JPH09176417A - Chlorine-containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. which exhibits an excellent weather resistance even when it contains only a small amt. of a phosphorus compd. by compounding a chlorine-contg. resins (e.g. a vinyl chloride resin) with a specific organophosphorus compd. SOLUTION: A chlorine-contg. resin is compounded with an organophosphorus compd. represented by formula I (wherein R1 to R4 are each a 4-25C alkyl, an alkenyl, an aryl, benzyl, an aralkyl, etc.; X is a residue of a polyhydric alcohl or phenol; and (n) is 1 or higher). Examples of the resin are a vinyl chloride resin, a chlorinated vinyl chloride resin, a chlorinated polyethylene resin, a vinylidene chloride resin, etc., and their mixtures with other resins. In producing an agricultural vinyl chloride resin article, the organophosphorus compd. in an amt. as small as 0.1-5 pts.wt., pref. 0.5-2 pts.wt., can impart an excellent weather resistance to the resin. A synergistic effect is obtd. when an org. phosphoric ester represented by formula II or III (wherein R5 to R7 are each an 8-25C alkyl; and M is zinc or an alkaline earth metal) is used jointly with the above organophosphorus compd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a chlorine-containing resin composition having excellent colorability, heat resistance and weather resistance.

[0002]

2. Description of the Related Art Chlorine-containing resins, typified by vinyl chloride resins, are used for films, sheets, hoses, etc. because of their excellent transparency, strength, economy, etc., and especially for agricultural vinyl such as houses and tunnels. Used in large quantities. However, these chlorine-containing resin products may cause curing, so-called weathering deterioration such as browning deterioration, and deterioration due to coloring and heat during processing under the influence of sunlight, dust, oxygen, etc. when used outdoors. Are known. Conventionally, various additives have been used to solve these problems, and in particular, organic phosphoric acid esters, organic phosphorous acid esters and the like are used for improving weather resistance deterioration (Japanese Patent Application Laid-Open No. 2-272048). Etc.) was still insufficient.

[0003]

From this point of view, the present invention aims to provide a chlorine-containing resin composition having excellent coloring properties, heat resistance, and weather resistance, and further, a chlorine-containing resin composition having excellent weather resistance. Organic phosphoric acid esters, which are conventional stabilizing aids in products, have no defects such as those found in organic phosphite, that is, they are stable to hydrolysis, have good compatibility, and contain chlorine. The purpose is to develop a stabilizer having an excellent effect of suppressing deterioration of a resin composition.

[0004]

Means for Solving the Problems The gist of the present invention is (1) general formula

A chlorine-containing resin composition comprising a compound represented by the formula:

Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and are C _{4 to} C ₂₅ alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups,
An alkoxyalkyl group, a C _{1 to} C ₁₈ alkyl-substituted aryl group, an aryloxyalkyl group, a polyoxyalkylenealkyl group, a polyoxyalkylenearyl group,
Represents an aralkyl group such as a benzyl group or phenylethyl,
X represents a polyhydric alcohol residue, a polyhydric phenol residue, a polyoxyalkylene polyhydric alcohol residue, and n is 1
The following integers are shown. (2) General formula

A compound represented by the formula: and a general formula

And / or

A chlorine-containing resin composition comprising a compound represented by the formula:

Embedded image

Embedded image However, R ₅ , R ₆ , and R ₇ each represent a C _{8 to} C ₂₅ alkyl group, which may be the same or different, and M represents zinc or an alkaline earth metal. It is.

For example, regarding a vinyl chloride resin composition for agriculture, tricresyl phosphate as an organic phosphoric acid ester is added to 100 parts by weight of a vinyl chloride resin for the purpose of improving weather resistance in the conventional formulation. 4 to 7 parts by weight, or 2 to 4 parts by weight of trixylenyl phosphate was added, but unless the addition amount is increased in this way, the weather resistance cannot be achieved to a practical level and the physical properties It also leads to disadvantages such as a decrease, in particular, a decrease in cold resistance in cold regions.

On the other hand, the organic phosphorus compound of the present invention has a very excellent weather resistance vinyl chloride resin composition with a small addition amount of 0.1 to 5.0 parts by weight, preferably 0.5 to 2.0 parts by weight. Give things. Furthermore, when 0.01 to 3.0 parts by weight, preferably 0.1 to 0.5 parts by weight of an organic phosphate metal salt is used in combination, the effect becomes more excellent.

An example of the manufacturing method is as follows. Trixylenyl phosphate, bisphenol A, and trixylenyl phosphite were charged at a molar ratio of 1: 1: 1, and transesterification reaction was performed using an alkali compound such as potassium carbonate or potassium hydroxide as a catalyst. By distilling off the by-produced xylenol, the target compound 1 can be obtained. However, the method for obtaining this compound is not limited to this method.

The chlorine-containing resin in the present invention means a vinyl chloride resin homopolymer or a resin mainly containing vinyl chloride,
Or chlorinated vinyl chloride or chlorinated polyethylene, such as vinyl chloride and vinyl acetate, vinylidene chloride,
It is a copolymer with ethylene, propylene, methacrylic acid ester, a urethane resin, a graft polymer, or a blended product with these resins.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The addition amount of Compound 1 is 0.1 to 5.0 parts by weight. A more preferable embodiment of the present invention is to use Compound 1 or Compound 1, Chemical Formula 2, Chemical Formula 3 and an epoxy resin in combination. Specific examples of usable compounds include bisphenol A type and novolak type. However, it is not limited to these. The amount of epoxy resin used is 0.05 to 5.0 parts by weight. In addition, in the present invention, if necessary, a plasticizer, a reinforcing agent, a processing aid, a heat stabilizer, a color preventing agent, a metal soap, a lubricant, a filler, a pigment, an organic phosphoric acid ester, an organic phosphorous acid ester. Conventionally used for chlorine-containing resins such as, dripping agent, anti-blocking agent, antioxidant, UV absorber, hindered amine light stabilizer, plate-out inhibitor, anti-fog agent, epoxy compound, heat retention improver, etc. It goes without saying that the additives mentioned above may be used appropriately.

The present invention will be specifically described below with reference to examples. Example The following compounds and known organic phosphoric acid esters were added to the above base compound individually or mixed in the ratios shown in Table 1 (Experiment Nos. 1 to 15), and calendered at 160 ° C. to give 0.1 mm. A thick film was made.

[0011]

Embedded image

[0012]

Embedded image

[0013]

[Chemical 6]

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image : Equivalent to the mixture of Chemical formula 2 and Chemical formula 3 Product name "LBT-1830" manufactured by Sakai Chemical Co., Ltd.

[0017]

Embedded image : Hindered amine compound manufactured by Ciba-Geigy, trade name "Kimasorb 944FL"

(Weather resistance test) Each of the films obtained above was exposed outdoors for 1 year and subjected to a tensile test with a tensile tester (TG-5000G, manufactured by Shimadzu Corporation), and a test piece that was not exposed. And the ratio was calculated. That is, the elongation (or breaking strength) of the test piece after exposure was divided by the elongation (or breaking strength) of the test piece before exposure, and the ratio (%) was evaluated as an outdoor ratio.

The test results are shown in Table 1.

[0020]

[Table 1]

[0021]

As described above, the chlorine-containing resin composition according to the present invention exhibits excellent effects in colorability, heat resistance and weather resistance.

Claims (2)

[Claims] 1. A chlorine-containing resin composition comprising a compound represented by the general formula: ## STR1 ##. Embedded image However, R ₁ , R ₂ , R ₃ , and R ₄ may be the same or different and are each a C _{4 to} C ₂₅ alkyl group, alkenyl group, cycloalkyl group, aryl group, alkoxyalkyl group, C 4. _{1 to} C ₁₈ alkyl-substituted aryl group, aryloxyalkyl group, polyoxyalkylenealkyl group, polyoxyalkylenearyl group, benzyl group, aralkyl group such as phenylethyl, and X is
A polyhydric alcohol residue, a polyhydric phenol residue, and a polyoxyalkylene polyhydric alcohol residue are shown, and n is an integer of 1 or more. 2. A chlorine-containing resin composition comprising a compound represented by the general formula: embedded image and a compound represented by the general formula: embedded image and / or Embedded image Embedded image However, R ₅ , R ₆ , and R ₇ each represent a C _{8 to} C ₂₅ alkyl group, which may be the same or different, and M is
Indicates zinc and alkaline earth metals.