TW201008985A - Process for producing polyolefin resin, polyolefin resin, its solution and film - Google Patents

Abstract

Provided are a process for producing a polyolefin resin comprising the steps of dissolving a polyolefin resin in a halogenated hydrocarbon solvent or a halogen-free solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds and acetal compounds, which halogen-free solvent have a boiling point of 70-140 DEG C and a solubility index of 13-20 MPa1/2 to prepare a polyolefin resin solution, and evaporating the solvent contained in the solution; and a process for producing a polyolefin resin comprising the steps of dissolving a polyolefin resin in a halogenated hydrocarbon solvent or the above-mentioned halogen-free solvent to prepare a polyolefin resin solution, cooling the solution to precipitate the polyolefin resin, and then evaporating the solvent in the polyolefin resin. The produced polyolefin resin gives films with reduced number of optical defects.

Description

201008985 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a polyolefin resin, a polyolefin resin, a solution thereof, and a film. [Prior Art] 聚烯烃 Polyolefin resin is used in a wide range of industries due to its economical, mechanical strength, transparency, formability, and hygienic properties. Polyolefin film is processed into a single layer or a multilayer film, which is first used as an optical mask. The cover film is widely used in the field of electronic materials and the like. Among these applications, the demand for the improvement of the film quality is rigorous year by year, and it is hoped that the fisheye which deteriorates the appearance of the film is reduced. For example, the protective film layer for dry f ilm resist is a polyolefin film with few fish eyes. The fisheye is a foreign matter mixed into the polyolefin resin, and the gel or the like is an original cause. In the manufacture of the high-quality film, the foreign matter and the gel amount in the polyolefin resin must be reduced. The term "fisheye" as used herein means that when a gel and/or a foreign matter is present in the film, the gel and/or foreign matter exhibit a refractive index different from that of the periphery, and are recognized in an optically inhomogeneous state. The heterogeneity of the refractive indices occurs when the gel and/or the foreign matter itself has a refractive index different from the refractive index of the film itself, and further, the resin flows when the gel and/or foreign matter are formed for the film. Sexual effects are also caused by optical inhomogeneities that are greater than the size of the gel and/or foreign matter itself. At the time of 201008985, the optical shift is not defined by the size of the gel and/or the foreign matter itself, but is defined by the size of the range in which the range of the circumference is optically offset. The term "gel" as used in the present invention means an uncrosslinked component in which the polyolefin resin is not sufficiently plasticized in the production process, or a component which additionally crosslinks the polyolefin resin via thermal experience. When the gel is present, the above-described optical shift occurs in the film, which significantly impairs the appearance of the film. In addition, the "foreign matter" is a material other than the polyolefin resin which is mixed with the outside during the process of producing the polyolefin resin or the polyolefin film, and examples thereof include fibers, inorganic materials, metals, and the like. Gels in polyolefin resins are known as unmelted gels and crosslinked gels. The crosslinked gel is a three-dimensional cross-linking of the olefinic resin, and the gel is heated and melted and dissolved in a solvent. On the other hand, the unmelted gel is a gel which is melted or dissolved by heating, and is subjected to melt mixing by i-axis or two-axis, and is extended by an extension or the like to maintain an unmelted gel ratio. High causes the appearance of fish eyes to cause deterioration of the appearance of the product. In particular, a polystyrene resin obtained by high-pressure radical polymerization using a vessel type reactor or a tubular reactor, such as ethylene-acetic acid ethylene vinegar copolymer or low-density polyethylene, etc., is known to have a large amount of the above. Uncrosslinked gel and crosslinked gel. The free radical hydrogen is extracted from the polymer formed in the high temperature reactor to form a branch. The branching is integrated into the reactor, and the high-pressure separator is connected to the reactor, and the granules of the granules are subjected to the turbulence of the turf in the process of commercial temperature. L _ w 饯 gel, or a conjugated gel that undergoes a cross-linking reaction. 201008985 - A method for inhibiting the formation of a gel, for example, a P-anthraquinone, W, has been proposed to produce a polyethylene resin having a small gel content by performing polymerization of ethylene in the presence of an antistatic agent (see Patent However, it is not possible to completely suppress the formation of condensate, and there is still an economic problem in that the gel content of the resin to be produced is extremely small. Patent Document 1: Japanese Patent Publication No. Sho 63_41926, on the other hand, A method of improving the appearance of a product by removing the crosslinked gel contained in the resin by removing the untwisted gel at the time of molding, for example, 'a method of providing a filtering device in a 1-axis or 2-axis extruder A metal mesh, a sintered metal filter, or the like is used as a material. The method of the transition is extremely effective for removing the cross-linked knee, but it is difficult to pass the filter due to deformation of the unmelted gel. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention is directed to the above problems, and an object thereof is to provide an appearance for the production of fish eyes and the like. A high-quality film having a reduced defect is a method for producing a useful polyolefin resin. Means for Solving the Problems As a result of intensive studies, the present inventors have found that a method of dissolving a solvent by dissolving a polyolefin resin in a specific solvent The polyolefin resin produced can provide a high-quality polyolefin film free from defects in appearance such as fish eyes, and the present invention has been completed. 5 201008985 Therefore, according to the present invention, a method for producing a polyolefin resin (hereinafter sometimes referred to as a (Manufacturing method)), comprising dissolving a polyolefin resin in a halogenated hydrocarbon, and dissolving it in an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether compound having a parameter of 13 to 20 MPa 1/2 from the point of the Buddha And a step of emulsification to select a V non-based solvent to prepare a polyhydrocarbon solution, and a step of successively evaporating the hydrolyzed hydrocarbon solvent or the non-m agent from the solution. Further, according to the present invention, a polyolefin is provided. The method for producing a resin (hereinafter sometimes referred to as "second manufacturing method") includes dissolving a polyolefin resin in a hydrocarbon solvent or dissolving at a stagnation point of 7Q to 14 (rc, solubility parameter) a step of preparing a polyolefin solution by using at least one non-dentate solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, _ compounds, and condensed compounds of 13 to 20 MPa 1/2, and subsequently cooling the solution to precipitate a polyolefin resin The step of further evaporating the hydrocarbon solvent or the non-dentate solvent from the precipitated polyolefin resin. According to the present invention, in order to reduce the uncrosslinked gel, the agglutination state is eliminated by the usual melt addition 2 Therefore, the agglomerated state of the unparent gel, which is the cause of the fisheye, is eliminated by using a hydrocarbon solvent or a specific non-Southern solvent. That is, 'the hydrocarbon containing the uncrosslinked gel will be used. The resin is mixed with a solvent in a hydrocarbon solvent or a specific non-self-solvent in which the hydrocarbon resin is dissolved, so that the aggregate of the polymer becomes a non-aggregated state. By this operation, the polymer bond is stabilized in the solvent, and even if it is re-centered, it does not return to the original agglutination structure, so that the formation of fish eyes does not occur. 201008985. Therefore, the polymerized hydrocarbon resin produced by the method of the present invention can provide a high-quality film in which the appearance defects such as fish eyes are greatly reduced. [Embodiment] Hereinafter, the present invention will be described in detail. The method for producing a first polyanthracene resin of the present invention comprises dissolving a polyfluorene hydrocarbon resin in a halogenated hydrocarbon solvent or dissolving in a boiling point of from 7 Å to 14 Torr. (: a step of preparing a polyolefin solution by dissolving at least one non-halogen solvent selected from an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether compound, and an acetal compound selected from the group consisting of 13 to 20 MPa 1/2) and continuing to be made from the solution The step of evaporating the smouldering solvent or the non-self-organic solvent. Each step is described below. 1) Dissolution step The "polyolefin resin" used in the production method of the present invention is not particularly limited. The "polyolefin resin" of the present invention means a single polymer of a carbon number 2 to fluorene alpha olefin, a copolymer of the olefin, and a copolymer of the olefin and other ethylenically unsaturated monomers copolymerizable. . The copolymer contains both random and desirable segments. The content of α-cation in the copolymer is 5% by weight or more. The polyolefin resin of the present invention further comprises a separate polymer of the alpha olefins and a chemical modification of the copolymer. Specific examples of the α-olefin include ethylene, propylene, butylene, pentene, etc. Among them, the production method of the present invention is more suitable for a single polymer polymer of ethylene. The olefin content in the copolymer is 5% by weight or more, preferably more than 7 201008985% by weight. Specific examples of the other ethylenically unsaturated monomer copolymerizable with the α-olefin include vinyl acetate, decyl acrylate, ethyl acrylate, and decyl decyl acrylate. Specific examples of the polyolefin resin include a polyethylene resin. The polyethylene resin includes high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDpE), linear low density polyethylene (L_LDPE), ultra low density polyethylene (V-LDPE), and the like. The linear low-density polyethylene (L-LDPE) may, for example, be an ethylene-α-olefin copolymer such as an ethylene-butene copolymer, an ethylene+hexene copolymer or an ethylene 1-octene copolymer. Other polyolefin trees include, for example, ethylene methylpentene-1 resin, ethylene-vinyl acetate S-copolymer (EVA), and saponified products thereof, ethylene-vinyl alcohol resin (EVOH) ethylene propylene copolymer (EPM). ), such as a vinyl polymer, a polypropylene homopolymer, a polypropylene hydroxy segment polymer polypropylene random polymer, or the like. Further, the use of such polyolefins can be used. Further, the polyolefins may be used singly or in combination of several. The polymerization method for synthesizing the polyolefin resin may be a generally known method: high pressure radical polymerization, medium to low polymerization, solution polymerization, slurry = combination, and the like. The polymerization catalyst ′ is a peroxide catalyst and Ziegler®. (Ziegler-Natta) Catalyst, metall 〇cene catalyst, etc., can be polymerized without any limitation using the catalyst. The molecular weight of the polyolefin resin used in the production method of the present invention is not limited as long as the (tetra) hydrocarbon resin is dissolved in a chlorinated solvent or a specific non-dentate solvent. The shape of the polyolefin resin used in the production method of the present invention is as long as the 201008985 '$ ene red resin is dissolved in a halogenated hydrocarbon solvent or a specific non-halogen solvent, for example, by strand cutting, etc. When the cylindrical granules obtained are obtained, the granules, the amorphous powders, the granules, the granules, etc., which are produced by underwater cutting, are further processed by a slurry method. Although the powdery particles are taken out from the reactor, the powdery polymers can be similarly used in the present invention. Further, the film of the polyolefin resin molded at one time in the production method of the present invention may be used as a raw material of the fiber or the molded body. In this case, the shape of the molded body is not limited. According to the production method of the present invention, a molded article of a polyolefin resin, particularly a powder, a high-quality film or the like can be produced. Any molded article such as a film can be produced by using the conventional smoky ash powder and a known molding method to be described later. The smouldering solvent used in the production method of the present invention is not limited as long as it dissolves the polyphenylene hydrocarbon resin. Specific examples of the toothed hydrocarbons are exemplified by U-di-ethane, 1,2-ethane, di-methane, gas-methane, gas, tri-ethane, 1'1'2-tri-ethane, and tetra Gasification solvent such as gasified carbon, three-gas ethylene, full-gas ethylene, etc.; evolution of bromine-based solvents such as acetyl bromide; urethane benzene, U-dialdehyde benzene, total gas gamma burning: perfluoroxin hospital, two-gas pentafluoropropane burning, etc. Gas-based solvent; desert gas hospital, a solvent containing bromine and mouse. These halogenated hydrocarbon solvents may be used in combination of two or more kinds. - The self-chemical hydrocarbons * #丨巾" is preferably a so-called hydrocarbon solvent which can dissolve the polysulfide resin from 8Q to 1st generation, and further, from the viewpoint of solvent evapotranspiration, 201008985

Halogenated hydrocarbons with a low boiling point are dissolved in AL Gangma. From these points of view, the best 1,1,2-tri-ethane. The non-halogen solvent used in the production method of the present invention is a non-halogen solvent which is a material which is not contained, and has a boiling point of γ 0 $ 1 λ n , (3) to 14 〇 c, and a solubility parameter of 13 to 20 MPa1/ At least one selected from the group consisting of aliphatic hydrocarbons, aryl quinones, steroids 1, ether compounds, and acetal compounds (hereinafter referred to as "non-dentate solvents"). When the boiling point is less than 70 t, it is difficult to dissolve the polyolefin resin at normal pressure or low pressure, and when the point exceeds 140 C, there is a problem that the energy cost when the solvent is evaporated is increased. Further, when the solubility parameter is outside the range of 13 to 2 〇 MPal/2, the dissolution of the polysulfide resin in (4) is difficult. Other hydrocarbons other than the aliphatic hydrocarbons, aromatic hydrocarbons, hydrazine compounds, and condensed compounds (hereinafter referred to as "other non-tetra" solvents, such as methyl ethyl ketone, diisopropyl ketone, diethyl ketone Ketone compound; acetonitrile, stupid: nitrile compound such as nitrile; butanol, isopropanol, alcoholate such as 2-methyl-2-butyring, amine compound such as monoethylamine or ethylenediamine, etc. It is difficult to dissolve the polyolefin resin in the solvent with a mass point of 7 to 140 C and a solubility parameter of 13 to 2 〇 MPal/2. a non-based solvent having a boiling point of 70 to 140 ° C and a solubility parameter of 13 to 2 〇MPam, for example, n-heptane, 2-methyl hexane, 3-methyl hexane, 2, 3-methyl Pentane, 2,4-dimethylpentane, n-octane, 2, 2, 3 -trimethylpentane, isooctane, 2,2,5-trimethylhexane, 1-heptene, 1-octene, methylcyclopentanol, cyclohexene, methylcyclohexene, ethylcyclohexene, cyclohexan and other aliphatic hydrocarbons such as benzene, toluene, m-xylene, p-xylene Aromatic fumes such as ethyl styrene; ether compounds such as cyclopentyl ethyl ether, ethyl amino ether, dioxane, dipropylene 10 201008985 ether; acetal such as diethyl acetal = two kinds can also be mixed In the above, the ratio is not particularly == system == In order to make the polyolefin resin solution into a uniform dissolved state, the hydrogen bonding force "h) is preferably 5MP or less. In these non-dentate solvents, 'the equilibrium 抑制', which is inhibited by the dissolution of the polyolefin resin, and the 1 匕 hydrocarbon tree can be dissolved in the 8G to 12th generation: the non-systemic solvent of the sputum, and further, the evapotranspiration by the solvent From the point of view, it is preferable to use a non-commercial system such as n-gumane, methylcyclohexane, toluene or cyclopentylmethyl bond. The non-dentate solvent may be at least one selected from the group consisting of aliphatic hydrocarbons, aromatic fumes, and acetal compounds, and may not interfere with the effects of the present invention. The weight ratio of other non-clear solvent 2 'non-(tetra), solvent and other (tetra)-based solvent varies depending on other non-dentate solvents contained, but for example, 70 to 99: 3〇 to 1 〇 modulation In the step of the hydrocarbon resin solution, the dissolution temperature b of the polybutanol resin may be adjusted according to the halogenated hydrocarbon solvent or the non-dentate solvent to be used and the polysmoke tree = and the dissolution temperature may be 6 G to the other. It is preferable that the economical position is preferably below the solvent (four) point and is dissolved at normal pressure. When the polyolefin tree is difficult to dissolve, if necessary, it can be dissolved at a temperature higher than the pressure point of the pressure vessel. The dissolution time depends on the shape of the polysmoked resin: and the dissolution temperature 'but may be from 20 minutes to 8 hours. The solution of the polyolefin resin must be completely carried out, and it is preferred to carry out bathing to achieve a predetermined solution viscosity. However, stirring at the time of dissolution is not essential. Further, the reactor used for dissolving 11 201008985 is a trough, a tubular shape, a horizontal type reactor, an extruder, and the like, and its shape and the like are not limited. - The polyolefin solution prepared by dissolving a halogenated hydrocarbon solvent or a non-dentate solvent by a polyolefin resin is preferably filtered in a state where the polyolefin is dissolved in order to further remove foreign matter in the polyolefin resin. As the filtration method, a conventional method can be used, for example, a metal cloth (mesh), a metal sintered filter known as a polymer filter, and a metallic non-woven fabric using a polymer material such as polypropylene or fluororesin. Not weaving, etc. These filter materials may be used singly or in combination of plural kinds. Furthermore, in order to improve the filtering accuracy (fUtrati〇n _ rating), the filtering can be carried out in multiple stages in sequence. A filtration method using a polymer transitioner can be used: a polymer filter using a cylindrical filter called a folding or a candle type, a combined rainbow type, or a blade disc type in which a plurality of disk-shaped transitions are combined Polymer transitioner. Further, it is also possible to use a composite polymer filter provided with a folding type or a candle type and a leaf disc type filter in the same filter. The filter material of the filter is not particularly limited. A sintered gold mesh, a sintered metal nonwoven fabric, or a sintered metal powder filter can be used. _ The accuracy of the low-viscosity polymer solution used for introduction into the concentrator is limited to the possibility of filtration. The higher the better, the better. 至 5 to 2 〇. " m fan filter. The filtration temperature is not particularly limited as long as it is at most the boiling point of the solvent to be used. The conditions for the filtration are such that the filtration efficiency is at least 95% or more, more preferably 99% or more, and the viscosity, the flow rate = and the pressure of the polymer solution, and the filter medium are preferably selected. Further, a flat tube type using a sintered metal mesh as a filter material other than a polymer filter, or a line filter having a flat plate type of 12 201008985 may be used. When the filtration of the polyolefin solution is insufficient once, it can be further divided into two. For example, after the polyolefin solution is filtered by a folding reactor, the polyene t* liquid is re-filtered by a concentrated high-concentration polysulfide solution by the above-mentioned concentration method with a blade type filter having high filtration precision. Methods. The concentration of the polyolefin solution is not particularly limited, and is appropriately set depending on the selected solvent, and a concentration of 0.1 to 50% by weight can be used.

When the above polyolefin resin is dissolved, various additives may be added to the fisheye, appearance, and physical properties of the film. For example, various additives such as wax may be added starting from a single or plural antioxidant selected from a powder system, a squama system, a sulfur system or the like. The fish solution obtained above is a film having an unextended film having a Mem (fisheye) of 1 Å or less and 2 m. 2) Evaporation step of a solvent. In the first production method of the present invention, a toothed smog solvent or The method of the non-evaporation-solvent evaporation, for example, a spray drying method in which a polybutanyl solution is spray-dried under reduced pressure to be powdered can be used. In the spray drying of the polyolefin solution, the poly-smoke solution is discharged from a small-diameter nozzle to a decompression vessel heated in a necessary manner, whereby the polyolefin solution is dropletized, and the droplets are aggregated. The degree of decompression of the olefin solution in which the dentate hydrocarbon solvent or the undiluted solvent is evacuated is appropriately selected depending on the selected halogenated hydrocarbon solvent or non-halogen/valley, and the temperature of the reduced pressure vessel. In order to dropletize the polyolefin solution, the droplets are allowed to evaporate the hydrocarbon solvent or the non-based solvent, and the degree of pressure reduction and temperature are not limited. Generally, the degree of decompression is in the range of 〇 13 201008985 200T rr, and the temperature is 2 〇 to i8 〇 c. The use of: = (tetra) hydrocarbon resin powder ' can be formed into a high-quality film by, for example, a one-axis or two-axis extruder by inflation molding, 1 ::: τ, but the molding method is not limited. First Production Method of the Invention Φ _ ^ ^ A method of evaporating a halogenated hydrocarbon solvent or a non-halogen solvent, for example, by using a film of a polyolefin solution continuously cast on a substrate to form a film, and secondarily by using a film A method of heating and drying. For example, various polymer films represented by a film made of polyacetate, such as polyethylene terephthalate (PET), w- 4 na-formic acid ethyl ester (PEN), and the like, and such a polyester The surface of the film is treated with a linaloic acid, and various films which are hard-coated by an acrylic resin or the like are applied, and various metal materials such as metal boxes, metal films, metal sheets, and the like, such as copper, stainless steel, and the like, are subjected to metal steaming. Various polymer films such as ρΕτ treated by ore. Further, if necessary, the polymer coater can be applied to the metal materials, and the inorganic coater can be applied. Further, it is also necessary to carry out the flow on the heated rotary metal drum, and it can be coated on the recycled polymer belt or metal belt. The method of extending the polyolefin solution on the substrate can be exemplified by a conventional method including a gravure coater, a knife coater (c〇Ma coater), a die coater, and a double winding. A method such as a double coater (double Mayer bar coater). In order to dissolve the polyolefin resin, it is necessary to heat, and when the boiling point of the solvent is low, in order to suppress the viscosity of the polyolefin solution from being rapidly volatilized by the halogenated hydrocarbon solvent or the non-type solvent during the process of the flow, it is preferred to use slit coating. Die coater, double Mayer bar coater. The base formed by the extension 14 201008985 . The thickness of the instant polyolefin solution on the material is 3 to 500 /zm, and the thickness of the polyolefin resin layer is 0.5 to 50 m. /minute. The drying of the layer of the polythene solution formed on the substrate can be carried out from one stage to multiple stages, and the temperature ranges from 5 Å to 2 Torr (rc, and can be dried at 50 to 10 in multi-stage drying (TC1 & drying) Further, the method may be carried out in two or more stages. Further, if necessary, the drying may be carried out in three stages or more. φ This drying can be carried out efficiently using an industrial drying furnace which is adjacent to the slit coater. The resin layer can be peeled off from the substrate after being sufficiently dried, or peeled off from the substrate at the stage of drying, and the polyolefin resin layer can be thinned by drying, winding, or the like. The second polyolefin resin of the present invention. a manufacturing method comprising the steps of: preparing a polyolefin solution by dissolving a polyolefin tree in a toothed hydrocarbon solvent or dissolving in a non-dental solvent; and subsequently cooling the solution to precipitate a polyolefin resin. Further, the step of evaporating the halogenated hydrocarbon solvent from the precipitated polyolefin resin is the same as that described in the first manufacturing method of the foregoing. 'Other steps are explained below. 2) Cooling step Dissolving step After the reaction, the polyolefin solution is cooled to precipitate the polyolefin resin. The cooling rate of the solution obtained by dissolving the polymer is not particularly limited, and is preferably 〇5 to 30 〇c/min for production efficiency and equipment cost reduction. The polyolefin is precipitated by cooling the solution. The shape of the precipitated solid is substantially in the form of a block or a granule on the surface of 2010 201085. 3) Evaporation of the solvent The solidified polyolefin is obtained by a conventional method, for example After the solvent is separated by a decantation method, the solvent in the solid is removed and dried to obtain a polymer. The drying temperature at this time is from room temperature to 15 〇〇c, and the pressure is 〇 1 至 to normal pressure. The drying time varies depending on the shape of the solid obtained or the dry shock used, from i minutes to 4. hour. The solid obtained in this manner can be pulverized and shaped at a low temperature, and formed by a conventional molding method such as a melt extrusion method or an inflation molding method. In the production method of the present invention, the poly-saturated hydrocarbon tree is dissolved in a polysulfide solution obtained by lapping or the above-mentioned non-self-organic solvent, and the content of the gel and/or foreign matter is small 'normally, as 20 (four) thick When the thin crucible is extended, the fisheye g of the long diameter m or more is less than or equal to a. The polyolefin resin obtained by the production method of the present invention usually has a gel or a foreign matter content per foot. It is less than one. Further: = (4) The content of the foreign matter of the aggregate is "the following (4), which is 3 or less / 20 g, preferably 1 or less / 2 〇 g. The film made of the polyolefin resin obtained by the production method of the present invention is wide and thick. In the unstretched film, the long diameter is 10 or less/m2, which is more than 3 or less/m is preferably less than 1/m2. The polythene resin film which is described as having a small amount of fish eyes, for example, a film for a resist film for a dry film resist for a wide range of dry film resists, which is preferably a film having a flatness and a flatness, and the thickness of the film is preferably 10 201008985 . To 50//m', the thickness accuracy is preferably 2#m or less. [Examples] The present invention is further illustrated by the following examples, which are intended to facilitate the understanding of the present invention. The present invention is not limited by the examples. <Polyolefin resin> (1) EVA (ethylene-vinyl acetate copolymer) U1trathene (registered trademark) 〇5A57C (MFR=15g/10 min, density=929kg/m3), manufactured by TOSOH Co., Ltd. (2) L-LDPE ( Linear low-density polyethylene-ethylene benzene copolymer) Nipolon-Z (registered trademark) TZ420 (MFR = 10g/10 min, density = 913 kg/m3), L-LDPEl (MFR = 4g/10 min, manufactured by T0S0H) Density=9〇〇kg/m3) L-LDPE2 (MFR=4g/10 min, density=923kg/m3) (3) LDPE (Low Density Polyethylene) • PetrotheneC registered trademark) 225 (MFR=3. 7g/10 Minute, density = 923kg/m3), T0S0H company

Petrothene (registered trademark) 204 (MFR = 7.0 g / 10 min, density = 922 kg / m3), LDPEl (MFR = 2.0 g / l min, density = 924 kg / m3) LDPE2 (MFR = 3.0 g / l) 〇min, density=924kg/m3) LDPE3 (MFR = 3.0g/l〇 min, density=924kg/m3) (4) HDPE (high density poly ping)

Nipolon Hard (registered trademark) 4010, manufactured by T0S0H, Inc. 17 201008985 (thickness: 125/zm) Teijin DuP〇nt (5) ΡΕΤ film Mel inex (registered trademark) Company-made "Measurement of fisheye" Due to long diameter 50/zm The above preparations..., eyes (f isheye) can be visually confirmed, using a fluorescent lamp, and the resulting thick sound s ^ Tian Zhuxiong and 15 to 5 〇em of the unstretched film are irradiated by the inner surface, and are visually 湔疋 5 m long. For the fisheye in the film, the number per lm2 is calculated. <Measurement of gel and foreign matter> 2 n The number of gels and foreign matter per 2 〇g of the resin was calculated from the number of lm per unit length of the fish eye having a long diameter of 5 G /z m or more. <Measurement of Film Thickness> A film thickness measuring device K 4 〇 2B manufactured by Anritsu Co., Ltd. was used. <Extension> The polymer solution dissolved in the same autoclave was placed on a gold-coated coater set to a width of 300 mm and 600 mm, and was pipetted to a nitrogen introduction valve having a 5 L scale manufactured by Unicontrols Co., Ltd. The installation of the pressurized tank has a heating cover. The polymer solution in the tank was pipetted to the gold form by pressurizing the tank. The tank and the gold type, a hose heater made by a misec (company), which is a pull-out valve at the lower part of the tank, is connected to a pipe constructed by Tefl〇n (registered trademark) and maintained at a predetermined temperature. The gold type temperature adjustment system was carried out using a gold-type thermostat TSW-75S manufactured by Nippon Gold Industries Co., Ltd., and a hose heater and a HST-120CT heating tank manufactured by MISEC (company) were used to adjust the temperature. Furthermore, in Examples 1 to 15, 18 201008985

The roll of the film which is close to the gold type is heated by a halogen heater (3⁄4丨# TDri〇〇 IRE182-N) manufactured by Iwasaki Electric Co., Ltd., and the temperature is adjusted by applying a voltage to the halogen heater. <film forming machine>

The 100C100 Labo Plastomill extruder made by Toyo Seiki Co., Ltd., the D25-20 f! Full-screw screw made by Toyo Seiki Co., Ltd., and the T-Gold type made by Toyo Seiki Co., Ltd. Film forming film. Example 1 EVA pellet 3. 2 kS ' and 1,1,2-trimethylethane 20 L (28. 8 kg), placed in a 3 °L autoclave and heated for 1 hour to dissolve to obtain a polyolefin Solution (EVA solution). 3L of the solution was pipetted to a 5L tank with an added value of 9〇c, and pipetted to a heated 300mm wide via a Teflon (registered trademark) hose attached with a heating cover held at 8 〇. Covered with gold type. The bath was pressurized, from a gold type maintained at 9 Å &gt; c, and the solution was continuously allowed to flow over a film of polyethylene naphthalate (PEN) as a substrate. The speed of the PEN film was set to 3 m/min. The film on the substrate was dried at 100 C to obtain an unstretched film having a thickness of 21.5 / / Π 1, and the fish skin of the unstretched film was measured by peeling off the PEN film. As a result, the fisheye of 5〇#m or more was one/in2, and it was confirmed that a film of good quality was obtained. In addition, the gel and foreign matter of 50//Hi or more of the result EVA are /2 (^. Example 2 L-LDPENipolon-Z (registered trademark) TZ42 〇 small particles 25 kg, and 1,1, 2-Lethane Ethylene 20L (28. 8kg), placed in 30L high pressure dad, 19 201008985 Add: Stir in UrC for 1 hour, dissolve it to obtain L-LDPE solution. 3L in this solution is pipetted to The bath is heated to (10), and the tank is filled with a Teflcm (registered trademark) hose that is held in a 1G (rc heating cover) to a heated gold type of 30 mm wide. The solution was allowed to flow over the pEN film as a substrate from a gold type maintained at 1/0 C. The speed of the pEN film was set to 3 m/min. The film on the substrate was dried at i〇〇&lt;t, and the resulting thickness was obtained. 22&quot; m unstretched film' was peeled off from the pEN film to measure the fisheye of the unstretched film. As a result, the fisheye of 5 〇M or more was 〇. 4 / m2, and it was confirmed that a film of good quality was obtained. From this result, 50 of the L-LDPE _

The gel and foreign matter of Vm or more are one or less and 2 〇g. Examples 3 to 10 Films were produced in the same manner as in Example 1 except for the polyolefin resin shown in Table 1, the amount of the resin, and the dissolution temperature. The evaluation results of fisheyes of 50 &quot; m or more of these unstretched films are shown in Table 1. As a result, fish eyes of 50 / z m or more were 〇 2 to i / m 2 , and it was confirmed that a good quality film was obtained. In addition, the result of the above-mentioned results is that the silicone resin is 5 Å or more and the kneading and foreign matter are 1 or less. 2 〇 ge xin 20 201008985 [Table 1] Example Polyolefin resin insertion amount (kg) Solvent wood 1 Placement amount (kg) Dissolution temperature (°C) Dissolution time (hr) Thickness of film (it/m) Fisheye of unstretched film (pieces/m2) 3 L_LDPE1 2.5 TCE 28.8 110 1 22 0 5 4 L~ LDPE2 ~~2~~ TCE 28.8 110 1 21 0 7 5 LDPEl 3. 6 TCE 28.8 110 1 22 0 5 6 LDPE2 3.9 TCE 28.8 110 1 23 〇9 7 LDPE3 3.9 TCE 28.8 110 1 20 0 6 8 LDPE*2 4.9 TCE 28.8 no 1 17 0 7 9 LDPE*3 5· 1 TCE 28.8 no 1 19 1 10 HDPE 3.2 TCE 28.8 120 1 23 1 吐.木 i iUi . i,i,2 dichloroethane*2 Petrothene (registered trademark ) 225 *3 Petrothene (registered trademark) 204 Example 11 L-LDPE Nipolon-Z (registered trademark) TZ420 «V TfiL ^ . 〇Kg ^ and 1,1,2-trimethylethane 20L (28. 8kg), The mixture was placed in a 30 L· autoclave, heated at 11 (rc was stirred for 1 hour, and dissolved to obtain an L_LDpE solution. The solution was filtered through a metal mesh of 60 〇 mesh while pipetting 3 L to warming to Loot: the capacity, by Attach a Tefl〇n (registered trademark) hose that is kept in the heating cover of the C., and pipette it to the coated gold type with a width of m after heating. Pressurize the groove and keep it at 10 (the gold of rc) Type, the solution was allowed to flow on the PEN film as a substrate. The speed of the PEN film was set to: 'min. The film on the substrate was dried at 1 〇rc, and the obtained thickness was measured by (4) stretching film, which was peeled off from the PEN film. The fisheye of the unstretched film. The fisheye of more than 50 em is 〇.丄/m2, and it is confirmed that the good product is: film. Furthermore, from the result, the long-term foreign matter on the gel of L-Cai. It is 1 or less / 2〇g. 21 201008985 Example 12 LDPE 1 small particles 2. 5kg, and 1,1,2-three gas hospital 20L (28. 8kg), placed in 30L high pressure dad, heated After stirring for 2 hours, it was dissolved to obtain a LDPE solution. The solution was filtered through a 200-mesh metal mesh, and 3 L of the solution was transferred to a 5 L tank heated to 1 〇〇t: and kept at 1 经由. The Tefl〇n (registered trademark) hose of the Art Heating Cover is pipetted to a heated 600mm wide coated gold type. The groove was pressurized, and the solution was allowed to flow on a 188//? thick ρ?τ film as a substrate by a gold type held at iio °c. At this time, the temperature of the back pressure roll (φr) φ of the base film was 75 t, and the speed of the PET film was set to 15 m/min. The film on the substrate was dried from 1 to 16 (r), and the obtained unstretched film having a thickness of 22/m was peeled off from the PET film to measure the fisheye of the unstretched film. As a result, the fisheye of 50# m or more was 0. 〇2/m2, and it was confirmed that a film of good quality was obtained. Further, from the results, the gel and foreign matter on the 5 〇... were 1 or less / 20 g. Example 13 EV EVA obtained in Example 1. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, A film having a thickness of 5 〇Mm and a width of 25 〇mm was obtained. As a result of measuring the obtained fish eye of the τ溽膘 without extending the thin amine, it was confirmed that the fisheye of 50 or more was 〇·5/m2 excellent &amp;;

The blade is slow and fruity. In addition, as a result, the gel and foreign matter of 5 Mm or more of EVA are one or less / 20 g. Example 14 A poly-smoke solution obtained by the same method as in Example 12 was allowed to cool under 22 201008985 *1 to precipitate a polymer, and was separated from the four-gas hexane as a solvent. After the decantation was removed by decantation, the solidified mass of the polymer was dried over 4 hours for 48 hours to obtain a white solid of 2.490 kg. The solid was extruded at a cyiinder temperature i9 (rc, gold type 19GC to obtain a film of thickness). The result of measuring the fisheye of the unstretched film was 50% or more of the fisheye. The film was confirmed to be a good quality film. In addition, the gel and foreign matter of 50 or more LDPE were one or two 〇g. β Example 15 The L-LI was placed in a 30 L autoclave. pE registered trademark) TZ420 small particles 2.5kg, perchloroethane 2〇L, heated under 11〇μ for 1 hour, dissolved to obtain L-ldpe solution. The liquid in the solution is transferred to the Liao trough which is heated to the loot, and is pipetted to the heated 3 by the TenTn (registered trademark) hose attached to the heating cover of the rc (rc).被mm wide coated gold type. The groove was pressed and held in a 1〇5χ:2 gold type. • The solution was allowed to flow over the PET film as a substrate. The speed of the PET film was set to 3 m/min. The upper film was dried at 1 Torr to 14 Torr, and the obtained film was peeled off from the PET film to measure the fisheye of the unstretched film. As a result, the fisheye of #m or more was 〇. 5 / m2 'confirmed excellent In addition, as a result, the gel and foreign matter of 50/zm or more of L-LDPE were less than or equal to 20 g. Comparative Example 1 EVA pellets were used at 180 ° C and had a gold-thickness of 15 cm width. The Labo Plastomill extruder with a shaft extruder was used to obtain a film having a thickness of 23 201008985 and a width of 250 mm. The fisheye of 100 // m or more of the obtained unstretched film was 90/m2, which was poor in film quality. EVA contains a plurality of gels and foreign matter of 100//m or more. Comparative Examples 2 to 10 In addition to the polyolefin resin and temperature shown in Table 2, A film was obtained by the same method as in Comparative Example 1. The evaluation results of fish eyes of 50 &quot; m or more of the unstretched films are shown in Table 2. These results contained a plurality of 70 to 100 // m The above fisheyes are of poor quality. Further, from these results, the polyolefin resin contains a plurality of gels and foreign bodies of 70 to 100 /zm or more. [Table 2] Comparative Example Polycarbonate Resin Labo Plastomill Temperature ( °C) One-axis extruder temperature (°C) Gold type (°C) Thickness of film (solution) Fisheye size of unstretched film (&quot;m) Fisheye of unstretched film (pieces/m2) 2 L- LDPE*1 170 170 190 21 80 40 3 L-LDPE1 170 170 190 22 90 30 4 L-LDPE2 170 170 190 21 70 25 5 LDPE1 180 180 180 21 80 18 6 LDPE2 180 180 180 19 100 16 7 LDPE3 180 180 180 23 90 18 8 LDPE*2 180 180 180 21 70 22 9 LDPE*3 180 180 180 21 70 21 10 HDPE 200 200 200 19 100 50 Note: ipolon-Z (registered trademark) ΓΖ420 *2 Petrothene (registered trademark) 225 3 Petrothene (registered trademark) 204 Example 16 EVA pellets 3. 2 kg, and methylcyclohexane (boiling point: 100. 9 ° C, solubility parameter :16. 0MPa1/2) 20L (15.4 kg), placed in a 30 L autoclave, and stirred at 95 ° C for 1 hour under heating to dissolve to obtain a polyolefin solution 24 201008985 (EVA solution). 3L of this solution was pipetted to a 5L tank heated to 95 liters, and piped to a heated 600 mm via a Tefl〇n (registered trademark) hose attached to a heating cover of 9 (rc). A wide coated gold type. The groove was pressurized, and the solution was allowed to flow over the pET film as a substrate by a gold type maintained at 90 ° C. At this time, the speed of the PET film was set to 3 m / min. The film was dried by 14 (TC drying, the obtained unstretched film having a thickness of 20 μm, and peeled off from the ρΕτ film to measure the fish eye of the unstretched film. As a result, the fisheye of 5〇# m or more Φ was identified as /ιη2 ' A film of good quality is obtained. Further, from the capsules, the gel and foreign matter of 50 μm or more of EVA are 〇2〇g.

NiP〇l〇nZ (registered trademark) TZ42〇 granules 25 kg, and methylcyclohexane 20 L (15.4 kg), placed in a 30 L autoclave, stirred at 95 ° C for 1 hour under heating to dissolve Polyolefin solution (L_LDpE solution). 3L of this solution was pipetted to a 5L tank heated to 95 ° C, and pipetted through a Tefl〇n (registered trademark) hose attached with a heating cover maintained at 90 ° C. 600mm wide coated gold type. The tank was pressurized, and the solution was allowed to flow over the pET film as a substrate from a gold type maintained at 1 〇〇 C. At this time, the speed of the PET film was set to 3 m/min. The film on the substrate was dried to 'unextended film of thickness 20 &quot; m, and the 纟m film was peeled off to measure the fish eye of the unstretched film. As a result, it was confirmed that a fisheye of 5 〇 &quot; m or more was 5 / in 2' to obtain a film of excellent quality. In addition, as a result, the gel and foreign matter of 5 〇απι or more of L_LDpE are one or less and 2 〇g. Example 18 LDPE1 granules 2. 5kg, and methylcyclohexane 2〇L (15 4kg), 25 201008985 placed in a 30L autoclave, stirred under heating for 2 hours at 95 °, dissolved to obtain a polyolefin solution (LDPE solution). After filtering the solution through a 2 〇〇 mesh metal mesh, pipette 3 L to a 5 L tank heated to i 00 ° C, via Tefl〇n (registered with a heating cover kept at 95 ° C) The trademark) hose is pipetted to a heated 600mm wide coated gold type. The bath was pressurized, and the solution was allowed to flow on the pET film as a substrate by a gold type maintained at 95 °C. At this time, the speed of the PET film was set to 15 m/min. The film on the substrate was dried at 160 C. The resulting unstretched film of thickness 20 was peeled off from the pET film to measure the fisheye of the unstretched film. As a result, it was confirmed that a fisheye of 5 〇 &quot; m or more was 0.1 or more. Further, from the results, the gel and foreign matter of 50/zm or more of the LDPE were i or less and 2 〇g. Example 19 EVA pellets 3. 2 kg, and toluene (boiling point: n 〇, solubility parameter: 18. 0 MPa 1/2) 20 L (17.4 kg), placed in a 30 L autoclave, heated under io ° ° stirring 1 After an hour, it was dissolved to obtain a polyolefin solution (eva bath). 3L of this solution was pipetted to a 5L tank heated to [(10), and piped to a Tefl〇n (registered trademark) hose attached to a heating envelope of rc The coated gold type was 600 mm wide. The groove was pressurized, and the solution was allowed to flow over the PET film as a substrate by a gold type held at ioo ° C. At this time, the speed of the PET film was set to 3 m/min. 2 /m2 ' The fisheye of the film is 0. 2 / m2 '. The film is dried at 140 C, and the unstretched film having a thickness of 20/zm is obtained, and the fish eye of the unstretched film is measured by peeling off the pET film. It was confirmed that a film of good quality was obtained. Further, from the results, the gel and foreign matter of 5 〇απι or more of EVA were i or less and 2 〇g. 26 201008985 . Example 20

The granules of LDPE2, 2.5 kg, and toluene 2 〇L (17.4 kg) were placed in a 3 〇L autoclave, and stirred at 11 Torr for 2 hours under heating to dissolve to obtain a polyolefin solution (LDPE solution). The solution was filtered through a 2 〇〇 mesh metal mesh, and 3L was pipetted to a temperature of 11 (rc 5 liter capacity, via a Tefl〇n (registered trademark) soft attached with a heating cover kept at 105C. The tube was pipetted to a heated 600 mm wide coated gold type. The groove was pressurized, and the solution was extended on a PET film as a substrate by a gold type maintained at φ 105 C. At this time, the PET film was The speed was set to 15 m/min. The film on the substrate was dried at 160 C, and the unstretched film having a thickness of 20 μm was dried, and the fish film was peeled off from the pet film to measure the fish eye of the unstretched film. As a result, the fisheye of 50 &quot; m or more was 0.1. In the case of /m2, it was confirmed that a film of good quality was obtained. Further, from the results, the gel and foreign matter of 50 y m or more of LDPE were less than or equal to 2 〇g.

LDPE3 small particles 2. 5kg, and toluene 2〇L (14.7 kg), placed in 30L φ &amp; high pressure dad 'heated at 1 〇 5t gave 2 hours to dissolve to obtain a polyolefin solution (LDPE solution) . The solution was filtered through a 2 〇〇 mesh metal mesh, and 3 L of the solution was transferred to a 5 L tank heated to 1 〇5 art, and Teflon was attached via a heating cover attached to a temperature of 10 ° C (registered). The trademark) hose is pipetted to a heated 600mm wide coated gold type. The tank was pressurized, and the solution was allowed to flow over the pET film as a substrate from a gold type maintained at 105 C. At this time, the speed of the PET thin medium was set to 15 m/min. The film on the substrate was dried at 160 C to obtain an unstretched film having a thickness of 20 μm, and the fish eye of the unstretched film was measured by peeling off the ρΕτ film. As a result, the fisheye 27 201008985 above 50 // m was 〇 1 / m2 'It was confirmed that a film of good quality was obtained. Further, from the results, the gel and foreign matter of 50/m or more of LDPE were one or less and 2 〇g. Example 22 3.2 kg of EVA pellets, And toluene 2〇L (17.4kg), placed in a 30L autoclave, heated at 10 (rc is stirred for a few hours to uniformly dissolve, then the liquid temperature is cooled to 9 (TC to obtain a polyolefin solution (EVA solution) 3L of this solution was pipetted to a 5L tank heated to 9 (rc, via a Teflon (registered trademark) hose attached to a heating cover of 9 (TC), and pipetted to warming. 600 mm wide coated gold type. The groove was pressurized, and the solution was allowed to flow on the tantalum film as a substrate by a gold type maintained at 9 〇 &lt; t φ. At this time, the speed of the ρ Ε τ film was set to 3 m / min. The film on the substrate was measured by 14 (rc drying, the resulting unstretched film of thickness 20 &quot; m, peeled off from the PET film to determine the unstretched film As a result, it was confirmed that a fish eye of m or more was m/m2, and it was confirmed that a film of good quality was obtained. Further, from the result, the gel and foreign matter of the EVA 5 〇&quot; The following /2 g. Example 23 EVA granules 3. 2 kg, and cyclopentyl methyl ether (boiling point: i 〇 6 ^, solubility parameter: 17 Mpa &quot; 2) 20 L (17 · 2 kg), placed 3 〇 L In an autoclave, the mixture was stirred at 95 ° C for 1 hour under heating to dissolve to obtain a polyolefin solution (EVA solution). 3 L of the solution was pipetted into a 5 L tank heated to 95 ° C, and attached thereto. The Tefl〇n (registered trademark) soft s held in a heating cover of 95 ° C was pipetted to a heated gold type of 600 mm wide. The groove was pressurized and kept at 95. (: In the gold type, the solution was allowed to flow over the pET film as a substrate. At this time, the speed of the PET film was set to 3 m/min. The film 28 on the substrate 201008985 • X 14〇C dried the unstretched film of the thickness, The pET film was peeled off and the fisheye of the unstretched film was measured. As a result, the fisheye of 5 〇&quot; was G. 1 / ^, and it was confirmed that a film of good quality was obtained. The result 'of the above EVA 50 / zm gel and foreign matter is less i / 2〇g. Example 24

Nipolon-Ζ (registered trademark) TZ42〇 pellet 3 2岵, and cyclopentyl methyl ether 20L (n. 2kg) ' placed in a 30L autoclave, heated at 100 c for 1 hour, dissolved to obtain Polyolefin solution (L_LI) pE solution). The 3 LS solution in the solution was transferred to a 加1 heated to 1 〇〇1, and pipetted to a heated 6 经由 via a TefI〇n (registered trademark) hose attached with a heating cover held in the loot. Mm wide coated gold type. The bath was pressurized, and the solution was allowed to flow on the pET film as a substrate by a gold type maintained at io °C. At this time, the speed of the PET film was set to 3 m/min. The film on the substrate was dried at 140 C to obtain an unstretched film having a thickness of 2 Å, which was peeled off from the pET film to measure the fish eye of the unstretched film. As a result, the fisheyes of 5 〇 &quot; m or more were 〇. 2 / m2 ’ confirmed to obtain a film of good quality. Furthermore, from this result, the gel and foreign matter of 50/zm or more of L-LDPE are! Below 2〇g. Example 25 3.2 kg of granules of LDPE1 and 20 L (17.2 kg) of cyclopentylmethyl ether were placed in a 30 L high pressure crucible and heated at 1 Torr. The crucible was allowed to stand for 1 hour and dissolved to obtain a polyolefin solution (LDpE solution). 3L of this solution was pipetted to a 5 l tank heated to 100 ° C, and pipetted to a heated 600 mm via a Teflon (registered trademark) hose attached with a heating cover maintained at 100 ° C. Wide coated gold type. The groove was pressurized and extended by a PET film held on i 〇 (rc 29 201008985. At this time, pET. The film on the substrate was 140. (: dry, gold type, the solution was applied as a substrate film) The speed was set to 3 m/min to obtain a thickness of 2 〇Am, _ 禾 禾 stretch film, peeled off from the PET film to measure the fish eye of the unstretched film. Its 杲, 5 n 叩 50 50 50 50 50 50 50 50 50 50 1. 1 / m2, and it was confirmed that a film of good quality was obtained, and as a result, the gel and foreign matter of 50 or more of LDPE were less than or equal to 2 〇g.

3.2 kg of small particles of Petr〇thene (registered trademark) 225, and 20 L (17.2 kg) of cyclopentyl methyl ether, placed in a high-pressure dad of 30 L, dissolved in 1 〇〇φ C and heated to obtain a poly Dilute hydrocarbon solution (ldpe solution). 3L of this solution was pipetted to a 5 L tank heated to 9 (rc, via a Teflon (registered trademark) hose attached with a heating cover kept at 100 C, and pipetted to 6 〇〇mm by the sister. A wide coated gold type. The groove was pressurized by a gold type held at 1 〇〇c. The solution was allowed to flow over the pET film as a substrate. At this time, the speed of the PET film was set to 3 m/min. The film was dried to obtain an unstretched film having a thickness of 20 nm, and the fish film was peeled off from the PET film to measure the fisheye of the unstretched film. As a result, the fisheye of 5 〇&quot;m or more was 个2 / m ' A good quality film was obtained. Further, from the results, the gel and foreign matter of 50/zm or more of LDPE were one or less and 2 〇g.

Petrothene (registered trademark) 2〇4 granules 3.2 kg, and cyclopentylmethyl group shouted 20 L (17.2 kg), placed in a 30 L autoclave, and heated at 1 ° C for 1 hour. It was dissolved to obtain a polyolefin solution (LDPE solution). 3L of this solution was pipetted into a 5L tank heated to 90 °C, and pipetted through a Teflon (registered trademark) hose with a heating cover of 30 201008985 • maintained at 10 °C.

To the heated 600mm wide coated gold type. The tank was pressurized, and the solution was allowed to flow over the pET film as a substrate from a gold type maintained at 1 °C. At this time, the speed of the PET film was set to 3 m/min. The film on the substrate was dried at 14 Torr to obtain an unstretched film having a thickness of 20 μm, which was peeled off from the PET film to measure the fisheye of the unstretched film. As a result, it was confirmed that fish eyes of 50 A m or more were 〇"/m2' to obtain a film of good quality. Furthermore, from this result, the number of clotting and foreign matter of LDpE or more is one or less and 2 〇g. Example 2 8 LDPE1 small particles 3.2 kg, and n-octane (boiling point: 125.6t, solubility parameter: 15.6MPaw) 2〇L (14.0 kg), placed in a 3〇L autoclave, heated at 100t_ , to dissolve it to obtain a concentrated smoke solution (LDPE / gluten). Pipette 3L of this solution to a 5L tank heated to 1 Torr, and pipette to a heated (with registered trademark) hose with a heating cover held at 1〇〇t: Wide coated gold type. The tank was pressurized and the solution was allowed to flow over the PET film as a substrate from a gold type maintained at 100 °C. At this time, the speed of the PET crucible was set to 3 m/min. The film of the substrate was dried at 160 C to obtain an unstretched film having a thickness of 20, which was peeled off from the PET film to measure the fisheye of the unstretched film. As a result, the fisheye of 5 〇&quot; was 〇. 3 / m2, and it was confirmed that a film of good quality was obtained. Furthermore, from the results, the condensed and foreign matter of 50&quot; of LDPE is i or less / 20 g. Example 29 The EVA solution obtained in Example 16 was powdered by a spray drying method. 31 201008985 The powder was produced on a 18 (TC using a Lab〇Plast〇mill extruder with a τ15 cm wide and a one-axis extruder) to produce a film with a thickness of 5 〇 &quot;111 and a width of 25 〇mm. As a result of the fisheye of the obtained unstretched film, it was confirmed that the fisheye of 5 〇〆m or more was excellent in 0.3/y. Further, from the results, the gel and foreign matter of MVA of 50 or more were used. The following /2 g. Example 3 0 The ldpe solution obtained by the same method as in Example 18 was subjected to a cold portion to precipitate a polymer, and separated from decylcyclohexane as a solvent. After decantation and removal, the solidified block polymer was vacuum dried in 4 〇® C for 48 hours to obtain a white solid 2 sen. The solid was taken up in a Ub〇PlaSt〇mU1 extruder at a cylinder temperature of 190°. C. Gold type fox 1 90 C is pressed to obtain a film of thick 纟5〇em. The result of measuring the fisheye of the unstretched film is more than 5 〇^m, and the fisheye is Q 7/m2, which is confirmed to be good quality. The film is further 'by the result' LDpE 5 〇 &quot; cation above the gel and foreign matter is 1 or less / 2 〇 g. Example 31 3.2 kg of LDPE1 pellets, and cyclopentyl methyl ether 17L (14 6 kg) and monoethyl ketone 3L (ketone compound, boiling point: 1 〇 2.2 乞, solubility parameter · 18.2 MPa 1/2) (2.4 kg) Place 3 liters of high pressure celite, stir at 1 ° C for 1 hour under heating, and dissolve to obtain a polyolefin solution (LDpE solution). Pipette 3 L of the solution until it is heated to 1 Torr. 5c's 5L #, via a Tefl〇n (registered trademark) hose with a heating cover that is kept in the loot, is pipetted to a heated 6-inch wide coated gold type. In the gold type of looc, the solution is allowed to flow over the pET film as a substrate. This 32 201008985

• At the time of 'film' speed is 3m/min. The film on the substrate was dried by UQ C to produce a non-stretched film of thickness 20 &quot; m, &amp; PET film peeling to determine the fish eye of the unstretched film. As a result, it was confirmed that a fisheye of 5 Mff or more was 0.2/in2' to obtain a film of excellent quality. Further, from the results, the gel and foreign matter of 50/Zm or more of LDPE were one or less and 2 〇g. Comparative Example 11

LDPE1 small particles 3.2kg, and n-decane (aliphatic hydrocarbon, boiling point: ❹ 150.8 ° C, solubility parameter: 16MPa1/2) 2 〇 L (14.4kg), placed in 30L high pressure dad, heated under the mix After 1 hour, it was dissolved to obtain a polyolefin solution (LDPE solution). 3L of this solution was pipetted to a 5L tank heated to loot, and pipetted to a heated 6 经由 via a Teflon (registered trademark) hose attached to a heating envelope of 1 〇 (rc). The coated gold type is mm wide. The groove is pressurized, and the solution is allowed to flow on the PET film as a substrate by holding it in a gold type of rc. At this time, the speed of the pET film is set to minute. The film was dried at 16 (rc, but insufficiently dried. ❹ Comparative Example 12 LDPE1 small particles 3. 2 kg, and n-hexane (aliphatic hydrocarbon, boiling point: 68.7 ° C, solubility parameter: 14.9 MPa &quot; 2) 2 〇 L (2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Dioxane (ether compound, Buddha point: 101. (:, solubility parameter: 20.5MPa1/2) 20L (20.7kg), placed in 30L of high pressure daddy 'heated at lOOt: stirred for 1 hour, to dissolve, 33 201008985 But no uniform solution was obtained. Comparative Example 14 LDPE1 small particles 3.2 kg' and methyl ethyl ketone (ketone compound Buddha point: 80 ° C, dissolved Degree parameter: i9MPa 1/2) 20L (16. lkg), placed in a high Μ Μ 八 八 〇 八 , , , , , , , , , 加热 加热 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( LDPE1 small particles 3.2kg' and acetonitrile (nitrile compound, boiling point μ °c ' solubility parameter: 24·6MPa&quot; 2) 20L (15 7kg), placed in 3〇l of the ancient pressure dad, heated under 8 (rc After stirring for 1 hour, it was dissolved, but no uniform solution was obtained. Comparative Example 16 LDPE1 pellet 3·2 kg 'and 1-butanol (alcohol compound, boiling point 117 ° C, solubility parameter: 23 1MPaw2) 2〇L ( 16. 2kg), placed in an autoclave, heated at i 0 (rc was stirred for a few hours to dissolve, but no uniform solution was obtained. Comparative Examples 17 to 25 In addition to the polyolefin resin shown in Table 3 and temperature The film was obtained by the same method as the comparative example. The results of the evaluation of the fisheyes of 5 〇 &quot; m or more of the unstretched films are shown in Table 3. These results contained a plurality of 7 〇 to 1 The fisheyes above 〇〇β m are of poor quality. Furthermore, from these results, the polyolefin contains a plurality of gels of 7 〇 to more than loom. 201008985 [Table 3] Comparative Example Polyolefin Resin Labo Plastomill Temperature (°C) One-Axis Extruder Temperature (°C) Fisheye Size of Unstretched Film (//m) Fisheye of Unstretched Film (/m2) 17 L-LDPE*1 170 170 80 40 18 L-LDPE1 170 170 90 30 19 L-LDPE2 170 170 70 25 20 LDPE1 180 180 80 18 21 LDPE2 180 180 100 16 22 LDPE3 180 180 90 18 23 LDPE*2 180 180 70 22 24 LDPE*3 180 180 70 21 25 HDPE 200 200 100 50 Note: *1 Nipolon-Z (registered trademark): TZ420 *2 Petrothene (registered trademark) 225 *3 Petrothene (registered trademark) 204 [Industrial [Advantage] The polyolefin resin produced by the production method of the present invention is suitable for producing a high-quality film in which fish eyes are greatly reduced, and has a wide range of applications. A particularly useful use is a protective layer for a thin electronic component represented by a protective film for dry film photoresist or a flexible solar cell. [Simple description of the diagram] None. [Main component symbol description] None. 35

Claims (1)

201008985 VII. Patent application scope: 1. A method for manufacturing a poly-smoke resin, comprising: dissolving a poly-hydrocarbon resin in a halogenated hydrocarbon solvent or dissolving in a Buddha point of 70 to 14 (rc, solubility parameter 13 to 20 MPa1) a step of preparing a polyolefin solution by selecting at least one non-based solvent selected from the group consisting of an aliphatic hydrocarbon, an aromatic hydrocarbon, an ether compound and an acetal compound, and subsequently evaporating the self-hydrocarbon solvent or the non-system solvent from the solution 2. The method for producing a polyolefin resin according to claim 1, wherein the step of evaporating the hydrocarbon solvent or the non-self-organic solvent comprises spray drying the cerium polyolefin resin under reduced pressure. 3. The method for producing a polyolefin resin according to claim 1, wherein the step of evaporating the hydrocarbon solvent or the non-antimony solvent comprises continuously stretching the polyolefin resin on the substrate. Thin film formation, followed by heating. 4. A method for producing a polyolefin resin, comprising dissolving a polyolefin resin in a halogenated hydrocarbon solvent or dissolving in a solubility range from 7 〇 to 14 〇〇C ' An emulsified step of preparing a polyolefin solution for at least one non-halogen solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds and depolymerized s products of 13 to 20 MPa 1/2, and subsequently cooling the solution to form a polythene The step of precipitating the hydrocarbon resin, and further evaporating the hydrocarbon solvent or the non-halogen solvent from the precipitated polyolefin resin. 5. The method for producing a polyolefin resin according to claim 4, wherein the halogenation is carried out. The method of producing the polyolefin resin 36 201008985 according to any one of claims 1 to 5, wherein the hydrocarbon solvent or the step of evaporating the non-halogen solvent is carried out under heating and/or under reduced pressure. The halogenated hydrocarbon solvent is ruthenium, osmium, and 2-trisethane. 7. The method for producing a polyolefin according to any one of the claims of the present invention, wherein the non-based solvent is in a solubility parameter. The chlorine bond force (5 h) is 5 MPa 1/2 or less. 8. A (four) hydrocarbon solution 'dissolves (iv) smog resin in i-hydrocarbon solvent or dissolves in the point of 7G to HGt from the point of the Buddha, and the solubility parameter is 13 to 20 MPa&quot; Aliphatic hydrocarbon, aromatic At least one non-halogen solvent I selected from the group consisting of a hydrocarbon, a hydrazine compound, and a shrinkage compound, and when one of r A 0n is a 20-thick unstretched film, the fisheye having a length of 5 〇 or more is 10 or less. /m2. 9. A polyolefin resin obtained by the manufacturing method of the above-mentioned patent application, which is characterized in that the gel or foreign matter is 1. Less than /20ge &quot; The film comprising the poly-hydrocarbon resin obtained by the manufacturing method of any one of the claims of the patent application is in the unextended sheet, and the fisheye is characterized by a fisheye having a length of 50 or more. One below /m2. 37 201008985 resin comprising the steps of dissolving a polyolefin resin in a halogenated hydrocarbon solvent or a halogen-free solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, ether compounds and acetal compounds, which halogen-free solvent have a boiling point of 70-140° C and a solubi1ity index of 13-20 MPa1/2 to prepare a polyolefin resin solution, and evaporating the solvent contained in the solution; and a process for producing a polyolefin resin comprising the steps of dissolving a polyolefin resin in a halogenated hydrocarbon solvent or The above-mentioned halogen-free solvent to prepare a polyolefin resin solution, coo ling the solution to precipitate the polyolefin resin, and then evaporating the solvent in the polyolefin resin. The produced polyolefin resin gives films with reduced number of optical defects. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None.