JPH0892328A - Production of weather resistant resin excellent in impact resistance - Google Patents

Abstract

PURPOSE: To facilitate control of graft ratio and obtain the subject resin having good moldability and processability and appearance of molding and excellent in impact resistance and weatherability by introducing a chloromethyl group- containing vinyl monomer component into an acrylic rubber molecular chain. CONSTITUTION: This method for producing a weatherable resin comprises adding (B) 30 200 pts.wt. of a monomer mixture containing 100-20wt.% of an aromatic vinyl monomer, 0-50wt.% of a vinyl cyanide monomer and 0-80wt.% of a 1-12C alkyl group-containing (meth)acrylic acid alkyl ester monomer component to (A) 100 pts.wt. of an acrylic rubber obtained by copolymerizing (A) 60-99.9wt.% of a 1-8C alkyl group-containing (meth)acrylic acid alkyl ester monomer component with 0.05-10wt.% of a chloromethyl group containing vinyl monomer component (preferably styrene, vinylester, vinyl ether, allyl ester or aryl ether), 0-40wt.% of other vinyl monomer component copolymerizable with these monomers and 0.05-5wt.% of a polyfunctional vinyl monomer component and having 0.05-5μm weight average particle diameter and subjecting the component A to graft polymerization with the component B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a weather resistant resin having excellent impact resistance. More specifically, the present invention relates to a method for producing a thermoplastic resin obtained by grafting a monomer mixture containing an aromatic vinyl monomer onto an acrylic rubber, which exhibits excellent impact resistance and weather resistance.

[0002]

2. Description of the Related Art Heretofore, many methods have been proposed and put to practical use, in which a hard resin is blended with rubber and the rubber-resin two-component system is reinforced by the rubber to produce a resin having excellent impact resistance. ABS resin is a representative of this kind of two-component resin, and the demand for it is ever increasing. However, in this ABS resin, a diene rubber is mainly used as a base rubber component, and the base rubber has an unsaturated double bond in the molecular chain. If this ABS resin molded product is exposed to sunlight while it is used outdoors, oxidation and molecular chain breakage will occur in the unsaturated double bond part of the rubber component, and if it is used outdoors for a long period of time, it will undergo significant discoloration and physical properties. There is a drawback that a decrease occurs. Therefore, the ABS resin based on the diene rubber is restricted in outdoor use, which is the biggest drawback of this resin. This drawback is
The resin of this kind can be slightly improved by adding an ultraviolet absorber, a light stabilizer, an antioxidant and the like, but the drawbacks of the resin of this kind have not been fundamentally improved.

In order to solve the above-mentioned drawbacks existing in the two-component resin having the diene rubber as the base rubber, many techniques using saturated rubber as the base rubber have been proposed. Acrylic ester-based rubber-like polymer (acrylic rubber) is an example of this, but resin having satisfactory properties even when diene rubber, which is a base rubber of general-purpose ABS resin, is replaced with saturated rubber and graft-polymerized. Can't get Indeed, in terms of weather resistance, general-purpose ABS using diene rubber as the base rubber
Although it is greatly improved as compared with resin, it is difficult to say that it is practically satisfactory because it has problems in impact strength and appearance of the molded product.

The rubber-resin two-component rubber-reinforcing resin represented by ABS resin is usually a latex-like rubber component containing water as a medium and a monomer mixture constituting a branch component of the graft copolymer. The resin obtained by graft copolymerization is used as it is or as a mixture with a separately manufactured hard resin. A latex rubber component with water as a medium,
The method of graft copolymerization is to control the particle diameter of the rubber component,
Since it is superior to other polymerization methods in controlling the polymerization temperature, reaction time, polymerization operation, etc., it is widely adopted as an industrial production method of rubber-reinforced resin.

Acrylic rubbers used as a base rubber component for imparting weather resistance generally exhibit superior properties when they have a crosslinked network structure. However, in order to obtain such a crosslinked structure acrylic rubber in a latex form, (a) a method of performing emulsion polymerization in the presence of a crosslinkable monomer, or (b) a method of crosslinking an emulsified acrylic rubber with an organic peroxide such as benzoyl peroxide (BPO). To be
However, acrylic rubber has the drawbacks that it is softer than diene rubber, has a low elastic modulus, is slow in elastic recovery, and is easily plastically deformed.

ABS using such soft rubber
When a rubber-resin two-component resin such as a resin is manufactured and injection molding is performed as a molding material, the deformation orientation of the rubber particles is remarkable, and pearly luster or flow marks may appear on the surface of the molded product. , The commercial value is reduced. In addition, such a molded product may have a large difference in 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.

As one of the methods for improving various drawbacks caused by using a soft rubber such as acrylic rubber, there is a method for controlling 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 significantly reduced in inverse proportion to the improvement in the appearance, and such original characteristics of the resin cannot be exhibited. On the contrary, when the degree of crosslinking of the rubber particles is low, the impact strength is improved, but the appearance of the molded product is deteriorated. Further, especially 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 is almost impossible to control the graft ratio and the degree of cross-linking of the rubber particles while maintaining the impact resistance and the weather resistance by allowing this double bond to be retained inside the rubber particles in an arbitrary amount. there were.

Further, in recent years, for the purpose of increasing the graft ratio of acrylic rubber, a resin having a copolymer containing a norbornene derivative (eg, norbornadiene, ethylidene norbornene, vinyl norbornene) as a base rubber has been proposed (special feature: Japanese Patent Publication No. 6-41497) discloses that when this copolymer is produced by a radical polymerization method,
The chain transfer is extremely large, which affects the polymerization rate and the degree of polymerization of the acrylic copolymer rubber (formation of free ends when crosslinked), and there is a drawback that the properties as a rubber cannot be sufficiently exhibited.

[0009]

DISCLOSURE OF THE INVENTION The inventor of the present invention intends to solve the above-mentioned various drawbacks that have been conventionally present in the field of rubber-resin two-component resin using acrylic rubber as a substrate. As a result, as a result of intensive studies, the present invention has been achieved. An object of the present invention is to introduce a vinyl monomer component containing a chloromethyl group into the acrylic rubber molecular chain, thereby facilitating control of the graft ratio, which was difficult in conventional acrylic rubber graft polymerization. Another object of the present invention is to provide a method for producing a resin having good molding processability and a good appearance of a molded article, and having excellent impact resistance and weather resistance.

[0010]

In order to solve the above problems, in the invention described in claim 1, a (meth) acrylic acid alkyl ester monomer component 60 having an alkyl group having 1 to 8 carbon atoms is used. ˜99.9% by weight, 0.05 to 10% by weight of a vinyl monomer component containing a chloromethyl group, 0 to 40% by weight of another vinyl monomer component copolymerizable therewith,
And polyfunctional vinyl monomer component 0.05 to 5% by weight
(However, the total amount of the monomer components is 100% by weight.), And the weight average particle size is 0.05 to 5
Aromatic vinyl monomer 100 to 20% by weight, vinyl cyanide monomer 0 to 100 parts by weight of acrylic rubber of μm
To 50% by weight, and an alkyl group (meth) acrylic acid alkyl ester monomer component having 1 to 12 carbon atoms 0 to
A means of adding 30 to 200 parts by weight of a monomer mixture containing 80% by weight and performing graft polymerization is taken.

[Detailed Description of the Invention] The present invention is described in detail below. [1] Acrylic Rubber In the present invention, an acrylic rubber having a specific composition and a specific particle size is used as the base rubber. This acrylic rubber serves as a base (stem) rubber at the time of graft polymerization, and also functions as an elastic body exhibiting a rubber reinforcing effect, and improves the impact resistance of the resin finally obtained. The acrylic rubber that can be used in the present invention is a vinyl monomer containing a (meth) acrylic acid alkyl ester monomer component having an alkyl group having 1 to 8 carbon atoms in an amount of 60 to 99.9% by weight and a chloromethyl group. Component 0.05 to 10% by weight, other copolymerizable vinyl monomer component 0 to 40% by weight, and polyfunctional vinyl monomer component 0.05 to 5% by weight (however, The total content of the components is 100% by weight.)
And a weight average particle diameter of 0.05 to
The rubber is 5 μm.

A constituent component of acrylic rubber (meth)
The acrylic acid alkyl ester monomer is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms. Specific examples of the acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate. Specific examples of the methacrylic acid alkyl ester include:
Melmethacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like can be mentioned. These ester compounds may be one kind or a mixture of two or more kinds.

The acrylic rubber contains the above-mentioned (meth) acrylic acid alkyl ester monomer in the range of 99.9 to 60% by weight (the total amount of the monomer components constituting the acrylic rubber is 100% by weight). Shall be included. This (meta)
Since the alkyl acrylate component contains other components, it does not exceed 99.9% by weight. Further, in order to exhibit 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 at low temperatures is low, which is not preferable. Particularly preferable range is 65 to 80% by weight.

The vinyl monomer having a chloromethyl group is
It functions in the molecular chain of acrylic rubber to control the graft ratio. Specific examples of the vinyl monomer having a chloromethyl group, styrene, vinyl ester, vinyl ether, allyl ester, allyl ether, or a compound consisting of (meth) acryl,
Chloromethyl styrene, chloroethyl vinyl ether,
Examples thereof include chloromethyl allyl ether, vinyl chloroacetate, allyl chloroacetate, and 3-chloro-2-hydroxypropyl methacrylate. These vinyl monomers having a chloromethyl group may be one kind or a mixture of two or more kinds.

The proportion of the vinyl monomer having a chloromethyl group contained in the acrylic rubber is 0.05 to 10% by weight.
It is necessary to choose within the range. The ratio of this monomer is 0.05
If the content is less than wt%, the grafting rate of the acrylic rubber is small, the graft ratio cannot be increased, and the impact resistance of the finally obtained resin cannot be improved, either of which is not preferable. On the other hand, when the proportion of the vinyl monomer having a chloromethyl group exceeds 10% by weight, the amount of chloromethyl groups contained in the molecular chain of the acrylic rubber increases, which not only deteriorates the weather resistance of the rubber but also causes grafting. In the polymerization, the graft reaction becomes excessive, the impact resistance of the resin finally obtained is lowered, and the cost becomes high. Especially preferable range is 0.2 to 5% by weight.

The acrylic rubber requires the polyfunctional vinyl monomer component described below in addition to the above-mentioned two types of components,
If necessary, other copolymerizable vinyl monomer may be included. Specific examples of the other copolymerizable monomer include aromatic vinyl monomers described later, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, acrylic amide, methacryloamide, vinylidene chloride, alkyl (carbon Vinyl ether, (meth) acrylic acid and the like. These other copolymerizable monomers,
It may be one kind or a mixture of two or more kinds. The ratio of the copolymerizable vinyl monomer component contained in the acrylic rubber is 0
It should be selected in the range of up to 40% by weight. When the content of the copolymerizable vinyl monomer component exceeds 40% by weight, various properties of the acrylic rubber such as elastic modulus are deteriorated, which is not preferable. Particularly preferred is the range of 0 to 30% by weight.

The polyfunctional vinyl monomer contained in the acrylic rubber has a function of crosslinking the (meth) acrylic copolymer and has two or more vinyl groups in one molecule of the monomer. Says monomer. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, and polyhydric alcohol acryl such as (poly) ethylene glycol dimethacrylate and trimethylolpropane triacrylate. Acid esters and methacrylic acid esters, diallylmates,
Examples thereof include diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate and allyl methacrylate. These polyfunctional vinyl monomers may be one kind or a mixture of two or more kinds.

The proportion of the polyfunctional vinyl monomer component contained in the acrylic rubber is selected in the range of 0.05 to 5% by weight. If it is less than 0.05% by weight, the degree of cross-linking of the acrylic rubber is low, so the rubber elasticity is small, and the rubber particles are significantly deformed in the molded product when graft polymerized, and impact resistance is exhibited. However, this is not preferable because the molded product becomes anisotropic. When it exceeds 5% by weight, the degree of cross-linking of the acrylic rubber becomes too high, resulting in loss of rubber elasticity and hardening. When such a hard rubber is graft-polymerized as a base rubber, the resulting resin has a reduced impact resistance, particularly a low temperature impact resistance, which is not preferable. A particularly preferred range is 0.1 to 2% by weight.

The acrylic rubber has a weight average particle size of 0.
It should be selected in the range of 05 to 5 μm. In the present invention, the weight average particle diameter of the acrylic rubber is measured by a system in which latex is dispersed in water at 23 ° C. by Nano Sizer ^™ manufactured by Coulter Electronics Ltd. of the United States. To tell. If the weight average particle size of the acrylic rubber is less than 0.05 μm, the rubber reinforcing effect cannot be exhibited, the impact resistance of the finally obtained resin is poor, and the rubber particles aggregate in the molded product. Then, the appearance of the molded product becomes poor, which is not preferable. 5
If it exceeds μm, it exceeds the appropriate range for exerting the rubber reinforcing effect, so the impact resistance of the resin finally obtained is poor, and flow marks are noticeable on the surface of the molded product obtained from such resin. It is not preferable because it becomes poor in appearance. Further, when the rubber is grafted by the emulsion polymerization method, the graft reaction becomes difficult. Particularly preferable range is 0.1 to 2 μm.

The acrylic rubber can be produced by a known emulsion polymerization method using water as a medium. In this emulsion polymerization, the composition of the inside and the surface of the acrylic rubber particles can be changed. For example, in order to enrich the vinyl monomer component having a chloromethyl group on the surface and the crosslinkable polyfunctional vinyl monomer component, these monomer components are not added at the initial stage of polymerization, or a small amount is added at the initial stage of polymerization. Is added, and by selecting conditions such that a large amount is added in the middle or late stage of the polymerization, rubber particles having a high rubber reinforcing efficiency can be produced.

When an acrylic rubber particle having a particle size larger than about 0.5 μm is required, it is difficult to directly produce it by a usual emulsion polymerization method.
It can be produced by a known method such as a microsuspension polymerization method or a method of enlarging a particle having a small particle diameter by a particle enlarging operation. By using the modified acrylic rubber thus obtained as a base rubber during graft polymerization, the graft ratio can be controlled arbitrarily.

As the emulsifier that can be used when the acrylic rubber is produced by a known emulsion polymerization method using water as a medium, the emulsifiers that have been conventionally used when producing this kind of rubber can be used without particular limitation. Specific examples of emulsifiers include:
Examples thereof include anionic surfactants such as fatty acid potassium, cationic surfactants such as quaternary ammonium salts, and nonionic surfactants such as polyethylene glycol derivatives. These may be one kind or a mixture of two or more kinds. When manufacturing by emulsion polymerization method, if necessary,
A polymerization initiator and a molecular weight modifier can be used. Polymerization initiators include water-soluble compounds such as potassium persulfate, which have been conventionally used in the production of this kind of rubber, oil-soluble organic peroxides such as benzoyl peroxide, and these and reducing agents. A so-called redox type initiator which is a combination thereof is used. As the molecular weight regulator, those conventionally used such as mercaptans can be used without particular limitation.

[2] Graft Polymerization According to the method of the present invention, the above acrylic rubber 100 is used.
100 parts by weight to 20 parts by weight of an aromatic vinyl monomer, 0 to 50 parts by weight of a vinyl cyanide monomer, and a (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms in the alkyl group It is indispensable to add 30 to 200 parts by weight of a monomer mixture containing 0 to 80% by weight of body components and perform graft polymerization. The monomer mixture component to be graft-polymerized on the acrylic rubber is grafted on the rubber in a branch shape,
The non-grafted hard component forms a matrix of rubber-resin binary resin.

Styrene is a typical example of the aromatic vinyl monomer, and α-methylstyrene,
Examples thereof include p-methylstyrene, o-methylstyrene, m-methylstyrene, t-butylstyrene, nuclear halogenated styrene, lower alkoxystyrene, trifluoromethylstyrene and the like. The present invention is not limited to these examples. These may be one kind or a mixture of two or more kinds. The ratio of the aromatic vinyl monomer in the monomer mixture to be graft-polymerized is 100.
It is selected in the range of up to 20% by weight. This ingredient is 20
If it is less than 10% by weight, the graft polymerizability of the monomer mixture onto the acrylic rubber will be poor, and the miscibility and compatibility will be poor when the finally obtained resin is mixed with other hard resin. , Not preferable.

Specific examples of the vinyl cyanide monomer include:
Examples thereof include acrylonitrile and methacrylonitrile, and these may be one kind or a mixture of two or more kinds. The proportion of the vinyl cyanide monomer in the monomer mixture to be graft-polymerized is selected in the range of 0 to 50% by weight. When the content of this component exceeds 50% by weight, the compatibility is deteriorated when the finally obtained resin is mixed with another hard resin, and the moldability and heat stability are deteriorated, which is not preferable.

Specific examples of the (meth) acrylic acid alkyl ester monomer component are as described for the (meth) acrylic acid alkyl ester monomer described in the section [1] Acrylic rubber. The (meth) acrylic acid lower alkyl ester monomer may be one kind or a mixture of two or more kinds. The proportion of the (meth) acrylic acid alkyl ester monomer in the monomer mixture to be graft-polymerized is selected in the range of 0 to 80% by weight. If this component exceeds 80% by weight, the graft ratio will change, and not only the polymerization conditions will need to be changed significantly in order to adjust the graft ratio, but also the properties of the graft-polymerized resin will change, and finally This is not preferable because the types of other hard resins that can be blended with the resulting resin are limited.

In the graft polymerization, a monomer mixture containing an aromatic vinyl monomer is selected in the range of 30 to 200 parts by weight with respect to 100 parts by weight of the above-mentioned acrylic rubber (based on solid content). Is preferred. If the amount of the monomer mixture is less than 30 parts by weight, a sufficient amount of resin to cover the surface of the rubber particles of the acrylic rubber latex cannot be produced by graft polymerization, and the graft ratio becomes small, and finally It is not preferable because it reduces the impact resistance of the obtained resin. When the amount of the monomer mixture exceeds 200 parts by weight, the graft ratio is saturated and becomes constant, the amount of resin not grafted increases, and the concentration of acrylic rubber in the finally obtained resin decreases, which is not preferable. . Particularly preferable range is 70 to 150 parts by weight.

According to the present invention, in order to graft the above-mentioned monomer mixture onto an acrylic rubber, a conventional emulsion polymerization method using water as a medium, an emulsion-suspension polymerization method, an emulsion-bulk polymerization method, an emulsion-solution weight method is used. It can be performed by a legal method, a microsuspension polymerization method, or the like. In the case of the emulsion polymerization method, conventionally used emulsifiers can be used without particular limitation. The emulsifier is
It may be the same as that described in the section [1] Acrylic rubber. When producing by the emulsion polymerization method, a polymerization initiator and a molecular weight modifier can be used if necessary. The polymerization initiator may be the same type as that described in the section [1] Acrylic rubber. As the molecular weight regulator, those conventionally used can be used without particular limitation. In the case of the emulsion-suspension polymerization method, the suspending agent which has been conventionally used for this type of graft polymerization can be used without limitation.

When carrying out the graft polymerization, the method of charging the above-mentioned monomer mixture, polymerization initiator, molecular weight modifier and the like into the polymerization vessel may be batch charging, divided charging or continuous charging. When the monomer mixture is post-charged, the proportion of the monomer mixture can be changed in the initial, middle and late stages. When carrying out graft polymerization,
First, a little graft reaction is performed by emulsion polymerization method,
Acrylic rubber particles are coated on the surface with a hard resin, and when it becomes possible to disperse only with rubber particles, a method is used in which the system changes from an emulsion system to a suspension system, a block system, or a solution system to continue graft polymerization. can do. Further, when the weight average particle diameter of the acrylic rubber is about 1 μm or more, the graft reaction can be directly carried out by the well-known microsuspension polymerization method without passing through the graft reaction by the emulsion polymerization method.

The resin (graft polymer) obtained by the method of the present invention has a graft ratio of 30 to 30 on the acrylic rubber.
It is preferably in the range of 150%. Graft ratio is 30
When it is less than%, the acrylic rubber particle surface cannot be coated with a hard resin, the miscibility with the matrix resin deteriorates, and agglomeration occurs between the rubber particles, resulting in impact resistance and appearance of the molded product. Is not preferable because it becomes poor. If the graft ratio exceeds 150%, the hardness of the graft-polymerized acrylic rubber becomes high, the rubber elasticity, especially the elasticity at low temperature, becomes low, and the impact resistance of the finally obtained resin is lowered, which is not preferable.

In the present invention, the graft ratio {G (%)} is expressed by the following formula: G (%) = {(A−R) / R} × 10
A value calculated from 0. Here, R is the weight of the acrylic rubber and can be calculated from the amount charged into the graft polymerization system. A is a dry weight of the insoluble matter obtained by dissolving the acrylic rubber-containing resin in the graft-polymerized resin in acetone at 23 ° C. and centrifuging to separate the soluble and insoluble matter.

Resin (A) obtained by the method of the present invention
Since it can be used as a molding material by itself, it can be used as it is as a molding material depending on the application. In many cases, the resin obtained by the method of the present invention,
A thermoplastic resin (B) different from this resin is blended and provided as a molding material.

As the thermoplastic resin (B) which can be blended,
Polystyrene, high impact polystyrene, SMA resin (styrene-maleic anhydride copolymer), AS resin (acrylonitrile-styrene copolymer), ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS
Resin (acrylonitrile-acrylic acid ester-styrene copolymer), AES resin (acrylonitrile-EPD
M-styrene copolymer), heat resistant ABS resin (acrylonitrile-butadiene-styrene-α-methylstyrene copolymer), super heat resistant ABS resin (acrylonitrile-
Butadiene-styrene-phenylmaleimide copolymer), MABS resin (methyl methacrylate-acrylonitrile-butadiene-styrene copolymer) and other styrene resins, polymethylmethacrylate, polyvinyl chloride, polyamides, polycarbonate, polybutylene terephthalate, polyethylene Examples thereof include terephthalate and polyphenylene oxide. These may be one kind or a mixture of two or more kinds.

The composition of the resin (A) obtained by the method of the present invention and the other thermoplastic resin (B) will differ depending on the use of the resin composition, but is usually based on 100 parts by weight of the resin (A). It is selected in the range of 1 to 300 parts by weight of the other thermoplastic resin (B). These thermoplastic resins are powders, beads, flakes, or pellets, and are used as a mixture of two or more kinds by a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, or a twin roll. The thermoplastic resin composition of In some cases, a method may be employed in which two or more of these polymers that have completed polymerization are mixed in an undried state, precipitated, washed, dried, and kneaded.

The thermoplastic resin composition comprising the resin (A) obtained by the method of the present invention and another thermoplastic resin (B) may be added, if necessary, within a range not impairing the object of the present invention.
Thermoplastic resin different from resin (A) and resin (B), inorganic filler, metal powder, reinforcing material, plasticizer, compatibilizer, heat stabilizer, light stabilizer, antioxidant, ultraviolet absorber, Various resin additives such as dyes, pigments, antistatic agents, lubricants and flame retardants can be added in appropriate combination.

The resin (A) obtained by the method of the present invention is used as it is, or other thermoplastic resin (B) and / or a thermoplastic resin composition in which various resin additives are added, if necessary, has a high impact resistance. Excellent in resistance and weather resistance, injection molding method,
It is made into a target molded article by various known molding methods such as extrusion molding method, compression molding method, hollow molding method, differential pressure molding method, etc., and can be used for applications requiring impact resistance and weather resistance. it can.

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition,
In the following examples, "parts" means parts by weight, and the physical properties of the thermoplastic resin composition were measured by the methods described below.

(1) Average particle diameter of rubber component As described above. Means the weight average particle diameter, unit: μm (2) Graft ratio to acrylic rubber As described above. (3) Izod impact strength Measured according to JIS K7110. Unit: Kg-cm /
cm (4) Tensile strength Measured according to JIS K7113. Unit: Kg / cm ²

(5) Appearance A test piece (thickness 2.5 mm, width 75 mm,
The length of 160 mm) was manufactured, and the appearance of the surface of this test piece was visually observed. The judgment result was displayed as follows. Good: A pearly luster and almost no flow marks were observed. Poor: Pearly luster and some flow marks are observed. (6) Weather resistance test A test piece for measuring Izod impact strength was placed on a sunshine weatherometer (WEL-SUN-DC type manufactured by Suga Test Instruments Co., Ltd.).
Fix it so that the carbon arc irradiates the notch surface, 1
After 20 minutes of one cycle (18 minutes of rain) for 600 hours of exposure, the Izod impact strength of the test piece was measured.

[Example 1] (i) Production of acrylic rubber Butyl acrylate (abbreviated as BA hereinafter) 268.5
g, acrylonitrile (hereinafter abbreviated as AN) 15 g,
Allyl methacrylate (hereinafter abbreviated as AMA) 1.5
g and 15 g of chloromethylstyrene (hereinafter abbreviated as CMS) were weighed and mixed to prepare a monomer mixture (I). In a glass flask with a capacity of 1 liter equipped with a stirrer, a raw material auxiliary agent addition device, a thermometer, a heating device, etc.
400 ml of deionized water and 1.5 g of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., Hitenol N-08) were charged, and the internal temperature was raised to 75 ° C. Then, in this flask, potassium persulfate (hereinafter abbreviated as KPS) was added to 12 ml of deionized water.
An aqueous solution in which 0.45 g was dissolved was added, then 12 g of the monomer mixture (I) was added, and the polymerization reaction was started at the same temperature.

15 minutes after the initiation of the polymerization reaction,
288 g of the remaining monomer mixture (I) was placed in a flask.
Continuous addition was performed at a rate of g / 10 minutes. 1 hour, 2 hours, and 3 hours after the start of the polymerization reaction,
An emulsifier (Hitenol N-08) was added in 0.9 g increments. Also, at the time when 2 hours have passed since the initiation of the polymerization reaction,
An aqueous solution prepared by dissolving 0.45 g of KPS in 12 ml of deionized water was added. About 3 hours and 15 minutes after the initiation of the polymerization reaction, the continuous addition of the monomer mixture (I) was completed. Further, the polymerization reaction was continued for 1 hour at the same temperature to complete the polymerization reaction, and an acrylic rubber latex was obtained. The weight average particle diameter of the obtained acrylic rubber was 0.27 μm.

(Ii) Preparation of Graft Polymer 35 g of styrene (hereinafter abbreviated as St), and AN1
5 g was weighed and mixed to prepare a monomer mixture (II). About 1/3 of the acrylic rubber latex produced in (i) above (solid content 100 g) was dispensed into the glass flask used in the above (i) Production of acrylic rubber, and 160 ml of deionized water was collected. With stirring and stirring, the internal temperature was raised to 75 ° C. under a nitrogen stream. 8 ml of an aqueous solution containing 0.3 g of KPS was added, followed by the monomer mixture (II)
Was continuously added at a rate of 4.2 g / 10 minutes, and the polymerization reaction was started at the same temperature. At 45 minutes and 1 hour and 30 minutes after the initiation of the polymerization reaction, 0.5 g of an emulsifier (Hitenol N-08) was added at each time. When 1 hour and 30 minutes have passed since the initiation of the polymerization reaction, the deionized water 5
An aqueous solution in which 0.2 g of KPS was dissolved in ml was added. About 2 hours after starting the polymerization reaction, the continuous addition of the remaining monomer mixture (II) was completed. Furthermore, the polymerization reaction was continued for 1 hour at the same temperature to complete the polymerization reaction, and a graft polymer latex was obtained. The latex was coagulated, washed with water and dried to obtain a powdery graft polymer. The graft ratio of the obtained graft polymer onto the acrylic rubber was 38%.

(Iii) Evaluation of physical properties of resin Graft polymer obtained by the method described in (ii) above and acrylonitrile / styrene copolymer (SAN, manufactured by Mitsubishi Kasei Co., Ltd.)
-C. (Hereinafter referred to as AS resin) so that the content of acrylic rubber in the resin is 20% by weight, and 0.3 parts of the ultraviolet absorber and 0.1 parts of magnesium stearate are added to 100 parts of the total amount of the resin. The parts were weighed and mixed, and kneaded with a kneading roll to obtain resin composition pellets. Test pieces for physical property evaluation were produced from the obtained resin composition pellets by a small injection molding machine, and various evaluation tests were conducted. The results are summarized in Table-2.

Examples 2 to 5 (i) Production of acrylic rubber In the example described in (i) of Example 1, the proportion of CMS used in the monomer mixture (I) is shown in Table 1. Acrylic rubber latex was obtained by the same procedure as in the same example except that the above was changed to. The weight average particle size of the obtained acrylic rubber is shown in Table 1. (ii) Production of Graft Polymer In the example described in (ii) of Example 1, the acrylic rubber latex obtained by the method of (i) above was used, and St and AN of the monomer mixture (II) were mixed. An acrylic rubber latex was obtained by the same procedure as in the same example except that the usage ratio was changed as shown in Table 2. The graft ratio of the obtained graft polymer to the acrylic rubber is shown in Table-2. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives were compounded and added in the same procedure as in the example described in (iii) of Example 1 to make resin composition pellets in the same procedure as in the same example, and various evaluations were performed in the same procedure. The test was conducted. The results are summarized in Table-2.

[Examples 6 to 9] (i) Production of acrylic rubber In the example described in (i) of Example 1, the kind of the chloromethyl group-containing vinyl monomer of the monomer mixture (I) and Acrylic rubber was changed in the same procedure as in the same example except that the usage ratio was changed as shown in Table-1 and the charged amount of BA was changed so that the total amount of the monomer mixture (I) was 300 g. A latex was obtained. The weight average particle size of the obtained acrylic rubber is shown in Table 1. (ii) Preparation of Graft Polymer In the examples described in Examples 2 to 5, the acrylic rubber latex obtained by the method (i) above was used, and the monomer mixture (I
I) St and AN usage ratios of 70g and 30 respectively
g, and the continuous addition rate of the monomer mixture (II) was changed to 8.
A graft polymer latex was obtained by the same procedure as in the examples described in Examples 2 to 5, except that the amount was changed to 4 g / 10 minutes. The graft ratio of the obtained graft polymer to the acrylic rubber is shown in Table-2. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives are compounded and added in the same procedure as in the example described in (iii) of Examples 2 to 5, and the resin composition pellets are prepared in the same procedure as in the same example, and various kinds are prepared in the same procedure. Was evaluated. The results are summarized in Table-2.

[Comparative Examples 1 to 3] (i) Production of acrylic rubber Same as Example 1 (i) except that CMS in the monomer mixture (I) was not used. An acrylic rubber latex was obtained by the same procedure as in.
The weight average particle size of the obtained acrylic rubber is shown in Table 1. (ii) Preparation of Graft Polymer In the example described in (ii) of Example 1, the monomer mixture (I
A graft polymer latex was obtained by the same procedure as in the example described in Example 1 except that the amounts of St and AN used in I) were changed as described in Table-2. The graft ratio of the obtained graft polymer to the acrylic rubber is shown in Table-2. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives were compounded and added in the same procedure as in the example described in (iii) of Example 1 to make resin composition pellets in the same procedure as in the same example, and various evaluations were performed in the same procedure. The test was conducted. The results are summarized in Table-2.

Comparative Examples 4 and 6 (i) Production of Acrylic Rubber In the example described in (i) of Example 1, the monomer mixture (I) had an extremely low CMS of 0.02% ( Comparative Example 4)
Then, an acrylic rubber latex was obtained by the same procedure as in the same example except that the content was changed to 15% (Comparative Example 6), which was extremely high. The weight average particle size of the obtained acrylic rubber is shown in Table 1. (ii) Preparation of Graft Polymer In the example described in (ii) of Example 1, the monomer mixture (I
A graft polymer latex was obtained by the same procedure as in the example described in Example 1 except that the amounts of St and AN used in I) were changed as described in Table-2. The graft ratio of the obtained graft polymer to the acrylic rubber is shown in Table-2. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives were compounded and added in the same procedure as in the example described in (iii) of Example 1 to make resin composition pellets in the same procedure as in the same example, and various evaluations were performed in the same procedure. The test was conducted. The results are summarized in Table-2.

Comparative Example 5 (i) Production of Acrylic Rubber In the example described in (i) of Example 1, the monomer mixture (I) contained an extremely small amount of polyfunctional monomer of 0.02.
An acrylic rubber latex was obtained by the same procedure as in the same example except that the percentage was changed. The weight average particle diameter of the obtained acrylic rubber was 0.29 μm. (ii) Preparation of Graft Polymer In the example described in (ii) of Example 1, the monomer mixture (I
A graft polymer latex was obtained by the same procedure as in the example described in Example 1 except that the amounts of St and AN used in I) were changed as described in Table-2. The graft ratio of the obtained graft polymer onto the acrylic rubber was 45%. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives were compounded and added in the same procedure as in the example described in (iii) of Example 1 to make resin composition pellets in the same procedure as in the same example, and various evaluations were performed in the same procedure. The test was conducted. Table 2 shows the results.

Comparative Example 7 (i) Production of Acrylic Rubber In the example described in (i) of Example 1, ethylidene norbornene was used instead of the polyfunctional monomer AMA in the monomer mixture (I). Was used and the reaction time was extended by 2 hours to obtain an acrylic rubber latex by the same procedure as in the same example. The weight average particle diameter of the obtained acrylic rubber was 0.24 μm. (ii) Preparation of Graft Polymer In the example described in (ii) of Example 1, the monomer mixture (I
A graft polymer latex was obtained by the same procedure as in the example described in Example 1 except that the amounts of St and AN used in I) were changed as described in Table-2. The graft ratio of the obtained graft polymer onto the acrylic rubber was 45%. (iii) Evaluation of physical properties of resin The graft polymer produced by the method described in (ii) above is
The S resin and other additives were compounded and added in the same procedure as in the example described in (iii) of Example 1 to make resin composition pellets in the same procedure as in the same example, and various evaluations were performed in the same procedure. The test was conducted. Table 2 shows the results.

[0050]

[Table 1] [Note] * 1 Chloromethylstyrene * 2 Vinyl chloroacetate * 3 2-Chloroethyl vinyl ether * 4 2-Hydroxy-3-chloromethacrylate * 5 Ethylidene norbornene * 6 Allyl methacrylate

[0051]

[Table 2] [Note] * 7 Styrene * 8 Acrylonitrile

From Table-1 and Table-2, the following is clarified. 1. In the resin obtained by the method of the present invention, the graft ratio to the acrylic rubber can be arbitrarily selected by changing the ratio of the chloromethyl group-containing vinyl monomer, regardless of the crosslinking of the rubber. 2. According to the method of the present invention, since the graft ratio to the acrylic rubber can be optimized within the range of 30 to 150%, the Izod impact strength is large and the reinforcing effect by the grafted acrylic rubber is excellent. 3. The resin obtained by the method of the present invention has good dispersion compatibility between the acrylic rubber-grafted rubber particles and the diluting hard resin, so that no flow mark appears on the surface of the injection-molded article and the appearance is excellent. A molded product is obtained. 4. The resin obtained by the method of the present invention has weather resistance equivalent to that of a conventional impact resistant resin based on an acrylic rubber containing no vinyl monomer component containing a chloromethyl group.

[0053]

INDUSTRIAL APPLICABILITY The present invention has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. According to the method of the present invention, the graft ratio to the acrylic rubber can be arbitrarily selected by selecting the amount of the vinyl monomer having a chloromethyl group to be introduced into the acrylic rubber. 2. According to the method of the present invention, by selecting the amount of the polyfunctional monomer, the acrylic rubber can be crosslinked by changing the degree of crosslinking, and the hardness and strength of the base rubber can be selected. Graft rubber particles grafted on rubber,
The resin has excellent dispersibility in a hard matrix resin, and a molded product 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 has an acrylic rubber having a saturated carbon-bonded main chain as a base rubber, and therefore has 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 necessary to prepare a resin composition having excellent impact resistance and weather resistance by kneading and mixing with these. You can

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Claims (5)

[Claims] 1. A (meth) acrylic acid alkyl ester monomer component 60 to 9 having an alkyl group having 1 to 8 carbon atoms.
9.9% by weight, 0.05 to 10% by weight of a vinyl monomer component containing a chloromethyl group, 0 to 40% by weight of another vinyl monomer component copolymerizable therewith, and a polyfunctional vinyl monomer. Acrylic rubber 100 obtained by polymerizing 0.05 to 5% by weight of a monomer component (however, the total amount of monomer components is 100% by weight) and having a weight average particle diameter of 0.05 to 5 μm. Aromatic vinyl monomer 100 to 2 parts by weight
A monomer mixture containing 0% by weight, 0 to 50% by weight of a vinyl cyanide monomer, and 0 to 80% by weight of a (meth) acrylic acid alkyl ester monomer component having an alkyl group having 1 to 12 carbon atoms. A method for producing a weather resistant resin having excellent impact resistance, which comprises adding 30 to 200 parts by weight and graft-polymerizing. 2. The method for producing a weather resistant resin having excellent impact resistance according to claim 1, wherein the acrylic rubber is in the form of a latex using water as a medium. 3. The vinyl monomer containing a chloromethyl group is a compound comprising any of styrene, vinyl ester, vinyl ether, allyl ester, allyl ether and (meth) acrylic residue. Item 1. A method for producing a weather-resistant resin having excellent impact resistance according to Item 1 or 2. 4. The weather resistance with excellent impact resistance according to claim 1, wherein the graft polymerization is carried out using water as a medium and an emulsifier and a polymerization initiator. Of producing a flexible resin. 5. The graft ratio of the resin obtained by the graft polymerization to the acrylic rubber is 30 to 150%, and the graft ratio is 30 to 150%.
Item 5. A method for producing a weather-resistant resin having excellent impact resistance according to item.