JP2006083332A - Vinyl chloride copolymer resin, method for producing the same and its resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride copolymer resin having excellent impact resistance, melt-flow property and transparency, a method for producing the resin and a resin composition containing the copolymer resin. <P>SOLUTION: The vinyl chloride copolymer resin is produced by the copolymerization of (A) a vinyl chloride monomer and (B) an n-butyl acrylate/methyl methacrylate copolymer produced by a bulk polymerization method, a solution polymerization method or a suspension polymerization method. The resin composition contains the copolymer resin. The ratio (wt.%) of the n-butyl acrylate component/methyl methacrylate component constituting the component B is set to 5/95 to 70/30 and the (A)/(B) ratio (wt.%) is set to 99.5/0.5 to 60/40. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a vinyl chloride copolymer resin obtained by copolymerizing a vinyl chloride monomer and an acrylic acid-n-butyl / methyl methacrylate copolymer, a method for producing the same, and a resin composition thereof. Relates to a vinyl chloride copolymer resin excellent in impact resistance and melt flow characteristics, and further excellent in transparency, a method for producing the same, and a resin composition thereof.

  Vinyl chloride resins are widely used in various molded products taking advantage of their characteristics, and various characteristics are required for each application. As such required characteristics, for example, in products in a flexible application field such as electric wire coating, wrap film, sheet, etc., high volume resistivity, good plasticizer absorbability, fish eye reduction, etc., pipes, In hard application fields such as joints, window frames, industrial transparent plates, films, etc., there are workability and thermal stability when processing into various molded products, basic physical properties such as tensile strength and impact strength after molding, etc. It is required to be good. Various attempts have been made to improve these required characteristics. As a technique disclosed so far, for example, in order to improve impact resistance and molding processability in a hard application field, a vinyl chloride resin is methacrylic. A method (Patent Document 1) of adding an acid methyl-butadiene-styrene copolymer (hereinafter abbreviated as MBS resin) or chlorinated polyethylene is disclosed. However, in this method, various reinforcing agents and additives are blended, which generally requires a large amount of reinforcing agents and additives, which is costly. Since the flow characteristics are poor, there are also problems in terms of manufacturing conditions such as an increase in the motor load of the extruder.

As a measure for improving the required properties without blending a large amount of these reinforcing agents and additives, for example, in order to improve impact resistance and bending elastic modulus, the secondary transition temperature of the (co) polymer is -10 ° C. or lower. An acrylic copolymer obtained by copolymerizing 80 to 99.5% by weight of an alkyl acrylate and / or alkyl methacrylate and 20 to 0.5% by weight of a polyfunctional monomer copolymerizable therewith by an emulsion polymerization method. A method of polymerizing a vinyl chloride monomer in the presence of a polymer (Patent Document 2), and a glass transition temperature of a homopolymer is at least −140 ° C. or more and less than 0 ° C. in order to improve impact resistance and fatigue resistance. 100 parts by weight of a mixed monomer composed of one kind of (meth) acrylate monomer and other radically polymerizable monomers added as necessary, and 0.1 to 10 multifunctional monomers And a method in which a resin obtained by graft copolymerization of a vinyl chloride monomer to an acrylic copolymer obtained by an emulsion polymerization method is used as a rigid vinyl chloride tube (Patent Document 3), etc. ing. However, in these methods, all of the acrylic copolymers are obtained by a conventionally known general emulsion polymerization method, and then in a vinyl chloride copolymer resin obtained by copolymerization with a vinyl chloride monomer, Since these acrylic copolymers exist in the form of particles, it has been disclosed that the vinyl chloride copolymer resin contributes to an improvement in impact resistance, but an improvement in melt flow characteristics during molding and transparency. There is no technical disclosure related to
Japanese Patent Laid-Open No. 9-278964 Japanese Patent Laid-Open No. 11-80282 JP 2003-148660 A

  An object of the present invention is to provide a vinyl chloride copolymer resin excellent in impact resistance and melt flow characteristics, and further excellent in transparency, a method for producing the same, and a resin composition thereof.

As a result of diligent research, the inventor has used an acrylic acid-n-butyl / methyl methacrylate copolymer produced by one method selected from a bulk polymerization method, a solution polymerization method, and a suspension polymerization method. The inventors have found that the above problems can be achieved and have completed the present invention.
That is, the present invention
(1) (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methacrylic acid produced by one method selected from bulk polymerization method, solution polymerization method and suspension polymerization method A vinyl chloride copolymer resin characterized by copolymerizing a methyl copolymer (claim 1),
(2) The ratio of (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methyl methacrylate copolymer is (A) / (B) = 99.5 wt% / 0.5 wt% The vinyl chloride copolymer resin according to claim 1 (claim 2), characterized in that it is in the range of -60 wt% / 40 wt%.
(3) Ratio of acrylic acid-n-butyl component and methyl methacrylate component constituting the acrylic acid-n-butyl / methyl methacrylate copolymer is acrylic acid-n-butyl component / methyl methacrylate component = 5 wt. % / 95% by weight to 70% by weight / 30% by weight of the vinyl chloride copolymer resin according to any one of claims 1 to 2 (claim 3),
(4) (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methacrylic acid produced by one method selected from bulk polymerization, solution polymerization, and suspension polymerization The method for producing a vinyl chloride copolymer resin according to any one of claims 1 to 3, wherein the methyl copolymer is copolymerized in an aqueous medium (claim 4),
(5) A vinyl chloride copolymer resin composition comprising the vinyl chloride copolymer resin according to any one of claims 1 to 3 (claim 5),
About.

  According to the present invention, it is possible to easily obtain a vinyl chloride copolymer resin and a resin composition thereof that are excellent in impact resistance and melt flow characteristics at the time of molding, and further excellent in transparency.

  The vinyl chloride monomer used in the present invention is not particularly limited. For example, vinyl chloride monomer, vinylidene chloride monomer, vinyl acetate monomer or a mixture thereof, or other copolymerizable with these, preferably after polymerization. A monomer having no reactive functional group in the polymer main chain, for example, one or a mixture of two or more selected from α-olefins such as ethylene and propylene may be used. When using 2 or more types of mixtures, it is preferable that the content rate of the vinyl chloride monomer which occupies for the whole vinyl chloride monomer is 50 weight% or more, especially 70 weight% or more. Among these, it is preferable to use only one of vinyl chloride monomer and vinylidene chloride monomer, and more preferable to use vinyl chloride monomer, from the physical properties of the copolymer resin obtained.

  Moreover, about the polymerization method at the time of obtaining acrylic acid-n-butyl / methyl methacrylate copolymer used by this invention, when a bulk polymerization method, a solution polymerization method, and a suspension polymerization method are used as a polymerization method, The present inventors have found a phenomenon that the melt flow characteristics of a vinyl chloride copolymer resin produced through subsequent processes are improved. As long as such effects are exhibited, the polymerization method is not particularly limited, but any one of a bulk polymerization method, a solution polymerization method, and a suspension polymerization method is preferable.

  The bulk polymerization method is not particularly limited, and can be carried out by a method within a range that does not impair the object of the present invention. For example, in a polymerization reactor equipped with a jacket, acrylic acid-n-butyl and methyl methacrylate and polymerization start After the agent is added and the air in the reactor is removed, the inside of the reactor is heated by a jacket to carry out the polymerization reaction.

  The polymerization initiator used in the bulk polymerization method is preferably soluble in n-butyl acrylate and methyl methacrylate. As such a polymerization initiator, 2,2′-azobisisobutyronitrile is used. 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators; Examples thereof include oxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, and other organic peroxide polymerization initiators. These may be used alone or in combination of two or more.

  Further, the solution polymerization method is not particularly limited, and can be carried out by a method within a range that does not impair the object of the present invention. For example, in a polymerization reactor equipped with a jacket and a stirrer, (a) acrylic acid-n-butyl and An organic solvent capable of dissolving all three substances of methyl methacrylate, (b) acrylic acid-n-butyl and methyl methacrylate and the resulting acrylic acid-n-butyl / methyl methacrylate copolymer, (c) a polymerization initiator Then, after the air in the reactor is removed, the inside of the reactor is heated by a jacket to carry out the polymerization reaction.

  As the organic solvent used in the solution polymerization method, particularly, as long as it can dissolve all three substances of acrylic acid-n-butyl and methyl methacrylate and the obtained acrylic acid-n-butyl / methyl methacrylate copolymer, There is no limitation, for example, hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), acetates (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetoacetate, acetylacetone, etc.) These may be used alone or in combination of two or more.

  The polymerization initiator used in the solution polymerization method is preferably soluble in acrylic acid-n-butyl and methyl methacrylate. As such a polymerization initiator, 2,2′-azobisisobutyro is used. Nitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators; benzoyl Examples thereof include peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, and other organic peroxide polymerization initiators. These may be used alone or in combination of two or more.

  Further, the suspension polymerization method is not particularly limited, and can be carried out by a method within a range that does not impair the object of the present invention. For example, pure water and a suspension dispersant are charged into a polymerization reactor equipped with a jacket and a stirrer. Then, after the air in the reactor is removed, -n-butyl acrylate and methyl methacrylate and a polymerization initiator are charged with stirring, and the inside of the reactor is heated by a jacket to carry out a polymerization reaction.

  Examples of the suspension dispersant used in the suspension polymerization method include partially saponified polyvinyl acetate, methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polyethylene oxide, polyvinyl pyrrolidone, polyacrylic acid, vinyl acetate-maleic acid copolymer, styrene- Organic polymer compounds such as maleic acid copolymer, gelatin and starch; poorly water-soluble inorganic fine particles such as calcium sulfate and tricalcium phosphate can be used, and these can be used alone or in combination of two or more.

  The polymerization initiator used in the suspension polymerization method is preferably soluble in acrylic acid-n-butyl and methyl methacrylate. As such a polymerization initiator, 2,2′-azobisisobutyrate is used. Nitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators; Examples thereof include benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, and other organic peroxide polymerization initiators. These may be used alone or in combination of two or more.

  The ratio of the acrylic acid-n-butyl component and the methyl methacrylate component constituting the acrylic acid-n-butyl / methyl methacrylate copolymer used in the present invention is particularly within the range that does not impair the object of the present invention. Although there is no restriction | limiting, It is preferable that it is the range of acrylic acid-n-butyl component / methyl methacrylate component = 5 weight% / 95 weight%-70 weight% / 30 weight%. If the ratio of the acrylic acid-n-butyl component and the methyl methacrylate component is in the range of acrylic acid-n-butyl component / methyl methacrylate component = 5 wt% / 95 wt% to 70 wt% / 30 wt%, The effects of improving the impact resistance, melt flow characteristics and transparency of the vinyl chloride copolymer resin obtained by copolymerizing the copolymer and vinyl chloride monomer can be balanced, and the copolymerization reaction is also stable. is there.

The ratio [(A) / (B)] of (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methyl methacrylate copolymer in the vinyl chloride copolymer resin of the present invention is as follows. There is no particular limitation as long as it does not impair the purpose, but preferably (A) / (B) = 99.5 wt% / 0.5 wt% to 60 wt% / 40 wt%, more preferably (A) 80 to 97% by weight and (B) 3 to 20% by weight. When the ratio of (B) is in the range of 0.5 wt% to 40 wt%, the effects of improving impact resistance, melt flow characteristics, and transparency can be balanced, and the copolymerization reaction is also stable. Furthermore, if it is the range of 3 weight%-20 weight%, the obtained vinyl chloride type | system | group copolymer will become a granular material, and transparency will become more favorable while the freedom degree of a processing method increases.
The average degree of polymerization or the average molecular weight of the vinyl chloride copolymer resin of the present invention is not particularly limited as long as the effects of the present invention are achieved, but it is measured according to JIS K 7367-2 from the balance of impact strength and moldability. The K value is preferably 50 to 95, and more preferably 55 to 90. Moreover, although it does not specifically limit as an average particle diameter, Usually, it is the range of 0.01-500 micrometers, Preferably it is the range of 0.1-300 micrometers.

  The method for producing the vinyl chloride copolymer resin of the present invention is not particularly limited, but copolymerization in an aqueous medium is preferable from the viewpoint of simplicity of polymerization control such as removal of polymerization reaction heat and suppression of runaway reaction, Examples of such polymerization methods include production methods such as suspension polymerization, fine suspension polymerization, and emulsion polymerization. Particularly preferred is a suspension polymerization method or a fine suspension polymerization method from the viewpoint of various physical properties of the vinyl chloride copolymer resin in consideration of the ease of particle control, residual monomer, bulk specific gravity and the like.

  The suspension polymerization method or fine suspension polymerization method used in producing the vinyl chloride copolymer resin of the present invention can be carried out by a method within a range that does not impair the object of the present invention, and charging of raw materials is also performed in the present invention. Any technique that does not impair the purpose can be used. For example, as the most general method, a method in which water is first charged and then a vinyl chloride monomer and an acrylic acid-n-butyl / methyl methacrylate copolymer are charged. A method of charging warm water after adding a vinyl chloride monomer and an acrylic acid-n-butyl / methyl methacrylate copolymer to a vinyl chloride monomer and an acrylic acid-n-butyl for the purpose of shortening the charging time and heating time / A method of charging methyl methacrylate copolymer and warm water simultaneously can be used.

  Further, in the suspension polymerization method or fine suspension polymerization method used in producing the vinyl chloride copolymer resin of the present invention, the suspension dispersant is particularly limited in a range not impairing the object of the present invention. Can be used without. Examples of such suspending and dispersing agents include partially saponified polyvinyl acetate; water-soluble cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and carboxymethylcellulose; polyethylene oxide; polyvinylpyrrolidone; polyacrylic acid; Organic polymer dispersants such as vinyl acetate-maleic acid copolymer; styrene-maleic acid copolymer; gelatin; starch and the like can be used, and these can be used alone or in combination of two or more.

  Furthermore, in the suspension polymerization method or the fine suspension polymerization method used in producing the vinyl chloride copolymer resin of the present invention, the polymerization initiator is not particularly limited and is an oil within a range not impairing the object of the present invention. A soluble polymerization initiator may be added, but it is preferable to use one or more of these initiators having a 10-hour half-life temperature of 30 to 65 ° C. Examples of such polymerization initiators include acetylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyneodecanoate, diisopropyl peroxydicarbonate, di (2-ethylhexyl) peroxydioxide. Carbonate, t-butylperoxypivalate, t-butylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 3,5,5-trimethyl Organic peroxide polymerization initiators such as hexanoyl peroxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2 Azo polymerization initiators such as' -azobis- (2,4-dimethylvaleronitrile) Is, it may be used alone or in combination of two or more. These oil-soluble polymerization initiators can be added without any particular restrictions. For example, when used by dissolving in an organic solvent, examples of the organic solvent include aromatics such as toluene, xylene, and benzene. Hydrocarbons; Aliphatic hydrocarbons such as hexane and isoparaffin; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate and dioctyl phthalate are used, and these should be used alone or in combination of two or more. Can do.

  In addition, antioxidants, polymerization degree regulators, chain transfer agents, pH regulators, gelling agents, antistatic agents, emulsifiers, stabilizers, scale inhibitors, etc. that are commonly used in the production of vinyl chloride resins As for the preparation amount and the preparation method, a technique within a range that does not impair the object of the present invention can be arbitrarily used without any problem.

  The polymerization temperature condition is not particularly limited, but the polymerization is preferably carried out at 30 to 70 ° C., which is a condition for producing a vinyl chloride resin having a K value of 50 to 95 measured according to JIS K 7367-2.

  Further, the polymerization reaction heat can be removed by a method within a range that does not impair the object of the present invention, for example, heat removal by an external or internal jacket, heat removal by a water baffle, a method using a reflux condenser, etc. Use in combination.

  According to such a production method, the copolymer resin can be obtained in the form of a latex or a slurry. However, there is no particular limitation on the method of drying the copolymer resin to obtain a granular copolymer resin. Examples include a method of drying by a spray drying method, a method of dehydrating a slurry and then drying by a fluidized drying method, and the like.

  Since the vinyl chloride copolymer resin of the present invention has excellent impact resistance and melt flow characteristics, and further excellent transparency, it can be used for applications that require such characteristics. For example, it can be suitably used in various fields such as pipes, joints, window frames, industrial transparent plates, films, electric wire coatings, wrap films, and sheets. A vinyl chloride copolymer resin composition for obtaining such a molded article is also one aspect of the present invention.

  The vinyl chloride copolymer resin composition of the present invention contains the vinyl chloride copolymer resin of the present invention as an essential component, and if necessary, a heat stabilizer, a lubricant, a stabilization aid, a processing aid, a filler, an oxidation agent. An inhibitor, a light stabilizer, a pigment, a plasticizer, and the like can be appropriately blended within a range that does not impair the object of the present invention.

  It does not specifically limit as a heat stabilizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such heat stabilizers include dimethyl tin mercapto, dibutyl tin mercapto, dioctyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, dibutyl tin laurate, dibutyl tin laurate. Organic tin stabilizers such as polymers; lead stabilizers such as lead stearate, dibasic lead phosphite and tribasic lead sulfate; calcium-zinc stabilizers; barium-zinc stabilizers; cadmium-barium stabilizers An agent etc. are mentioned, These may be used independently or may use 2 or more types together. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Moreover, it does not specifically limit as a lubricant, The thing of the range which does not impair the objective of this invention can be used. Examples of such lubricants include paraffin wax-based lubricants, polyolefin wax-based lubricants, stearic acid-based lubricants, alcohol-based lubricants, and ester-based lubricants. These may be used alone or in combination of two or more. good. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Furthermore, it does not specifically limit as a stabilizing aid, The thing of the range which does not impair the objective of this invention can be used. Examples of such stabilizing aids include epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphoric acid ester. These may be used alone or in combination of two or more. May be. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Moreover, it does not specifically limit as a processing aid, The thing of the range which does not impair the objective of this invention can be used. Examples of such processing aids include acrylic acid-n-butyl / methyl methacrylate copolymer, acrylic acid-2-ethylhexyl / methyl methacrylate copolymer, acrylic acid-2-ethylhexyl / methyl methacrylate / methacrylic acid. Examples thereof include acrylic processing aids such as acid-n-butyl copolymer, and these may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Furthermore, it does not specifically limit as a filler, The thing of the range which does not impair the objective of this invention can be used. Examples of such fillers include calcium carbonate, magnesium carbonate, lithium carbonate, kaolin clay, gypsum, mica, talc, magnesium hydroxide, calcium silicate, borax and the like, and these may be used alone or in combination of two or more. May be used in combination. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Moreover, it does not specifically limit as an antioxidant, The thing of the range which does not impair the objective of this invention can be used. Examples of such antioxidants include phenolic antioxidants, and these may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Furthermore, it does not specifically limit as a light stabilizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such light stabilizers include salicylic acid ester-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based UV absorbers; hindered amine-based light stabilizers, and the like. You may use the above together. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Moreover, it does not specifically limit as a pigment, The thing of the range which does not impair the objective of this invention can be used. Examples of such pigments include organic pigments such as azo, phthalocyanine, selenium and dye lakes; inorganic pigments such as oxides, molybdenum chromates, sulfides / selenides, ferrocyanides, etc. These may be used alone or in combination of two or more. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  Furthermore, it does not specifically limit as a plasticizer, The thing of the range which does not impair the objective of this invention can be used. Examples of such plasticizers include phthalate plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, and dibutyl phthalate; tricresyl phosphate, trixyl phosphate, triphenyl phosphate Phosphate plasticizers such as fetes; fatty acid ester plasticizers such as di-2-ethylhexyl adipate and di-2-ethylhexyl sebacate, etc., and these may be used alone or in combination of two or more. Also good. Further, the amount used is not particularly limited as long as the object of the present invention is not impaired.

  In addition, flame retardants, antistatic agents, reinforcing agents, modifiers and the like within a range that does not impair the object of the present invention can be blended without limitation, and the amount used is not particularly limited. As long as the purpose is not impaired.

  The method for producing the vinyl chloride resin composition of the present invention is not particularly limited, and a predetermined amount of vinyl chloride copolymer resin is blended, and if necessary, various additives (heat stabilizer, lubricant, stabilization aid). Additives, processing aids, fillers, antioxidants, light stabilizers, pigments, plasticizers, flame retardants, antistatic agents, reinforcing agents, modifiers, etc.), for example, ribbon blenders, super Manufactured by a method such as mixing or kneading uniformly by a conventional method such as hot blending or cold blending using a mixer, tumbler mixer, Banbury mixer, Henschel mixer, mixing roll, etc. and / or a mixing kneader. Just do it. There is no particular limitation on the blending order and the like at that time, and any technique within the range not impairing the object of the present invention can be used. For example, after blending vinyl chloride copolymer resin and various additives for the purpose of blending vinyl chloride copolymer resin and various additives at once, and for the purpose of uniformly blending liquid additives. A method of blending a liquid additive or a method of blending a liquid additive after first blending a vinyl chloride copolymer resin, and finally blending various additives of a granular material, and further blending various additives first. Then, a method of blending a vinyl chloride copolymer resin, etc. can be used.

  The vinyl chloride copolymer resin composition of the present invention thus produced may be used for various molding processes as it is, and further, kneaders such as a kneader, an extruder, a pelletizer, and / or a kneading granulator, etc. After being kneaded or kneaded and granulated using, it may be subjected to various molding processes.

  The vinyl chloride copolymer resin composition of the present invention includes blister packaging products, leather products, agricultural films, shrink films, calendar products such as various sheets, laminated films on substrates such as PVC steel sheets, and laminated press sheets. Raw materials: Pipes, flat plates, corrugated sheets, films, tapes, sheets, foamed boards or sheets, window frames, other molded products such as irregular profiles, injection molded products such as joints, valves, bottles, duct boots, bellows, etc. Blow-molded products: Used to be molded into various products such as toys, signboards, masks, vacuum-molded products such as press mats, etc.

EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to a following example. Here, unless otherwise specified, “parts” in the examples means “parts by weight”. The methods for measuring impact resistance, melt flow characteristics, and transparency are as follows.
(B) Impact resistance Izod impact at 23 ° C and 0 ° C using a test piece with a type A notch cut into a type 1 test piece according to the JIS K7110 Izod impact strength test method The strength (hereinafter referred to as Izod impact strength, the unit is kJ / m ² ) is determined and evaluated. In the measurement at 23 ° C., a test piece that is allowed to stand for 48 hours in a constant temperature and humidity chamber at a room temperature of 23 ° C. and a relative humidity of 50% is used. In the measurement at 0 ° C., a test piece that was allowed to stand for 48 hours in a constant temperature and humidity chamber with a room temperature of 23 ° C. and a relative humidity of 50% was immersed in a liquid bath adjusted to 0 ° C. for 5 minutes. The impact is given within 5 seconds after taking out from the liquid tank.
(B) Melt flow characteristics In accordance with the flow test method for thermoplastic resin specified in JIS K7210 Annex C, using a Koka type flow tester CFT-500C manufactured by Shimadzu Corporation, a test temperature of 180 ° C. and a die length The resin flow value per second under the conditions of 1 mm in length, 1 mm in die diameter, and test load of 9.8 × 10 ² N (hereinafter abbreviated as Koka type B method flow value. The unit is ml / s × 10 ⁻² .) For evaluation.
(C) Transparency According to the method for determining the haze of a transparent material specified in JIS K7136 and the test method for the total light transmittance of a transparent material specified in JIS K7361-1, a turbidimeter NDH manufactured by Nippon Denshoku Industries Co., Ltd. A haze (hereinafter referred to as Haze) and total light transmittance (hereinafter referred to as T%) of a 1 mm-thick test piece that was allowed to stand for 48 hours in a constant temperature and humidity chamber at a room temperature of 23 ° C. and a relative humidity of 50% using the −300A type. (The unit is%.)

<Method for producing acrylic acid-n-butyl / methyl methacrylate copolymer>
The acrylic acid-n-butyl / methyl methacrylate copolymer was produced according to the following procedure. The weight average molecular weight of the obtained acrylic acid-n-butyl / methyl methacrylate copolymer was about 100,000 in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC). It was. For this GPC measurement, a Waters GPC system (product name 510) was used, and Shodex K-802.5 and K-804 (polystyrene gel column) manufactured by Showa Denko KK were used with chloroform as the mobile phase. And measured in a room temperature environment.

(Production Example 1) Production of acrylic acid-n-butyl / methyl methacrylate copolymer by solution polymerization method (Part 1)
In a 2 L separable flask equipped with a reflux tube, a stirrer and a jacket, 50 parts of n-butyl acrylate (hereinafter abbreviated as BA), 50 parts of methyl methacrylate (hereinafter abbreviated as MMA), 50 parts of isopropyl alcohol, 50 of ethyl acetate Part, 0.2 part of benzoyl peroxide and 2.5 parts of lauryl peroxide were charged, and the inside of the reaction vessel was purged with nitrogen. Next, the temperature in the reaction vessel was raised to 65 ° C. through warm water through the jacket while stirring to initiate the reaction. After 8 hours, the internal temperature was raised to 75 ° C., and stirring was continued for 4 hours. When 12 hours had elapsed from the start of the reaction, the reaction was terminated, and the volatile matter was distilled off under reduced pressure to obtain a viscous liquid BA / MMA copolymer (hereinafter abbreviated as P (BA / MMA) -1).

Production Example 2 Production of BA / MMA Copolymer by Suspension Polymerization Method In a 2 L separable flask equipped with a reflux tube, a stirrer and a jacket, 300 parts of pure water, a saponification degree of about 80 mol%, and an average polymerization degree of about 2000 The partially saponified polyvinyl acetate 0.7 part was charged and the inside of the reaction vessel was purged with nitrogen. Next, 50 parts of BA, 50 parts of MMA and 0.9 part of 2,2′-azobisisobutyronitrile were charged with stirring, and the reaction was started by raising the temperature in the reaction vessel to 70 ° C. through warm water in the jacket. After cooling for 4 hours, the reaction was terminated, and the reaction product was separated into solid and liquid, washed thoroughly with pure water, dried and a rubbery BA / MMA copolymer (hereinafter abbreviated as P (BA / MMA) -2). )

(Production Example 3) Production of BA / MMA copolymer by bulk polymerization method A 2 L separable flask equipped with a jacket was charged with 50 parts of BA, 50 parts of MMA and 0.3 part of 2,2′-azobisisobutyronitrile. The inside of the reaction vessel was purged with nitrogen. Subsequently, the temperature inside the reaction vessel was raised to 60 ° C. through warm water through the jacket to start the reaction. The reaction was terminated by cooling after 8 hours to obtain a bulk BA / MMA copolymer (hereinafter abbreviated as P (BA / MMA) -3).

Production Example 4 Production of BA / MMA Copolymer by Solution Polymerization Method (Part 2)
A bulk BA / MMA copolymer (hereinafter referred to as P (BA / MMA)-) was produced by the same production method as in Production Example 1 except that the amount of BA used in Production Example 1 was changed to 5 parts and the amount of MMA was changed to 95 parts. Abbreviated as 4).

Production Example 5 Production of BA / MMA Copolymer by Solution Polymerization Method (Part 3)
A rubbery BA / MMA copolymer (hereinafter referred to as P (BA / MMA)) was produced by the same production method as in Production Example 1 except that the BA amount used in Production Example 1 was 30 parts and the MMA amount was 70 parts. Abbreviated to -5).

Production Example 6 Production of BA / MMA Copolymer by Solution Polymerization Method (Part 4)
A liquid BA / MMA copolymer (hereinafter referred to as P (BA / MMA)-) was produced by the same production method as in Production Example 1 except that the BA amount used in Production Example 1 was 70 parts and the MMA amount was 30 parts. 6).

(Production Example 7) Production of BA / MMA copolymer by emulsion polymerization method In a 2 L separable flask equipped with a dropping tube, a stirrer and a jacket, 0.8 part of sodium dioctylsulfosuccinate previously dissolved in pure water and potassium persulfate 0.05 part was added and pure water was added to make the total amount of pure water 200 parts, and then the inside of the reaction vessel was purged with nitrogen. Next, the temperature inside the reaction vessel was raised to 70 ° C. through warm water through the jacket while stirring, and 50 parts of BA and 50 parts of MMA were added dropwise at a rate of about 20 parts per hour while continuing stirring. Stirring was continued for 90 minutes while maintaining the internal temperature of the reaction vessel at 70 ° C. after the completion of the dropping, and then cooled to obtain a latex of BA / MMA copolymer (hereinafter abbreviated as P (BA / MMA) -7). It was. A part of this latex was taken out while stirring, added with an aqueous calcium chloride solution, salted out and solidified, solid-liquid separated, washed with water and dried to obtain a solids concentration of about 30% by weight.

(Production Example 8) Production of poly (acrylic acid-n-butyl) by a solution polymerization method In a 2 L separable flask equipped with a reflux tube, a stirrer and a jacket, 100 parts of BA, 50 parts of toluene, 50 parts of ethyl acetate, benzoyl peroxide 0.3 parts was charged, and the inside of the reaction vessel was purged with nitrogen. Next, the temperature in the reaction vessel was raised to 70 ° C. through warm water through the jacket while stirring to initiate the reaction. After 5 hours, the internal temperature was raised to 75 ° C. and stirring was continued for 2 hours. When 7 hours had elapsed from the start of the reaction, the reaction was terminated, and volatile components were distilled off under reduced pressure to obtain liquid poly (acrylic acid-n-butyl) (hereinafter abbreviated as PBA).

(Production Example 9) Production of polymethyl methacrylate by a solution polymerization method Except that BA used in Production Example 8 was changed to MMA, bulk polymethyl methacrylate (hereinafter referred to as PMMA) was produced by the same production method as Production Example 8. Abbreviated).

Example 1
In a stainless steel polymerization machine having a volume of 25 liters equipped with a jacket and a stirrer, 0.1 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000, t-butylperoxyneodecanoate 0.03 parts, 0.01 parts of 1,1,3,3-tetramethylbutylperoxyneodecanoate are charged, and after degassing, 93 parts of vinyl chloride monomer and 7 parts of P (BA / MMA) -1 Then, 150 parts of warm water at 60 ° C. was charged, and polymerization was carried out at a polymerization temperature of 57 ° C. for about 6 hours. After recovering unreacted monomers in the polymerization machine, the polymerization machine was cooled and the slurry was discharged. The obtained slurry was dehydrated and dried in a hot air dryer at 55 ° C. for 24 hours to obtain vinyl chloride / {P (BA / MMA) -1} graft copolymer resin A as a white powder.

  Next, with respect to 100 parts of the obtained copolymer resin A, 1.5 parts of an organic tin heat stabilizer (TVS # 8831: manufactured by Nitto Kasei Co., Ltd., dioctyltin mercapto), a lubricant (Calcoal 86: manufactured by Kao Corporation), 1.0 part of stearyl alcohol) is blended to obtain a vinyl chloride copolymer resin composition, and the composition is 180 ° C. using a H0S-2103 type 8-inch roll (outer diameter: about 20 cm) manufactured by Nippon Roll Co., Ltd. A roll sheet having a thickness of about 1 mm was produced under the condition of a roll for 3 minutes. The obtained roll sheet was divided into three parts, the first point was cut into a predetermined size, and then several tens of sheets were stacked, and 185 ° C., pressure 5 MPa using Shindo SF type hydraulic press machine manufactured by Shindo Metal Industry Co., Ltd. Was pressed for about 10 minutes to prepare a test plate having a thickness of 5 mm, and then a test sample for impact resistance evaluation was prepared by cutting and used for measurement. The second point was cut into approximately 3 mm squares and used for measurement of melt flow characteristics. The third point is cut into a predetermined size and then stacked several times. Using a Shindo SF hydraulic press manufactured by Shindo Metal Industry Co., Ltd., press for about 10 minutes at 185 ° C. and 5 MPa pressure to test the thickness of 1 mm. A plate was prepared and subjected to transparency evaluation. The results are shown in Table 1.

(Example 2)
The same production method as in Example 1 except that the amount of the vinyl chloride monomer used in the polymerization of Example 1 was 99.5 parts and the amount of P (BA / MMA) -1 was 0.5 parts. , Vinyl chloride / {P (BA / MMA) -1} graft copolymer resin B was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 3)
Except for the amount of vinyl chloride monomer used in the polymerization of Example 1 being 80 parts and the amount of P (BA / MMA) -1 being 20 parts, the same production method as in Example 1 was used. {P (BA / MMA) -1} graft copolymer resin C was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

Example 4
Except that the amount of the vinyl chloride monomer used in the polymerization of Example 1 was 60 parts and the amount of P (BA / MMA) -1 was 40 parts, the same production method as Example 1 was used. {P (BA / MMA) -1} graft copolymer resin D was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 5)
In a stainless steel polymerization machine similar to that used in any of Examples 1 to 4, 150 parts of pure water, 0.08 part of partially saponified polyvinyl acetate having a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000, 0.0015 part of polyethylene oxide having an average molecular weight of about 4.5 million, 0.05 part of 1,1,3,3-tetramethylbutylperoxyneodecanoate are charged, and after degassing, 93 parts of vinyl chloride monomer and 7 parts of P (BA / MMA) -1 was charged and polymerized at a polymerization temperature of 33 ° C. for about 15 hours. After recovering unreacted monomers in the polymerization machine, the polymerization machine was cooled and the slurry was discharged. The obtained slurry was dehydrated and dried in a hot air dryer at 55 ° C. for 24 hours to obtain vinyl chloride / {P (BA / MMA) -1} graft copolymer resin E as a white powder.

  Next, roll / press processing was performed in the same manner as in Example 1 except that 20 parts of DOP (product name: DOP, manufactured by J Plus Co., Ltd.) as a plasticizer was blended with 100 parts of the obtained copolymer resin D. The impact resistance, melt flow properties and transparency were evaluated. The results are shown in Table 1.

(Example 6)
A stainless steel polymerization machine similar to that used in any of Examples 1 to 5 was charged with 0.3 part of partially saponified polyvinyl acetate having a degree of saponification of about 88 mol% and an average degree of polymerization of about 3500, and a degree of saponification of about 78 mol %, Partially saponified polyvinyl acetate having an average degree of polymerization of about 900, 0.15 part of saponified polyvinyl acetate, methoxyl group content of about 20 mol%, hydroxypropoxyl group content of about 8 mol%, and 2% viscosity at 20 ° C. of about 30000 mPa · s. 0.02 part of certain hydroxypropyl methylcellulose, 0.6 part of stearic acid-n-butyl, 0.02 part of t-butylperoxyneodecanoate, 0.02 part of 3,5,5-trimethylhexanoyl peroxide After charging and degassing, 93 parts of vinyl chloride monomer and 7 parts of P (BA / MMA) -1 were charged, and then 400 parts of 60 ° C. warm water was added, and the polymerization temperature was 64 ° C. It was polymerized 6 hours. After recovering the unreacted monomer in the polymerization machine, the polymerization machine was cooled and the latex was discharged. The obtained latex was dehydrated and dried in a hot air dryer at 55 ° C. for 24 hours to obtain vinyl chloride / {P (BA / MMA) -1} graft copolymer resin F as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 7)
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to P (BA / MMA) -2 of Production Example 2, vinyl chloride / {P (BA / MMA) -2} Graft copolymer resin G was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 8)
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to P (BA / MMA) -3 of Production Example 3, vinyl chloride / {P (BA / MMA) -3} graft copolymer resin H was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

Example 9
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to P (BA / MMA) -4 of Production Example 4, vinyl chloride / {P (BA / MMA) -4} Graft copolymer resin I was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 10)
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to P (BA / MMA) -5 of Production Example 5, vinyl chloride / {P (BA / MMA) -5} graft copolymer resin J was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Example 11)
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to P (BA / MMA) -6 of Production Example 6, vinyl chloride / {P (BA / MMA) -6} graft copolymer resin K was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

(Comparative Example 1)
A vinyl chloride homopolymer resin was produced in the same manner as in Example 1 except that the amount of the vinyl chloride monomer used in the polymerization of Example 1 was 100 parts and P (BA / MMA) -1 was not used. Was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

  Both the Izod impact strength and the Koka type B method flow value are low, which is not preferable.

(Comparative Example 2)
Compounded in the same manner as in Example 1 except that 3 parts of MBS resin (Kane Ace B56: manufactured by Kaneka Corporation) was added as an impact resistance improver to 100 parts of the vinyl chloride homopolymer resin obtained in Comparative Example 1. Rolled / pressed and evaluated for impact resistance, melt flow properties and transparency. The results are shown in Table 1.

  Although the Izod impact strength is slightly improved as compared with the case of Comparative Example 1, the Koka type B method flow value is low, which is not preferable.

(Comparative Example 3)
Except that P (BA / MMA) -1 used in the polymerization in Example 1 was changed to P (BA / MMA) -7 in Production Example 7, vinyl chloride / {P (BA / MMA) -7} graft copolymer resin L was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

  Although the Izod impact strength is improved, the Koka type B method flow value and transparency are low, which is not preferable.

(Comparative Example 4)
Except that P (BA / MMA) -1 used in the polymerization of Example 1 was changed to PBA of Production Example 8, a vinyl chloride / PBA graft copolymer resin was converted into a white powder by the same production method as in Example 1. Got as.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

  Although the Izod impact strength and the Koka type B method flow value are improved, the transparency is low, which is not preferable.

(Comparative Example 5)
Except that P (BA / MMA) -1 used in the polymerization in Example 1 was changed to PMMA in Production Example 9, vinyl chloride / PMMA graft copolymer resin was converted into a white powder by the same production method as in Example 1. Got as.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

  Both the Izod impact strength and the Koka type B method flow value are low, which is not preferable.

(Comparative Example 6)
In the same production method as in Example 1, except that the amount of vinyl chloride monomer used in the polymerization of Example 1 was 99.9 parts and the amount of P (BA / MMA) -1 was 0.1 parts. , Vinyl chloride / {P (BA / MMA) -1} graft copolymer resin M was obtained as a white powder.

  This was blended in the same manner as in Example 1 and rolled / pressed to evaluate impact resistance, melt flow characteristics and transparency. The results are shown in Table 1.

  Both the Izod impact strength and the Koka type B method flow value are low, which is not preferable.

Claims (5)

  (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methyl methacrylate copolymer produced by one method selected from bulk polymerization method, solution polymerization method and suspension polymerization method A vinyl chloride copolymer resin characterized by copolymerizing a polymer.   The ratio of (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methyl methacrylate copolymer is (A) / (B) = 99.5 wt% / 0.5 wt% to 60 wt%. 2. The vinyl chloride copolymer resin according to claim 1, which is in a range of% / 40% by weight.   The ratio of acrylic acid-n-butyl component and methyl methacrylate component constituting the acrylic acid-n-butyl / methyl methacrylate copolymer is acrylic acid-n-butyl component / methyl methacrylate component = 5% by weight / 95. The vinyl chloride copolymer resin according to any one of claims 1 to 2, wherein the content is in a range of wt% to 70wt% / 30wt%.   (A) vinyl chloride monomer and (B) acrylic acid-n-butyl / methyl methacrylate copolymer produced by one method selected from bulk polymerization method, solution polymerization method and suspension polymerization method The method for producing a vinyl chloride copolymer resin according to any one of claims 1 to 3, wherein the coalescence is copolymerized in an aqueous medium.   A vinyl chloride copolymer resin composition comprising the vinyl chloride copolymer resin according to claim 1.