JPS6150978B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a chlorine-containing resin composition, and its purpose is to provide a chlorine-containing resin composition that is non-toxic or low-toxic and has excellent heat resistance, initial coloring properties, and transparency. . Chlorine-containing resins, such as polyvinyl chloride resin, have various problems such as significant discoloration and decomposition due to heat during processing, and deterioration with long-term use. It is customary to add various stabilizers to the product. Conventionally used butyltin stabilizers, lead stabilizers such as tribasic lead sulfate, tribasic lead maleate, lead stearate, and stabilizers such as cadmium stearate have excellent performance. , their toxicity has become a problem, and in recent years, various non-toxic or low-toxic stabilizers have been proposed to replace them, and have come into widespread use. As such stabilizers, various compounds such as barium, calcium, magnesium, zinc, etc., organic octyltin compounds, organic phosphorus compounds, epoxy compounds, etc. are used.
In particular, zinc compounds have insufficient heat resistance, so it is common to use them in combination with other stabilizer components.
Although various combination formulations have been provided, they all have advantages and disadvantages, and are still not sufficient. In order to meet these strict demands, the present inventors have conducted numerous experimental studies over a long period of time, and have finally developed a low-toxicity or non-toxic resin that can replace lead-based stabilizers by combining them as shown below. The inventors have discovered that a composition can be obtained, and have completed the present invention. The present invention uses (1) general formula as a stabilizer component. [(ROOCCH ₂ CH ₂ ) ₂ SnOOCCH=CHCOO] One or more compounds represented by _p , where R is an alkyl group having 1 to 18 carbon atoms, and X is -
S(CH ₂ )nCOOR', -SR', -OOCR'-
OOCCH=CHCOOR′, -OR′, R′ is 1
Indicates an alkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, and an alkoxyalkyl group having up to 18 carbon atoms. n represents an integer of 1 to 4, and P represents an integer of 1 to 10. (2) Organic acid metal salts (3) Alkali or alkaline earth metal oxides, hydroxides, carbonates, sulfates, phosphates, phosphites, silicates, borates, titanates Alternatively, it is a chlorine-containing resin composition containing one or more selected from these basic salts, and by such a combination, it is possible to achieve low toxicity and excellent heat resistance, initial coloring property, and transparency. Thus, a composition with a high degree of stability can be obtained. general formula [(ROOCCH ₂ CH ₂ ) ₂ SnOOCCH=CHCOO] Examples of the ester tin compound represented by _p include the following compounds. Bis(carbomethoxyethyl)tin diisooctylmercaptoacetate bis(carbomethoxyethyl)tin diisooctylmercaptopropionate bis(carbomethoxyethyl)tin lauryl mercaptopropionate bis(carbomethoxyethyl)tin ethylene glycol bismercaptopropionate pionate bis(carbomethoxyethyl)tin distearylcaptopropionate bis(carbomethoxyethyl)tin sulfide bis(carbomethoxyethyl)tin dilauryl mercaptide bis(carbomethoxyethyl)tin distearyl mercaptite bis(carbomethoxyethyl) ethyl) tin dilaurate, bis(carbomethoxyethyl), tin distearate, bis(carbomethoxyethyl), tin dibutyl maleate, bis(carbomethoxyethyl), tin maleic acid polymer, etc., and their preferred blending amounts are based on 100 parts of resin. It is 0.01 to 4 parts by weight. Conventionally, organotin compounds for use as stabilizers are represented by the general formula R ₂ SnX ₂ , R ₂ SnO, R ₃ SnX, R ₃ Sn-O-SnR ₃ (R is an alkyl group, a phenyl group, and X is a halogen). Derivatives of compounds are known, among which derivatives where R is an octyl group are known to be nontoxic. However, octyltin derivatives in which R is an octyl group are expensive to manufacture and are not necessarily satisfactory in terms of heat resistance, transparency, etc. In comparison, the ester tin compound used in the present invention is cheaper and has superior performance, and is particularly effective when used in a combination composition as in the present invention. Examples of the organic acid metal salts include the following compounds. As metal salts of organic acids, the metal components are Ca, Mg,
Ba, Sr, or Zn, and the organic components are benzoic acid, salicylic acid, pt-butylbenzoic acid, lauric acid, myristic acid, balmitic acid, stearic acid, ricinoleic acid, linoleic acid, linoleic acid, and oleic acid. acid, neodecanoic acid, 2-ethylhexoic acid, naphthenic acid, behenic acid, isostearic acid, carbolic acid, octylcarboxylic acid, nonylcarboxylic acid, etc., and the preferred blending amount of these is 0.1 to 5 parts by weight per 100 parts of resin. . Commonly used as alkali or alkaline earth metal oxides, hydroxides, carbonates, sulfates, phosphates, phosphites, silicates, borates, titanates, or their basic salts. Any compound known in the art may be used, and a suitable amount of these compounds is 0.05 to 3 parts by weight per 100 parts of resin. In addition to the above-mentioned stabilizer components, other stabilizer components and stabilizing aid components may be added to the composition of the present invention. In addition, plasticizers, foaming agents, antistatic agents, flame retardants, surfactants,
Various additives such as colorants, mold release agents, viscosity modifiers, antifungal agents, ultraviolet absorbers, fillers, etc. may be added. The stabilizer component and other additives may be added to the resin as they are, or may be added in the form of a mixed one-pack or in the form of a composite granule that is granulated and integrated. Chlorine-containing resins to which the present invention can be applied include polyvinyl chloride resins, copolymers of vinyl chloride and other monomers such as vinyl acetate, ethylene, maleic acid, acrylonitrile, butadiene, styrene, vinylidene chloride, and polyvinylidene chloride. , chlorinated polyolefin, chlorinated rubber, etc. This will be explained in detail below using examples. Example 1 To 100 parts by weight of vinyl chloride resin, 0.5 parts of zinc stearate, 0.5 parts of pentaerythritol, 0.5 parts of stearyl alcohol, and the prescribed amounts of the compounds shown in Table 1 were added, and the mixture was heated to 170 parts using a heated roll for testing. A sheet with a thickness of 0.2 mm was prepared by kneading at ℃ for 5 minutes. The sheet was then exposed in a gear oven at 180°C and the time to blackening was measured to test heat resistance. Further, the sheet was pressed at 170° C. for 5 minutes to evaluate initial colorability and transparency. The results are shown in Table 1.

[Table] Example 2 To 100 parts by weight of vinyl chloride resin, 50 parts of DOP (dioctyl phthalate), 0.2 parts of calcium stearate, 1.0 part of zinc stearate, 1.0 part of polyethylene wax, and the specified amounts of the compounds shown in Table 2 were added. In addition, heat resistance, initial colorability, and transparency were tested in the same manner as in Example-1.

[Table] Example 3 0.2 parts of bis(carbomethoxyethyl)tin di-i-octyl acetate, 0.5 parts of barium maleate, 1.0 parts of butyl stearate and the compounds shown in Table 3 were added to 100 parts by weight of vinyl chloride resin. A predetermined amount was added to produce a sheet in the same manner as in Example 1, and the heat resistance and initial colorability were tested.

[Table] Example 4 To 100 parts by weight of vinyl chloride resin, 50 parts of dioctyl phthalate, 0.2 parts of barium stearate,
A sheet was prepared in the same manner as in Example 1 by adding 0.7 part of zinc stearate, 0.3 part of di(carbomethoxyethyl)tin dilaurate, and a predetermined amount of the compound shown in Table 4, and the heat resistance was tested. Also, cut the sheet into small pieces, put 2g of this into a test tube, fix Congo Red test paper at the tube opening, and
The test tube was immersed in an oil bath kept at ℃, and the time required for the test paper to turn blue due to the generation of hydrogen chloride due to thermal decomposition was measured to evaluate the hydrochloric acid scavenging ability.

【table】

Claims (1)

[Claims] 1. As a stabilizer component (1) General formula [(ROOCCH ₂ CH ₂ ) ₂ SnOOCCH=CHCOO] One or more compounds represented by _P , where R is an alkyl group having 1 to 18 carbon atoms, and X is -
S(CH ₂ ) _o COOR', -SR', -OOCR', -
OOCCH=CHCOOR′, -OR′, R′ is 1
Indicates an alkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, and an alkoxyalkyl group having up to 18 carbon atoms. n represents an integer of 1 to 4, and P represents an integer of 1 to 10. (2) Organic acid metal salts (3) Alkali or alkali, earth metal oxides,
A chlorine-containing resin composition containing one or more selected from hydroxides, carbonates, sulfates, phosphates, phosphites, silicates, borates, titanates, or basic salts thereof.