JPH0131545B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a halogen-containing resin composition, and more specifically, a halogen-containing resin composition that contains an octyltin mercaptide compound and a dioctyltin diisostearate as a stabilizer, has excellent thermal stability and lubricity, and is resistant to plate-out and bloom. The present invention relates to a resin composition. When halogen-containing synthetic resins are subjected to heat molding, they tend to undergo thermal decomposition mainly due to dehydrohalogenation, resulting in deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. Maneku. In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Many stabilizers have been used for this purpose, such as metallic soaps, organotin compounds, epoxy compounds, polyhydric alcohols, organophosphorus compounds, organosulfur compounds, phenolic compounds, and ultraviolet absorbers. Among them, organic tin compounds are known as outstanding heat stabilizers, but they are insufficient to prevent the thermal deterioration of resins under harsh processing conditions, and they do not prevent the discoloration of resins due to thermal deterioration, especially the initial discoloration. cannot be prevented. In addition, sulfur-containing organotin compounds such as organotin mercaptide and organotin mercaptocarboxylate have relatively excellent thermal stability among organotin stabilizers and are characterized by little initial coloring. In processing resins under such conditions, thermal stability and initial coloring properties are still insufficient, and these sulfur-containing organotin compounds also inherently have the disadvantage of poor processability, weather resistance, etc. Furthermore, although organic tin carboxylate compounds have relatively good processability, their thermal stability and colorability are insufficient and are unsatisfactory for practical use. Although it has been proposed to use a sulfur-containing organotin compound and an organotin carboxylate in combination, the effects of the conventionally known combinations are still insufficient, and further improvements are needed. Moreover, most of the conventionally used organic tin compounds are butyltin compounds, and because butyltin compounds are toxic, their use is often restricted. It has been desired to improve the stability, colorability, processability, etc. of the resin contained. In order to solve these problems, the inventors of the present invention have made extensive studies and found that it has excellent stability against deterioration due to light and heat, has very low toxicity, has excellent lubricity, and has excellent plate compatibility. We have succeeded in developing a halogen-containing resin composition that is less likely to cause outflow and bloom. That is, in the present invention, 100 parts by weight of the halogen-containing resin,
(a) Formula n-C ₈ H ₁₇ Sn[S(CH ₂ ) _n COOR] ₃ , (n-
C ₈ H ₁₇ ) ₂ Sn [S (CH ₂ ) _n COOR] ₂ or [(n-
0.01 to 3 _parts by weight of at least one of C8H17) _2SnS ( _CH2 ) _nCOO ] (in the formula, R represents an alkyl group having 8 to 18 carbon atoms; m represents 1 _or 2); and (b)
G-n-octyltin diisostearate from 0.01
The object of the present invention is to provide a halogen-containing resin composition in which 5 parts by weight of the halogen-containing resin composition is added. Compounds represented by the formula n-C ₈ H ₁₇ Sn [S(CH ₂ ) _n COOR] ₃ used in the present invention include n-octyltin tris(2-ethylhexylmercaptoacetate), n-octyltin tris(iso octyl mercaptoacetate),
n-octyltin tris (cetylmercaptoacetate), n-octyltin tris (lauryl mercaptoacetate), n-octyltin tris (n-
octylmercaptoacetate), n-octyltin tris (2-ethylhexylmercaptopropionate), n-octyltin tris (isooctylmercaptopropionate), n-octyltin tris (stearylmercaptopropionate)
etc. can be mentioned. Also, the formula: (n-C ₈ H ₁₇ ) ₂ Sn [S (CH ₂ ) _n COOR] ₂
Compounds represented by include di-n-octyltin bis(isooctylmercaptoacetate), di-n-octyltin bis(2-ethylhexylmercaptoacetate), di-n-octyltin bis(myristylmercaptoacetate), and di-n-octyltin bis(myristylmercaptoacetate). -n-octyltin bis(lauryl mercaptoacetate),
D-n-octyltin bis (cetyl mercaptoacetate), di-n-octyl tin bis (C _12-15 alkyl mercaptoacetate), di-n-octyl tin bis (stearyl mercaptoacetate), di-n-octyl tin bis (iso-tridecyl mercaptoacetate), di-n-octyltin bis(iso-octadecyl mercaptoacetate), di-
Examples include n-octyltin bis(isooctylmercaptopropionate), di-n-octyltinbis(laurylmercaptopropionate), and di-n-octyltinbis(stearylmercaptopropionate). In addition, when using octyltin mercaptoalkanoic acid ester salt as the octyltin mercaptide compound, mono-n-octyltin tris(mercaptoalkanoic acid ester) salt and di-n-octyltin bis(mercaptoalkanoic acid ester) salt are used in combination. It is preferable to do so. The amount of the octyltin mercaptide compound according to the present invention added is 0.01 to 3 parts by weight per 100 parts by weight of the resin, and the amount of dioctyltin diisostearate added is 0.01 to 5 parts by weight per 100 parts by weight of the resin. be. The polymer composition of the present invention includes phthalate plasticizers or other ester plasticizers, polyester plasticizers, phosphate plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers. can be used as appropriate depending on the purpose. Adding an antioxidant to the polymer composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so it can be used as appropriate depending on the purpose of use.
These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like. If an ultraviolet absorber is added to the polymer composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates,
In particular, nickel or chromium salts or chelates, triazine types, etc. are included. Others, as necessary, such as metal soaps, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants,
Fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, photodegradants, nonmetallic stabilizers, boric acid esters, thiourea derivatives, processing aids, mold release agents, reinforcing agents, etc. may be included. can. Examples of the halogen-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride,
Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride, vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer Polymer, 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-isoprene copolymer, vinyl chloride-chlorine propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-malic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, Halogen-containing synthetic resins such as vinyl chloride-acrylonitrile copolymers and internally plasticized polyvinyl chloride, and the above halogen-containing synthetic resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, or ethylene-acetic acid. Polyolefins such as vinyl copolymers and ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer,
Blended products with acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, etc. can be mentioned. The following examples illustrate the effects of the halogen-containing polymer composition according to the present invention, but the present invention is not limited to these examples. Example 1 A sheet with a thickness of 1 mm was prepared by kneading roll processing using the following formulation, and a heat deterioration test at 190°C, heat coloring after 60 minutes at 190°C, and initial coloring test were conducted. The results are shown in Table 1. (Formulation) PVC (Geon103EP8) 100 parts by weight Stearyl alcohol 0.5 Polyethylene wax 0.3 Stabilizer (Table 1) (Table 1) The evaluation method for thermal coloring and initial coloring tests is on a 10-point scale: 1 (good) ←→ It was given a score of 10 (bad).

【table】

[Table] Example 2 A test was conducted in the same manner as in Example-1 using the following formulation. The results are shown in Table 2. (Composition) PVC (Geon103EP8) 100 parts by weight Impact modifier (Metablen W-529) 5 Processing aid (Metablen P-700) 1 Stabilizer (Table 2) (Table 2)

【table】

[Table] Example 3 A test was conducted in the same manner as in Example-1 using the following formulation. The results are shown in Table 3. (Composition) PVC (Geon103EP8) 100 parts by weight Impact modifier (Kane Ace B-22)
5 Dioctyl phthalate 1.5 Stearyl alcohol 0.5 Montan wax 0.2 Stabilizer (Table 3) (Table 3)

【table】

[Table] Example 4 A test was conducted in the same manner as in Example-1 using the following formulation. The results are shown in Table 4. (Composition) PVC (Geon103EP8) 100 parts by weight Impact modifier (Kane Ace FM) 15 Processing aid (Kane Ace PA-20) 2 Charcoal 5 Polyethylene wax 1 Stabilizer (Table 4) (Table 4)

【table】

【table】

Claims (1)

[Scope of Claims] 1. 100 parts by weight of halogen-containing resin, (a) formula n-
C ₈ H ₁₇ Sn [S (CH ₂ ) _n COOR] ₃ , (n-C ₈ H ₁₇ ) ₂ Sn
[S(CH ₂ ) _n COOR] ₂ or [(n-C ₈ H ₁₇ ) ₂ SnS
(CH ₂ ) _n COO] (in the formula, R represents an alkyl group having 8 to 18 carbon atoms. m represents 1 or 2) and (b) di-n -A halogen-containing resin composition containing 0.01 to 5 parts by weight of octyltin diisostearate.