JPS6011942B2 - Halogen-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermally stabilized chlorine-containing resin compositions, particularly polypinyl chloride resin compositions.

Chlorine-containing resins, such as polyvinyl chloride resin (hereinafter referred to as PVC)
) tends to decompose due to heat during hot molding, etc., resulting in poor color tone of processed products and deterioration of mechanical substances.

That is, the color tone is initially pale yellow, but changes to brown and then black. In order to prevent these harmful effects, lead-based and cadmium-based organic and inorganic compound stabilizers have traditionally been added. Due to the environmental health problems caused by the toxicity of lead and cadmium generated during the processing and disposal of PVC products, there is an urgent need to switch to safer stabilizers. However, the effectiveness of conventional stabilizers that do not contain lead or cadmium, which are considered safe according to the voluntary regulations of the PVC Tableware Sanitation Council, etc., is considerably inferior to that of lead-based or cadmium-based stabilizers.

In particular, although some of these stabilizers other than lead-based and cadmium-based stabilizers greatly improved heat resistance, they were still unsatisfactory in terms of deterioration of color tone. As a result of repeated research from this perspective, the present inventors have provided as the present invention a chlorine-containing resin composition that is heat resistant, does not particularly cause deterioration of color tone, and contains a stabilizer that does not contain the above-mentioned harmful metals. be. That is, the present invention provides a chlorine-containing resin composition with
2-[4,4'-(3-mercapto-2-hydroxy-propoxy)-diphenyl]-propane and 'rho zinc,
A chlorine-containing resin composition containing at least one of titanium, antimony, tin, aluminum, magnesium, zirconium, or silicon oxide, hydroxide, carbonate: aluminosilicate.

The 2,2-[4,4-(3-mercapto-2-hydroxy-propoxy)-diphenyl]-propane (hereinafter referred to as DMPA) used in the present invention has the following structural formula and its production method About ErichToblev
:1 &EC Prodhada t ReSarCh and
Development, Vol & No. 4 De
cem batte l969415. J. M. Lalancet
teand M. Labibents; Tetrahe
Dron Letter No. 16PP1401-1
404.1973 can be referred to.

To give a specific example, a 500-k reactor is equipped with a dehydrator, a dropping funnel, and a male inlet pipe, and ``150 methanol is charged, 4k9 of sodium hydrogen sulfide is dissolved in it, and hydrogen sulfide is blown into it to saturate it. 212-[404'-(3,2-epoxypropoxy)-diphenyl]-propane 150k9 dissolved in 44 kg of methanol was added dropwise at a reaction temperature of 20-30 pm, and then enough hydrogen sulfide was added in a theoretical amount or more. After that, the mixture was evaporated and heated to remove methanol, and at the same time, excess hydrogen sulfide was removed and the catalyst was removed by passing through a sieve during heating to reduce the viscosity to 10,000.
DM with SH equivalent of 200 or more at ~20,000 centipoise
PA is obtained. DMPA of RU'I alone has insufficient performance to have a stabilizing effect on chlorine-containing resins, and is not as good as the present invention. Used in combination with the above DMPA {
Raw zinc, titanium, antimony, tin, aluminum, magnesium, zirconium or silicon oxides,
Typical examples of hydroxides or carbonates include zinc oxide, titanium oxide, antimony oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, silicon oxide and its hydrate; zinc hydroxide, ammonium hydroxide, Examples include magnesium hydroxide, zirconium hydroxide, silicon hydroxide: zinc carbonate, magnesium carbonate, and the like.

It has been reported that these oxides, hydroxides, and carbonates are conventionally used as stabilizers for polyvinyl chloride resin, but as shown in the comparative example below, the stabilizing effect is small and it is not practical. There isn't. This time, by using it in combination with DMPA, the stability effect was greatly increased. Examples of the aluminosilicate of the
)3), beryl (Mg(OH)2Si40,o), beryl (Be3AI2Si60,8), feldspar (KAISi30
8), Zeolite (Na2 mountain 2Sj30,.

) "Mica (KA13(OH)2Si30,o), china clay (Yama 2031$i020 is 20) A compound that is said to be a filler for PVC and exists in large quantities in nature.These compounds are preferably finely divided into Grind into 1 to 5 pieces and use in combination. Chlorine-containing resin with DMPA (a) above and (o) zinc, titanium, antimony, tin, aluminum, magnesium, zirconium or silicon oxides and hydroxides. and carbonate; the addition method of adding one or more types of aluminosilicate is preferably 180% at the time of molding the resin.
It can be blended using a heated roll of ~220 qo, or it can be preblended in advance and extruded while being mixed using an extruder, and then extruded into a cooled mold to be molded.

The amount of DMPA added is preferably 0.02 to 2 parts by weight, particularly preferably 0.1 to 15 parts by weight, per 10 parts by weight of the chlorine-containing resin, and {o} of zinc, titanium,
oxides, hydroxides and carbonates of antimony, tin, aluminum, magnesium, zirconium or silicon;
The amount of one or more aluminosilicate added is 1
Preferably from 0.02 to 3 parts by weight, particularly preferably from 0.02 to 3 parts by weight, particularly preferably from 0.1 to 0 parts by weight
~2 parts by weight is good. Examples of the chlorine-containing resin stabilized in the present invention include polyvinyl chloride, polypinylidene chloride,
Typical examples include chlorinated polyethylene, chloroprene rubber, chlorinated rubber, or mixtures thereof; examples of these chlorine-containing resins include pinyl acetate resin, nitrile butadiene rubber, acrylic resin, ABS resin, and AS resin. It may be contained in an amount less than or equal to % by weight.

In the present invention, DMPA (〇) and (〇) zinc, titanium, antimony, tin, aluminum, magnesium,
Zirconium, silicon oxides, hydroxides and carbonates; one or more aluminosilicates and optionally phosphites such as trioctyl phosphite, trinonyl phosphite, triphenyl phosphite, diphenyl isooctyl phosphite, nonylphenyllusy n
Phenolic antioxidants such as monopropyl phosphite, 2.6-di-tert-butyl para-cresol, 4.4-
Thiobis (6-tert-butyl-m-cresol), dialkylthiobispropionate, etc., and plasticizers such as di-(ethylhexyl) phthalate, di-n -Octyl phthalate, di-(ethylhexyl)tetrahydrophthalate, di(2-ethylhexyl)adibate, di-n
- Add phthyl sebagate, tricresyl phosphate, etc., epoxy stabilizers such as epichlorohydrin and bisphenol A polymer, epoxidized soybean oil, etc., and ultraviolet absorbers such as penzotriazole type, benzophenone type, etc. You can also do it.

In addition to these, organic chelators, pigments, fillers, foaming agents, antistatic agents, anti-fog agents, anti-plate-out agents, surface treatment agents, thickeners, flame retardants, anti-glare agents, anti-glare agents, etc. , bactericidal agents, metal deactivators, photodegradants, nonmetallic stabilizers, thiourea derivatives, processing aids, mold release agents, etc. can be added. The following examples show the effects on PVC, which is a typical chlorine-containing resin of the present invention, but the present invention is not limited by these examples, and various modifications may be made within the scope of the present invention. Of course, it is possible to change.

Examples 1 to 10 The following formulation was added to PVC (average polymerization degree of hesh onloIEP 1450, straight 10th hesh passage amount of 60% or more) using a 6″ roll at a temperature of 145 to 150°C for 5 minutes, Press molding is preheated for 2 minutes at 150:00, and the pressure is 1.
00 kg/m for 5 minutes, and then cooled at room temperature for 10 minutes at 180 k9/m.

The test sample was a JIS K6723 soft vinyl chloride compound. Dumbbell No. 3 test pieces were made using a JIS K6723 soft vinyl chloride compound, and they were heated and aged using a Gar type air heating aging tester JIS K6301-1969 to determine the stabilizing effect of each stabilizer and the degree of PVC coloration. An evaluation was conducted.

Composition PVC IO parts by weight Dioctyl phthalate (plasticizer) 1 parts by weight Stabilizer See Table 1 for compounding amounts Table 1 Zinc white, zinc carbonate, zinc sulfide, titanium oxide, silicon trioxide, magnesium silicate, silicic acid Soda etc. have almost no effect.

Moreover, if only DMPA:3 is used, the PVC will be colored quickly and is not practical. However, when the DMPA of the present invention is used in combination with the above-mentioned compounds of zinc oxide, antimony trioxide, and magnesium silicate, a synergistic effect with the stabilizer of the present invention is observed.

In addition, the test piece to which the stabilizer of the present invention has been added has better physical properties than the test piece to which no additive has been added, since it is a flexible body that remains the same as an unaged product even if it is colored after aging. Examples 11-16 The same PVC was used as in Examples 1-10, and the test sample preparation and processing methods were also the same.

Compound PVC IO parts by weight Dioctyl phthalate (plasticizer) 5 parts by weight Stearic acid monoglyceride (lubricant) 0.5 parts by weight Stabilizer
For compounding amounts, see Table 2. *Test method: A test piece was prepared using JIS K6723 soft vinyl chloride compound, and the tensile test was conducted at room temperature of 25±1° C. and at a tensile rate of 200 min.

Claims (1)

[Claims] 1. For the chlorine-containing resin composition, (a) 2.2-[4.
4'-(3-mercapto-2-hydroxy-propoxy)-diphenyl]-propane, (b) zinc, titanium,
A chlorine-containing resin composition containing at least one of antimony, tin, aluminum, magnesium, zirconium, or silicon oxide, hydroxide, carbonate: aluminosilicate. 2 0 of the substance (a) per 100 parts by weight of chlorine-containing resin
．． 02 to 20 parts by weight, and 0.02 to 30 parts by weight of the substance (b) are added to the composition according to claim 1. 3. The composition according to claim 1 or 2, wherein the chlorine-containing resin is a polyvinyl chloride resin.