JPS63162747A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which has excellent resistance to impact and weather, etc. and does not cause chalking, by blending a vinyl chloride resin with a chlorinated polyethylene, an adipic acid derivative, a specified inorg. material and an epoxy resin in a specified weight ratio. CONSTITUTION:100pts.wt. vinyl chloride resin (A) is mixed with 2-15pts.wt. chlorinated polyethylene (B), 0.5-5pts.wt. adipic acid derivative (C) (e.g., di-n- butyl adipate), 0.1-5pst.wt. inorg. material (D) selected from the group consisting of lead oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, basic lead salts and coprecipitates thereof with silica gel and 0.5-10pts.wt. epoxy resin (E) having a plurality of reactive alpha-epoxy groups per molecule (e.g., glycidyl ether of bisphenol). The resulting vinyl chloride resin compsn. is suitable for use in the production of building window frames, rain gutter, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition containing a vinyl chloride resin as a main component, and its purpose is to provide a vinyl chloride resin composition that has excellent impact resistance and hardening properties. be.

Currently, resin compositions with impact resistance are produced as extruded products.
It is formed into pipes, sheets, gutters, profile extrusions, window frames, etc. It is also molded into injection products such as pipe handles and various electrical parts. Additionally, as a calendar product.

It is formed into industrial sheets, plates, wall coverings, etc. This resin composition is generally improved by adding impact modifiers such as methyl methacrylate-butadiene-styrene ternary copolymer resin (MBS) and acrylonitrile-butadiene copolymer rubber (NBR). It is being done. But, Has, NO
Although R improves impact resistance, it has the disadvantage of poor weather resistance. In addition, when chlorinated polyethylene is used as an impact modifier, there is no decrease in weather resistance;
In general, lead-based stabilizers are mainly used as stabilizers, and when left for a long time, the stabilizer tends to chalk on the surface of the molded product, which is unfavorable for the aesthetics of the product.Furthermore, the stabilizer If a tin-based stabilizer is used as a solvent, drawbacks such as chalking can be improved, but this tin-based stabilizer has a problem in terms of cost. For these reasons, there is a drawback that it is not possible to obtain a composition that has practically acceptable weathering properties and has excellent chalking properties.

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From the above, the present invention does not have these drawbacks (problems), that is, it not only has excellent impact resistance, but also has good weather resistance, excellent heat resistance, and has excellent chalking resistance during molding. The object of the present invention is to obtain a resin composition that is unlikely to form on the surface of objects.

r, ta? According to the present invention, these problems can be solved by (A) 100 parts by weight of vinyl chloride resin, (B) chlorinated polyethylene.
2.0 to 15 parts by weight, (C) adipic acid derivative 0.5
~5.0 parts by weight, (D) at least one inorganic member selected from the group consisting of lead oxides, magnesium oxide, magnesium hydroxide, aluminum hydroxide, and basic salts of lead and their co-precipitates with silica gel; Substance 0.1
-5.0 parts by weight and (E) 0.5 to 10 parts by weight of an epoxy resin having at least two reactive α-epoxy groups in one molecule.

It can be solved by The present invention will be explained in detail below.

(A) Vinyl chloride resin The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer and vinyl chloride.
The degree of polymerization of this vinyl chloride resin, which is a copolymer with a compound having at least one copolymerizable double bond with vinyl chloride (preferably 45% by weight or less), is usually 800 to 3.
Typical examples of compounds having at least one double bond include vinylidene chloride, ethylene, propylene, vinyl acetate, acrylic acid and methacrylic acid and their esters, and maleic acid. and their esters and acrylonitrile. These vinyl chloride resins are obtained by homopolymerizing or copolymerizing vinyl chloride alone or vinyl chloride and the vinyl compound in the presence of a free radical catalyst, and the manufacturing method is widely used. It is used in many ways.

(B) Chlorinated polyethylene The chlorinated polyethylene used in the present invention can also be obtained by chlorinating polyethylene powder or particles in an aqueous suspension, or by chlorinating polyethylene dissolved in an organic solvent. (preferably obtained by chlorination in aqueous suspension)
Generally, it is amorphous or crystalline chlorinated polyethylene having a chlorine content of 20 to 50% by weight, and particularly preferably amorphous chlorinated polyethylene having a chlorine content of 25 to 45% by weight.

Said polyethylene is obtained by homopolymerizing ethylene or copolymerizing ethylene with at most 10% by weight of α-olefin (generally having at most 12 carbon atoms). Its density is generally 0.91
0 to 0.9701x/cm''. Also, its molecular weight is 50,000 to 700,000.

(C) Adipic Acid Derivatives Furthermore, the adipic acid derivatives used in the present invention are generally those widely used as plasticizers, chelating agents, lubricants, etc. in the rubber and resin industries. The adipic acid derivative usually has at most 16 carbon atoms (preferably 13 or less) than adipic acid.
A typical example of a preferred adipic acid derivative is di-n-butyl.
Adipate, di(2-ethylhexyl)adipate,
Examples include adipic acid esters such as diisodecyl adipate, di(n-octyl, n-decyl) adipate, diisononyl 7-dipate, benzyl-octyl 07-dipate, and di-(butoxy-ethyl-ethyl) adipate.

These adipic acid derivatives are available from the Rubber Digest company line “
Handbook, Rubber and Plastic Compound Chemicals (Rubber Digest, published in 1972), pp. 155 to 157
It is written on the page.

(D) Inorganic substance The inorganic substance used in the present invention is lead oxide,
Selected from magnesium oxide, magnesium hydroxide and aluminum hydroxide and basic salts of lead and their coprecipitates with silica gel. Typical examples of lead oxides include -lead oxide (PbO), red lead (dilead tetroxide, pb3)
o4) and the like, and examples of the basic salts of lead include basic lead silicate and tribasic lead sulfate. Furthermore, the proportion of silica gel in the coprecipitate of lead basic salt and silica gel is usually 10 to 80% by weight (preferably,
10-50% by weight, preferably 20-50% by weight), the average particle size of these inorganic substances is generally 0.5-3
00IL11, preferably from 0.5 to 200 IL hazy, and particularly preferably from 1.0 to 1504 m. These inorganic substances may be used alone or in combination of two or more.
(Published by Uhachi-Digest Co., Ltd. in 1972), pages 5 to 380.

(E) Epoxy resin Furthermore, the epoxy resin used in the present invention has two or more reactive α-epoxy groups in one molecule, and can be cured with a curing agent. These resins are currently used in adhesives, coating materials, cast products,
It is widely used as a molded product, and its molecular weight is usually 300 to eooo (preferably 300 to 500
0).

As a representative example of this epoxy resin, one obtained by reacting epichlorohydrin with an active hydrogen compound having active hydrogen such as phenolic -OH, carboxylic acid -0008, and amine -NH2 is preferably used. The most common epoxy resins, such as Epicote and Epon-Araldite, are obtained by reacting bisphenol A (4,4°-dioxydiphenylpropane) and epichlorohydrin, but the epoxy resins obtained by this reaction are the most popular. suitable. Additionally, commonly manufactured materials can also be used. Typical examples include glycidyl ethers of dihydric phenols, glycidyl ethers of bisphenols (e.g., those mainly composed of diphenolic acid, those mainly composed of bisphenol A and p-xylene dichloride condensate), glycidyl ethers of polyphenols, and fatty acids. Examples thereof include glycidyl ethers of dialcohols and trialcohols of the group and other alcohols, and glycidyl ethers of amines or amides. The manufacturing method, types, etc. of these epoxy resins are described in detail in Shunsuke Muratachi, Ryohei Oda, and Minoru Iki, ``Plastic Handbook'' (Breakfast Shoten, published in 1978), pages 272 to 277. .

(F) Composition ratio (composition ratio) The combination ratio (composition ratio) of other composition components to 100 parts by weight of vinyl chloride resin is as follows.

For chlorinated polyethylene, it is 2.0 to 15 parts by weight,
2.0 to 12 parts by weight is desirable, especially 2.5 to 1
0 parts by weight is preferred.

The amount of the adipic acid derivative is 0.5 to 5.0 parts by weight, preferably 0.5 to 4.0 parts by weight, and particularly preferably 1.0 to 4.0 parts by weight.

Furthermore, the total amount of inorganic substances is 0.5 to 5
．． 0 parts by weight, preferably 1.0 to 5.0 parts by weight, particularly preferably 1.0 to 4.5 parts by weight.

In addition, for epoxy resin, it is 0.5 to 10 parts by weight,
It is preferably 1.0 to 10 parts by weight, particularly preferably 1.0 to 7 parts by weight.

If the composition ratio of chlorinated polyethylene to vinyl chloride resin is less than the lower limit, a composition with excellent impact resistance cannot be obtained.On the other hand, if it is blended above the upper limit, a composition with excellent impact resistance and weather resistance cannot be obtained. However, the tensile strength and stiffness are very low and the ideal composition may not be obtained.

Furthermore, if the composition ratio of the adipic acid derivative is less than the lower limit, a composition with good processability and photostability (particularly, chalking property) cannot be obtained. Light stability is slightly improved, but significant properties and slippage occur during processing. Further, if the total amount of the inorganic substances is less than the lower limit, a composition with good thermal stability cannot be obtained. On the other hand, if the composition ratio of the epoxy resin is below the lower limit, although the thermal stability will improve slightly, it may cause bleeding on the surface of the molded product or poor dispersibility. A composition with good thermal stability and photostability cannot be obtained.On the other hand, even if the upper limit is exceeded, the thermal stability and photostability will improve slightly, but the kneading processability (workability) will be affected. becomes difficult.

(G)! Although the composition of the present invention can be obtained by uniformly blending the above-mentioned substances such as mixing methods and molding methods, fillers, plasticizers, oxygen, and ozone commonly used in the vinyl chloride resin and resin industry may also be used. Additives such as heat and light (ultraviolet) stabilizers, lubricants and tackifiers may be added depending on the intended use of the composition.

When producing the composition of the present invention, the blending (mixing) method may be to use a mixer commonly used in the technical field such as an oven roll, dry blender, Banbury mixer, and Nigoo mixer. Among these mixing methods, in order to obtain a more uniform composition, two or more of these mixing methods may be applied (for example, after mixing in advance with a dry blender, the mixture may be mixed using an oven roll). method of mixing).

In producing the composition of the present invention, all the ingredients may be mixed at the same time, but some of the ingredients may be mixed in advance and then other ingredients may be mixed into the resulting mixture ( For example, after premixing chlorinated polyethylene with an adipic acid derivative and an inorganic substance,
Method of mixing the resulting mixture with vinyl chloride resin and epoxy resin).

The composition of the present invention can be used by molding it into a desired shape using a molding machine such as an extrusion molding machine, an injection molding machine, a compression molding machine, or a calendar molding machine that is commonly used in the general vinyl chloride resin industry. Ru.

As described above, the composition of the present invention has excellent weather resistance. Furthermore, the brittleness, chalking, and mechanical properties observed in molded products of commonly used vinyl chloride resin compositions are also significantly improved, and from these points of view, the composition of the present invention is a composition of extremely high practical value. It is a thing.

The present invention will now be described in more detail with reference to Examples.

In addition, in the Examples and Comparative Examples, the Charpy impact test was measured according to JIS K7111. Also,
In the heat deformation test, the product was left in a gear oven at a temperature of 190°C, and the color change after 10, 30, and 60 minutes was observed with the naked eye, and the state of color change was evaluated in the following three stages.

O: No discoloration Δ: Slight discoloration ×: Changed to black Furthermore, weather resistance was determined by exposing the molded product (sample) outdoors for 1 month, 3 months, and 6 months, and observing the surface of the molded product (sample) with the naked eye to determine the state of discoloration. is shown in the following three stages.

O: No chalking Δ: Slight chalking ×: Chalking occurred and the surface became white.

Examples 1 to 12, Comparative Examples 1 to 8 A vinyl chloride homopolymer having an average degree of polymerization of 1450 was used as the vinyl chloride resin. Ethylene-butene-1 copolymer containing 5.2% by weight of butene-1 as chlorinated polyethylene (density 00825 g/cm",
Average molecular weight approximately 200,000) was chlorinated in an aqueous suspension to produce non-grade chlorinated polyethylene (chlorine content 35.2% by weight, Mooney viscosity (MSl, 4.100"C) 80
) was used. In addition, as an adipic acid derivative, di(butoxy ethoxy ethyl) adipate (hereinafter referred to as rDAE)
AJ) was used.

Furthermore, as an inorganic substance, magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd., hereinafter referred to as r
D-IJ), magnesium hydroxide with an average particle size of about 1 pm (manufactured by Kyowa Chemical Industry Co., Ltd., hereinafter r D-2J)
aluminum hydroxide (manufactured by Showa Light Metal Co., Ltd., hereinafter referred to as rD-3J) with an average particle size of about 10 pm, and tribasic lead sulfate (manufactured by Kosei Co., Ltd., hereinafter referred to as rD-3J) with an average particle size of about 75 gm. 7.0 g/cm'', hereinafter r D-4J
13-
54) was used. Furthermore, as an epoxy resin,
A condensate of albisphenol A and epichlorohydrin (hereinafter referred to as rE-IJ) with an average molecular weight of about 550!
3 and a condensate of the same type with an average molecular weight of about 830 (hereinafter referred to as rE-24), each of the above ingredients (the amount of each is shown in Table 1), and calcium stearate (as a lubricant). .5 parts by weight was used.

Using an open roll whose surface temperature was set in advance to 180°C, 100 parts by weight of PVC was uniformly rolled for 10 minutes at the proportions (compounding amounts) of other composition components shown in Table 1. The mixture was sufficiently kneaded to give the following properties and formed into a sheet. Each sheet obtained was pressed to 200 kg/crn using a heat press set at 180°C.
Sheets with a thickness of 2 mm and 4 mm were produced under pressure (gauge pressure).

The obtained sheet having a thickness of 2 mm was subjected to a heat discoloration test and a weather resistance test. Further, a Charpy impact test was conducted on a sheet having a thickness of 4+m. The results obtained are shown in Table 2.

In addition, in Comparative Examples 1 and 5, dehydrochlorination occurred during cross-wiring using a roll, and no pressed sheet was obtained.

The resin composition obtained by the present invention not only has excellent heat discoloration resistance, but also exhibits the following effects.

(1) Good weather resistance.

(2) It is relatively inexpensive.

(3) Chalking will not occur even if exposed outdoors.

(4) Excellent impact resistance.

The composition of the present invention not only has the above-mentioned good effects, but also has excellent moldability, so it can be used in a wide variety of fields. Typical uses are shown below.

(1) Window frames for building materials (2) Profile extrusion profile (3) Rain gutters (4) Irregular extrusion plate

Claims (1)

[Claims] (A) 100 parts by weight of vinyl chloride resin, (B) 2.0 to 15 parts by weight of chlorinated polyethylene, (C) 0.5 to 5.0 parts by weight of adipic acid derivative, (D) Lead 0.1 to 5.0 parts by weight of at least one inorganic substance selected from the group consisting of oxides of magnesium oxide, magnesium hydroxide, and aluminum hydroxide, and basic salts of lead and their coprecipitates with silica gel; (E) A vinyl chloride resin composition comprising 0.5 to 10 parts by weight of an epoxy resin having at least two reactive α-epoxy groups in one molecule.