JP3507581B2 - Vinyl chloride resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel vinyl chloride resin composition having excellent matting properties, impact resistance and weather resistance. 2. Description of the Related Art In recent years, among vinyl chloride resin molded products used for housings such as building articles, vehicle parts, audio equipment, communication equipment, and OA equipment, matte molded articles having a matte appearance have become luxurious. And it has become preferred because of its good feel. In response to such market demands, various matting techniques have been developed, for example, calcium carbonate, a method of filling a large amount of an inorganic filler such as talc,
Examples thereof include a method of painting with an acrylic paint, and a method of embossing with a press or a roll. However, in the above-mentioned method, impact resistance and workability are reduced, and in the above-mentioned method, the number of coating steps is increased, which leads to an increase in cost. In the above-mentioned method, equipment such as an embossing die is required. Furthermore, since the embossed portion is clogged with resin during processing, there are drawbacks such as the occurrence of gloss spots. As a method for improving the above-mentioned disadvantages, a method of adding a partially cross-linked vinyl chloride resin to an ordinary vinyl chloride resin (Japanese Patent Application Laid-Open No. 54-80854) and a method of improving the same (Japanese Patent Publication No. 1-24944). JP-A-61-3234), a method of adding a partially crosslinked acrylic styrene resin having a specific particle size to a vinyl chloride resin.
No. 6) is disclosed. However, and in the method,
Compared to the case where no partially cross-linked vinyl chloride resin or partially cross-linked acrylic styrene resin is added, the matte properties and impact resistance are improved, but when trying to develop a sufficient matte effect It is necessary to increase the amount of addition,
As a result, there is a problem that impact resistance is reduced. In order to improve such a decrease in impact resistance, a method of adding a methyl methacrylate-butadiene-styrene copolymer (hereinafter referred to as MBS) or an acrylic rubber-based reinforcing agent as a reinforcing agent is used. However, if sufficient impact resistance is to be exhibited, the amount of addition increases, and as a result, there is a problem that the tensile strength of the molded article is significantly reduced. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and an object of the present invention is to provide a molding having excellent matting performance and excellent impact resistance and tensile strength. An object of the present invention is to provide a vinyl chloride resin composition from which a body can be obtained. [0008] The vinyl chloride resin composition of the present invention has (a) a homopolymer having a secondary transition point of -20 ° C.
A mixture of the following alkyl (meth) acrylate and a copolymerizable monomer having a secondary transition point of the homopolymer (b) exceeding −20 ° C. and an acrylic copolymer composed of a polyfunctional monomer, It is characterized by comprising a vinyl chloride graft copolymer obtained by graft copolymerization of vinyl and a partially crosslinked vinyl chloride resin, thereby achieving the above object. The acrylic copolymer comprises a mixture of an alkyl (meth) acrylate (a) and a copolymerizable monomer (b) and a polyfunctional monomer. The above alkyl (meth) acrylate (a)
Is not particularly limited as long as the homopolymer has a secondary transition point of −20 ° C. or less.
As the acrylate, for example, ethyl acrylate,
n-propyl acrylate, isobutyl acrylate,
n-butyl acrylate, n-hexyl acrylate,
2-ethylhexyl acrylate, n-octyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate, 2-acryloyloxyethyl succinic acid, etc., may be used alone or in combination of two or more. . The above-mentioned copolymerizable monomer (b) is a monomer which can be copolymerized with the above-mentioned alkyl (meth) acrylate (a) and has a secondary transition point higher than -20 ° C.
For example, methyl acrylate, isopropyl acrylate, t-butyl acrylate, n-tetradecyl acrylate, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, n-tetradecyl methacrylate, n- Alkyl (meth) acrylates such as butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 2-acryloyloxyethyl phthalic acid; styrene, α-
Aromatic vinyls such as methylstyrene and vinyltoluene;
Unsaturated nitriles such as acrylonitrile and methacrylonitrile; and vinyl esters such as vinyl acetate and vinyl propionate. These may be used alone or in combination of two or more. The above alkyl (meth) acrylate (a)
When the amount of the copolymerizable monomer (b) increases in the mixture of the copolymerizable monomer (b) and the copolymerizable monomer (b), the impact strength of the vinyl chloride graft copolymer described below decreases. The copolymerizable monomer (b) may not be mixed. The above-mentioned polyfunctional monomer is used for crosslinking an acrylic copolymer, and includes ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bifunctional monomers such as neopentyl glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol Trifunctional monomers such as tri (meth) acrylate; pentafunctional or higher monomers such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate;
(Di) triallyl compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl succinate, triallyl isocyanurate; and divinyl compounds such as divinylbenzene and butadiene. In the acrylic copolymer, when the amount of the polyfunctional monomer is small, the crosslinking density is decreased and the impact strength is decreased. When the amount is large, the crosslinking density is increased and the impact resistance is decreased. A mixture 100 of the alkyl (meth) acrylate (a) and the copolymerizable monomer (b)
The amount is limited to 0.1 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on parts by weight. In the present invention, the method for obtaining a crosslinked acrylic copolymer is not particularly limited.
Emulsion polymerization, suspension polymerization and the like can be used, but the emulsion polymerization is preferred from the viewpoint of developing impact strength. At this time, a commonly used dispersion emulsifier, polymerization initiator, pH adjuster,
An antioxidant and the like may be added. Examples of the dispersion emulsifier include anionic surfactants, nonionic surfactants, partially saponified polyvinyl alcohol, cellulose dispersants, and gelatin. Examples of the polymerization initiator include peroxides. Water-soluble polymerization initiators such as potassium sulfate, ammonium persulfate, and hydrogen peroxide; organic peroxides such as benzoyl peroxide and lauroyl peroxide; azo polymerization initiators such as azobisisobutyronitrile. . When the acrylic copolymer is obtained by an emulsion polymerization method, the polymerization method is not particularly limited. For example, (1) pure water, a dispersing emulsifier and a water-soluble polymerization initiator in a jacketed polymerization reactor. Add the agent, add the alkyl (meth) acrylate (a), copolymerizable monomer (b) and polyfunctional monomer under nitrogen gas pressure and emulsify, and then heat up the inside of the reactor with a jacket to start the reaction. Polymerization method,
(2) Pure water, a dispersing emulsifier, and a water-soluble polymerization initiator are charged into a jacketed polymerization reactor, and alkyl (meth) acrylate (a) and a copolymerizable monomer (b) are added under a nitrogen stream pressure.
And a monomer dropping method in which a polyfunctional monomer is dropped to start a reaction. (3) Pure water and a water-soluble polymerization initiator are charged into a jacketed polymerization reactor, and then an alkyl (meth)
An emulsion dropping method in which an emulsion obtained by emulsifying an acrylate (a), a copolymerizable monomer (b), a polyfunctional monomer and a dispersing emulsifier with high-speed stirring is added dropwise, may be mentioned. When the average particle size of the acrylic copolymer obtained by the above polymerization method is small, impact resistance is hardly exhibited, and when the average particle size is large, mechanical strength such as bending strength and tensile strength is significantly reduced. It is preferably from 0.5 to 3 μm. In the present invention, the vinyl chloride graft copolymer is obtained by graft copolymerizing vinyl chloride with the above acrylic copolymer. The method of the graft copolymerization is not particularly limited, and examples thereof include an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method. In particular, the suspension polymerization method is preferable from the viewpoint of production. When a vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride with the above acrylic copolymer is obtained by a suspension polymerization method, pure water, a polymerization initiator, the above acrylic A system copolymer (latex), a suspension stabilizer (dispersant) and, if necessary, a polymerization degree regulator are added. The inside of the reactor is sealed to eliminate air in the system, and then the inside of the reactor is stirred. While adding the vinyl chloride monomer and, if necessary, another vinyl compound, the inside of the reactor is heated by a jacket to start graft copolymerization. This graft copolymerization is an exothermic reaction, and the reaction temperature is controlled as required. After completion of the polymerization reaction, unreacted vinyl chloride is removed out of the system to obtain a vinyl chloride graft copolymer slurry. By dehydrating and drying this slurry according to a conventional method, a vinyl chloride graft copolymer is obtained. The above graft copolymerization reaction is preferably performed by a radical polymerization method. Examples of the radical polymerization initiator used in the radical polymerization method include lauroyl peroxide, t-butylperoxypivalate, and diisopropylperoxydicarbonate. , Organic peroxides such as dioctyl peroxydicarbonate; 2,2-
Azobisisobutyronitrile, 2,2-azobis-2,
Oil-soluble polymerization initiators such as azo compounds such as 4-dimethylvaleronitrile; and water-soluble polymerization initiators such as potassium persulfate and ammonium persulfate. The amount of the polymerization initiator used is preferably 100 to 1,000 ppm based on the vinyl chloride monomer. Examples of the suspension stabilizer (dispersant) include methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol and partially saponified products thereof, gelatin, polyvinylpyrrolidone, starch, and maleic anhydride-styrene copolymer. ,
These may be used alone or in combination of two or more. The use amount of the above-mentioned suspension stabilizer (dispersant) is preferably from 100 to 2,000 ppm based on the vinyl chloride monomer. In the above-mentioned vinyl chloride graft copolymer, when the amount of the acrylic copolymer used as the backbone polymer is small, the impact resistance is not improved, and when the amount is large, the impact resistance is improved. Since the decrease in tensile strength and the like becomes remarkable, the content is limited to 3 to 30% by weight, preferably 5 to 15% by weight, based on the total of the acrylic copolymer and the vinyl chloride monomer. When the average degree of polymerization of the above vinyl chloride graft copolymer is low, the elongation at break and impact resistance of the molded article are reduced, and when the average degree is high, the fluidity is deteriorated and molding becomes difficult. And more preferably 4
00 to 1,400. The average degree of polymerization was determined by JI
It is a value converted from the viscosity measured according to SK6721. The vinyl chloride resin composition of the present invention comprises the above vinyl chloride graft copolymer and a partially crosslinked vinyl chloride resin. The above partially crosslinked vinyl chloride resin is a copolymer of a vinyl chloride monomer and a crosslinking agent; a mixture containing a vinyl chloride monomer as a main component and a monomer copolymerizable with the vinyl chloride monomer; And obtained by, for example, copolymerizing in an aqueous medium by an emulsion polymerization method or a suspension polymerization method. Examples of the crosslinking agent include diallyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl maleate, and divinyl benzene; diaryl compounds such as polyethylene glycol di (meth) acrylate and 1,3-butylene (meth) acrylate. (Meth) aquarylate compound; trimethylolpropanetri (Meth)
And tri (meth) aqualylate compounds such as aqualylate and trimethylolethanetri (meth) aqualylate. Examples of monomers copolymerizable with the vinyl chloride monomer include α-olefins such as ethylene, propylene and butylene; vinyl esters such as vinyl acetate and vinyl propionate; isobutyl vinyl ether, cetyl vinyl ether and phenyl ether. Vinyl ethers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate and phenyl methacrylate; (meth) acrylic esters; aromatic vinyls such as styrene and α-methylstyrene; (meth) acrylonitrile and the like Vinyl halides such as vinylidene chloride and vinylidene fluoride; unsaturated dicarboxylic esters such as dimethyl maleate and dimethyl fumarate; unsaturated dicarboxylic anhydrides such as maleic anhydride; Nylmaleimide, non-polar monomers such as N-substituted maleimides such as N-cyclohexylmaleimide, and the like, even when used alone,
Two or more kinds may be used in combination. When the gel fraction of the partially crosslinked vinyl chloride resin is small, the matting performance is reduced, and when the gel fraction is large, the impact resistance and thermal stability are reduced.
% By weight, more preferably 1 to 30% by weight. The average degree of polymerization of the above partially crosslinked vinyl chloride resin is from 500 to 500, since the impact resistance decreases when the degree of polymerization decreases, and the flowability deteriorates and the molding becomes difficult when the degree increases.
2,000 is preferable, and as a commercially available product of such a vinyl chloride resin, for example, “XEL-
C "," XEL-D "and the like. The average degree of polymerization of the partially crosslinked vinyl chloride resin is determined according to JIS K67.
It is a value converted from the viscosity of the non-crosslinked portion measured according to No. 21. In the vinyl chloride resin composition of the present invention, when the amount of the partially crosslinked vinyl chloride resin decreases, the matting effect decreases, and when the amount increases, the impact resistance remarkably decreases. The amount is limited to 5 to 60 parts by weight, preferably 1 to 100 parts by weight of the polymer.
0 to 50 parts by weight. The vinyl chloride resin composition of the present invention may further contain, if necessary, a heat stabilizer, a stabilization aid, a lubricant, a processing aid, an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler. ,
Additives such as pigments, flame retardants, and low smoke generating agents may be added. Examples of the heat stabilizer include organic solvents such as dibutyltin mercapto, dioctyltin mercapto, dimethyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, dibutyltin laurate and the like. Tin-based stabilizer;
Lead-based stabilizers such as tribasic lead sulfate, dibasic lead sulfite, dibasic lead phosphite, dibasic lead stearate, lead stearate; calcium stearate, zinc stearate,
Organic metal-based stabilizers such as barium stearate; complex stabilizers such as calcium-zinc-based, barium-zinc-based, barium-calcium-based, and barium-cadmium-based stabilizers; Examples of the stabilizing aid include epoxidized soybean oil and phosphoric acid ester. Examples of the antioxidant include bisphenol A and butylhydroxytoluene. Include, for example, calcium carbonate, talc, and the like. Examples of the plasticizer include di-n-octyl phthalate, di-n-octyl adipate, and trimellitic acid-tri-2-ate.
Ethylhexyl and the like are mentioned, and as the pigment, for example, titanium oxide, carbon black and the like are mentioned. Examples of the lubricant include natural wax, paraffin wax, polyethylene wax, stearic acid, calcium stearate, stearyl alcohol, and butyl stearate. Examples of the flame retardant include antimony trioxide, hydroxide Aluminum and magnesium hydroxide are exemplified. As the method for preparing the vinyl chloride resin composition, any conventionally known method can be adopted. For example, hot blending or cold blending may be performed using a stirrer. The molding methods include extrusion molding, injection molding, vacuum molding, calendar molding,
Press molding method and the like can be mentioned. Embodiments of the present invention will be described below. Preparation of Acrylic Copolymer In a reaction vessel equipped with a stirrer and a reflux condenser, 240 parts by weight of distilled water, 1 part by weight of lauryl alcohol sulfate, 0.1 part by weight of ammonium persulfate, and a predetermined amount of n- 10 parts by weight of butyl acrylate (described as n-BA in the table), methyl methacrylate (described as MMA in the table), trimethylolpropane triacrylate (described as TMP-A) and ethylene glycol dimethacrylate were charged. After replacing the inside of the reaction vessel with nitrogen, 65
The mixture was heated to a temperature of 5 ° C. and reacted while stirring for 5 hours to obtain an acrylic copolymer latex having a solid content concentration shown in Table 1. Preparation of Vinyl Chloride Graft Resin A predetermined amount of an acrylic copolymer latex (in terms of solid content) and pure water shown in Table 1 were mixed with 520 g of a 3% by weight aqueous solution of partially saponified polyvinyl acetate, and t-butylperoxy. Together with 0.8 g of neodecanoate and 1 g of α-cumylperoxy neodecanoate, they were charged all at once into a 22-liter polymerization vessel equipped with a stirring blade. Next, the air in the polymerization vessel was removed by a vacuum pump, 3100 g of vinyl chloride monomer was added, and the mixture was dissolved by stirring for 20 to 30 minutes, and then polymerization was started at 64 ° C. Five hours after the start of the polymerization, the internal pressure of the polymerization vessel was 7 kg / cm ^2.
The polymerization was stopped at the stage when the temperature decreased to. After removing unreacted vinyl chloride monomer, the obtained slurry was dehydrated and dried by a conventional method to obtain a white powdery vinyl chloride graft copolymer [(I) to (VIII)] in the yield shown in Table 1. Obtained. [Table 1] (Examples 1 to 3, Comparative Examples 1 to 8) Tables 2 to 4
And vinyl chloride resin partially crosslinked ("XEL-" manufactured by Kanegafuchi Chemical Co., Ltd.)
D ") or a partially crosslinked acrylic styrene resin (" F-410 "manufactured by Mitsubishi Rayon Co., Ltd.) and an octyltin mercapto-based stabilizer (" TVS # 883 "manufactured by Nitto Chemical Co., Ltd.)
1)) 2.5 parts by weight, an acrylic processing aid ("METABLEN P-501" manufactured by Mitsubishi Rayon Co., Ltd.) 1 part by weight, and a stearic acid-based lubricant ("METABLEN F" manufactured by Kawaken Fine Chemical Co., Ltd.)
-3 ") 1.5 parts by weight, polyethylene wax-based lubricant (" High Wax 220mp "manufactured by Mitsui Petrochemical Co., Ltd.)
5 parts by weight, 1 part by weight of a calcium stearate-based lubricant (“SC-100” manufactured by Sakai Chemical Co., Ltd.) and 2 parts by weight of titanium oxide are supplied to a Henschel mixer and stirred at about 100 ° C.
Temperature. Then, about 30 ℃ in the cooling mixer
After cooling, a vinyl chloride resin composition was obtained. Comparative Example 9 A predetermined amount of vinyl chloride resin ("TS-800E" manufactured by Tokuyama Sekisui Co., Ltd.) and a partially crosslinked vinyl chloride resin ("XEL-" manufactured by Kanegafuchi Chemical Co., Ltd.) shown in Table 4
D ") and MBS resin (" BTA-7 "manufactured by Kureha Chemical Co., Ltd.)
31 "), 2.5 parts by weight of an octyltin mercapto-based stabilizer (" TVS # 8831 "manufactured by Nitto Chemical Co., Ltd.), an acrylic processing aid (" METABLEN P-5 "manufactured by Mitsubishi Rayon Co., Ltd.)
01 ") 1 part by weight, 1.5 parts by weight of stearic acid-based lubricant (" METABLEN F-3 "manufactured by Kawaken Fine Chemical Co., Ltd.), 0.5 part by weight of polyethylene wax-based lubricant (" High Wax 220mp "manufactured by Mitsui Petrochemical Co., Ltd.) Parts, 1 part by weight of a calcium stearate-based lubricant (“SC-100” manufactured by Sakai Chemical Co., Ltd.) and 2 parts by weight of titanium oxide were supplied to a Henschel mixer, and the temperature was raised to about 100 ° C. while stirring. Next, the mixture was cooled to about 30 ° C. with a cooling mixer to obtain a vinyl chloride resin composition. The above vinyl chloride resin composition was supplied to a twin-screw extruder to obtain a plate-like molded product having a thickness of 3 mm. The following performance evaluation was performed on the plate-like molded body, and the results were shown in Table 2.
To 4. (1) Impact test The Charpy impact strength of the plate-like molded article was measured in accordance with JIS K7211. (2) Using a matte gloss meter (“VG-1D” manufactured by Nippon Denshoku Co., Ltd.), the glossiness of the above plate-shaped molded product with respect to 60 ° incident light was measured. (3) Tensile test The tensile strength of the plate-shaped molded article was measured in accordance with JIS K7113. [Table 2] [Table 3] [Table 4] The constitution of the vinyl chloride resin composition of the present invention is as described above, and is not only excellent in matting properties but also excellent in impact resistance and tensile strength, and high quality. It is possible to provide a molded article having a good touch.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-127337 (JP, A) JP-A-62-36412 (JP, A) JP-A-3-74438 (JP, A) JP-A 61-127 126173 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 51/06 C08F 265/06

Claims (1)

(57) [Claims] (1) The homopolymer has a secondary transition point of -20 ° C.
The following alkyl (meth) acrylates 80 to 100
100% by weight of a mixture of (b) 20 to 0% by weight of a copolymerizable monomer having a secondary transition point of a homopolymer of more than -20 ° C.
Vinyl chloride obtained by graft copolymerizing vinyl chloride at a ratio of 97 to 70% by weight with respect to 3 to 30% by weight of an acrylic copolymer comprising 0.1 to 30 parts by weight of a polyfunctional monomer and 0.1 to 30 parts by weight of a polyfunctional monomer. A vinyl chloride resin composition comprising 100 parts by weight of a graft copolymer and 5 to 60 parts by weight of a partially crosslinked vinyl chloride resin.