JPS596244A - Stabilizing composition for halogen-containing resin - Google Patents

Abstract

PURPOSE:To provide the titled stabilizing compsn. which does not cause plateout and bleeding and gives halogen-contg. resins having excellent long-term heat stability, initial coloration, transparency, etc., containing a specified alkyleneimine compd. as the main component. CONSTITUTION:An alkyleneimine compd. of the formula (wherein R is a 2- 26C mono- or polyhydric alcohol residue; R' is H, methyl; n is 1-4) is used as a main component. Pref. a metallic compd. of the formula MX (wherein M is Li, Na, K, etc.; X is an org. carboxylic acid, phenol, halogen), such as sodium caproate or sodium stearate, is added to said imine compd. to obtain the desired stabilizing compsn. for halogen-contg. resins. The alkyleneimine compd. of the formula can be obtd. by reacting ethyleneimine or propyleneimine with a polyfunctional acrylic monomer derived from an alcohol and acrylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilizing composition for halogen-containing resins. More details include long-term thermal stability, initial coloring properties,
The present invention relates to a stabilized composition that provides a 6T halogen-containing resin with good transparency.

Generally, in resins containing chlorine, hydrogen chloride is eliminated by heat during molding, resulting in undesirable coloring. Therefore, in order to reduce this coloration at processing temperatures,
It is common practice to add 111 or more stabilizers to resin compositions. Conventionally, such stabilizers include Baliuno 1, calcium, magnesium, cadmium,
In addition to lead or zinc compounds, organic tin compounds, organic phosphorus compounds, epoxy compounds, and the like are known. Examples of these stabilizers include lithium, sodium,
potassium, barium, magnesium, strontium,
Examples include salts of metals such as zinc, cadmium, lead, aluminum, or tin and organic carboxylic acids having 2 to 20 carbon atoms, or ferulates of these metals. Suitable examples include lithium stearate, calcium myristate,
Examples include barium stearate, zinc stearate, aluminum stearate, magnesium laurate, barium nonyl fertate, zinc benzoate, and the like. Examples of organotin stabilizers include methyl, butyl or octyltin laurate, maleate or mercabutisod, and specifically, L-plusdec and Rubber Additives Practical Handbook 1.
, Kagaku Kogyosha, pages 170-176.

Although these compounds are used alone or in combination, they often have drawbacks such as low coloring prevention ability and impairing the inherent transparency of the resin. In particular, non-toxic stabilizers that do not use cadmium or lead compounds have reduced long-term thermal stability.
It's not satisfying. In order to compensate for this long-term thermal stability, proposals have been made to improve it by adding small amounts of epoxy compounds, polyol compounds, phosphite compounds, etc.

However, although they show an improvement effect on coloring, their epoxies and polyols have poor initial coloring properties, and fumesphite has a poor initial coloring property.
Each has drawbacks such as causing the to-out 1 phenomenon.

As a result of various studies, the present inventors decided to incorporate one or two of the compounds represented by the following general formula into a halogen-containing resin, which has excellent long-term thermal stability and also has plate-out and bleed phenomena. The present inventors have discovered that the resin does not exhibit the following properties, and that the initial colorability, transparency, and 1 of the resin are improved, leading to the present invention.

The present invention also relates to the general formula [wherein R is an alcohol residue having 2 to 26 carbon atoms; R' is a hydrogen atom or a methyl group; n is an alcohol residue having 1 to 4 carbon atoms; is an integer.] Provided is a stabilizing composition for a halogen-containing resin comprising one or more of the compounds shown below.

The alkylene imine compound represented by the general formula J2 has an unstable three-membered ring and is highly reactive and highly volatile, so it is partially used in &aw processing agents, dyes, adhesives, paints, etc. However, attempts are being made to utilize its reactivity to apply it to various uses.

In the present invention, by reacting ethyleneimine or propyleneimine with various acrylates, the molecular weight is increased, volatility is reduced, and the compatibility with halogen-containing resins is improved. It is possible to provide a halogen-containing resin composition that can significantly improve the long-term thermal stability of the resin and also has excellent initial coloring properties, unlike conventionally known epoxies, polyols, etc.

Specifically, the alkylene imine compounds represented by the general formula used in the present invention include monohydric alcohols such as 2-ethylhexanol, decanol, oleyl alcohol, and stearyl alcohol, ethylene glycol, propylene glycol, butylene glycol, and butylene glycol. Polyhydric alcohols with 2 carbon atoms such as 1,6-hexanediol, neopendel glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, dipentaerythritol, etc. It is obtained by reacting a polyfunctional acrylic monomer obtained from ~26 alcohols and acrylic acid with ethyleneimine or propyleneimine, for example, trimethylolpropane-triβ-aziridinylpropio. Nate is a typical example. In particular, the boiling point is 211 Q due to volatility during processing and molding.
℃ or lower, preferably 250℃ or higher.

The stabilized composition of the present invention contains a metal compound represented by 6) which is an alkyl group, a phenol group, or a halogen group represented by the above general formula. May contain.

The metal compound that can be used in the present invention is an organic carboxylic acid constituting 'ζ, and 'ζ is preferably a saturated or unsaturated fatty acid or an aromatic acid having 6 to 22 carbon atoms. Typical carboxylic acids include caproic acid, Cabrylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, araxic acid, behenic acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid,
Linoleic acid, linuric acid, isostearic acid, benzoic acid, m-)ruyl acid, p-1-butylbenzoic acid, naphthenic acid, 2-ethylhexylic acid as a synthetic carboxylic acid,
These include neoacid and persatic acid. Examples of phenols include carbolic acid, cresol, pt-butylphenol, p-octylphenol, and nonylphenol. Of these metal compounds, Da-Zn, Ra-
It is particularly preferable to use a combination of metal compounds such as MH-7, n, and Ca-Zn.

Examples of halogen-containing resins that can be added to the stabilizing composition of the present invention include polyvinyl chloride, vinyl chloride, and copolymers copolymerizable with the same, graft polymers, block polymers, (examples of comonomers include Olefin rA such as ethylene and propylene, vinyl m acid, vinyl laurate, saturated acid vinyl esters such as methacrylic acid methyl ester, unsaturated acid alkyl esters, fulkyl vinyl ethers such as lauryl vinyl ether, maleic acid, acrylonitrile, styrene , medylsudirine, vinylidene chloride, vinylidene fluoride, etc.), and further polyvinyl chloride and e.g. acrylonitrile-butadiene-styrene,
Polymer blends of methacrylic acid megyl ester-gutadiene-styrene terpolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, etc., and post-treated products of polyvinyl chloride with algoryl, etc., post-chlorine It is a halogen-containing resin such as a compound.

The stable A6 composition of the present invention may contain other stabilizers such as those listed above.
Organic nonmetallic stabilizers other than the alkyleneimine compounds represented by the general formula can also be used in combination as long as they do not impede the object of the present invention.

For example, 2-phenylin 1-9, dibenzoylmethane, sifyl diourea, sedil and stearyl β-aminocrotonic acid ester, 1,3 and I 4-butanediol bis β-aminocrotonic acid ester, diodieg astragalus. recall bisβ-aminocrotonic acid ester,
Nitrogen-containing compounds such as isocyanuric acid and its derivatives such as tris(2-hydroxyethyl) cyanurate, polyhydric alcohols such as pentaerythritol, mannitol, and sorbitol, benzoic acid, medylbenzoic acid, licolic acid, maleic acid, cinnamon , p-tert-butylbenzoic acid, carboxylic acids such as crotonic acid, organic non-metallic compounds such as boric acid ester, 100-osyglycolic acid ester, etc. In addition, mono- or diorganotin mercaptide-based compounds can also be used.

Others as necessary, such as commonly used plasticizers, antioxidants, organic phosphites, ultraviolet absorbers, pigments, etc.
Fillers, surface treatment agents, flame retardants, fluorescent agents, fungicides,
Plate-out inhibitors, photodegradants, processing aids, mold release agents, viscosity reducing agents, reinforcing agents, and the like can be included in the stabilizing composition for halogen-containing resins of the present invention.

When blending the composition of the present invention with a halogen-containing resin, the amount of the composition to be blended is from 0.001 to 100 parts by weight of the halogen-containing resin as an alkyleneimine compound represented by the general formula.
It is usually used in an amount of 3.0 parts by weight, preferably 0.05 to 1.0 parts by weight.

If the amount is less than 0.0 (11 parts by weight), the effect of addition will be small, and if it is used in an amount greater than 3.0 parts by weight, the initial coloring properties will be improved, but the long-term coloring properties will tend to deteriorate.

A suitable amount is 50 to 99.8% by weight, preferably 67 to 99% by weight. The ratio of the metal compound to the halogen-containing resin is usually 0.00 parts by weight per 100 parts by weight of the resin. O1~4
It is culm by weight.

The following examples do not demonstrate the effects of the stabilizing composition for halogen-containing resins according to the present invention.

However, the scope of the present invention is not limited only to the scope of the examples.

Example 1 In order to examine the stabilizing effect of the stabilizing composition containing the alkylene imine compound of the present invention on polyvinyl chloride, a sheet was prepared by kneading the following composition with two rolls at 170° C. for 5 minutes. This sheet was subjected to a thermal stability test at 175° C. in an open gear, and the degree of discoloration was compared. Further, this sheet was pressed for 5 minutes at 170° C. and lOOkg/cd, and the transparency and colorability were compared.

These results are shown in Table 1.

Compound) Polyvinyl chloride (Zeon 103 EF' manufactured by Roki Zeon Co., Ltd.) I Of 11 parts by weight Diophylphthalate 40
〃Barium stearate 0.5
〃Zinc stearate 0
．． 5 Additives shown in Table-1 (alkyleneimine compounds, etc.) Amounts not shown in Table-1/
' , )'' / , /'”- / Example 2 The same procedure as in Example 1 was carried out except that stearic acid variuno was changed to stearic acid in the formulation of Example 1. A test was conducted and the results are shown in Table 2.

The evaluation of the test results and the types of additives are the same as in Table-1.
,ru.

/ 7/' / / / /' / / / Example 3 Polyvinyl chloride (Nippon Zeon Co., Ltd., Pion 103 EP) 100 parts by weight Dioctyl phthalate 40 Calcium stearate 0.5 Zinc stearate 0.5 Trimedium A sheet was obtained in the same manner as in Example 1 except for the following formulation: rollbropan-tri-shio-2-methylaziridinylpropionate O,]//L. The physical properties of this sheet were as follows.

Black decomposition time at 170°C 35 minutes Plate out wiping test 2 Example 4 Polyvinyl chloride (Zeon 103 R:, P) 100 parts by weight Dioctyl phthalate 40 Stanclair T-135 (Methyl tin mer) Captide, manufactured by Dainippon Ink Chemical Co., Ltd. 1.0 Trimethylolpropane to tri-β-2-methylaziridinylpropionate 0.1 The above formulation was followed, and the other conditions were the same as in Example 1 to make a sheet. The physical properties of this sheet were as follows.

Claims (1)

[Scope of Claims] A stabilizing composition for a halogen-containing resin comprising one or more compounds represented by the following general formula. [In the formula, R is an alcohol residue having 2 to 26 carbon atoms; R' is a hydrogen atom or a methyl group; n is an integer of 1 to 4; ]