JPH0550541B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a vinyl chloride resin composition, and more particularly to a vinyl chloride resin composition that has excellent weather resistance and impact resistance and is suitable for use as a building material. (Prior Art) Vinyl chloride resin has excellent physical and mechanical properties and has many uses such as hard, semi-hard, and soft. However, when a vinyl chloride homopolymer is used for hard materials, it has the disadvantage of poor impact resistance and weather resistance. In order to improve these drawbacks, we have developed a durable vinyl chloride graft copolymer obtained by graft copolymerizing vinyl chloride onto an ethylene-vinyl acetate copolymer, a polymer blend of vinyl chloride homopolymer and various elastomers. Impact composition (Special Publication 1979-
18819) Compositions made of vinyl chloride graft copolymers (Japanese Patent Publication No. 39-17067) obtained by graft copolymerizing vinyl chloride to alkyl acrylate polymers have been developed. (Problems to be Solved by the Invention) However, although the polymer blend in such conventional vinyl chloride resin compositions can improve impact resistance, it is said that weather resistance and flexural modulus are reduced. It has defects. In addition, the composition has improved weather resistance and flexural modulus compared to the above-mentioned polymer blend of a homopolymer and an elastic body, but
The defect is that impact resistance and flexural modulus are affected by processing conditions. Further, although the impact resistance of the composition is improved compared to the above-mentioned polymer blend of a homocopolymer and an elastomer, the composition has the drawback that the flexural modulus is still insufficient. As described above, each of the compositions known to date has advantages and disadvantages, and therefore their applications are limited to some extent. The purpose of the present invention is to have excellent impact resistance and flexural modulus,
Furthermore, it is an object of the present invention to provide a vinyl chloride resin composition that has excellent weather resistance. (Means for Solving the Problems) In order to achieve the above object, the present inventors have made extensive studies and found that an alkyl acrylate and/or a homopolymer having a secondary transition point of -10°C or lower Or a vinyl chloride resin made by graft copolymerizing vinyl chloride onto an acrylic copolymer of alkyl methacrylate and a polyfunctional monomer, silicone oil containing polydimethylsiloxane, mineral oil, nonionic surfactant and nonyl. Special nonionic surfactants with phenol ethylene oxide added, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluorotrimethylammonium salts, perfluoroalkyl betaines, and perfluoroalkyl EO adducts. Discovered that by adding a predetermined amount of an antifoaming agent such as an alkyl compound, a vinyl chloride resin composition with excellent impact resistance and flexural modulus, as well as excellent weather resistance, could be obtained, and the present invention was completed. It came to this. That is, the present invention provides a vinyl chloride resin in which 99 to 70 parts by weight of vinyl chloride is graft copolymerized to 1 to 30 parts by weight of a copolymer of alkyl acrylate and/or alkyl methacrylate and a polyfunctional monomer. 100 parts by weight, silicone oil, mineral oil,
Provided is a vinyl chloride resin composition with excellent weather resistance and impact resistance, characterized in that it contains 0.01 to 10 parts by weight of at least one selected from nonionic surfactants and perfluoroalkyl compounds. It is something to do. The acrylic copolymer used in the present invention is
It is a copolymer of alkyl acrylate and/or alkyl methacrylate and a polyfunctional monomer.
It is advantageous for the alkyl acrylate and/or alkyl methacrylate to have a secondary transition point of -10°C or less as a polymer alone, from the viewpoint of improving impact resistance. acrylate, n-propyl acrylate,
Iso-butyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-octyl methacrylate, n-decyl methacrylate, n-dodecyl methacrylate, lauryl methacrylate, etc. It will be done. In this case, the amount of alkyl acrylate and/or alkyl methacrylate used is preferably 99 to 70% by weight in the acrylic copolymer. If the amount exceeds 99% by weight, no improvement in the flexural modulus can be expected, and if the amount is less than 70% by weight, the impact resistance will decrease, which is not preferable. In addition, polyfunctional monomers are monomers that can be copolymerized with alkyl acrylate and/or alkyl methacrylate and participate in crosslinking etc. in the copolymer or graft copolymer,
For example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1 , (poly)alkylene glycol acrylates or methacrylates such as 4-butylene glycol dimethacrylate, polyallyl compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, and diallyl succinate, divinylbenzene, butadiene, and the like. The amount of polyfunctional monomer used is preferably 1 to 30% by weight, and 1% by weight in the acrylic copolymer.
If it is less than 30% by weight, no improvement in flexural modulus can be expected, and if it exceeds 30% by weight, the impact resistance will decrease, which is not preferable. Alkyl acrylate and/or used in the present invention
Alternatively, an acrylic copolymer of alkyl methacrylate and a polyfunctional monomer can be obtained by a polymerization method such as emulsion polymerization, solution polymerization, bulk polymerization, etc. using generally known emulsifiers, dispersants, catalysts, etc. Emulsion polymerization is preferably employed to advantageously carry out the present invention. To obtain a copolymer by a general emulsion polymerization method, for example, pure water, an anionic emulsifier, and a water-soluble polymerization catalyst are placed in a jacketed polymerization reactor, the air inside the can is removed, and then the alkyl Acrylate and/or alkyl methacrylate and a polyfunctional monomer are charged, and after emulsification, the inside of the can is heated with a jacket to carry out a copolymerization reaction. This copolymerization reaction is an exothermic reaction, and the internal temperature is controlled by a jacket as necessary. After the reaction is completed, unreacted monomers are removed from the can to obtain an acrylic copolymer. The method of charging into the polymerization reactor is not limited. Further, if necessary, a particle size adjusting agent for the acrylic copolymer, a catalyst decomposition accelerator for controlling the copolymerization reaction, etc. may be added. Next, in the present invention, the acrylic polymer thus obtained is used as a backbone polymer for graft copolymerization. In this case, the appropriate amount of the acrylic copolymer to be used is 1 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount of the acrylic copolymer used is less than 1 part by weight, the impact resistance will not be sufficient, and if it exceeds 30 parts by weight, the impact resistance will improve, but the flexural modulus will decrease, which is not preferable. Examples of the graft copolymerization method of the present invention include suspension polymerization, emulsion polymerization, solution polymerization, and solvent-free polymerization, but in order to carry out the present invention advantageously, suspension polymerization is preferred. is desirable. When carrying out the suspension polymerization method, the amount of water used is 1 to 5 times, preferably 1 to 3 times, the total amount of the acrylic copolymer and vinyl chloride monomer. A method for obtaining a graft copolymer resin by a general suspension polymerization method includes, for example, adding pure water, a suspension stabilizer such as hydroxypropyl methylcellulose, a radical polymerization initiator,
If necessary, a polymerization degree reducing agent is added, and the acrylic copolymer is added thereto and suspended, the air inside the can is then removed, and then vinyl chloride is charged together with other vinyl compounds as required. Thereafter, the inside of the can is heated with a jacket to dissolve the acrylic copolymer in the vinyl chloride and initiate graft copolymerization. Graft copolymerization is an exothermic reaction, and the internal temperature is controlled by the jacket as necessary. After the reaction is complete, unreacted vinyl chloride is removed from the can,
A slurry-like graft copolymer resin is obtained. The slurry is dehydrated and dried according to a conventional method to obtain a graft copolymer resin. Furthermore, the charging method to the polymerization reactor is not limited, and among the charged raw materials such as pure water, suspension stabilizer, acrylic copolymer, and vinyl chloride, the acrylic copolymer is replaced with vinyl chloride. A method of melting and charging is also adopted. In graft copolymerization, other monomers may be present in the coexistence within a range that does not reduce impact resistance, weather resistance, and flexural modulus. In addition, it is advantageous to carry out the graft copolymerization by a radical polymerization method, and the radical polymerization initiators used for this purpose include lauroyl peroxide, tert-butyl peroxypivalate,
Organic peroxides such as diisopropyl peroxydicarbonate and dioctyl peroxydicarbonate; oils of azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile; Examples include soluble polymerization initiators, and water-soluble polymerization initiators such as potassium persulfate and ammonium persulfate. The amount of these polymerization initiators used is preferably 0.005 to 1.0 parts by weight per 100 parts by weight of monomer such as vinyl chloride. Dispersants include methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, polyvinyl alcohol and its partially saponified products, gelatin, polyvinylpyrrolidone, organic substances such as starch, and inorganic substances such as magnesium carbonate, calcium carbonate, and calcium phosphate. may be used alone or in combination. The amount used is usually 0.01 to 1.0 parts by weight per 100 parts by weight of vinyl chloride. Furthermore, in this graft copolymerization, a chain transfer agent used in conventional methods for polymerizing vinyl monomers may be added in an amount of 0.001 to 10 parts by weight per 100 parts by weight of a monomer such as vinyl chloride. In the present invention, nonionic surfactants such as silicone oils containing polydimethylsiloxane, mineral oils, special nonionic surfactants to which nonylphenol ethylene oxide, etc. are added, perfluoroalkyl carboxylates, perfluoroalkyl carboxylates, Antifoaming agents selected from perfluoroalkyl compounds, including alkyl phosphate esters, perfluorotrimethylammonium salts, perfluoroalkyl betaines, and perfluoroalkyl EO adducts, used alone or in combination. The appropriate amount of antifoaming agent to be added is 0.01 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.If it is less than 0.01 part by weight, no improvement in weather resistance or impact resistance can be expected, and if it exceeds 5 parts by weight, the bending elasticity will deteriorate. This is not preferable because the rate decreases. The antifoaming agent may be added between the start of polymerization and the end of polymerization, or may be added by spraying after the resin has dried. Furthermore, it may be added at the time of compounding. Considering economic efficiency, the most recommended method is to add it at the time of blending. The composition of the present invention preferably contains 70 to 00% by weight of an alkyl acrylate and/or alkyl methacrylate whose homopolymer has a secondary transition point of -10°C or lower and 30 to 1% by weight of a polyfunctional monomer. The main components are a vinyl chloride resin and an antifoaming agent, which are obtained by graft copolymerizing 99 to 70 parts by weight of vinyl chloride to 1 to 30 parts by weight of a polymerized acrylic copolymer, and other resins as necessary. It is obtained by appropriately adding and blending plasticizers, stabilizers, lubricants, fillers, ultraviolet absorbers, antistatic agents, antioxidants, pigments, conductivity imparting agents, flame retardants, etc. Other resins that can be added include ethylene/vinyl acetate copolymer, ethylene/vinyl acetate/vinyl chloride ternary copolymer, ethylene/vinyl acetate/
Add any resin that is compatible with PVC, such as carbon monoxide ternary copolymer, chlorinated polyethylene, acrylonitrile/butadiene/styrene ternary copolymer, methyl acrylate, methyl methacrylate/butadiene/styrene ternary copolymer, etc. I can't help it. Furthermore, in the present invention, it is possible to add a plasticizer within a range that does not deteriorate the physical and mechanical properties of the composition. Examples of such plasticizers include phthalate, trimellitate, adipate, phosphate, Type plasticizers, epoxy plasticizers, and polyester plasticizers are used. Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate and lead stearate, metal soap-based stabilizers such as calcium stearate and zinc stearate, and organotin-based stabilizers such as octyltin mericcaptite and dibutyltin malate. are used, and co-stabilizers such as epoxy stabilizers, organic phosphites, aminocrotonic esters, 2-phenylindole, pentaerythritol, sorbitol, and phosphite chelators are used. Examples of lubricants include hydrocarbon lubricants such as natural paraffin, liquid paraffin, and polyethylene wax;
Fatty acid lubricants such as stearamide, fatty acid amide lubricants such as stearamide, ester lubricants such as ethylene glycol monostearate,
Higher alcohol-based lubricants such as stearyl alcohol and metal soap-based lubricants such as calcium laurate are used. Fillers include calcium carbonate, kaolin,
Examples include clay, gypsum, titanium oxide, magnesium hydroxide, and calcium silicate. As ultraviolet absorbers, benzophenones such as 2,4-dihydroxybenzophenone, 2-(2'-
Benzotriazole-based UV absorbers such as hydroxy-5-methylphenylbenzotriazole, and salicylic acid ester-based UV absorbers such as phenyl salicylate are used. As antistatic agents, anionic surfactants,
Cationic surfactants, nonionic surfactants, etc. are used. Examples of antioxidants include bisphenols such as 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), monophenols such as 2,6-di-tert-butylphenol,
A hydroquinone antioxidant such as 2,5-ditertiarybutylhydroquinone is used. Pigments include carbon black, titanium oxide,
Barium sulfate or the like is used. Carbon black, silver powder, and copper powder are used as the conductivity imparting agent. Examples of flame retardants include known halides such as chlorinated paraffin, chlorinated polyethylene, perchloropentacyclodecane, hexabromobenzene, decabromodiphenyl ether, and tetrabromobisphenol A, antimony trioxide, antimonates, Inorganic compounds such as barium metaborate, zinc borate, and aluminum hydroxide are used. The composition of the present invention can be obtained by blending the vinyl chloride resin with an antifoaming agent and the various additives mentioned above, and uniformly mixing the mixture by a conventionally known method using a Henschel mixer, ribbon blender, etc. can get. When actually using the composition, a single-screw extruder, twin-screw extruder, or multi-screw extruder can be employed. A method is also adopted in which pellets are made into pellets and then molded. The action of the antifoaming agent used in the present invention is as follows:
It is believed that when added to a resin, it exhibits a lubricating effect within the resin, and this effect absorbs impact, thus improving impact resistance. Generally, when impact resistance improves, rigidity such as flexural modulus decreases, but in the resin composition of the present invention, the rigidity hardly decreased. The fact that impact resistance could be significantly improved without reducing rigidity is something that could not have been predicted from conventional technology. It is clear from a comparison of the following Examples and Comparative Examples that by adding the antifoaming agent to the resin composition of the present invention, the impact resistance and weather resistance are improved without reducing the rigidity. . (Effects of the Invention) The vinyl chloride resin composition of the present invention is excellent in weather resistance, impact resistance, and flexural modulus for hard materials. Therefore, it is suitably used for building materials such as window frames and decking materials. (Example) The present invention will be specifically described below with reference to Examples. Note that the parts shown in the examples are parts by weight. Examples 1 to 5, Comparative Examples 1 to 3 2700 kg of deionized water and partially saponified polyvinyl alcohol were placed in a polymerization machine with an internal volume of 7 m ³ equipped with a stirring blade.
2.05Kg, methylcellulose 2.05Kg, 2,2'-azobisisobutyronitrile 0.075Kg, 2,2'-azobis-2,4-dylmethylvaleronitrile 0.24Kg
Then, 600 kg of acrylic copolymer latex having the composition shown in Table 1 was charged, and after removing the air inside, 1410 kg of vinyl chloride was charged, and after melting at 35°C for 1 hour, polymerization was carried out at 57°C. After 10 hours from the start of polymerization, the internal pressure of the polymerization machine decreased to 6.5Kg/ ^cm2 .
Unreacted monomers were collected and the slurry was dehydrated and dried to obtain 1275 kg of white powder resin. The degree of polymerization of this resin was 1030, and the content of components other than vinyl chloride was 7.0%. Next, each component was mixed with the above graft copolymer according to the formulation shown in Table 1 to prepare a powder. For mixing, the resin and compounding agents were placed in a No. 7 Henschel mixer and stirred for 3 minutes at a temperature of 50°C. Knead this powder with a roll at 180℃ for 10 minutes,
A 3 mm thick sheet was produced by press molding at 180°C, and its impact resistance and weather resistance were measured. Results first
Shown in the table. Example 6 Polymerization was carried out in the same manner as in Example 1, and the internal pressure was 6.5.
Kg/ ^cm2 , silicone antifoaming agent TSF-
451 (manufactured by Toshiba Silicone Co., Ltd.) at 1.5 kg, the unreacted monomer was collected, and the slurry was dehydrated and dried to obtain 1300 kg of white powder resin. The degree of polymerization of this resin was 1040, and the content of components other than vinyl chloride was 6.9%. Next, this resin was treated in the same manner as in Example 1 to form a 3mm
It was processed into a thick sheet and its impact resistance and weather resistance were measured. The results are shown in Table 1. Example 7 Polymerization was carried out in the same manner as in Example 1, and after the slurry was dehydrated and dried, 3 kg of a mineral oil-based antifoaming agent Pronal P-805X (manufactured by Toho Chemical Co., Ltd.) was sprayed onto the resin using a sprayer. 1275 kg of white powder was obtained. The degree of polymerization of this resin was 1030, and the content of components other than vinyl chloride was 7.0%. Next, this resin was treated in the same manner as in Example 1 to form a 3mm
It was processed into a thick sheet and its impact resistance and weather resistance were measured. The results are shown in Table 1. In addition, the test methods in the above Examples and Comparative Examples are as follows. Shalpey impact strength was measured according to JIS K-6745. The flexural modulus was measured according to JIS K-6740. Weather resistance was measured by irradiating with a carbon arc sunshine weatherometer (spray 12/60 minutes, black panel temperature 63°C) for 200H, 500H, and 1000H, and measuring the shear peace impact strength. From Table 1, it can be seen that the composition of the present invention is suitable as a material for window frames and decking materials because it has excellent weather resistance without any decrease in impact resistance or flexural modulus.

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Claims (1)

[Claims] 1 Copolymer of alkyl acrylate and/or alkyl methacrylate and polyfunctional monomer 1-
100 parts by weight of a vinyl chloride resin obtained by graft copolymerizing 99 to 70 parts by weight of vinyl chloride to 30 parts by weight,
Vinyl chloride type with excellent weather resistance and impact resistance, characterized by adding 0.01 to 10 parts by weight of at least one selected from silicone oil, mineral oil, nonionic surfactant, and perfluoroalkyl compound. Resin composition.