JPS5817143A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain a vinyl chloride resin composition excellent in the resistance to heat distortion and shock and the workability, by incorporating an impact strength improver and a specified copolymer. CONSTITUTION:20-80wt% 2-isopropenylnaphthalene (with optionally alpha-methylstyrene), 1-70wt% methyl methacrylate, 5-30wt% acrylonitrile and 0-30wt% other monomers are polymerized in the presence of a crosslinked polymer (having a softeining temperature higher than that of a vinyl chloride used) that has been prepared from 10-70pts.wt. one or more monomer selected from among methyl methacrylate, acrylontrile, (alpha-methyl)styrene and 2-isopropenyl-naphthalene and 0.01-7pts.wt. polyfunctional monomer (e.g. divinylbenzene), and the resulting copolymer is used in the present composition. That is, to 20-80wt% vinyl chloride (A) are added an impact strength improver (B) and the above copolymer (C) in a total amount[(B)+(C)]of 80-20wt% with the weight ratio of (B) to (C) being 90-40:10-60.

Description

[Detailed Description of the Invention] The present invention has good heat deformation resistance. The present invention relates to a vinyl chloride resin composition having impact resistance and processability.

As is well known, the practical heat deformation temperature line for vinyl chloride resin moldings is 70°C am, and since it is not suitable for applications at temperatures higher than this, various methods are used to increase the heat distortion temperature of vinyl chloride resin moldings. Attempts have been made. Examples of this include Special Publication No. 45-24867 and Special Publication No. 48-1.
No. 8101, but these compositions have problems in processability.

Specifically, in order to improve the heat deformation resistance of vinyl chloride resin, the former is made by adding styrene/acrylonitrile/methyl methacrylate/α-methylstyrene copolymer to the vinyl chloride resin, and the latter is made by adding α-methylstyrene/methyl to the vinyl chloride resin. Add methacrylate/acrylonitrile copolymer.

However, in order to provide sufficient heat deformation resistance, it is necessary to
As mentioned above, it is necessary to add preferably 20% by weight or more.

For this reason, the processability of these compositions is significantly different from that of compositions comprising a vinyl chloride resin and an impact strength improver. (Generally, vinyl chloride resin alone does not have sufficient impact strength, so for applications that also require impact resistance, it is common to mix impact and soundness improvers, and the above two inventions also improve impact strength.) Although specific examples are shown in the examples, the compositions based on the above two inventions have a particularly high die swell ( dig swell) becomes larger. The compositions based on the above two inventions differ greatly in processability from conventional vinyl chloride resin compositions, and tend to be difficult to accept in fields such as profile extrusion and pipe extrusion, which require strict dimensional accuracy of molded products. be.

The present inventors have arrived at the present invention as a result of their earnest efforts to impart heat deformation resistance and impact resistance to vinyl chloride resin while maintaining the same processability as vinyl chloride resin compositions. It is.

That is, the present invention relates to vinyl chloride resin), impact strength improver (b), methyl methacrylate, acrylonitrile, styrene, and α-methylstyrene.

In the presence of a crosslinked polymer obtained by polymerizing 10 to 70 parts by weight of one or more mixed monomers selected from 2-isopropenylnaphthalene and 001 to 7 parts by weight of a polyfunctional monomer. , 2-isopropenylnaphthalene or ti2
- isopropenylnaphthalene and α-methylstyrene mixture 20-80% by weight, methyl methacrylate 1-70% by weight.

Mixed monomer 90-3 consisting of 5-50% by weight of acrylonitrile and 0-30% by weight of a monomer copolymerizable with these
0 parts by weight of copolymer 0, 20 to 80 parts by weight of vinyl chloride resin (4), and impact strength improver (6 parts by weight).
) and copolymer 0, the total weight of both is 80 to 20% by weight and 69.
And based on the total amount of both (6) and 0, copolymer 0 is 9
0-40% by weight.

The present invention relates to a vinyl chloride resin composition having good heat deformation resistance, impact resistance, and processability, characterized in that the impact strength improver (6) is 10 to 60% by weight.

The present invention will be explained in more detail below.

The impact strength improver (6) used in the present invention may be any agent as long as it can impart sufficient impact strength to the vinyl chloride resin.
It can be anything that is normally used. Examples of such materials include crosslinked or non-crosslinked methyl methacrylate/butadiene/styrene-based copolymers, acrylonitrile/butadiene/styrene-based copolymers, and methyl methacrylate/alkyl acrylate/styrene-based copolymers. A copolymer with

There are chlorinated polyethylene, chlorosulfonated polyethylene, etc., and one type or two or more types can be used.

Copolymer (C) is a mixture of 2-isopropenylnaphthalene or 2-improbenylna-7'talene and α-methylstyrene in an amount of 20 to 80% by weight in the presence of 10.01 to 77 parts by weight of a crosslinked polymer. .

Adding 90 to 50 parts by weight of a mixed monomer consisting of 1 to 70 parts by weight of methyl methacrylate, 5 to 50 parts by weight of acrylonitrile, and 0 to 50 parts by weight of one or more monomers copolymerizable with these. Polymerized and nine.

In the composition of the present invention, as a method for producing the copolymer (C), in the presence of a crosslinked polymer, 2-isopropenylnaphthalene or a mixture of 2-isopropenylnaphthalene and α-methylstyrene, methyl methacrylate, acrylonitrile, and a copolymer thereof are used. It is important to carry out addition polymerization of mixed monomers with polymerizable monomers. For example, by reversing the polymerization order, or by copolymerizing a crosslinked polymer and 2-isopropenylnaphthalene or a mixture of 2-isopropenylnaphthalene and α-methylstyrene, methyl methacrylate, acrylonitrile, and a monomer copolymerizable with these. A method in which the combined materials are separately manufactured and mixed is not preferred because the impact strength of the target composition decreases.

Here, addition polymerization is used in a broader sense than graft polymerization, and 2-isoglobenylnaphthalene iL< is a mixture of 2-isoglobenylnaphthalene and α-methylstyrene, methyl methacrylate, It is not limited to the case where all of the mixed monomers consisting of acrylonitrile and monomers copolymerizable with these are graft polymerized, but some of the mixed monomers are polymerized to 11 that does not undergo graft polymerization, resulting in a simple polymer blend form. This also includes cases.

Among the monomers that are addition-polymerized in the presence of crosslinked polymers, 2-
Isonorobenylnaphthalene helps improve heat deformation resistance. 2-Isonorobenylnaphthalene may be partially substituted with α-methylstyrene. The mixing ratio of 2-isonorobenylnaphthalene and α-methylstyrene may be arbitrary, but preferably 90/10 to 10/90. 2-Isonorobenylnaphthalene fL<U2-Isonorobenylnaphthalene and α-methylstyrene mixture is 20
If it is more than 80% by weight, it will not be effective, and if it is more than 80% by weight, the target composition will lack toughness and polymerization by normal radical polymerization will become difficult. Acrylonitrile is a copolymer (C)
It is used in an amount of 5 to 30% by weight to impart compatibility with vinyl chloride resin. If the amount is less than 5% by weight, the addition loses its significance, and if it is more than 30% by weight, it will cause undesirable coloration and a decrease in heat deformation resistance of the target composition. Methyl methacrylate is important for increasing the compatibility between the copolymer and the vinyl chloride resin, and is important for improving polymerization.
0 weight-' is used. If it is less than 1% by weight, the significance of its addition is lost, and if it is more than 70% by weight, it reduces the heat deformation resistance of the target composition, which is not preferable.

Along with these monomers, one or more copolymerizable monomers may be added.

These monomers include styrene, vinyltoluene, etc.
- Aromatic vinyls other than methylstyrene, methacrylonitrile, vinyl acetate, methacrylic acid, acrylic acid, maleic acid, fumaric acid.

Itaconic acid and esters thereof can be used in a range of 0 to 50%.

It goes without saying that a chain transfer agent such as mercaptan can also be added for the purpose of controlling the degree of polymerization.

As for the crosslinked polymer, it is necessary that the softening temperature of the crosslinked polymer is higher than that of the vinyl chloride resin. 10 to 70 parts by weight of a mixture of one or more selected from methyl methacrylate, acrylonitrile, methacrylonitrile and styrene, α-methylstyrene, and 2-isonorobenylnaphthalene, and a polyfunctional monomer α01-7 A product obtained by adding and polymerizing parts by weight is used. Crosslinked Polymer Co., Ltd. Polymerization is carried out by a conventional method, but emulsion polymerization is particularly preferred since it is easy to obtain a product with a high degree of polymerization.

This first stage crosslinked polymer improves the processability of the composition of the present invention, especially the I! of die swell during extrusion molding. It is necessary to reduce the degree of die swell to below the level of die swell of conventional vinyl chloride resin/impact strength improver compositions, and if it is less than 1a01 part by weight, the effect of reducing die swell is small, and if it is more than 77 parts by weight, it is necessary to The strength of the composition decreases.

Note that among the monomers that can be used as monomers constituting the crosslinked polymer, α-methylstyrene and 2-(soprobenylnaphthalene) are particularly effective as monomers that increase the softening temperature.

The polyfunctional monomer may be used in an amount of α01 to 7 parts by weight, which is sufficient to effect effective crosslinking without impairing the acupuncture properties of the target composition.

Examples of such polyfunctional monomers include divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate)
, 1,3-butanediol dimethacrylate, allyl acrylate.

Examples include allyl methacrylate.

Vinyl chloride resin (A) is polyvinyl chloride or 80% by weight
The above vinyl chloride and monomers copolymerizable with it, such as vinylidene chloride and vinyl acetate.

Vinyl stearate, acrylic ester, methacrylic ester, styrene, acrylonitrile, ethylene,
These include copolymers with one or more types of propylene, derivatives such as post-chlorinated products, and mixtures of one or more types of these.

The composition of the present invention is a mixture of the five resins (A), (B), and (C), and the mixing ratio is the impact strength improver (
B) 10 to 60% by weight, copolymer (C) 90 to 40% by weight, totaling 80 to 20% by weight of both resins, and vinyl chloride resin (A) 20 to 80% by weight.

(A), (B), and (C) may be mixed by a conventional method such as a Banbury mixer, mixer roll, or extruder, but they may be mixed in a latex state and then coagulated.

If the vinyl chloride resin is 80% by weight or more, the heat deformation resistance 1 mechanical properties of the composition will not be sufficient, and if the vinyl chloride resin is 20% by weight or more, the excellent properties of the vinyl chloride resin will not be recognized.

For this reason, the impact strength improver (B) and copolymer (0) are used in a total amount of 80 to 20% by weight based on 20 to 80% by weight of the vinyl chloride resin. (
In the total amount of B) and copolymer (C), if the copolymer (C) is 90 weight*S or more and the plaster strength improver (B) is 10 weight or less, the impact strength of the composition decreases. Also, copolymer (
If C) is 40% by weight or more than 60% by weight, it is not preferred because the heat deformation resistance of the composition will decrease.

The composition of the present invention optionally contains a heat stabilizer.

Light stabilizers, processing aids 1, colorants, fillers, etc. may be added.

The composition of the present invention has excellent heat deformation resistance and impact resistance, and is suitable for injection molding and extrusion molding. It is particularly suitable for fields requiring dimensional accuracy of molded products such as profile extrusion and pipe extrusion. In this case, existing processing equipment for vinyl chloride resin can be used without any changes, and the industrial effect is great.

Examples will be described below, but the present invention is not limited thereto.

In the examples, all parts by weight (1 part by weight) are all parts by weight.

Examples 1 to 5 In a reaction vessel equipped with a stirrer, 250 parts of distilled water and 50 parts of potassium nonaoleate previously dissolved in water were added.

Dioctylsulfo-sodium acid 0.2 parts, sodium formaldehyde sulfoxylate dihydrate, ferrous sulfate heptahydrate*O, 3 parts, ethylenecyonetetraacetate disodium dihydrate α0 1 part, cumene Hydroperoxide and the first stage monomer having the composition and amount shown in Table 1 were charged, the inside of the reaction vessel was replaced with nitrogen, and the mixture was heated for 60 minutes with stirring.
The temperature was raised to .degree. C., and the reaction was continued at this temperature for 16 hours.

Thereafter, sodium formaldehyde sulfoxylate dihydrate, cumene hydroperoxide and Table 1
The second stage monomer having the composition shown in 1 was charged and allowed to react at 60°C until the conversion rate reached approximately 100%.

After cooling, the latex produced was precipitated using hydrochloric acid, then neutralized, filtered through fml, washed with water, and dried to obtain a powdery copolymer (C
-1) to (C-S) were obtained.

9A formaldehyde sulfoxylate 2
The amounts of the hydrate and cumene hydroperoxide used are 0.4 parts and α3 parts, respectively, per 100 parts of the mixed monomer in both the first stage and the second stage.

The above copolymer 28 weight - 9 parts BTA as an impact strength improver
-1
) 60 parts by weight of resin, 20 parts of dioctyltin mercapto compound, 1.0 g of polymerized organotin mercapto compound, 5 parts of stearyl alcohol α, butylene glycol monchnic acid ester (partially saponified product)
112 parts were mixed and kneaded for 5 minutes using a mixing roll with a surface temperature of 190°C. The nine sheets obtained were further heated at 200°C.
Tests were conducted on the press-molded samples, and the results shown in Table 2 Examples 1 to 5 were obtained.

Example 6 In a reaction vessel equipped with a stirrer, 250 parts of distilled water and sodium rhododecyl sulfonate preliminarily dissolved in water were added. C1, potassium persulfate Q, 06 parts, sodium bisulfite α015 parts and α-methylstyrene 15 parts, methyl methacrylate)
12g, 5 parts of acrylonitrile, divinylbenzene α9
After purging the inside of the reaction vessel with nitrogen, the temperature was raised to 60°C with stirring, and the reaction was allowed to proceed for 16 hours.

After adding 0.4 parts of potassium persulfate and 05 parts of sodium bisulfite α, 34.3 parts of 2-isoglobenylnaphthalene, 14.7 parts of α-methylstyrene, 10.5 parts of methyl methacrylate, Acrylonitrile 10
．． 5 parts of n-dodecyl mercaptan and 0.21 parts of n-dodecylmercaptan were added continuously over 8 hours.

After reacting for 24 hours, the latex produced was salted out with common salt, then filtered, washed with water, and dried to obtain a powdered copolymer (
C-6) was obtained.

Polyvinyl chloride (average degree of polymerization 1000) was added to this copolymer (C-6) in exactly the same manner as in Example 1.

A test was conducted on a composition mixed with BTA-mFl,
The results shown in Table 2 Example 6 were obtained.

Comparative Examples 1 and 2 250 tons of distilled water and 40 parts of potassium oleate dissolved in Ib caulking water were placed in a reaction vessel equipped with a stirrer.

12 parts of sodium diocdel sulfosuccinate, 4 parts of sodium formaldehyde sulfoxylate dihydrate α, 5 parts of ferrous sulfate heptahydrate a00.

Ethylenediaminetetraacetic acid disu) Licum dihydrate α0
1 part, 3 parts of cumeno 1 hydroba-oxide a and Table 1
Mixed monomers with the desired composition were charged into the first and second stages of the copolymer (C-5) shown in Figure 3. After purging the inside of the reaction vessel with nitrogen, the temperature was raised to 60°C with stirring. at a temperature of 24
Allowed time to react.

After cooling, the produced latex was precipitated using hydrochloric acid, and then neutralized, filtered, washed with water, and dried to obtain a powdery copolymer (R-1
), (R-2) was obtained.

As a sanitary strength improver, 28 weight of the above (R-1) or (R-2) copolymer was added to 60 weight of BTA-mF112 weight and polyvinyl chloride (average polymerization f 1000), and it was refreshed. Samples were prepared by adding stabilizers and other additives in the same manner as in Example 1, and the test results shown in Table 2 Comparative Examples 1 and 2 were obtained.

The same composition as in Example 1 was prepared by adding only BTA-IIIFl to the polyvinyl chloride of Example 1, and a test was conducted.The results are shown in Comparative Example 5.

As is clear from Table 2, Examples 1 to 6 exhibit excellent heat deformation resistance, needle impact resistance, and processability, but Comparative Example 2, which does not contain a crosslinked copolymer, has poor processability. Further, Comparative Example 1, which contains only a crosslinked copolymer in the composition, has excellent processability, but is inferior in heat deformation resistance and impact resistance as compared to the examples.

Comparative Example 3, which does not contain the copolymer of the present invention, is excellent in other properties but poor in heat deformation resistance.

Examples 7-8 Tests were conducted in exactly the same manner as in Example 1 for the compositions shown in Table 3 consisting of copolymer (C-2), BTA-I [Fl, and polyvinyl chloride (degree of polymerization 1000). The results are shown in Table 3 Examples 7-B.

Claims (1)

[Scope of Claims] Vinyl chloride resin (A, impact strength improver (6) and one or two selected from methyl methacrylate, acrylonitrile, styrene, α-methylstyrene, and 2-f nogropenylnaphthalene) Mixed monomers of 10 to 70
In the presence of a crosslinked polymer obtained by polymerizing the heavy lid part and 01 to 7 parts by weight of a polyfunctional monomer, a mixed mixture of 2-isoglobenylnaphthalene or 2-ingropenylnaphthalene and α-methylstyrene 2 80 1ppyv-t 1-70% by weight, acrylonitrile 5-80%
50 weight t* and a mixed monomer consisting of 0 to 30 weight of one or more monomers copolymerizable with these 90 to 5
The vinyl chloride resin (6) contains 20 to 80 parts by weight of the impact strength improver (6).
), copolymer 0, total weight of both is 80 to 20 - Amatsu,
and heat deformation resistance characterized in that the total amount of both impact strength improver (6) and copolymer 0 is 90 to 40% by weight - 9 balance is impact strength improver (B) , a vinyl chloride resin composition with good impact resistance and processability.