JPH02160856A - Polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prepare a polyvinyl chloride resin compsn. excellent in prevention of the thermal discoloration and sweat-out by compounding a polyvinyl chloride resin with a polyester plasticizer and stabilizers including an epoxy compd., an org. phosphite ester and a monoalkyltin mercapto compd. CONSTITUTION:100 pts.wt. polyvinyl chloride resin (e.g. polyvinyl chloride) is compounded with pref. 5-100 pts.wt. polyester plasticizer (e.g. a plasticizer synthesized from adipic acid and 1,3-butylene glycol), and stabilizers, pref. 0.5-5 pts.wt. epoxy compd. (e.g. epoxidized soybean oil), pref. 0.05-1 pts.wt. org. phosphite ester (e.g. triisodecyl phosphite), and pref. 0.3-3 pts.wt. monoalkyltin mercapto compd. [e.g. digbutyltin bis(isooctylthioglycolate)].

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a vinyl chloride resin composition used for oil-resistant boots, oil-resistant hoses, automobile interior materials, leather, and the like.

"Prior Art" Vinyl chloride resin compositions tend to suffer from thermal deterioration mainly due to dehydrochlorination reactions during thermoforming. Processed products made of resin that have undergone such thermal deterioration cause problems such as thermal changes and deterioration of mechanical properties.

For this reason, vinyl chloride resin compositions contain metal soap stabilizers such as lead stearate, cadmium stearate, calcium stearate, barium stearate, and zinc stearate, or tin stabilizers such as dialkyltin compounds. agents, etc. are added. In particular, since footwear, hoses, and the like are manufactured by injection molding or extrusion molding, relatively high heat resistance may be required of the vinyl chloride resin composition. In such cases, tin-based stabilizers, particularly stabilizers containing dialkyltin bis(isooctylthioglycolate) as a main component, are used.

Furthermore, since the vinyl chloride resin composition itself is a hard resin, it is necessary to plasticize it depending on the use. Plasticization methods include internal plasticization, which involves copolymerizing vinyl chloride monomers and vinyl acetate monomers during resin production, and plasticization by blending a plasticizer with vinyl chloride resin. There is an external plasticization method. This is usually done using an external plasticization method in which plasticization is performed using a plasticizer.

Examples of plasticizers used to plasticize vinyl chloride resin include dioctyl phthalate, diisodecyl phthalate, dioctyl adipate, trioctyl trimellitate, and polyester. When non-volatility, oil resistance, and non-migration properties are required for the material, high molecular weight plasticizers such as trimetate trialkyl ester and polyester are used as plasticizers.

[Problems to be Solved by the Invention] However, when a dialkyltin mercapto stabilizer is used as a stabilizer for a vinyl chloride resin composition plasticized with these polyester plasticizers, the stabilizer causes polyester There is a problem that the system plasticizer is hydrolyzed. This causes a problem in that when a product made of the vinyl chloride resin composition is stored, the surface of the product sweats and becomes sticky, causing the product to lose its value.

In order to solve the above problem, attempts have been made to add an epoxy compound, an organic phosphite, a monoalkyltin mercapto compound, and a dialkyltin mercapto compound in combination as stabilizers, but this method does not improve heat coloring resistance, Improvements in sweat resistance, etc. were insufficient.

"Means for Solving the Problem" The present invention solves the problem by adding a polyester plasticizer as a plasticizer and an epoxy compound, an organic phosphite ester, and a monoalkyl tin mercapto compound as a stabilizer to a vinyl chloride resin. It was used as a means to do so.

``Effect'' Vinyl chloride resin compositions to which an epoxy compound, organic phosphite, or monoalkyl tin mercapto compound is added as a stabilizer and a polyester plasticizer as a plasticizer sweat during storage and the surface becomes sticky. There's nothing to do,
No coloring when heated.

The vinyl chloride resin composition of the present invention will be explained in detail below.

The feature of the present invention is to add a polyester plasticizer as a plasticizer to a vinyl chloride resin, and an epoxy compound as a stabilizer.
A phosphorous acid ester and a monoalkyltin mercapto compound are added.

The above-mentioned monoalkyltin mercapto compound is preferably a compound represented by the following general formula (+).

S (CFlt)n, C0OR+ / R, Sn-S (CHt)n-C00Rt
(1)\S-(C)l,)n3-C00R3 (in the formula, R is an alkyl group having 1 to 12 carbon atoms, 1, R
t, Rt, and Rs are an alkyl group, benzyl group, cyclohexyl group, or alkoxyalkyl group having 8 to 14 carbon atoms. These may be the same or different from each other. Further, n + + II t and n are ■ or an integer of 2. ) Examples of compounds shown in formula (2) include monomethyltin tris (octylthioglycolate), monomethyltin tris (3-methoxybutylthioglycolate), monomethyltin tris (benzylthioglycolate), and monomethyltin tris (octylthioglycolate). propionate), monomethyltin tris(3-methoxythiopropionate),
Monobutyltin tris (octylthioglycolate),
Monobutyltin tris (tridisylthioglycolate)
, Monobutyltin Tris (Stearylthioglycolate), Monobutyltin Tris (Cyclohexylthioglycolate), Monobutyltin Tris (Benzylthioglycolate), Monobutyltin Tris (Octylthiopropionate), Monobutyltin Tris (Tridecyl thiopropionate), monobutyltin tris (stearylthiopropionate), monobutyltin tris (benzylthiopropionate), monobutyltin tris (cyclohexylthiopropionate), monobutyltin tris (cyclohexylthiopropionate), pionate), Monooctyltin Tris (Octylthioglycolate), Monooctyltin Tris (Decylthioglycolate), Monooctyltin Tris (Tridecylthioglycolate), Monooctyltin Tris (Cyclohexylthioglycolate) , monooctyltin tris (benzylthioglycolate),
Monooctyltin tris (methoxybutylthioglycolate), monooctyltin tris (octylthiopropionate), monooctyltin tris (decylthioglycolate), monooctyltin tris (nonylthiopropionate), monooctyltin tris (nonylthiopropionate) Tris (tridecylthiopropionate), monooctyltin tris (stearylthiopropionate), monooctyltin tris (
Examples include methoxybutylthiopropionate), monooctyltin tris (benzylthiopropionate), and monooctyltin tris (cyclohexylthiopropionate).

The amount of the monoalkyl tin mercapto compound added is preferably 0.3 to 3 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.3 parts by weight, the molded product may be colored, and if it exceeds 3 parts by weight, it may sweat and the surface may become sticky.

The organic phosphites used in the present invention include diphenyldecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (di nonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite,
Tris(lauryl-2-thioethyl)phosphite, tetratridecyl-1,1,3-tri's(2methyl-5
°-tert-butyl-4°-oxydiphenyl)butane diphosphite, tetra(C0,~CI5 mixed alkyl)4,4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert butylphenyl) phosphite, tris(4-oxy-3,
5-di-tert-butylphenyl) phosphite, 2
-Ethylhexyl diphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4
, 4°-isopropylidene diphenol polyphosphite, diphenylbis[4,4°-n-butylidenebis(
2-tert-butyl-5-methylphenol)]thiogetanol diphosphite, bis(octylphenyl)bis(4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol))-1, 6-hexanediol diphosphite, phenyl-44'isoipropylidene diphenolbentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-tert-butyl-5 -methylphenol)diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tristearylphosphite, octyldiphenylphosphite, diphenyltridecylphosphite, phenyldi(tridecyl)phosphite, tris(2-cyclophosphite) xylphenyl) phosphite, ditridecyl di(2-chlorohexyl phenyl) hydrogenated bisphenynol diphosphite, di(2,4-di-tert-butylphenyl)cyclohexyl phosphite, 2,4-di-tert-butylphenyl
ert-butylphenylnoisodecyl phosphite, tris(butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis(2-cyclohexylphenyl) acid phosphite, bis(2゜4-dite)
and rt-butylphenyl) acid phosphite.

The amount of the organic phosphite added in the present invention is preferably 0.05 to 1 part by weight per 100 parts by weight of the vinyl chloride tree. Here, if it is less than 0.05 part by weight, the initial heat-resistant coloring property will be poor, and if it exceeds 1 part by weight, the long-term heat-resistant coloring property will be poor.

Epoxy compounds used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil,
Epoxidized flower oil, epoxidized linseed oil fatty acid butyl ester, epoxidized butyl stearate, epoxidized methyl stearate, epoxidized octyl stearate, epoxidized butadiene, epoxy resin (this epoxy resin contains polyhydric phenols and epichlorohydrin or It is obtained by reaction with methyl epichlorohydrin and is a bisphenol type and novolac type epoxy resin).

The amount of the epoxy compound added in the present invention is
0.5 parts by weight to 5 parts by weight per 1100! parts is suitable. If it is less than 0.5 parts by weight, the heat coloring resistance is insufficient and the molded product may be colored, and if it exceeds 5 parts by weight, mold is likely to grow.

The polyester plasticizer in the present invention is a compound having three or more ester groups in one molecule.

This compound is a reaction product of a polybasic acid and m alcohols, a reaction product of a monocarphonic acid and a polyhydric alcohol,
A reaction product of a dibasic acid and a dihydric alcohol is neutralized with m alcohols or monocarboxylic acids.

Here, the polybasic acid has three or more carboxylic acids in one molecule, and includes, for example, pyromellitic acid, trimellitic acid, and acid anhydrides thereof.

Moreover, polyhydric alcohol has three or more hydroxyl groups in one molecule, and includes, for example, pentaerythritol, trimethylolpropane, dipentaerythritol, and the like.

Dibasic acids include glutaric acid, succinic acid, adipic acid,
Examples include azelaic acid, sepathic acid, phthalic acid, and terephthalic acid.

Examples of dihydric alcohols include ethylene glycol, l 2-
Propylene glycol,! , 3 butylene glycol, 1
．． 4 butanediol, neopentyl glycol, l 5
-bentanediol, 2,2.6 trimethylbentanediol, 1,6-hexanediol, and the like.

Examples of m-alcohols include butanol, hexanol, octatool, nonyl alcohol, decanol, tridecanol, benzyl alcohol, cyclohexanol, and the like.

Examples of monocarboxylic acids include octylic acid, decanoic acid, caprylic acid, m-triylic acid, and p-tert-butylbenzoic acid.

The amount of the polyester plasticizer added in the present invention is preferably 5 to 100 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount is less than 5 parts by weight, oil resistance may be insufficient, and if it exceeds 100 parts by weight, sweating may occur and the surface may stick.

As the vinyl chloride resin used in the present invention, a mixture of vinyl chloride and vinylidene chloride or a monomer copolymerizable with vinyl chloride and vinylidene chloride is prepared by bulk polymerization,
It is manufactured by a conventional method such as a suspension polymerization method or an emulsion polymerization method.

Examples of monomers copolymerizable with vinyl chloride and vinylidene chloride include vinyl esters such as vinyl acetate, acrylic esters such as methyl acrylate and butyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. , vinyl cyanides such as acrylonitrile and methacrylate trile, and α-olefins such as ethylene and propylene.

Examples of plasticizers that can be added to the vinyl chloride resin composition of the present invention include phthalate ester plasticizers such as dibutyl phthalate, dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate, and dibasic acids such as adipic acid and sepathic acid. Polyester plasticizers obtained by reacting 1.3 with dihydric alcohols such as butylene glycol and ethylene glycol, ester plasticizers such as dioctyl adipate and dinonyl adipate, phosphorus plasticizers such as tricresyl phosphate, These include chlorinated plasticizers such as chlorinated paraffin.

Furthermore, the vinyl chloride resin composition of the present invention can also contain, for example, pigments, ultraviolet absorbers, fillers, lubricants, processing aids, reinforcing materials, etc., as necessary. Incidentally, although dialkyl Sparrow/Lukabuto compounds are not normally used, they can be added as long as they do not impair the effects of the present invention.

The vinyl chloride resin composition of the present invention may also contain metal soap stabilizers such as barium/zinc and calcium/zinc, monobutyltin trioctoate, monobutyltin trilaurate, monobutyltin trineodecanate, and monobutyltin trilaurate. Butyltin trisesterate, monooctyltin trioctoate, monooctyltin trineodecanate, monooctyltin tristearate, monobutyltin tris (monomethyl maleate), monobutyltin tris (monobenzyl maleate), monobutyltin tris (monobutyltin tris) butylmalate), monobutyltin tris (monooleyl maleate), monobutyltin tris (monoctyl maleate), monooctyltin tris (monoethyl maleate), monooctyltin tris (monoctyl maleate), monooctyltin Monoalkyltin stabilizers such as tris (monostearyl malate), β-diketone compounds such as dibenzoylmethanestearoylbenzoylmethane, 2,6-tert-butyl-4-entylphenol, 4,4"-thiobis (6-tert-
It is also possible to add antioxidants such as butyl-3-methylphenol) and 2.2'-methylenebis-(6-tert-butyl-4-methylphenol).

"Example" 100 parts by weight of vinyl chloride resin with an average degree of polymerization of 1450, 10 parts by weight of calcium carbonate, 1.3 parts by weight of adipic acid
A polyester plasticizer consisting of butylene glycol (
Average molecule! 2500) and 40 parts by weight of dioctyl phthalate were added to prepare a vinyl chloride resin composition. A predetermined amount of the stabilizer shown in Table 1 was added to this and Examples 1 to 1
Comparative Example 1 was prepared by adding a predetermined amount of the stabilizer shown in Table 2.
~12. This was kneaded for 5 minutes using a 6-inch roll at 150°C to form a sheet of 1 ml and 1 thickness. Then,
Place three of the above sheets on top of aluminum foil, cover with aluminum foil, and place this in a 2 mm thick mold that has been preheated to 200°C and heat to 200°C.
A press heat resistance test was conducted using a press.

The results of the above test were evaluated based on the following evaluation criteria.

Heat resistance evaluation criteria: 1, colorless 2, light yellow 3, yellow 4, brown 5, black Also, the sheet obtained by kneading with the rolls at 150°C for 5 minutes was placed in a 2ffi + I + thick mold and pressed at 200°C for 5 minutes. Thereafter, it was cooled using a cooling press to obtain a pressed sheet having a thickness of 2IllI11.

After this press sheet was left in a constant temperature and humidity chamber at 70° C. and 95% relative temperature for a predetermined number of days, the sweating property of the press sheet was observed. The results were evaluated based on the following evaluation criteria.

O No sweating was observed.

× I'm sweating.

Table 1 shows the formulation and evaluation results of each stabilizer in Examples 1 to 15 of the present invention. Further, Table 2 shows the formulation of each stabilizer in Comparative Examples 1 to 2 and the evaluation results thereof.

(Hereafter, blank space) As is clear from Tables 1 and 2, the vinyl chloride resin composition of the present invention has excellent perspiration resistance and heat coloring resistance.

[Effect of the Invention J The present invention provides a vinyl chloride resin characterized in that a polyester plasticizer as a plasticizer and an epoxy compound, an organic phosphite, and a monoalkyl tin mercapto compound as a stabilizer are added to a vinyl chloride resin. Since it is a type resin composition, it has an extremely excellent heat-resistant discoloration prevention effect and good perspiration resistance. Therefore, the vinyl chloride resin composition of the present invention is suitably used for footwear such as boots, leather, film sheets, and the like.

Claims (2)

[Claims] (1) A vinyl chloride resin composition characterized in that a polyester plasticizer as a plasticizer and an epoxy compound, an organic phosphite, and a monoalkyl tin mercapto compound as stabilizers are added to a vinyl chloride resin. (2) 5 to 100 parts by weight of a polyester plasticizer, 0.5 to 5 parts by weight of an epoxy compound as a stabilizer, and 0.5 parts by weight of an organic phosphite based on 100 parts by weight of a vinyl chloride resin.
A vinyl chloride resin composition characterized in that it contains 0.05 to 1 part by weight of a monoalkyl tin mercapto compound and 0.3 to 3 parts by weight of a monoalkyltin mercapto compound.