JP3284654B2 - Solid stabilizer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid stabilizer composition used for processing a thermoplastic resin and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, when a thermoplastic resin is heated and processed, various additives have been used because the resin alone is not capable of processing because of a severe thermal change. .

For example, organic tin stabilizers, metal soap stabilizers, epoxy stabilizers, organic phosphorus stabilizers, lubricants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, pigments, fillers, etc. No.

[0004] Under such circumstances, when a liquid stabilizer is added to a resin, particularly as an additive to be added to the resin, the resin and the liquid material are not uniformly mixed, and a so-called Mamako phenomenon is likely to occur.

[0005] This is a problem especially when the resin is a chlorine-containing resin and the liquid is an organic tin stabilizer.

Accordingly, the present inventors have aimed to find a stabilizer composition and a method for producing the same which solve the above problems.

[0007]

SUMMARY OF THE INVENTION A stabilizer composition according to the present invention comprises a solid stabilizer composition for a thermoplastic resin comprising, as a main component, 150 to 400 parts by weight of a dipentaerythritol fatty acid ester per 100 parts by weight of an organotin stabilizer. It is.

The method for producing the composition according to the present invention is characterized in that the ester and the organotin stabilizer are sufficiently mixed at a temperature not lower than the temperature at which the ester is melted, and the mixture is cooled and solidified. It is a manufacturing method.

Here, the organic tin stabilizer is dimethyltin bis (isooctyl mercaptoacetate) 〃 (2-ethylhexyl mercaptoacetate) 〃 (lauryl mercaptide) 〃 (suraaryl mercaptide) 〃 (mercaptoethyl tall oil) (Fatty acid ester) 〃 (mercaptoethyl butyl succinate) 〃 (2-mercaptoethyl caprylate) 〃 (2-mercaptoethyl stearate) 〃 (2-mercaptoethyl oleate) 〃 (2-hydroxy C _{10 to} C ₁₄ mixed) (Alkyl mercaptide) 〃 (2-octanoyl oxide decyl mercaptide) 〃 (2-lauroyl oxide decyl mercaptide) 〃 (isooctyl mercapto propionate) 〃 (monothioglycol octylate) monomethyl tin Squirrel (isooctylmercaptoacetate) 〃 (2-ethylhexylmercaptoacetate) 〃 (laurylmercaptide) 〃 (suraarylmercaptide) 〃 (mercaptoethyl-tol-to-fatty acid ester) 〃 (mercaptoethyl-butylsuccinate) 〃 (2-mercaptoethyl caprylate) 〃 (2-mercaptoethyl stearate) 〃 (2-mercaptoethyl oleate) 〃 (2-hydroxy C ₁₀ -C ₁₄ mixed alkyl mercaptide) 〃 (2-octanoyl oxide decyl) (Mercaptide) 〃 (2-lauroyloxidedecylmercaptide) 〃 (isooctylmercaptopropionate) 〃 (monothioglycoloctylate) dimethyltin sulfide dimethyltin-β-mercaptopropione Tobis [monomethyltin di (isooctylmercaptoacetate) sulfide] [[(isooctylmercaptopropionate)]] [[((monothioglycoloctylate)]] poly (thiobis-n-methyltinsulfide) dibutyl Tin bis (isooctyl mercapto acetate) 〃 (2-ethylhexyl mercapto acetate) 〃 (lauryl mercaptide) 〃 (stearyl mercaptide) 〃 (mercaptoethyl tall oil fatty acid ester) 〃 (mercaptoethyl butyl succinate) 〃 (2-mercaptoethyl caprylate) 〃 (2-mercaptoethyl stearate) 〃 (2-mercaptoethyl oleate) dibutyltin bis (alkyl mercaptide mixed with 2-hydroxy C4 _{10 to} C ₁₄ ) 〃 (2-octanoyl oxide decyl mercaptide) 〃 (2-lauroyl oxide decyl mercaptide) 〃 (isooctyl mercaptopropionate) 〃 (monothioglycol octylate) monobutyltin tris (isooctyl mercaptoacetate) 〃 (2-ethylhexyl mercaptoacetate) 〃 (lauryl mercaptide) 〃 (stearyl mercaptide) 〃 (mercaptoethyl tall oil fatty acid ester) 〃 (mercaptoethyl butyl succinate) 〃 (2-mercaptoethyl caprylate) ) 〃 (2-mercaptoethyl stearate) 〃 (2-mercaptoethyl oleate) 〃 _(2-hydroxy-C 10 _{-C 14} mixed A rutile Melka descriptor id) 〃 (2-octanoyloxy dodecyl Melka descriptor ) (2-Lauroyloxidedecylmercaptide) 〃 (isooctylmercaptopropionate) 〃 (monothioglycoloctylate) poly (thiobis-n-butyltin sulfide) dioctyltin bis (isooctylmercaptoacetate) 〃 (2-ethylhexyl mercaptoacetate) 〃 (lauryl mercaptide) 〃 (stearyl mercaptide) 〃 (mercaptoethyl tall oil fatty acid ester) 〃 (mercaptoethyl butyl succinate) 〃 (2-mercaptoethyl caprylate) ) Dioctyltin bis (2-mercaptoethyl stearate) 〃 (2-mercaptoethyl oleate) 〃 (2-hydroxy C ₁₀ -C ₁₄ mixed alkyl mercaptide) 〃 (2-octanoyl oxide decyl) (Mercaptide) 〃 (2-Lauroyloxidedecylmercaptide) 〃 (Isooctylmercaptopropionate) 〃 (Monothioglycoloctylate) Monooctyltin tris (Isooctylmercaptoacetate) 〃 (2-Ethylhexylmercaptoacetate) 〃 (Lauryl mercaptide) 〃 (stearyl mercaptide) 〃 (mercaptoethyl tall oil fatty acid ester) 〃 (mercaptoethyl butyl succinate) 〃 (2-mercaptoethylcaprylate) 〃 (2-mercaptoethyl stearate) ) 〃 (2-mercaptoethyl oleate) 〃 _(2-hydroxy-C 10 _{-C 14} mixed alkyl Melka descriptor id) 〃 (2-octanoyloxy-dodecyl mercaptan Tide) 〃 (2-lauroyl peroxide (Silmercaptide) 〃 (isooctylmercaptopropionate) 〃 (monothioglycoloctylate) poly (thiobis-n-octyltin sulfide) dipropyltin sulfide, dibutyltin sulfide, dibenzyltin sulfide, dihexyltin sulfide, Di-2-ethylhexyltin sulfide, di (isobutyl) tin sulfide, di (isoamyl) tin sulfide, di (isohexyl) tin sulfide, 2-ethylbutyltin sulfide, butyltin sesquisulfide, hexyltin sesquisulfide, isooctyltin sesquisulfide , Heptyltin sesquisulfide, n-octyltin sesquisulfide, S-butyltin sesquisulfide, propyltin sesquisulfide, isoamyltin sesquisulfide Fido, compounds and mixtures of two or more of these such as 2-ethylhexyl tin sesqui sulfide and the like. Most of these are liquid but some are solid.

The ester referred to here is a fatty acid ester of dipentaerythritol, specifically, dipentaerythritol hexastearate.

The composition of the present invention may further comprise, if necessary,
For example, crosslinking agents, pigments, fillers, foaming agents, antistatic agents, anti-fogging agents, plate-out preventing agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, anti- ● agents, bactericides, metal deactivators, light Deterioration agents, processing aids, release agents, reinforcing agents, stabilizers other than organotin stabilizers, and the like can be included.

Although the resin to which the composition of the present invention is applied is a thermoplastic resin, it is blended and used mainly when processing a chlorine-containing resin.

For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, post-chlorinated vinyl chloride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer Copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-
Maleic anhydride terpolymer, vinyl chloride-styrene-
Acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isobrene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid Halogen-containing synthetic resins such as ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the above-mentioned halogen-containing resins And polyethylene, polypropylene, polybutene, α-olefin polymer such as poly-3-methylbutene or ethylene-vinyl acetate copolymer, polyolefin such as ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, styrene And other monomers (eg anhydrous Copolymers with oleic acid, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, acrylate-butadiene-styrene copolymer, blended products with methacrylate-butadiene-styrene copolymer, etc. Can be mentioned.

The compounding ratio of the organotin stabilizer and the ester is at least 150 parts by weight based on 100 parts by weight of the organotin stabilizer.

When the amount of the ester is 150 parts by weight or less, the solid stabilizer composition becomes soft, and there is a problem in handling and use.

On the other hand, when the amount of the ester exceeds 500 parts by weight, the relative ratio of the organotin stabilizer to the ester decreases, and when the lubricity is the same, the amount of the organotin stabilizer becomes insufficient. cause.

Conversely, when the amount of the organotin stabilizer is the same,
The thermal stability is satisfactory, but the quality is reduced due to excess ester.

The solid stabilizer composition according to the present invention is used in a known form, for example, in the form of granules, flakes, pellets or the like, if necessary.

When granulated, the average particle size is usually 0.1 mm.
When it is less than 0.1 mm, dust tends to be formed, and when an automatic weighing machine is used, it does not flow sufficiently.

If it is more than 10 mm, it is too large to be sufficiently dispersed when added to the resin.

The method for producing the solid stabilizer composition according to the present invention is obtained by sufficiently mixing a predetermined amount of an organotin stabilizer and a predetermined amount of dipentaerythritol fatty acid ester at a temperature above the melting point of the ester, and cooling and solidifying the mixture. Can be

Specifically, a known method is applied. For example, extrusion granulation (screw type, ram type, roll type, cylindrical type, etc.), crushing type granulation, injection granulation (plasma type, deformation type, air cooling injection type, spray drying granulation (rotating disk type,
Nozzle type). (“Latest Powder Process Technology Integration (Basic Technology Crepe)”, published by the Industrial Technology Center Co., Ltd.
Editing The latest powder process technology compilation editorial committee, 12
(Pages 7 to 145)

As a method for forming a flake, there is a method in which a molten liquid is adhered on a metal plate in a thin film form, solidified, and then scraped off with a knife to form a flake. (Editor of "Chemical Engineering Handbook"
Published by The Chemical Engineering Association Maruzen p68
9)

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments.

[0025]

EXAMPLES 1-4, COMPARATIVE EXAMPLES 1-3 Dipentaerythritol hexastearate (melting point) per 100 parts by weight of di-n-octyltin bis (isooctylmercaptoacetate) (trade name: TN-870, manufactured by Sakai Chemical) 66 ° C) to 120
Each part by weight shown in Table 1 was mixed in a completely liquid state at a temperature of ° C., made into a uniform liquid, poured into a stainless steel vat, and cooled and solidified.

The surface of the obtained solid product was pressed with a finger, and the surface was solid. The bleeding of di-n-octyltin bis (isooctylmercaptoacetate) was determined.

As comparative examples, 100 parts by weight of dipentaerythritol hexastearate, 100 parts by weight of polyethylene wax, and 200 parts by weight were used for determination.

[0028]

Example 5 100 parts by weight of a mixture of dimethyltin bis (isooctylmercaptoacetate) and monomethyltin tris (isooctylmercaptoacetate), 300 parts by weight of RIQUESTER SL-02 (dipentaerythritol hexastearate manufactured by RIKEN VITAMIN) and SC -100
160 parts by weight of calcium stearate (manufactured by Sakai Chemical) were uniformly melted at about 100 ° C. in a heating kneader, dispersed by adding 100 parts by weight of gray pigment, poured into a stainless steel vat, and cooled and solidified.

2. Pulverize with a feather mill (5 mm net).
A granular stabilizer composition having sieving fluidity was obtained through a 5-mesh net.

[0030]

Comparative Example 4 Like the fifth embodiment, RIQUESTER SL-0
A granular stabilizer composition was obtained using 300 parts by weight of High Wax 200P (polyethylene wax manufactured by Mitsui Petrochemical) instead of 2.

[0031]

Example 6 A vinyl chloride pipe was extruded using the granular stabilizer produced in Example 5, and the extrusion amount and surface properties were observed.

Formulation Granular stabilizer of Example 5 2 {charcoal 3}

The temperature was raised to 90 ° C. with a supermixer and the mixture was discharged, and a VP-20 pipe was extruded.

At an extrusion rate of 114 kg / H, a clean pipe having a good surface and inner surface was obtained.

[0035]

Comparative Example 5 A pipe of VP-20 was extruded under the same conditions as in Example 6 using the stabilizer obtained in Comparative Example 4.

The extrusion rate was 93 kg / H, which was lower than that of Example 6, and the surface and the inner surface of the pipe were finely roughened.

[0037]

As explained in detail above, the solid stabilizer composition according to the present invention overcomes the drawbacks which have conventionally been a problem when solidifying a liquid organotin stabilizer and adding it to a resin. It was possible to provide a manufacturing method therefor.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-4738 (JP, A) JP-A-53-102353 (JP, A) JP-A-55-125144 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 27/06

Claims (2)

(57) [Claims] A solid stabilizer composition for a thermoplastic resin comprising 100 parts by weight of di-n-octyltin bis (isooctylmercaptoacetate) and 150 to 400 parts by weight of dipentaerythritol hexastearate as main components. 2. A solid for a thermoplastic resin , wherein the ester and di-n-octyltin bis (isooctylmercaptoacetate) are sufficiently mixed at a temperature not lower than the melting point of the ester according to claim 1 , and the mixture is cooled and solidified. A method for producing a stabilizer composition.