TWI320771B - Article having high barrier property - Google Patents

Description

1320771 18784pif.doc IX. Inventive Note: This application claims to apply to the Korean Intellectual Property Office on December 7, 2004, and to apply for Korean Patent Application No. 10-2004-0102214 and April 22, 2005. The priority of the Korean Patent Application No. 10-2005-0033527 filed by the Korean Intellectual Property Office is hereby incorporated by reference in its entirety. TECHNICAL FIELD OF THE INVENTION The present invention relates to articles having high barrier properties and having a fluorine-coated inner wall, wherein a nano-inserted clay and a resin having a barrier resin are dispersed in a specific form. In a polyolefin resin matrix. Further • [Prior Art] - General-purpose resins such as polyethylene (polyethylene) and polypropylene (p〇iypr〇pyIene) are used in many fields due to their excellent plasticity, mechanical properties and moisture resistance. However, the use of such resins is limited to packaging or containers of agrochemicals and foods that are excellent in chemical and oxygen barrier properties. Therefore, the general-purpose resin is multi-layered for packaging or containers of the materials by co-extrusion, lamination, coating, and the like with other resins. Ethylene-vinyl alcohol (ethylene_vinyUlc〇h〇1, ev〇h) copolymers and polyfluorene (P〇iyamide) resins are used in multilayer plastic products because of their transparency and good gas properties. However, since ethylene-ethyl alcohol co-polymers and polyamine resins are more expensive than general-purpose resins, even when a small amount of these resins are used, a resin composition having good barrier properties is required. At the same time, when a nano-sized insert clay is mixed with a polymeric compound to form a fully flaking, partially bribed, inserted or partially inserted nanocomposite, 5 18784pif.doc has improved barrier properties due to its morphology. Thus, there is a hindrance to the use of this nano-composite. Not all, even after molding, this is important for the morphology of the nanocomposite to maintain its fully exfoliated, partially exfoliated, inserted or partially inserted and the fully exfoliated morphology facilitates improved barrier properties. In particular, when a molded article is prepared from the composition of the nanoparticle and the matrix polymer, the morphology of the nanocomposite dispersed in the matrix polymer is important for improving the barrier properties.疋 At the same time, in order to improve the solvent and vapor barrier properties of polyethylene and other polymers used in barrier-free containers, fluorine coatings are often used on the inner walls of molded articles. This method is disclosed in U.S. Patent No. 2,811,468 A (J. ff.) and U.S. Patent No. 3,862,284 (Dixon et al.). In U.S. Patent No. 2,811,468 A, first, fluorinated polyethylene at room temperature to provide improved resistance as a coating for packaging foods and waste. Also described in this patent is a method of making a blow molded container in which a reactive fluorine-containing fluid medium is used to conform the molten polyethylene parison to the outer shape of the mold. In this method, in the chamber, by contacting the surface of the polyethylene with a fluorine-containing gas at room temperature for 2 to 150 minutes to have a fluorine concentration of 〇.3 to 3.5% by weight (based on the weight of the polyethylene), To fluorinate polyethylene film and container wall. U.S. Patent No. 3, Vessel, No. 284 A discloses the production of a blow molded thermoplastic article having improved barrier properties by fluorinated scent. In this method, a reactive gas containing an inert gas and 0.1 to 10% by volume of fluorine is injected into the parison to expand the parison into a desired shape. The injection is carried out for about $ seconds and is performed at a high temperature. Next, the parison was cooled to recover a reactive gas and a container was obtained by IJ20771 18784 pif.doc. A blow molding method is used to produce a fuel tank (commercially available under the trade name of Airopak) which is excellent in resistance to hydrocarbons. In this method, the parison is expanded with an inert gas and then degassed. Thereafter, a reactive gas containing 1 to 1% by weight of fluorine is injected into the parison to form the parison into a desired shape. Next, the reactive gas is removed from the parison and the resulting container is removed from the mold (a number of blow molding methods have been developed since the development of the high temperature blow molding process by Dixon et al., and some, for example, U.S. Patent No. 4, It is disclosed in U.S. Patent No. 4,617,077 and U.S. Patent No. 7,869,859.

Since the fluorine applied to the container prevents the material from penetrating, the fluorine coating can improve the barrier properties of the container. In a container made of polyethylene and coated with fluorine, the thickness of the coating is increased to meet more stringent environmental regulations. When the thickness of the fluorine coating is large, the fluorine coating in the fuel tank or the filling tube (where the contents are frequently exchanged) can be gradually removed over a long period of time due to frequent exchange of the contents, resulting in a decrease in the barrier property. As this problem becomes known, the use of fluorine coatings in vehicle fuel tanks or fill tubes is significantly reduced. S SUMMARY OF THE INVENTION The present invention provides a fluorine coated article having excellent mechanical strength and excellent oxygen, organic solvent and gas barrier properties, wherein the nanocomposite is dispersed in a specific form in a matrix polymer, and even molded. After that, it still maintains its peeling form. The article was made using a composition having good barrier properties and it had a thin fluorine coating. Due to the good barrier properties of the inner wall of the article, the article prevents penetration and penetration of the contents even when the fluorine coating is released. According to one aspect of the present invention, the present invention provides an article having a barrier-resistant and fluorine-coated inner wall, the 5H article being manufactured from a dry mix composition, which is the 94142900 Chinese specification without a sizing correction page 18784pif. Doc

The L material comprises: 40 to 96 parts by weight of a polyolefin resin; and 5 to 60 parts by weight of a barrier-resistant nanocomposite comprising an intercalated clay and a group selected from the group consisting of the following: At least one resin having barrier properties: ethylene vinyl alcohol (EVOH) copolymer, polyamine, ionomer, and polyvinyl alcohol (P〇lyVinyi alc〇ho); and 1 to 30 parts by weight Compatibilizer. The weight ratio of the barrier resin to the intercalated clay in the nanocomposite was 58.0: 42.0 to 99.9: 0.1. The compatibilizer is selected from the group consisting of ethylene-ethylene anhydride-acrylic acid copolymer, ethylene-ethyl aery late copolymer, ethylene-acrylic acid alkyl ester-propyl Ethylene-acrylate acrylate-acrylic acid copolymer, maleic anhydride modified (graft) high-density polyethylene, modified by cis-succinic anhydride (graft) linear low-density polyethylene (maleic anhydride modified (graft) linear low-density polyethylene), ethylene-alkyl (meth) acrylate-methacrylic acid (meth) acrylate (meth) Acrylate-(meth)acrylic acid copolymer), ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, maleic acid needle One or more compounds of the group consisting of the modified (grafted) ethylene-vinyl acetate copolymer. A barrier article is a container, film, tube or sheet. The coating of the inner wall of the fluorine coating has a thickness of 0.02 to 1 lym. 1320771 18784pif.doc According to another aspect of the present invention, there is provided a method of producing an article having barrier properties comprising: by dry mixing 40 to 96 parts by weight of a polyolefin resin, 0.5 to 6 parts by weight of having a barrier nanocomposite and 1 to 30 parts by weight of a compatibilizing agent to prepare a barrier nanocomposite composition comprising an intercalated clay and a group selected from the group consisting of At least one resin having barrier properties: ethylene-vinyl alcohol (EVOH) copolymer, polyamine, ionic polymer, and polyvinyl alcohol (PVA); molding the composition to form an article; and coating the mold with fluorine One of the inner walls of the article. In one embodiment of the present invention, the polyolefin resin may be at least one compound selected from the group consisting of high density polyethylene (HDJPE), low density polyethylene (i〇w density poly ethylene). , LDPE), linear low-density polyethylene (unear i〇w densit, polyethylene, LLDPE), ethylene-propylene copolymer, metallocene polyethy丨ene, and polypropylene . The polypropylene may be at least one compound selected from the group consisting of homopolymer of propylene, propylene copolymer (c〇p〇lymer 〇f propylene), and pentylene metal (metau〇). Cenep〇iypr〇pyiene) and a composite resin having improved physical properties by adding talc, a flame retardant or the like to a homopolymer or copolymer of propylene. In another embodiment of the present invention, the intercalation clay may be at least one material selected from the group consisting of: montmorillonite, bentonite, kaolin 9 18784pif.doc (kaolinite), mica (mica), hectorite, fluorohectorite 'saponite', saponite, beidelite, nontronite 'stevensite', insect to Vermiculite, hallosite, volkonskoite, suconite, magadite, and kenyalite. In another embodiment of the present invention, the polyamidamine can be: nylon 4.6, Nike, 6, 6.6, Nylon 6.10, Nylon 7, Nylon 8, Nylon 9, Nylon 11, Nylon 12. A nylon 46, MXD6, amorphous polyamine, a copolymerized polyamine containing at least two of these polyamines or a mixture of at least two such polyamines. In another embodiment of the invention, the ionic polymer may have a melt index (190 〇 c, 2, 16 gram) per 1 〇 〇.1 to ίο克. In another embodiment of the invention, the fluorine coating can be performed using a high temperature blow molding process. [Embodiment] The present invention will now be described in more detail. A barrier article according to an embodiment of the present invention is prepared from a dry mix composition, the composition comprising: 40 to 96 parts by weight of polyglycol resin. Up to 60 parts by weight of a barrier nanocomposite, The invention comprises inserting clay and at least one resin selected from the group consisting of: ethylene-ethylene glycol (EVOH) copolymer, polyamin, ionic polymerization 1320771 18784pif.doc

At least one of the group consisting of at least - (10) E), a linear low-density polyethylene polybide, a metallocene poly(tetra), and a poly- 1-4 copolymerization group: Object

Maojin. • A propylene homopolymer, a propylene copolymer, a pentylene metal, a propanol, a homopolymer or a co-flame retardant to propylene, and the like. ', μ content is healthy 4 (} to % by weight, and more preferably read. If the content of the polyene grease is less than 4G parts by weight: to form. If the content of the poly-smoke tree is greater than % by weight , blocking sexual friend 0

It may be prepared by mixing an intercalation clay with at least one resin selected from the group consisting of ethylene-ethyl alcohol (EV〇H) copolymer, polyamidamine, ionic polymer and polyvinyl alcohol (pVA). Nanocomposite. The prepared nanocomposite has a form of complete flaking, partial flaking, insertion or partial insertion. The weight ratio of the barrier resin to the intercalated clay in the nanocomposite is 58.0 : 42.0 to 99.9 : 0.1, and preferably 85.0 : 15.0 to 99.0 : 1 · 〇. If the weight ratio of the barrier resin to the inserted clay is less than 58.0: 42·0 ', the inserted clay coalesces and is difficult to disperse. If the weight ratio of the barrier resin to the inserted clay is greater than 99.0:1.0, the barrier improvement is negligible. 1320771 18784pif.doc The inserting clay is preferably organically inserted into the clay. The organic material to be inserted into the clay is preferably from 1 to 45% by weight. When the content of the organic material is less than 1% by weight, the 'inserted clay' has poor compatibility with the resin having barrier properties. When the content of the organic material is more than 45% by weight, it is difficult to insert a resin having a barrier property. The organic material has at least one functional group selected from the group consisting of primary ammonium to quaternary ammonium. , phosphonium, maleate, succinate, acrylate, benzylic hydrogen, oxazoline, and dimethyl Two hard fat waking money (dimethyldistearylammonium). The inserted clay comprises a material selected from the group consisting of montmorillonite, bentonite, kaolin, mica, saponite, laponite, saponite, beidellite, nontronite, strontite, worm to stone, kaolinite, and weikang. At least one material of earth, Shakang soil, Mage soil and Kenny soil; and the organic material preferably has a selected from the group consisting of first-grade ammonium to fourth-grade money, scales, cis-butanoic acid vinegar, broken vinegar vinegar, acrylic acid a functional group of benzyl gas, oxazoline and dimethyl distearyl ammonium. The ethylene-vinyl alcohol copolymer is included in the nano-composite, and the ethylene content in the ethylene-vinyl alcohol copolymer is preferably from 10 to 50 mol%. If the content of the & ene is less than 10 mol%, it is difficult to perform the glare molding because of poor workability. If the content of ethylene exceeds 50 mol%, oxygen and liquid resistance are insufficient. If the nanocomposite includes polyamine, the polyamine can be: 4.6, resistant to 6, resistant to 6.6, and only 6.10, accounting 7, and 8u', only to 9, 9 , nylon 12, nylon 46, MXD6, amorphous polyamine, 12 1320771 18784 pif.doc A copolymerized polyamine containing at least two of these polyamines or a mixture of at least two such polyamines. Amorphous polyamine refers to polyamine having insufficient crystallinity, that is, when measured by differential scanning calorimetry (DSC) (ASTM D-3417, 10 ° C/min), it does not have an endotherm. Crystal melting peak.

In general, diamines and ditoxaic acids can be used to make polyamines. Examples of diamines include: hexamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4, 4_3,4-trimethylhexamethylenediamine, bis(4-aminocyclohexyl)methane, 2,2-bis(4-amino ring) Hexyl) 2,2-bis(4-aminocyclohexyl)isopropylidene, 1,4-diaminocyclohexene C 1,4-diaminocyclohexane ), 1,3-diaminocyclohexane ( 1 , 3-diaminocyclohexane ) 'meta-L-toluenediamine C meta-xylenediamine ), 1,5 • 1,5-diaminopentane, 1, 4-aminobutane (1,4-diaminobutane) ), 1,3-aminopropylpropane (1,3-diaminopropane), 2-ethyldiamine butylate

(2-ethyldiaminobutane ) ' 1,4-diaminomethylcyclohexyl C 1,4-diaminomethylcyclohexane ) ' methane-xylenediamine, alkyl substituted or unsubstituted m-phenylenediamine (m -phenylenediamine) and p-phenylenediamine. Examples of di-lowering acid include: pyridyl substituted or unsubstituted isophthalic acid 13 1320771 I8784 pif.doc (isophthalic acid), terephthalic acid, adipic acid, sebacic acid (sebacic) Acid ), butanedicarboxylic acid, and the like. The polyamine prepared using the lipid monoamine and the aliphatic bis-acid is a general semicrystalline polyamine (also referred to as crystalline nylon) and is not an amorphous polyamine. Polyamines prepared using aromatic diamines and aromatic dicarboxylic acids are difficult to handle using conventional melting methods. Thus, when one of the diamines and dicarboxylic acids used is aromatic and the other is a month, it is preferred to prepare an amorphous polyamine. The aliphatic group of the amorphous polyamine is preferably a CrCu aliphatic or a CrCs aliphatic group. The aromatic group of the amorphous polyamine is preferably a substituted CrC6 monocyclic or bicyclic aromatic group. However, the above amorphous polyamines are not preferred in the present invention. For example, metaxylenediamine adipamide is easily crystallized when heated or oriented during the thermoforming process, and therefore, it is not preferred. Examples of preferred amorphous polyamines include: hexamethylenediamine isophthalamide; hexamethylenediamine having a ratio of phthalic acid/terephthalic acid between 99/1 and 60/40 Terephthalamide terpolymer: 2,2,4-trimethylhexamethylenediamine terephthalamide #2,4-trimethylhexamethylenediamine terephthalamide # a mixture of 2,4,4-trimethylhexamethylenediamine terephthalamide; hexamethylenediamine or 2-methylpentanediamine and isophthalic acid, a copolymer of phthalic acid 14 18784pif.doc acid or a mixture thereof. When a polydecylamine having a terpene terephthalic acid content based on hexamethylenediamine m-xylyleneamine/p-benzoic acidamine is used, it should be combined with, for example, 2-methyldiaminopentane (2- Another monoamine of methyidiaminopentane) is mixed to produce a processable amorphous polyamine. The above amorphous polyamine containing only the above monomers may contain a small amount of a decylamine such as caprolactam or lauryl lactam as a comonomer. It is important that the polyamine is amorphous. Thus, any comonomer that does not crystallize the polyamine can be used. Approximately 10 weights may also be included in the amorphous polyamine. /. Or lower liquid or solid plasticizers such as glycerol (g ycer〇le), sorbitol, toiuenesulfoneamide (Santicizer 8 monsanto). For most applications, the glass transition temperature Tg of amorphous polyamine (measured under dry conditions, meaning that the water content is 〇12% by weight or less) is about 7〇_17〇C ' And preferably about 8〇-16〇. Hey. The unblended amorphous polyamine has about 125 in a dry state. (Tg of Tg. The lower limit of Tg is not known 'but 7 〇 C is a suitable lower limit. The upper limit of Tg is also unclear. However, when polyamine having a Tg of about 170 C or higher is used, it is difficult to thermoform. Therefore, since Tg is too high, it is not possible to thermoform a polyamine having an aromatic group-containing acid and an amine, and thus it is not suitable for the purpose of the present invention. The polystyrene may also be a semi-crystalline polyamine. Preparation of semi-crystalline polyamines using an internal amine or amino acid such as nylon 6 or resistant to 11 or by condensing 5 such as hexyl-amine with succinic acid, adipic acid or It can be prepared by the dibasic acid of sebacic acid. The polydecylamine can be a copolymer or a terpolymer such as hexamethylene/adipic acid and caprylic acid amine (capr〇iactame) 15]8784pif.doc ^polymer (resistant Polyamide 6, 66). Mixtures of two or more crystalline polyamidoamines may also be used. Semi-crystalline and amorphous polyamines are prepared by condensation polymerization well known in the art. Included in the ionic polymer, the ionic polymer preferably = copolymer of solder acid and ethylene 'has a melting rate of Q1 to 1G per minute. The number (190 ° C, 2,160 g). The content of the naphthalene = compound is preferably 〇 · 5 i 6 〇 heavy parts, and more preferably resistance. The content of the right nano composite is less than 0.5 parts by weight, The weight, yttrium, and yttrium are negligible. If the yttrium of the nanocomposite is greater than 60, the replacement part is difficult to process. The more the land === the point soil is peeled off in the resin with barrier properties to form a damper film. The better, this is because the exfoliation is inserted into the clay and ultimately lacks mechanical properties. Therefore, it is necessary to insert and bond the nano-sized inserts into the clay and insert them into the clay. The 贞m is placed in the tree, which maximizes the ability of the polymer chain and the resistance to block. ',, such as large' to form a stable anti-H body and liquid =, poly_ compatibility, to form A hydrocarbon group of a polar group: a hydrocarbon polymer of a polar group. When using a resin having a polar resin and a barrier property, the compatibilizing agent has a stable structure to the polyolefin, and the affinity of the molded article To obtain a 16]8784pif.doc compatibilizer may comprise a compound selected from the group consisting of: epoxy modified poly Epoxy-modified polystyrene copolymer, ethylene-vinyl anhydride-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-alkyl acrylate-acrylic acid copolymer, maleic anhydride modification (grafting High-density polyethylene, maleic anhydride modified (grafted) polypropylene, maleic anhydride modified (grafted) linear low-density polyethylene, ethylene-alkyl (meth)acrylate-( Mercapto)acrylic acid copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, maleic anhydride modified (grafted) ethylene-vinyl acetate copolymer and modified body thereof. The content of the compatibilizer is preferably from 1 to 30 parts by weight, and more preferably from 3 to 5% by weight. If the compatibilizer content is less than 1 part by weight, the article molded from the composition is inferior in mechanical properties. If the compatibilizer content is more than 30 parts by weight, the composition is difficult to form. When an epoxy modified polystyrene copolymer is used as a compatibilizing agent, it is preferably a main chain comprising 70 to 99 parts by weight of styrene and 1 to 30 parts by weight of the epoxy compound represented by Formula 1 and comprising 1 to 8 parts by weight of a branched copolymer of an acrylic monomer represented by Formula 2. Η Η ~"R~C\7C-R' (1) wherein R and R are each independently a Ci-C2 steroid residue or a C5-C20 aromatic residue having a tapered bond at the end. (2) (2) 1320771 18784pif.doc Maleic anhydride modified (grafted) high density polyethylene, maleic anhydride modified (grafted) polypropylene, maleic anhydride modified (connected The branched low-density polyethylene and the maleic anhydride modified (grafted) ethylene-vinyl acetate copolymer each preferably have 0.1 to 10 parts by weight of maleicene based on 100 parts by weight of the main chain. Branching of an acid anhydride. When the maleic anhydride content is less than 0.1 part by weight, it does not function as a compatibilizer. When the maleic anhydride content is more than 10 parts by weight, it is not preferred due to an unpleasant odor. The composition of the present invention is prepared by dry blending a barrier-like granular nanocomposite, a compatibilizing agent, and a polyolefin resin in a pellet mixer at a constant composition ratio. The article having high resistance according to the present invention is obtained by molding the dry-mixed composition and coating the inner wall of one of the containers with fluorine. That is, the method comprises: forming a barrier by dry mixing 40 to 96 parts by weight of a polyolefin resin, 0.5 to 60 parts by weight of a barrier-resistant nanocomposite, and 1 to 30 parts by weight of a compatibilizing agent. a nanocomposite composition comprising a plugged clay and at least one resin selected from the group consisting of ethylene-vinyl alcohol (EVOH) copolymer, polyamine, An ionic polymer and polyvinyl alcohol (PVA); molding the composition to form an article; and coating the inner wall of one of the molded articles with fluorine. The self-drying hybrid nanocomposite composition is manufactured by melt blending the composition in an extruder and molding the molten blend, and then coating the inner wall of the article 18 18784 ΐ ^ ^ 用 with fluorine Items with high resistance. The article can be made by blow molding, whip dust forming, Kayborg forming or injection molding. Articles with high resistance can be containers, thin months, membranes or tubes. Fluorine coating is carried out using a σ/ dish σ human plastic forming method (Koyutakahukikomi forming method), and the thickness of the fluorine coating layer may be 〇2 to 11 //m. Before the wall contacts the nanocomposite composition (the container is mainly composed of it), the coating wall prevents the inclusions from penetrating. Even when the contents penetrate the fluorine coating, the nanocomposite composition The outer wall of the composition prevents penetration of the inclusions, which demonstrates excellent resistance. 9. The following is a more detailed description of the invention by way of example only. The following examples are merely intended to increase the understanding of the invention and are not intended to limit the scope of the invention EXAMPLES The materials used in the following examples are as follows: EVOH · E105B (Kuraray 5 Japan) 耐 6 6 : ΕΝ 500 (KP Chemicals) Ionic polymer: SURLYN 8527 (Dupont, USA) HDPE_g-MAH: Compatibilizer, ΡΒ3009 ( CRAMPTON) Polyolefin Resin: High Density Polyethylene (BDO 390, LG ClffiM, Melt Index: 0.3 g per 10 minutes, Density: 0.949 g/cm3 (g/cm3)) Clay: Closite 30B (SCP) Heat Stabilizer :IR 1098 (Songwonlnc.) Preparation Example 1 (Preparation of EVOH/inserted clay nanocomposite) 19 1320771 18784 pif.doc 97 wt./〇 ethylene-vinyl alcohol copolymer (Ev〇h; E-105B (B)浠 contains I. 44% by mole); Kuraray; Japan; Index: 5.5 g per 10 minutes; density: 1.14 g/cm 3 ) placed in the main hopper of a twin-screw extruder (SMPlatek co-rotating twin-screw extruder; furnace 40). Then '3 wt% respectively As an organic montmorillonite inserted into clay (Southern Intercalated Clay Products, USA; C20A) and 〇.i parts by weight of the total weight of the EVOH copolymer and the organic montmorillonite, IR 1 as a heat stabilizer 〇98 was placed in the side of the twin-screw extruder into the hopper to prepare a granular EVOH/insert clay nanocomposite. The extrusion temperature conditions were 180-190-200-200-200-200-2001 and the screw was 300. Rotation / minute (ipm) rotation, and the discharge condition is 4 〇 kg / hr (kg / hr) - Preparation Example 2 (Preparation of nylon 6 / insert clay nanocomposite) 97% of the polyamine (Nylon 6) placed in the main hopper of a twin-screw extruder (sm Platek co-rotating twin-screw extruder; φ4〇). Next, 3, % of the organic montmorillonite inserted into the clay and & 醯 吁 与 与 与 与 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡 冡098 was placed in the side feed hopper of a twin-screw extruder to prepare a granulated polyamide/inserted clay nanocomposite. The extrusion temperature conditions are 220-225-245-245-245-245-245. (:, screw 卩 3〇0 rpm / 鏠, , and the discharge condition is 40 kg / hr. 制备 Preparation Example 3 (Preparation of ionic polymer/inserted clay nanocomposite)

Put 97 weight ° / ◦ ionic polymer into a twin screw extruder (SM 20 18784pif.doc

Platek co-rotating twin-screw extruder; the main hopper of furnace 40). Next, 3 wt% of the organic montmorillonite as the clay and the IR 1098 as the heat stabilizer in terms of 100 parts by weight of the total weight of the ionic polymer and the organic montmorillonite were placed in the twin screw. The side of the extruder is fed into a hopper to prepare a granular ionic polymer/inserted clay nanocomposite. The extrusion temperature conditions are 220-225-245-245-245-245-245. (:, the screw was rotated at 300 rpm) and the discharge condition was 40 kg/hr. Example 1 25 parts by weight of EVOH/inserted clay obtained in Preparation Example 1 was dry-mixed in a dumble mixer (dumble mixer) The composite, the bismuth by weight of the compatibilizer and 69 parts by weight of the high-density polyethylene, and using blow molding to open (SMC blow molding machine, 6 phi) at 19 〇 - 205-205-205. Under the condition of pressure temperature, the dry mixture will be wiped out from the end of the blown machine, and the blank will be shaped into a mold of 1000 ml of agrochemical container. Use inertia, body (nitrogen). Pressurize the type chain 6 Seconds to 】 broken / square English leaves (blocking) two [force. Then 'reduced the pressure in the container and let the Wei Wei gas second. Use 3 with nitrogen and! to 1%% of the gas reactive gas to the container =6 seconds to about 100 cc/sq ft (〇7 MPa (clear 。.), release the pressure and degas the container for 15 seconds. Then, pressurize with inert gas for 6 seconds to about! (four) / square Ying Yu (〇7 MPa) Idle iC 'release _ force and degas the container for h5 seconds. Finally, use Pa) Rong J and add 6 seconds to about 1 〇"/平才英# (〇.7 "Device: Πί=ί state and there is a fluorine coating of inner 1220771 18784pif.doc wall with 0.2//m in the mold. Example 2 will be in a double cone mixer (mydcm-ioo, MYE0NG wo〇micron SYSTEM) 25 parts by weight of the yoke 6/insert clay nitrite compound obtained in Preparation Example 2, 6 parts by weight of the compatibilizer, and 69 Å of the density polyethylene were dry-mixed for 3 G minutes to make a plastic molding machine (SMC blow molding) The forming machine, 6〇phi), is used to dry the mixture under the condition of the thickness of the hidden 2〇5_2〇5_2〇5〇c. The end of the self-blow molding machine is broadcasted into a shape of 3 ml. Injection of the product container. The parison is pressurized with an inert gas (nitrogen) for a pressure of from 6 seconds to 1 Torr/square Torr. Then, the pressure in the vessel is lowered and the vessel is degassed for 15 seconds. The reaction gas of nitrogen bismuth and 1 to 10% of fluorine gas repressurizes the container for 6 seconds to a pressure of about 1 0.02 Å/〇 吋 (〇7 MPa). Thereafter, the pressure is released and the benefits are obtained. Degas for 1.5 seconds. Then re-pressurize the vessel with inert nitrogen for 6 seconds to a pressure of about 10 ^ psi (0 7 MPa). Thereafter, release the force and remove the container. 1.5 seconds. Finally, the vessel was repressurized with inert nitrogen to a pressure of about 100 psi (0 7 MPa). Thereafter, the valley was returned to atmospheric pressure and removed from the mold. The molded container contained an inner wall having a fluorine coating layer of 0.2/zm thick. Example 3 4 parts by weight of the obtained yoke obtained in Preparation Example 2 in a double cone type mixer (MYDCM-100, MYEONG W0〇MICRON SYSTEM) 6/Into the clay nanocomposite, 2 parts by weight of the compatibilizer, and 94 parts by weight of the high density $48 dry mix 30 > A blow molding machine 22 1320771 18784 pif.doc (SMC blow molding machine, 60 phi) was used at 190-205-205-205. (: Extrusion of the dry mixture under extrusion temperature conditions. The type extruded from the end of the blow molding machine, and the blank into a mold of a (8) ml agrochemical container. Use inert gas*. Body (nitrogen) The parison is pressurized for a pressure of from 6 seconds to 100 pounds per square inch. Next, the pressure in the vessel is lowered and the vessel is degassed for M seconds. Subsequently, a reactive gas pair containing nitrogen and 1 to 10% of fluorine gas is used. The container is then pressurized for a further 6 seconds to a pressure of about 1 〇〇 psi (0.7 MPa). Thereafter, the pressure is released and the vessel is degassed for 5 seconds. Next, the vessel is repressurized with inert nitrogen. Seconds climbs to the house (0.7 MPa). After that, the dust is released and the container is degassed for 1.5 seconds. Finally, the container is repressurized with inert nitrogen for 6 seconds to 1 lb./sq. The pressure of 吋 (〇·7 MPa) was followed, and the port was only removed to atmospheric pressure and removed from the mold. The resulting molded container had an inner wall having a fluorine coating of 0.2//m thick. Example 4 40 parts by weight of the nylon 6/insert obtained in Preparation Example 2 in a double-cone mixer (MYDCM-100, MYEONG WOO MICRON SYSTEM) The nanocomposite, the bismuth by weight compatibilizer and 42 parts by weight of high density polyethylene were dry mixed for 3 minutes. Using a blow molding machine (SMC blow molding machine, 60 phi) at 190_2 〇 5_2 〇 5 2 〇 5t: The dry mixture was extruded at the extrusion temperature. The parison extruded from the end of the blow molding machine was placed in a mold set to a 1000 liter agrochemical container. The parison was pressurized with an inert gas (nitrogen). Pressure in seconds to 100 psi. Then, reduce the pressure in the vessel and degas the vessel for 15 seconds. Then, pressurize the vessel for 6 seconds with a reactive gas containing nitrogen and 1 to 10% fluorine. 23 1320771 18784pif.doc to a pressure of about 100 psi (0.7 MPa). Thereafter, the pressure is released and the vessel is degassed for 1.5 seconds. Then, the vessel is repressurized with inert nitrogen. 6 seconds to about 100 Pounds per square inch (〇.7 MPa). Thereafter, release the pressure and degas the vessel for 1.5 seconds. Finally, add the waste to the vessel for 6 seconds to about 100 cc/square with inert nitrogen. The British leaf (0.7 MPa) is repeated. After that, the container is returned to atmospheric pressure and removed from the mold. The obtained molded container contained an inner wall having a fluorine coating layer having a thickness of 0·2/ζπι. Example 5 25 parts by weight of Preparation Example 3 in a double cone type mixer (MYDCM-100, MYEONG W〇〇MICRON SYSTEM) The ionic polymer/inserted clay nanocomposite obtained, the 6 parts by weight of the compatibilizer, and the 69 parts by weight of the high density polyethylene were dry-blended for 30 minutes. Using a blow molding machine (SMC blow molding machine, 60 phi) at 190-205-205-205.拨 The dry mixture is squeezed under the conditions of extrusion temperature. The parison extruded from the end of the blow molding machine was placed in a mold set to a 1000 ml agrochemical container. The parison is pressurized with an inert gas (nitrogen) for a pressure of 6 seconds to 100 psi. • Next, reduce the pressure in the container and degas the container for 1.5 seconds. Subsequently, a reactive gas containing nitrogen and 1 to 10% of fluorine gas was used to cough. The pressure of seconds to about 10 MPa (10 MPa) was placed at 6 pressures and the contents were degassed for 1.5 seconds. Next, pressurize the vessel with inert nitrogen for 6 seconds to about 1 lb./sq. ft. (7 MPa) and release the vessel for 15 seconds. Finally, after repressurizing with inert gas for 6 seconds to about 100 cc/square y (〇.7 MPa), the container is returned to the atmosphere and moved from the mold. 24 1320771 18784pif.doc The container contains one with 0.2# The inner wall of the m-thick fluorine coating. Example 6 was obtained in the preparation example 2 of the 190-205-205-205 挤压 extrusion temperature condition in the dry mixed state, respectively, by the belt feeder K-TR〇N No. 2, No. 3 and the 15 heavy wounds. Nylon 6/insert clay nanocomposite, 7-fold compatible compatibilizer and 78 parts by weight of high-density polyethylene are simultaneously placed in the main hopper of a blow molding machine (SMC blow molding machine, 6〇phi) . The pattern from the end (4) of the blow molding machine is placed in a mold that is shaped as a chemical container. Pressurize the chain with an inert gas (nitrogen) for 6 seconds to =^^. Next, reduce the fortune (4) force and make the capacity = two with nitrogen and 1 to the fluorine gas, the neck: ί Ά ‘ release the force and degas the container for 1.5 seconds. Then, with the inert gas, the macro will cry iv will be a singular force ^ seconds to about 100 stone side / square inch time (〇.7, with inert nitrogen on the Xuan Cry, to make the valley reduce milk seconds. The most (10) megapascals of the exhibition seconds to 'about 1 〇 0 stone side / square inch and removed from the mold. $ 吏 回复 回复 回复 回复 回复A container having a barrier property was produced in the same manner as in Example 25 1320771 18784 pif.doc 2 except that organic Mongolian soil was not used as the inserting clay. In Comparative Example 3, a mixed temperature condition τ of 85-195-195_195t was used, and blow molding was used to form SMC. Plastic molding machine '6〇phi) extruded polyethylene (BD 叩, ancient) will be molded from the mouth of the mouth > the end of the machine broadcasted the type of chain released to open) for the touch pen Sheng agricultural chemicals container In the model. Use the inert gas (nitrogen) to pressurize the type for 6 seconds to 100%. Next, lower the contents of the container and degas the meter for 5 seconds. Subsequently, the vessel was repressurized with a reactive rolling stock containing nitrogen and 1 to 10% of fluorine gas for a period of 6 seconds to about 丨(9) cc/square 忖 (^7 MPa). Thereafter, the force is released and the container is degassed for a second. 4, re-pressurize the container with inert nitrogen for 6 seconds to about (10) broken / square inch ^ 〇 · 7 MPa) (four). Thereafter, the force was released and the container was degassed for 5 seconds. After the extraction, the inert nitrogen gas is used to repressurize the vessel for 6 seconds to about 1 lb./sq. ft. (0.7-MPa). Thereafter, the container is returned to the atmosphere and removed from the mold. The resulting molded container contained an inner wall having a 氟2_thick fluorine coating. Experimental Example a) Liquid-blocking toluene, Desys herbicide (!% deltamethrin + emulsifier, stabilizer and solvent; KyungNong), Bats^ insecticide (50/. BpMC + 5〇) The %2 emulsifier and solvent) and water were placed in the containers manufactured in Examples 1 to 6 and Comparative Examples 丨 to 3. Next, after 3 days, the weight change was measured under forced discharge conditions at 50 °C. For toluene, the change in weight was further measured at room temperature. 26 1320771 18784pif.doc b ) Gas barrier (cubic centimeters per square meter · day · atmospheric pressure (cc / m2. day · atm)) at temperatures of 23 ° C and 50% relative humidity, examples 1 to 6 and The containers prepared in Comparative Examples 1 to 3 were placed separately for 1 day. Next, the gas permeability (MoconOX-TRAN 2/20, U.S.A.) was measured.

Table 1 Gas barrier oxygen breakthrough (square centimeters / square meter · 24 hours · atmospheric pressure (cm2 / m2.24 hrs · atm)) moisture penetration (g / square meter · 24 hours (g / m2-24 hrs )) Example 1 5.3 1.04 Example 2 2.5 1.05 Example 3 9.6 0.98 Example 4 -1.83 1.01 Example 5 11.1 1.02 Example 6 1.96 1.02 Comparative Example 1 35.4 1.32 Comparative Example 2 34.8 1.26 Comparative Example 3 56.4 2.03 27 18784pif.doc Table 2 Classification Liquid Resistive liquid resistance

Weight change at 253⁄4

_Instance g Instance 3 0.008 ^088^18?

Comparative Example 1 0.430 4.593 Example 2 Comparative Example 3

6.304

Desys 0.105 0.061 0.091 0.052 0.094 0.054 1.126 1.312 1.638

As shown in Tables 1 and 2, - ^ /s, , _ $' compared to the comparative example 1 5 见 See the containers of Examples 1 to 6, to the containers of 3, the JLh I of the present invention is absolute. Products with resistance to the month of the month have excellent resistance to oxygen, organic solvents and moisture. (4) Mechanical strengths Although the present invention has been disclosed in the preferred embodiments as above, and the present invention is defined, any person skilled in the art can make a few changes without departing from the scope of the invention _ 28 1320771 18784pif.doc The scope of protection of the present invention is defined by the scope of the appended claims. [Simple diagram description] None [Main component symbol description] None

29

Claims (1)

1320771 Revision date: July 3, 1997 Japanese patent range without slash correction This ten, the scope of patent application: 1. A kind of barrier-resistant article, with a fluorine coated inner wall, and prepared from dry mixed composition, The barrier article comprises: 40 to 96 parts by weight of a polyolefin resin; a heterogeneous H-domain complex, the naphthalene: clay and at least a resin having a barrier property, the B = Γ a group consisting of a polyamine, an ionic polymer, and a polyvinyl alcohol; and 1 to 30 parts by weight of a compatibilizing agent, which has a barrier property in the = t composite. The weight ratio of the inserted clay to the clay is 58.0 : 42.0 To 99.9 : 0.1, wherein the compatibilizer is selected from the group consisting of ethylene-ethylene & ethyl acrylate copolymer, ethyl acetoacetate, _ (four) 酉 1 yam == cis dianhydride Branch) high-density polyethylene, cis-butan = phthalic anhydride modified (grafted) linear low-density polyethylene, ethoxylated acid vinegar-(mercapto)acrylic acid copolymer, ethyl-acrylic acid ^Astrology, ethylene·acetic acid B-copolymer, cis-dianhydride ethylene-vinyl acetate In the group consisting of copolymers, or the household 1 _ _ _ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 2. As stated in item I of the patent application and at 111. The inserted clay is selected from the group consisting of montmorillonite and bentonite, lining stone, fluoridated fossil, m stone, green: ^ stone mother, 30 1320771 18784pif.doc vermiculite, multi-water kaolin, Weikang At least one compound of the group consisting of earth, Shakang soil, Magi soil, and Kenney soil. 3. The article of the invention of claim 1, wherein the insert clay comprises from 1 to 45% by weight of an organic material. 4. The article of claim 3, wherein the organic material has at least one functional group selected from the group consisting of a first grade to a fourth grade, a scale, a maleic acid vinegar. Broken sour vinegar, acenaphthyl vinegar, benzoyl hydrogen, oxazoline and dinonyl distearyl ammonium. 5. The article of the invention of claim 1, wherein the ethylene vinyl alcohol copolymer contains from 1 to 50 mol% of ethylene. 6. For example, the article having the resistive property mentioned in Item 1 of the patent scope, wherein the polyamine is resistant to 4.6, resistant to theory 6, financial to 6.6, resistant to 6.10, and only to 7, nylon 8, resistant On the basis of 9, 9, or 12, MXD6, amorphous polyamine, a copolymerized polyamine containing at least two of the polyamines or a mixture of at least two of the polyamines. 7. The article of the invention of claim 6, wherein the amorphous polyamine has a glass transition temperature of about 8 〇 13 〇ΐ:. 8. The article of the invention of claim 6, wherein the amorphous polyaxial axis is selected from the group consisting of hexamethylenediamine and benzoic acid/ The ratio of p-diamine to hexamethylenediamine/p-benzoguanamine terpolymer; 2 2 4• monoamine p-terephthalic acid disk 2 4 4-dimethyl-p ' ' soil mono-compound: and hexamethylene diamine or 2: A; 曱 pentyl = stupid mixed formic acid or a mixture of the copolymer of dicarboxylic acid, as described in the block diagram of 31 1320771 18784pif.doc The article, the eight-day non-Japanese 0 wire _ is a ratio of hexamethylenediamine benzene = one formazan with a ratio of 7 〇:3 formic acid. Indoleamine/p-dimethylamine ternary 10. As claimed in the patent scope, the ionic polymer has an index of extinction per 10 minutes (190 ° C, 2,160 g). Knife,, in. to 10 grams of melting method, the production of materials with barrier and fluorine coating (four) by dry mixing 40 to 96 #旦eight parts by weight of the barrier nano 2D.5 Up to 60 clay and at least one selected from the group consisting of:; B: Nai compound comprising - inserting polymer and polyethylene glycol - (4) material, poly-, ion-molding the nano-composite resin; The coating, an inner wall field of the article... and the fluorine coating range 11 manufactured are resistant to coating and coating. ^Method, method, method for forming a pure fluorine coating according to item 11 of the invention, which has the properties of resistive and force-pressing into #/·+, 6 °D, is formed by blow molding, Manufactured by mask forming, 遂 forming or 料. Earth secret m 32