JP3077244B2 - Weatherable thermoplastic resin composition and molded article using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weatherable thermoplastic resin composition and a molded article using the same.

[0002]

2. Description of the Related Art Conventionally, AAS resins, AES resins and the like have been used as weather resistant thermoplastic resins for profile extrusion. However, these resins are excellent in weather resistance, impact resistance and heat resistance, but have a drawback that they are inferior in appearance of a die line or the like generated at the time of profile extrusion.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and provides a thermoplastic resin capable of producing a molded article having excellent impact resistance, heat resistance and moldability, especially excellent appearance and weatherability. It is intended to provide compositions and molded articles.

[0004]

Means for Solving the Problems The present inventors have found that by mixing a mixture of a thermoplastic resin having a specific composition with dimethylpolysiloxane oil having a viscosity of 1,000 to 30,000 centistokes and dioctyl adipate, the weather resistance of a molded article and the like are improved. They have found that a thermoplastic resin composition having excellent molded appearance can be obtained, and have completed the present invention.

That is, the present invention provides a polyfunctional monomer of 0.1.
To 20% by weight, 50 to 99.9% by weight of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, and 0 to 30% by weight of another copolymerizable vinyl compound (a). ) 95 to 60 parts by weight and 5 to 40 parts by weight of the diene polymer (b) are blended so that the total of the components (a) and (b) becomes 100 parts by weight, and the polymerization rate is 5
After performing emulsion polymerization until the amount becomes 0 to 93%, in the presence of 5 to 50 parts by weight of a graft polymer rubber (A) obtained by terminating the polymerization, 0 to 100% by weight of an aromatic vinyl compound;
Monomers (B) 95 to 95% comprising methacrylic acid ester 0 to 100% by weight and vinyl cyanide compound 0 to 40% by weight
50 parts by weight, the total of the components (A) and (B) was 100
A thermoplastic resin (hereinafter, referred to as thermoplastic resin (I)) obtained by blending and polymerizing so as to be parts by weight (hereinafter referred to as thermoplastic resin (I)).
0 parts by weight, 10 to 80 parts by weight of a thermoplastic resin (hereinafter referred to as thermoplastic resin (II)) obtained by polymerizing 65 to 85% by weight of an aromatic vinyl compound and 15 to 35% by weight of a vinyl cyanide compound Was added to a resin mixture obtained by blending the thermoplastic resin (I) and the thermoplastic resin (II) so that the total amount of the thermoplastic resin (I) and the thermoplastic resin (II) was 100 parts by weight.
The present invention relates to a weather-resistant thermoplastic resin composition obtained by mixing 0 to 30,000 centistokes of dimethylpolysiloxane oil and dioctyl adipate, and a molded product obtained by molding using the weather-resistant thermoplastic resin composition.

First, the thermoplastic resin (I) will be described. The thermoplastic resin (I) comprises (A) (a) 0.1 to 20% by weight of a polyfunctional monomer, 50 to 99.9% by weight of an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, and 95 to 95% by weight of a polymerizable monomer mixture composed of 0 to 30% by weight of another copolymerizable vinyl compound
60 parts by weight and 5 to 40 parts by weight of the diene polymer (b) are blended so that the total of the components (a) and (b) becomes 100 parts by weight, and the polymerization rate is 50 to 93%. After the emulsion polymerization is carried out until the following conditions, the polymerization is terminated, and in the presence of 5 to 50 parts by weight of a graft polymer rubber obtained, (B) 0 to 100% by weight of an aromatic vinyl compound, 0 to 100% of a methacrylate ester 95 to 50 parts by weight of a monomer consisting of 0 to 40% by weight of a vinyl cyanide compound and
It is obtained by blending and polymerizing so that the total of the components (A) and (B) is 100 parts by weight.

The polyfunctional monomer which is one component of the polymerizable monomer mixture of the component (a) used for producing the graft polymer rubber of the component (A) includes triallyl cyanurate and triaryl cyanurate. Polyvinyl compounds such as allyl isocyanurate, divinyl benzene, triacryl formal, and ethylene glycol dimethacrylate and polyallyl compounds can be used. Among them, particularly, resins in which triallyl cyanurate and triallyl isocyanurate are finally obtained Is preferred because it has the best impact resistance. The polyfunctional monomer is used at 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in the polymerizable monomer mixture (a). If the amount is less than 0.1% by weight, the degree of crosslinking is insufficient, and the impact resistance and the appearance of the molded article are inferior. If the amount exceeds 20% by weight, the degree of crosslinking becomes excessive and the impact resistance decreases.

Examples of the alkyl acrylate having an alkyl group having 1 to 13 carbon atoms, which is one component of the polymerizable monomer mixture of the component (a), include ethyl acrylate,
There are butyl acrylate and 2-ethyl exyl acrylate, among which butyl acrylate is particularly preferred. The alkyl acrylate is used in an amount of 50 to 99.9% by weight in the polymerizable monomer mixture (a), and 65 to 99.5%.
Preferably it is used in% by weight. If the amount is less than 50% by weight, the properties of the acrylic rubber deteriorate.

The polymerizable monomer mixture of the component (a) further contains another copolymerizable vinyl compound, if necessary. Other copolymerizable vinyl compounds that can be used include acrylonitrile, styrene and the like, and are used in an amount of 0 to 30% by weight in the polymerizable monomer mixture (a).
It is preferably used in the range of weight%. 30% by weight
When the ratio exceeds the above, the characteristics of the acrylic rubber cannot be sufficiently obtained.

As the diene polymer as the component (b), polybutadiene, butadiene-styrene copolymer and the like can be used.

To produce the graft polymer rubber of the component (A) used in the present invention, 95 to 60 parts by weight of the polymerizable monomer mixture of the component (a) and the diene polymer 5 of the component (b) are used. To 40 parts by weight, the total of the components (a) and (b) being 100
The polymerizable monomer mixture is emulsion-polymerized in the presence of a diene-based polymer. If the amount of the diene polymer is less than 5 parts by weight, the impact resistance and the appearance of the molded product are insufficient, and if it exceeds 40 parts by weight, the weather resistance is poor.

The emulsion polymerization for obtaining the graft polymer rubber can be carried out by a method generally known to those skilled in the art. In the present invention, this emulsion polymerization is carried out at a conversion of 100.
% To 50% to 93%, preferably 60% to 90%
Stopping at is an essential condition for obtaining high impact resistance. If the degree of polymerization is less than 50%, the ratio of copolymerization with the monomer of component (B) in the subsequent step will increase, and the heat distortion temperature will decrease. The polymerization rate is 93%
If the ratio exceeds the above, the effect of improving impact resistance cannot be sufficiently obtained.

In the emulsion polymerization for obtaining the graft polymer rubber of the component (A), as a small amount of an emulsifier, an anionic emulsifier such as sodium oleate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, or a polyoxyethylene cetyl ether. Such a nonionic emulsifier may be used. Further, as the polymerization initiator, for example, a redox-based polymerization initiator composed of persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate, which is used in ordinary emulsion polymerization, is used.

Next, in the presence of 5 to 50 parts by weight of the thus obtained graft polymer rubber of the component (A), 95 to 50 parts by weight of the monomer as the component (B) are mixed with the components (A) and (B). )) The thermoplastic resin (I) is produced by mixing and polymerizing the components so that the total of the components is 100 parts by weight. Here, if the amount of the graft polymer rubber is less than 5 parts by weight, the impact resistance of the finally obtained resin is reduced, and if it exceeds 50 parts by weight, the mechanical strength and the heat distortion temperature are reduced.

As the aromatic vinyl compound used as the monomer of the component (B), α-substituted styrene such as α-methylstyrene and α-ethylstyrene, chlorostyrene,
Vinyltoluene, nucleus-substituted styrene such as t-butylstyrene, styrene, and the like; also, a cyanide vinyl compound such as acrylonitrile and methacrylonitrile; and a methacrylate ester such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate Can be used. In the component (B), the amount of the vinyl cyanide compound was 40%.
If the amount is more than 10% by weight, the moldability decreases.

In order to polymerize the monomer of the component (B) in the presence of the graft polymer rubber of the component (A), an emulsion polymerization method is used.
A polymerization method such as a suspension polymerization method and a solution polymerization method can be employed. At the time of polymerization, an emulsifier, a polymerization initiator, a chain transfer agent and the like can be appropriately added. As the polymerization initiator, a redox initiator such as persulfate or cumene hydroperoxide-sodium formaldehyde sulfoxylate is preferably used in an amount of about 0.1 to 2% by weight based on the component (B). As the chain transfer agent, t-dodecyl mercaptan or the like is preferably used in an amount of about 1% by weight or less based on the monomer of the component (B). The polymerization is from 20 to 10
It is preferable to carry out at a temperature of 0 ° C, especially 50 to 90 ° C. Note that the same conditions may be adopted when producing the graft polymer rubber.

The monomer of the component (B), which is polymerized in the presence of the graft polymer rubber of the component (A), can be polymerized all at once, polymerized by dividing it into several batches, or polymerized in a single monomer. Although any polymerization method such as a method of performing polymerization while dropping a body may be adopted, as a first step, 5 to 30% by weight of the monomer is blended to achieve a polymerization rate of 50% or more. It is preferable to polymerize the remaining amount of the monomer (B) as the second stage after the polymerization. Such a two-stage polymerization method is preferable because a resin having further improved fluidity, heat distortion temperature and impact resistance can be obtained. The first polymerization is preferably in the range of 5 to 30% by weight of the component (B), and if it is less than 5% by weight, there is no difference from the case where the whole amount is polymerized in one step, and if it exceeds 30% by weight, (B) There is a tendency that the effect of improving the impact resistance and the effect of increasing the heat distortion temperature by dividing and polymerizing the components are reduced.
Further, it is preferable that after the polymerization rate progresses at 50% or more in the first stage, the remaining amount of the monomer (B) is added and polymerization is performed. If the degree of polymerization in the first stage is less than 50%, the effects of improving the heat distortion temperature and impact resistance tend to be reduced.

The monomer of the component (B) used in the first stage and the second stage separately in each stage is composed of 0 to 100% by weight of an aromatic vinyl compound and 0 to 100% by weight of a methacrylate. % And 0 to 40% by weight of the vinyl cyanide compound, and the total amount is preferably 100% by weight.

Next, the thermoplastic resin (II) will be described. The thermoplastic resin (II) is an aromatic vinyl compound 65-65.
85% by weight, preferably 70-80% by weight and 15-35% by weight of the vinyl cyanide compound, preferably 20-30%
It is obtained by polymerizing weight%. If the amount of the aromatic vinyl compound is less than 65% by weight, the fluidity becomes poor,
If it exceeds 85% by weight, the impact resistance and the heat denaturation temperature decrease. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, α-ethylstyrene, α-fluorostyrene, α-chlorostyrene, bromostyrene, methylstyrene, butylstyrene and the like. Further, as the vinyl cyanide compound, acrylonitrile, methacrylonitrile, and the like can be used.

Further, if necessary, other vinyl monomers can be used in combination. When another vinyl monomer is used in combination, the other vinyl monomer is added in an amount of 0 to 20% by weight, and the total amount including the other monomer is 100% by weight. Other vinyl monomers used as needed include methyl acrylate, acrylates such as ethyl acrylate, acrylic acid, vinyl carboxylic acids such as methacrylic acid, maleimide,
N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-
Maleimide monomers such as phenylmaleimide; and vinylcarboxylic acid amide monomers such as acrylamide and methacrylamide.

The production of the thermoplastic resin (II) includes emulsion polymerization,
It can be performed by a known polymerization method such as suspension polymerization and solution polymerization.

In the thermoplastic resin composition of the present invention,
A total of 100 to 80 parts by weight of the thermoplastic resin (I) and 10 to 80 parts by weight of the above thermoplastic resin (II) is 100
It is blended so as to be parts by weight to form a resin mixture. Here, if any one of the thermoplastic resins (I) and (II) is out of this range, the resulting composition will be inferior in heat resistance, impact resistance and the like.

In the thermoplastic resin composition of the present invention,
The resin mixture of the thermoplastic resins (I) and (II) is further mixed with dimethylpolysiloxane oil having a viscosity of 1,000 to 30,000 centistokes at 25 ° C. and dioctyl adipate. If the viscosity of the dimethylpolysiloxane oil is less than 1000 centistokes,
There is no effect of improving the appearance of the molded article, and if it exceeds 30,000 centistokes, the compatibility with the resin decreases, and clouding occurs on the surface of the molded article. The mixing amount of dimethylpolysiloxane oil is preferably 0.1 to 10% by weight based on the mixture of the thermoplastic resin. If the amount is less than 0.1% by weight, the effect of improving the appearance of the molded article is small, and if it exceeds 10% by weight, the impact resistance tends to decrease. The dimethylpolysiloxane oil is particularly preferably mixed in an amount of 0.3 to 3% by weight.

The mixing amount of dioctyl adipate is preferably 0.1 to 5% by weight based on the mixture of the thermoplastic resin. If the amount is less than 0.1% by weight, the effect of improving the appearance of the molded article is small, and if it exceeds 5% by weight, the heat denaturation temperature tends to decrease. The mixing amount of dioctyl adipate is particularly 0.5 to 0.5.
Preferably it is 3% by weight.

When the thermoplastic resin composition of the present invention is used as a molding material, it is possible to use a commonly used stabilizer such as a phenolic antioxidant and an ultraviolet absorber.

The obtained resin composition is excellent in moldability, and is molded by a known molding method such as extrusion molding to obtain various molded products. The obtained molded article is excellent as a building material part, an outdoor molded article, and the like because it has excellent appearance, weather resistance, impact resistance, and the like. In other words, when the thermoplastic resin composition of the present invention is used, since the acrylic rubber is used, it is stable against ultraviolet rays, and even when exposed outdoors for a long time, without reducing the mechanical strength, the appearance of the molded product is reduced. While maintaining
By mixing dimethylpolysiloxane oil and dioctyl adipate, a molded article having excellent appearance can be obtained.

[0027]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Production of Acrylic Graft Polymer Rubber as Component (A) A polybutadiene latex (manufactured by Sumitomo Nogatack Co., Ltd., SN-
800) 300 parts of uniformly mixed fatty acid potassium 8
Parts, 0.09 parts of sodium sulfite and 200 parts of ion-exchanged water
After charging 0 parts and mixing and stirring, butyl acrylate 70
0 parts and 14 parts of triallylisocyanurate are uniformly mixed and added. This emulsified solution was replaced with nitrogen, and then an aqueous solution of 0.5 part of potassium persulfate and 300 parts of ion-exchanged water prepared in another container was added and mixed, and the temperature was raised to 60 to 65 ° C. The polymerization was carried out at 60-65 ° C. for about 3 hours, and cooled to stop the polymerization. At this time, the polymerization rate was 71%.

(2) Emulsion polymerization of thermoplastic resin (I) The above (1) was placed in a 4 liter reaction vessel equipped with a stirrer.
1 part of sodium lauryl sulfate, 5 parts of fatty acid potassium and 650 parts of ion-exchanged water are uniformly dissolved in 400 parts of the acrylic graft polymer rubber produced in the above. To this, 0.25 part of cumene hydroperoxide, 23 parts of acrylonitrile and 47 parts of styrene were uniformly mixed and added while stirring, followed by purging with nitrogen, and then 3 parts of sodium formaldehyde sulfoxylate were dissolved in 70 parts of ion-exchanged water. The mixture is added, the temperature is raised to 65 ° C., and the temperature is maintained for about 1 hour to bring the polymerization rate to 70%. Meanwhile, another three containers are prepared, and 7 parts of potassium carbonate and 60 parts of ion-exchanged water are placed in the first container, and 10 parts of fatty acid potassium and 450 parts of ion-exchanged water are placed in the second container. And 1.5 parts of cumene hydroperoxide, 1.7 parts of t-dotesylmercaptan, 150 parts of acrylonitrile and 38 parts of styrene.
Add 0 parts and dissolve each.

Thereafter, the contents of these three vessels were mixed and dropped into the above-mentioned reaction vessel over about 2 hours.
Polymerize at ° C. Polymerized at 65 ° C for about 5 hours and the polymerization rate was 8
When the content becomes 5 to 90%, an aqueous solution in which 1.2 parts of potassium persulfate is dissolved in 50 parts of ion-exchanged water is added, and the polymerization temperature is raised to 80 ° C., and polymerization is carried out for about 2 hours. Complete. At this time, the polymerization rate was 98%. The latex-like reaction solution obtained here was salted out in hot water in which alum was dissolved, and dehydrated and dried to obtain a powdery thermoplastic resin (I).

(3) Production of thermoplastic resin (II) (aromatic copolymer) 30 parts of a 10% by weight aqueous solution of basic calcium phosphate and sodium dodecylbenzenesulfonate were placed in a 4 liter reaction vessel equipped with a stirrer. 0.5 parts and ion exchange water 120
Add 0 parts and stir. To this, 740 parts of styrene, 260 parts of acrylonitrile, 5 parts of lauroyl peroxide, 3 parts of t-dotesylmercaptan and 0.55 parts of bis-tert-butylperoxycyclohexane are uniformly mixed and added. Thereafter, polymerization was completed at 105 ° C. for 2 hours to complete the polymerization. At this time, the polymerization rate was 98%.
The polymer particles obtained here were washed with water, dehydrated and dried to obtain thermoplastic resin (II) (aromatic copolymer) particles.

Example 1 A mixture of 450 parts of the thermoplastic resin (I) and 550 parts of the thermoplastic resin (II) obtained by the above production method was mixed with 3 parts of dimethylpolysiloxane oil having a viscosity of 10,000 centistokes at 25 ° C. In addition, 10 parts of dioctyl adipate is mixed, and 20 parts of titanium oxide and 5 parts of a stabilizer (composed of a hindered phenol-based antioxidant, a hindered amine-based light stabilizer and a benzotriazole-based ultraviolet absorber) are further mixed. Was extruded with a 30 mmφ extruder into pellets. Using the pellets, a round pipe having a diameter of 30 mm was prepared with an extruder and the appearance was evaluated. Further, a predetermined molded product (test piece) specified by ASTM was prepared by an injection molding machine, and the mechanical properties and weather resistance were evaluated using the test piece. Table 1 shows the results.

Evaluation method: Round pipe appearance In order to measure the surface irregularities of the molded product, the surface roughness was measured at a scanning distance of 3 mm from the top of the round pipe by a surface roughness meter. Izod Impact Strength Measured with 1/8 "notch according to ASTM D256. Heat Deformation Temperature Heat resistance was measured at 1/2" 264 psi according to ASTM D648. Melt flow rate The fluidity was measured at 220 ° C./5 kg according to JIS-K7310. Weather resistance (surface gloss) A test for accelerating weather resistance was conducted by a sunshine weather meter, and the surface gloss was measured at an incident angle of 60 using a gloss meter.
゜, measured at a reflection angle of 60 °.

Comparative Examples 1 and 2 Comparative Example 1 was evaluated in the same manner as in Example 1, except that dimethylpolysiloxane oil was not mixed, and Comparative Example 2 was not mixed with dioctyl adipate. Table 1 shows the results.
Shown in

[0035]

[Table 1]

Examples 2 and 3 Test pieces were prepared and evaluated in the same manner as in Example 1 except that 10 parts and 20 parts of dimethylpolysiloxane oil having a viscosity of 10,000 centistokes at 25 ° C. were mixed respectively. Table 2 shows the results.

Examples 4 to 6 Test pieces were prepared and evaluated in the same manner as in Example 1 except that 5, 20 and 30 parts of dioctyl adipate were mixed respectively. Table 2 shows the results.

[0038]

[Table 2]

Examples 7 and 8 In Example 7, 3 parts of a dimethylpolysiloxane oil having a viscosity of 5000 centistokes at 25 ° C. were prepared.
Then, a test piece was prepared and evaluated in the same manner as in Example 1 except that 3 parts of dimethylpolysiloxane oil of 12,500 centistokes was mixed. Table 3 shows the results.

Comparative Examples 3 and 4 In Comparative Example 3, 3 parts of dimethylpolysiloxane oil having a viscosity of 100,000 centistokes at 25 ° C., and in Comparative Example 4, 3 parts of dimethylpolysiloxane oil having a viscosity of 100 centistokes were mixed. A test piece was prepared and evaluated in the same manner as in Example 1. Table 3 shows the results.

[0041]

[Table 3]

[0042]

Industrial Applicability The thermoplastic resin composition of the present invention has excellent impact resistance, moldability, heat resistance, especially excellent appearance and weatherability of molded articles, and is a molded article used for building material parts or used outdoors. Ideal for By using the thermoplastic resin composition of the present invention, it is possible to improve the appearance of a molded article without deteriorating the inherent weather resistance of the thermoplastic resin, and in particular, to obtain a deformed material having a good appearance by profile extrusion. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C08F 285/00 C08F 285/00 (72) Inventor Shoichi Murakami 14 Goi Minamikaigan, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Company Goi Factory (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08L 51/00 C08K 5/11 C08L 25/12 C08L 83/04 C08F 285/00

Claims (5)

(57) [Claims] 1. A polyfunctional monomer in an amount of 0.1 to 20% by weight, an alkyl acrylate having an alkyl group having 1 to 13 carbon atoms in an amount of 50 to 99.9% by weight, and another copolymerizable vinyl compound 0 95 to 60 parts by weight of a polymerizable monomer mixture (a) consisting of 5 to 30% by weight and a diene polymer (b) 5 to 5%
40 parts by weight, the total of the components (a) and (b) is 100
Parts by weight, emulsion polymerization is performed until the polymerization rate becomes 50 to 93%, and then, in the presence of 5 to 50 parts by weight of the graft polymer rubber (A) obtained by terminating the polymerization,
0 to 100% by weight of an aromatic vinyl compound, 0 to 100% by weight of a methacrylate, and 0 to 100% by weight of a vinyl cyanide compound
95 to 50 parts by weight of a monomer (B) consisting of 40% by weight,
A thermoplastic resin obtained by blending and polymerizing the components (A) and (B) so that the total of the components is 100 parts by weight (hereinafter, referred to as a thermoplastic resin).
A thermoplastic resin (hereinafter referred to as a thermoplastic resin) obtained by polymerizing 20 to 90 parts by weight of a thermoplastic resin (I), 65 to 85% by weight of an aromatic vinyl compound and 15 to 35% by weight of a vinyl cyanide compound. (Referred to as (II)) 10-80
Parts by weight of the thermoplastic resin (I) and the thermoplastic resin (II) so that the total is 100 parts by weight.
A weatherable thermoplastic resin composition comprising a mixture of centistokes dimethylpolysiloxane oil and dioctyl adipate. 2. The amount of dimethylpolysiloxane oil is:
The weatherable thermoplastic resin composition according to claim 1, wherein the content is 0.1 to 10% by weight based on the resin mixture. 3. The weatherable thermoplastic resin composition according to claim 1, wherein the amount of dioctyl adipate is 0.1 to 5% by weight based on the resin mixture. 4. The weatherable thermoplastic resin composition according to claim 1, wherein the polyfunctional monomer in the polymerizable monomer mixture (a) is triallyl isocyanurate or triallyl cyanurate. . 5. A molded article obtained by molding using the weatherable thermoplastic resin composition according to claim 1, 2, 3 or 4.