ³ _y (OH) _{2x + 3y−2z} (A ²⁻ ) _z · aH ₂ O (2)
In the formula, M ² is a divalent metal ion such as Mg, M ³ is a trivalent metal ion such as Al, A ²⁻ is a divalent anion such as CO ₃ ,
x, y and z are positive numbers satisfying 8 ≧ x / y ≧ 1/4 and z / x + y> 1/20,
a is a number satisfying 0.25 ≦ a / x + y ≦ 1.0.
A composite metal hydroxide having is used.

Of these composite metal hydroxides, the formula (3)
Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) · 4H ₂ O (3)
Is a natural mineral known as hydrotalcite, and these minerals and homologues are disclosed in Japanese Patent Publication No. 47-32198 and Japanese Patent Publication No. 48 relating to the application of Kyowa Chemical Industry Co., Ltd.
-29477 and the method described in Japanese Patent Publication No. 48-29478.

These hydrotalcites, especially the formula (4)
Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) · 3H ₂ O (4)
It is already known that the compound represented by is excellent in the ability to trap chloride ions, and this can also be used.

Utilizing the property that these hydrotalcites are easily ion-exchanged in a state sufficiently dispersed in water, that is, the property that carbonate ions are ion-exchanged with other anions, The introduced one can also be used.

[Dorsonite]
As dosonite, the following formula (1):
mAl ₂ O ₃ · (n / p) M _{2 / p} O · X · kH ₂ O (1)
In the formula, X is an inorganic or organic anion mainly composed of carbonate radicals,
M is an alkali metal or alkaline earth metal,
m is a number from 0.3 to 1,
n is a number from 0.3 to 2,
k is a number from 0.5 to 4,
p is the valence of the metal M,
In particular, in the formula (1), it is most preferable that M is sodium and X is a carbonate group.

Dawsonite is a basic carbonate mineral of sodium and aluminum known per se, and its synthesis method is also disclosed in Japanese Patent Publication Nos. 47-38318 and 54-177.
No. 18, JP 56-22628, JP 57-44604, JP 5
JP-A-7-61625, JP-A-59-83933, JP-A-63-100017, JP-B-1-24731, JP-B-2-58205, JP-A-3-27111.
6 and the like.

[Zeolite]
Zeolite is not limited to natural and synthetic materials. For example, A type, X type, Y type, Pc type,
L-type zeolite and the like, analthym, chabazite, mordenite, erionite, clinoptilolite are used, and naturally ion-exchanged with ions such as Ca, Zn, Mg, Sn, Ti, and Pb can also be used. The average particle size is 0.1 to 20 μm, preferably 1 to 10 μm, and 50 to
Those having a cation exchange capacity of 650 meq / 100 g are preferred, but 4A zeolite is particularly preferred.

In the chlorinated vinyl chloride resin composition of the present invention, a compounding agent known per se can be blended according to a formulation known per se. For example, the composition of the present invention includes a metal soap heat stabilizer, a plasticizer, a lubricant, an antioxidant, a filler, a weathering stabilizer, an anti-aging agent, a light stabilizer, an ultraviolet absorber, an antistatic agent, and a strengthening agent. Agents, modifying resins or rubbers, basic inorganic compounds, perchloric acid, perchlorates, epoxy compounds, fatty acid salts, fatty acid esters, polyhydric alcohols or esters thereof, organic phosphites, etc. Impact enhancer, antibacterial agent, chelating agent, flame retardant, etc.
Well-known resin compounding agents, such as an electrical insulation improvement agent and a coloring inhibitor, are mentioned.

[Lubricant]
Lubricants include (a) fluid, natural or synthetic paraffin, microwax, polyethylene wax, chlorinated polyethylene wax and other hydrocarbons, (b) stearic acid, lauric acid and other fatty acids, (c) Fatty acid monoamides or bisamides such as stearamide, palmitic acid amide, oleic acid amide, esylic acid amide, methylene bisstearamide, ethylene bisstearamide, (d) butyl stearate,
Hardened castor oil, ester type such as ethylene glycol monostearate, (e) alcohol type such as cetyl alcohol, stearyl alcohol, (f) lead stearate,
Metal soaps such as calcium stearate and (g) mixed systems thereof are generally used.

[Antioxidant]
Examples of the antioxidant used in the present invention include phenol-based antioxidants, sulfur-based antioxidants, and phosphite-based antioxidants.
As the phenolic antioxidant, both bisphenol type antioxidants and sterically hindered phenolic antioxidants are used. For example, bisphenol A, bisphenol B, bisphenol F, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (
3,5-ditert-butyl-4-hydroxyphenyl) -propionate, distearyl (3
, 5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,1,3-tris (2-methyl-4-hydroxy-5
Tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert Tributyl-4-hydroxylbenzyl) isocyanurate, triethylene glycol bis [(
3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
These phenolic antioxidants can be used alone or in combination, and may be used in combination with an antioxidant other than phenolic.

Examples of the sulfur-based antioxidant include dilauryl thiodipropionate, dimyristyl,
Examples include dialkylthiodipropionates such as distearyl and β-alkyl mercaptopropionates of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate).

Examples of the phosphite antioxidant include 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, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite And di (nonylphenyl) pentaerythritol diphosphite.
These antioxidants can be used alone or in combination, and may also be used in combination with other antioxidants.

[Light stabilizer]
Examples of the light stabilizer include hindered amine light stabilizers, such as 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl. Stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5- Ditertiarybutyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionate, bis (2 , 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6, -Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4 -Piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate Bis (2,2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di ( Tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxy) Carbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2,2) , 6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4 , 6-Bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12-tetraaza Dodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro-s-triazi / N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) And hexamethylenediamine / dibromoethane condensate.

[Organic phosphite]
Examples of organic phosphites include diphenyldecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (dinonyl). Phenyl) phosphite, trilauryltrithiophosphite, trilaurylphosphite, bis (neopentylglycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, diisodecylpentaerythritol diphosphite, tris (lauryl) -2-thioethyl) phosphite or the like is used.

[Impact enhancer]
As an impact strengthening agent, for example, a multi-component resin obtained by graft polymerization of monomers such as methyl methacrylate, styrene, and acrylonitrile on a copolymer rubber mainly composed of chlorinated polyethylene containing 30 to 40% chlorine and acrylic ester. Acrylonitrile / butadiene / styrene resin, metal methacrylate / butadiene / styrene resin, vinyl acetate / ethylene copolymer resin, and the like.

Inorganic compounds include aluminosilicate metal salt, magnesium hydroxide, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium silicate, talc, alkali aluminum composite hydroxide salt, calcium-magnesium solid solution, alkaline earth metal Examples thereof include silicate particles.

Alkaline earth metal silicates include magnesium silicate, calcium silicate, barium silicate, etc., but have substantially alkaline earth metal silicate on the surface of the alkaline earth metal hydroxide particles, As a whole, it is preferable that the molar ratio of SiO ₂ / MO (wherein M is an alkaline earth metal) is in the range of 0.01 to 0.90, preferably 0.10 to 0.30. As the alkaline earth metal (M), a composite of magnesium and calcium is preferable. In this case, the molar ratio of magnesium and calcium is preferably Mg: Ca = 10: 0 to 6: 4.

Flame retardants include, of course, halogenated flame retardants, antimony, zircon, molybdenum, aluminum, silica, titanium oxides, hydroxides and sulfides, zinc borate, zinc stannate, zinc hydroxystannate, and these zinc compounds. And metal hydroxide surface-treated products.

For the purpose of improving electrical insulation, amorphous silica, calcined kaolin, aluminum oxide, aluminum silicate, titanium white, titanium phosphate, zirconium phosphate and the like can be blended.

Other organic acid metal salt compounds can also be added as needed, specifically having 6 to 6 carbon atoms.
22 fatty acids such as caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, Alternatively, sodium, potassium, magnesium, calcium, barium and zirconium such as a mixture thereof can be used.

These organic acid metal salt compounds are blended in an amount of 0.1 to 5 parts by weight, preferably 0.1 to 1.0 parts by weight, per 100 parts by weight of the chlorinated vinyl chloride resin.

As the organic compounding agent, a silicone-based surface treatment agent, a fatty acid, and a fatty acid salt are used. Silicone surface treatment agents include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, cyclic polydimethylsiloxane, alkyl-modified silicone oil, amino-modified silicone oil, silicone polyether copolymer, diffusion pump oil, fatty acid Modified silicone oil, fluorosilicone oil, resin modifying oil, etc. can be used. It is particularly preferable to use dimethyl silicone oil.

[Composite stabilizer]
The stabilizer used in the present invention is in the form of powder, that is, in the form of powder or in the form of granules.
It can be used as a one-pack stabilizer. For the production of granules, extrusion granulation,
Known granulation methods such as spray granulation, rotary disk granulation, rolling granulation, and compression granulation can be used. The particle size of the powder can be arbitrarily adjusted according to the purpose, and it is generally preferable that the particle size is in the range of 50 μm to 5 mm, particularly 70 μm to 2 mm.

[Chlorinated vinyl chloride resin]
Examples of the vinyl chloride resin before chlorination used in the chlorinated vinyl chloride resin used in the present invention include, for example, vinyl chloride homopolymer; vinyl chloride monomer, and unsaturated bond copolymerizable with the vinyl chloride monomer. A copolymer with a polymerizable monomer having the following; a graft copolymer obtained by graft copolymerizing vinyl chloride with a polymer may be mentioned, and these may be used alone or in combination of two or more.

The polymerizable monomer having an unsaturated bond is not particularly limited, and examples thereof include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; butyl vinyl ether and cetyl. Vinyl ethers such as vinyl ether; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, and phenyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; N-phenylmaleimide N-substituted maleimides such as N-cyclohexylmaleimide and the like may be used, and these may be used alone or in combination of two or more.

The polymer for graft copolymerization of vinyl chloride is not particularly limited as long as vinyl chloride is graft-polymerized. For example, ethylene-vinyl acetate copolymer; ethylene-vinyl acetate-carbon monoxide copolymer; Ethylene-ethyl acrylate copolymer; ethylene-butyl acrylate-carbon monoxide copolymer; ethylene-methyl methacrylate copolymer; ethylene-propylene copolymer; acrylonitrile-butadiene copolymer; polyurethane;
Chlorinated polyethylene; chlorinated polypropylene and the like may be mentioned, and these may be used alone or in combination of two or more.

The chlorinated vinyl chloride resin used in the present invention may be used not only as a polymer as described above but also in a blend with other resins. For example, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyethylene, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer Also, it can be blended with an acrylic resin or the like at a predetermined ratio.

The molding process of the chlorinated vinyl chloride resin composition of the present invention can be carried out by various molding methods such as extrusion molding, injection molding, compression molding, inflation, calendering, coating, etc. after mixing or mixing by known methods. it can.

  The invention is illustrated in more detail by the following examples. The test method was as follows.

(1) Blacking time The sheet obtained according to the following mixed composition preparation conditions was cut and placed in a gear oven heated to 185 ° C., and the time until the sheet was completely blackened was measured.
(Mixing composition preparation conditions)
The following compound A was premixed and then kneaded for 3 minutes at 185 ° C. with an 8-inch roll to obtain a thickness of 1
mm sheets were obtained.
Compound A part by weight
100 parts of CPVC (HA-53K manufactured by Sekisui Chemical Co., Ltd.)
Impact strengthening agent (Kureha Chemical Industries Kureha BTA-751) 5.0 parts
Lubricant (SL-02 made by RIKEN vitamins) 1.5 parts
Stabilizer See table

(2) Vicat softening point The sheet obtained according to the above mixing composition preparation conditions is cut and preheated with a 190 ° C. press 3
For 5 minutes at a pressure of 10 MPa to produce a sheet having a thickness of 3 mm. JIS K-7206 (Vicat softening temperature test method) using a softening temperature measuring device (model: S-3M) manufactured by Toyo Seiki Seisakusho Co., Ltd.
In accordance with the following conditions.
Load: 50N
Temperature increase rate: 50 ° C / hr

(Examples 1 to 10)
Each evaluation was performed by adding the number of parts shown in Table 1 to 100 parts by weight of CPVC. The results are shown in Table 1.

(Comparative Examples 1-8)
Each evaluation was performed by adding the number of parts shown in Table 2 to 100 parts by weight of CPVC.
The results are shown in Table 2.

Claims (6)

  It is characterized by containing (A) 0.1 to 10 parts by weight of a tertiary phosphate and (B) 0.01 to 10 parts by weight of an organotin stabilizer for 100 parts by weight of a chlorinated vinyl chloride resin. A stabilized chlorinated vinyl chloride resin composition.   The chlorinated vinyl chloride resin composition according to claim 1, wherein the (A) triphosphate is tricalcium phosphate.   (B) The chlorinated vinyl chloride resin composition according to claim 1 or 2, wherein the organotin stabilizer is an alkyl mercaptotin stabilizer.   The chlorinated vinyl chloride resin composition according to any one of claims 1 to 3, further comprising at least one selected from magnesium-aluminum composite oxide, dawsonite, and zeolite (C).   The chlorination according to claim 4, wherein the magnesium-aluminum composite oxide, dawsonite, and zeolite (C) are present in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the chlorinated vinyl chloride resin. Vinyl chloride resin composition.   The chlorinated vinyl chloride resin composition according to claim 4, wherein the magnesium-aluminum composite oxide is a hydrotalcite compound.