CN1922264A - Vinyl chloride resin composition - Google Patents

Abstract

A vinyl chloride resin composition which, even when various compounding ingredients are not added thereto in a large amount, shows excellent melt flow characteristics without lowering the softening temperature and mechanical strength/properties of the molding to be obtained therefrom; and a molding formed from the composition. The vinyl chloride resin composition is characterized by being obtained by adding to a vinyl chloride resin a vinyl chloride copolymer resin obtained by copolymerizing a vinyl monomer with a macromonomer having a main chain comprising a polymer of an ethylenically unsaturated monomer having a double bond.

Description

Vinyl chloride resin composition

technical field

The present invention relates to a vinyl chloride resin composition and a molded article using the composition. More specifically, it relates to a vinyl chloride-based resin composition having excellent melt flow characteristics without lowering the softening temperature and mechanical strength properties of the molded article, and a molded article using the composition. More specifically, the present invention relates to a method for obtaining a molded article capable of suppressing occurrence of pitting on the surface of a molded article when calendering is performed using a vinyl chloride-based resin having an average degree of polymerization or an average molecular weight within a range generally used in calendering applications. (air mark) and corrugated (flow mark), a vinyl chloride-based resin composition of a calendered molded article with excellent surface conditions, and a calendered vinyl chloride-based resin molded article using the composition; and use in injection molded articles Vinyl chloride-based resin composition and its use for obtaining injection-molded articles with no decrease in strength and physical properties and excellent fluidity during molding processing when injection-molding vinyl chloride-based resins with an average degree of polymerization or average molecular weight within the range normally used in Injection-molded vinyl chloride-based resins containing the composition; and extruded molded articles using vinyl chloride-based resins having an average degree of polymerization or an average molecular weight within a range generally used in extrusion-molded articles, especially pipes Rigid vinyl chloride resin composition useful for hard extruded products requiring impact strength and fracture toughness strength as a new long-term durability indicator for high quality, and extruded hard plastics using the composition Vinyl chloride resin molded body.

Background technique

Vinyl chloride resin is widely used in various moldings by effectively utilizing its characteristics, but it has a thermal decomposition temperature close to the processing temperature, and it is difficult to exhibit sufficient fluidity and mechanical strength properties (such as impact strength, tensile strength, fracture strength, etc.) Toughness, strength, etc.) and other processing-related issues. In order to overcome this problem, there are known methods of, for example, copolymerizing other monomers on vinyl chloride monomers, or mixing plasticizers or other resinous substances into vinyl chloride resins. However, these methods have the disadvantage of not being able to solve the problems involved in processing while maintaining the excellent physicochemical properties inherent in vinyl chloride resins, such as when vinyl chloride monomers are copolymerized with other monomers or when plasticizers are added, resulting molded The softening temperature of the body is lowered, the mechanical strength is poor, and in most cases when other resin samples are mixed, the melt viscosity of the resin mixture is reduced, thereby improving the apparent processability, but due to poor compatibility with vinyl chloride resin , so the mechanical properties and transparency of the molded body obtained are poor.

On the other hand, in order to improve the impact strength, which is one of the physical properties of mechanical strength, it is disclosed that, for example, methyl methacrylate-butadiene-styrene copolymer (hereinafter referred to as MBS resin) is added to vinyl chloride resin. Or chlorinated polyethylene (hereinafter abbreviated as CPE) as the method of impact reinforcing agent (patent document 1). However, when these reinforcing agents are blended into vinyl chloride resin, in order to impart sufficient mechanical strength, a large amount of reinforcing agents must be blended, which requires cost, and the fluidity during molding processing cannot be improved, such as extruders. Problems in manufacturing conditions such as increased motor load. In addition, in order to promote gelation during molding processing or improve fluidity and secondary processability without reducing the mechanical properties and transparency of vinyl chloride resin moldings, it has been proposed, for example, to use methyl methacrylate A method of blending a copolymer as a main component as a processability improver (Patent Document 2). However, although this method promotes gelation without degrading the characteristics of vinyl chloride resin, and can obtain a molded article with excellent transparency, secondary processability, and porosity, it has a fatal disadvantage that it cannot Waves are generated on the surface of the calendered sheet, which lowers the commercial value of the molded article. Furthermore, in order to improve the waviness, for example, a method of blending a copolymer having a low degree of polymerization mainly composed of methacrylate other than methyl methacrylate as a workability improving agent has been proposed (Patent Document 3). However, although this method improves waviness, it also sacrifices the preferred effects of reducing pitting and improving secondary workability imparted by the method described in Patent Document 2, which also leads to a decrease in the commercial value of the molded article. relevant. In recent years, the market has become more and more demanding on quality. As long as it can suppress the occurrence of waviness and also reduce pitting, it will become a very useful technology in industry.

Here, the so-called pockmarks refer to portions where the air entrained in the molten resin is not removed during melt kneading, and the traces thereof remain in the form of dots or streaks on the surface of the molded article. In addition, the so-called waviness means that when a part of the molten resin mass generated in the roll gap passes through the gap, due to the change of flow velocity and resin temperature before and after passing through the gap, it becomes a rib-like or stripe-like pattern and remains on the surface of the molded body. part.

Moreover, as a method of improving required properties without adding a large number of reinforcing agents and additives, there are literatures disclosing the following methods: For example, in order to improve impact strength and fatigue resistance, using conventionally known general A vinyl monomer was graft-copolymerized on an acrylic copolymer obtained by emulsion polymerization, and the resulting resin was used as a rigid vinyl chloride pipe (Patent Document 4). However, although it is disclosed that this method contributes to the improvement of the impact strength of the obtained vinyl chloride-based copolymer resin, the effect of improving the fracture toughness is not clear.

Patent Document 1: Japanese Unexamined Patent Publication No. 9-278964

Patent Document 2: Japanese Patent Publication No. 53-2898

Patent Document 3: Japanese Unexamined Patent Publication No. 1-247409

Patent Document 4: JP-A-2003-148660

Contents of the invention

An object of the present invention is to provide a vinyl chloride-based resin composition excellent in melt flow properties without lowering the softening temperature and mechanical strength properties of the molded article, and a vinyl chloride-based resin molded article using the composition. In addition, an object of the present invention is to provide a vinyl chloride-based resin composition for imparting a calendered molded article such as a sheet that suppresses pitting and waviness and has an excellent surface condition, and a calendered vinyl chloride-based resin molded article using the composition. . Furthermore, an object of the present invention is to provide a vinyl chloride-based resin composition for injection molded articles that has good fluidity during molding without lowering the strength and physical properties without compounding a large amount of various additives, and a product using the composition. Injected vinyl chloride resin molded body. Furthermore, an object of the present invention is to provide a rigid vinyl chloride-based resin composition for extrusion processing capable of imparting high impact strength and high fracture toughness without compounding a large number of types of reinforcing agents, and a composition using the same. extruded rigid vinyl chloride resin moldings.

As a result of earnest research by the present inventors, it was found that by using a vinyl chloride-based resin composition containing a vinyl chloride-based copolymer resin obtained by copolymerizing a vinyl-based monomer and a macromonomer, The resulting macromonomer has a polymer composed of a double bond-containing ethylenically unsaturated monomer in its main chain, which can achieve the above-mentioned problems, and completed the present invention.

That is, the present invention relates to:

(1) A vinyl chloride-based resin composition characterized in that a vinyl chloride-based copolymer resin obtained by copolymerizing a vinyl-based monomer and a macromonomer is added to the vinyl chloride-based resin. The result is that the macromonomer has a polymer consisting of a double bond-containing ethylenically unsaturated monomer in the main chain.

(2) The vinyl chloride resin composition, characterized in that based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component is 0.1 to 5 parts by weight.

(3) A vinyl chloride-based resin composition, characterized in that the macromonomer component accounts for 3 to 50% by weight of the vinyl chloride-based copolymer resin.

(4) A molded article formed from the above-mentioned vinyl chloride-based resin composition.

(5) A molded body, characterized in that it is molded by calendering.

(6) The molded body is characterized in that it is formed by injection molding.

(7) Formed body, characterized in that it is shaped by extrusion.

According to the vinyl chloride-based resin composition of the present invention, a vinyl chloride-based resin molded article having excellent melt flow properties without lowering the softening temperature and mechanical strength properties can be obtained. In addition, according to the vinyl chloride resin composition of the present invention, it is possible to obtain a calendered vinyl chloride resin molded article in which pinholes and waviness are suppressed. Furthermore, according to the vinyl chloride-based resin composition of the present invention, it is possible to obtain injection molded articles of vinyl chloride-based resins such as joints and valve products, which have good fluidity during molding processing and do not decrease in strength and physical properties. Furthermore, according to the vinyl chloride resin composition of the present invention, it is possible to obtain extruded rigid vinyl chloride resins such as pipes having high impact strength and high fracture toughness strength without compounding a large amount of various reinforcing agents and additives. Formed body.

Detailed ways

The vinyl chloride resin composition of the present invention is characterized in that it is vinyl chloride obtained by copolymerizing a vinyl monomer and a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer in its main chain. The method of adding the quasi-copolymer resin to the vinyl chloride-based resin and molding the composition into various moldings is not particularly limited, and examples include calendering, injection molding, extrusion, blow molding, Common methods of molding vinyl chloride-based resins such as press molding and vacuum molding. In the present invention, the average degree of polymerization or average molecular weight of the vinyl chloride-based resin used in these various molding processes is not particularly limited as long as the effect of the present invention can be obtained. Similarly for resinoids, the K value measured in accordance with JIS K 7367-2 is in the range of 50 to 95. Here, calendering using a vinyl chloride-based resin refers to a molding process in which a resin composition is poured into a heated roll, melt-kneaded and rolled, and cooled and solidified into a sheet shape. As the vinyl chloride-based resin used, It is preferable to have an average degree of polymerization having a K value in the range of 58 to 68 measured in accordance with JIS K 7367-2. In addition, the so-called injection molding processing method using vinyl chloride resin means that a resin composition etc. is fed into a heating cylinder by a screw, and the composition etc. are heated and melted by using the heat of the cylinder and the shear generated by the screw. It flows, injects the molten resin composition, etc. into a mold, and cools and solidifies to obtain a molded body. The vinyl chloride resin used has a K value in the range of 55 to 61 measured in accordance with JIS K 7367-2. The average degree of polymerization is more suitable. In addition, the extrusion processing method using vinyl chloride resin refers to sending a resin composition, etc. into a heating cylinder with a screw, and heating and melting the composition, etc., using the heat of the cylinder and the shear generated by the screw. It flows, makes it pass through the mold at the front end, and cools and solidifies it with water to obtain a molded body. As the vinyl chloride resin used, it has a K value of 60 to 73 measured in accordance with JIS K 7367-2. The average degree of polymerization in the range of is more suitable. In addition, the average particle size is not particularly limited regardless of the molding method, but is usually in the range of 50 to 300 μm.

It should be noted that "adding a vinyl chloride-based copolymer resin to a vinyl chloride-based resin" means mixing the two resins after polymerization, and the method is not particularly specific as long as it is within the range where the effects of the present invention can be obtained. Limitations, can exemplify the method of mixing latex and/or slurry-like substances after polymerization, the method of mixing powders and grains obtained by drying latex and/or slurry, mixing latex-like or slurry-like substances and The method of mixing powder and granule, etc.

As the vinyl-based monomer constituting the vinyl chloride-based copolymer resin used in the present invention, there is no particular limitation, and it is possible to use, for example, a vinyl chloride monomer, a vinylidene chloride monomer, a vinyl acetate monomer, or a mixture of these, or In addition, it can be copolymerized with these monomers, preferably monomers without reactive functional groups on the main chain of the polymerized polymer, such as one or more mixtures of α-olefins such as ethylene and propylene. When a mixture of two or more is used, the content of the vinyl chloride monomer is preferably 50% by weight or more, particularly preferably 70% by weight or more, of the total vinyl monomers. Among them, it is preferable to use only either vinyl chloride monomer or vinylidene chloride monomer, and it is more preferable to use vinyl chloride monomer in view of the physical properties of the obtained copolymer resin.

The so-called macromonomer generally refers to an oligomer molecule having a reactive functional group at the end of the polymer. The macromonomer used in the present invention has a polymer composed of a double bond-containing ethylenically unsaturated monomer on its main chain, which is produced by radical polymerization, and has a reactive functional group at the molecular end. At least one group having a polymerizable carbon-carbon double bond selected from an allyl group, a vinylsilyl group, a vinyl ether group, a dicyclopentadienyl group, and the following general formula (1) per molecule.

From the good aspect of reactivity with vinyl monomers, the group with polymerizable carbon-carbon double bonds is particularly preferably the following general formula (1):

-OC(O)C(R)=CH ₂ (1)

represented group.

In the formula, the specific examples of R are not particularly limited, and are preferably selected from, for example, -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), -C ₆ H ₅ A group selected from , -CH ₂ OH, and -CN, more preferably -H, -CH ₃ .

A polymer composed of a double bond-containing ethylenically unsaturated monomer as the main chain of the macromonomer used in the present invention is produced by radical polymerization. The radical polymerization method can be classified as a "general radical polymerization method", which simply copolymerizes a monomer having a specific functional group and a vinyl monomer using an azo compound, a peroxide, etc. as a polymerization initiator; "Controlled radical polymerization", which can introduce specific functional groups at controlled positions such as terminals.

Since the "general radical polymerization method" only probabilistically introduces monomers with specific functional groups into polymers, it is necessary to use a relatively large amount of such monomers when it is desired to obtain a polymer with a high functionalization rate. In addition, since radical polymerization is performed, the molecular weight distribution is wide, and it is difficult to obtain a polymer with low viscosity.

The "controlled radical polymerization method" can also be classified into the "chain transfer agent method", which can obtain a vinyl polymer with a functional group at the end by using a chain transfer agent with a specific functional group for polymerization; and "living free radical "Polymerization method", which grows by polymerizing the growing terminal without causing a termination reaction, and can obtain a polymer with a molecular weight that approximately meets the design.

The "chain transfer agent method" can obtain a polymer with a high functionalization rate, but requires a chain transfer agent with a specific functional group for the initiator. In addition, similarly to the above-mentioned "general radical polymerization method", since it is radical polymerization, the molecular weight distribution is wide, and it is difficult to obtain a polymer with low viscosity.

Unlike these polymerization methods, the "living radical polymerization method" is as described in International Publication No. WO99/65963 related to the applicant's own invention. Since the polymerization rate is fast, the coupling between radicals and the like are likely to cause a termination reaction. It becomes a radical polymerization that is difficult to control, but it is difficult to produce a termination reaction. While obtaining a polymer with a narrow molecular weight distribution, for example, the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is about 1.1 to 1.5, The molecular weight can be freely controlled by the feed ratio of monomer and initiator.

Therefore, the "living radical polymerization method" can obtain a polymer with a narrow molecular weight distribution and low viscosity, and since a monomer having a specific functional group can be introduced into almost any position of the polymer, in the present invention, as a polymer having the above-mentioned specific functional group The production method of the vinyl polymer, which is a more preferable polymerization method.

In the "living radical polymerization method", the "atom transfer radical polymerization method" ( Atom Transfer Radical Polymerization: ATRP), because it not only has the characteristics of the above-mentioned "living radical polymerization method", but also has a halogen at the end that is more conducive to the conversion reaction of the functional group, and the design freedom of the initiator and catalyst is large. The production method of the vinyl polymer is more preferable. As this atom transfer radical polymerization method, Matyjaszewski et al., J.Am.Chem.Soc. 1995, volume 117, page 5614, etc. are mentioned, for example.

As the production method of the macromonomer constituting the vinyl chloride-based copolymer resin used in the present invention, which of these methods is used is not particularly limited, and a controlled radical polymerization method is usually used. Further, from the viewpoint of ease of control, etc., Preference is given to using living radical polymerization, especially atom transfer radical polymerization is most preferred.

In addition, there is no particular limitation on the polymer composed of a double bond-containing ethylenically unsaturated monomer that is included in the main chain of the macromonomer constituting the vinyl chloride-based copolymer resin used in the present invention. As the ethylenically unsaturated monomer having a double bond, various monomers can be used. Examples include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth) n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate , phenyl (meth)acrylate, cresyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxy (meth)acrylate Butyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylic acid -2-aminoethyl ester, γ-(methacryloxypropyl)trimethoxysilane, ethylene oxide adduct of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, ( 2-trifluoromethylethyl methacrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, (meth)acrylate Base) 2-perfluoroethyl acrylate, perfluoromethyl (meth)acrylate, bis-perfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethyl (meth)acrylate Methyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc. (methyl) ) acrylic monomers; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and its salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters of maleic acid, and dioxane Alkyl esters; fumaric acid, mono- and di-alkyl fumaric acid esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide , Butylmaleimide, Hexylmaleimide, Octylmaleimide, Dodecylmaleimide, Stearylmaleimide, Phenylmaleimide , cyclohexylmaleimide and other maleimide monomers; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide Monomers; vinyl esters such as vinyl acetate, vinyl propionate, trimethyl vinyl acetate, vinyl benzoate, vinyl laurate; olefins such as ethylene and propylene; butadiene, isoprene and other conjugated dienes; allyl chloride, allyl alcohol, etc. These may be used alone, or two or more kinds may be copolymerized. Among these, styrene-based monomers or (meth)acrylic monomers are preferred in view of the physical properties of the product and the like. It is more preferably an acrylate monomer or a methacrylate monomer, still more preferably an acrylate monomer, and most preferably butyl acrylate. In the present invention, those obtained by copolymerizing these preferred monomers and other monomers can be used. In this case, it is preferable to contain these preferred monomers in a weight ratio of 40% or more. Here, for example, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

The macromonomer constituting the vinyl chloride copolymer resin used in the present invention is characterized in that it has a polymer composed of these double bond-containing ethylenically unsaturated monomers on the main chain, and has at least 1 reactive functional group.

Moreover, the macromonomers that can be copolymerized with vinyl monomers that constitute the vinyl chloride copolymer resin used in the present invention can be used only one kind, or can use two or more kinds of ethylenically unsaturated monomonomers at the same time. different macromonomers.

In all the vinyl chloride-based copolymer resins used in the present invention, the fraction occupied by the macromonomer component having a polymer composed of a double bond-containing ethylenically unsaturated monomer in the main chain, as long as the present invention is obtained The range of the effect is not particularly limited, but it is preferably 3 to 50% by weight. If the fraction of the macromonomer component of the polymer composed of a double bond-containing ethylenically unsaturated monomer on the main chain is in the range of 3 to 50% by weight, the following effects can be expected: the copolymerization reaction is stable, and The obtained vinyl chloride-based copolymer resin is in the form of powder, which is easy to handle and increases the degree of freedom of the processing method. In addition, by using the obtained vinyl chloride-based copolymer resin, it is possible to obtain a vinyl chloride-based resin composition excellent in melt flow characteristics without lowering the softening temperature and mechanical strength properties of the molded article. In particular, when a molded article is obtained from the vinyl chloride-based copolymer resin composition of the present invention by various molding processing methods such as calendering, injection molding, and rigid extrusion, the macromonomer components in all the vinyl chloride-based copolymer resins used The occupied fraction is not particularly limited as long as the effect of the present invention is obtained, but is preferably 5 to 50% by weight. If the fraction of the macromer component is in the range of 5 to 50% by weight, by using the obtained vinyl chloride-based copolymer resin, it is possible to obtain a calendered vinyl chloride-based resin molded article in which pinholes and waviness are suppressed. In addition, Injected vinyl chloride-based resin moldings such as joints and valve products can be obtained with good fluidity during molding and no reduction in strength and physical properties. In addition, without adding a variety of large amounts of reinforcing agents and additives, it is possible to obtain high-impact Extrusion of rigid vinyl chloride-based resin molded products such as pipes with high strength and high fracture toughness.

The average degree of polymerization or average molecular weight of the vinyl chloride-based copolymer resin used in the present invention is not particularly limited as long as the effect of the present invention is obtained, and it is in accordance with JIS K 7367-2 in the same way as commonly produced and used vinyl chloride-based resins. The measured K value is in the range of 50-95. In addition, the average particle size is not particularly limited, but is usually in the range of 0.01 to 500 μm, preferably in the range of 0.1 to 300 μm, and more preferably in the range of 50 to 300 μm. As long as the average particle size is in the range of 50 to 300 μm, it is possible to provide a raw material with a balance of various required quality characteristics.

In the present invention, a vinyl chloride-based copolymer resin obtained by copolymerizing a vinyl-based monomer and a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer in the main chain is added to the vinyl chloride-based copolymer resin. For use in resins, based on 100 parts by weight of vinyl chloride resin, the content of the macromonomer component in the vinyl chloride copolymer resin is not particularly limited as long as it is within the range of the effect of the present invention, but it is preferable to add the The vinyl chloride-based copolymer resin is in the range of 0.1 to 5 parts by weight. If the content of the macromonomer component in the vinyl chloride copolymer resin is in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin, it is possible to provide a raw material with a balanced variety of required quality properties. . Wherein, when the vinyl chloride-based copolymer resin of the present invention is used for injection molding, based on 100 parts by weight of the vinyl chloride-based resin, the content of the macromonomer component in the vinyl chloride-based copolymer resin is as long as the content of the present invention is obtained. The range of the effect is not particularly limited, but it is preferable to add the vinyl chloride-based copolymer resin in a range of 0.1 to 1 part by weight. If the content of the macromonomer component in the vinyl chloride copolymer resin is in the range of 0.1 to 1 part by weight based on 100 parts by weight of the vinyl chloride resin, the fluidity during molding and the stability of the molded body can be improved. Raw material with balanced strength and physical properties.

For the manufacture method of the vinyl chloride-based copolymer resin used in the present invention, there is no particular limitation, from the viewpoint of the simplicity of polymerization control, the copolymerization in aqueous medium is preferred, such polymerization methods include: suspension polymerization, microsuspension polymerization method, emulsion polymerization and other production methods. Among them, the suspension polymerization method is preferable in order to obtain a vinyl chloride-based copolymer resin having an average particle diameter in the range of 50 to 300 μm. By such a production method, the vinyl chloride-based copolymer resin in the form of latex or slurry can be obtained, and the method of drying it to obtain the vinyl chloride-based copolymer resin in powder form is not particularly limited, and examples thereof include spraying the latex A method of drying by a drying method, a method of drying by a flow drying method after dehydrating a slurry, a method of drying by a static drying method after dehydrating a slurry, and the like.

In the present invention, a vinyl chloride-based copolymer resin obtained by copolymerizing a vinyl-based monomer and a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer in the main chain is added to the vinyl chloride-based copolymer resin. Used in resins, the monomers constituting the vinyl chloride resin are mainly composed of vinyl chloride monomers, specifically, individual vinyl chloride monomers, or contain greater than or equal to 50% by weight, especially greater than or equal to 70% by weight of vinyl chloride monomer, which can be copolymerized with vinyl chloride monomer, preferably a mixture of monomers with no reactive functional groups on the main chain of the polymerized polymer and vinyl chloride monomer. Monomers that can be copolymerized with vinyl chloride monomers include: vinyl esters such as vinyl acetate and vinyl propionate; α-olefins such as ethylene, propylene, and isobutyl vinyl ether; 1-chloropropene, 2- Chlorinated olefins such as chloroprene; (meth)acrylates such as methyl (meth)acrylate; maleic anhydride, acrylonitrile, styrene, vinylidene chloride, etc. These can be used alone or in combination or multiple combinations.

The method for producing the vinyl chloride resin used in the present invention is not particularly limited. From the viewpoint of ease of polymerization control, polymerization in an aqueous medium is preferred. Such polymerization methods include, for example, suspension polymerization and microsuspension polymerization. , Emulsion polymerization and other manufacturing methods. Among them, it is the same as the vinyl chloride resin used in the molding and processing methods of the usual vinyl chloride resin such as calender molding method, extrusion molding method, injection molding method, blow molding method, press molding method, vacuum molding method, etc., It is preferably produced by suspension polymerization. According to such a production method, the vinyl chloride resin can be obtained in the form of latex or slurry, and the method of drying it to obtain a vinyl chloride resin in powder form is not particularly limited, and examples thereof include spray drying the latex A method of drying, a method of dehydrating the slurry and then drying by a flow drying method, a method of dehydrating the slurry and then drying by a static drying method, and the like.

Wherein, based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component of the polymer consisting of ethylenically unsaturated monomers containing double bonds on the main chain in the vinyl chloride copolymer resin is given by It is calculated by the following calculation formula (2).

Z＝X×Y÷100 (2)

Z: Based on 100 parts by weight of the vinyl chloride resin, the content of the macromonomer component of the polymer consisting of ethylenically unsaturated monomers containing double bonds on the main chain in the vinyl chloride copolymer resin (weight share)

X: In the vinyl chloride-based copolymer resin, the fraction (% by weight) occupied by the macromonomer component having a polymer composed of a double bond-containing ethylenically unsaturated monomer on the main chain

Y: The number of parts (parts by weight) of the vinyl chloride-based copolymer resin to be added relative to 100 parts by weight of the vinyl chloride-based resin

In the vinyl chloride resin composition of the present invention, a vinyl chloride resin, a vinyl monomer and a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer on the main chain The vinyl chloride-based copolymer resin obtained by copolymerization is an essential component, and heat stabilizers, lubricants, stabilizing aids, processing aids, fillers, antioxidants, Light stabilizers, pigments, plasticizers, etc.

The heat stabilizer is not particularly limited, and those within the range not affecting the object of the present invention can be used. Such heat stabilizers include, for example: dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin maleate, dibutyltin maleate polymer, dioctyltin maleate, dioctyltin maleate polymer, Organotin heat stabilizers such as dibutyltin laurate and dibutyltin laurate polymer; lead heat stabilizers such as lead stearate, dibasic lead phosphite, and tribasic lead sulfate; calcium-zinc heat stabilizers ; Barium-zinc heat stabilizer; Cadmium-barium heat stabilizer, etc., these can be used alone, or two or more can be used at the same time. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the lubricant is not particularly limited, and those within the range that does not affect the purpose of the present invention can be used. Such lubricants include, for example: paraffin-based lubricants, polyolefin wax-based lubricants, stearic acid-based lubricants, alcohol-based lubricants, ester-based lubricants, etc., which can be used alone or in combination of two or more use. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention. When used, it is preferably in the range of 3 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the stabilizing assistant is not particularly limited, and those within the range that does not affect the object of the present invention can be used. Such stabilizing aids include, for example: epoxidized soybean oil, epoxidized linseed oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, phosphoric acid ester, etc., which can be used alone, It is also possible to use 2 or more kinds simultaneously. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention. When used, it is preferably in the range of 3 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the processing aid is not particularly limited, and those within the range not affecting the object of the present invention can be used. Such processing aids are, for example: n-butyl acrylate/methyl methacrylate copolymer, 2-ethylhexyl acrylate/methyl methacrylate copolymer, 2-ethylhexyl acrylate/methacrylic acid Acrylic processing aids such as methyl ester/n-butyl methacrylate copolymer and the like may be used alone or in combination of two or more. In addition, the usage amount is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 10 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the filler is not particularly limited, and those within the range that does not affect the purpose of the present invention can be used. Such fillers include, for example, calcium carbonate, magnesium carbonate, lithium carbonate, kaolin, gypsum, mica, talc, magnesium hydroxide, calcium silicate, borax, etc., which can be used alone or in combination of two or more . In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 1000 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the antioxidant is not particularly limited, and those within the range that does not affect the object of the present invention can be used. Such antioxidants include, for example, phenolic antioxidants and the like, and these may be used alone or in combination of two or more. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the photostabilizer is not particularly limited, and those within the range that does not affect the object of the present invention can be used. Such light stabilizers include, for example: ultraviolet absorbers such as salicylates, benzophenones, benzotriazoles, and cyanoacrylates; hindered amine light stabilizers, etc., which can be used alone or Two or more kinds can be used simultaneously. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the pigment is not particularly limited, and those within the range not affecting the purpose of the present invention can be used. Such pigments include, for example, organic pigments such as azo, phthalocyanine, shihlin, and dye lakes; and inorganic pigments such as oxides, molybdenum chromate, sulfide selenide, and ferrocyanide. etc. These may be used alone or in combination of two or more. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention, and it is preferably used in a range of 5 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, the plasticizer is not particularly limited, and those within the range not affecting the object of the present invention can be used. Such plasticizers include, for example: di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dibutyl phthalate and other phthalates. Formate plasticizers; phosphate plasticizers such as tris(cresyl) phosphate, tris(xylyl) phosphate, triphenyl phosphate, etc.; di-2-ethylhexyl adipate, di-sebacate - Fatty acid ester plasticizers such as 2-ethylhexyl ester, etc. These may be used alone or in combination of two or more. In addition, the amount used is not particularly limited as long as it is within the range that does not affect the purpose of the present invention. When used, it is preferably in the range of 100 parts by weight or less with respect to 100 parts by weight of the vinyl chloride resin.

In addition, within the range that does not affect the purpose of the present invention, flame retardants, antistatic agents, reinforcing agents, modifiers, etc. can also be blended without limitation according to needs, and the usage amount is not particularly limited, as long as it does not affect the performance of the present invention. The scope of the purpose of the present invention is enough.

The production method of the vinyl chloride resin composition of the present invention is not particularly limited, and can be produced by the following methods: compounding a set amount of vinyl chloride copolymer resin and vinyl chloride resin, and compounding various additives (thermal heat) as needed. Stabilizers, lubricants, stabilizing aids, processing aids, fillers, antioxidants, light stabilizers, pigments, plasticizers, and flame retardants, antistatic agents, reinforcing agents, modifiers, etc.), Using mixers such as ribbon mixers, super mixers, drum mixers, Banbury mixers, Henschel mixers, mixing rollers, etc. Blending and other conventional methods for uniform mixing or mixing and kneading. The order of compounding at this time and the like are not particularly limited, and any technique within the range that does not affect the purpose of the present invention can be used arbitrarily. For example, the method of mixing vinyl chloride resin, vinyl chloride copolymer resin and various additives at one time can be used; in order to uniformly mix liquid additives, first mix vinyl chloride resin, vinyl chloride copolymer resin and powders and granules. Additives, and then with the method of liquid additives; or first with vinyl chloride resin and vinyl chloride copolymer resin, and then with liquid additives, and finally with various powder additives method; also first with vinyl chloride resin and Various additives, and then the method of blending vinyl chloride-based copolymer resins, etc.

The vinyl chloride-based resin composition of the present invention produced as described above can be directly used in various molding processes, and kneading machines such as co-kneaders, extruders, and pelletizers and/or kneading and pelletizing machines can also be used. After kneading or kneading and granulation, it can be used for various molding processes.

Example

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. Wherein, without special explanation, "part" in the examples means "weight part", and "%" means "weight %".

<Production of macromonomers having polymers composed of ethylenically unsaturated monomers containing double bonds in the main chain>

Production of a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer in its main chain was carried out in accordance with the procedures described in the following production examples.

(Manufacturing example 1)

CuBr (5.54 g) was added to a 2 L separable flask equipped with a reflux tube and a stirrer, and the inside of the reaction container was replaced with nitrogen. Acetonitrile (73.8 ml) was added and stirred in an oil bath at 70°C for 30 minutes. Thereto were added n-butyl acrylate (132 g), methyl 2-bromopropionate (7.2 ml), and pentamethyldiethylenetriamine (4.69 ml) to start a reaction. While heating and stirring at 70° C., n-butyl acrylate (528 g) was continuously added dropwise over 90 minutes, followed by further heating and stirring for 80 minutes.

The reaction mixture was diluted with toluene, passed through an activated alumina column, and then the volatile components were distilled off under reduced pressure to obtain single-terminal Br group poly(n-butyl acrylate).

Methanol (800 ml) was charged into the flask, and cooled to 0°C. Potassium tert-butoxide (130 g) was added thereto in portions. This reaction solution was kept at 0° C., and a methanol solution of acrylic acid (100 g) was dropped. After completion of the dropping, the temperature of the reaction solution was returned from 0°C to room temperature, and then the volatile components of the reaction solution were distilled off under reduced pressure to obtain potassium acrylate (CH ₂ =CHCO ₂ K).

In a 500ml flask with a reflux tube, add the single-end Br-based poly(n-butyl acrylate) (150g), potassium acrylate (7.45g), and dimethylacetamide (150ml) obtained, and heat and stir at 70°C for 3 Hour. Dimethylacetamide was distilled off from the reaction mixture, dissolved in toluene, passed through an activated alumina column, and the toluene was distilled off to obtain a single-end acryloyl poly(n-butyl acrylate) macromonomer.

<Manufacture of vinyl chloride-based copolymer resin obtained by copolymerizing a vinyl-based monomer and a macromonomer having a polymer composed of a double bond-containing ethylenically unsaturated monomer in its main chain>

Production of vinyl chloride-based copolymer resins obtained by copolymerizing vinyl-based monomers and macromonomers having polymers composed of ethylenically unsaturated monomers containing double bonds in the main chain is as described in the following production examples steps to proceed.

(Manufacturing example A) Production of vinyl chloride-based copolymer resin with a fraction of macromonomer component of 3%

After degassing the 25-liter stainless steel polymerization reactor equipped with a jacket and a stirrer, 97 parts of vinyl chloride monomers were charged, and then the single-end acryloyl poly(n-butyl acrylate) macromolecule of Production Example 1 was added. 3 parts of the monomer, and then warm water was passed through the jacket to raise the temperature inside the polymerization reactor to 30° C., and stirred for 5 minutes at a rotation speed of 900 revolutions per minute. Pass water into the jacket to cool the temperature in the polymerization reactor to below 20°C, then add 0.1 part of partially saponified polyvinyl acetate with a degree of saponification of about 80 mol% and an average degree of polymerization of about 2000, and neodecyl peroxide 0.0216 parts of tert-butyl acid, 0.024 parts of bis(3,5,5-trimethylhexanoyl) peroxide, and then 150 parts of warm water at 60°C were added, and polymerized at a polymerization temperature of 66.5°C for about 6 hours. After recovering the unreacted monomer in the polymerizer, the polymerizer is cooled and the slurry is discharged from the tank. The resulting slurry was dehydrated and dried at 55° C. for 24 hours with a hot air drier to obtain a white powder of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin A.

(Production example B) Production of vinyl chloride-based copolymer resin with a fraction of macromonomer component of 5%

In Production Example A, 95 parts of vinyl chloride monomers and 5 parts of single-end acryloyl poly(n-butyl acrylate) macromonomers in Production Example 1 were added, except that the same operation was performed as in Production Example A to obtain vinyl chloride / white powder of poly(n-butyl acrylate) graft copolymer resin B.

(Production example C) Production of vinyl chloride-based copolymer resin with a fraction of macromonomer component of 20%

In Production Example A, 80 parts of vinyl chloride monomer and 20 parts of the single-end acryloyl poly(n-butyl acrylate) macromonomer of Production Example 1 were added, except that the same operation was performed as in Production Example A to obtain vinyl chloride / White powder of poly(n-butyl acrylate) graft copolymer resin C.

(Manufacturing example D) Production of vinyl chloride-based copolymer resin with a fraction of macromonomer component of 50%

In Production Example A, 50 parts of vinyl chloride monomer and 50 parts of the single-end acryloyl poly(n-butyl acrylate) macromonomer of Production Example 1 were added, except that it was performed in the same manner as Production Example A to obtain vinyl chloride / white powder of poly(n-butyl acrylate) graft copolymer resin D.

(Example 1)

Organotin heat stabilizer (TVS#8831: Nitto Kasei Co., Ltd. dioctyltin mercapto) 2 parts, dibasic acid ester lubricant (Loxiol G-60: manufactured by Cognis Japan Co., Ltd.) 0.3 part, montanic acid partially saponified ester lubricant (Wax-OP: manufactured by Hekisto Japan Co., Ltd.) 0.3 2 parts, mixed with a Henschel mixer until the resin temperature reached 110°C, and then cooled to below 50°C, with 2 parts of vinyl chloride/poly(n-butyl acrylate) contact resin obtained in Production Example B per 100 parts of polyvinyl chloride resin. branch copolymerized resin B to obtain a vinyl chloride resin composition, and the composition was made with a HOS-2103 type 8-inch roller (outside diameter of about 20 cm) manufactured by Nippon Roller Manufacturing Co., Ltd. at 20 rpm of the front roller, 18 rpm of the rear roller, and Under the conditions of 180° C. and 5 minutes of rolling, a roll sheet with a thickness of about 1 mm was produced. The obtained roll sheet was divided into two parts, and one part was shredded into about 3 mm squares for evaluation of melt flow characteristics. In addition, the other part is cut into a specified size and dozens of pieces are stacked together, and pressed with a Sindo type SF hydraulic press made by Shinto Metal Industry Co., Ltd. at 185°C and a pressure of 5 MPa for about 10 minutes to produce a thickness of 5mm. The test plate was cut and processed into samples for evaluation of softening temperature, impact strength and tensile strength, which are one of the physical properties of mechanical strength, and used for various measurements.

Among them, the evaluation methods of melt flow properties, softening temperature, impact strength and tensile strength are as follows.

(1) Melt flow characteristics

Based on the thermoplastic resin flow test method specified in JIS K7210 Appendix C, using the Koka flow tester CFT-500C manufactured by Shimadzu Corporation, the test temperature is 180°C, the mold length is 1mm, the mold diameter is 1mm, Under the condition of a test load of 9.8×10 2 N, the flow value of the resin per 1 second (hereinafter abbreviated as the flow value of the Koka formula B method. The unit is ml/s×10 ^-2 ) was obtained and evaluated.

(2) softening temperature

Based on the Vicat softening temperature test method stipulated in JIS K7206, a test piece with a length of 20mm, a width of 20mm, and a thickness of 3mm was used for 88 hours in a constant temperature and humidity room with a room temperature of 23°C and a relative humidity of 50%. Under the conditions of starting temperature 40°C, heating rate 50°C/h, and test load 50N, Vicat softening temperature (hereinafter abbreviated as Vicat softening temperature; unit: °C) was obtained and evaluated.

(3) Impact strength

Based on the Izod impact strength test method stipulated in JIS K7110, the Izod impact strength (hereinafter It is abbreviated as Izod impact strength. The unit is kJ/m ² ) for evaluation. In addition, when measuring at 23 degreeC, the test piece which was left still for 48 hours in the constant temperature and humidity chamber of 23 degreeC of room temperature and 50% of relative humidity was used. In addition, when measuring at 0°C, a test piece that was left still for 48 hours in a constant temperature and humidity chamber at a room temperature of 23°C and a relative humidity of 50% was used, and then immersed in a liquid tank adjusted to 0°C for 5 minutes. The test piece was subjected to a shock within 5 seconds after it was taken out of the liquid tank.

(4) Tensile strength

Based on the tensile test method stipulated in JIS K7162, using a test piece of type 1A that was left in a constant temperature and humidity room with a room temperature of 23°C and a relative humidity of 50% for 48 hours, the test speed at a test speed of 10mm/min was obtained. , and the tensile strength at 23° C. (hereinafter referred to as σy; the unit is MPa) were evaluated.

The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 2)

In embodiment 1, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in the manufacture example B, but every 100 parts of polyvinyl chloride resin is coordinated with 10 parts of the vinyl chloride/poly(n-butyl acrylate) obtained in the manufacture example A Poly(n-butyl acrylate) graft copolymer resin A was performed in the same manner as in Example 1 except that to obtain a vinyl chloride-based resin composition, which was subjected to roll/press processing in the same manner as in Example 1, and the evaluation was improved. Formula B flow value, Vicat softening temperature, Izod impact strength and σy. The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.3 parts.

(Example 3)

In embodiment 1, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example B, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in 0.5 parts of the polyvinyl chloride resin was coordinated with the manufacture example C. Poly(n-butyl acrylate) graft copolymer resin C was performed in the same manner as in Example 1 to obtain a vinyl chloride-based resin composition, and the composition was subjected to roll/press processing in the same manner as in Example 1, and the evaluation was improved. Formula B flow value, Vicat softening temperature, Izod impact strength and σy. The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 4)

In embodiment 3, every 100 parts of polyvinyl chloride resin coordinates 5 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin C, operate in the same way as embodiment 3 except that, obtain vinyl chloride resin composition , The composition was subjected to roll/press processing in the same manner as in Example 3, and the flow value of the Gaohua formula B method, Vicat softening temperature, Izod impact strength and σy were evaluated. The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1 part.

(Example 5)

In embodiment 1, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example B, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in 0.2 parts of the manufacture example D is coordinated with 0.2 parts of polyvinyl chloride resin. Poly(n-butyl acrylate) graft copolymer resin D was performed in the same manner as in Example 1 to obtain a vinyl chloride-based resin composition, and the composition was subjected to roll/press processing in the same manner as in Example 1, and the evaluation was improved. Formula B flow value, Vicat softening temperature, Izod impact strength and σy. The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 6)

In embodiment 5, every 100 parts of polyvinyl chloride resin coordinates 10 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin D, in addition, operate in the same way as embodiment 5, obtain vinyl chloride resin composition , The composition was subjected to roll/press processing in the same manner as in Example 5, and the flow value of the Gaohua formula B method, Vicat softening temperature, Izod impact strength and σy were evaluated. The results are shown in Table 1.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 5 parts.

(comparative example 1)

In Example 1, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Production Example B was not mixed, and the same operation as Example 1 was performed except that to obtain a vinyl chloride-based resin composition. The composition was subjected to roll/press processing in the same manner as in Example 1, and the flow value, Vicat softening temperature, Izod impact strength, and σy of the Koka formula B method were evaluated. The results are shown in Table 1. The flow value of Gaohua formula B method, Izod impact strength and σy are all lower than those of Examples 1-6, which is not preferable.

(comparative example 2)

In Comparative Example 1, 10 parts of di-2-ethylhexyl phthalate (product name DOP, manufactured by Jiei Plus Co., Ltd., hereinafter abbreviated as DOP) was further blended as a plasticizer, and in addition, it was mixed with In the same manner as Comparative Example 1, a vinyl chloride-based resin composition was obtained, and the composition was subjected to roll/press processing in the same manner as in Comparative Example 1, and the flow value, Vicat softening temperature, Izod impact strength, and σy of the Koka formula B method were evaluated. The results are shown in Table 1. Vicat softening temperature, Izod impact strength, and σy are all lower than Comparative Example 1, which is not preferable.

(comparative example 3)

In Comparative Example 1, 2 parts of a methyl methacrylate-based processing aid (Metaburen P-551A: manufactured by Mitsubishi Rayon Co., Ltd.) was further mixed, and the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 1. The composition was subjected to roll/press processing in the same manner as in Comparative Example 1, and the flow value, Vicat softening temperature, Izod impact strength, and σy were evaluated by the high-efficiency formula B method. The results are shown in Table 1. Vicat softening temperature, Izod impact strength, and σy are all lower than Comparative Example 1, which is not preferable.

(comparative example 4)

In Comparative Example 1, 3 parts of an impact reinforcing agent (Metabolen C-323A: manufactured by Mitsubishi Rayon Co., Ltd., MBS resin) was further blended, and the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 1. This composition was subjected to roll/press processing in the same manner as in Comparative Example 1, and the flow value, Vicat softening temperature, Izod impact strength, and σy of the Koka formula B method were evaluated. The results are shown in Table 1. The flow value of Gaohua formula B method, Vicat softening temperature and σy are all lower than those of Comparative Example 1, and the improvement effect is not sufficient.

(comparative example 5)

In Example 2, every 100 parts of polyvinyl chloride resin is combined with 1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin A obtained in Manufacturing Example A, except that it is operated in the same way as in Example 1 to obtain For the vinyl chloride resin composition, the composition was subjected to roll/press processing in the same manner as in Example 1, and the flow value of the high-grade formula B method, Vicat softening temperature, Izod impact strength, and σy were evaluated. The results are shown in Table 1. The characteristic values evaluated were all below Comparative Example 1, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.03 parts.

(comparative example 6)

In Comparative Example 5, every 100 parts of polyvinyl chloride resin is combined with 20 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D obtained in Manufacturing Example D, except that it is operated in the same way as in Example 5 to obtain For the vinyl chloride resin composition, the composition was subjected to roll/press processing in the same manner as in Example 5, and the flow value of the high-grade formula B method, Vicat softening temperature, Izod impact strength, and σy were evaluated. The results are shown in Table 1. Vicat softening temperature, Izod impact strength, and σy are all lower than Comparative Example 1, which is not preferable.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 10 parts.

Table 1 Macromonomer component accounts for the fraction (weight %) of whole vinyl chloride copolymer resin: X The number of added parts (parts by weight) per 100 parts by weight of vinyl chloride-based resin vinyl chloride-based copolymer resin: Y Content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight): Z ^*1) Types and parts of additives other than vinyl chloride resins, vinyl chloride copolymer resins, heat stabilizers, and lubricants Flow value of Gaohua formula B method ml/s×10 ^-2 Vicat softening temperature (℃) Izod impact strength (kJ/m ² ) σy (MPa) 0°C 23°C Example 1 5 2 0.1 none 2.5 80.2 3.3 6.3 48.2 2 3 10 0.3 none 3.3 80.0 3.5 6.8 49.3 3 20 0.5 0.1 none 2.8 80.2 3.2 6.0 47.8 4 20 5 1 none 4.0 79.8 3.8 7.3 49.7 5 50 0.2 0.1 none 3.0 80.2 3.2 6.0 48.0 6 50 10 5 none 5.4 79.2 4.0 7.5 50.1 comparative example 1 - 0 0 none 0.6 80.0 3.0 4.7 46.0 2 - 0 0 D0P 10 parts by weight 7.6 66.2 3.5 5.0 38.9 3 - 0 0 Processing aid ^*2) 2 parts by weight 1.0 80.2 2.5 3.8 41.8 4 - 0 0 3 parts by weight of MBS resin 0.7 80.5 7.5 9.8 43.5 5 3 1 0.03 none 0.6 78.0 2.9 4.6 45.9 6 50 20 10 none 10.2 73.6 3.0 3.7 42.3

*1) Value calculated from the following formula when vinyl chloride/poly(n-butyl acrylate) graft copolymer resin is added to polyvinyl chloride resin and used.

Z＝X×Y÷100

Z: content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight)

X: Macromonomer component accounted for the fraction of the whole vinyl chloride copolymer resin (weight %)

Y: The number of parts (parts by weight) of the vinyl chloride-based copolymer resin to be added relative to 100 parts by weight of the vinyl chloride-based resin

*2) Processing aid: Methyl methacrylate processing aid

(Example 7)

Organotin heat stabilizer (T-17MOK: manufactured by Kyodo Pharmaceutical Co., Ltd. , mercaptooctyltin) 1.2 parts, polymer complex ester lubricant (Loxiol G-74: manufactured by Cognis Japan Co., Ltd.) 1.6 parts, polyol ester lubricant (Loxiol G-16: manufactured by Cognis Japan Co., Ltd.) 0.9 parts, 10 parts of impact reinforcing agent (カネエ一ス B-51: manufactured by Kaneka Co., Ltd., methyl methacrylate-butadiene-styrene copolymer, hereinafter abbreviated as MBS resin), mixed with a Henschel mixer until the resin The temperature was set to 110°C, and then cooled to below 50°C, and 2 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Production Example B was mixed with 100 parts of polyvinyl chloride resin to obtain a vinyl chloride-based resin composition As a material, the composition was made with a HOS-2103 type 8-inch roll (about 20 cm in outer diameter) manufactured by Nippon Roull Manufacturing Co., Ltd., under the conditions of 15 rpm of the front roll, 16 rpm of the rear roll, 180° C., and 3 minutes of roll. Become a roll sheet with a thickness of about 1.0mm and a width of 30cm. This roll sheet was visually observed, and pitting was evaluated on a 5-point scale based on the following criteria.

5: No pits can be seen at all

4: Almost no pits can be seen

3: Pockets can be seen, but practically no problem

2: Pockets are generated, which is a practical problem

1: The occurrence of pitting is obvious, and the surface of the sheet is poor

The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

In addition, an organotin heat stabilizer (MARK 17M: manufactured by Crompton Co., Ltd. , mercaptooctyltin) 1 part, special ester lubricant (Loxiol G-70S: manufactured by Cognis Japan Co., Ltd.) 0.3 parts, polyol ester lubricant (Loxiol G-16: manufactured by Cognis Japan Co., Ltd.) 0.4 parts, impact-reinforced 6 parts of resin (Kaneeichisu B-521: manufactured by Kaneka Co., Ltd., MBS resin), mixed with a Henschel mixer until the temperature of the resin reached 110°C, then cooled to below 50°C, mixed with 100 parts of polyvinyl chloride resin 2 parts of vinyl chloride/poly(n-butyl acrylate) graft-copolymerized resin B obtained in Production Example B to obtain a vinyl chloride-based resin composition, the composition was manufactured with Nippon Roull Manufacturing Co., Ltd. HOS-2103 type 8 An inch roll (about 20 cm in outer diameter) was made into a roll sheet with a thickness of about 0.5 mm and a width of 35 cm under the conditions of front roll 17 rpm, rear roll 16 rpm, 200° C., and 3-minute roll. This roll sheet was visually observed, and waviness was evaluated on a 5-point scale according to the following criteria.

5: No ripples can be seen at all

4: Almost no ripples can be seen

3: Ripples can be seen, but practically no problem

2: Corrugation is generated, and there are practical problems

1: The generation of ripples is obvious, and the surface of the sheet is poor

The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Embodiment 8)

In embodiment 7, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example B, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in 0.5 parts of the polyvinyl chloride resin was mixed with the manufacture example C. Poly(n-butyl acrylate) graft copolymer resin C was performed in the same manner as in Example 7 to obtain a vinyl chloride-based resin composition, and the composition was rolled in the same manner as in Example 7 to evaluate pitting and waviness. . The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 9)

In embodiment 8, every 100 parts of polyvinyl chloride resin coordinates 5 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin C, in addition, operate in the same way as embodiment 8, obtain vinyl chloride resin composition , The composition was rolled in the same manner as in Example 8, and the pitting and waviness were evaluated. The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1 part.

(Example 10)

In embodiment 7, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example B, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example D is mixed with 0.2 parts per 100 parts of polyvinyl chloride resin. Poly(n-butyl acrylate) graft copolymer resin D was performed in the same manner as in Example 7 to obtain a vinyl chloride-based resin composition, and the composition was rolled in the same manner as in Example 7 to evaluate pitting and waviness. . The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 11)

In Example 10, every 100 parts of polyvinyl chloride resin is coordinated with 10 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D, except that it is operated in the same way as in Example 10 to obtain a vinyl chloride resin composition , The composition was rolled in the same manner as in Example 10, and pitting and waviness were evaluated. The results are shown in Table 2.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 5 parts.

(comparative example 7)

In Example 7, the vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in Production Example B was not mixed, except that it was operated in the same manner as in Example 7 to obtain a vinyl chloride-based resin composition. This composition was rolled in the same manner as in Example 1, and pitting and waviness were evaluated. The results are shown in Table 2. Pockets and ripples are worse than those of Examples 7-11, which is not preferable.

(comparative example 8)

In Comparative Example 7, 2 parts of a methyl methacrylate-based processing aid (Metaburen P-551A: manufactured by Mitsubishi Rayon Co., Ltd.) was further mixed, and the vinyl chloride-based resin combination was obtained in the same manner as in Comparative Example 7. The composition was rolled in the same manner as in Comparative Example 7, and pitting and waviness were evaluated. The results are shown in Table 2. Moiré was inferior to Examples 7 to 11, and the improvement effect was insufficient.

(comparative example 9)

In Comparative Example 7, 10 parts of di-2-ethylhexyl phthalate (product name DOP, manufactured by Jiei Plus Co., Ltd., hereinafter abbreviated as DOP) was further blended as a plasticizer, and in addition, it was mixed with A vinyl chloride resin composition was obtained in the same manner as in Comparative Example 7, and this composition was rolled in the same manner as in Comparative Example 7 to evaluate pitting and waviness. The results are shown in Table 2. Moiré was inferior to Examples 7 to 11, and the improvement effect was insufficient.

(comparative example 10)

In Example 7, every 100 parts of polyvinyl chloride resin is combined with 1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in Manufacturing Example B, except that it is operated in the same way as in Example 7 to obtain A vinyl chloride resin composition was rolled in the same manner as in Example 7, and pitting and waviness were evaluated. The results are shown in Table 2. The pitting was worse than that of Examples 7 to 11, and the improvement effect was not sufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.05 parts.

(comparative example 11)

In Example 8, every 100 parts of polyvinyl chloride resin is mixed with 0.1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin C obtained in Manufacturing Example C, except that it is operated in the same way as in Example 8 to obtain A vinyl chloride resin composition was rolled in the same manner as in Example 2, and pitting and waviness were evaluated. The results are shown in Table 2. Pockets and ripples are worse than those of Examples 7-11, which is not preferable.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.02 parts.

(comparative example 12)

In Example 8, every 100 parts of polyvinyl chloride resin is mixed with 30 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin C obtained in Manufacturing Example C, except that it is operated in the same way as in Example 8 to obtain A vinyl chloride resin composition was rolled in the same manner as in Example 8, and pitting and waviness were evaluated. The results are shown in Table 2. Pockets and ripples are worse than those of Examples 7-11, which is not preferable.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 6 parts.

(comparative example 13)

In Example 10, every 100 parts of polyvinyl chloride resin is mixed with 0.1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D obtained in Manufacturing Example D, except that it is operated in the same manner as in Example 10 to obtain A vinyl chloride resin composition was rolled in the same manner as in Example 10, and pitting and waviness were evaluated. The results are shown in Table 2. Moiré was inferior to Examples 7 to 11, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.05 parts.

(comparative example 14)

In Example 10, every 100 parts of polyvinyl chloride resin is combined with 20 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin D obtained in Manufacturing Example D, except that it is operated in the same way as in Example 10 to obtain A vinyl chloride resin composition was rolled in the same manner as in Example 10, and pitting and waviness were evaluated. The results are shown in Table 2. Pockets and waviness are worse than those of Examples 7-11, which is not preferable.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 10 parts.

Table 2 Macromonomer component accounts for the fraction (weight %) of whole vinyl chloride copolymer resin: X The number of parts used (parts by weight) of vinyl chloride copolymer resin: Y Content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight): Z ^*1) Addition of processing aids (parts by weight) ^*2) Number of plasticizers added (parts by weight) ^*3) Ma Kong ^*4) Ripple ^*4) Example 7 5 2 0.1 0 0 5 4 8 20 0.5 0.1 0 0 5 5 9 20 5 1 0 0 4 5 10 50 0.2 0.1 0 0 5 5 11 50 10 5 0 0 3 3 comparative example 7 - 0 0 0 0 1 1 8 - 0 0 2 0 4 2 9 - 0 0 0 10 3 2 10 5 1 0.05 0 0 2 3 11 20 0.1 0.02 0 0 2 2 12 20 30 6 0 0 2 1 13 50 0.1 0.05 0 0 3 2 14 50 20 10 0 0 2 1

*1) Value calculated from the following formula when vinyl chloride/poly(n-butyl acrylate) graft copolymer resin is added to polyvinyl chloride resin and used.

Z=X×Y÷100 where Z: the content of macromonomer components based on 100 parts by weight of vinyl chloride resin (parts by weight)

            X: The fraction of macromonomer components in all vinyl chloride-based copolymer resins (weight %)

           Y: The number of added parts (parts by weight) of vinyl chloride-based copolymer resin relative to 100 parts by weight of vinyl chloride-based resin

*2) Processing aid: Methyl methacrylate processing aid

*3) Plasticizer: DOP

*4) Judgment criteria for pitting and waviness

Pocket 5: no pockmarks at all Corrugation 5: no ripples at all

4: Almost no pockmarks 4: Almost no ripples

3: Pockets can be seen, but there is no problem in practice 3: Ripples can be seen, but there is no problem in practice

2: Pockets are produced, there are practical problems 2: Ripples are produced, there are practical problems

1: Pockets are obvious, and the surface of the sheet is poor 1: Ripples are obvious, and the surface of the sheet is poor

(Example 12)

Organotin heat stabilizer (TVS#8831: Nitto Kasei Co., Ltd. dioctyltin mercapto) 2.0 parts, 0.2 parts of oxidized polyethylene lubricant (ACPE629A: manufactured by Allied Chemical Co., Ltd.), 0.5 parts of dibasic ester lubricant (Loxiol G-60: manufactured by Cognis Japan Co., Ltd.) Mix in a Henschel mixer until the resin temperature reaches 110°C, then cool to below 50°C, mix 2 parts of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin obtained in Production Example B per 100 parts of polyvinyl chloride resin B, obtaining a vinyl chloride resin composition. This composition was supplied to a single-screw extruder (VS50m/m extruder FH50-239 manufactured by Tanabe Plastics Co., Ltd.), and a granulator (Isuzu Kakiki Co., Ltd. manufactured plastic processing machine SCF- 100) Perform granulation. The pellets were supplied to an injection molding machine (AUTOSHOT T Series 75D manufactured by FANUC Corporation), and the spiral flow was evaluated. The results are shown in Table 3. The longer the spiral flow length, the better the flowability during molding.

Then, a rectangular sample for evaluation of impact strength (Izod impact strength) and a dumbbell-shaped sample for evaluation of tensile strength (σy) were molded by the same injection molding machine and provided for evaluation. The results are shown in Table 3.

It should be noted that various conditions for granulation, evaluation of spiral flow, and molding of rectangular and dumbbell-shaped samples were set as follows.

<Pelleting conditions>

Screw speed: 30rpm

Cylinder temperature

Barrel-1: 150°C

Barrel-2: 170°C

Barrel-3: 180°C

Note: The serial number of the barrel is numbered in the order of 1, 2, 3 from the raw material supply side (hopper side) to the extrusion direction, that is, to the front end of the screw.

Head mold temperature

Mold 1: 190°C

Mold 2: 190°C

Note: The serial number of the mold is numbered in the order of 1 and 2 from the front end of the screw to the extrusion direction.

<Evaluation of Spiral Flow>

Injection unit temperature

Unit 1: 170°C

Unit 2: 180°C

Unit 3: 190°C

Note: The unit serial number is numbered in the order of 1, 2, 3 from the raw material supply side (hopper side) to the extrusion direction, that is, to the front end of the screw.

Nozzle temperature: 190°C

Mold temperature: 40°C

Injection speed: 50mm/s

Holding pressure: 1300kg/cm ²

Pressure holding time: 3sec

Injection and holding pressure switching position: 2mm

Maximum injection pressure: 1300kg/cm ²

Maximum injection time: 3sec

Maximum packing speed: 5mm/s

Back pressure: 100kg/ ^cm2

Screw revolution: 50rpm

Cooling time: 20sec

<Forming of rectangular and dumbbell-shaped samples>

Injection unit temperature

Unit 1: 170°C

Unit 2: 180°C

Unit 3: 190°C

Note: The unit serial number is numbered in the order of 1, 2, 3 from the raw material supply side (hopper side) to the extrusion direction, that is, to the front end of the screw.

Nozzle temperature: 190°C

Mold temperature: 40°C

Injection speed: 20mm/s

Holding pressure: 800kg/cm ²

Pressure holding time: 5sec

Injection and holding pressure switching position: 5mm

Maximum injection pressure: 1500kg/cm ²

Maximum injection time: 5sec

Maximum packing speed: 5mm/s

Back pressure: 100kg/ ^cm2

Screw revolution: 50rpm

Cooling time: 20sec

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 13)

In embodiment 12, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in the manufacture example B, every 100 parts of polyvinyl chloride resin is coordinated with 0.5 parts of the vinyl chloride/poly(n-butyl acrylate) obtained in the manufacture example C n-butyl acrylate) graft copolymerization resin C, in addition to the same operation as in Example 12, to obtain a vinyl chloride resin composition, the composition is used in the same manner as in Example 12 to evaluate the helical flow length, Izod Impact strength and σy. The results are shown in Table 3.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 14)

In embodiment 13, every 100 parts of polyvinyl chloride resin coordinates 5 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin C, in addition, operate in the same way as embodiment 13, obtain vinyl chloride resin composition , the composition was evaluated in the same manner as in Example 13 for the spiral flow length, Izod impact strength, and σy. The results are shown in Table 3.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1 part.

(Example 15)

In Example 12, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example B, 0.2 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example D was coordinated with 0.2 parts per 100 parts of polyvinyl chloride resin. Poly(n-butyl acrylate) graft copolymer resin D, except that it was performed in the same manner as in Example 12 to obtain a vinyl chloride-based resin composition, and the helical flow length of the composition was evaluated in the same manner as in Example 12. , Izod impact strength and σy. The results are shown in Table 3.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 16)

In Example 15, every 100 parts of polyvinyl chloride resin is coordinated with 2 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D, except that it is operated in the same way as in Example 15 to obtain a vinyl chloride resin composition , the composition was evaluated in the same manner as in Example 15 for the helical flow length, Izod impact strength, and σy. The results are shown in Table 3.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1 part.

(comparative example 15)

In Example 12, the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Production Example B was not mixed, and the same procedure as Example 12 was performed except that the vinyl chloride-based resin composition was obtained. For this composition, the spiral flow length, Izod impact strength and σy were evaluated in the same manner as in Example 12. The results are shown in Table 3. The values of spiral flow length, Izod impact strength, and σy were all lower than those of Examples 12 to 16, which was not preferable.

(Comparative Example 16)

In Comparative Example 15, 3 parts of an impact reinforcing agent (Metabolen C-323A: manufactured by Mitsubishi Rayon Co., Ltd., MBS resin) was further blended, and the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 15. For this composition, the spiral flow length, Izod impact strength, and σy were evaluated in the same manner as in Comparative Example 15. The results are shown in Table 3. Both the spiral flow length and the values of σy were lower than those of Examples 12 to 16, and the improvement effect was insufficient.

(Comparative Example 17)

In Comparative Example 16, except that 3 parts of CPE (Daisorak H-135, manufactured by Daiso Co., Ltd., Daisorak H-135) was blended instead of the impact reinforcing agent, the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 16. In the same manner as in Comparative Example 16, the helical flow length, Izod impact strength, and σy were evaluated. The results are shown in Table 3. Both the spiral flow length and the values of σy were lower than those of Examples 12 to 16, and the improvement effect was insufficient.

(Comparative Example 18)

In Comparative Example 16, instead of the impact reinforcing agent, 5 parts of di-2-ethylhexyl phthalate (product name DOP, manufactured by JEY PLAS CO., LTD., hereinafter abbreviated as DOP) as a plasticizer were blended, except Other than that, the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 16, and the helical flow length, Izod impact strength, and σy of this composition were evaluated in the same manner as in Comparative Example 16. The results are shown in Table 1. Both the Izod impact strength and the value of σy were lower than those of Examples 12 to 16, and the improvement effect was insufficient.

(Comparative Example 19)

In Comparative Example 16, 1 part of a methyl methacrylate processing aid (Metaburen P-551A: manufactured by Mitsubishi Rayon Co., Ltd.) was blended instead of the impact reinforcing agent, and the chlorine was obtained in the same manner as in Comparative Example 16. For the vinyl resin composition, the helical flow length, Izod impact strength, and σy of this composition were evaluated in the same manner as in Comparative Example 16. The results are shown in Table 3. Both the spiral flow length and the values of σy were lower than those of Examples 12 to 16, and the improvement effect was insufficient.

(comparative example 20)

In Example 12, every 100 parts of polyvinyl chloride resin is mixed with 1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in Manufacturing Example B, except that it is operated in the same way as in Example 12 to obtain For the vinyl chloride resin composition, the helical flow length, Izod impact strength and σy of this composition were evaluated in the same manner as in Example 12. The results are shown in Table 3. The values of spiral flow length, Izod impact strength, and σy were all lower than those of Examples 12 to 16, and approximately equal to those of Comparative Example 15, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.05 parts.

(comparative example 21)

In Example 15, every 100 parts of polyvinyl chloride resin is combined with 3 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin D obtained in Manufacturing Example D, except that it is operated in the same way as in Example 15 to obtain For the vinyl chloride resin composition, the helical flow length, Izod impact strength and σy of this composition were evaluated in the same manner as in Example 15. The results are shown in Table 3. Both the Izod impact strength and the value of σy were lower than those of Examples 12 to 16, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1.5 parts.

table 3 Macromonomer component accounts for the fraction (weight %) of whole vinyl chloride copolymer resin: X The number of added parts (parts by weight) of the vinyl chloride-based copolymer resin relative to 100 parts by weight of the vinyl chloride-based resin: Y Content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight): Z ^*1) Types and parts of additives other than vinyl chloride resins, vinyl chloride copolymer resins, heat stabilizers, and lubricants Spiral flow length (mm) Izod impact strength (kJ/m ² ) σy (MPa) Example 12 5 2 0.1 none 435 3.3 50.7 13 20 0.5 0.1 none 430 3.2 50.8 14 20 5 1 none 460 3.4 51.3 15 50 0.2 0.1 none 425 3.3 51.0 16 50 2 1 none 455 3.5 50.9 comparative example 15 - 0 0 none 400 3.1 50.6 16 - 0 0 3 parts by weight of MBS resin 385 5.0 47.8 17 - 0 0 CPE 3 parts by weight 415 3.1 48.1 18 - 0 0 DOP 5 parts by weight 425 2.7 40.0 19 - 0 0 Processing aid ^*2) 1 part by weight 415 3.3 46.0 20 5 1 0.05 none 400 3.2 50.0 twenty one 50 3 1.5 none 470 2.5 45.2

*1) Value calculated from the following formula when vinyl chloride/poly(n-butyl acrylate) graft copolymer resin is added to polyvinyl chloride resin and used.

Z=X×Y÷100 where Z: the content of macromonomer components based on 100 parts by weight of vinyl chloride resin (parts by weight)

            X: The fraction of macromonomer components in all vinyl chloride-based copolymer resins (weight %)

           Y: The number of added parts (parts by weight) of vinyl chloride-based copolymer resin relative to 100 parts by weight of vinyl chloride-based resin

*2) Processing aid: Methyl methacrylate processing aid

(Example 17)

With respect to 100 parts of polyvinyl chloride resin (Kanebinyl S1001: manufactured by Kaneka Co., Ltd., vinyl chloride homopolymer resin, K value 68), an organotin heat stabilizer (TM694: manufactured by Katsuta Chemical Co., Ltd., 1.0 parts of mercaptomethyltin), 0.5 parts of special fatty acid ester lubricant (Rikesta SL-02: manufactured by Riken Bitumin Co., Ltd.), 0.3 parts of polyethylene lubricant (Hiwax 220MP: manufactured by Mitsui Chemicals Co., Ltd.), paraffin Lubricant (H-155: manufactured by Nippon Seimei Co., Ltd.) 0.2 parts, filler (Bai Yanhua CCR: manufactured by Shiraishi Industry Co., Ltd., calcium carbonate) 3.0 parts, mixed with a Henschel mixer until the resin temperature reached 110°C, and then After cooling to below 50°C, 2 parts of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Production Example B was mixed with 100 parts of polyvinyl chloride resin to obtain a vinyl chloride resin composition. This composition was supplied to a Conical extruder (manufactured by Toshiba Corporation, TEC/55DV), and molded into a Φ75 tube (inner diameter: 75 mm, wall thickness: 5 mm). Test pieces were cut out from the obtained tubes, and impact strength (Izod impact strength) and fracture toughness strength (slope value) were evaluated. The results are shown in Table 4.

In addition, the measuring method of fracture toughness intensity|strength is as follows. That is, according to "Fracture Characterization of Tough Polymers Using the J Method" described in "Polymer Eng. and Sci." 26, 760 (1986) by S. Hashemi and J. G. Williams, the apparent Jc and slope values were obtained and evaluated.

That is, the length Δa of the crack is obtained from the thickness of the sample and the area of the crack. At this time, the energy (kJ/m ² ) applied to the crack is plotted against Δa to obtain a straight line. The value of this straight line at Δa=0 is called the apparent Jc value, which represents the energy required for the initiation of new crack formation. In addition, the slope (slope value) of this straight line represents the energy required to propel a crack, and is a value reflecting fracture toughness. In this example, the fracture toughness strength was evaluated particularly by the slope value. The larger the slope value becomes, the greater the energy required to propel the crack, and thus, the larger the slope value, the higher the fracture toughness strength.

In addition, various conditions at the time of tube molding were set as follows.

Screw revolution: 15rpm

Feeder rotation speed: 10rpm

Cylinder temperature

Barrel-1: 180°C

Barrel-2: 180°C

Barrel-3: 175°C

Barrel-4: 175°C

Note: The serial number of the barrel is numbered in the order of 1, 2, 3, 4 from the raw material supply side (hopper side) to the extrusion direction, that is, to the front end of the screw.

Head mold temperature

Mold 1: 170°C

Mold 2: 180°C

Mold 3: 185°C

Mold 4: 195°C

Mold 5: 200°C

Note: The serial number of the mold is numbered in the order of 1, 2, 3, 4, 5 from the front end of the screw to the extrusion direction.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 18)

In Example 17, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example B, 0.5 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example C was coordinated with 0.5 parts per 100 parts of polyvinyl chloride resin. Poly(n-butyl acrylate) graft copolymer resin C was performed in the same manner as in Example 17 to obtain a vinyl chloride-based resin composition. The composition was molded and cut in the same manner as in Example 17, and the Izod impact strength was evaluated. and slope value. The results are shown in Table 4.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 19)

In Example 18, every 100 parts of polyvinyl chloride resin is coordinated with 5 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin C, except that it is operated in the same way as in Example 18 to obtain a vinyl chloride resin composition , The composition was molded and cut in the same manner as in Example 18, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 1 part.

(Example 20)

In Example 17, instead of the vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example B, 0.2 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin B obtained in Manufacturing Example D was mixed with 0.2 parts per 100 parts of polyvinyl chloride resin Poly(n-butyl acrylate) graft copolymer resin D was performed in the same manner as in Example 17 to obtain a vinyl chloride-based resin composition. The composition was molded and cut in the same manner as in Example 17, and the Izod impact strength was evaluated. and slope value. The results are shown in Table 4.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.1 part.

(Example 21)

In Example 20, every 100 parts of polyvinyl chloride resin is coordinated with 10 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D, except that it is operated in the same way as in Example 20 to obtain a vinyl chloride resin composition , The composition was molded and cut in the same manner as in Example 20, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 5 parts.

(comparative example 22)

In Example 17, the vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in Production Example B was not mixed, and the same operation was performed as in Example 17 to obtain a vinyl chloride-based resin composition. This composition was molded and cut in the same manner as in Example 17, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, which was not preferable.

(comparative example 23)

In Comparative Example 22, 3 parts of an impact-reinforcing agent (Metabolen C-323A: manufactured by Mitsubishi Rayon Co., Ltd., MBS resin) was further blended, and a vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 22. This composition was molded and cut in the same manner as in Comparative Example 22, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. The slope value was lower than that of Examples 17 to 21, and the improvement effect was insufficient.

(comparative example 24)

In Comparative Example 23, except that 6 parts of an impact reinforcing agent was mixed, the vinyl chloride-based resin composition was obtained in the same manner as in Comparative Example 23, and the composition was molded and cut in the same manner as in Comparative Example 23, and the Izod impact strength was evaluated. and slope value. The results are shown in Table 4. The slope value was lower than that of Examples 17 to 21, and the improvement effect was insufficient.

(comparative example 25)

In Example 17, every 100 parts of polyvinyl chloride resin is combined with 1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin B obtained in Manufacturing Example B, except that it is operated in the same way as in Example 17 to obtain The vinyl chloride resin composition was molded and cut in the same manner as in Example 17, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.05 parts.

(comparative example 26)

In Example 18, every 100 parts of polyvinyl chloride resin is mixed with 0.1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin C obtained in Manufacturing Example C, except that it is operated in the same way as in Example 18 to obtain The vinyl chloride resin composition was molded and cut in the same manner as in Example 18, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.02 parts.

(comparative example 27)

In Example 18, every 100 parts of polyvinyl chloride resin is combined with 30 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin C obtained in Manufacturing Example C, except that it is operated in the same way as in Example 18 to obtain The vinyl chloride resin composition was molded and cut in the same manner as in Example 18, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 6 parts.

(comparative example 28)

In Example 20, every 100 parts of polyvinyl chloride resin is blended with 0.1 part of vinyl chloride/poly(n-butyl acrylate) graft copolymer resin D obtained in Manufacturing Example D, except that it is operated in the same manner as in Example 20 to obtain A vinyl chloride resin composition was molded and cut in the same manner as in Example 20, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 0.05 parts.

(comparative example 29)

In Example 20, every 100 parts of polyvinyl chloride resin is mixed with 20 parts of vinyl chloride/poly(n-butyl acrylate) graft copolymerization resin D obtained in Manufacturing Example D, except that it is operated in the same way as in Example 20 to obtain A vinyl chloride resin composition was molded and cut in the same manner as in Example 20, and the Izod impact strength and slope value were evaluated. The results are shown in Table 4. Both the Izod impact strength and the slope value were lower than those of Examples 17 to 21, and the improvement effect was insufficient.

It should be noted that the composition is based on 100 parts of polyvinyl chloride resin, and the content of poly(n-butyl acrylate) macromonomer component is 10 parts.

Table 4 Macromonomer component accounts for the fraction (weight %) of whole vinyl chloride copolymer resin: X The number of added parts (parts by weight) of the vinyl chloride-based copolymer resin relative to 100 parts by weight of the vinyl chloride-based resin: Y Content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight): Z ^*1) The number of added parts of impact reinforcing agent (parts by weight) ^*2) Izod impact strength (kJ/m ² ) slope value 0°C 23°C Example 17 5 2 0.1 0 6.8 10.8 28.8 18 20 0.5 0.1 0 6.5 10.3 26.7 19 20 5 1 0 7.3 11.1 30.5 20 50 0.2 0..1 0 6.0 9.7 25.0 twenty one 50 10 5 0 5.9 9.2 33.8 comparative example twenty two - 0 0 0 3.0 3.7 18.8 twenty three - 0 0 3 7.5 9.2 20.3 twenty four - 0 0 6 10.5 13.7 21.9 25 5 1 0.05 0 3.3 4.0 19.8 26 20 0.1 0.02 0 3.0 3.8 19.0 27 20 30 6 0 3.7 6.6 21.8 28 50 0.1 0.05 0 3.1 3.5 19.3 29 50 20 10 0 4.0 7.5 22.2

*1) Value calculated from the following formula when vinyl chloride/poly(n-butyl acrylate) graft copolymer resin is added to polyvinyl chloride resin and used.

Z＝X×Y÷100

Z: content of macromonomer component based on 100 parts by weight of vinyl chloride resin (parts by weight)

X: Macromonomer component accounted for the fraction of the whole vinyl chloride copolymer resin (weight %)

Y: The number of parts (parts by weight) of the vinyl chloride-based copolymer resin to be added relative to 100 parts by weight of the vinyl chloride-based resin

*2) Impact enhancer: MBS resin

The vinyl chloride resin composition of the present invention can be molded and processed into rolled products such as foam packaging products, leather products, agricultural films, shrink films, and various sheets; laminated films on base materials such as vinyl chloride steel plates; laminated sheets Sheets for lamination; joints, valves and other injection moldings; pipes, flat plates, corrugated boards, films, tapes, sheets, foam boards or sheets, window frames, other special-shaped contours and other extrusion moldings; bottles, conduits Blow-molded products such as rubber sleeves and corrugated pipes; various products such as vacuum-formed products such as toys, billboards, masks, and pressed bottom plates.

Claims (7)

1. A vinyl chloride resin composition, characterized in that a vinyl chloride copolymer resin is added to the vinyl chloride resin, and the vinyl chloride copolymer resin is obtained by copolymerizing vinyl monomers and macromonomers Yes, the macromonomer has a polymer composed of a double bond-containing ethylenically unsaturated monomer in its main chain. 2. The vinyl chloride resin composition according to claim 1, wherein the content of the macromonomer component is 0.1-5 parts by weight based on 100 parts by weight of the vinyl chloride resin. 3. The vinyl chloride resin composition according to any one of claims 1 to 2, characterized in that the macromonomer component accounts for 3 to 50% by weight of the vinyl chloride copolymer resin. 4. A molded article comprising the vinyl chloride-based resin composition according to any one of claims 1 to 3. 5. The molded body according to claim 4, characterized in that it is molded by calendering. 6. The molded body according to claim 4, characterized in that it is molded by injection molding. 7. The molded body according to claim 4, characterized in that it is formed by extrusion molding.