JPS58154747A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives moldings having improved appearance, and resistance to light and impact, by adding an acrylic copolymer as an impact-proofing agent and an organotin compd. as a stabilizer to a chlo- rine-contg. resin. CONSTITUTION:A chlorine-contg. resin compsn. is obtd. by adding 1-20pts.wt. acrylic copolymer contg. no butadiene as an impact-proofing agent and 0.1- 10pts.wt. one or more organotin compds. of formulasI, II, III wherein R<1> is a 1-12C alkyl, a group of formula IV (wherein R<3> is a 1-8C alkyl, alkenyl); R<2> is a 10-20C alkyl, alkenyl; n is 1,2 as a stabilizer to 100pts.wt. chlorine-contg. resin such as PVC or vinylidene chloride resin. Since the components have good dispersibility in one another, the compsn. has good moldability and extrusion workability during processing, gives moldings having excellent resistance to light and impact and good appearance after processing, and is suitable for use in the production of window frames, deck materials, outer wall materials, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chlorine-containing resin composition with improved appearance, light resistance and impact resistance.

Acrylonitrile, butadiene,
Attempts have been made to increase impact resistance by blending impact reinforcing agents such as styrene resin, methyl methacrylate/butadiene/styrene resin, vinyl acetate/ethylene copolymer, and chlorinated polyethylene. On the other hand, a sulfur-containing organotin stabilizer and a malate-based organotin stabilizer are added for the purpose of thermally stabilizing polyvinyl chloride blended with an impact strengthener.

However, these polyvinyl chloride compositions
Due to the poor dispersibility between impact strengtheners and stabilizers, moldability (lubricity) and extrusion workability decrease during processing, impairing the appearance and making it difficult to provide sufficient impact strength to the processed product. However, if the product is exposed outdoors for a long period of time, the impact strength will gradually decrease.

Recently, building materials 1, such as window frames and decking materials.

It has been applied to rain gutters, exterior wall materials, etc., and there is a strong desire to develop polyvinyl chloride with particularly good appearance, light resistance, and impact resistance.

As a result of research from the above viewpoint, the present inventors have found that by using an acrylic copolymer that does not contain butadiene as an impact strengthener and an alkyl ester organotin compound having a specific number of carbon atoms as a stabilizer, the processability and light resistance can be improved. We have succeeded in obtaining a chlorine-containing resin composition that has improved properties, as well as excellent impact resistance and appearance.

That is, 1 the present invention is based on the general formula (I ), (ID and (1) RISn(S(CH
2)nCOOR2)2 (1:]RASn[00
CCH-CHCOOR2〕2 [mouth] R15n(
OOCCH=CHCOOR2)3 [■] [In the formula, R1 is an alkyl group having 1 to 12 carbon atoms, a group -CH2
CH2C00R (where R3 represents an alkyl group or alkenyl group having 1 to 8 carbon atoms), and R2 represents an integer having 1 to 2 carbon atoms. This is a chlorine-containing resin composition characterized in that 10 parts by weight of chlorine-containing resin is added to the copolymer.

Used in the present invention as an impact toughener. The butadiene-free acrylic copolymer contains at least one acrylic compound selected from acrylonitrile, methacrylic ester, and acrylic ester in its molecule as a monomer constituent unit constituting the copolymer. means. however.

The copolymer shall not contain any butadiene structural units.

Examples of such butadiene-free acrylic copolymers include 2.

Acrylonitrile/chlorinated polyethylene/styrene copolymer.

Styrene/acrylonitrile copolymer.

Acrylic rubber/acrylonitrile/styrene copolymer.

Acrylic rubber/methyl methacrylate/acrylonitrile copolymer.

Methyl methacrylate/ethyl acrylate/acrylonitrile copolymer.

Methyl methacrylate/butyl acrylate/acrylonitrile copolymer.

Butyl acrylate, acrylic acrylate, methyl methacrylate, acrylonitrile copolymer, methyl methacrylate, ethyl acrylate copolymer.

Methyl methacrylate/butyl acrylate copolymer.

Ethylene/ethyl acrylate copolymer.

Ethylene-butyl acrylate copolymer.

Styrene/butyl acrylate/methyl methacrylate copolymer.

Styrene/ethyl acrylate/methyl methacrylate copolymer.

Butyl acrylate, triallyl annulate, styrene, methyl methacrylate copolymer.

Examples include metinoco methacrylate/isobonyl methacrylate copolymer.

The above general formula (1), which is added as a stabilizer to the present invention, (
In the organotin compounds represented by [3] and (III), R1 is an alkyl group such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl, etc., and R3 is methyl, ethyl, propyl, butyl, amyl. , alkyl groups such as octyl, vinyl groups,
Allyl group is mentioned.

Examples of R include alkyl groups such as delen, lauryl, myristyl, cetyl, stearyl, aracic, and alkenyl groups such as oleyl and dodecenyl. Also, for the alkyl group in R2.

[1 commercially available under the name ALFOLJ, e.g. 10-12 carbon atoms (C1o-12), 12-14 carbon atoms (C1o-12),
12-14), mixed alcohol with carbon numbers 12-18 (0m2-18), carbon numbers 16-18 (C16-18),
For example, a mixed alcohol having 11 to 15 carbon atoms (C11 to 15), commercially available under the name ``Diadol'', ``
Also included are mixed alkyl groups and branched alkyl groups derived from branched synthetic alcohols having 18 carbon atoms (Cts), which are commercially available under the names of ``Diadol'' and ``Oxocol''.

These stabilizers can be used alone or in combination of two or more. That is, the above general formulas [I], (Illll and (II
In the organotin compound represented by I), CI), (I
The compound I) or (III) is each independently [I]
and [■].

CI) and (1), (mouth) and (In) and (I) and (II
) and (III) can be added in combination of two or three types.

In the present invention, the amount of the impact strengthener and stabilizer added is 1 to 20 parts by weight, respectively, per 100 parts by weight of the chlorine-containing resin.
It is 0.1 to 10 parts by weight. If the impact strength agent exceeds 20 parts by weight, it will affect the physical properties 9 of the chlorine-containing resin, such as the softening point, and is not practical.

Moreover, if it is less than 1 part by weight, sufficient impact strength cannot be imparted.

The impact toughening agent of the present invention does not contain a butadiene structural unit in the acrylic copolymer. When the butadiene structural unit is present, a certain degree of impact strength can be obtained in the product, but there is a drawback that the product has poor light resistance and the impact strength decreases extremely over time.

Examples of the chlorine-containing resin of the present invention include vinyl chloride resin, vinylidene chloride resin, vinyl chloride, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl chloride.77+
Styrene, ethylene, fluoropyrene.

Methyl methacrylate, dialkyl fumarate.

Alternatively, mention may be made of copolymers formed by polymerization with one or more comonomers such as malate and the like.

The chlorine-containing resin composition of the present invention is a chlorine-containing resin.

Impact tougheners, stabilizers and other additives if necessary.

For example, it can be blended with a lubricant, an antioxidant, a pigment, a coloring agent, and a filler according to a conventional method such as a Banbury mixer, a mixing roll, a calender roll, or an extruder.

The thus obtained chlorine-containing resin composition of the present invention can be prepared by conventional methods such as injection molding, blow molding, vacuum molding,
It can be easily processed using various molding methods such as blow molding, extrusion molding, and injection blow molding.

The resulting molded products are widely used in building materials, pipes, parts, and other parts.

Since the chlorine-containing resin composition of the present invention has good mutual dispersibility among its constituent components, it has excellent moldability (lubricity) and extrusion workability during processing, and has excellent appearance, light resistance, and impact resistance after processing. A molded product is obtained.

Therefore, the molded product obtained according to the present invention is particularly suitable for use in building materials 9 such as window frames, decking materials, rain gutters, and exterior wall materials that require light resistance and impact resistance.

Next, the present invention will be explained with reference to Examples. In addition.

Parts in the examples indicate parts by weight.

Example 1 100 parts of vinyl chloride resin (Geon 103EP, manufactured by Nippon Zeon Co., Ltd.), 10 parts of butyl acrylate/acrylic acrylate/methyl methacrylate/acrylonitrile copolymer (Kane Ace FM, manufactured by Kanebuchi Chemical Co., Ltd.) as an impact strength agent, stable A mixture of 3 parts of the organotin compound of the present invention shown in Table 1 below as an agent and 1 part of a lubricant (EW-200, manufactured by Riken Vitamin Co., Ltd.) was placed in an extruder (screw diameter 20 I
'11. At L/D 22, compression ratio 3), 5 fights
A 10 fl lot rod was prepared and subjected to a Shalepy impact test.

Further, as a comparative example, a lot rod was prepared in the same manner using the same formulation as in Example 1, except that 3 parts of the organic tin compound of the comparative example shown in Table 1 below was used instead of the organic tin compound of Example 1. A Charpy impact test was conducted.

The above results are shown in Table 1.

Example 2 100 parts of vinyl chloride resin (Geon 103EP-8, manufactured by Nippon Zeo Co., Ltd.), 5 parts of acrylonitrile-styrene-chlorinated polyethylene (AC5, manufactured by Showa Denko K.K.) as an impact strengthener, and the following Table 2 as a stabilizer. 2.5 parts of the organic tin compound of the present invention and 1 part of a lubricant (EW-200° manufactured by Impaction Vitamin Co., Ltd.) were blended, a rod rod was prepared in the same manner as in Example 1, and a Nyaruby impact test was conducted.

Further, as a comparative example, a lot rod was prepared in the same manner using the same formulation as in Example 2, except that 25 parts of the organic tin compound of the comparative example shown in Table 2 below was used instead of the organic tin compound of Example 2. , Charpy impact test was conducted.

The above results are shown in Table 2.

(8E) Marks *1 to 7 in Table 2 indicate alkyl groups derived from alcohols that are commercially available under the following trademarks.

*I ALFOL 1012 (manufactured by Condea Chemie) *2 ALFOL 1214 () *3 ALFOU 1218 () *4 ALFOL 1618 () *5 Diador 1315 (manufactured by Mitsubishi Kasei) *6
Diadol 115L (#) *7 Okinokol 180 (manufactured by Nichikagaku Co., Ltd.) Example 3 Vinyl chloride resin (S-1008, manufactured by Kanekabuchi Kagaku Co., Ltd.) 10
0 parts, styrene, butyl acrylate, methyl methacrylate (Metaprene W-300. Manufactured by Mitsubishi Rayon Co., Ltd.) 2
0 parts, 20 parts of the organotin compound of the present invention shown in Table 3 below, and 1 part of a lubricant (EW-200) were blended, and a Charpy impact test was conducted in the same manner as in Example 1.

A Charpy impact test was also carried out using 2.0 parts of the organotin compound of the comparative example shown in Table 3 below. 15 parts of the impact strengthener of the invention, 4 parts of diptyltin bis(stearyl β-mercaptopropionate), 1 part of lubricant (EW-200) and 03 parts of titanium oxide (R-650, manufactured by Sakai Chemical Co., Ltd.) were blended, A 5×10fi lot rod was prepared in the same manner as in Example 1. A weather resistance test was conducted on the obtained lot rod using a sun/key/weather meter (manufactured by Suga Test Instruments Co., Ltd.).
The impact strength was measured every 7 hours.

Similarly, weathering tests were carried out using the organotin compounds of Comparative Examples shown in Table 3 below, and when conventionally known impact strengthening agents were used, and the 7 YARPI impact strength was measured.

The above results are shown in Table 4.

Table 4 (Note) The symbols in Table 4 indicate the following.

(a); Dibutyltin bis(stearyl β-mercaptoglobionate) (stabilizer of the present invention) (b); Dibutyltin bis(butyl β-mercaptopropionate) (stabilizer of comparative example) *1 Fuace FM (manufactured by Kanebuchi Chemical Co., Ltd.) *2 Metapre/W-300 (manufactured by Mitsubishi Rayon Co., Ltd.) *3 Kafuace B-12 (manufactured by Kanebuchi Chemical Co., Ltd.) *4 Dynoranoku H
-135 (manufactured by Osaka Soda Co., Ltd.) Patent applicant: Nitto Kasei Co., Ltd. Representative Patent attorney: Tetsuya Matsunaga

Claims (1)

[Scope of Claims] 1. For 100 parts by weight of chlorine-containing resin, (a) 1 to 20 parts by weight of an acrylic copolymer not containing butadiene as an impact strengthener, and (b) a primary stabilizer as an acrylic copolymer. General formula CI
), (II) and (ill) J Sn (S (CH2
)ICOOR2)2 (I:]RmuSn[06C
CH=CHCOOR2]2[■]R5n(00CCH=
CHCOOR)3 (IID [in the formula, R has 1 to 1 carbon atoms]
12 alkyl group, group -CH2CH2COOR3 (here, R3 represents an alkyl group or alkenyl group having 1 to 8 carbon atoms), R2 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, and n represents an alkyl group or alkenyl group having 1 to 2 carbon atoms. A chlorine-containing resin composition, characterized in that 0.1 to 10 parts by weight of one or more organotin compounds represented by the following integer is added to the copolymer.