JPH044208A - Vinyl chloride-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride-based copolymer excellent in weather resistance with hardly any deterioration in mechanical properties by copolymerizing vinyl chloride monomer with a specific cyanoacrylate compound. CONSTITUTION:The objective copolymer is obtained by copolymerizing 100wt.% vinyl chloride monomer with a cyanoacrylate compound (e.g. ethyl alpha-diphenyl-beta- cyano-acrylate or ethyl alpha-butyl-alpha-methyl-beta-cyano-acrylate) expressed by the formula (R1 and R2 are alkyl or phenyl; R3 is 1-4C alkyl) in an amount of >=0.05wt.%, preferably 0.05-0.1wt.%. with 100 pts.wt. resultant copolymer, is blended 0-200 pts.wt. plasticizer to afford a vinyl chloride-based resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a vinyl chloride resin composition with improved weather resistance.

More specifically, a substance represented by the following general formula (1) (wherein,
R1 and R1 represent an alkyl group, or 0R3 represents a C8-C4 alkyl group).

A vinyl chloride copolymer containing 0,0% by weight or more of O,
This is a vinyl chloride copolymer resin composition characterized by containing 200[')IR.

[Prior art and its problems] Vinyl chloride resin compositions are suitable for extrusion molding, blow molding, Calendar molding, injection molding,
It is widely used in the form of various molded products such as vacuum forming, as well as leather, sheets, films, etc.

However, it is known that vinyl chloride resin compositions are sensitive to ultraviolet rays, causing deterioration of color, deterioration of mechanical properties, etc., and cannot withstand long-term use.

In order to prevent these harmful effects, compounds such as benzophenone, benzotriazole, cyanoacrylate, piperidine, etc. have been added to the formulation. Showa 8l-IH,
863, Japanese Patent Publication No. 51-20.211) Many of these compounds cause coloring when added in large amounts, and their use is also restricted due to blooming phenomenon and poor compatibility with other additives. Ta.

As a result of intensive research aimed at improving the drawbacks of such vinyl chloride resin compositions, the present inventors have found that molded products made from vinyl chloride resin compositions made of vinyl chloride polymers and plasticizers that have undergone specific polymerization are extremely useful. The present invention was completed based on the discovery that the material has good weather resistance and little deterioration in mechanical properties.

As will be clear from the above description, an object of the present invention is to provide a vinyl chloride resin composition that has excellent weather resistance without impairing its physical properties.

[Measures to solve the problem] The present invention has the following configurations (1) and (2).

(1) A vinyl chloride copolymer made by copolymerizing 100% by weight of a vinyl chloride monomer and 0.05% by weight or more of a substance represented by the following general formula.

(In the formula, R,, R2 is an alkyl group or, R3 is C
+””represents a C4 alkyl group).

(2) Vinyl chloride copolymer 10 described in item (11) above
A vinyl chloride resin composition containing 0 to 200 parts by weight of a plasticizer.

To explain the present invention in more detail, it is a vinyl chloride copolymer obtained by copolymerizing a specific cyanoacrylate compound represented by the above formula (I) with a vinyl chloride polymer.

Specifically, as this cyanoacrylate compound, α
Examples include -diphenyl-β-cyano-acrylic acid ethyl ester, α-butyl-α-methyl-β-cyano-acrylic acid ethyl ester, and α-phenyl-α-methyl-β-cyano-acrylic acid ethyl ester. I can do it.

The chlorine used as a raw material for the vinyl chloride copolymer of the present invention is a mixture of vinyl chloride chloride and a cyanoacrylate compound. The amount of this cyanoacrylate compound is not particularly limited, but is 0.01 to 1.0% by weight based on 100% by weight of vinyl chloride.

If the amount of the cyanoacrylate compound is too large, the resulting copolymer will have good weather resistance, but will have poor coloration and will be unfavorable for compatibility with other additives.

Compatibility is largely due to the vinyl chloride resin, and over a long period of time, additives such as weather resistance improvers (ultraviolet absorbers), softeners, and antistatic agents ooze out, causing bleeding and blooming phenomena. It cannot withstand long-term use.

The vinyl chloride copolymer of the present invention improves weather resistance by copolymerizing with a cyanoacrylate compound, suppresses bleeding and blooming phenomena, and enables long-term use.

If the amount of the cyanoacrylate compound is too small, it will not contribute to improving weather resistance.

Therefore, the amount of cyanoacrylate compound is 0.03~
0.5% by weight is preferred, especially 0.05-0.1% by weight
is preferred.

In addition, the degree of polymerization of this copolymer is 400 to 3000
If it is less than 400, the mechanical properties of the film or sheet will deteriorate, and if it exceeds 3,000, the molding temperature will increase, making processability difficult.

As raw materials for the vinyl chloride copolymerization of the present invention, in addition to vinyl chloride polymers and cyanoacrylate compounds, vinyl polymers and the like can be used as copolymerization components.

Typical examples of such vinyl monomers include vinylidene halides such as vinylidene chloride, vinyl esters such as vinyl acetate, vinyl ethers such as methyl vinyl ether, and α-olefins such as ethylene and propylene. be able to.

The method for producing the copolymer of the present invention is a method of polymerizing vinyl chloride resin containing a specific cyanoacrylate compound using a catalyst. The catalyst used here is not particularly limited, but it is preferable that the catalyst has a 10-hour half-life temperature of 50° C. or less based on the degree of polymerization of the resulting copolymer.

Specific examples include 2.2°-azobis[2,4-dimethylvaleronitrile], 2.2°-azobisisobutyronitrile, dimethyl-2,2-azobisisobutyrate, 2,2°- Azo compounds such as azobis(2-methylbutyronitrile) and t-butyl peroxyvivalate, t
- Alkyl peroxy esters such as butyl peroxyisopropyl carbonate and t-butyl peroxy acetate, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, and lauroyl peroxide, acetyl peroxide, benzoyl peroxide, etc. Examples include diacyl peroxide such as oxide.

The polymerization method is not particularly limited, and any known polymerization method for vinyl chloride can be used as is, and any of suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization can be used. It is advantageous in that porous S+ fat particles can be obtained and the polymer particles can be dried easily.

The polymerization temperature is set depending on the desired degree of polymerization of the copolymer. Furthermore, the type of dispersant used during polymerization is not particularly limited.

In the vinyl chloride resin composition of the present invention, the following may be added to the copolymer as long as the spirit of the present invention is not impaired.

Heat stabilizers (Ca-Zn series, Ba-Zn series, tin series, pbz
etc.), lubricants, plasticizers, epoxy compounds, fillers, processing aids, pigments, etc. can be added as appropriate.

[Example] The present invention will be explained in detail in Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist of the invention. means parts by weight.

The compounds used, polymerization methods, and test methods employed in Examples and Comparative Examples are shown below.

(1) Compounds used in the vinyl chloride copolymer: Table 1 shows the symbols and chemical formulas of the cyanoacrylate compounds, benzophenone compounds, and benzotriazole compounds used in the vinyl chloride copolymer.

(2) Tensile test: Elongation (%), 100% modulus (kg/cm') and strength at break (kg/c 2) were measured in accordance with JIS K-6723.

(3) Tensile test residue *: Tensile test residual rate after the weather resistance test.

(4) Weather resistance test: Sunshine Weather Meter WE
L-5UN-DC type (manufactured by Suga Test Instruments ■) [Conditions: Coblack panel temperature: 63°C Humidity: 60% Spray time/cycle: 12 minutes/60 minutes (s) y I
(yellowness) measurement: SM color computer 5M-
5-Is-28 type (manufactured by Suga Test Instruments) (6) Thermal stability:
l x 20 x 10mm (D test piece at 180℃
It was kept in a gear type oven adjusted to the desired temperature, and the time until coloring was measured.

(7) Hard [: According to JIS K-6723.

(8) II match method! The inside of a polymerization vessel with an internal volume of 2,001 cm equipped with a stirrer was replaced with nitrogen gas, and then 100 kg of water and polyvinyl alcohol with a saponification degree of 74% (polymerization degree 700) as a suspending agent were used.
．． 12 parts by weight (based on 100 parts by weight of vinyl chloride monomer),
100 parts by weight of vinyl chloride containing predetermined amounts of cyanoacrylate compounds, benzophenone compounds, and benzotriazole compounds, 0.03 parts by weight of t-butyl peroxyneodecanoate as a catalyst, and 0 parts by weight of cumyl peroxyneodecanate. .02 parts by weight, vinyl chloride body S
After charging O, Okg, the polymerization temperature is 5 at the same time as the start of charging.
The polymerization is stopped when the temperature is raised to 1 t and the internal pressure of the polymerization vessel reaches 6.0 kg/co+'G, and this is dehydrated and dried to obtain a polymer.

Examples 1-2, Comparative Examples 1-4 Vinyl chloride homopolymer (B), copolymer containing 0.05% by weight of compound A as a copolymer component (A-■), same < 0.10% by weight Copolymer containing 0.05% by weight of copolymer component F (F-I)
, the same (copolymer containing 0.10% by weight (F-11)
, a copolymer containing 0.05% by weight of copolymer molecules (T
-1), a copolymer containing 0.1% by weight (T-
11) was produced according to the polymerization method described above. These polymerization results are shown in Table 2.

For each 100 parts by weight of these polymers, 50 parts of DOP,
150
℃ for 7 minutes with an 8-inch roll and 160℃ press to prepare 1 sv receipt composition (b, a-1, a-II,
f-1°f-11, t-1, t-11) were obtained.

Yellowness (Y
The results are shown in Table 3.

As is clear from the same table, compound A is 0.05.0.10
The composition (a-I, a-11) using the copolymer (^-■, A-11) containing % by weight had a weather resistance test of 10
A composition using a copolymer containing compounds F and T and having a low yr value at 00 hours (f-I, f-II・ti, t
-11) showed superior weather resistance.

Comparative Examples 6 to 11 0.05 parts and 0.10 parts of compound A (a', a'') and 0.0 parts of compound F were added to the vinyl chloride homopolymer (B).
05 parts, 0. 1O part combination (f', f''), compound T
After blending 0.05 parts and 0.10 parts (t", t") of Shown in the table.

As is clear from the same table, compared to the blended composition, the copolymer composition containing compound A (^-I^-n)
The Yl@ of the 0@ weather resistance test was low, indicating good weather resistance.

Examples 3 to 4, Comparative Examples 12 to 22 Hardness, thermal stability test, tensile test, and tensile test retention rate conducted on the compositions used in Examples 1 to 2 and Comparative Examples 1 to 11 according to the weather resistance test. The results are shown in Table 5.

As is clear from the same table, the composition (A-1,8-II) using a copolymer containing compound A contains compounds F, T
A composition using a copolymer containing, and compounds A and F
, has better thermal stability than the composition containing T.
The tensile strength retention rate and elongation retention rate in the time weathering test are high, indicating excellent weather resistance.

Table 1 Symbols of compounds used in vinyl chloride copolymer Example A Cyanoacrylate ethyl-2-cyano-3,3-diphenylacrylate Comparative Example F Benzophenone 2-hydroxy-4-n-octoxybenzophenone Comparative Example T Benzotriazole CH.

Claims (2)

[Claims] (1) A vinyl chloride copolymer made by copolymerizing 100% by weight of a vinyl chloride monomer and 0.05% by weight or more of a substance represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 are alkyl groups, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_3 represents an alkyl group of C_1 to C_4). (2) Vinyl chloride copolymer 1 according to claim (1)
A vinyl chloride resin composition comprising 0 to 200 parts by weight of a plasticizer.