JPH0745609B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having good weather resistance, impact resistance and moldability.

[0002]

2. Description of the Related Art Thermoplastic resins, particularly vinyl chloride resins (hereinafter abbreviated as PVC) are widely used as general-purpose resins, but their mechanical properties are not always satisfactory. That is, PVC is inferior in impact strength, particularly impact strength with a notch, and various modifiers have been proposed for the purpose of improving such impact strength.

The most effective method among these proposals is so-called MBS resin in which a conjugated diene elastic body is graft-polymerized with a methacrylic acid alkyl ester and an aromatic vinyl compound, and a conjugated diene elastic body is graft-polymerized with a vinyl cyan compound and an aromatic vinyl compound. It is known to blend the ABS resin with PVC. However, since these MBS resins and ABS resins contain many double bonds in the main chain of the elastic body component, when used outdoors for a long time, they tend to cause a choking phenomenon, a drop in impact strength, etc. and are not suitable for outdoor applications. .

Also proposed is a method of using an elastic body in which a saturated alkyl acrylate is partially replaced by a conjugated diene. In this case, although a high impact strength improving effect is exhibited, it has a drawback that the weather resistance is not so good as that of the MBS resin or the ABS resin.

Further, a resin composition having a good weather resistance is prepared by blending a copolymer obtained by using a saturated polyacrylic acid alkyl ester as an elastic body and graft-polymerizing an alkyl methacrylic acid ester, an aromatic vinyl compound and a vinyl cyan compound with PVC. Have also been proposed.

However, these copolymers show a considerable impact strength-improving effect under well kneading conditions (hereinafter referred to as low-sliding condition) even though they are not as good as MBS resin, but a large amount of lubricant is used. In the case where there is no kneading (hereinafter referred to as a high-sliding condition) such as when it is processed, or when it is processed at a relatively low temperature, almost no effect of improving the impact strength is exhibited.

[0007]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive investigations made by the present inventors in view of the present situation, it is found that evenly dispersing a multi-layer graft copolymer using an alkyl acrylate elastomer in PVC has impact strength developing properties. The glass transition temperature (hereinafter abbreviated as Tg) of the outermost layer is 0 ° C. or lower, and the Tg of the second layer from the outermost layer is 60, paying attention to the large contribution to
A multi-layered graft copolymer having at least a three-layer structure in which the Tg of the third layer from the outermost layer is 0 ° C. or less,
For example, when this is blended with PVC, such a multi-layered graft copolymer is likely to melt quickly even under high slip conditions and low shear stress, the PVC composition accelerates gelation, and the dispersed state becomes extremely good. Such a PVC composition is capable of exhibiting high impact strength under a wide range of molding conditions from high shear stress under low slip conditions to low shear stress under high slip conditions as described above. We filed a patent application earlier that we found that it was effective as an impact resistance modifier, but as a result of further studies, we further added to this multilayer graft copolymer a specific copolymerized acid containing a specific unsaturated acid monomer as an essential component. A blend of a specific amount of coalescent acts as a better impact resistance modifier and has good workability,
The inventors have found that the surface gloss is excellent and the weather resistance is also good, and thus the present invention has been accomplished.

[0008]

The present invention provides a thermoplastic resin 1
Of the polymer constituting the outermost layer (A), which is composed of 100 parts by weight of a monomer selected from the group consisting of acrylic acid alkyl ester, methacrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound. The glass transition temperature is 0 ° C. or lower, the glass transition temperature of the polymer forming the second layer (B) from the outermost layer (A) is 60 ° C. or higher, and the third layer (C) from the outermost layer (A) is formed. (A), (B) and (C) in which the glass transition temperature of the polymer to be used is 0 ° C. or lower
To 100 parts by weight of a multi-layer graft copolymer (1) having a multi-layer structure consisting of at least a three-layer structure and containing 0 to 5 wt% of a polyfunctional crosslinking agent in each layer.
0.1 to 20 parts by weight of a copolymer (2) obtained by copolymerizing 3 to 30% by weight of an unsaturated acid monomer and 97 to 70% by weight of a vinyl monomer copolymerizable therewith are blended. It is a thermoplastic resin composition comprising 3 to 50 parts by weight of an impact resistance modifier, which is excellent in weather resistance, impact resistance and moldability.

The impact modifier of the present invention comprises a blend of the above-mentioned multilayer graft copolymer (1) and copolymer (2), and the above-mentioned multilayer graft copolymer has at least three stages. It is essential to have a multi-layer structure of three or more layers obtained by polymerizing over four layers, and the fourth layer counting from the outermost layer is a four-layer graft consisting of a polymer having a homopolymer Tg of 60 ° C. or higher. Even if it is a copolymer, the fifth layer counted from the outermost layer is a multi-layered graft copolymer such as a five-layered graft copolymer composed of a polymer having a homopolymer Tg of 0 ° C. or lower. It may be present, and even in such a case, the impact resistance improving effect is similarly shown.

The group of monomers constituting the multi-layer graft copolymer (1), which is one component of the impact modifier of the present invention, is an alkyl acrylate, an alkyl methacrylate, an aromatic vinyl compound and vinyl cyan. It is composed of compounds.

The alkyl acrylate is preferably one having an alkyl group having 2 to 10 carbon atoms, for example, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, acrylic acid. Examples include octyl and 2-ethyl-hexyl acrylate.

As the methacrylic acid alkyl ester,
An alkyl group having 1 to 4 carbon atoms is preferable, and examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate. To be Methyl methacrylate is particularly preferable in consideration of compatibility with PVC.

Examples of the aromatic vinyl compound include styrene, α-substituted styrene, nucleus-substituted styrene and its derivatives such as α-methylstyrene, chlorostyrene and vinyltoluene.

Furthermore, examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile.

The component of the outermost layer (A) constituting the multilayer graft copolymer (1) is selected from the above monomer group so that the Tg of the outermost layer (A) itself is 0 ° C. or lower. The composition ratio of the monomer in the outermost layer (A) is 60 to 100% by weight of alkyl acrylate, 0 to 40% by weight of methacrylic acid alkyl ester, and 0 to 40 of aromatic vinyl compound.
It can be used in the range of 0% to 20% by weight of the vinyl cyan compound. When the Tg of the outermost layer (A) itself exceeds 0 ° C, the final modifier obtained is blended with PVC and molded, and the (A) layer portion melts slowly, resulting in a desired impact resistance improving effect. Is difficult to obtain.

The proportion of the outermost layer (A) in the total amount of the multi-layer graft copolymer is preferably 10 to 50% by weight, and the proportion of less than 10% by weight has a small effect of improving impact resistance.
A proportion of more than 0% by weight is not preferable because the moldability when blending with PVC and molding becomes poor.

The components of the outermost layer (A) to the second layer (B) are selected from the above monomer group so that the Tg of the layer (B) itself is 60 ° C. or higher. The composition ratio of the monomer in the layer (B) is 0 to 10 methacrylic acid alkyl ester.
It can be used in the range of 0% by weight, 0 to 100% by weight of aromatic vinyl compound, 0 to 30% by weight of vinylcyanide compound, and 0 to 20% by weight of alkyl acrylate. When the Tg of the layer (B) itself is less than 60 ° C, the multilayer graft polymer is likely to aggregate and the impact resistance is poor. As a component of the layer (B), when blended with PVC, alkyl methacrylate is preferable, and methyl methacrylate is particularly preferable. An aromatic vinyl compound improves its fluidity during blend molding with PVC, but when used in a large amount, its compatibility deteriorates and its impact resistance decreases. A vinyl cyan compound is preferable because it promotes gelation during blending with PVC, but when used in a large amount, it tends to cause coloration during molding and deteriorates its processability.

The proportion of the layer (B) in the total amount of the multilayer graft copolymer is preferably 20 to 60% by weight, and 20% by weight.
If it is less than the above range, the molding processability at the time of blending with PVC and molding is inferior, which is not preferable. On the other hand, if the proportion exceeds 60% by weight, the amount of the elastic material component in the whole multilayer graft copolymer is reduced, and the impact resistance improving effect is small, which is not preferable.

Further, the third layer (C) from the outermost layer (A)
The component (1) is selected from the monomer group so that the Tg of the layer (C) itself is 0 ° C. or lower. The composition ratio of the monomer in the layer (C) is 60 to 10 of alkyl acrylate.
It can be used in the range of 0% by weight, 0 to 40% by weight of methacrylic acid alkyl ester, 0 to 40% by weight of aromatic vinyl compound, and 0 to 20% by weight of vinyl cyan compound. When the Tg of the layer (C) itself exceeds 0 ° C., the elastic properties of the layer (C) itself are impaired, and it is difficult to obtain the desired impact resistance improving effect.

The proportion of the layer (C) in the total amount of the multilayer graft copolymer is preferably 10 to 60% by weight, and 10% by weight.
If it is less than 60% by weight, the impact resistance improving effect is small, and if it exceeds 60% by weight, the molding processability at the time of blending with PVC and molding is inferior.

The polyfunctional crosslinking agent according to the present invention not only facilitates the graft cross-linking in the production of the above-mentioned multilayer graft copolymer, but also greatly improves the coagulability of the emulsion polymer latex. . As the polyfunctional crosslinking agent, divinylbenzene, diacrylic acid ester or dimethacrylic acid ester which is an ester of polyhydric alcohol with acrylic acid or methacrylic acid, or triallyl cyanurate, triallyl isocyanurate, allyl acrylate, allyl methacrylate. , Diallyl itaconate, diallyl phthalate and the like. From the viewpoint of graft crossing property, a cross-linking agent having an allyl group is preferable.

The proportion of the polyfunctional crosslinking agent in each layer is 0.
~ 5% by weight. When it is used in an amount of more than 5% by weight, the outermost layer (A) or layer (C) which is an elastic layer too impairs the elastic properties. Further, since the compatibility of the resin layer (B) with PVC is deteriorated, the effect of improving impact resistance is reduced, which is not preferable. The proportion of the polyfunctional crosslinking agent in each layer is 0.1 to 0.1 in consideration of the coagulability of the emulsion polymer latex during the production of the multilayer graft copolymer and the impact resistance improving effect of the resulting multilayer graft copolymer. 3% by weight
Is preferred.

The multilayer graft copolymer in the present invention is preferably produced by a usual emulsion polymerization method.

Examples of emulsifiers include anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl phosphate ester salts, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene. Nonionic surfactants such as fatty acid esters, sorbitan fatty acid esters and glycerin fatty acid esters, and cationic surfactants such as alkylamine salts can be used. These surfactants can be used alone or in combination. Further, depending on the kind of the emulsifier, when the pH of the polymerization system is on the alkaline side, an appropriate pH adjusting agent can be used in order to prevent the hydrolysis of the alkyl acrylate.

As the polymerization initiator, an ordinary inorganic initiator such as a persulfate or an organic peroxide, an azo compound or the like may be used alone, or the above compound and a sulfite, a hydrogen sulfite, a thiosulfate, a A single metal salt, sodium formaldehyde sulfoxylate, etc. may be combined and used as a redox initiator. Preferred persulfates as the initiator are sodium persulfate, potassium persulfate, ammonium persulfate and the like, and as the organic peroxide, t-
Butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide and the like.

A chain transfer agent may be used to control the molecular weight of the polymer, and alkyl mercaptan having 5 to 20 carbon atoms can be used.

Polymerization is carried out at a temperature above the decomposition temperature of the initiator,
Under normal emulsion polymerization conditions, at least the outermost layer (A), the second outermost layer (A) to the second layer (B) and the outermost layer (A) to 3
This can be done so that the second layer (C) has the structure as described above. At this time, the polymerization in each of the steps can be carried out while adding the whole amount of each monomer or a mixture of the monomers at once, or continuously adding the whole amount or a part thereof. However, from the viewpoints of stability of polymerization, removal of heat of polymerization reaction, etc., it is preferable to carry out the polymerization while adding the whole amount or a part thereof.

The copolymer (2), which is another component of the impact modifier of the present invention, contains 3 to 30% by weight of an unsaturated acid monomer and 97 to 90% of a vinyl monomer copolymerizable therewith. It is obtained by copolymerization with 70% by weight, and the emulsion polymerization method is preferable as the production method thereof.

The unsaturated acid monomer is an acid group-containing monomer such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, maleic anhydride or butenetricarboxylic acid. The amount of unsaturated acid monomer in the copolymer (2) is 3% by weight.
If the amount is less than the range, it is not preferable because it is blended with the multilayer graft copolymer (1) and used as an impact resistance modifier because the impact resistance improving effect is small. If it exceeds 30% by weight, the latex obtained by emulsion polymerization is not stable, and when it is blended with the latex of the above-mentioned multilayer graft copolymer (1), the latex stability is deteriorated and the processability is deteriorated. It is not preferable because it causes it.

Examples of the vinyl monomer copolymerizable with the unsaturated acid monomer include acrylic acid alkyl esters, methacrylic acid alkyl esters, aromatic vinyl compounds, vinyl cyan compounds, and the like. The members of the group can be used alone or in a mixture.

When the copolymer (2) is produced by emulsion polymerization, the same emulsifiers, polymerization initiators, chain transfer agents and the like that can be used in the production of the multilayer graft copolymer (1) are used. It can be used and can be copolymerized in the same manner as in the production of the multilayer graft copolymer (1).

The impact modifier of the present invention is a blend of the multi-layer graft copolymer (1) and the copolymer (2) obtained as described above, and the blending ratio thereof is the multi-layer graft copolymer ( 1) 100 parts by weight of copolymer (2) is 0.1 to 2
0 parts by weight. If the blending amount of the copolymer (2) is less than 0.1 part by weight, the impact resistance improving effect is small, and if the blending amount exceeds 20 parts by weight, the latex becomes unstable when both copolymers are latex blended. Alternatively, when this modifier is blended with PVC, the workability is deteriorated, which is not preferable.

In carrying out the present invention, the multi-layer graft copolymer (1) and the copolymer (2) are blended by mixing the respective latexes in the above-mentioned compounding ratio in terms of solid content. It may be collected by powdering or acid precipitation and washed with water after filtration, or may be collected in powder form by spray drying or freeze-drying. It can also be recovered by the method described in JP-A-57-187322. Further, a method of blending individual powders of the multi-layered graft copolymer (1) and the copolymer (2) later may be used. The method obtained by the above-mentioned latex blend is particularly preferable.

By blending the impact modifier of the present invention with various thermoplastic resins, the thermoplastic resin is imparted with high impact resistance and good processability, and the molded article also has good weather resistance. It is what

The proportion of the impact modifier of the present invention incorporated into the thermoplastic resin is 3 to 5 relative to 100 parts by weight of the thermoplastic resin.
0 parts by weight. If it is less than 3 parts by weight, the impact resistance improving effect is small, and if it exceeds 50 parts by weight, the mechanical properties originally possessed by the thermoplastic resin are impaired, which is not preferable. Here, the thermoplastic resin is PVC,
Examples thereof include polycarbonate resin, polyester resin, acrylonitrile-styrene resin, and methyl methacrylate-styrene resin. As PVC, in addition to polyvinyl chloride, a vinyl chloride-based copolymer containing 70% by weight or more of vinyl chloride can be used. As the monomer to be copolymerized with vinyl chloride, ethylene, propylene, vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid ester, methacrylic acid ester and the like are used.

The impact modifier of the present invention and the thermoplastic resin are preferably mixed in a powder form, for example, by a ribbon blender, a Henschel mixer or the like, and a known kneading machine,
For example, it is molded by a mixing roll, a Banbury mixer, an extruder, an injection molding machine and the like. When blending, known stabilizers, plasticizers, lubricants, colorants and the like may be added as necessary.

[0037]

The present invention will be described in detail with reference to the following examples. In the examples, "part" and "%" are "part by weight",
It means "% by weight". Also, the Tg of the copolymer
Is obtained from the Fox equation.

Example 1 (a) Production of Multilayer Graft Copolymer (1) 190 parts of nitrogen-exchanged deionized water was placed in a reaction vessel,
While dissolving 1.2 parts of semi-hardened beef tallow fatty acid soap and 0.6 part of potassium persulfate and maintaining it at 70 ° C., n-butyl acrylate 19.85 parts and triallyl isocyanurate 0.15 as the layer (C) component. The mixture of parts was added dropwise over 1 hour. After the dropping, hold for 1 hour while keeping the same temperature,
The polymerization was completed. The polymerization rate was 99.0%.

A mixture of 49.7 parts of methyl methacrylate and 0.3 part of triallyl isocyanurate as a layer (B) component was added dropwise to this polymer latex for 2 hours while maintaining the temperature at 70 ° C., and the addition was completed. After that, the mixture was held for 1 hour to complete the polymerization. The polymerization rate was 99.5%.

0.2 part of potassium persulfate was dissolved in 10 parts of water and added to the obtained polymer latex, and 29.8 parts of n-butyl acrylate and 0.2% triallyl isocyanurate as components of layer (A). Part of the mixture was added dropwise over 90 minutes while maintaining the temperature at 70 ° C., and maintained for 1 hour after completion of the addition to complete the polymerization. The polymerization rate was 99.3%, and the average particle size of the obtained graft copolymer was 0.25 μ.

(B) Manufacture of copolymer (2) 200 parts of ion-exchanged water whose atmosphere was replaced with nitrogen was put in a reaction vessel,
Dissolve 3 parts of semi-cured tallow fatty acid soap and 0.6 part of potassium persulfate, add a mixture of 90 parts of ethyl acrylate and 10 parts of methacrylic acid dropwise over 4 hours while maintaining the temperature at 70 ° C, and hold for 3 hours. Conduct and polymerize copolymer (2)
A latex was obtained. The polymerization rate was 99.9% or more.

(C) Latex blend and polymer recovery 100 parts of the multi-layered graft copolymer (1) latex (as solid content) was placed in a reaction vessel equipped with a stirrer, and 2 parts of copolymer (2) latex (as solid content). ) Was added with stirring for 10 seconds, and the mixture was stirred for 15 minutes.

The latex mixture thus obtained was added to a sulfuric acid aqueous solution, coagulated by acid precipitation, washed, dehydrated, and dried to recover a polymer in powder form (Example 1-1)).

Table 1 also shows various changes in the addition amount of the copolymer (2).

(D) Production of compounded composition with vinyl chloride resin 100 parts of vinyl chloride resin having an average degree of polymerization of 1100, 1.0 part of tribasic lead sulfate, 0.3 part of dibasic stearic acid, lead stearate 2.4 parts, 0.3 parts of stearic acid, 0.3 parts of polyethylene wax, and 10 parts of the respective modifiers obtained in the above (c) were added, and 11 parts were added in a Henschel mixer.
The temperature was raised to 5 ° C. to obtain a uniform mixture. This vinyl chloride resin composition was subjected to square bar molding under the following conditions with a 30 mm single screw extruder.

Cylinder 1 150 ° C. Cylinder 2 165 ° C. Cylinder 3 180 ° C. Die 200 ° C. Screw CR = 3.0, 30 mmφ Full flight screw It was measured according to ASTM D-256.
The results of these measurements are shown in Table 1.

[0047]

[Table 1]

From the above results, it is understood that the impact resistance improving effect is improved by blending the copolymer (2) in a specific amount.

Example 2 The same operation as in (a) of Example 1 was carried out, except that the components of layer (C) were 39.75 parts of 2-ethylhexyl acrylate and 0.25 parts of allyl methacrylate, and layer (B). ) Is 27.9 parts of methyl methacrylate, 11.9 parts of styrene, and 0.2 parts of allyl methacrylate, and the component of layer (A) is 2.85 parts of 2-ethylhexyl acrylate and 0.95 parts of allyl methacrylate. As 15 parts, a multilayer graft copolymer (1) latex was obtained. This multilayer graft copolymer latex 1
4 parts (as solid content) of the copolymer (2) latex obtained in (b) of Example 1 was blended with 00 parts (as solid content), and the same procedure as in (c) of Example 1 was performed. The polymer was recovered. This polymer was treated in the same manner as in (d) of Example 1 to obtain a vinyl chloride resin composition. Table 2 shows the results of measuring the impact resistance of this composition by the same method as in Example 1 (d). In the same manner as in Example 1 except that the types of the monomer and the cross-linking agent of the layer (C) component, the layer (B) component and the layer (A) component and the number of parts used are changed as shown in Table 2. A blend of 100 parts (as solid content) of the multi-layered graft copolymer (1) latex obtained by the operation and 4 parts (as solid content) of the copolymer (2) latex obtained in (b) of Example 1 respectively. Table 2 also shows the results obtained by measuring the impact resistance of the vinyl chloride resin composition obtained by the same operation as in (c) and (d) of Example 1 by the same evaluation method.

[0050]

[Table 2]

The abbreviations in Table 2 are as follows, and the same applies to the subsequent cases.

2EHA: 2 ethylhexyl acrylate MMA: methyl methacrylate St: styrene AN: acrylonitrile AMA: allyl methacrylate As can be seen from Comparative Examples 3 and 4, a layer component (C) or a layer component (A) having a high Tg. It can be seen that the impact resistance improving effect is small. Further, it can be seen that the powder property is deteriorated when the layer component (B) has a lower Tg than in Comparative Example 4 '.

Example 3 Butyl acrylate 85 as copolymer (2) latex
Parts and 15 parts of acrylic acid were polymerized in the same manner as in (b) of Example 1 to obtain a copolymer (2) latex. 3 parts of this copolymer (2) latex (as solid content) was blended with 100 parts (as solid content) of the multi-layer graft copolymer (1) latex obtained in Example 1 (a), and Example 1 Table 3 shows the impact resistance of the vinyl chloride resin composition obtained by the same operation as in (c) and (d). Table 3 also shows the evaluation results of the copolymer (2) latex whose composition and addition amount were changed.

[0054]

[Table 3]

The abbreviations in Table 3 are as follows, and the same applies to the subsequent cases.

BA: n-Butyl Acrylate AA: Acrylic Acid IA: Itaconic Acid EA: Ethyl Acrylate MA: Methyl Acrylate MAA: Methacrylic Acid CA: Crotonic Acid From the above results, the copolymer (2) is not contained in the latex. It can be seen that those with less saturated acid have less impact improving effect, and those with more saturated acid deteriorate latex stability after blending.

Example 4 In (a) of Example 1, sodium lauroylbenzene sulfonate was used as an emulsifier, sodium formaldehyde sulfoxylate was used as a catalyst, and 29.8 parts of n-butyl acrylate was used as a component of the layer (C). 0.2 parts of triallyl cyanurate, t-butyl hydroperoxide 0.
15 parts, methyl methacrylate 3 as a component of layer (B)
6.8 parts, acrylonitrile 3 parts, triallyl cyanurate 0.2 part, t-butyl hydroperoxide 0.15
Parts, n-octyl acrylate 2 as a component of layer (C)
Example 1 except 9.8 parts, triallyl cyanurate 0.2 part, t-butyl hydroperoxide 0.15 part
The same operation as in -1) was carried out to obtain a multilayer graft copolymer (1) latex.

100 parts of this multi-layered graft copolymer (1) latex (as solid content) was blended with 2 parts of the copolymer (2) latex of (b) of Example 1 (as solid content) to prepare Example 1 The same operation as in (c) of Example 1 was performed to recover the polymer. This polymer was treated in the same manner as in (d) of Example 1 to obtain a vinyl chloride resin composition. The results of measuring the impact resistance of this composition by the same method as in Example 1 (d) are shown in Table 4. Table 4 also shows the amounts of the cross-linking agent in the components of each layer and the ratio of the monomers alone changed.

[0059]

[Table 4]

The abbreviations in Table 4 are as follows.

TAC: triallyl cyanurate OA: n-octyl acrylate As shown in Table 4, those containing a large amount of a crosslinking agent in each component
It can be seen that the impact resistance improving effect is small.

Example 5 A commercially available PVC modifier, methyl methacrylate-butadiene-styrene resin (MBS resin), chlorinated polyethylene (ClPE), and the modifier obtained in Example 1-1) were used as examples. A PVC composition was obtained in the same manner as in (d) of 1 above. Table 5 shows these weather resistances. The weather resistance is indicated by the Izod impact strength and the degree of coloration after accelerated exposure treatment with a weatherometer (Toyo Rika WE-II type).

[0063]

[Table 5]

The indication of the degree of coloring in Table 5 is as follows.

◯: Almost no coloration and good. Δ: Slightly colored, which is not very preferable. X: Colored and defective.

From the results shown in Table 5, it is understood that the modifier according to the present invention has very good weather resistance (initial impact retention rate, coloration) as compared with commercially available MBS and ClPE.

Example 6 20 parts of the modifier obtained in (a) to (c) of Example 1, 80 parts of a polycarbonate resin, 0.2 part of an antioxidant and 0.1 part of calcium stearate were placed in a Henschel mixer. 30m with the cylinder temperature set to 240 ℃
Pelletized with an mφ extruder. After drying, a test piece was prepared by an injection molding machine, and the impact strength was measured by the same evaluation method as in Example 1 (d). The results are shown in Table 6. The results of various changes in the addition amount of the copolymer (2) are also shown in Table 6.

[0068]

[Table 6]

As described above, the modifier according to the present invention exhibits a good impact resistance improving effect on the polycarbonate resin.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 33:06)

Claims (3)

[Claims] 1. An outermost layer comprising 100 parts by weight of a thermoplastic resin and a monomer selected from the group consisting of acrylic acid alkyl ester, methacrylic acid alkyl ester, aromatic vinyl compound and vinyl cyan compound. The polymer constituting A) has a glass transition temperature of 0 ° C. or lower, the polymer constituting the second layer (B) from the outermost layer (A) has a glass transition temperature of 60 ° C. or higher, and 3 from the outermost layer (A). The polymer constituting the th layer (C) has a glass transition temperature of 0 ° C. or lower, and has a multilayer structure composed of at least three layers of layers (A), (B) and (C), and each layer has each layer With respect to 100 parts by weight of the multi-layered graft copolymer (1) containing 0 to 5% by weight of a polyfunctional crosslinking agent, 3 to 3 parts of the unsaturated acid monomer are added.
0% by weight and vinyl monomer 97 to 7 copolymerizable therewith
Copolymer (2) obtained by copolymerizing 0% by weight
A thermoplastic resin composition comprising 3 to 50 parts by weight of an impact modifier which is mixed with 20 parts by weight and which has good weather resistance, impact resistance and moldability. 2. The glass transition of the impact graft modifier multi-layer graft copolymer according to claim 1, wherein the outermost layer (A) constitutes a layer (A) from the monomer group. At least one monomer 95-1 selected so that the temperature is 0 ° C. or lower
It is a polymer composed of 00% by weight and 0 to 5% by weight of a polyfunctional crosslinking agent, and its proportion in the multilayer graft copolymer is 1
0 to 50% by weight, the second layer (B) from the outermost layer (A)
95% to 100% by weight of at least one monomer selected so that the glass transition temperature of the polymer constituting the layer (B) from the group of monomers is 60 ° C. or higher, and a polyfunctional crosslinking agent. 0
To 5% by weight, and the proportion of the polymer in the multilayer graft copolymer is 20 to 60% by weight, and the outermost layer (A).
The third layer (C) is at least one monomer 95-100 selected from the group of monomers such that the polymer constituting the layer (C) has a glass transition temperature of 0 ° C. or lower. weight%
A thermoplastic resin composition comprising a polymer containing 0 to 5% by weight of a polyfunctional cross-linking agent, and having a structure in which the proportion in the multilayer graft copolymer is 10 to 60% by weight. 3. A thermoplastic resin composition, wherein the resin mixed with the impact modifier according to claim 1 is at least one thermoplastic resin selected from vinyl chloride resins and polycarbonate resins.