JPH0791346B2 - Method for producing resin having excellent weather resistance and impact resistance - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a resin having excellent weather resistance and impact resistance. More specifically, a thermoplastic resin obtained by graft-polymerizing an aromatic vinyl monomer or the like on acrylic rubber,
The present invention relates to a method for producing a resin having excellent weather resistance and impact resistance.

"Prior Art" Conventionally, many methods have been known in which a hard resin is compounded with rubber and reinforced by the rubber to produce a resin having excellent impact resistance. ABS resin is a representative of this type, and the demand for it is increasing year by year, but diene rubber is mainly used as the base rubber component, and the weather resistance of this base rubber is Badness limits the outdoor use of ABS resins based on diene rubber, which is the greatest weakness of this resin. This drawback can be somewhat prevented by adding an ultraviolet absorber or an antioxidant to this type of resin, but the weather resistance of this type of resin has not been fundamentally improved.

From such a viewpoint, various proposals have been made to use saturated rubber as the base rubber. An example of this is an acrylate ester rubbery polymer (acrylic rubber).
Even if the diene rubber as the base rubber is simply replaced with the acrylic rubber and graft polymerization is carried out, a resin having satisfactory properties cannot be obtained. Regarding the weather resistance, the diene rubber is used as the base rubber and is greatly improved compared to the ABS resin, but there is a problem in the appearance and impact strength of the molded product, and it is said that it is satisfactory in practice. It's hard.

A rubber-resin two-component rubber-reinforcing resin typified by an ABS resin is usually obtained by graft-polymerizing a monomer mixture forming a branch component of a graft copolymer to a latex-like rubber component using water as a medium. The obtained resin is used as it is or as a mixture with a separately manufactured hard resin.

An acrylic rubber used as a rubber component that imparts weather resistance generally exhibits superior properties when it has a crosslinked network structure. Emulsion polymerization is carried out in the coexistence of a polymer, or a method of crosslinking an emulsified acrylic rubber with an organic peroxide such as benzoyl peroxide (BPO) is used. However, acrylic rubber has the drawbacks of being softer than diene rubber, having a low elastic modulus, slow elastic recovery, and being easily plastically deformed. When such a soft rubber is used to manufacture a resin such as a rubber-resin two-component ABS resin and injection molding is performed as a molding material, the deformation orientation of the rubber particles is remarkable and the surface of the molded product has a pearl. The product value is lowered because it shows luster and produces flow marks. Further, such a molded product may have a large mechanical strength such as impact strength depending on the flow direction at the time of molding and the location of the molded product, which causes variations in mechanical strength and appearance.

One of the methods for improving various drawbacks caused by using these acrylic rubbers is to control the degree of crosslinking of rubber particles. When the degree of cross-linking is increased, the appearance of the above-mentioned molded article is improved, but the impact strength is greatly reduced in accordance with the improvement in the appearance, and such original characteristics of the resin cannot be exhibited. On the contrary, if the degree of crosslinking of the rubber is made gentle, the impact strength is improved but the appearance of the molded product is deteriorated. In particular, in the case of acrylic rubber, graft polymerization is difficult because there are no double bonds on the surface and inside of the rubber particles. It was almost impossible to control the graft ratio and the degree of cross-linking of the rubber particles while maintaining the weather resistance and impact resistance by allowing this double bond to be retained inside the rubber particles in an arbitrary amount. .

[Problems to be Solved by the Invention] The present inventor has found that a rubber using an acrylic rubber as a base rubber
The present invention has been achieved as a result of extensive research aimed at solving the above-mentioned various drawbacks existing in the conventional method for producing a two-component resin resin. That is, a vinyl monomer component containing an amino group in the acrylic rubber molecular chain is introduced, and an acrylic vinyl compound containing a vinyl group is obtained by addition-reacting an aromatic vinylic compound containing a chloromethyl group on the amino group of the acrylic rubber. By using the modified acrylic rubber obtained as above as the base rubber, it is possible to arbitrarily control the graft ratio, which was conventionally difficult in the graft polymerization of acrylic rubber, and to improve the moldability and appearance of the molded product. The present invention is intended to provide a method for producing a resin having good weather resistance and excellent impact resistance.

"Means for Solving Problems" The gist of the present invention is that the acrylic rubber has a weight average rubber particle diameter of 0.1 to 5 µm, and the acrylic rubber has 1 to 10 carbon atoms in the alkyl group. Acrylic ester monomer component of alcohol 8 of 99.9 to 60% by weight, vinyl monomer component 0 to copolymerizable with the above acrylic ester
It comprises 40% by weight, 0.05 to 5% by weight of a polyfunctional vinyl monomer component and 0.05 to 10% by weight of an amino group-containing vinyl monomer component (provided that the total amount of the monomer components is 100% by weight). To 100 parts by weight of the acrylic rubber, 0.05 to 10 parts by weight of a chloromethyl group-containing aromatic vinyl compound is added to form a quaternary ammonium salt by addition reaction with the amino group in the acrylic rubber molecular chain, and then the aromatic A unit amount containing 100 to 20% by weight of a vinyl group monomer, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 80% by weight of a methacrylic acid ester monomer of an alcohol having an alkyl group having 1 to 12 carbon atoms A method for producing a resin having excellent weather resistance and impact resistance, which comprises adding 30 to 200 parts by weight of a body mixture and grafting.

Hereinafter, the present invention will be described in detail.

The acrylic rubber in the present invention serves as a trunk during graft polymerization, and also functions as an elastic body that gives a rubber reinforcing effect, and improves the impact resistance of the finally obtained resin.

The acrylic rubber which can be used in the present invention has a weight average rubber particle diameter of 0.1 to 5 μm, and the acrylic rubber has an alkyl acrylate monomer component 99.9 of an alcohol having 1 to 8 carbon atoms. ˜60% by weight, vinyl monomer component copolymerizable with the above acrylic ester 0
~ 40 wt%, polyfunctional vinyl monomer component 0.05 ~ 5 wt%
And an amino group-containing vinyl monomer component in an amount of 0.05 to 10% by weight (however, the total amount of the monomer components is 100% by weight).

The acrylic acid ester monomer that is a constituent of the acrylic rubber is an acrylic acid ester monomer of an alcohol having an alkyl group having 1 to 8 carbon atoms. As a specific example,
Examples thereof include esters of alcohols having an alkyl group having 1 to 8 carbon atoms such as ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. These acrylic acid esters may be one kind or a mixture of two or more kinds.

The acrylic rubber that can be used in the present invention must contain the acrylic acid ester monomer component in an amount of 99.9 to 60% by weight (the total amount of the monomer components constituting the acrylic rubber is 100% by weight). This acrylic ester component, since the acrylic rubber contains other components,
It does not exceed 99.9% by weight. Further, in order to impart rubber elasticity, it must be 60% by weight or more. If it is less than 60% by weight, the effect of reinforcing the rubber on the graft-polymerized resin is small and the impact resistance becomes small, which is not preferable.

As the vinyl monomer copolymerizable with the acrylic ester, an aromatic vinyl monomer described below, a vinyl cyanide monomer described below, acrylamide, methacrylamide,
Examples thereof include vinylden chloride, alkyl vinyl ether, alkyl vinyl ester, methacrylic acid ester and halogen-substituted compounds thereof. These are 1 or 2
It may be a mixture of two or more species.

The amount of the copolymerizable vinyl monomer contained in the acrylic rubber should be selected in the range of 0 to 40% by weight. When the copolymerizable vinyl monomer component exceeds 40% by weight, various properties of the acrylic rubber as a rubber are deteriorated, which is not preferable.

The polyfunctional vinyl monomer in the present invention has a function of cross-linking the acrylic rubber containing the acrylic ester as a main component and contains two or more vinyl groups in one molecule of the monomer. Refers to vinyl monomers. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, methacrylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate, and acrylics. Acid ester, diallylmate,
Examples thereof include triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, and allyl methacrylate. These may be one kind or a mixture of two or more kinds.

The amount of the polyfunctional vinyl monomer contained in the acrylic rubber should be selected in the range of 0.05 to 5% by weight. When the content of the polyfunctional vinyl monomer component exceeds 5% by weight, the acrylic rubber is excessively crosslinked and loses elasticity of the rubber to become hard, and the hardened rubber is graft-polymerized as a base rubber to obtain a resin. When this is produced, the impact resistance of the molded article, especially the low temperature impact resistance, is reduced, which is not preferable. If the polyfunctional vinyl monomer content is less than 0.5% by weight,
Due to lack of crosslinking, the elasticity of rubber is small, and when it is graft-polymerized into a resin, rubber particles are significantly deformed in the molded product, impact resistance is reduced, and anisotropy occurs, which is not preferable. .

The amino group-containing vinyl monomer is in the molecular chain of the acrylic rubber, the chloromethyl group-containing aromatic vinyl compound is added to the amino group of the acrylic rubber, and the vinyl group is added to the acrylic rubber. Is introduced to serve as a base point of the graft polymer chain at the time of graft polymerization, and the graft ratio is adjusted.

Specific examples of the amino group-containing vinyl monomer include vinyl monomers containing a pyridine ring such as 2 vinyl pyridine and 4 vinyl slidine, NN-dimethylaminoethyl acrylate, NN-dimethylaminoethyl methacrylate, NN-
Examples thereof include acrylic acid esters, methacrylic acid esters and acrylamide derivatives containing aminoalkyl groups such as dimethylamiopropylacrylamide. These may be one kind or a mixture of two or more kinds.

The amount of the amino group-containing vinyl monomer contained in the acrylic rubber should be selected in the range of 0.05 to 10% by weight. When the amino group-containing vinyl monomer exceeds 10% by weight, properties such as weather resistance of the actal rubber are deteriorated, and a crosslinking reaction occurs due to the chloromethyl group-containing aromatic vinyl compound added during the graft polymerization, The graft ratio becomes excessive and the impact resistance of the resin decreases. Also, 0.05
If it is less than 10% by weight, the vinyl group cannot be introduced into the cyclyl rubber, and the graft ratio cannot be increased when such a rubber is used as the base rubber, and the impact resistance of the resin finally obtained is small. Is not preferred.

In order to effectively achieve the object of the present invention, the acrylic rubber should have a weight average rubber particle diameter in the range of 0.1 to 5 μm.

In the present invention, the weight average rubber particle size means the U.S. Coulter
ー Nanosizer manufactured by Coulter Electronics Ltd.
(Coulter Nano-Sizer^TM) At 23 ℃
It is measured by a system dispersed in water.

When the weight average rubber particle size of the acrylic rubber is smaller than 0.1 μm, the rubber-reinforcing effect is lost when the resin is produced by graft polymerization, and the impact resistance of the resin becomes extremely small. In this case, the rubber particles agglomerate and the appearance of the molded product becomes poor, which is not preferable. When the weight average rubber particle diameter exceeds 5 μm, the rubber particle exceeds the appropriate rubber particle diameter range having a rubber reinforcing effect, so that the impact resistance of the resin becomes small, and flow marks are conspicuous due to the rubber particles on the surface of the molded product. As a result, the appearance becomes poor, which is not preferable.

The acrylic rubber having the above weight average rubber particle diameter can be produced by a known emulsion polymerization using the above-mentioned monomer component and water as a medium. In this emulsion polymerization, in order to change the composition of the surface and the inside of the acrylic rubber particles, for example, to enrich the surface of the crosslinkable polyfunctional vinyl monomer component and amino group-containing vinyl monomer component,
By adding and adding these monomer components in the latter half of the polymerization, it is possible to produce more impact-resistant rubber particles having a rubber-reinforcing effect. Further, when the weight average rubber particle diameter of the acrylic rubber is desired to be larger than about 0.5 μm, it is difficult to produce a latex containing an acrylic rubber having a large particle diameter by a usual emulsion polymerization method. It is preferable to employ the seeding emulsion polymerization method described above, a known operation for increasing the size of rubber particles having a small particle size, or the like, or a known microsuspension polymerization method.

According to the method of the present invention, the acrylic rubber, by adding a chloromethyl group-containing aromatic vinyl compound, by addition reaction with an amino group in the acrylic rubber molecular chain,
It is a quaternary ammonium salt.

When a chloromethyl group-containing aromatic vinyl compound is added little by little to the latex of the acrylic rubber and dispersed, the rubber swells and absorbs these compounds, and the room temperature is maintained between the amino group and the chloromethyl group in the acrylic rubber molecular chain. With the above, the addition reaction occurs almost quantitatively to form a quaternary ammonium salt. By this addition reaction, a vinyl group can be introduced and modified in the acrylic rubber. By using the modified acrylic rubber thus obtained as a base rubber in the graft polymerization, the graft ratio can be controlled arbitrarily.

Specific examples of the chloromethyl group-containing aromatic vinyl compound include chloromethylstyrenes such as m-chloromethylstyrene and p-chloromethylstyrene. These may be one kind or a mixture of two or more kinds.

The amount of the chloromethyl group-containing aromatic vinyl compound added to the acrylic rubber is 0.0 based on 100 parts by weight of the former.
5 to 10 parts by weight. The amount of the latter to be added does not have to be equivalent to the amino group in the acrylic rubber molecular weight chain, and may be any amount within the above range. Preferably, the amount is slightly over the equivalent amount. The chloromethyl group-containing aromatic vinyl compound that has not reacted with the amino group is
It is consumed in the next graft polymerization reaction. However, if the amount of the latter added exceeds 10 parts by weight, a crosslinking reaction occurs during the graft polymerization, the graft ratio becomes excessive, and the impact resistance of the resin decreases. In addition, the amount of chloromethyl group-containing aromatic vinyl compounds that do not contribute to the addition reaction increases, which is not economical. The amount added
If it is less than 0.05 parts by weight, the vinyl group cannot be introduced into the acrylic rubber, the graft ratio is lowered, and the impact resistance of the resin is reduced, which is not preferable.

In the method of the present invention, the acrylic rubber modified by the above method is used as a base rubber, and 100 to 20% by weight of an aromatic vinyl monomer, 0 to 50% by weight of a vinyl cyanide monomer and the carbon number of an alkyl group are added to the base rubber. A monomer mixture containing 0 to 80% by weight of a methacrylic acid ester monomer of alcohol having 1 to 12 is added to 30 to 200 parts by weight with respect to 100 parts by weight of the acrylic rubber and grafted.

Specific examples of the aromatic vinyl monomer include styrene and α-
Examples include α-alkylstyrene such as methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, vinylnaphthalene and the like. These may be one kind or a mixture of two or more kinds.

The ratio of the aromatic vinyl monomer in the monomer mixture is
Must be 100 to 20% by weight. If this ratio is less than 20% by weight, the graft polymerizability will be poor, and the miscibility and compatibility will be poor when the produced resin is mixed with another hard resin.

Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. They are,
It may be one kind or a mixture of two or more kinds. The proportion of vinyl cyanide monomer in the monomer mixture should be 0 to 50% by weight. If it exceeds 50% by weight, the compatibility between the graft-polymerized resin and the other resin is lowered and the moldability becomes poor, which is not preferable.

Specific examples of the methacrylic acid re-ester monomer in the present invention include a methacrylic acid ester of an alcohol having an alkyl group having 1 to 12 carbon atoms such as methyl methacrylate, n-butyl melicrylate, cyclohexyl methacrylate and lauryl methacrylate. can give. These may be one kind or a mixture of two or more kinds. The proportion of the methacrylic acid ester monomer in the monomer mixture should be 0 to 80% by weight. If it exceeds 80% by weight, not only the graft polymerizability changes, it is necessary to change the polymerization conditions, but also the characteristics of the graft-polymerized resin change and the types of other resins to be mixed are limited.

When the amount of the monomer mixture when grafted on the acrylic rubber is less than 30 parts by weight, a sufficient amount of resin can be generated by graft polymerization to cover the surface of the rubber particles of the acrylic rubber latex. However, the rubber particles are aggregated with each other, and the graft ratio is reduced, which lowers the impact resistance of the resin, which is not preferable. If the amount used exceeds 200 parts by weight, the graft ratio will be saturated and constant, only the resin not graft-polymerized will increase, and the concentration of acrylic rubber in the resin will decrease, which is not preferable.

According to the present invention, the above-mentioned monomer mixture can be grafted onto the acrylic rubber by a conventional emulsion polymerization method using water as a medium. When employing the emulsion polymerization method, potassium persulfate, a known polymerization initiator such as hydroperoxide, an anionic surfactant such as fatty acid potassium,
Known emulsifiers such as calaon surfactants such as quaternary ammonium salts and nonionic surfactants such as polyethylene glycol derivatives can be used. As the emulsifier used for this graft polymerization, it is preferable to use, for example, an anionic surfactant and a nonionic surfactant together in consideration of the emulsion stability during the addition reaction to the modified acrylic rubber.

The monomer mixture to the graft polymerization system containing the latex-like modified acrylic rubber at the time of performing the graft polymerization may be added all at once, dividedly, or continuously. Preferably, the monomer mixture, the emulsifier and the like are appropriately divided and added after a certain period of time according to the polymerization rate of the graft polymerization. At this time, the properties of the graft polymer on the surface of the rubber particles can be arbitrarily changed by appropriately changing the additive composition of the monomer mixture, for example, from the initial stage of the polymerization to the later.

In carrying out this graft polymerization, a slight graft reaction is first carried out by an emulsion polymerization method, and the surface of the acrylic rubber particles is coated with a hard resin. It is also possible to adopt a method in which the system is transferred from the system to a suspension system, a solution system or a bulk polymerization system and the graft polymerization is continued. Further, when the weight average rubber particle diameter of the acrylic rubber is about 1 μm or more, the graft reaction can be directly carried out by a well-known microsuspension polymerization method without passing through the graft reaction by the emulsion polymerization method.

The graft ratio of the resin obtained by the present invention to the acrylic rubber is preferably 30 to 80%. When the graft ratio is less than 30%, the surface of the acrylic rubber particles cannot be coated with the hard resin, the miscibility with the resin is deteriorated, and in the resin molded product, agglomeration between rubber particles occurs and It is not preferable because the impact property and the appearance become poor. If the graft ratio exceeds 80%, the hardness of the acrylic polymer graft-polymerized increases, the rubber elasticity is lost especially at low temperatures, and the impact resistance of the resulting resin is reduced, which is not preferable.

In the present invention, the graft ratio means a value calculated by the following formula.

G: The desired graft ratio.

R: The weight of acrylic rubber. Specifically, it is the weight of an acrylic rubber composed of an acrylic ester, a vinyl monomer copolymerizable with an acrylic ester, a polyfunctional vinyl monomer and an amino group-containing vinyl monomer. Calculated from the amount charged.

A: The weight of the acetone insoluble component of the acrylic rubber in the graft-polymerized resin. Specifically, the resin containing the graft-polymerized acrylic rubber is dispersed and dissolved in acetone at 23 ° C., and is centrifuged to separate into insoluble matter and soluble matter. The dry weight is the insoluble matter.

The resin obtained by the method of the present invention can be directly used for molding and the like. In addition, other thermoplastic resins such as polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethylene-propylene-diene-styrene copolymer (AES resin) ), Polymethylmethacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide and the like, and kneading and mixing can be used for weather resistance and impact resistance.

The resin obtained by the method of the present invention includes various kinds and amounts of lubricants, mold release agents, colorants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, fillers and the like which do not impair the properties of the resin. The resin additives can be added in an appropriate combination.

The resin having excellent weather resistance and impact resistance obtained by the method of the present invention is a target molded article by various processing methods such as injection molding method, extrusion molding method and compression molding method, and has excellent weather resistance and impact resistance. It can be used for required applications.

"Effects of the Invention" As described above, the present invention has particularly remarkable effects as described below, and its industrial utility value is extremely large.

(1) According to the method of the present invention, it is possible to introduce a required amount of a vinyl group having a polymerization activity into the acrylic rubber, and therefore, the graft ratio to the acrylic rubber can be arbitrarily optimized.

(2) Further, the hardness and strength of the rubber can be optimized by making the inside of the acrylic rubber into a crosslinked network, so that the one grafted with such a rubber as the base has a good dispersibility in the resin. It gives excellent graft rubber particles.
Therefore, a molded article excellent in impact resistance and appearance can be produced from the resin obtained by the method of the present invention.

(3) The resin obtained by the method of the present invention uses acrylic rubber having a saturated carbon-bonded main chain as a base rubber, and therefore has extremely excellent weather resistance.

(4) Since the resin obtained by the method of the present invention has excellent compatibility with other hard thermoplastic resins, it is possible to produce a resin composition having excellent weather resistance and impact resistance by kneading and mixing. it can.

[Examples] Next, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 (i) Production of acrylic rubber Butyl acrylate (hereinafter abbreviated as BA) 268.5 g, acrylonitrile (hereinafter abbreviated as AN) 15
g, ethylene glycol dimethacrylate (hereinafter abbreviated as EGDM) 1.5 g, and 4-vinylpyridine (hereinafter 4 V)
Abbreviated as P. ) 15 g was weighed and mixed to prepare a mixture (I). 400 ml of deionized water and 1.5 g of an emulsifier (Hitenol N-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were placed in a 1-glass flask equipped with a stirrer and heated to 75 ° C. under a nitrogen stream. Then, in this flask, potassium persulfate (hereinafter abbreviated as KPS. 12 ml of aqueous solution (0.45 g of KPS
including. ) Was added, and then 12 g of the mixture (I) was added, and the polymerization reaction was started at the same temperature. 15 minutes after starting the polymerization reaction, 288 g of the remaining mixture (I) was continuously added to the polymerization system at an addition rate of 16 g / 10 minutes.

After 1 hour, 2 hours, and 3 hours from the start of the polymerization reaction, 0.9 g of the emulsifier hythenol was added.
2 hours after starting the polymerization reaction, 12 ml of KPS aqueous solution
(Containing 0.45 g KPS) was added. About 3 hours and 15 minutes after the initiation of the polymerization reaction, the addition of the mixture (I) was completed. Furthermore, the polymerization reaction was continued at the same temperature for 1 hour to complete the reaction, and an acrylic rubber latex was obtained. The weight average rubber particle diameter was measured. The results are shown in Table 1.

(Ii) Addition reaction of chloromethylstyrene A latex of acrylic rubber obtained by the method described in (i) above was charged in a glass flask having a volume of 1, and the temperature inside the flask was maintained at 75 ° C with stirring. Meanwhile, 15 g of chloromethylstyrene (hereinafter abbreviated as CMS) was added. After the addition, continue stirring for 15 minutes, then cool and add CMS.
A latex of acrylic rubber that had undergone the addition reaction of was obtained.

(Iii) Production of Resin by Graft Polymerization 35 g of styrene (hereinafter abbreviated as St) and 15 g of AN were weighed to prepare a monomer mixture (II).

About 1/3 of the latex of acrylic rubber to which CMS was added as described in (ii) above (including 100 g of rubber solid content) was collected, and 160 ml of deionized water was provided with a stirrer.
The mixture was placed in a glass flask and heated at 75 ° C under a nitrogen stream. Add 8 ml of KPS aqueous solution (containing 0.3 g of KPS),
Then, the monomer mixture (II) was added to the polymerization system at an addition rate of 4.2 g / 10 minutes, and the graft polymerization reaction was started at the same temperature. After 45 minutes and 1 hour and 30 minutes from the start of the polymerization reaction, 0.5 g each of the emulsifier hythenol was added, and after 1 hour and 30 minutes, 5 ml of an aqueous KPS solution (containing 0.2 g of KPS) was added. Added additionally.

Approximately 2 hours after the initiation of the polymerization reaction, the addition of the monomer mixture (II) was completed, and subsequently, at the same temperature, for another hour.
The reaction was continued for 30 minutes to complete the polymerization reaction.

The graft-polymerized latex was aggregated by salting out, washed and dried to obtain a resin. The graft ratio of the obtained resin was measured.

The results are shown in Table 1.

(Iv) Measurement of mechanical properties of resin The resin obtained by the method described in (iii) above and
Acrylonitrile / styrene resin (hereinafter abbreviated as AS resin)
It SAN C. Mitsubishi Monsanto Kasei Co., Ltd.
The content of acrylic rubber is 20% by weight.
A pellet of the composition was made.

The composition diluted with this AS resin was molded into a test piece using a small injection molding machine. The appearance of the test piece was as good as that of the ABS resin. Izod impact strength (with notch) was measured according to JIS K7110, and tensile strength was measured according to JIS K7113.

The results are shown in Table 1.

Examples 2-5 (i) Production of acrylic rubber Same as described in Example 1 (i).

(Ii) Chloromethylstyrene addition reaction In the example described in Example 1 (ii), the procedure was the same as in Example (ii) except that the amount of CMS charged was changed as shown in Table 1. .

(Iii) Manufacture of Resin by Graft Polymerization In the example described in Example 1 (iii), the amount of St and AN charged was changed as shown in Table 1, and the resin was produced by the above (ii) CMS addition reaction. A latex was used and the addition rate was adjusted so that the continuous addition time of the monomer mixture (II) was maintained as 2 hours as in the same example. Other than this, the graft reaction was carried out by the same procedure and method as in Example 1 (iii) to obtain a resin.

(Iv) Measurement of mechanical properties of resin By the same procedure and method as in the example described in Example 1 (iv), an evaluation test was performed using the resin produced in (iii) above. The appearance of the test piece was as good as ABS resin. The results are shown in Table 1.

Examples 6 to 8 and Comparative Examples 1 to 4 (i) Manufacture of Acrylic Rubber In the example described in Example 1 (i), Table 1 shows the types and charging amounts of the amino group-containing vinyl monomer component. The amount of BA was adjusted so that the total amount of the mixture (I) was 300 g. Except for this, the procedure and method were the same as in Example 1 (i).

(Ii) Addition reaction of chloromethylstyrene As in the examples described in Examples 2 to 5, the charged amount of CMS was changed as shown in Table 1 and the latex produced in (i) above was used. Otherwise, the procedure and method were the same as in the same example.

(Iii) Production of Resin by Graft Polymerization In the examples described in Examples 2 to 5, the charge amounts of St and AN were changed to St 70 g and AN 30 g, respectively, and the latex obtained by the addition reaction in (iii) above was used. The addition rate of the monomer mixture (II) was changed to 8.4 g / 10 minutes. Other than this, the same procedure and method as in Examples 2 to 5 were adopted.

(Iv) Measurement of Mechanical Properties of Resin The mechanical properties of the resin produced in (iii) above were measured by the same procedure and method as in the examples described in Examples 2 to 5. The appearance of the test pieces was as good as ABS in Examples 6 to 8 and Comparative Example 4, but in Comparative Examples 1 to 3, flow marks due to the acrylic rubber were recognized on the surface of the test pieces and were poor. . The results are shown in Table 1.

Table 1 shows the following.

(1) With respect to the resin obtained by the method of the present invention, the graft ratio to the acrylic rubber can be arbitrarily selected depending on the amount of the addition reaction of CMS, regardless of the crosslinking of the rubber.

(2) The resin obtained by the method of the present invention can be optimized in a graft ratio of 30 to 80%, so that it has a large Izod impact strength and an excellent reinforcing effect on the grafted acrylic rubber.

(3) The resin obtained by the method of the present invention has a good dispersion compatibility between the graft rubber particles of the acrylic rubber and the diluting hard resin, so that the appearance of the injection molded product is excellent without flow marks.

Claims (5)

[Claims] 1. A weight average rubber particle diameter of an acrylic rubber is 0.
1 to 5 μm and the number of carbon atoms of the alkyl group is 1 to 8
Acrylic ester of alcohol monomer component 99.9-60
% By weight, 0 to 40% by weight of a vinyl monomer component copolymerizable with the above acrylic ester, and a polyfunctional vinyl monomer component of 0.
05 to 5% by weight and amino group-containing vinyl monomer component 0.05
To 10 parts by weight (however, the total of the monomer components is 100% by weight), 100 parts by weight of the acrylic rubber is added 0.05 to 10 parts by weight of the chloromethyl group-containing aromatic vinyl compound. A quaternary ammonium salt is formed by addition reaction with an amino group in the chain, and then,
Aromatic vinyl monomer 100 to 20% by weight, vinyl cyanide monomer 0 to 50% by weight, and alcohol methacrylic acid ester monomer of alkyl group having 1 to 12 carbon atoms 0 to 80% by weight
A method for producing a resin having excellent weather resistance and impact resistance, which comprises grafting 30 to 200 parts by weight of a monomer mixture containing 2. A method for producing a resin having excellent weather resistance and impact resistance according to claim 1, characterized in that the acrylic rubber is in the form of a latex using water as a medium. . 3. The chloromethyl group-containing aromatic vinyl compound is chloromethylstyrene, and any one of claims (1) and (2) is set forth.
The method for producing a resin having excellent weather resistance and impact resistance according to the item. 4. The graft polymerization is carried out using water as a medium and an emulsifier and a polymerization initiator, according to any one of claims (1) to (3). A method for producing a resin having excellent weather resistance and impact resistance. 5. The graft ratio of a resin obtained by graft polymerization to an acrylic rubber is 30 to 80%, and any one of claims (1) to (4) is set forth. The method for producing a resin having excellent weather resistance and impact resistance according to the item.