JP3125933B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized vinyl chloride resin composition, and more particularly, to a coloring property with time obtained by adding a surface-treated calcium carbonate and a specific metal salt to a vinyl chloride resin. The present invention relates to a vinyl chloride-based resin composition improved in the above.

[0002]

2. Description of the Related Art Vinyl chloride resins such as polyvinyl chloride resins are most widely used as general-purpose plastics. However,
The resin is generally inferior in stability to heat and light, and has a disadvantage of causing thermal decomposition mainly of dehydrohalogenation during heat molding. For this reason, the mechanical properties of the processed product are deteriorated, the color tone is deteriorated, and the like, resulting in a significant disadvantage.

In order to avoid such disadvantages, it has been proposed to use various stabilizers alone or in combination of several types. For example, in addition to various metallic soaps, organic tin compounds, lead salt compounds, etc., epoxy compounds, organic phosphite compounds and the like have been used as various auxiliaries, and quite satisfactory effects have been obtained.

[0004] In the production of a molded article of a vinyl chloride resin, various fillers are also used for the purpose of improving mechanical strength and opacity, etc. In particular, calcium carbonate has these effects. It is widely used because of its large size and non-toxicity. That was a problem.

[0005] In order to solve such problems caused by the blending of calcium carbonate, the surface of calcium carbonate particles is treated with various surfactants such as fatty acids, resin acids, amines, lignin, and organic substances such as fatty acid esters. Attempts have been made to add, and problems such as moldability and surface unevenness have been solved.However, when calcium carbonate surface-treated with these organic substances is added, molded products may become colored during long-term use. However, there is a drawback that the material cannot be used, and its improvement has been strongly desired.

It is known that β-diketone compounds such as dehydroacetic acid and dibenzoylmethane are effective for improving the coloring of vinyl chloride resins, but β-diketone compounds such as calcium carbonate surface-treated with an organic substance are incorporated. -The effect of the diketone compound was extremely weak and was not practically satisfactory.

[0007]

Means for Solving the Problems In view of the above situation, the present inventors have made various studies and found that a metal salt of an organic carboxylic acid, an organic carboxylic acid metal salt, and an organic carboxylic acid were added to a surface-treated vinyl chloride resin containing calcium carbonate. The present inventors have found that a remarkable stabilizing effect can be obtained by adding a metal salt of phosphoric acid and phosphorous acid or a metal salt of phenol and a zinc salt of dehydroacetic acid, and arrived at the present invention.

That is, the present invention relates to a vinyl chloride resin 1
00 parts by weight, (1) surface-treated calcium carbonate 5
40 parts by weight , (2) 0.05 to 10 parts by weight of a metal salt of an organic carboxylic acid, a metal salt of an organic phosphoric acid and a phosphorous acid or a metal salt of a phenol, and (3) a metal salt of dehydroacetic acid.
An object of the present invention is to provide a vinyl chloride-based resin composition having improved coloring property with time, which is obtained by adding 0.01 to 10 parts by weight of a zinc salt .

Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail.

[0010] Generally, calcium carbonate is produced by mixing dense limestone with anthracite or coke until lime is produced and calcining it, and then injecting carbon dioxide gas into the hydrated lime to precipitate fine crystals. But
It has the disadvantages that it tends to form secondary agglomerates when dried, and that it is easy to make a cake when mixed with plastic. The surface-treated calcium carbonate of the component used in the present invention improves these, and in order to improve dispersibility, fatty acid, resin acid, cationic activator, surface-treated with an organic substance such as lignin, Generally commercially available products can be used as they are.

Commercially available surface-treated calcium carbonates include, for example, CALVIC-CC (manufactured by Inoue Lime Co., Ltd.), Elflex-D, PA (manufactured by Yonesho Lime Co., Ltd.), Hakushinka U, CCR (manufactured by Shiraishi Industry Co., Ltd.) And Neolite SP (manufactured by Takehara Chemical), MSK-P (manufactured by Maruo Calcium) and the like.

The amount of these surface-treated calcium carbonates to be added is 5 to 100 parts by weight of the vinyl chloride resin.
40 parts by weight.

The metal constituting the metal salt of an organic carboxylic acid, the metal salt of an organic phosphoric acid and a phosphorous acid or the metal salt of a phenol used in the present invention is L.
i, Na, Ca, K, Ba, Mg, Sr, Zn, Sn,
Cs, Al, organic Sn salts, and the like.

The organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid, and lauric acid. , Tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3, 5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, Salicylic acid, p-tert-octylsalicylic acid, elaidic acid, oleic Acid, linoleic acid, linolenic acid,
Monovalent carboxylic acids such as thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, and isophthalic acid Acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid,
Maleic acid, fumaric acid, citraconic acid, metaconic acid,
Dihydric carboxylic acids such as itaconic acid, aconitic acid, thiodipropionic acid or monoesters or monoamide compounds thereof; butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanic acid, pyromellitic acid, etc. Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids.

The above organic phosphoric acid and phosphorous acid include, for example, mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl,
-Xylyl, -octylphenyl, -nonylphenylphosphoric acid, pyrophosphoric acid, phosphorous acid and the like.

Examples of the above phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, and isophenol. Octyl phenol, 2-ethylhexyl phenol, tertiary nonyl phenol, decyl phenol, tertiary octyl phenol, isohexyl phenol, octadecyl phenol, diisobutyl phenol, methyl propyl phenol, diamyl phenol, methyl isohexyl phenol, methyl tertiary octyl phenol and the like can be mentioned.

The amount of the metal salt of the organic carboxylic acid, the metal salt of the organic phosphoric acid and the phosphorous acid or the metal salt of the phenol is 0.05 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. Parts, preferably 0.1 to 8 parts by weight.

[0018]

The amount of zinc salt of dehydroacetic acid added is as follows:
0.01 to 1 based on 100 parts by weight of vinyl chloride resin
0 parts by weight, preferably 0.05 to 5 parts by weight.

The above-mentioned components and components used as a stabilizer in the composition of the present invention can be individually compounded in a vinyl chloride resin, or they can be used as a mixture. Can also be used as a so-called composite stabilizer containing other stabilizers or auxiliary components as necessary.

The vinyl chloride resin used in the present invention includes, for example, polyvinyl chloride, post-chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, chloride Vinyl-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-alkyl , Cycloalkyl or arylmaleimide copolymer, vinyl chloride
Styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer,
Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-
Vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, vinyl chloride-acrylonitrile copolymer,
Vinyl chloride resin such as vinyl chloride-urethane copolymer and the above vinyl chloride resin and α such as polyethylene, polypropylene, polybutene and poly-3-methylbutene
Polyolefins such as olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, styrene and other monomers (eg, maleic anhydride, butadiene, acrylonitrile) And acrylonitrile-butadiene-styrene copolymer, methacrylate-butadiene-styrene copolymer, and blends with polyurethane.

An excellent synergistic effect is exhibited by using an organic phosphite compound and / or an epoxy compound in combination with the vinyl chloride resin composition of the present invention.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono and di mixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl Trithiophosphite,
Bis (neopentyl glycol) / 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, tetra (C12-15
Mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2 -Tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl • 4,4
4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl).
1,1,3-tris (2-methyl-5-tert-butyl-4
-Hydroxyphenyl) butane triphosphite and the like.

The amount of the organic phosphite compound to be added is 0.01 to 100 parts by weight of the vinyl chloride resin.
To 5 parts by weight, preferably 0.1 to 3 parts by weight.

The epoxy compounds usable in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, and epoxidized castor oil. Safflower oil, epoxidized linseed oil fatty acid butyl, methyl epoxy stearate, -butyl, 2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,
Examples thereof include 2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate.

The amount of the epoxy compound to be added is 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

The composition of the present invention may further comprise, for example, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol,
Polyhydric alcohol compounds such as mannitol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, glycerin, tris (2-hydroxyethyl) isocyanurate, and β-diketone compounds such as dehydroacetic acid and dihydroacetic acid; Nonmetal stabilizing aids such as benzoylmethane, stearoylbenzoylmethane, and ester-containing β-diketone compounds can be used in combination.

The composition of the present invention may contain an ester plasticizer such as a phthalate ester plasticizer or an adipic ester plasticizer, or a polyester plasticizer, a phosphate ester plasticizer, or a chlorine plasticizer. And other plasticizers and the like can be appropriately used depending on the application.

As inorganic compounds, modified and unmodified synthetic hydrotalcites, zeolite compounds, calcium phosphate, magnesium phosphate and the like can be used in combination depending on the intended use.

Further, in order to obtain a non-toxic or low-toxic vinyl chloride resin composition, a non-toxic or low-toxic metal salt such as an organic carboxylic acid is usually selected and used. A vinyl chloride resin composition which is poisonous and has good heat stability can be obtained.

If necessary, the composition of the present invention may contain, for example, a crosslinking agent, a filler such as barium sulfate, a pigment,
Foaming agent, antistatic agent, anti-fog agent, plate-out inhibitor,
A surface treatment agent, a lubricant, a light stabilizer, a flame retardant, a fluorescent agent, a fungicide, a bactericide, a photodegradation agent, a processing aid, a release agent, an antioxidant, and the like can be appropriately included.

The stabilized vinyl chloride resin composition of the present invention can be used for all processing methods and applications. Examples of these processing methods include calendering, extrusion, injection, blowing, powder slash, paste, casting, and other processing methods.

[0033]

The following examples illustrate the stabilizing effect of the composition of the present invention. However, the present invention is not limited by the following examples.

Embodiment 1

The following components were roll-kneaded and then pressed to form a sheet having a thickness of 1 mm. The sheet was measured for thermal stability in an oven at 190 ° C., initial colorability, and colorability after aging in an oven at 70 ° C. for one week. The results are shown in Table 1 below.

<Blending> Parts by weight Polyvinyl chloride resin 100 Dioctyl phthalate 40 CCR ^{* 1} 20 Epoxidized soybean oil 2 Barium stearate 0.4 Zinc stearate 0.4 Tetra (C12-15 mixed alkyl) -4,4 ′ -0.5 isopropylidene diphenyl phosphite barium perchlorate 0.2 sample compound (Table 1) 0.45

* 1: Organic acid-treated calcium carbonate manufactured by Shiraishi Industry Co., Ltd.

The coloring property was evaluated on a scale of 1 to 10, where 1 indicates no discoloration and 10 indicates that the coloring is extremely remarkable.

[0039]

[Table 1]

Embodiment 2

Specimens were prepared in the same manner as in Example 1 using the following formulations, and heat stability in an oven at 190 ° C., initial coloring, and aging for 14 and 28 days in an oven at 65 ° C. After the coloring, the coloring property was measured. The results are shown in Table 2 below.

<Blending> Parts by weight Polyvinyl chloride resin 100 Dioctyl phthalate 50 MSK-P ^{* 2} 10 Epoxidized linseed oil 2 Barium oleate 0.8 Zinc metatoluate 0.4 Phenyl ditridecyl phosphite 1.0 Dibenzoyl Methane 0.05 Sample compound (Table 2) 0.5

* 2: Fatty acid-treated calcium carbonate manufactured by Maruo Calcium Co., Ltd.

[0044]

[Table 2]

Embodiment 3

To see the effect of using the vinyl chloride resin composition of the present invention in combination with a metal perchlorate, a test piece was prepared by the same operation as in Example 1 using the following compound. The heat stability in an oven at 190 ° C., the initial colorability and the colorability after aging in an oven at 70 ° C. for 10 days were evaluated. The results are shown in Table 3 below.

<Blending> parts by weight polyvinyl chloride resin 100 di (C8-12 alkyl) phthalate 70 white glossy CCR 20 epoxidized soybean oil 3 titanium oxide 10 zinc octylate 0.5 barium stearate 1.0 zinc dehydroacetate 0.5 Metal perchlorate (Table 3) 0.5

[0048]

[Table 3]

From the results of each of the examples, it can be seen from the results that the vinyl chloride resin containing calcium carbonate whose surface has been treated with an organic substance is colored with the lapse of time by using a metal salt of an organic carboxylic acid, a metal salt of an organic phosphoric acid and a phosphorous acid, or phenol. It is evident that the combined use of a class of metal salts with a zinc salt of dehydroacetic acid provides a significant improvement.

On the other hand, when a β-diketone compound such as dehydroacetic acid is added in place of zinc dehydroacetate, the effect of preventing coloration over time is hardly observed, and the effect of the present invention is very specific. It is clear that it is.

[0051]

The vinyl chloride resin composition of the present invention has excellent coloring properties over time, despite the fact that calcium carbonate surface-treated with an organic substance is incorporated.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C08K 5/52 C08K 5/52 9/04 9/04 (72) Inventor Shinji Shinbube 5-chome, Shirahata, Urawa-shi, Saitama No. 13 Asahi Denka Kogyo Co., Ltd. (56) References JP-A-48-103647 (JP, A) JP-A-60-192743 (JP, A) JP-A-1-252649 (JP, A) JP-A Sho 53-78250 (JP, A) JP-A-53-43739 (JP, A) JP-A-55-43144 (JP, A) JP-A-51-34940 (JP, A) JP-A-58-27734 (JP, A A) JP-A-55-747 (JP, A) JP-A-52-77157 (JP, A) JP-A-54-154441 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C08L 27/06

Claims (1)

(57) [Claims] 1. 100 parts by weight of a vinyl chloride resin,
(1) 5 to 40 parts by weight of surface-treated calcium carbonate,
(2) Metal salts of organic carboxylic acids, metal salts of organic phosphoric acids and phosphorous acids or metal salts of phenols 0.05 to
10 parts by weight and (3) zinc salt of dehydroacetic acid 0.0
A vinyl chloride resin composition containing 1 to 10 parts by weight and having improved colorability over time.