JPS5936660B2 - Molding composition for obtaining molded products with high impact resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has enhanced impact strength and moisture impermeability;
Moreover, the present invention relates to modified impact molding compositions that retain most of the other desirable properties of conventional impact molding compositions.

The present invention also relates to impact-resistant molding compositions which, in addition to such modifications, further reduce the flammability of the molded articles. A particularly preferred type of impact molding composition is a mixture of turbolimers, which are copolymerized three specific monomers, and graft polymers obtained by grafting the same monomers mentioned above onto polybutadiene.

Although the preferred compositions described above consist mostly of terpolymer and minor amount of graft polymer, the monomers used to prepare the terpolymer and graft to the polybutadiene are methyl methacrylate, styrene, and acrylonitrile. U.S. Patent No. 3,354,238 (Schmi
A preferred impact resistant composition, as described in dtyo et al., November 21, 1967, consists of the following compositions (all parts and percentages are by weight):
: terpolymer 70-95% and graft polymer 5-30%; terpolymer contains C67-72 parts methyl methacrylate, 18-22 parts styrene and 8-12 parts
parts of acrylonitrile; graft polymer is 67 to 80
1 part methyl methacrylate, 17 to 21 parts styrene, and 1 to 13 parts acrylonitrile, with a ratio of polybutadiene to graft monomer mixture of 2:1 to 3:1. The present invention is directed to a particularly desirable class of modified impact molding compositions as described above, the modification being effected by the addition of vinyl chloride polymer 5 to the base composition.

During its addition, one stabilizer of the vinyl chloride polymer is added alone or in combination with one stabilizer and one flame retardant organometallic compound. For convenience in the following discussion, the prior art mixed composition of terpolymer and graft polymer will be referred to as the "base composition" and the composition of the present invention will be referred to as the "modified composition." The above basic compositions are very attractive in the molding industry for the production of thin-walled containers and similar applications. However, in some cases, this base composition may not be strong enough to be useful in applications where particularly high impact strength is required over other properties. Additionally, for applications where low moisture permeability is required,
May be slightly too transparent. As a result, there is a need in the art to provide impact molding compositions that modify the base composition to provide higher levels of impact resistance and moisture impermeability while retaining most of the other desirable properties. It brings remarkable progress to the world and meets the long-awaited expectations of the world.
The present invention provides a high impact strength composition comprising: (1) a terpolymer consisting of methyl methacrylate, styrene and acrylonitrile;
95%, (2) 5-3 polyptadiene grafted with methyl methacrylate, styrene and acrylonitrile
0%, in addition to (3) vinyl chloride polymer and (
4) an organotin compound as a stabilizer for the vinyl chloride polymer;
The ratio of the total amount of components 1) and (2) is 40 to 95%, the ratio of component (3) is also 5 to 60%, and the ratio of the stable weight 4) is 1. based on the weight of Seongju 3). 0~5.0
%. According to a preferred embodiment of the present invention, the following composition having high impact strength is provided, the composition of which is (1) a terpolymer consisting of methyl methacrylate, styrene, and acrylonitrile containing 70 to 70% 9
5%, (2) polyptadiene grafted with methyl methacrylate, styrene, and acrylonitrile.
~30%, in addition to (3) vinyl chloride polymer, (
4) an organotin compound as a stabilizer for the vinyl chloride polymer; and (5) a flame retardant organometallic compound for making the composition flame retardant, excluding the stabilizer and flame retardant. The total ratio of components (1) and (2) in the final composition is 40 to 95%, the ratio of component (3) is also 5 to 60%, and the stabilizer (4) is the same as component (3). 1 to 5% based on the weight of
), (3) 0.25 to 0.25 based on the total weight of each component
It is 5.0% by weight. Modified compositions of the present invention without flame retardants have significantly superior impact strength and significantly reduced moisture permeability compared to the base composition.

The modified composition of the present invention with additional flame retardant added has not only the excellent impact strength and moisture impermeability mentioned above, but also has flame retardancy not present in the basic composition. These results in terms of impact resistance and moisture barrier properties are completely unexpected given that the vinyl chloride used is a brittle polymer without attractive impact strength. Compositions of the present invention may consist of at least four components, and in preferred embodiments at least five components.

Its ingredients are as follows. (1) Terpolymer of methyl methacrylate, styrene and acrylonitrile; (
2) polybutadiene graft-polymerized with a mixed monomer of methyl methacrylate, styrene, and acrylonitrile; (3) vinyl chloride polymer; (4) organic stabilizer for vinyl chloride polymer; and, if desired, (5) heat-resistant organic metal Compound.

When preparing the composition of the invention, the basic composition consists of the components (
Consisting of 1) and component (2), where (1) is 70-95%
, (2) is the remainder, that is, 5 to 30%.

In addition to this basic composition, component (3), a vinyl chloride polymer, is present. The modified composition contains 40 to 95% of the base composition consisting of the above proportions (1) and (2), and correspondingly 5 to 60% of the component (3), namely the vinyl chloride polymer. Furthermore, in addition to the above components (1), (2) and (3), component (4), that is, organotin as a vinyl chloride polymer stabilizer, is present in an amount of 1 to 5% based on the weight of the vinyl chloride polymer. Finally, if desired, an organometallic compound as a flame retardant in component (5) is present in an amount of 0.25 to 5% based on the total polymer composition weight of (1), (2) and (3). Component (1), the terpolymer, consists of methyhestylene methacrylate and acrylonitrile as described above. US Pat. No. 33
54238, a particularly preferred terpolymer contains 67 to 72 parts of methyl methacrylate, 17 to 21 parts of methyl methacrylate,
1 part styrene and 8 to 12 parts acrylonitrile, such terpolymers are representative of those suitable for use in the compositions of the present invention. The graft-polymerized polyptadiene of component (2) is one grafted with a monomer mixture consisting of methyl methacrylate, styrene and acrylonitrile as described above.

Particularly suitable grafted polybutadienes for use in the present invention are monomers consisting of 67 to 80 parts of methyl methacrylate, 17 to 21 parts of styrene, and 1 to 13 parts of acrylonitrile, as shown in U.S. Pat. No. 3,354,238. Grafted with polymer mixing, the ratio of polybutadiene to the monomer mixture is from 2:1 to 3:1. The vinyl chloride polymer of component (3) can be a homopolymer or some type of copolymer.

The latter include 90-97% vinyl chloride and 3-10% vinylidene chloride and 85-95% vinyl chloride and 5-15%.
A copolymer of vinyl acetate is used. In order for the composition to have the desired increased impact strength, ASTM-
The vinyl chloride must have a molecular weight such that the logarithmic viscosity number measured by method D-1243-60-A is at least 0.50. A variety of useful vinyl chloride homopolymers and copolymers are commercially available and well known. component(
4) Organotin stabilizers for vinyl chloride polymers are selected from a variety of known compounds having the general formula:

[Here KKx is an integer of 1 to 3, R is alkyl, cycloalkyl, aralkyl, alkaryl or aryl, k
is one of the groups of R or carboxylic acid R2COOH
or a residue of carboxylic acid ester R2COOR3 (where R3 is one of the groups of R5, or R2 is alkylene,
Cycloalkylene, aralkylene, alkarylene, or corresponding to the above R group, but with one hydrogen removed from the R group, 2
When R'' is a carboxylic acid with an appropriate structure and reactivity, the residue may be cyclized.

For example, dibutyltin β-mercaptopropionate is a typical example. Examples included in the above general formula are: dibutyltin bis(ω-carboxylauryl mercaptide),
Butyltin tris (isooctylmercaptoacetate)
, tributyltin lauryl mercaptide, dibutyltin bis (lauryl mercaptide), dibutyltin bis (octyl mercaptide), dibutyltin bis (benzyl mercaptide), dibutyltin bis (xylyl mercaptide), dibutyltin pis (cyclohexyl mercaptide) dibutyltin bis(phenyl mercaptide), dibutyltin bis(phenyl mercaptide), dioctyltin bis(
lauryl mercaptide), dioctyltin bis(octyl mercaptide), dioctyltin bis(benzyl mercaptide), dioctyltin bis(xylyl mercaptide),
Dioctyltin bis (cyclohexyl mercaptide), synchrohexyl tin bis (lauryl mercaptide), dimethyl tin bis (lauryl mercaptide), dimethyl tin bis (benzyl mercaptide), dimethyl tin bis (cyclohexyl mercaptide), dimethyl tin xylyl bis ( Mercaptide), Dioctyltin β-mercaptopropionate, Dibutyltin bis(isooctylmercaptoacetate), Dioctyltin bis(isooctylmercaptoacetate), Synchhexyltin bis(isooctylmercaptoacetate), Dimethyltin bis(isooctylmercaptoacetate) Diphenyltin bis(isooctyl mercaptoacetate), dibutyltin bis(lauryl mercaptoacetate), dibutyltin bis(benzyl mercaptoacetate), dibutyltin bis(cyclohexyl mercaptoacetate), dimethyltin bis(octyl glycolate) and di-n -Octyltin bis(isooctylthioglycole-1).

Other reports on organotin stabilizers include U.S. Pat.
No. 24717 (Gottlieb et al., 1969.1)
(dated March 28). The amount of organotin stabilizer present in the compositions of this invention ranges from 1 to 5% based on the weight of the vinyl chloride polymer. Component (5), the organometallic compound flame retardant, should be used in an amount such as to impart flame retardancy to the shaped composition;
Generally 0.25 per total weight of 1), (2) and (3)
~5.0% preferably 0.25-3.0%.

Flame retardant compounds useful here include, for example, synchropentanenyl iron, chromium stearate, nickel naphthenate, lead naphthenate, cobalt naphthenate, manganese naphthenate, zirconium octoate, iron stearate, copper stearate. , zinc stearate, chromium acetylacetonate, iron plate acetylacetonate, molybdenum acetylacetonate, vanadyl acetylacetonate and nickel acetylacetonate. The composition of the present invention comprises:
For example, the components may be mixed using a suitable mixer or a premixed mixture may be extruded. When preparing by kneading, ingredients (1) and (2)
For example, on a two-roll mill, 250 to 450
'F (121.1℃~232.2℃) preferably 30
Mill at a temperature of 0 to 400 T (149°C to 204.4°C) until a homogeneous melt is obtained. Next, component (3),
(4) and if desired (5) and optionally a mixture of other ingredients required for other purposes such as dyes, pigments, fillers, UV absorbers, plasticizers, etc.
Knead for 0 minutes. When the molding composition of the invention is prepared by extrusion, components (3), (4) and, if necessary, (5) and other desired or required components are pre-mixed at room temperature in a Hobart mixer. It is best to mix in a suitable mixer such as.

The thus premixed components and component l), respectively, are mixed in a suitable mixing device, such as, for example, a twin cone mixer. The final mixture is then 300-450T (149-2
32°C) preferably 350-400'F (176.6°C)
-204.4°C) using a single screw or two screw extruder. Any other mixing method can be used to mix the ingredients to prepare the compositions of the invention.

For example, a ball mill or emulsion mixing may be used if uniform mixing is possible. The molding compositions of the invention can be molded by any conventionally customary method, such as blow molding, injection molding, compression molding or vacuum forming, thereby providing storage and transportation for industrial, commercial and household products. It is possible to mold the following articles.

and automobile battery cases, transport boxes and similar products.
・Can be used for shapes. However, the present invention has essential relevance to products that are subjected to severe physical abuse. In a further preferred embodiment, the present invention is of essential relevance to products that are subject to severe physical abuse, as well as continuous exposure to high temperatures, with the potential for destruction or contact with fire. The following examples are presented to explain the invention in further detail.

All parts and percentages in the examples are by weight unless otherwise indicated. Examples 1-10 A terpolymer of methyl methacrylate, styrene and acrylonitrile (69/20/11) at a rubber-to-monomer ratio of 87% and methyl methacrylate, styrene and acrylonitrile (78/19/3) at a rubber-to-monomer ratio of 3/3. 30 parts of an acrylic multipolymer consisting of 13% polyptadiene grafted with 2.
Knead on this roll rubber mill to obtain a homogeneous melt.

Calculated using ASTM-D-1243-60-A method: 1.
A blended mixture of 30.0 parts of polyvinyl chloride having a logarithmic viscosity of 11, 1.2 parts of dimethyltin bisoctylthioglycolate and 1.2 parts of synchropentanenyl iron is added and kneaded for 5 minutes. The resulting composition is pressed between two plates of a molding press at 350 degrees (176.6°C) for 5 minutes and then cooled to room temperature while being pressed. A transparent 1/IC sheet is obtained. The same procedure was followed except that the iron compound used in Example 1 was replaced with another organometallic compound. The effect of modified organometallic compounds on the flame retardancy of the final product is shown in Table 1 below. The results in the table are based on the oxygen index, which is a measure of the flame retardancy of a system. This refers to the minimum oxygen concentration (volume %) in nitrogen mixed gas.
- According to "4. Definitions" of ASTM D2863-JMoV.
]. In this series of tests, the oxygen index was approximately 2.
If a sample of 4.0 is held vertically and burned from the bottom, the entire sample will burn out, but samples with an index of about 27.0 or higher will not burn. Examples 11-17 Grafted rubber-resin composition 7 in the method of Example 1
The same procedure is repeated except that 0 parts of polyvinyl chloride and 30 parts of polyvinyl chloride are used.

The results are shown in Table 1. In this system, a sample with an oxygen index of 21.2 or less will burn if ignited as in the above example, but a sample with an oxygen index of about 23.5 or higher will not burn. Example 18~
25 The method of Example 1 is tried again, but with the amount of grafted polybutadiene terpolymer system being 40 parts and the amount of polyvinyl chloride being 60 parts.

Similar flame retardant improvements were obtained using the organometallic compounds of Examples 1-2-8. Examples 26-32 The salts used in Examples 11-17 are each added to a mixture of 95 parts of the grafted polybutadiene terpolymer of Example 1 and 5 parts of polyvinyl chloride.

Here again, a flame-retardant composition is obtained, as indicated by an increase in the oxygen index. Examples 34-41 A series of compositions according to the invention were prepared following the method of Example 1 but varying the amounts of polyvinyl chloride (PVC) and organometallic compound.

The following table shows the increase in oxygen index (0.I.) obtained. Examples 42-45 The stabilizer in Example 1 was replaced with the following: commercially available organotin mercaptan, dibutyltin bisisooctyl mercaptoacetate, tributyltin lauryl mercaptide, and Thorium-cadmium complex.

The results regarding improving the flame retardancy of the final compositions (products) are almost similar. Example 46 The method of Example 1 was repeated with the following changes.

The logarithmic viscosity number of polyvinyl chloride is 0.50 (the measurement method is the same as above) and the formulation of the acrylic multipolymer is 67.
/22/11 terpolymer of methyl methacrylate/styrene/acrylonitrile 90% and 68/21/
10% polybutadiene grafted with 11 methyl methacrylate/styrene/acrylonitrile at a rubber to monomer ratio of 3/1. Once again a highly flame retardant composition was obtained. Example 47 The method of Example 1 was used to prepare 7 acrylic multipolymers.
84% methyl methacrylate/styrene/acrylonitrile terpolymer of 2/22/6 and 80/17
16% polybutadiene grafted with methacrylic acid methino-blown styrene/acrylonitrile of 2.5/1 at a rubber to monomer ratio of 2.5/1.

This resulted in an excellent flame retardant composition. Example 48 A highly effective flame retardant composition was obtained by replacing the polyvinyl chloride of Example 1 with a vinyl chloride/vinyl acetate (95/5) copolymer.

Example 49 The copolymer of Example 48 was mixed with vinyl chloride/vinylidene chloride (
What if I replace it with a 90/10) copolymer? Similarly valid results were obtained.

Example 50 Methyl methacrylate/styrene/acrylonitrile (6
9/20/11) terpolymer 87% and methyl methacrylate/styrene/acrylo nitrile (78/
60 parts of an acrylic multipolymer consisting of 13% polybutadiene grafted with 19/3) at a rubber-to-monomer ratio of 3/1 was milled on a two-roll rubber mill at 350'P (176.
6° C.) to obtain a homogeneous melt.

A blend of 3.2 parts of polyvinyl chloride with a logarithmic viscosity of 1.11 calculated by ASTM-D-12434-60-A method and 0.15 parts of dimethyltin bisoctylthioglycolate was added and mixed for 5 minutes. Knead. The obtained composition was heated to 350 ml.
After pressurizing for 5 minutes between two plates of a molding press at 1:' (176.6° C.), the sample was cooled to room temperature while being pressurized. A transparent sheet having the cardner impact values shown in the table below is obtained.
Example 51 60 parts of the acrylic multipolymer of Example 50 above are milled on a two roll rubber mill at 350''F (176.6C) until a homogeneous melt is obtained.

A blend of 6.7 parts of polyvinyl chloride and 0.3 parts of a commercially available organotin mercaptan stabilizer as described above (Example 50) is added and kneaded for 5 minutes. This final composition was mixed between two caul plates (metallic partition plates) of a forming press at 350T (1
Pressurize for 5 minutes (76.6°C) and cool to room temperature while maintaining pressure.
A transparent sheet having the cardner impact values shown in the table below is obtained. Example 52 The procedure of Example 50 is repeated except that 10.5 parts of polyvinyl chloride and 0.5 parts of stabilizer are used.

Example 53 The method of Example 50 is carried out in exactly the same manner, using 15.0 parts of polyvinyl chloride and 0.75 parts of stabilizer.

Example 54 The method of Example 50 is carried out in exactly the same manner, except that 26.0 parts of polyvinyl chloride and 1.3 parts of stabilizer are used.

Example 55 The method of Example 50 was applied to polyvinyl chloride.
．． Using exactly the same procedure except using 0 part and 2.0 parts of stabilizer gives similar results as shown in the table.

Example 56 75 of the commercially available multipolymer composition described in Example 50
0 parts at 350'F (176.6°C) until a homogeneous melt.
) on a two-roll rubber mill.

Logarithmic viscosity number 1.11 (ASTM-D-124360-A
A mixture of 200 parts of polyvinyl chloride (according to the method), 50 parts of butylethylhexyl phthalate as a plasticizer and 10 parts of dibutyltin bisisooctylmercaptoacetate was added and kneaded for 5 minutes. The composition is removed from the mill, cooled, granulated, and injection molded into test bars at 400'F. The results of the impact tests are shown in Table V. Example 57 The same procedure as in Example 56 is repeated except that the polyvinyl chloride has a logarithmic viscosity of 0.92.

The impact performance of the test samples obtained is shown in Table V. Example 58 The same procedure was carried out as in Example 56, except that the logarithmic viscosity of polyvinyl chloride was 0.86, and the results are shown in Table V.

Example 59 The same method as in Example 56 was carried out except that the logarithmic viscosity of polyvinyl chloride was 0.77, and the results are shown in Table V.

M) Example 60 50 parts of the polyvinyl chloride of Example 50, 2.5 parts of tributyltin lauryl mercaptide and 7.5 parts of di(2-ethylhexyl phthalate) were mixed in a Hobart mixer at room temperature for 10 minutes.
Mix for a minute.

Claims (1)

[Claims] 1 (i) 70 to 95% by weight of a terpolymer consisting of methyl methacrylate, styrene and acrylonitrile;
and (ii) 5-3 polybutadiene grafted with methyl methacrylate, styrene and acrylonitrile.
and (iii) a vinyl chloride polymer and (iv) an organotin compound as a stabilizer for said vinyl chloride, the proportions of each component being equal to said components (i) and (i).
i) together in the above proportions represent from 40 to 95% by weight of the final composition excluding component (iv) and component (ii)
A composition for forming highly impact-resistant moldings, characterized in that i) is also 5 to 60% by weight of the final composition, and component (iv) is 1 to 5% by weight based on component (iii). thing.