WO1995033008A1

WO1995033008A1 - Fluororesin-containing resin composition, process for producing the same, and thermo-forming sheet and foam made therefrom

Info

Publication number: WO1995033008A1
Application number: PCT/JP1995/001030
Authority: WO
Inventors: Taizo Aoyama; Tetsuo Okura; Kazuhiro Hara; Kiyoyuki Namura; Ryuji Fukuda; Haruo Tomita
Original assignee: Kanegafuchi Kagaku Kogyo Kabushiki Kaisha
Priority date: 1994-05-31
Filing date: 1995-05-29
Publication date: 1995-12-07

Abstract

A fluororesin-containing resin composition comprising 0.001-50 parts by weight of fibrous polytetrafluoroethylene (A) and 100 parts by weight of a dispersant (B) having a mean particle diameter of 0.1-800 νm, and a production process therefor; another fluororesin-containing resin composition comprising the above resin composition and a polyolefin (C), and a production process therefor; and thermo-forming sheet and foam made from these compositions.

Description

Akira Itoda Fluororesin-containing resin composition and its manufacturing method, and the resulting thermoforming sheets and foams Technical field

The present invention relates to a fluorine resin-containing resin composition, a method for producing the same, and a thermoforming sheet and a foam obtained therefrom. In more detail, it has excellent impact resistance and surface properties, further improved melting properties, and improved workability (formability). ), A fluororesin-containing resin composition suitably used for various molded articles and the like, a process for producing the same, and a molding from the fluororesin-containing resin composition. And a thermoforming sheet and a foam having excellent physical properties as described above. Background art

Conventionally, as a raw material for a molded article, a polyrefin having low physical properties and good physical properties has been widely used.

However, propylene, for example, not only has the disadvantage of poor transparency, but also has low viscosity and low tension when melted. Therefore, it is inferior to vacuum moldability (hereinafter referred to as thermoformability), calender moldability, blow moldability, foaming moldability, etc. for the sheet. Polyethylene, polyvinyl chloride,

Compared to ABS resin, it has low rigidity, low impact resistance at low temperatures, poor surface properties (surface gloss), poor applicability, etc., and low hardness. There is a disadvantage in workability.

Therefore, in order to improve the transparency of the polypropylene, In addition, conventionally, mixing a nucleating agent with polypropylene has been tried. However, in such attempts, the effect of improving the transparency by the nucleating agent was insufficient, and processing such as thermoforming required for transparency was also required. There is almost no effect of improving the properties, and there are problems such as a decrease in the surface properties of the obtained molded article. Furthermore, some nucleating agents emit an odor during processing, and the use of the obtained molded articles in the food packaging field is particularly restricted. There was a problem.

Also, in order to improve the workability of the polypropylene, the polypropylene and the like are generally mixed mechanically with the polypropylene. It is. However, since the effect of improving the workability by the polyethylene is insufficient, a large amount of the polyethylene is required, and a large amount of the polyethylene is required. When using a lens, there are problems that the rigidity of the obtained mixture is reduced and the transparency of the molded body is reduced. Attempts have also been made to improve the viscosity and tension during melting by increasing the molecular weight of the polyolefin. However, if a high molecular weight polyrefin is used, extrusion, one of the important processing methods, is said to be difficult. There is a big problem.

In addition, in order to improve the melting characteristics of the polypropylene, a technique has been proposed in which the polypropylene is branched by radiation or peroxide. It is. However, the problem is that if such technology is adopted, the number of manufacturing processes will increase, and it will be difficult to recycle the obtained molded body. O

It has also been proposed to improve the processability of polyethylene by adding an uncrosslinked acryl-based polymer to the polyethylene. (U.S. Pat. No. 4,156,703). However, the compatibility between the polyethylene and the uncrosslinked acryl-based polymer is insufficient, and the acryl-based polymer is uncrosslinked. Therefore, at the time of calendar molding, extrusion molding, etc., the acrylic polymer separates from the polystyrene, and the roll surface of the power renderer, When attached to the die surface of the extruder (hereinafter referred to as plateout), the workability of the mixture is reduced. is there .

In order to improve the inherent low rigidity of polyolefin, it is possible to add polyethylene to the above-mentioned polypropylene, for example. In order to prevent the stiffness of the mixture from decreasing, inorganic fillers and the like are added to the polyrefin. However, if an inorganic filler or the like is added, the compatibility between the polyolefin and the inorganic filler is reduced, and poor dispersion of the inorganic filler occurs. For example, there is a problem that the surface properties of a molded product such as a sheet are significantly reduced.

In addition, an attempt was made to improve the blow moldability by adding a fluorinated polymer to a polyolefin (Japanese Unexamined Patent Application Publication No. Hei 3-1818324). Japanese Patent Application Laid-Open No. Hei 5 (1995) -214184, and an attempt to improve the processability by adding polytetrafluoroethylene to polypropylene. Is being done. However, in each of these attempts, the fluorine-containing polymer and the polytetrafluoroethylene are simply polyolefins. Since it is only added to the fin, the effect of improving additive properties such as blow molding is not satisfactory.

In addition, in order to improve the impact resistance of the polypropylene, a rubber component such as ethylene-propylene rubber is generally used to reduce mechanical impact. Poly, such as by mixing or block copolymerization It is being introduced to the propylene. However, it is difficult to control the dispersed particle size by mechanically mixing the rubber components or introducing the rubber components into the polypropylene by block copolymerization. Therefore, the use efficiency of the rubber component is low, and the effect of improving the impact resistance by the rubber component becomes insufficient. Also, in order for the rubber component to fully exhibit the effect of improving the impact resistance, a large amount of the rubber component is required, so that the rigidity of the obtained mixture is increased. The problem is that it drops. Further, there is a problem that the surface gloss of the obtained molded body is reduced due to the large particle diameter of the dispersed rubber component.

Conventionally, a core-type modifier, which has been widely used as an impact resistance improver for polyvinyl chloride resin, has a predetermined particle size. The rubber component (core layer) can be efficiently dispersed, and the impact resistance can be improved while reducing the rigidity of polyvinyl chloride resin. It is something that can be done. Nevertheless, the core-type denaturing agent has poor compatibility with non-polar porphyrins, and therefore has a low molecular weight. The problem is that they are almost inaccessible.

Therefore, it has been proposed to add the core shell type modifier to a polyrefin in the presence of a specific compatibilizer (Japanese Patent Laid-Open No. — 185 037, U.S. Pat. No. 4,997,884). However, when the compatibilizing agent is used, the process of synthesizing the compatibilizing agent is complicated, and the cost is increased due to the use of the compatibilizing agent. There are problems such as rising and complicating the system.

As described above, no resin has been proposed that simultaneously satisfies the properties such as excellent impact resistance, surface properties, and workability at the same time. Therefore, the development of a resin composition that satisfies such physical properties at the same time and a molded article obtained therefrom have been desired.

The present invention has been made in view of the conventional technology, has excellent physical properties such as impact resistance, surface properties, and workability, and is suitable for various molded articles. The purpose of the present invention is to provide a resin composition to be used, a method for producing the same, and a sheet and a foam obtained therefrom. Disclosure of invention

The present invention comprises (1) polytetrafluoroethylene (A) and a dispersant (B) having an average particle size of 0.1 to 800 / zm. The amount of tetrafluoroethylene (A) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the dispersant (B), and A fluororesin-containing resin composition in which lafluoroethylene (A) is fiberized (hereinafter referred to as “resin composition (I)”), and ② an average particle diameter of 0.1 to 80. 0.1 μm of the dispersant (B) was mixed with 100 parts by weight of polytetrafluoroethylene (A) in an amount of 0.001 to 50 parts by weight under high shearing force. A method for producing a resin composition (I) characterized in that the polytetrafluoroethylene (A) is fiberized; and ③ polytetrafluoroethylene. The styrene (A) and average particle size are 0.1 l 800 ^ m of the dispersant (B), and the amount of the polytetrafluoroethylene (A) was 100 parts by weight of the dispersant (B). 0.01 to 50 parts by weight, and the resin composition (I) in which the polytetrafluoroethylene (A) is fiberized; Fluorine resin-containing resin composition consisting of refine (C) (hereinafter referred to as resin composition (Π)) ), And 100 parts by weight of a dispersant (B) having an average particle diameter of 0.1 to 800 // m per 100 parts by weight of polytetrafluoroethylene (A). ) 0.001 to 50 parts by weight are preliminarily mixed under a high shearing force, and the polytetrafluoroethylene (A) is fiberized to obtain a resin composition. A method of producing a resin composition (Π) comprising producing the resin composition (I) and mixing the resin composition (I) and a polyolefin (C). ⑤ Polytetrafluoroethylene (A) and a dispersant (B) having an average particle diameter of 0.1 to 800 t / m (B) The amount of the phenol oleethylene (A) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the dispersant (B), and the polytetrafluoroethylene is used. The resin composition (I) in which the polyethylene (A) is fiberized is And a thermoforming sheet comprising a resin composition (（) comprising polyolefin (C) and polytetrafluoroethylene (（) A) and a dispersant (B) having an average particle size of 0.1 to 800 / m and the amount of the polytetrafluoroethylene (A) is The dispersant (B) was 0.01 to 50 parts by weight with respect to 100 parts by weight, and the polytetrafluoronorethylene (A) was fiberized. The present invention relates to a foam composed of a resin composition (Π) composed of a resin composition (I) and a polyolefin (C). BEST MODE FOR CARRYING OUT THE INVENTION As described above, the resin composition (I) of the present invention comprises polytetrafluoroethylene (A) and average particles. It is composed of a dispersant (B) having a diameter of 0.1 to 800 / m, and the amount of the polytetrafluoroethylene (A) is determined by the dispersant (B) 1 0.001 to 50 parts by weight with respect to 0.0 parts by weight. Trafluoroethylene (A) is a fiberized composition, and the polytetrafluoroethylene (A) used in the present invention is mainly composed of: It is a component for improving the processability of the resin composition (I) obtained.

As the polytetrafluoroethylene (A), the resin composition (I) is converted into a fiber by the shearing force applied when the resin composition (I) is removed. It only needs to be a polytetrafluoroethylene o

As the polytetrafluoroethylene which is fiberized by the shearing force, for example, a dispersion obtained by an emulsion polymerization method is not agglomerated. Powders, and powders comprising polymers obtained by the suspension polymerization method, and the like. Among these, the dispersion obtained by the emulsion polymerization method is agglomerated because of the fact that the fiber is easily formed into fibers by shearing force. Uda is preferred.

Representative examples of the polytetrafluoroethylene (A) include, for example, Polyfluoro TFE — F103 and Polyfluoro TFE — F10 4, Polyfluorin TFE — F201 (hereafter, manufactured by Daikin Industries, Ltd.), Teflon TFE — 6J, Teflon TFE — 7J, Teflon 6C—J (the above, manufactured by Mitsui Dupont Fluorochemical Canole Co., Ltd.).

The average particle size of the polytetrafluoroethylene (A) is 100 when considering the ease of mixing with the dispersant (B) and the dispersibility. ~ 700 / zm, preferably 300-600 μ ^, more preferably 400-500 im. The polytetrafluoroethylene (A) is mixed with a dispersant (B) under a high shearing force and fiberized.

In order to sufficiently exhibit the effect of improving the processability, the maximum fiber diameter of the fiber-reinforced polytetrafluoroethylene (A) is 10 m or less. Preferably, it is less than 5 / m, more preferably less than 2 // m, and the smallest fiber diameter is usually 0.01 m It should be at least about 0.10 tzm, preferably about 0.01 tzm. Furthermore, since fiberized polytetrafluoroethylene (A) has a network structure, its fiber length is generally determined. Cannot be determined. The fiber length is about 3 m or more, preferably about 5 / m or more, because workability is improved by increasing the tension during melting. Preferably, it is about 1 Om or more.

As described above, since the polytetrafluoroethylene (A) is fiberized in the resin composition (I), the resin composition (I) ), For example, when it is mixed with a polyolefin (C) described below, the effect of improving the processability exhibited by the obtained resin composition (Π) can be reduced. It becomes even bigger.

The dispersing agent (B) used in the present invention is capable of effectively dispersing and fiberizing polytetrafluoroethylene (A), and also comprises a resin. It is a component that gives the resin composition (I) the improvement effects such as impact resistance, workability, and surface properties exhibited by the composition (I).

The dispersant (B) effectively disperses and fibrils the poly (tetrafluoroethylene) (A) and exhibits the above-mentioned improvement effect. For example, there is no particular limitation. Representative examples of the dispersant (B) include, for example, Coregile Powders made of foot copolymers, polyolefin powders, inorganic powders, etc., may be used alone or in combination. The above can be used in combination. In view of the dispersibility of polytetrafluoroethylene (A) and the impact resistance of the resin composition (I), core shell Powders comprising a raft copolymer are preferred. In addition, from the viewpoint of low cost, a polyrefin powder is preferred.

For example, the core-graft copolymer includes a cross-linked rubber-like polymer as a core layer, and a hard layer made of a vinyl-based compound as a seal layer. This is a core-type graphite copolymer. The concept of the core-shell graph copolymer is, for example, that a cross-linked rubber-like polymer forming a core layer and a hard shell component are graph-copolymerized. And the copolymer obtained.

Examples of the core rubber / graft copolymer include a crosslinked rubbery polymer (b—1) and a crosslinked rubbery polymer (b—1). A graphite copolymer with a polymerizable vinyl compound (b-2) is preferably used.

The crosslinked rubber-like polymer (b-1) includes, for example, processability and impact resistance exhibited by the obtained core-graft copolymer. In order to further improve the improvement effect of the polymer, a polymer having a glass transition temperature of 25 ° C or less is preferred.

In addition, the vinyl compound (b—2) includes a glass transition temperature of the homopolymer of the vinyl compound (b—2) of 25 ° C. or more. Certain monomers are preferred to avoid agglomeration of the core-shell graft copolymer.

In addition, the glass transition temperature and the measuring method are as follows. Speaking of Polymer Node Book (INTERSCIENCE

PUBLISHERS, 2nd edition, 1975), and in the present invention, the glass transfer temperature of the polymer is based on the following formula. The value determined based on

1 / T g = W a no T g a + W b / τ g b

T g: Gas of the copolymer consisting of component a and component b

Transfer temperature (° C)

T g a Glass transition temperature of component a (° c)

T g b 7 ras transfer temperature of component b (in)

w a Weight fraction of component a

w b Weight fraction of component b

Specific examples of the rubber-like polymer used as a raw material of the crosslinked rubber-like polymer (b-1) include, for example, gen-based rubber and acryl. There are various types of rubber, such as rubber, rubber, silicone rubber, etc. They can be used alone or as a mixture of two or more.

Representative examples of the above-mentioned benzene rubber include, for example, 60 to 100% by weight of the benzene rubber and other vinyl copolymerizable with the benzene rubber. Such as diene-based rubber containing 0 to 40% by weight of metal compounds.

刖 Jenic compounds used in self-generating rubber include, for example, benzene, isoprene, and black-mouthed plane. can give . They can be used alone or as a mixture of two or more. Among them, the viewpoint that the obtained core-shell graft copolymers are much more effective in improving processability and impact resistance. Therefore, butadiene is preferred o Examples of other vinyl compounds which can be copolymerized with the above-mentioned diene compound include styrene, α-methizolestyrene and the like. Aromatic vinyl compounds of the following formula: methyl methacrylate, methyl methacrylate, methacryloleic acid η — petinole, methacrylic acid i-petit Metal, methacrylic acid t-butyl, methacrylic acid 2 -ethylhexyl, methacrylic acid stearylsole, etc. Alkyl ester of methyl acrylate having 1 to 22 carbon atoms in the kill group; methyl acrylate, methyl acrylate, ethyl acrylate Acid n—butyl alcohol, acrylic acid i-methyl, acrylic acid t—butyl, acrylic acid 2—ethyl hexyl, acrylic acid Tear lily For example, the alkyl group has 1 to 22 carbon atoms of the alkyl group, alkyl acrylate ester; acrylonitrile, metalacryloyl. Unsaturated nitrinole compounds such as nitrile; maleic anhydride, methacrylic acid, acrylic acid, methacrylonitrile amide, acrylonitrile Amido, dimethyl methacrylate amino, dimethyl acrylate amino, hydroxy methacrylate, hydroxymethyl Acid-free bases such as metal, hydroxyethyl creatate, glycidyl methacrylate, glycidyl acrylate, etc. And vinyl compounds having a reactive functional group such as carboxyl group, amino group, hydroxy group, epoxy group, etc. can give . They can be used alone or as a mixture of two or more.

In addition, as the above-mentioned diene rubber, the diene compound 60 to: L00% by weight, preferably 70 to 100% by weight, and other vinyl compounds The rubber comprising from 0 to 40% by weight, preferably from 0 to 30% by weight of the compound is processed by the obtained core-monograft copolymer. It is desirable because it improves the effect of improving the properties, impact resistance and surface properties. A typical example of the above-mentioned acrylic rubber is, for example, an alkyl ester of acrylic acid having an alkyl group of 2 to 22 carbon atoms. 100% by weight and other vinyl compounds co-polymerizable with the alkyl acrylate ester 0 to 40% by weight. Les-related rubber etc. are exposed.

For example, an alkyl ester of acrylic acid having 2 to 22 carbon atoms in the alkyl group used in the acrylic rubber is, for example, Acrylic acid, acrylic acid n — butyl, acrylic acid i — butyl acrylate, acrylic acid t — butyl, acrylic acid 2 — acrylate Examples include chilled hexyl and stearinol acrylate. They can be used alone or as a mixture of two or more. Among them, the process of improving the processability and impact resistance of the obtained cohesion enograft copolymer is far superior, and it is inexpensive. From this point of view, acrylic acid n-butyl is preferred.

Other vinyl conjugates copolymerizable with the above-mentioned alkyl acrylate are, for example, copolymerizable with the above-mentioned gen-based compound. Aromatic vinyl compounds exemplified as other vinyl compounds; Alkyl esters of methacrylyl acid having 1 to 22 carbon atoms in the alkyl group; Methyl acrylate; unsaturated nitrile compound; acid anhydride group, carboxyl group, amino group, hydroxy group, epoxy group For example, vinyl compounds having a reactive functional group such as a base may be used. They can be used alone or as a mixture of two or more.

The acrylic rubber is 60 to 100% by weight, preferably 65 to 100% by weight, of an alkyl acrylate ester. % And other vinyl compounds from 0 to 40% by weight, preferably from 0 to 35% by weight. This is desirable because it improves the processability and impact resistance of the shell-graft copolymer.

As the above-mentioned rubbers, for example, ethylene-propylene-jengom, butyrum-gum and the like can be used.

Examples of the silicone rubber include, for example, a polymethylsiloxango rubber.

By cross-linking rubber-like polymers such as the aforesaid jen-type rubber, acryl-type rubber, olefin-type rubber, silicone rubber and the like. Thus, a crosslinked rubbery polymer (b-1) can be obtained.

The method for the crosslinking is not particularly limited. For example, the method for self-crosslinking by Bujjen, divinylbenzene, 1,

3 — Method using polyfunctional crosslinking agents such as butanediol resin methacrylate, methacrylic acid aryl, acrylic acid aryl There is a method using a graphitizing agent such as diaryl phthalate, a method using a peroxide, and the like. It can be appropriately selected and used depending on the type of the rubbery polymer. In order to crosslink an acrylic rubber, a method using a combination of a polyfunctional crosslinking agent and a graphitizing agent, or a method using a graphitizing agent is used. Adopting the method used is preferable from the viewpoint that, when cross-linking occurs, a graph active site is generated at the same time.

The bridge gel content of the obtained crosslinked rubbery polymer (b-1) is adjusted so as to be 50% by weight or more, preferably 60% by weight or more. And are desired. If the amount of the crosslinked gel is not less than the lower limit, the obtained resin composition (I) may be, for example, a polyolefin (C) described later. Distributed to In the case of using the obtained resin composition (用), the resin composition applied to the roll surface when performing calendar molding, etc. However, there is a tendency that no plate is formed and the effect of improving workability is sufficiently exhibited.

The crosslinked gel content is defined as, for example, the crosslinked rubbery polymer is immersed in a good solvent of a rubber component such as toluene or methyloketketone for 48 hours. The figure shows the percentage of insoluble matter separated by the ultracentrifuge after the separation.

The vinyl compound (b—2) can be copolymerized with, for example, a diene compound in the example of the cross-linked rubbery polymer (b—1). Aromatic vinyl compounds exemplified as other vinyl compounds; alkyl acrylates having 1 to 22 carbon atoms in the alkyl group; Alkyl acrylate having 1 to 22 carbon atoms in the alkyl group; Unsaturated nitrile compound; Acid anhydride group, carboxyl Examples include vinyl compounds having a reactive functional group such as a group, an amino group, a hydroxyl group, or an epoxy group. They can be used alone or as a mixture of two or more.

In addition, as the vinyl compound (b-2), at least one of the aromatic vinyl compound and the alkyl methacrylate ester is used. 1100% by weight び and other vinyl compounds that can be copolymerized with these components 00-50% by weight may cause a decrease in polymerizability or cost up. It is preferable because it is difficult.

In addition, from the viewpoint of good polymerizability and low cost, the aromatic vinyl compounds include styrene and α-methylstyrene. Particularly preferred is an alkyl ester of methacrylolinoleic acid, in which the alkyl group has 1 to 1 carbon atoms. The ester of 4 is particularly preferred.

The core-graft copolymer is obtained by graft-polymerizing a vinyl compound (b-2) with a crosslinked rubber-like polymer (b-1). It is obtained by

In order to further improve the improvement effects such as workability and impact resistance exhibited by the obtained core-graft copolymer, it is necessary to use a cross-linked rubber. The amount of the rubbery polymer (b-1) should be 40% by weight or more, that is, the amount of the vinyl compound (b-2) should be 60% by weight or less. Is preferred. Further, in order to prevent the core-silica-graft copolymer from agglomerating, the amount of the crosslinked rubber-like polymer (b-1) should be 95% by weight or less. In particular, the amount of the vinyl compound (b-2) should be 5% by weight or more, especially 10% by weight or less, that is, 90% by weight or less. And are preferred.

The core-graphite copolymer can be obtained by a conventional radical polymerization method, for example, a suspension polymerization method or an emulsion polymerization method. Any polymerization method can be employed. Among these, the emulsification polymerization method is preferred from the viewpoint that control such as particle diameter and particle structure is easy.o

The average particle size of the thus obtained core-shell graphit copolymer is intended to improve the surface properties of the obtained resin composition (I). Considering this, it should be less than 3 // m, preferably less than 2.5 m. In the present invention, the obtained core-graft copolymer can be obtained by adding an acid, a salt, a coagulant and the like during the polymerization. The particles can be enlarged to form a powder having a specific average particle size described later. Such Corel Graph Typical examples of copolymers include Kaneace B, Kanease M, and Kanease FM (all manufactured by Kaneka Chemical Co., Ltd.). Etc. are exterminated.

Representative examples of the polyrefin powder of the dispersant (B) include, for example, polypropyrene, high-density polyethylene, and low-density polyethylene. Polyethylene, Linear Low Density Polyethylene, Poly1 — Butene, Polyisobutylene, Propylene and Echilen, and Z Or 1-random or block copolymer in any ratio with butene, in any ratio of ethylene and propylene Ethylene-Propylene-Jen terpolymer, Polymethylenolepentene, Cyclopentene having 10% or less by weight of a gen component Cyclic polyolefins, such as copolymers of evening gen with ethylene and / or propylene, ethylene or propylene Pyrene and 50% by weight or less, such as vinyl acetate, alkyl methacrylate ester, alkyl acrylate ester, and Yoshika Random, block or graphitic copolymers with vinyl compounds such as group vinyl, etc. have a specific average particle diameter as described below. The powder adjusted in this way is exposed. They can be used alone or as a mixture of two or more.

Among the polyrefin powders, propylene powder obtained by polymerizing a monomer component containing 50% by weight or more of propylene is used. Powder comprising a polyolefin and a propylene polyolefin, and a simple substance containing 50% by weight or more of ethylene. It is a mixture with an ethylene-based olefin obtained by polymerizing the monomer components, and the amount of the ethylene-based olefin is determined by the amount of the ethylene-based olefin. Polypropylene Ref. 1

A mixture of 0.1 to 100 parts by weight based on 100 parts by weight However, it is preferred because it is versatile and low cost

Representative examples of the inorganic powder of the dispersant (B) include, for example, heavy calcium carbonate, light calcium carbonate, evening water, and glass fiber. , Magnesium carbonate, my strength, kaolin, calcium sulfate, barium sulfate, titanium dioxide, white carbon, carbon Inorganic powders such as bomb black, hydroxide hydroxide, alumina oxide, magnesium hydroxide, molten silica, etc. It is. They can be used alone or as a mixture of two or more. Among them, from the viewpoint of availability, heavy calcium carbonate, light potassium carbonate and talc are preferred.

Further, according to the present invention, there are provided a powder, a polyrefin powder and an inorganic substance comprising the above-mentioned core-graft copolymer. No ,. In addition to thermoplastics, there are also thermoplastic elastomers such as blocks of styrene and butadiene or random copolymers. And a powder consisting of a crosslinked elastomer such as hydrogenated product, polybutadiene and the like and a hydrogenated product thereof are mixed with a dispersant (B). One of the great features of the present invention is that the dispersant (B) has an average particle diameter of 0.1 to 800 m.

If the average particle size of the dispersant (B) is less than 0.1 m and if it exceeds 800 / m, polytetrafluoroethylene is used. When the resin (A) is not sufficiently dispersed and fibrous, the molded product obtained by using the resin composition (I) is treated with polytetrafluoroethylene (A). Lumps remain and surface properties As a result, the effects of improving impact resistance, surface properties, workability, etc., become insufficient. In view of the above, the average particle size is 50 m or more, preferably 100 m or more, and 700 m / m or less, preferably 500 m or less. I want something o

The average particle size of the dispersant (B) is such that different tile sizes of about 6 sizes are piled up in descending order of the mesh size. Pour the dispersant (B) dispersed in water using a surfactant, and calculate from the weight ratio of the dispersant (B) accumulated in each mesh according to the particle size diagram. Get out. In addition, the average particle diameter can be measured by other general powder measurement methods.

The method for adjusting the average particle diameter of the dispersant (B) so as to fall within the above range is not particularly limited. In general, any method of controlling the particle size of the powder, such as agglomeration, grinding, sieving, etc., can be used. For example, as described above, the average particle size of a powder composed of a coercie-dahlaf copolymer can be adjusted by agglomeration as described above. it can . The average particle size of the polyrefin powder can be adjusted by controlling the particle size during polymerization or changing the conditions during freeze-milling. The average particle size of the inorganic powder can be adjusted by pulverization and sieving.

The resin composition (I) of the present invention is obtained by mixing a polytetrafluoroethylene (A) and a dispersant (B) under a high shear force. By making the fiber (A) sufficiently fibrous, it can be strengthened.

The amount of the polytetrafluoroethylene (A) is from 0.001 to 50 parts by weight based on 100 parts by weight of the dispersant (B). It is. As long as the amount of such polytetrafluoroethylene (A) is extremely small, the processability imparted to the resin composition (I) is not sufficient. Any improvement effect will be insufficient. In addition, when the amount of polytetrafluoroethylene (A) is too large, it is difficult to reduce the cost. The versatility is reduced, and the fiberized polytetrafluoroethylene (A) is more likely to form aggregates. From the above viewpoint, the amount of polytetrafluoroethylene (A) is preferably at least 0.01 part by weight based on 100 parts by weight of the dispersant (B). More than 0.05 parts by weight, more preferably more than 0.01 parts by weight, and less than 50 parts by weight, preferably less than 40 parts by weight. More preferably not more than 30 parts by weight

Polytetrafluoroethylene (A) and a dispersant (B) are mixed under high shear to disperse Polytetrafluoroethylene (A). In the case of fiberization, a stirring and mixing method using a stirrer such as a hensyl mixer, for example, a single screw extruder, a twin screw extruder, etc. A melt kneading method using an extruder, a roll kneader, or the like can be employed.

In the present invention, as long as the polytetrafluoronorethylene (A) is fiberized in the obtained resin composition (I), the above-mentioned stirring and mixing is carried out. There are no particular restrictions on operating conditions such as the method and the melt-kneading method.

The stirring and mixing method has an advantage of low cost, and the melt-kneading method can use a pellet-shaped resin composition (I). There are advantages.

When using the stirring and mixing method, the poly (tetrafluoroethylene) (A) and the dispersant (B) are mixed at room temperature. The mixture may be stirred and mixed with each other, or both may be heated to a temperature at which both are not deteriorated or deteriorated, and then mixed with stirring.

Further, in the present invention, the stirring and mixing method and the melt-kneading method can be used in combination. For example, after mixing the polytetrafluoroethylene (A) and the dispersing agent (B) using a helical mixer, the mixture is obtained. The extruded mixture can be melt-kneaded using an extruder and extruded to produce pellets 0

The resin composition (I) of the present invention is produced as described above, and the resin composition (I) expresses the resin composition (I). Add additives, such as stabilizers, lubricants, nucleating agents, etc., as needed, in order to further enhance the effect of improving, for example, surface properties. be able to . The additive may be added to other components at the time of stirring and mixing or melt kneading, for example, and the timing of addition is not particularly limited.

Representative examples of the above stabilizers include, for example, pentaerythritolyl teretrax [3— (3,5—di-t-butynole 4-hide) Roxy vinyl) Propirate], Tri-legging connector [3-(3-t-Petit 5-Metizoret) 4—Hydroxyphenyl) propionate] and other phenolic stabilizers, and tris (monononylvinyl) phospho Phosphites and other phosphorus-based stabilizers, such as phosphates and tris (2, 4—Jetyl phenyl phenyl), dilauryl thiodipro Dioxin-based stabilizers such as pionates are required. They can be used alone or as a mixture of two or more. The amount of the stabilizer is usually about 0.01 to 3 parts by weight relative to 100 parts by weight of the dispersant (B). Preferably, it is about 0.05 to 2 parts by weight. Typical examples of the lubricant include saturated or unsaturated fatty acids such as, for example, raurilic acid, palmitic acid, oleic acid, and stearic acid. Sodium, cascade, magnesium salt, etc. are exposed. They can be used alone or as a mixture of two or more. The amount of the lubricant is usually about 0.1 to 3 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the dispersing agent (B). Is desired.

Representative examples of the nucleating agent include, for example, sodium benzoate, bisbenzylidene sonore, and vis (p-methyl) Benzylidene) Solbitol, bis (p-ethylbenzylidene) Sonorebito Nore, Sodium 1-2, 2—Methylenbi (4, 6 — di-t — butyl phenol) Phosphite, phenol, titanium oxide, azo phenol — T — Petite Benzoate. They can be used alone or as a mixture of two or more. The amount of the nucleating agent is usually about 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the resin composition (I). It is hoped that it is about. The nucleating agent is used in an amount of about 0.01 to 10 parts by weight, preferably 0,:! To 5 parts by weight, based on 100 parts by weight of the resin composition (I). It can be added to the dispersant (B) so that the amount becomes about parts.

As described above, the resin composition (I) of the present invention can impart physical properties such as excellent workability, impact resistance, surface properties, and the like, as described later. It can be used as a modifier for the resin composition (II) containing the polyolefin (C). As described above, the resin composition (Π) of the present invention has a polytetrafluorophenol (A) and an average particle size of 0.1 to 800 / zm. (B), and the amount of the poly (ethylene glycol) ethylene (A) is 0.0 with respect to 100 parts by weight of the dispersant (B). 0 to 50 parts by weight, and a resin composition in which the polytetrafluoroethylene (A) is fiberized.

A composition comprising (I) and a polyolefin (C).

O o

Among the dispersants (B) used in the resin composition (I), the core-graft copolymer is a polytetrafluoroethylene copolymer. It is preferable from the viewpoint of the dispersibility of the polyethylene (A), the impact resistance of the obtained molded article, and the like, and among them, the obtained resin composition (II) In consideration of the thermal coloring of the resulting molded article, a copolymer that does not deteriorate thermally at the molding temperature of polyolefin (C) is preferred.

In addition, the above-mentioned polyrefin powder of the dispersant (B) is easily dispersed in the polyrefin (C) and is inexpensive. Is better. Among them, powders that can easily mix the resin composition (I) and the polyolefin (C) are obtained. O It is preferable because it does not leave foreign matter on the molded body and improves its surface properties and transparency.

In order to easily mix the resin composition (I) and the polyolefin (C), the melt flow of the polyolefin (C) is used. -Use a polyrefined powder that has a similar amount of index to the index as the dispersant (B). And preferably a polyrefin powder having substantially the same composition as the polyrefin (C). It is even more preferable to use one.

The refractive index of the dispersant (B) is determined from the viewpoint that the transparency of the obtained resin composition (Π) can be further improved. Preferably, it is substantially the same as that of the refine (C).

In this specification, the fact that the refractive indices are practically the same means that the difference between the two refractive indices is 0 to 0.02. Further, from the viewpoint that the transparency of the resin composition (（) can be further improved, the difference in the refractive index is 0 to 0.01, Preferably it is between 0 and 0.05.

The refractive index is determined, for example, by Polymer Handbook (John Wiley and Sands Inc.). ), Third Edition, 1989), and the refractive index of the polymer is calculated proportionally based on the weight fraction of the constituent monomers. This is the value obtained.

An example of the dispersant (B), which is a core-graft copolymer. Among powders, for example, a powder having a refractive index substantially the same as that of polypropylene, for example, has an emulsifying weight. A copolymer obtained by copolymerizing 50% by weight of crosslinked polybutadiene rubber obtained by a legal method with 50% by weight of methyl methacrylate. The resulting powder, n-acrylic acid n-butyl 70% by weight, and the styrene 30% by weight Ingredient 100% by weight 70% by weight of cross-linked acrylic rubber obtained by emulsion polymerization of a monomer to which 1 part by weight of acrylic acid was added, and methyl methacrylate 2 Monomer composition consisting of 7% by weight and 3% by weight of styrene For example, a powder made of a copolymer obtained by copolymerizing a component with a polymer is obtained.

Polyolefins (C) used in the resin composition (組成) include, for example, polypropylene, high-density polyethylene, and low-density polyethylene. Polyethylene, Linear Low Density Polyethylene, Poly1 — Butene, Polyisobutylene, Propylene and Echilen, and Or 1 — random or block copolymer in any ratio with the pentene, any ratio between the ethylene and the propylene in any ratio Ethylene-Propylene-Jen ternary copolymers, polymethylpentenes, cyclopentanes with a gen content of 10% by weight or less Cyclic polyolefins, such as copolymers of tagenes with ethylene and propylene, or ethylene, or propylene Less than 50% by weight of len, such as vinyl acetate, alkyl acrylate methyl ester, alkyl acrylate acrylic ester, and aromatic compounds Random, block or graft copolymers with vinyl compounds such as vinyl, etc. can be obtained. They can be used alone or as a mixture of two or more.

Among the polyolefins (C), propylene obtained by polymerizing a monomer component containing 50% by weight or more of propylene is used. Polymerization of propylene-based olefins, and the propylene-based olefins, and a monomer component containing 50% by weight or more of ethylene. It is a mixture with the obtained ethylene-based olefin, and the amount of the ethylene-based olefin is the amount of the propylene-based olefin. Mixtures in an amount of 0.1 to 100 parts by weight to 100 parts by weight of fine powder are preferred from the viewpoint that they are easily available and inexpensive.

Among the propylene-based olefins described above, At least one selected from propylene, ethylene-propylene random copolymer and ethylene-propylene block copolymer. One is preferred because it is readily available and inexpensive. Among the ethylene-based polyolefins, low-density polyethylene, linear low-density polyethylene, and high-density polyethylene are included. At least one selected from the group is preferred because it is readily available and inexpensive.

Also, among the polyolefins (C), the index of melt mouth is less than 10 g <10 minutes, preferably 5 g 10. Or less, more preferably 2.5 g Z 10 minutes or less, the effect of high tension on melting and excellent workability. Is desired because it is sufficiently expressed. The melt flow index can be weighed 2.16 kg in accordance with the method described in ASTMD 1 238, and is a propylene-based polyreflection. The temperature is measured at 230 ° C for olefins, and at 190 ° C for ethylene-based polyrefin.

In the present invention, as described above, the refractive index of the dispersant (B) and the refractive index of the polyolefin (C) are practically the same. It is preferred that the dispersant (B) and the polyrefin (C) are appropriately selected and used so that The refractive index of a typical polyolefin (C) is, for example, that the refractive index of polypropylene is 1.503, and that of high-density polyolefin. The refractive index of the lens is 1.545, the refractive index of the low-density polyethylene is 1.51, the refractive index of the linear low-density polyethylene is 1.52, Po Li one 1 over butene down a refractive index of 1. 5 1 2 5, the refractive index of the port Li main Chi le pen Te emissions is Ru 1. 4 5 9 to 1.4 6 5 teeth ⁵ fit.

The resin composition (π) of the present invention comprises the resin composition (I). And a polyrefin (C) can be obtained by mixing them.

The amount of the resin composition (I) is determined in order to sufficiently improve the effect of the obtained resin composition (Π) such as processability imparted to the obtained resin composition (Π). It is preferred that the amount be 0.01 parts by weight or more, preferably 0.05 parts by weight or more, based on 100 parts by weight of the olefin (C). In order to reduce the cost and enhance the versatility, the amount of the resin composition (I) is set to 100 parts by weight of the polyolefin (C). It is desired that the amount be no more than 20 parts by weight, preferably no more than 10 parts by weight, and more preferably no more than 6 parts by weight.

Further, in the resin composition (（), the amount of the resin composition (I) with respect to the polyrefin (C) is adjusted so as to be within the above range. Preferably, the polytetrafluoroethylene (A) and the dispersant (B) that constitute the resin composition (I) are each used. Is preferably contained in the resin composition (II) within the following range.

The amount of the polytetrafluoroethylene (A) is set so that the effect of improving the workability can be sufficiently improved. It is desired that the amount be at least 0.01 parts by weight, preferably at least 0.05 parts by weight, based on 0 parts by weight. In addition, the amount of the polytetrafluoroethylene (A) is set to a value that is low in order to reduce cost and enhance versatility. (C) 100 parts by weight or less, preferably not more than 10 parts by weight, preferably not more than 5 parts by weight, and more preferably not more than 3 parts by weight. Yes.

The amount of the dispersant (B) is such that the polytetrafluoroethylene (A) is effectively dispersed and fiberized. In order to achieve this, at least 0.002 parts by weight, and preferably at least 0.25 parts by weight, of 100 parts by weight of the polyolefin (C). I want to. In addition, the amount of the dispersant (B) is determined by the amount of the polyolefin (C) in order to sufficiently exhibit the inherent properties such as heat resistance and rigidity. (C) 100 parts by weight or less, preferably 100 parts by weight or less, more preferably 70 parts by weight or less, and more preferably 50 parts by weight or less. I want it.

The method of mixing the master batch and the polyrefin (C) is not particularly limited, and includes, for example, an extrusion mixing method and a roll mixing method. Which can be adopted. The mixing conditions depend on the types of polytetrafluoroethylene (A), dispersant (B), and polyolefin (C) used. It is preferable to adjust it appropriately.

The resin composition (Π) of the present invention is produced as described above. If necessary, the resin composition (は) may be, for example, an inorganic filler or a nucleator. Agents, stabilizers, lubricants, etc. can be mixed. Such inorganic fillers, nucleating agents, stabilizers and lubricants are used, for example, when the resin composition (I) is mixed with the polyolefin (C). O o

The inorganic filler is used in a calendar molding process to improve the rigidity, heat resistance, paintability, printability, etc. of the obtained resin composition (π). Prevents sticking to the roll surface, improves the additivity, improves the surface properties of the obtained molded body, and has the property of realizing a lower cost. A component

0

A typical example of the inorganic filler is heavy carbonic acid. Carbonate such as canole gum, light calcium carbonate, etc., talc, glass fiber, magnesium carbonate, my strength, kaolin, Calcium sulfate, sulfuric acid sulfate, titanium dioxide, white carbon, carbon black, hydroxylated aluminum, Magnesium hydroxide, molten silica, etc. are required. They can be used alone or as a mixture of two or more. Among them, from the viewpoint of availability, calcium carbonate such as heavy calcium carbonate and light calcium carbonate, and tanole Is preferred. The average particle diameter of the inorganic filler is about 10 // m or less, and preferably about 5 m or less, depending on the resin composition (Π) obtained. This is desirable from the viewpoint of improving the surface properties.

The amount of the inorganic filler is 0.1 part by weight with respect to 100 parts by weight of the polyolefin (C) so that the effect of improving rigidity and the like can be sufficiently exhibited. It should be at least 1 part by weight, preferably at least 1 part by weight. In order to improve the surface properties of the obtained resin composition (Π), the amount of the inorganic filler is preferably 100 parts by weight of polyolefin (C). It is desired to be less than 400 parts by weight, preferably less than 350 parts by weight, and more preferably less than 300 parts by weight.

The nucleating agent is a component having the property of improving the transparency, surface properties, and rigidity of the obtained resin composition (Π).

Representative examples of the nucleating agent include, for example, compounds exemplified as nucleating agents that can be used in the production of the resin composition (I). Is exacerbated. They can be used alone or as a mixture of two or more.

The amount of the nucleating agent has the effect of improving transparency and surface properties. In order to sufficiently improve the content, it is required to be at least 0.01 part by weight, preferably at least 0.05 part by weight, based on 100 parts by weight of the resin composition. This is what you want. The amount of the nucleating agent is 2 parts by weight with respect to 100 parts by weight of the resin composition (（) so as not to reduce the transparency. Less than 1.5 parts by weight, preferably less than 1.5 parts by weight.

Examples of the stabilizer include the compounds exemplified as the stabilizer that can be used in the production of the resin composition (I). . They can be used alone or as a mixture of two or more. The amount of the stabilizer is usually about 0.01 to 3 parts by weight, preferably 0.05 to 100 parts by weight of the polyolefin (C). It is desired to be about 2 parts by weight.

Examples of the lubricant include the compounds exemplified as lubricants that can be used in the production of the resin composition (I). They can be used alone or as a mixture of two or more. The amount of the lubricant is usually about 0.1 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin (C). Parts.

In the present invention, polytetrafluoronorylene (A) and a dispersant (B) having a specific average particle size are used in a specific weight ratio, and these are used. The resin composition (I) is produced by mixing under high shearing force to make the polytetrafluoroethylene (A) into fibers, and then preparing the resin composition (I). One of the great features is that the mixture of I) and the polyrefin (C). As a result, in the obtained resin composition (Π), the fully fiberized polytetrafluoroethylene (A) is uniformly obtained. By dispersing, the appearance of the molded article obtained from the resin composition (II) is improved. In addition, the tension at the time of melting increases, causing the sheet to be easily taken off during molding of the calendar, and the molten resin to be drawn down during thermoforming or blow molding. In addition, cell foaming during foam molding is improved, and the moldability by calendar molding, thermoforming, pro-molding, foaming molding, etc. is improved. In addition, the amount of discharge during extrusion and the surface condition of the extruded body such as a sheet and a film are improved, and the extrudability is improved. Furthermore, by mixing the polytetrafluoroethylene (A) with the dispersant (B) in advance, the polytetrafluoroethylene can be obtained. The blocking of the styrene (A) has been improved, and the mixing of the polytetrafluoroethylene (A) and the polyolefin (C) has been improved. It has become easier.

As described above, the resin composition (Π) of the present invention has significantly improved workability, impact resistance, and surface properties. Therefore, when the conventional resin composition is used, the resin composition (III) is used even if it is difficult to mold the resin composition. In some cases, various useful moldings can be produced.

Examples of the molding method used for the resin composition (II) include a calendar molding method, an extrusion molding method, a thermal molding method, an injection molding method, and a blow molding method. -Molding method, foam molding method, etc. are required.

For example, the molding method used to produce the thermoforming sheet of the present invention does not impair the transparency of the resulting sheet. There is no particular limitation, and an extrusion molding method using, for example, a single-screw extruder or a twin-screw extruder is preferably used. In addition, it is possible to perform calendar molding on the sheet for thermal molding obtained by the extrusion molding method, for example.

The thickness of the thermoforming sheet obtained as described above is not particularly limited, and may be appropriately adjusted according to the purpose of use. The thickness of such a sheet is usually preferably about 0.05 to 3 mm.

The sheet for thermoforming of the present invention has improved transparency, and particularly improved workability and surface properties. Therefore, when the conventional sheet was used, the thermoforming sheet was used even if the method was difficult to mold. In some cases, it is possible to produce various useful thermoformed bodies.

Representative examples of the thermoforming method applied to the thermoforming sheet of the present invention include, for example, a vacuum forming method and a pressure forming method. By these thermoforming methods, it is possible to obtain a thermoformed body having excellent transparency, surface properties, etc.

For example, the foam of the present invention can be obtained by performing foam molding using the resin composition (樹脂) and a foaming agent.

The foaming agents used in the present invention include volatile foaming agents (physical foaming agents) and decomposable foaming agents (chemical foaming agents), and have a high foaming ratio. A volatile foaming agent is preferable from the viewpoint that a foam is easily obtained.

Representative examples of the volatile foaming agents include, for example, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, and fluorinated aliphatic hydrocarbons. As the aliphatic hydrocarbon, For example, propane, butane, pentane, hexane, etc. are given. Examples of the chlorinated aliphatic hydrocarbon include, for example, methyl chloride, methylene dichloride and the like. The above-mentioned fluorinated aliphatic hydrocarbons include, for example, trichloro-mouth monofunctional fluoromethane (Fleon-11), dichlorodiphenylene For example, Rometan (Freon-1 12), dichlorotetrafluorofluoroethane (Freon-1 114), etc. can be produced. They can be used alone or as a mixture of two or more. Of these, aliphatic hydrocarbons are the most preferred, given the recent environmental concerns.

Representative examples of the decomposable foaming agent include, for example, azodicarbonamide, trihydrazinotriazine, benzenesulfur Semi-solid Solenoid, Jizoamino Benzene, N, Ν '— Ginitorosopentamethylenetetramine, Ν, N'- Chinole N, N '— Ginitroterev olenoic acid imide, azodicarboxylic acid olevonic acid, rhodium, ρ, ρ' — oxbisbenzene Surhonyl hydrazide, etc. can be obtained. They can be used alone or as a mixture of two or more.ο

The amount of the foaming agent is from 1 to 50 parts by weight based on 100 parts by weight of the resin composition (Π) from the viewpoints of the expansion ratio of the foam to be obtained, the stability of the cells, and the surface properties. It is desired to be present in parts by weight, preferably 5 to 40 parts by weight.

As the foam molding method, for example, a molding method such as an extrusion foam molding method or a bead foam molding method can be employed. Among these, the extrusion foaming method is preferred from the viewpoint that the productivity of the foam is excellent, and a foam having a high expansion ratio is obtained. Bead foam molding is preferred from the viewpoint of It is better. The foam obtained by the extrusion foaming method is a low cost foam, and the foam obtained by the bead foaming method is It is a foam with excellent dimensional accuracy, appearance, etc.

In order to manufacture a foamed body by the extrusion foaming molding method, a single-axis extrusion in which a die having a shape corresponding to the shape of a desired molded body is attached. It is preferable to use a machine or a twin-screw extruder. The molding temperature is a temperature equal to or higher than the melting point of the polyolefin (C) or a temperature equal to or higher than the decomposition temperature if a decomposable foaming agent is used. It is preferred that the temperature be lower than the temperature at the tip of the cylinder.

The expansion ratio of the foam obtained as described above is preferably 2 to 10 times, preferably 3 to 8 times, and the foam is preferably For example, it can be used for thermal insulation, building materials, structural materials, etc.

Before the foam is produced by the bead foam molding method, first, for example, the pellet of the resin composition (Π) and the volatile foaming agent are hermetically sealed. After encapsulating the pellet in a container and holding it at about 20 to 90 ° C for 5 to 20 hours to impregnate the pellet with the volatile foaming agent, remove the pellet from the closed container. The pellets are heated and pre-foamed by water steam, hot water, hot air, etc. to produce pre-foamed particles. Next, the obtained pre-expanded particles are filled into a mold having, for example, a water vapor passage hole, and heated to obtain a foam.

The expansion ratio of the foam obtained as described above is 10

Preferably it is up to 60 times, preferably 15 to 45 times, and the foam may be, for example, insulation, cushioning material, bumper core, etc. It can be used as a material. Further, in addition to the above, the resin composition (Π) may be produced by calendar molding or extrusion molding to produce a film-shaped molded article. And can be done. Also, for example, by injection molding or blow molding using a pellet produced by molding from the resin composition (II), It is possible to produce injection moldings or hollow moldings, respectively.

Next, the fluororesin-containing resin composition of the present invention, the production method thereof, and the thermoforming sheets and foams obtained therefrom will be described based on Examples. As will be described in more detail, the present invention is not limited to only such embodiments.

Example I

Production Example 1

The crosslinked polybutadiene rubber was obtained by emulsion polymerization of butadiene. The average particle size of the obtained crosslinked polybutadiene rubber was 0.25 / im, and the crosslinked gel content was 85% by weight.

The latex (glass transfer temperature: 180 ° C) of the crosslinked polybutadiene rubber was added to 75 parts by weight (solid content) of methyl methacrylate. (Glass transfer temperature when used as a homopolymer: 105 ° C) 15 parts by weight and styrene (when used as a homopolymer) Glass transition temperature: 100 ° C.) 25 parts by weight of a monomer component consisting of 10 parts by weight was added, and no graphite copolymerization was carried out by emulsion polymerization. A core copolymer copolymer (hereinafter referred to as copolymer (b) -1) was obtained. The final conversion was 98%, and the average particle size of the copolymer (b) -1 was 0.26 m.

This copolymer (b)-The latex of 1 is salted off, dehydrated and dried to give a copolymer having an average particle diameter of 220 // m. (b) — 1 powder was obtained.

Production Example 2

Acrylic acid n-butyl alcohol 100 parts by weight and a monomer component consisting of 1 part by weight of methacrylic acid acrylate are cross-linked acrylic by emulsion polymerization. I got rubber. In addition, methacrylic acid was used as a cross-linking agent and a graphitizing agent. The average particle size of the obtained bridged acrylic rubber was 0.2 m, and the crosslinked gel content was 85% by weight.

The latex (glass transition temperature: about 154 ° C.) of the crosslinked acrylic rubber was added to 70 parts by weight (solid content) of methyl methacrylate (methyl methacrylate). Glass transition temperature of homopolymer: 105 ° C) 25 parts by weight and n-butyl methacrylate

(Glass transition temperature when used as a homopolymer: 20 ° C) A monomer component consisting of 5 parts by weight (only the monomer component was used as a polymer. (Glass transition temperature at this time: about 8.8 ° C) 30 parts by weight are added, and graphite copolymerization is not performed by emulsification polymerization. Foot copolymer (hereinafter referred to as copolymer)

(b) — 2). The final conversion is 98%, the average particle size of the copolymer (b) -2 is 0.22 izm, and the latex of the copolymer (b) -2 is salted. Dehydrated and dried to give a copolymer with an average particle size of 180 // m

(b) 12 powders were obtained.

Example 1

Polypropylene (Mesolet flow index at 230 ° C: 0.5 g Z 10 min, powder (average particle size): 250 m, below , PP-1) 100 parts by weight of polytetrafluoroethylene (Polyflon TFE-F104, 2 parts by weight of B are added, and these are stirred at a high speed for 5 minutes at room temperature using a benzyl mixer. PTFE was fiberized to obtain a resin composition (A).

Example 2

A resin composition (B) was prepared in the same manner as in Example 1 except that the amount of PTFE was changed to 20 parts by weight in Example 1.

Example 3

In Example 1, except that the copolymer (b) -1 was used instead of PP_1, a resin composition (C) was obtained in the same manner as in Example 1. Was.

Example 4

In Example 2, PP—110 parts by weight was changed to PP—150 parts by weight and copolymer (b) —150 parts by weight. Resin composition (D) was obtained in the same manner as in (2).

Comparative Example 1

In Example 4, a resin composition (A ') was obtained in the same manner as in Example 4 except that PPTFE was not used.

Example 5

Polypropylene (Melt flow index at 230 ° C: 0.5 g Z 10 minutes, pellet (particle size): approx. 3 mm, Hereafter referred to as PP-2) After hand blending 50 parts by weight, 125 parts by weight of the copolymer (b) and 1 part by weight of PTFE, These were extruded using a twin-screw extruder (screw screw diameter: 44 mm, L / Ώ: 30). C was extruded and kneaded at 100 rpm to obtain a resin composition (E). Example 6

In Example 5, PP—250 parts by weight and copolymer (b) —250 parts by weight were changed to PP—110 parts by weight, and the amount of PTFE was 2 parts by weight. Other than the above, a resin composition (F) was obtained in the same manner as in Example 5.

Example 7

2 parts by weight of PTFE is added to 110 parts by weight of PP-1 and these are stirred at a high speed for 5 minutes at room temperature using a helical mixer to fibrillate the PTFE and mix the mixture. Yes. After hand blending the obtained mixture with PP-288 weight parts, these were used with the same twin-screw extruder as used in Example 5. Then, the mixture was extruded and kneaded at 200 ° C. and 100 rpm to obtain a resin composition (G).

Examples 8 to 12 and Comparative Examples 2 to 4

In Example 7, the resin compositions (H) to (L) and the resin composition were changed in the same manner as in Example 7 except that the composition was changed as shown in Table I-11. (B ') to (D'). In addition, PP-3 in Table 1 indicates the melt-to-inlet force at 230 ° C. 3. The average particle size is 700 / m. Represents propylene powder.

[Margins below]

Table I-1 Composition ()

Resin composition Example No. Components agitated with a henshenole mixer Components kneaded with a twin-screw extruder

No.Polyolefin copolymer PTF E Polyolefin

8 PP 1 (20) (2) PP-2 (78) (H)

9 PP-1 (20) (2) PP-3 (78) (I)

10 ― (b)-1 (10) (2) PP-2 (88) (J)

11 ― (2) PP-2 (88) (K)

12 (b) I

CO 1 (20) (2) PP-3 (78) (Shi) Comparative Example o

2 PP 1 (10) o PP-2 (90) (Β ')

3 (b) ― 1 (10) PP-2 (90) (C)

4 PP-2 (90) (D ')

Example 3

P P 2 100 parts by weight of resin composition (A) 5 parts by weight

These are extruded and kneaded at 200 ° C and 50 rpm using a single-screw extruder (screw diameter: 40 mm ヽ LD: 28). I got

The melt tension (g) of the obtained pellets was determined using a capillary graph (manufactured by Toyo Seiki V) having a die with a diameter of 2 mm and a length of 10 mm. , At 200 ° C, at an extrusion speed of 20 mm, and at a pull-out speed of 1 m / min. The results are shown in Table I-12.

Melt flow index at 230 ° C was measured using the pellets in accordance with ASTM D1238. . The results are shown in Table I-12.

The pellets obtained were roll-kneaded at 200 ° C to prepare a sheet. The sheet was press-molded to obtain a test piece compliant with the following ASTM test.

Using the test piece, apply the method described in ASTM-D256 and the method described in ASTM-D790, and conduct a razor impact resistance test and a bending elasticity test in accordance with the method described in ASTM-D790. Was carried out. The results are shown in Table I-12.

In the same manner as described above, a sheet having a size of 100 mm X 10 mm and a thickness of 1.5 mm is formed from the pellet, and an opening of the sheet has a width of 76 mm. The sheet was fixed with a clamp to a size of X76 mm and left for 30 minutes in an oven set at 190 ° C. Then, the K-down (mm) at the center of the sheet was measured. The results are shown in Table I-12.

Further, in the same manner as above, a magnitude of 10 A sheet with a thickness of O mmxl 100 mm and a thickness of 1.5 mm was formed. The surface condition (appearance) of such a sheet was visually observed and evaluated based on the following evaluation criteria. The results are shown in Table I-2.

(Evaluation criteria)

A: The surface is homogenous, and no fibrous aggregates are observed.

B: The surface is almost homogenous, although it is only slightly recognized.

C: The surface is heterogeneous and many agglomerates are observed. Examples 14 to 28 and Comparative Examples 5 to 11

A pellet was manufactured in the same manner as in Example 13 except that the composition was changed as shown in Tables I-12 and I-3 in Example 13; Test pieces and sheets were prepared using the pellets.

The physical properties of the obtained pellets, test pieces and sheet were examined in the same manner as in Example 13. The results are shown in Tables I-12 and I-13.

In addition, the LDPE in Table I-2 and Table I-13 has a melt flow index at 190 ° C of 0.25 g Z10 min. Represents density polyethylene.

[Margins below] Composition (parts by weight)

Example 1

Polyole 5 Haya Ώ:

Melt tension Equilibrium resistance (kg'cmZcm) surface

Surface number Resin composition /, index ratio (kg, down

Fin (C) (g) (gZlO content) 23 to 20 cm2) (mm)

13 PP-2 (100)

No 3 ZO 15 0.8 4 3 14000 2 A

14 PP-2 (100) D _ _ Ο 20 20 0 7 5 3 1 ΠΩ 0 n A

PP-2 (100), Ό) 1 R8 6 1 ΩΩΠ 1 A u PP— 2 (1 ο0 CO0), し 1 1 L7 fn Λ 9 7 n \ J A ο

17 (C) (5) 16 0.8 8 6 11000 2 A

18 PP-2 (100) (D) (5) 16 0.5 6 4 13000 2 A

19 PP-2 (100) (E) (5) 16 0.5 7 4 13 500 1 A

20 PP— 2 (100) (F) (5) 15 0.8 4 3 14000 0 A

21 PP-2 (100) J 15 0.7 4 3 14000 1 A

22 PP— 2 (100) (ri) o) 15 0.7 5 3 14000 o A

O Q PP-2 (100) 1 no o no 1 o 1 1.nu 5 3 o cr r Λ

24 PP-2 (100) (J) (5) 15 0.5 7 6 14000 2 B

25 PP-2 (100) (J) (10) 16 0.5 8 6 13000 1 B

PP-2 (100)

26 (J) (5) 17 0.7 10 7 11000 3 B LDPE (20)

27 PP—2 (100) (K) (5) 20 0.4 10 6 12000 0 A

28 PP-2C100) (L) (5) 18 0.6 10 6 11000 2 A

^^ ^ 2 »ζ J 3: π ^ i

Table I — 3

Composition (weight part)

Shio ¾) t example l 'J a, _i.

a Melt flow

Bolji melt melt strength Shochu impact (kg'cmZcm) Book 1

Surface

No. Resin composition Other index ratio (kg / down

Fin (C)

I CV〇〇 (gZIO) 23 to 20 ° C cm 2) i.mm)

5 PP-2 (100) ― ― 9 0.7 3 2 14000 90 A

6 PP-2 (100) (Α ') (5) 9 0.7 5 3 13000 60 A

7 PP-2 (100) (Β ') (5) 9 0.9 3 2 14000 90 A

t

8 PP— 2 (100) (C) (5) 8 0.8 5 3 13000 62 A

9 (D,) (5) 8 0.8 5 3 13000 58 A

10 PP-2 (100) copolymer 12 0.6 5 4 14000 30 C

(b)-1 (5)

11 8 0.8 5 3 11000 65 A

As shown in 13 to 28, the polyrefin (C) and the polyrefin and / or core-graft copolymer are A resin composition (A) in which the poly (tetrafluoroethylene) (A) is mixed with the poly (tetrafluoroethylene) (A), and the polytetrafluoroethylene (A) is fiberized. (L) has a higher melting tension than the resin compositions obtained in Comparative Examples 5 to 11, and can be formed by thermoforming or blow molding. It can be seen that the drawdown power, which is an indicator, is extremely small and has a significantly improved workability. Furthermore, the surface condition of the molded article (sheet) obtained from the resin composition (Π) of Examples 13 to 28 was good, and the appearance was improved. This is the strength.

Further, a very thin section cut out of the roll sheet obtained in Example 16 was stained with ruthenium tetroxide, and this was used as a transmission type. The resin composition (電子) was observed under an electron microscope (magnification: × 1000) to examine the presence of polytetrafluoroethylen (A) in the resin composition (Π). As a result, it was confirmed that PTF E had a diameter of about 0.05 to 0.3 / / 1 and a length of about 5 to 20πι, and was fibrous.

Example 2 9 to 33 and Comparative Example 1 2

In Example 13, light-weight calcium carbonate (average particle diameter: 0.15 m) surface-treated with a fatty acid as an inorganic filler was used. Same as Example 13 except that 50 parts by weight of the light calcium carbonate was added to 100 parts by weight of indium (C), and the composition was changed as shown in Table I-14. Then, a pellet was manufactured, and a test piece and a sheet were prepared using the pellet.

Examine the physical properties of the pellets, test pieces and sheets obtained. Table I — 4

Composition (weight part)

Example Melt flow

Holler Impact resistance (kg · cmZcm) Bending elasticity Draw

No. Inorganic Ϊ¾θϊ5κ Nof

Resin composition index rate (kg / down

Fin (G) Filler (g) (gZIO content) 23 ° C-20 cm2) (mm)

29 PP— 2 (100) (C) (5) (50) 15 0.5 11 6 15000 1 A

30 PP— 2 (100) (B) (5) (50) 16 0.4 13 7 14000 0 A

31 PP— 2 (100) (G) (5) (50) 14 0.7 10 6 18000 0 A

32 PP-2 (100) (J) (5) (50) 14 0.5 15 8 15000 0 A

33 PP—2 (100) (K) (5) (50) 20 0.4 22 9 14000 0 A Comparative example

12 PP— 2 (100) (50) 10 0.6 7 3 16000 90 A

.呌 From the results shown in Table I-14, as shown in Examples 29 to 33, when the inorganic filler was further used, the obtained resin composition (H ) Has a very small drawdown, which is an indicator of thermoforming, blow molding, etc., and has improved workability. As a result, it can be seen that it is further improved in impact resistance. Further, it can be seen that the appearance of the molded article (sheet) obtained from the resin composition (II) is further improved.

Example ! !

Examples 1 to 5 and Comparative Examples 1 to 3

Acryl-based core-shell darafto copolymer (trade name: Kaneace FM, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) in the amount shown in Table II-1 The amount of polytetrafluoroethylene powder shown in Table II-1 (trade name: Polyfluorene TFE-F104) was applied to the emulsion polymerization method. The powder obtained by aggregating the obtained dispersion, manufactured by Daikin Industries, Ltd. (hereinafter, referred to as TFE-F) is referred to as Henschelmi. Using a xer, high-speed stirring (150 rpm) at room temperature for 10 minutes, and simultaneously mixing these, apply a shearing force to fiberize TFE-F, A composition was produced.

Pellet of phomopolypropylene which is a polyolefin (C) with the amount of resin composition shown in Table II-1 (trade name: Hypopoly) Ru-B200, manufactured by Mitsui Petrochemical Industry Co., Ltd., refractive index: 1.503, methylo-fluoro-index: 0.5 g ZIO, below, high Using a single-screw extruder (screw diameter: 40 mm, LZD: 28) at 100 ° C, 500 parts by weight (port B) The mixture was extruded and kneaded at rpm to obtain a pellet of the resin composition. Incidentally, the core phenolic copolymers having an average particle size of 24.6 m, 14.7 m or 7 O / zm used in Examples 3 to 5 were obtained from Prepare Ness FM by sieving using a 60-mesh timer tile or a 140-mesh timer. Was The average particle size of the core-graft copolymer remaining on the 60-mesh tile flyer was 24 6 / m, and the 60-mesh The average particle size of the core-graft copolymer that has passed through the insulators and remained in the mesh-type tire tray is 140. 4 7 // m, the average particle diameter of the core graft copolymer passed through the mesh tile array was 140 m. .

In Comparative Example 2, a predetermined amount of Hyper B and TFE-F was used without using the core-graft copolymer and the single-screw extruder was used. And extruded and kneaded in the same manner to obtain pellets of the resin composition.

Using the obtained resin composition, the processability, impact resistance, bending elastic modulus, melt tension, appearance of sheet, and melt flow are as shown below. I checked the index. The results are shown in Table II-2.

(Machinability (Drawdown))

The resin composition was roll-kneaded at 200 ° C. for 3 minutes to produce a sheet having a thickness of 1 mm. Two sheets obtained are overlapped and this is 200. After press-molding with C at 30 kg Z cm ² and 10 minutes, this is referred to as 50 kg cm ² and 10 minutes at room temperature. After cooling under the following conditions, a sheet having a thickness of 1.5 mm was obtained. A 300 mm X 400 mm test piece was cut from this sheet.

The obtained test piece is applied to the opening force of the sheet. Secure the sheet with clamps to a size of 98 mm and place it in an oven set at 190 ° C for 10 minutes. After leaving, the drawdown (mm) at the center of the sheet was measured.

Impact)

Two ~

刖 Prepare a 1/4 inch thick test piece in the same manner as described in St: (Workability), and follow the method described in ASTM-D256 to obtain a test piece. Izod with a switch The impact resistance was measured.

(Bending elastic modulus)

Flexural modulus was measured according to the method described in ASTM-D790

(Melting tension)

Using a capillary graph (manufactured by Toyo Seiki Co., Ltd.) having a diameter of 2 mm and a length of 10 mm, extruded at 200 ° C

The melt tension of the resin composition was measured at a take-up speed of 20 m / min and a take-up speed of 1 m / min.

(Appearance of the sheet)

The resin composition was roll-kneaded and press-molded at 200 ° C. to produce a 1.5-mm-thick sheet. The surface condition of the obtained sheet was visually observed, and evaluated based on the following evaluation criteria.

(Evaluation criteria)

A: No aggregates of polytetrafluoroethylene are observed

B Aggregates of fibrous polytetrafluoroethylene are slightly observed ^) O

Clusters of C polytetrafluoroethylene are observed. (Menoret Flow Index)

ASTM — 230, according to the method described in D1232. At C (Propylene-based olefin) or 190 ° C (Ethylene-based olefin) Was measured. Table Π — 1 Composition

Resin composition

Example:

Core shell

TFE

Number B Number F

Graph copolymer

Amount Amount

Average particle size (m) (parts by weight)

(Weight part)

1 100 180 5 0.1

2 100 180 0.5 0.1

3 100 246 5 0.1

4 100 147 5 0.1

5 100 70 5 0,1 Comparative example

1 100

2 100 0.1

3 100 180 0.1 0.1 Table Π — 2 Physical properties

Λ¾1

Example Impact resistance Menole flow Workability

(kgcm / cm) Flexural modulus Melt tension

Number index (drawdown) sheet appearance

(kg / cm ² )

C shi u u (g) (for gZio) (mm)

1 8 6 14000 16 0.4 47 A

1 D 1 15 0 5 58 A

8 6 1 a

14 n u n u n 1

u 0 A A

A 8 6 14000 16 0.4 52 A

5 8 6 14000 16 0.4 61 B Comparative example

1 3 2 14000 9 0.7 150 A

2 4 3 14000 11 0.6 105 C

3 4 3 14000 12 0.6 103 C

Based on the results shown in Table II-2, when the resin composition (Π) obtained in Examples 1 to 5 was used, the core-shell No polymer and no polytetrafluoroethylene were used. The resin composition of Comparative Example 1 and the core-polygraph copolymer were used. The resin composition of Comparative Example 2 and the core shell graphite copolymer (dispersant (Β)) and polytetrafluoroethylene were not removed. Compared with the resin composition of Comparative Example 3 in which the weight ratio ((Β) / (A)) to styrene (/) is 100 Z100, the thermoformability and the blow moldability are higher. It can be seen that the drawdown of the sheet, which is an indicator of workability, is greatly improved. When compared with the resin compositions of Comparative Examples 2 and 3, the appearance of the sheet was improved by using the resin compositions (樹脂) of Examples 1 to 5. I understand that. Also, in Examples 1 to 5, if a core-graft copolymer having an average particle diameter of 100 m or more was used, the sheet You can see that the appearance is especially good.

Further, in order to observe the presence form of polytetrafluoroethylene in the resin composition (Π), the sheet obtained from the resin composition (Π) was used. A very thin section cut out was stained with ruthenium tetroxide and observed with a transmission electron microscope (magnification: 10000). As a result, it was observed that polytetrafluoroethylene was in a fibrous form. In addition, in order to make it easy to observe the polytetrafluoroethylene, the amount of the case FM was set to 25 weight in Example 1. Parts, and the amount of TFE-F was changed to 0.5 parts by weight, except that the resin composition (II) produced in the same manner as in Example 1 was used as a sample.

Examples 6 to 7 and Comparative Example 4 In Example 1, instead of the core-graft copolymer, as shown in Table III-3, the flop plane QB 200 was obtained. 50 P (Sumitomo Seika Co., Ltd., homopolypropylene frozen-pulverized powder, average particle size 250 μm, refractive index 1.53, below -Plan QB), Snow Light SSS (manufactured by Maruo Calcium Co., Ltd., calcium carbonate, average particle diameter 1.8 m) or Hypolite B200P (Mitsui Petrochemical Industries, Ltd., Polypropylene Powder, average particle diameter: 100 m) was used as the dispersant (B). Otherwise, a resin composition was prepared in the same manner as in Example 1, and the physical properties of the obtained resin composition were evaluated. The results are shown in Table II-4.

[Margins below]

Table Π — 3 compositions (weight part)

Resin composition

Example

Hypol dispersant (Β)

No.

Β TFE-I F Flowbren High Pole Snow Light

QB Β200Ρ SSS

6 100 0.1 5

t

7 100 0.1 5 Comparative example

100 0.1 5

Four

Table Π — 4 Physical properties

Examples Example of resistance to arcade Melt flow Workability

Number (kgcm / cm) Flexural modulus Melt tension

Index (Drawdown) Sheet appearance (kg / cm ^) (g)

23 ° C-20 ° C (gZio) (mm)

6 5 3 14000 16 0.6 58 A

7 5 3 14000 16 0.5 65 B Comparative example

4 3 14000 11 0.6 95 C 4

From the results shown in Table II-4, it was found that as a dispersant (Β), homopolypropylene having an average particle size of 25 Ozm was freeze-ground. When using powder (Floprene QB) and using calcium carbonate (Snowlite) with an average particle size of 1.8

When using SSS), as in Example 1, the drawdown of the sheet is greatly improved, and the appearance of the sheet is also greatly improved. You can see. On the other hand, a polypropreneno having an average particle diameter of 1000 μm. When using powder (no dipole B200P), the improvement effect of the sheet drawdown is small and the portability It can be seen that the fluoroethylene is not sufficiently dispersed and the appearance of the sheet is poor. Examples 8-9 and Comparative Examples 5-6 (Nucleating agent or inorganic filler) Example using filler)

In the same manner as in Example 1, the flop plane QB (average particle diameter 250 / m) or the case FM (average particle diameter 180 μm) and TFE-F were used. The resin composition was manufactured by high-speed stirring with a helix mixer to form TFE-F into fibers.

The obtained resin composition and Hyper B were added to the nucleating agent (Gel All DH (manufactured by Shin Nihon Rika Co., Ltd.) in the amount shown in Table II-5. Bis (p-methyl benzylidene) sono-reitol or heavy calcium carbonate (trade names: Snolite SSS, Maruo Calushiu) Was added, and a resin composition was prepared in the same manner as in Example 1, and the physical properties of the obtained resin composition were evaluated. The transparency was evaluated by the method, and the results are shown in Table II-6.

(transparency) A test piece having a thickness of 1.0 mm and a size of 3 O mm x 3 O mm was prepared in the same manner as in the method described in (Workability) above, and conformed to the method described in ASTM-D1003. Then, the transparency of the test piece was examined. In Table II-6, T represents total light transmittance (%), and HAZE represents turbidity (%).

[Margins below]

Table II — 5 compositions (weight part)

Example resin composition

Nyponore

No.Nucleating agent Canolecum carbonate Floprene iKanee-B

TFE-I F

QB FM

8 100 0.5 0.1 5 9 100 50 0.1 5 Example

100 0.5

Five

6 100 50

Table _ _ 6 Physical properties

Example Impact resistance (kg · cm / cm) Lightness (%)

ca Melt tension Flexural modulus Transparency (draw sheet number

(g) 23 ° C-20 ° C (kg / cm ² ) T HAZE Town (mm)

8 16 5 3 15000 86 53 55 A

C

9 16 8 6 15000 41 A

Comparative example

9 3 2 16000 86 55 144 A 5

6 10 3 2 16000 137 A

Based on the results shown in Table II-6, when mixing the resin composition with the polyolefin (C), a specific amount of the nucleating agent was also added to them. When the obtained resin composition (（) of Example 8 was used, the obtained sheet was prepared by mixing only a nucleating agent into a nanopore. It has the same appearance and transparency as the sheet made of the resin composition of Comparative Example 5 obtained above, has a higher melt tension, and has better workability. It can be seen that the drawdown of the sheet, which is an indicator, has been greatly improved, and the balance of impact resistance and rigidity has been greatly improved.

Further, the resin composition of Example 9 obtained by mixing a specific amount of an inorganic filler (calcium carbonate) with the resin composition and the polyolefin (c) was used. In the case of using (ii), the obtained sheet was obtained by mixing only the inorganic filler (calcium carbonate) with Hyperpole. The sheet has the same appearance and rigidity as the sheet made of the resin composition of Example 6, has an increased melt tension, and is an indicator of workability. It can be seen that the drawdown has been greatly improved, and the shock resistance and stiffness of the lance have been greatly improved.

Example JI

Production Example 1 (Production of core shell graft copolymer)

Butadiene was polymerized by the usual emulsion polymerization method to obtain a bridged polybutadiene rubber. No cross-linking agent was used. The obtained rubber had a glass transition temperature of 180 ° C, a particle diameter of 0.25 // m, and a crosslinked gel content of 85% by weight. 75 parts by weight (solid content) of the obtained polybutadiene rubber, 15 parts by weight of methyl methacrylate and 15 parts by weight of styrene 25 parts by weight of a monomer component consisting of 0 parts by weight was subjected to graph-polymerization by a usual emulsion polymerization method to obtain a polymer. e The conversion of the obtained polymer was 98%, and the particle size was 0.2 to βm. The obtained dispersion of the polymer is salted out, dehydrated and dried by a usual method, and the powder of the core-shell graph copolymer (Β) -1 is removed. Yes. The average particle size of the powder was 250 / m.

Production Example 2 (Production of core shell graft copolymer)

A monomer component consisting of 100 parts by weight of n-butyl acrylate and 1 part by weight of methacrylic acid is polymerized by a usual emulsion polymerization method. To obtain a crosslinked polyethylene acrylate rubber. The obtained rubber had a glass transition temperature of 55 ° C, a particle size of 0.2 // m, and a crosslinked gel content of 85% by weight. 70 parts by weight (solid content) of the obtained cross-linked butyric rubber of polyacrylic acid, 25 parts by weight of methyl methacrylate and metal 30 parts by weight of a monomer component consisting of 5 parts by weight of acrylic acid n-butyl was subjected to graphitization copolymerization by a usual emulsion polymerization method to obtain a polymer. The conversion of the obtained polymer was 98%, and the particle size was 0.22 // m. The obtained polymer dispersion was salted out, dehydrated and dried by a usual method to obtain a powder of a core phenolic copolymer (B) -2. . The average particle size of the powder was 200 μm.

Examples 1 to 4 and Comparative Examples 1 to 4

The core-graft copolymer shown in Table m-1 and the polytetrafluoroethylene shown in Table m-1

(Product name: POLYFLON TFE-F104, manufactured by Daikin Industries, Ltd.) Powder produced by aggregating the dispersion obtained by the emulsion polymerization method. And TFE-F) with high-speed stirring (150 rpm) at room temperature for 10 minutes using a helical mixer, and mix these. And at the same time TFE — F was fiberized by applying shearing force to produce a resin composition.

The amount of the resin composition shown in Table m-1 and the amount of the polyolefin (c :) homopolypropylene (trade name Noipore B2 Melt D-index, manufactured by Mitsui Petrochemical Industry Co., Ltd .: 0.5 g Z 10 minutes, hereinafter referred to as Hyper B 9) 100 weight Using a single-screw extruder (screw diameter: 40 mm ゝ L / D: 28), the parts were extruded and kneaded at 200 ° C and 50 rpm, and the resin composition was extruded. Based on the pellet of

In Comparative Examples 2 to 4, the resin composition was not prepared from the core-shell graphite copolymer and TFE-F in advance, and a predetermined amount of high Pole B, core shell graft copolymer and TFE-F were similarly extruded and kneaded with the single-screw extruder to obtain a resin composition pellet. Got

Using the obtained resin composition, the processability, impact resistance, bending elastic modulus, melt tension, appearance of the sheet and melt flow are as follows. The index was checked. O The results are shown in Table m-2.

(Additiveness)

The resin composition was roll-kneaded at 200 ° C. for 3 minutes to prepare a sheet having a thickness of 1 min. Two sheets obtained are overlapped, and this is 200. After press molding with C at 30 kg Z cm ² and 10 min, at room temperature, 50 kg / cm ² and L 0 min. After cooling, a 1.5 mm thick sheet was obtained. A 100 mm x 100 mm specimen was cut from this sheet.

The obtained test piece was clamped with a frame having an opening of 76 mm x 76 mm in size, and was dropped on the leg of the frame. Attach the metal object for the drop measurement and leave the sheeted frame in an oven set at 190 ° C for 30 minutes. After that, I measured the draw down mm at the center of the sheet.o

(Shock resistance)

A 4 inch thick ϊζ piece was prepared in the same manner as in the above (workability), and the test piece was knocked in accordance with the method described in ASTM-D256. Izzt with lip Impact resistance was measured ο

(Bending elastic modulus)

The bending elastic modulus was measured according to the method described in AST II-D790.

(Melting tension)

Using a capillary graph (manufactured by Toyo Seiki Co., Ltd.) having a diameter of 2 mm and a length of 10 mm, extruding speed at 200 ° C and 20 ° C The melt tension of the resin composition was measured at mm / min and at a take-up speed of 1 m.

(Appearance of the sheet)

The surface condition of the sheet obtained by rolling and kneading the resin composition at 200 ° C was visually observed, and evaluated based on the following evaluation criteria.

(Evaluation criteria)

A: No aggregates of polytetrafluoroethylene are observed o

B Aggregates of fibrous polytetrafluoroethylene were slightly observed.

C: Clusters of polytetrafluoroethylene are observed. (Melt flow index) The melt flow index was measured at 230 in accordance with the method described in ASTM — D1238.

Table m

Composition

Resin composition

Example Highpole

Core—Shell Graph TFE-F Number B

Amount of copolymer

(Weight part)

Amount

1 100 (B)-1 5 0.1

2 100 (B)-1 5 1.0

3 100 (B)-1 10 0.1

4 100 (B)-2 5 0.1 Comparative example

100

1

2 100 (B)-1 5 0.1

3 100 (B)-1 10 0.1

4 100 (B)-2 5 0.1

Table m

Physical properties

Examples Mouth Resistance Menoleto Flow Workability

(kgcm / cm) Flexural modulus Melt tension

Number Index (Drawdown)

(Appearance of kgZcm (g)

23 ° C-20 ° C (for gZIO) \ nrn

1 8 6 14000 16 0.5 1 A

2 8 5 16000 17 0.3 0 B

3 9 7 13000 17 0.4 0 A

4 8 6 14000 16 0.5 1 A ratio W v \

3 2 14000 9 0.7 90 A 1

2 5 4 14000 12 0.6 34 C

3 6 4 13000 13 0.6 30 C

4 5 3 14000 12 0.6 20 C

Based on the results shown in Table m-2, the core siezograft copolymer and TFE-F were mixed with a helical mixer, and TFE-F To produce a resin composition, and the resin composition of Examples 1 to 4 obtained by using the resin composition.

In order to use (Π), the use of a resin composition consisting of coresole graphite copolymer and fiberized TFE-F is not required. Compared with the resin composition, the melt tension is increased, and the sheet drawdown, which is an indicator of processability such as thermoformability and blow moldability, is significantly reduced. It can be seen that the appearance of the sheet has been improved as well.

Furthermore, in order to observe the existence form of the polytetrafluoroethylene in the resin composition (Π), the molded article made of the resin composition (Π) was cut. The resulting very thin sections were stained with ruthenium tetroxide and observed with a transmission electron microscope (magnification: 100,000). As a result, it was observed that the polytetrafluoroethylene was fibrous. In addition, in order to easily observe the polytetrafluoroethylene, the core shell graph in Example 1 was used. Resin produced in the same manner as in Example 1 except that the amount of polymer (B)-1 was changed to 25 parts by weight and the amount of TFE-F was changed to 0.5 part by weight. The composition (Π) was used as a sample.

Examples 5 to 9

(1) Examples 5 to 8: The core-graft copolymer shown in Table m-3 and the amount of TFE-F and TFE-F shown in Table m-3 After blending 5 parts by weight of the high-pole B with these, the two-screw extruder screw diameter: 44 mm, LZD: 30) At 200 ° C and 100 rpm After kneading, the TFE-F was fiberized to produce a resin composition (I).

(2) Example 9: The amount of core-shell graft copolymer and TFE-F shown in Table III-3 were measured with a Henschel mixer. The mixture was stirred at a high speed for 10 minutes at room temperature to fibrillate TFE-F to obtain a mixture. After this mixture and the amount of nipple B in the amount shown in Table m-3 were subjected to node blending, biaxial extrusion was performed in the same manner as in Examples 5 to 8 above. The resin composition (I) was manufactured using a machine.

The amount of the resin composition (I) shown in Table m-3 and the remaining Hipol B were kneaded with a single screw extruder in the same manner as in Example 1, and the resin composition (ペ) Pellet was obtained. The physical properties of the obtained resin composition (II) were evaluated in the same manner as in Example 1. The results are shown in Table m-4.

[Margins below]

Table in 3

Composition

脂 Fat composition (I)

Example Highpole

Core enograft TFE I F Noipole No. J Amount of copolymer B

(Weight part)

Type (parts by weight) (parts by weight)

5 95 (B)--1 5 0.1

6 95 (B)--1 5 1.0 5

7 95 (B)--1 10 0.15

8 95 (B)-2 5 0.1

9 100 (B)-1 1 0. 1 3.9

Table DI — 4 properties

Example w-resistance Menoleto flow Workability

(k · cmZcm) ftt If ¾ ¾ ¾ ¾ <· & g rais½ H ¾KE no J

(kg / cm ² ) (g)

-20 ° C (for gZio)

5 7 6 14000 15 0.5 2 B

6 8 5 16000 17 0.4 0 B

7 8 6 13000 16 0.5 1 B

8 8 6 14000 16 0.5 3 B

9 5 4 14000 17 0.4 0 A

Based on the results shown in Table m-4, the core-graft copolymer, TFE-F and a part of Hypo-B were kneaded with a twin-screw extruder. Then, TFE-F is fiberized to produce a resin composition (I), and the resin composition (Π) obtained by using the resin composition (I) is used. Is to prepare a resin composition (I) by kneading each component with a helix mixer, fiberizing TFE-F, and using the resin composition (I). As in the case of the resin composition (Π), the melt tension has been increased and the melt flow index has been reduced, which is an indicator of workability. It can be seen that the drawdown of the vehicle has been greatly improved, and the appearance of the seat has also been improved.

Also, the core copolymer graft copolymer and TFE-F were stirred at a high speed with a heterogeneous mixer, and the TFE-F was allowed to react with a fiber. And a part of Hyper B are kneaded with a twin screw extruder to produce a resin composition (I), and the resin composition obtained by using the resin composition (I) is obtained. To use (ii), knead the components only with a hen-shell mixer or twin-screw extruder and fiberize TFE-F. Similarly to the resin composition (Π) obtained using the resin composition (I), the melt tension is increased and the melt flow index is reduced. It can be seen that the drawdown of the sheet, which is an indicator of workability, has been improved, and the appearance of the sheet has been further improved. .

Examples 10 to 13 and Comparative Example 5 (Example using inorganic filler)

In the same manner as in Example 1, the core-silver graft copolymer and TFE-F were stirred at a high speed with a helical mixer to convert TFE-F into fibers. A resin composition was manufactured. Table m CJ1 '

+

However

Resin composition of course

Example High-Pole Carbonate

Core Shienoregraft TFE-F

Number B Quantity Amount

Copolymer

(Parts by weight) (parts by weight)

Type (parts by weight) (parts by weight)

10 100 50 (B)-1 50 0.1 1 11 100 50 (B)-1 5 1.0

,

12 100 50 (B)-1 10 0.1

'13 100 50 (B)-2 5 0.1

Factory

Comparative example

100 50

5 m

Factory ^

^ 呌_s N

. ^ ^ ^ ^ ^ θ)) ^ 挪 ^ J ^ s s s I

1 Table m 6 rJi ΈΕ

荬例リリ -r r

Tension sheet numbercm / cm; Flexural modulus Melting

Index (drawdown)

(kg / cm ² )

23 ° C 20. C (for gZio) (mm)

10 1 1 6 15000 15 0.5 1 A

11 12 6 17000 17 0.3 0 B

12 13 7 14000 16 0.4 0 A

13 1 1 6 15000 15 0.5 0 A Comparative example

7 3 16000 10 0.6 90 A 5

The results are shown in Table m-6, the resin composition consisting of the core copolymer graphite copolymer and TFE-F, calcium carbonate and ha. When using the resin composition (Π) obtained from Iponore B, the core resin graft copolymer and fiberized material were used. Compared to a resin composition that does not use a resin composition consisting of TFE-F, the melt tension is higher and the sheet loader is an indicator of workability. It is clear that the wings have been significantly improved and are well balanced with the impact and rigidity balance.

Example IV

Production Example 1

Acrylic acid n — A monomer component consisting of 70 parts by weight of butylene, 30 parts by weight of styrene, and 1 part by weight of methacrylic acid 100 parts by weight A part by weight was subjected to emulsion polymerization to obtain a crosslinked acrylic rubber. In addition, methacrylic acid was used as a cross-linking agent and a graphitizing agent. The average particle size of the obtained crosslinked acrylic rubber is 0.2 m, and the crosslinked gel content is 85% by weight.

Acrylic rubber rubber (glass transfer temperature: approx. 23 ° C) 70 mass parts of methacrylic acid methyl (solid content) (Glass transition temperature when used as a homopolymer: 105 ° C) 27 parts by weight and styrene (when used as a homopolymer) (Glass transition temperature: 100 ° C) 30 parts by weight of a monomer component consisting of 3 parts by weight are added, and these are subjected to a graphitization copolymerization by an emulsion polymerization method. Thus, a corecyanoleft copolymer (b) (hereinafter, referred to as a copolymer (b)) was obtained. The final conversion was 98%, and the refractive index of the copolymer (b) was 1.503. The wax of the copolymer (b) was salted, dehydrated and dried to obtain a powder of the copolymer (b) having an average particle size of 180 μm.

Production Example 2

Polypropylene (Melt flow index at 230 ° C: 0.5 g Z 10 min, refractive index: 1.503 (Polymer No. 3rd edition, listed value), powder (average particle diameter): 250 // m, hereinafter referred to as PP-1) 100 parts by weight of poly Add 2 parts by weight of tetrafluorophenol (Polyflon TFE-F104, manufactured by Daiken Industries, Ltd .; hereinafter, referred to as PTFE). These were stirred at a high speed for 5 minutes at room temperature using a helical mixer to fibrillate the PTFE and obtain a resin composition (A).

Production Example 3

In Preparation Example 2, except that the amount of PTFE was changed to 20 parts by weight, the same procedure as in Preparation Example 2 was repeated except that the resin composition (B) was used.

In Preparation Example 2, the polymer composition (b) was used in place of PP-1, except that the resin composition was changed in the same manner as in Preparation Example 2.

(c) was obtained.

Production Example 5

In Construction Example 3, P P — 110

50 parts by weight and copolymer (b). A resin composition (D) was obtained in the same manner as in Production Example 3 except that the amount was changed to 50 parts by weight.

Comparative Production Example 1

In Example 5, PTFE was not used. A resin composition (Α ′) was obtained in the same manner as in Preparation Example 5.

Production Example 6

Ρ Ρ After hand blending 110 parts by weight and 2 parts by weight of PTFE, these were extruded into a twin-screw extruder (screw diameter: 44 mm, Using LZD: 30), the mixture was extruded and kneaded at 200 ° C. and 100 rpm to fiberize PTFE, thereby obtaining a resin composition (E).

Production Example 7

In Production Example 6, PP-110 parts by weight was changed to PP-150 parts by weight and copolymer (b) 50 parts by weight, and the amount of PTFE was changed to 1 part by weight. Then, a resin composition (F) was obtained in the same manner as in Production Example 6.

Production Example 8

Add 2 parts by weight of PTFE to 100 parts by weight of PP-1 and stir them at high speed for 5 minutes at room temperature using a helical mixer to fiberize the PTFE. The mixture was obtained. The obtained mixture was extruded and kneaded at 200 ° C. and 100 rpm using the same twin-screw extruder as that used in Production Example 6 to obtain a resin composition (G). .

Production Example 9

2 parts by weight of PTFE is added to 110 parts by weight of PP-1 and these are stirred at a high speed for 5 minutes at room temperature using a helical mixer to fibrillate the PTFE and mix the mixture. Yes. Polypropylene (Polypropylene) (Melt flow index at 230 ° C: 0.58 min, refractive index: 1.50 min) 3 (Polymer Handbook, 3rd edition, published values), Pellet (particle size): about 3 mm, hereinafter referred to as PP-2) 8 8 Weight parts After blending, these were used in Production Example 6. The mixture was extruded and kneaded at 200 ° C. and 100 rpm with the same twin-screw extruder as that used to obtain a resin composition (H).

Production Examples 10 to 13 and Comparative Production Examples 2 to 3

In Preparation Example 9, the composition was changed as shown in Table W-1, except that the resin compositions (I) to (I) were the same as in Preparation Example 9.

(L) and resin compositions (B ') to (C') were obtained. In addition, PP-3 in Table 1 shows that the melt tip at 230 ° C has an index of 3. Og ZIO and a refractive index of 1.53 (poly It represents polypropylene powder with an average particle size of 700 zm (Marhandbook, 3rd edition, published values).

[Margins below]

IV-1 Composition ()

Resin composition with twin screw extruder

¾¾ Ja -S- "

No. of kneaded components Polyolefin copolymer (b) P T F E

10 PP 1 (20) (2) PP-2 (78) (I)

11 PP-1 (20) (2) PP-3 (78) (J)

12 (10) (2) PP-2 (88) (K)

13 (20) (2) PP-3 (78) (L) Comparative production example

2 PP 1 (10) PP-2 (90) (Β ')

3 (10) PP-2 (90) (C)

Example 1

5 parts by weight of the resin composition (A) is mixed with 100 parts by weight of PP-2, and these are extruded into a single screw extruder (screw diameter: 40 mm, L / D: 28). 2 0 0 using C. The mixture was extruded and kneaded at 50 rpm to give pellets.

The melt tension (g) of the obtained pellets was measured using a capillary graph (manufactured by Toyo Seiki Co., Ltd.) having a die with a diameter of 2 mm and a length of 10 mm. Yes, 200. C: Measured at an extrusion speed of 20 mm / min and a take-up speed of 1 mZ. The results are shown in Table IV-2.

Using the pellet, measure the melt flow index at 230 ° C according to the method described in ASTM-D1238. did . The results are shown in Table IV-2.

Next, the obtained pellets were roll-kneaded at 200 ° C to produce a sheet, and the sheet was press-molded to obtain each of the following ASTMs. A test piece conforming to the test was obtained.

Using the obtained test piece, the Izod impact resistance test and bending were performed according to the method described in ASTM-D256 and the method described in ASTM-D790. An elasticity test was performed. The transparency was examined according to the method described in ASTM — D103. The results are shown in Table IV-2. T in the column of transparency in Table IV-2 indicates total light transmittance, and HAZE indicates turbidity.

In the same manner as described above, a sheet having a size of 100 mm x OO mm and a thickness of 1.5 mm is formed from the pellet, and the opening of the sheet has a width of 76 mm. Fix the sine with a clamp to a size of X76 mm and leave it in an oven set at 190 ° C for 30 minutes. After that, the sheet Φ Drawdown (mm) in the center was measured. The results are displayed

This is shown in IV-2.

Further, a sheet having a size of 100 mm X 100 mm and a thickness of 1.5 mm is formed from the pellet in the same manner as described above, and the sheet is formed. The surface condition (appearance) was visually observed, and evaluated based on the following 5 parity standards. The results are shown in Table IV-2.

(Evaluation criteria )

A: The surface is homogenous, and no fibrous aggregates are observed.

B Aggregates are only slightly visible, but the surface is almost homogeneous.

C: The surface is heterogeneous and many agglomerates are observed. Examples 2 to 16 and Comparative Examples 1 to 7

In Example 1, except that the composition was changed as shown in Table IV-2 and Table IV-3, a pellet was produced in the same manner as in Example 1 and the pellet was produced. Specimens and sheets were prepared using the rod.

The physical properties of the obtained pellets, test pieces and sheet were examined in the same manner as in Example 1. The results are shown in Table IV-2 and Table IV-13.

In addition, the LDPE in Tables W-2 and W-3 has a refractive index of 0.25 g Z at 10 ° C at 190 ° C, and is refracted. Represents low-density polyethylene with a rate of 1.51 (Polymer Handbook, 3rd edition, published values). Table IV

Composition (weight part)

Example

Mezoletov

Melting tension Melt tension Impact resistance (kg · cm / cm) Transparency (%) Bending elasticity

Surface number Resin composition Index (kg / down

Fin (C) (g) (gZIO content) 23 V _ 20 T HAZE cm 2) (mm)

9

1 ΡΡ-2 (100) (A) (5) c

1 O Π Q 4 3 88 69 14UUU i A

2 ΡΡ-2 (100) (B) (5) 20 0.7 5 3 89 64 14000 0 A

3 ΡΡ-2 (100) (C) (5) 16 0.5 8 6 90 69 14000 1 A

4 ΡΡ-2 (100) (C) (10) 17 0.4 9 7 89 67 13000 0 A

5 (C) (5) 16 0.8 8 6 88 69 11000 2 A

LDPE (20)

6 PP-2 (100) (D) (5) 16 0.5 6 4 89 67 13000 2 A

7 PP-2 (100) (E) (5) 15 0.6 4 3 88 67 14000 0 A

8 PP-2 (100) (F) (5) 16 0.5 7 4 88 64 13 500 1 A

9 PP-2 (100) (G) (5) 15 0.8 4 3 88 64 14000 0 A

10 rr— ^ UUU, 15 0.7 4 3 87 65 14000 1 A

1 丄 PP— 2 (100) (I ヽ) (* 5 c ヽ) c

1 O Π 7 5 3 89 66 1 Lily υ π ur Λ Q PP-2 (100) (J) (5) c

10 π 5 3 90 64 丄 4 lili υ A

0 i

13 PP-2 (100) (K) (5) 15 0.5 7 6 87 65 14000 2 B

14 PP-2 (100) (K) (10) 16 0.5 8 6 88 65 13000 1 B

PP-2 (100)

15 (K) (5) 17 0.7 7 4 86 65 11000 3 B LDPE (20)

16 PP-2 (100) (L) (5) 18 0.6 8 6 87 69 11000 2 A

Table IV — 3

From the results shown in Table IV-2 and Table IV-3, as shown in Examples 1 to 16, the polyrefin (C) and the polyrefin were obtained. Or copolymer core copolymer and polytetrafluoroethylene (A) are mixed together, and the polytetrafluoroethylene (A) is mixed. When a resin composition (Π) consisting of a resin composition (A) to (L) in which fluoroethylene (A) is fiberized is used, a specific ratio is required. Compared to the resin compositions of Comparative Examples 1 to 7, the HAZE (turbidity) is particularly low, the transparency is improved, and the melt tension is increased. In other words, drawdown, which is an indicator for thermoforming, blow molding, etc., is small, and it is evident that workability can be improved significantly. Furthermore, the surface condition of the molded article (sheet) obtained from the resin composition (Π) of Examples 1 to 16 was good, and the transparency was also improved. I know something.

Further, a very thin section cut out from the sheet obtained in Example 4 was stained with ruthenium tetroxide, and this was transmitted through a transmission electron microscope. Observation was carried out at a magnification of 1,000 times, and the presence form of polytetrafluoroethylene (A) in the resin composition (Π) was examined. As a result, it was confirmed that PTFE had a diameter of about 0.05 to 0.3 zm and a length of about 5 to 20 / zm, and was fibrous.

Examples 17 to 21 and Comparative Example 8

In Example 1, bis (p-methylbenzylidene) solvitol was added as a nucleating agent to 100 parts by weight of the pellet of the resin composition. On the other hand, pellets were produced in the same manner as in Example 1 except that 0.5 parts by weight were added, and the composition was changed as shown in Table W-4, and the pellets were produced. The test pieces and sheets were prepared using the method. Factory -r

φ τ s,

o 呌

^ ^. ^ 1 ^ ^ ¾ ^ ぃ Π Sίν tl Table iv

From the results shown in Table IV-4, as shown in Examples 17 to 21, when the nucleating agent was further used, especially when thermoforming and broiling were used.ー The drawdown, which is an indicator of molding, etc., is small, the workability can be improved significantly, and the transparency of the molded product (sheet) is also low. It will be appreciated that it can be further improved.

Example V

Example 1

Rubber-based core copolymer (Kaneace M511, manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle size: 200 / m, refractive index: 1) 5 2) 5 parts by weight and polytetrafluoroethylene phenyl, ⁰ powder (Polyfluoro TFE-F104, Daikin Industries, Ltd.) (Average particle size: 500 β m) 0.1 parts by weight was stirred at room temperature for 10 minutes in a helical mixer and mixed at the same time. Shearing force was applied to the fiber to make the polytetrafluoronorylene ethylene. This mixture was mixed with homopolypropylene (melt flow index at 230 ° C: SgZ10O, refractive index: 1.503) ) Pellet of 100 parts by weight and sorbitol-based nucleating agent (C1, bis (p-methisolenbenzylidene) solvitol) 0.3 parts by weight of a single-screw extruder (screw diameter: 50 mm, L / D: 28) with a T die attached at 200 ° C and 50 rpm (The content of fiberized polytetrafluoroethylene: 0.1 part by weight based on 100 parts by weight of homopolypropylene) , And extruded to obtain a lmm thick sheet. The obtained sheet had sufficient impact resistance as a sheet for thermoforming.

The transparency of the obtained sheet is defined as the total light transmittance (%) (in Table V-1, denoted as T) and HAZE (turbidity). (%) Was measured. In addition, 45 ° dalo (%) was measured in terms of luminous intensity in accordance with the method described in JISK7105. The results are shown in Table V-1.

Also, cut out the obtained sheet to a size of 300 mm x 400 mm, and set the opening of the sheet to a size of 29.8 mm x 398 mm. Fix the sheet with a clamp so that it becomes 250 mm. After leaving for 40 seconds in an oven heated to C, the drawdown (mm) at the center of the sheet was measured. The results are shown in Table V-1.

Examples 2 to 11 and Comparative Examples 1 to 4

In Example 1, a sheet having a thickness of 1 mm was obtained in the same manner as in Example 1, except that the composition was changed as shown in Table V-1. The sheets obtained in Examples 2 to 11 had sufficient impact resistance as a sheet for thermoforming.

With respect to the obtained sheet, transparency, glossiness and drawdown were examined in the same manner as in Example 1. The results are shown in Table V-1.

Incidentally, in Examples 2 to 11, the content of the polished polytetrafluoroethylene in any of the polyolefins (C) It is the same as the amount of polytetrahydronorethole ethylene added to 100 parts by weight (parts by weight).

Further, in Comparative Examples 3 and 4, the rubber-based coresile graph copolymer and the polytetrafluoroethylene were used as the phenols. The mixture was agitated in a mixer, and when they were mixed, a shearing force was applied at the same time, but the polytetrafluoroethylene remained in powder form. However, it was not fiberized.

The abbreviations in Table V-1 indicate the following contents. (Polytetrafluoroethylene (A))

A-1

04, manufactured by Daikin Industries, Ltd., average particle size: 500 m)

A-2 powder (Teflon τ FE — 6 J,

Mitsui DuPont Fluoro Chemical Canole Co., Ltd.)

A-3 Molding powder (Teflon TF E _

7 J Mitsui DuPont Fluoro Chemical Canole Co., Ltd.)

A 4 Molding, ° powder (Teflon TE — 9

14-J, manufactured by Mitsui Dupont Fluorochemicals Co., Ltd., not fiberized)

A-5 Powder for solid lubrication (Teflon TLP — 10F — manufactured by Well DuPont Fluorochemicals Co., Ltd., fiberized)

(Dispersant (B))

B-1: Gum-based core schizograft copolymer (Kaneace M511, manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle size: 200; tm, refractive index: 1.5 2) B-2: homopolypropylene (Melt flow index at 230 ° C: 3 g Z 10 min) , Refraction index: 1.503) frozen crushed powder (average particle diameter: 250 ^ m)

(Polyrefin (C))

C-11: Homopolypropylene (Melt flow index at 230 ° C: 3 g Z 10 min, refractive index: 1.503)

C-2: Ethylene propylene random copolymer (Molelet flow index at 230 ° C:

0.5 g Z 10 minutes, refractive index: 1.5 500)

C-3 Homopolypropylene (only at 230 ° C)

Low index: 0. s gz i o, refractive index: 1.53)

C-14 Low density polyethylene (Meltoff at 160 ° C)

Low index: 0.25 g Z 10 minutes, refractive index: 1.5 1)

(Nucleating agent)

D-1: sorbitol nucleating agent (C 1, bis (p-methylbenzylidene) sorbitol)

D 2 Lin-based nucleating agent (SODIUM 2,2—Methylenvis (4,6—Di-t-butylphenol) Phosphite)

[Margins below]

Table v

76 70

From the results shown in Table V-1, the fiberized polytetrafluoroethylene, the dispersant and the polydisperse, as in Examples 1-11, were obtained. The sheet obtained from the resin composition consisting of an olefin (Π) is a resin composition in which no polytetrafluoroethylene is used. Sheets obtained from the products (Comparative Examples 1 and 2) and from the resin composition in which the polytetrafluoroethylene is not fiberized Compared to the sheets (Comparative Examples 3 and 4), the drawdown, which is an indicator of thermoforming, is much smaller and the workability is better. At the same time, it is clear that the transparency, the glossiness, and the surface properties are also excellent.

Further, a very thin section cut out from the sheet obtained in Example 3 was stained with ruthenium tetroxide, and this was then transmitted through a transmission electron microscope. Observation was carried out at a magnification of 100,000 times) to examine the form of polytetrafluoroethylene in the resin composition (Π). As a result, it was confirmed that the polytetrafluoroethylene had a diameter of about 0.1 to 1 lm, a length of about 3 to 10 / m, and was fibrous. Was. From this, as described above, the sheet for thermoforming according to the present invention can be readily translucent, and at the same time, can be readily surface and workable. This was due to the fact that the resin composition (（) contained fiberized polytetrafluoroethylene. .

Example VI

Examples 1 to 10 and Comparative Examples 1 to 7

The dispersants (B) shown in Table VI-1 and Table VI-2 and the polytetrafluoronorethylene shown in Table VI-1 and Table VI-2 (A) with a powder mixer The mixture was stirred at high speed for 5 minutes at room temperature, and at the same time, high shear was applied at the same time to form the polytetrafluoroethylene (A) into a fiber, thereby preparing a mixture.

Mixtures of the amounts shown in Table VI-1 and Table VI-2, and the polyrefin (C) 100 shown in Table VI-11 and Table VI-2 The parts were extruded and kneaded at 180 ° C and 50 rpm using a single-screw extruder (screw screw diameter: 50 mm, L / Ό: 28), and the resin composition was extruded. I got the pellets.

As a blowing agent, a mixture having a higher content of i-butane than that of n-butane is added to this pellet, and these are tandem extruded. Machine (screw diameter: ① 40 mm, ② 50 mm, rotation speed: ① 70 rpm, ② 20 rpm) with a 0.6 mm slit die (temperature approx. From C), the foam was extruded and foamed at a discharge rate of 9 kg hours to obtain a plate-like foam. The foaming agent was used in an amount of 3 parts by weight based on 100 parts by weight of the pellet of the resin composition. The foam obtained had excellent surface properties and had sufficient impact resistance as a building material.

In Example 5, a mixture of citric acid and sodium bicarbonate, which are foaming nucleating agents, was added in an amount of 0.1 parts by weight to 100 parts by weight of the resin composition. Parts by weight were added, and these were extruded and foamed from a slit die of a tandem extruder in the same manner as described above. In Comparative Examples 1 to 5, only the dispersant (B) was stirred with a Henschel mixer without using the polytetrafluoroethylene (A). Then, this was mixed with a polyrefin (C). In Comparative Examples 6 and 7, polytetrafluoroethylene (A) and a dispersant (B) were mixed under high shearing force. However, the polytetrafluoroethylene (A) remained in powder form and was not fiberized. There Changed the rotational speed of the single-screw extruder from 50 rpm to 100 rpm, but the polytetrafluoroethylene was not sufficiently fiberized. 0

The abbreviations in Table VI-1 and Table VI-2 indicate the following:

(Polytetrafluoroethylene (A))

F 0 4 Fine powder (Polyfront T F E —

F104, manufactured by Daikin Industries, Ltd.)

F 20 FINE POWDER (POLYFLON T F E —

F201, manufactured by Daikin Industries, Ltd.)

7 J Molding No. Udaichi (Teflon T F

E-17J, manufactured by Mitsui Dupont Fluorochemicals Co., Ltd.)

9 4 Molding. Udaichi (Teflon TE

9 1 4 — J, Mitsui's Dupont Fluorocarbon Co., Ltd., not fiberized)

OF — Powder for body lubrication (Teflon TLP — 10

F-I, Mitsui's Dupont Fluorochemical

Co., Ltd., not fiberized)

(Dispersant (B))

Core-assoleated (I) rubber-based core-assisted graft copolymer (Canace FM2

0, manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle size: 250 m) Core-copolymer () rubber-based core-copolymer (co-polymer) Case M 5 1

1. Manufactured by Kanegafuchi Chemical Industry Co., Ltd., average particle diameter: 200 // m Folding rate: 1.5 2) Frozen pulverized powder: Homopolypropylene (at 230 ° C)

Frozen pulverized powder having an average particle size of 0.5 g Z: 10 min, refractive index: 1.53) (average particle size: 250 um) )

Polyolefin (C) (Homopolypropylene)

W 50 Sumitomo Chemical Co., Ltd.

W 5 0 1

D 50 Sumitomo Chemical Co., Ltd.

D 5 0 1

H 50 Sumitomo Chemical Co., Ltd.

H 5 0 1

Z0A Sumitomo Chemical Co., Ltd. Sumitomo Novlen

Z 1 0 1 A

[Margins below]

Table vi

Composition

Polyolefin (C) mixture

Example

Porite t Rafluolo

Melt flow dispersant (

(No. B)

Homopolyethylene (A) Foam nucleating agent Ino-T

Pyrene type Quantity

(gZlO content) Species Species

(Parts by weight) (parts by weight)

1 W501 6 F 104 1 Core shell body (I) 5

W501 6 F 104 1 Frozen crushed powder 5

o W501 6 F 104 0.5 Frozen ground powder 5

A W501 6 F 104 2 Frozen ground powder 5

W501 6 F104 1 Frozen ground powder 5 0.1 u W501 6 F201 1 Frozen ground powder 5

7 W501 6 7-J 1 Frozen ground powder 5 I

8 D501 0.5 7-J 1 Frozen ground powder 5

9 H501 3 7-J 1 Frozen ground powder 5

10 Z 101 A 20 7-J 1 Frozen ground powder 5

Table VI

Composition

Polyolefin (C) mixture

Fushiagei V '}

Porite t Rafluolo

Melt flow dispersion

No. Homopolyethylene (A) agent (B)

index

Hill type B

(gZIO content) Species Species

(Parts by weight) (parts by weight)

1 W501 6 Core shell (I) 5

2 W501 6 Frozen ground powder 5

3 D501 0.5 Frozen ground powder 5

4 H501 3 Frozen ground powder 5

5 Z 101 A 20 Frozen ground powder 5

6 W501 6 914-J 0.1 Core shell (II) 5

7 W501 6 1 OF-J 0.1 Core shell (体) 5

Next, the melt tension of the obtained resin composition, the crystallization temperature of the resin in the resin composition, and the foaming ratio and closed cell rate of the obtained foam are as follows. The measurement was performed based on the method described in (1). The results are shown in Table VI-3.

(Melting tension)

Using a capillary graph (manufactured by Toyo Seiki Co., Ltd.), the piston speed is 5 mm, the bow I speed is 1 m / min, and the temperature in the pallet. The melt tension of the resin composition was measured at 200 ° C (crystallization temperature).

Using a differential scanning calorimeter (DSC-7, manufactured by Parkerma Co., Ltd.), the temperature was kept at 200 ° C for 5 minutes, and then the temperature was lowered at a rate of 10 ° CZ. The temperature of the crystallization peak of the resin at that time was measured, and this was taken as the crystallization temperature.

(Expansion ratio)

The density of the foam was measured according to the method described in JIS K7222, and the following formula was obtained.

Expansion ratio = 0.9 Z. Density

The expansion ratio was determined based on the above.

(Closed cell rate)

The closed cell ratio was measured using a multi-type chromometer (manufactured by Yuasa Aionix Co., Ltd.) according to the method described in ASTM D2856-.

[Margins below] Table VI — 3

Physical properties

Example Resin composition Bubble number Melt tension Crystallization temperature Expansion ratio Closed cell ratio

(g) (° C) (times) (%)

1 5.2 129 8.5 62

2 5.2 129 8.3 73

4.5 127 7.2 68 λ 6.5 130 8.6 74

5.2 129 7.2 β A

4.8 127 7.1 68

7 4.2 126 6.3 64

8 10.3 127 6.5 68

9 7 /. 9 B 1 丄 9 7 Q

Ο Ό

10 3.2 130 3.4 77 Comparative example

0.3 120

1

o 0.3 120

3 3.2 1 13

4 0.6 1 16

5 0 125

6 0.6 121

7 0.3 120 As shown in Table VI-3, the resin compositions of Comparative Examples 1 to 5 in which the polytetrafluoroethylene (A) was not used were foamed. It was not. In addition, the resin compositions of Comparative Examples 6 and 7 in which non-fibrous polytetrafluoronorylene (A) was used were polytetrafluoroethylene. As if the fluoroethylene (A) had not been used, it did not foam and the effect of the polytetrafluoroethylene was confirmed. What they do

On the other hand, a specific amount of fiberized polytetrafluoroethylene (A) and a dispersant are added to the polyrefin (C).

The resin compositions (Π) of Examples 1 to 10 obtained by mixing the mixture obtained from (B) have a high crystallization temperature, a high melt tension, and a high workability. The resin composition

It can be seen that the foam obtained from (ii) has a favorable expansion ratio and a high closed cell rate. Industrial applicability

The fluororesin-containing resin composition of the present invention has excellent impact resistance and surface properties, and further has improved and improved melting properties. Shows workability (formability).

Therefore, among the fluororesin-containing resin compositions of the present invention, the resin composition (I) is, for example, a modifier for the resin composition (Π). Therefore, it can be suitably used. Further, from the resin composition (（), various moldings such as the thermoforming sheets and foams of the present invention having excellent physical properties as described above can be obtained. The body is shaped.

Furthermore, the fluororesin-containing resin composition can be easily produced by the production method of the present invention.

Claims

Range of blue demand

1. Polytetrafluoroethylene (A) and a dispersant (B) having an average particle size of 0.1 to 800 // m The amount of lafluoroethylene (A) varies depending on the dispersant.

(B) 0.01 to 50 parts by weight with respect to 100 parts by weight, wherein the polytetrafluoroethylene (A) is a fiberized fiber. A resin composition containing a fluorine resin.

2. The claim that the polytetrafluoroethylene (A) is a powder obtained by aggregating the dispersion obtained by the emulsion polymerization method. The fluororesin-containing resin composition according to claim 1.

3. The fluororesin-containing resin composition according to claim 1, wherein the fiberized polytetrafluoroethylene (A) has a fiber diameter of 10 m or less.

4. The fluorine resin-containing resin composition according to claim 1, wherein the dispersant (B) is a powder made of a core-shell graft copolymer.

5. A crosslinked rubber-like polymer (b-1) having a glass transition temperature of 25 ° C or lower in the core graphite copolymer, from 40 to 95% by weight, The glass transition temperature of the homopolymer is 25. C or more, and a cross-linked rubbery polymer (b-1) and a vinyl copolymerizable compound (b-2) that can be copolymerized with graphite (5 to 60% by weight) The fluororesin-containing resin composition according to claim 4, which is a united product.

6. The fluororesin-containing resin composition according to claim 1, wherein the dispersant (B) is a polyrefin powder.

7. The claim wherein the dispersant (B) is an inorganic powder. The fluororesin-containing resin composition according to claim 1.

8. The fluororesin-containing resin composition according to claim 1, wherein the dispersant (B) has an average particle diameter of 50 to 700 // m.

9. The fluororesin-containing resin composition according to claim 1, wherein the dispersant (B) has an average particle diameter of 100 to 500 // m.

10. Dispersant having an average particle size of 0.1 to 800/111 (8) 100 parts by weight of polytetrafluoroethylene (A) per 100 parts by weight. 0 to 50 parts by weight are mixed under a high shearing force to convert the polytetrafluoroethylene (A) into a fiber. Production method of resin composition containing silicone resin 0

11. Polytetrafluoroethylene (A) and a dispersant (B) having an average particle size of 0.1 to 800 m, and the polytetrafluoroethylene (A) The amount of the fluoroethylene (A) is 0.001 to 50 parts by weight with respect to 100 parts by weight of the dispersant (B), and Fluororesin consisting of a fluororesin-containing resin composition (I) in which the ethylene (A) is fiberized and a polyolefin (C) Contained resin composition.

12. Claims wherein the amount of the fluororesin-containing resin composition (I) is 0.01 to 20 parts by weight based on 100 parts by weight of the polyolefin (C). The fluororesin-containing resin composition according to claim 11.

13. The amount of polytetrafluoroethylene (A) is 0.0001 to 10% by weight with respect to 100 parts by weight of polyolefin (C). Parts of the dispersant (B). The fluororesin-containing resin composition according to claim 11, wherein the amount is 100 parts by weight.

14. Claims in which the polyethylene glycol (A) is a powder obtained by aggregating the dispersion obtained by the emulsion polymerization method. 13. The fluororesin-containing resin composition according to item 11.

15. The fluororesin-containing resin according to claim 11, wherein the fiberized polytetrafluoroethylene (A) has a fiber diameter of 10 / zm or less. Composition.

16. The fluororesin-containing resin composition according to claim 11, wherein the dispersant (B) is a powder made of a core-graft copolymer.

17. The core-silver copolymer has a glass transition temperature

The crosslinked rubber-like polymer (b-1) having a temperature of 25 ° C or less is 40 to 95% by weight, and the glass transition temperature of the homopolymer is 25 ° C or more. It is a graphite copolymer of a crosslinked rubber-like polymer (b-1) and a vinyl copolymerizable compound (b-2) of 5 to 60% by weight. The fluororesin-containing resin composition according to claim 16.

18. The fluororesin-containing resin composition according to claim 11, wherein the dispersant (B) is a polyrefin powder.

19. The dispersant (B) is an inorganic powder.

11. The fluororesin-containing resin composition according to item 11.

20. The fluororesin-containing resin composition according to claim 11, wherein the dispersant (B) has an average particle size of 50 to 700 c / m.

21. The fluororesin-containing resin set according to claim 11, wherein the dispersant (B) has an average particle size of 100 to 500111. Adult.

22. The fluororesin-containing resin composition according to claim 11, wherein the refractive index of the dispersant (B) is substantially the same as the refractive index of the polyolefin (C). object.

23. A propylene-based polylene obtained by polymerizing a monomer component in which olefin (C) contains 50% by weight or more of propylene. The fluororesin-containing resin composition according to claim 11, which is a fin.

24. A propylene-based polylene obtained by polymerizing a monomer component in which olefin (C) contains 50% by weight or more of propylene. A mixture of refine and an ethylene-based polyolefin obtained by polymerizing a monomer component containing 50% by weight or more of ethylene. And the amount of the ethylene-based olefin is 0.1 to 100 parts by weight with respect to 100 parts by weight of the propylene-based olefin. The fluororesin-containing resin composition according to claim 11, which is a claim.

25. 100 parts by weight of dispersant (B) having an average particle diameter of 0.1 to 800 / m and 100 parts by weight of polytetrafluoroethylene (A) 0. 0 1 to 50 parts by weight are mixed in advance under a high shearing force, and the polytetrafluoronorylene (A) is fiberized to obtain a fluororesin-containing resin. A fluororesin-containing resin characterized by producing the composition (I) and mixing the fluororesin-containing resin composition (I) with a polyolefin (C) The composition of the composition.

26. Claims wherein the amount of the fluororesin-containing resin composition (I) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyolefin (C). Item 26. The process for producing a fluororesin-containing resin composition according to Item 25.

27. A thermoforming sheet comprising the fluororesin-containing resin composition according to claim 11.

28. A foam comprising the fluororesin-containing resin composition according to claim 11.