JPS606749A - Halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide a stabilized halogen-contg. resin compsn. having improved transparency and resistance to discoloration and weather, by incorporating hypophosphorous acid or a hypophosphite metal salt in a halogen-contg. resin. CONSTITUTION:A stabilized halogen-contg. resin compsn. is obtd. by incorporating hypophosphorous acid or a metal hypophosphite such as sodium hypophosphite in a halogen-contg. resin such as PVC or chlorinated polyethylene. The halogen-contg. resins such as PVC or chlorinated polyethylene. The halogen- contg. resins such as PVC are deteriorated by heat during molding and articles prepd. therefrom are discolored by ultraviolet rays. Accordingly, they do not give excellent articles. By adding hypophosphorous acid and/or its metal salt, the transparency and resistance to discoloration and weather can be greatly improved. 0.01-5.0pts.wt. hypophosphorous acid or metal salt is added to 100pts.wt. resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a stabilized composition of a chlorine-containing resin. More specifically, the present invention relates to a stabilized composition of a rogen-containing resin that has improved color resistance, weather resistance, and transparency.

Generally, it is known that polyvinyl chloride and other chlorine-containing resins become colored due to heat deterioration during molding and weather resistance deterioration mainly due to ultraviolet rays after the product is made, making it impossible to produce an excellent product. There is. In order to improve these problems, metal salt compounds, epoxy compounds, antioxidants, ultraviolet absorbers, organic phosphite esters and the like have been used singly or in any combination thereof. Organic phosphorous esters and ultraviolet absorbers are particularly effective in improving weather resistance, but a fully satisfactory product has not yet been obtained.

In view of these points, as a result of intensive studies, the present inventors have discovered that hypophosphorous acid and its metal salt compounds have a remarkable effect on improving color resistance, weather resistance, and transparency, leading to the present invention.

Conventionally, for ABS resin, polyolefins were produced by using C (Japanese Patent Publication No. 42-12530) using hypophosphite as a stabilizer, and alkaline earth metal salts of the following group phosphates in combination with phosphorus compounds having a specific structure. Adding flame retardancy to etc. (
JP-A-51-109940) μ is known to be 1%, but the fact that these compounds contribute to the stabilization of I-containing resins was completely unexpected and the discovery was surprising.

[Structure of the invention]

The present invention further specifically includes hypophosphorous acid and or its metal salts.

This is a stabilized halogen-containing/resin compound composition obtained by adding one or more of the compounds represented by the general formula to a cogen resin. Among the metals represented by M in the above general formula, ,
Group (a) metals include Li, Na, K, etc., and group (2) metals include iMg, Oa, Ba, Zn.

cd etc., and as alkyltin, mono, di, tristylstin, mono, dibutyltin, mono, di.

Examples include trioctyltin.

Representative examples of compounds used in the present invention are as follows:
(Black is shown in Examples below).

[Representative compounds]

Black 1 Hypophosphite shop 2 Lithium hypophosphite boiled 4 Potassium hypophosphite A5 Magnesium hypophosphite plate 6 Calcium hypophosphite plate 7 Barium hypophosphite, volume 8 Zinc hypophosphite A9 Cadmium hypophosphite A l 0th Manganese phosphite A I 1 Nickel hypophosphite 1 to 12 Cadmium hypophosphite 1613 Dibutyltin hypophosphite A14 Dioctyltin hypophosphite A, 15 Monomethyltin hypophosphite [Halogen-containing resin to be stabilized] Stable in the present invention Examples of halogen-containing resins that are subject to Chemical Formula 9 are as follows.

Polyvinyl chloride, copolymers of vinyl chloride and compounds that can be copolymerized with it, graft polymers, block polymers (comonomers include olefins such as ethylene and propylene, vinyl acetate, vinyl laurate, methyl methacrylate) saturated acid vinyl esters, such as
unsaturated acid alkyl esters, noalkyl vinyl ethers such as lauryl vinyl needles, maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, vinyliso7 fluoride, etc.), and polyvinyl chloride, such as acrylonitrile-butadiene-styrene, methacrylic acid. Polymer blends of methyl ester-butadiene-styrene ternary boron, chlorinated polyethylene, ethylene-vinyl acetate copolymers, etc., polyvinyl chloride post-treated products with alcohol etc., post-chlorinated products, etc., and these resins. There are polymer funds, etc.

In the present invention, the amount of the compound having the above general formula added is 0.01 to 5.0 parts by weight per 100 parts by weight of the resin.

[Example of substances that can be used together]

In the present invention, all of the compounds shown below can be included together with these compounds as necessary.

That is, acidic, neutral, and basic D-a group, I[a group, ■b group,
■It is an organic acid salt of group b, and the organic acids used in these include 2-ethylhequinic acid, neo acid, lauric acid, stearic acid, instearic acid, hydroxystearic acid, ricinoleic acid, oleic acid, caproic acid. , palmitic acid, 12-hydroxystearic acid, myristic acid, octylic acid, inoctylic acid, nophenylstearic acid,
Or a dibasic acid such as maleic acid, malonic acid, sebacic acid, azerai/acid, adipic acid, phthalic acid, cyclohexanocarboxylic acid and a straight chain or side chain of 1 to 18 carbon atoms, substituted or unsubstituted, saturated or Unsaturated alcohol, alkoxy alcohol, L<ld, total number of carbon atoms is 5 to 18
Semi-esterification of cycloalkyl, arylalkyl, aryl, al, and kylaryl hydroxy compounds
Substituted and unsubstituted aliphatic carboxylic acids such as benzoic acid, methylbenzoic acid, t-butylbenzoic acid, cinnamic acid, salicylic acid, naphthenic acid, pyrrolidone carboxylic acid, acetoacetate and their condensates, Zoylacetone, dibenzoylmethane, stearoylpencil, rosin acid, octylphenol, nonylphenol, t-
Butylphenol Qil.

Other stabilizers, such as organotin compounds, may also be used in combination. Examples and L7 include mono- or dialkyltin fatty acid salts or aromatic acid salts, mono- or dialkyltin maleate salts and polymer salts, mono- or dialkyltin maleate salts, mono- or dialkyltin mono- or simalate salts. Also, difatty acid salts, mono- or dialkyltin mono- or cimaleic acid ester salts, mono- or di-aromatic acid salts, mono- or dialkyltin mercaptocarboxylic acid salts and polymer salts, mono- or dialkyltin sulfides and polymer salts, mono- or dialkyltin sulfides and polymer salts. Tin mercaptocarboxylic acid ester salt, mono- or dialkyltin mercaptocarboxylic acid ester mono- or disulfide salt, mono- or dialkyltin mercaptocarboxylic acid ester oxide salt, mono- or dialkyltin mercaptide, mono- or dialkyltin mercaptide, mercapto acid ester salt , mono- or dialkyl u fatty acid alkyl mercaptide, mono- or di-disulfide, and the tin compound described in JP-A-51-44149.

Furthermore, organic non-metallic stabilizers may also be used in combination as long as they do not completely inhibit the purpose. Examples of these organic nonmetallic stabilizers include 2-phenylindole, diphenylthiourea,
cetyl and stearyl β-aminocrotonic acid ester,
(2) Nitrogen-containing compounds such as 3 and 1,4-butanediol bis β-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester, incyanuric acid and its derivatives, such as tris(2- and droxyethyl) cyanurate, etc. Polyhydric alcohols such as pentaerythritol, mannitol, and nrubitol, benzoic acid, methylbenzoic acid, da+jcolic acid, maleic acid,
Carboxylic acids such as cinnamic acid, p-tert-butylbenzoic acid, crotonic acid, acetoacetate and its condensates, boric acid ester, thiodiglycolic acid ester, malonic acid 7-diester, benzoylacetone, di- Examples include benzoylmethane, stearoylbenzoylmethane, dehydroacetic acid%'f7) β-diketone, and the like. An antioxidant may be used in the composition of the present invention, if necessary. These antioxidants include hindered phenols, alkylidene or poly(alkylphenols) bonded via alkylidene, poly(alkylphenols) bonded via sulfur, and 7-enol derivatives (in-containing phenolic antioxidants). There are alkanoic acids and their alkyl esters, such as lauryl stearate thiodipropionate and sulfur-containing compounds such as dilauryl thiodipropionate; Monophenyldidecyl phosphite, tricresyl phosphate, tonosnonylphenyl phosphite, triscyclohexylphenyl phosphite, trisphenylphenyl phosphite, tris(diglobile/g-11col) phosphite, tris(ethoxyethoxyethyl) phosphite phyto, tris(4,4'-)゛thinodenbis(4-t-butyl-5-methylphenol)]phosphite, diphenylphosphite, mono-2-ethylhequinylphosphite, tetra(trif' yL) -4,4'-ingropyride/diphenyl diposphite, tetra(phenyl) diglopyrene glycol cyphosphite, heptakis(nonylphenyl)tetrakis (bisphenol A)
Pe/taphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, heptakis (diglobylene glycol) triphosphite, bis (neopentyl glycol) diglobyre/glycol diphosphite, tetrakis (butoxyethoxyethyl) ethylene glycol diphosphite Phyto, bis(cyclohexyl phenyl) bis(phenylethyl) 1,4-
Divinediol diphosphite, potassium didecyl phosphite.

Zinc di(octyl phosphite), butoxyethyl ethyl calcium phosphate, stearic acid/dilauryl 1ffi barium phosphate, tricresyl phosphate, trioctyl phosphate, tris(butoxyethyl) phosphate,
xylenyl diphenyl phosphate 7ate, monolauryl phosphate, lauryloxypolyethoxy phosphate,
di-t-butyl phenoxy polyethoxy phosphate,
onyloxypolyethoxydilauryl phosphate,
Other spiro-type phosphites such as distearylbentaerythritol diposphite, didecylbentaerythritol diphosphite, diphenylbentaerythritol/I-diphosphite, cage-type phosphite and tris(laurylthio)phosphite, tetrakis(mercaptooctyl) 1 ．． ．． 6-dimethylcaptohexylene diphosphite, pentakis(dodecylmercapto)bis(
1,6-hexylene dimercapto) triphosphite,
There are phosphites and phosphates such as 0,0'-diimpropylthiol phosphate and zinc dibutyl dithiophosphate.

If the UV absorber is completely added to the present invention, it can improve weather resistance (strength), so it can be used alone or in combination depending on the purpose of use.These include benzophenone, benzotriazole, salicylate, Examples include acrylates, hindered amines, metal chelates, especially nickel and chromium salts, etc.Also, phthalate ester-based OT plasticizers or other ester-based plasticizers or polyester-based plasticizers, and acid ester-based plasticizers. agents, chlorine plasticizers, other plasticizers, and epoxy compounds such as epoxidized soybean oil, epoxidized vegetable oils such as epoxidized linseed oil, butyl eboxysuguarate, otatile eboxystearate, and 2-ethyl. Xyltol oil fatty acid ester, epoxidized allyl epoxy stearate, epoxidized tetrahydrophthalic acid dioctyl ester, epoxidized cyclohexanedicarboxylic acid disguaryl Epoxidized ester, 4,4'-inoglopylidene diphenol and shrimp chlorhydride Epoxy compounds such as epoxy resins such as polycondensed metals may also be used in combination if necessary.

Calcium carbonate, calcium oxide, etc. as necessary.
Calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate,
Zinc sulfide, magnesium carbonate, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, silicic anhydride, sodium silicate, magnesium silicate, calcium silicate, zeolite, hydrotalcite, activated clay, talc, lily V-i, Bengala,
Asbestos, antimony trioxide and other fillers, fluorescent agents, fungicides, plate-out inhibitors, antifogging agents,
Crosslinking agents, lubricants, surfactants, reinforcing agents, processing aids, mold release agents, viscosity reducing agents, etc. can all be included in the composition of the rogen-containing resin of the present invention.

[Examples and effects]

Next, the effects of the stabilizing composition for a rogen-containing resin according to the present invention will be shown by Examples.

The test results used in the examples are indicated by the codes below.

The stages are shown and displayed.

(The following is a blank space) Example 1 In order to examine the stabilizing effect of the compound used in the present invention on polyvinyl chloride resin, 17
The mixture was kneaded with two rolls at 0° C. for 10 minutes, and a plate-out test was conducted. My father compared the color resistance and transparency of this sheet.

The results are shown in Table-1.

Formula (parts by weight) Polyvinyl chloride resin 100 Dioctyl phthalate 50 Epoxidized soybean oil 2.0 Stearic acid/calcium acid 0.4 Zinc stearate 0.4 Didecyl monophenyl phosphor (T0.5) Additives Table -
1 The above formulation contains known stabilizers.

Table 1 Example 2 In order to examine the stabilizing effect of the compound used in the present invention on polyvinyl chloride resin, 18
The mixture was kneaded with two rolls at 0° C. for io minutes to form a film with a thickness of 0.2 g. This film fl 80 C-100
kgfiyn2 for 3 minutes to compare color fastness and transparency. My father exposed this film outdoors for one year and compared its weather resistance.

The results are shown in Table 2.

Blend (parts by weight) Polyvinyl chloride resin 100 Dioctyl phthalate 40 Tricresyl phosphate 5 EBOKI 7 resin 2 Rubin monopalmite 11,5 Ethylene bisstearoylamide 0.3 Octyl diphenyl phosphite 0.5 Diphenyl phosphite]・
0.1 Barium stearate 0.4 Zinc stearate 0.4 Additives Table 2 The above formulation contains known stabilizers.

Table 2 Written amendment 1, Indication of the case, Patent Application No. 114770/1983, 2, Name of the invention, including: - Rogen resin composition 3, Person making the amendment: Katsuta Kako Co., Ltd. 4, Agent Higashiguto Chiyoda-ku Marunouchi 2-4-1-5, Date of amendment order Vol. 6, Specification to be amended, page 11, lines 10 to 11 "Tetrakis (mercaptooctyl) 1,6-dimethylcabutohexylene diphosphite""Tetrakis" (
mercaptooctyl) 1,6-dimercaptohexylene diphosphite”.

Applicant: Katsuta Kako Co., Ltd. Agent Sakamoto Sakae −

Claims (1)

[Claims] Contains... rogen resin, hypophosphorous acid and one of its metal salts
A stabilizing composition containing one or more rogen resins.