Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
  • C08F216/04—Acyclic compounds
  • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
  • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
  • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
  • C08K5/053—Polyhydroxylic alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier

Definitions

• the present invention relates to a polyvinyl alcohol-based resin composition capable of providing a melt-molded body having excellent gas barrier properties and a melt-molded body of the resin composition.
• PVA Polyvinyl alcohol
• a PVA-based resin is used as a gas barrier layer for the container or packaging film. Or the resin composition thereof is used,
• molded products such as containers and films are manufactured by melt molding from the viewpoint of productivity.
• PVA polyvinyl alcohol
• a modified PVA-based resin that can be melt-molded is also proposed. Has been done. (For example, a PVA-based resin having a side chain 1,2-diol structure described in JP-A-2002-284818, JP-A-2004-285143, JP-A-2006-95825, and the like).
• a plasticizer may be added to the PVA-based resin composition for melt molding such as a packaging film and a container (for example, Japanese Patent Application Laid-Open No. 2001-288321). Are known.
• Japanese Unexamined Patent Publication No. 2002-284818 Japanese Unexamined Patent Publication No. 2004-285143 Japanese Unexamined Patent Publication No. 2006-95825 Japanese Unexamined Patent Publication No. 2001-288321
• the excellent gas barrier property of the PVA-based resin is based on the high crystallinity of the PVA molecular chain, the crystallinity of the modified PVA-based resin containing a plasticizer or copolymerized with other monomers is disturbed. There is a problem that the gas barrier property is lowered. Further, when the PVA-based resin is continuously melt-molded for a long time, there is room for improvement in thermal stability, such as generation of deteriorated products due to heat.
• the present invention has been made in view of such circumstances, and an object of the present invention is to provide a PVA-based resin composition that can be melt-molded and has excellent gas barrier properties.
• the present inventors have focused on a modified PVA-based resin containing a primary hydroxyl group in a known side chain as a melt-moldable PVA-based resin, and further, the modified PVA-based resin has a multivalent value of 5 to 15 carbon atoms.
• the decrease in gas barrier property due to denaturation can be suppressed and further improved by blending alcohol, and the present invention has been completed.
• the polyvinyl alcohol-based resin composition of the present invention contains a polyvinyl alcohol-based resin having a primary hydroxyl group in the side chain and a polyhydric alcohol having 5 to 15 carbon atoms.
• the polyhydric alcohol is preferably at least one selected from the group consisting of dipentaerythritol and pentaerythritol.
• the total content of the dipentaerythritol and the pentaerythritol per 100 parts by weight of the polyvinyl alcohol-based resin is preferably 0.1 parts by weight or more and less than 50 parts by weight.
• the polyvinyl alcohol-based resin is preferably a polyvinyl alcohol-based resin having a structural unit represented by the following formula (3).
• R 1 -R 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent, and X is a bonding chain.
• the resin composition of the present invention preferably has a pellet shape.
• the present invention also includes a melt-molded body of the resin composition of the present invention and a multilayer structure including a layer made of the resin composition.
• the polyvinyl alcohol-based resin composition of the present invention has improved stretchability and gas barrier properties as compared with the case of a PVA-based resin having a primary hydroxyl group in the side chain, which is the main component, alone.
• the polyvinyl alcohol-based resin composition of the present invention is a polyvinyl alcohol-based resin having a primary hydroxyl group in the side chain (sometimes referred to as “PVA-based resin containing a primary hydroxyl group in the side chain”) and has a large number of carbon atoms of 5 to 15. It is a composition containing valent alcohol.
• the side chain primary hydroxyl group-containing PVA-based resin is a vinyl alcohol unit represented by the following formula (1), which constitutes polyvinyl alcohol, and a vinyl ester unit (formula (2) below) which is an unkenken moiety.
• a modified PVA-based resin containing a structural unit having a primary hydroxyl group in the side chain Refers to a modified PVA-based resin containing a structural unit having a primary hydroxyl group in the side chain.
• the side chain 1 and 2 diol-containing units represented by the following formula (3) are preferable.
• vinyl ester-based monomer examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl capricate, vinyl laurate, vinyl stearate, and vinyl benzoate. , Vinyl acetate and the like, but vinyl acetate is economically preferably used.
• the vinyl ester unit is included when the saponification degree is less than 100%.
• Ra depends on the type of vinyl ester-based monomer used, and when a vinyl acetate monomer is used, it becomes a methyl group.
• R 1 to R 6 are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert. -It is a butyl group or the like, and may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group or a sulfonic acid group). More preferably, it is a hydrogen atom.
• R 1 to R 6 may all be the same or different, but preferably all are hydrogen atoms.
• the end of the side chain becomes a primary hydroxyl group, which is preferable in that the reactivity with an adhesive resin such as an acid-modified polyolefin resin is improved and the formation of a laminate is facilitated.
• the bonded chain (X) is a single bond or a hydrocarbon group such as an alkylene group, an alkenylene group, an alkynylene group, a phenylene group or a naphthylene group (these hydrocarbon groups are a fluorine atom, a chlorine atom, a bromine atom and the like).
• R is independent of each other
• It is an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is an integer of 1 to 5).
• X is preferably a single bond, an alkylene group having 6 or less carbon atoms (particularly a methylene group), or -CH 2 OCH 2 -in terms of stability during production or use, and above all, in terms of thermal stability and high temperature. Single bonds are most preferred in terms of stability under lower conditions and under acidic conditions.
• the most preferable structural unit as the structural unit represented by the formula (3) is the side chain 1,2-diol-containing unit represented by the following formula (3a).
• the modification rate (content) of the PVA-based resin having a primary hydroxyl group in the side chain is usually 0.1 to 20 mol%, preferably 0. It is 5 to 15 mol%, more preferably 1 to 10 mol%, and particularly preferably 2 to 8 mol%. If the modification rate is too low, the reactivity with an adhesive resin such as an acid-modified polyolefin resin tends to decrease, and if it is too high, the crystallization rate becomes too slow to form a laminate with another resin. In some cases, the appearance tends to deteriorate, such as deformation of the laminate.
• the number average degree of polymerization (measured according to JIS K6726) of the side chain primary hydroxyl group-containing PVA resin (preferably the side chain 1,2-diol-containing PVA resin) having the above structure is usually 150 to 4000. It is preferably 200 to 2000, more preferably 250 to 800, and even more preferably 300 to 600. If the average degree of polymerization is too low, it tends to be difficult to form a stable shape during melt molding, and if it is too high, the viscosity of the resin composition tends to be too high and molding tends to be difficult.
• the viscosity of the aqueous solution may be used as an index of the average degree of polymerization of the PVA-based resin.
• the viscosity of the 4 wt% aqueous solution at 20 ° C. measured according to JIS K6726 is usually 1.5 to 20 mPa ⁇ s, preferably 2 to 12 mPa ⁇ s, and particularly preferably 2.5 to 8 mPa ⁇ s. s. If the viscosity is too low, it tends to be difficult to form a stable shape during melt molding, and if it is too high, molding tends to be difficult. In addition, the coating workability when applying an aqueous solution tends to decrease.
• the saponification degree of the PVA-based resin (preferably the PVA-based resin containing 1,2-diol side chains) is usually 70 to 99.9 mol%, preferably 75 to 99.7 mol%, and is particularly preferable. Is 78-99.5 mol%. If the degree of saponification is too low, the flexibility tends to be too high, and the shape stability during lamination tends to decrease. The degree of saponification was measured in accordance with JIS K6726.
• the side chain primary hydroxyl group-containing PVA-based resin having the above structure is produced, for example, by the production method disclosed in JP-A-2002-284818, JP-A-2004-285143, and the like. be able to.
• the side chain primary hydroxyl group-containing PVA resin used in the present invention has a range that does not impair the melt moldability of the side chain primary hydroxyl group-containing PVA resin (specifically, 12 mol% or less, preferably 10). (Mole% or less) may contain repeating units based on the copolymerization monomers as shown below.
• Possible copolymerization monomers include, for example, olefins such as ethylene, propylene, isobutylene, ⁇ -octene, ⁇ -dodecene, ⁇ -octadecene; acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid.
• Unsaturated acids such as or salts thereof or mono or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; amides such as acrylamide and methacrylamide; olefin sulfones such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid.
• alkyl vinyl ethers N-acrylamide methyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallylvinylketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxypropylene Polyoxyalkylene (meth) allyl ethers such as (meth) allyl ethers; polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylates and polyoxypropylene (meth) acrylates; polyoxyethylene (meth) acrylamides and polys.
• Polyoxyalkylene (meth) acrylamide such as oxypropylene (meth) acrylamide; polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine , Polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol and other hydroxy group-containing ⁇ -olefins. And derivatives such as acylated products thereof.
• the side chain primary hydroxyl group-containing PVA-based resin that can be used in the resin composition of the present invention may be one kind or a mixture of two or more kinds.
• combinations of PVA-based resins having different saponification degrees, degree of polymerization, modification rate, etc., combinations of PVA-based resins having different types of side chain primary hydroxyl group-containing units, and the like can be mentioned. ..
• the resin composition of the present invention is characterized in that a polyhydric alcohol having 5 to 15 carbon atoms is used as a gas barrier property improving type plasticizer.
• polyhydric alcohols having 5 to 15 carbon atoms include pentaerythritol (C 5 H 12 O 4 , melting point 238 to 260 ° C.), dipentaerythritol (C 10 H 22 O 7 , melting point 210 to 218 ° C.), and mannitol. (C 6 H 14 O 6 , melting point 166 to 168 ° C.) and the like.
• pentaerythritol, dipentaerythritol, or a combination thereof which are polyhydric alcohols having a melting point higher than the melting point of the polyvinyl alcohol-based resin which is the main component of the resin composition, are preferable.
• a polyhydric alcohol having 5 to 15 carbon atoms can act as a plasticizer for a PVA-based resin, which not only contributes to lowering the melting point of the composition but also improves fluidity during melting.
• a plasticizer for a polyvinyl alcohol-based resin it is generally known to use a plasticizer that is liquid at room temperature, such as glycerin and polyethylene glycol. These liquid plasticizers can reduce the flow viscosity of the polyvinyl alcohol-based resin and can contribute to the improvement of workability during kneading and stretching. However, these liquid plasticizers tend to lower the gas barrier property as compared with the case of the PVA-based resin alone, and cannot fully exhibit the superiority of the PVA-based resin as the original gas barrier film.
• the gas barrier property can be improved as compared with the case where the PVA-based resin alone is used. That is, it can act as a plasticizer of a gas barrier property improving type.
• the hydroxyl group of the vinyl alcohol unit in the PVA chain and the hydroxyl group of dipentaerythritol aggregate by hydrogen bonding by entering the amorphous portion of the PVA-based resin It is thought that it was because he was able to increase his power.
• glycerin and polyethylene glycol are liquids at room temperature, it is considered that the cohesive force between hydroxyl groups does not increase, and even if they contribute to plasticization, they cannot contribute to the improvement of gas barrier properties.
• polyhydric alcohols having 5 to 15 carbon atoms such as pentaerythritol and dipentaerythritol (hereinafter, these polyhydric alcohols may be referred to as “gas barrier property improving type plasticizer”) are obtained by stretching a film-shaped molded product. Sex can also be improved. That is, when a film formed with the resin composition of the present invention containing a polyhydric alcohol having 5 to 15 carbon atoms such as pentaerythritol and dipentaerythritol is stretched, the film is formed with a resin composition not containing these. A higher draw ratio can be applied than the film.
• polyhydric alcohols having 5 to 15 carbon atoms such as pentaerythritol and dipentaerythritol exist as solids at the stretching temperature, and therefore may act as an effective plasticizer even during the stretching treatment. Conceivable.
• the gas barrier property improving type plasticizer can be contained in an amount of 0.1 part by weight or more and less than 50 parts by weight per 100 parts by weight of the polyvinyl alcohol resin, preferably 1 part by weight or more and 5 parts by weight or more and 10 parts by weight or more. , 11 parts by weight or more, 12 parts by weight or more, 15 parts by weight or more.
• the upper limit of the content is preferably 38 parts by weight or less, 35 parts by weight or less, 30 parts by weight or less, and 28 parts by weight or less. Within this range, the preferred content is selected depending on the melt molding method applied and the type of polyhydric alcohol used.
• the content of the gas barrier property improving type plasticizer is too small, the gas barrier property improving effect cannot be obtained, and if the content is too large, melt molding becomes difficult, and the content ratio of the polyvinyl alcohol-based resin in the composition. Is relatively low, which may lead to a decline in the gas barrier property itself.
• pentaerythritol can be synthesized by condensing acetaldehyde and formaldehyde in a basic environment, and a commercially available product (for example, Perstorp's "Pentamono”) can also be used.
• the dipentaerythritol is generally obtained as a by-product of (i) pentaerythritol synthesized by aldol condensation between aldehyde and formaldehyde, and (ii) polypentaerythritol using phosphoric acid, sulfuric acid or the like from pentaerythritol. It can be produced by a method of synthesizing a mixture, (iii) a method of reacting ureas with pentaerythritol, or the like. In any of the synthetic methods, dipentaerythritol is obtained as a mixture with other compounds.
• metal hydroxide is added to a solution obtained by reacting pentaerythritol and aldehydes. It is preferable to add a compound or an alkaline earth metal hydroxide to react.
• a commercially available product may be used, and examples of the commercially available product include "Di-Penta90" manufactured by Perstorp.
• dipentaerythritol usually contains about 5% by weight of pentaerythritol as a by-product, if it is necessary to accurately control the content of pentaerythritol, purified or highly pure dipentaerythritol is required. It is preferable to use tall.
• the polyhydric alcohol as a gas barrier improving type plasticizer may be used alone, but preferably pentaerythritol and dipentaerythritol are used in combination.
• pentaerythritol usually contains pentaerythritol as an impurity
• pentaerythritol it can be used alone.
• the content ratio (DPE / PE) of both compounds is preferably appropriately selected according to the type of melt molding method.
• the mixing ratio (DPE / PE) of both compounds is preferably 10 or more, particularly preferably 30 or more, and 100 or less, further 70 or less. Is preferable.
• pentaerythritol is contained as a by-product of dipentaerythritol, the content thereof is 1/10 or less of the content of dipentaerythritol (DPE / PE is 10 or less).
• the mixing ratio (DPE / PE) of both compounds is 0.1 to 10, preferably 0.3 to 5, and more preferably 0.5 to 2. That is, it is preferable that pentaerythritol and dipentaerythritol are contained in nearly equal amounts.
• the reason why the preferable mixing ratio of both compounds is determined according to the type of molding method is not clear, but the melt-extruded film is cooled by air cooling in the inflation method, whereas in the T-die method, a cooling roll is used. It is considered that there is a factor in the difference in the cooling method.
• the resin composition of the present invention contains a polyhydric alcohol that can act as a plasticizer, but is within a range that does not impair the effects of the present invention (less than 3% by weight of the plasticizer). Other plasticizers may be contained.
• the resin composition of the present invention contains other polymers within a range that does not impair the effects of the present invention (particularly melt moldability and gas barrier properties) (for example, less than 30% by weight of the composition). May be.
• the polymer that can be contained include various thermoplastic resins such as polyamide, polyester, polyethylene, polypropylene, and polystyrene.
• reinforcing agents fillers, pigments, dyes, lubricants, antioxidants, and antistatic agents are used within a range that does not impair the effects of the present invention (10% by weight or less of the composition).
• the resin composition of the present invention having the above composition can suppress a decrease in gas barrier property due to denaturation due to the coexistence of a polyhydric alcohol having 5 to 15 carbon atoms, and is a side chain primary hydroxyl group-containing PVA-based resin.
• the gas barrier property can be improved as compared with the case of a single substance.
• a polyhydric alcohol having 5 to 15 carbon atoms is used as a plasticizer, the stretchability is also improved, and when the plasticizer is not contained or when a conventional liquid plasticizer (such as glycerin) is contained. Compared with this, it is possible to increase the draw ratio of the film molded body. Further, the thermal stability of the resin composition is also improved, and there is also an effect that the long-run property in melt molding is improved.
• the resin composition having the above composition can be obtained by (i) a method of dry-blending a gas barrier-improving type plasticizer and other components with a PVA-based resin and then melt-kneading the resin composition, and (ii) an aqueous solution of the PVA-based resin. And a method of mixing a gas barrier property improving type plasticizer and other components.
• the method (i) is preferable, and a pellet-shaped resin composition can be obtained.
• the order in which the polyhydric alcohols are added may come first.
• it may be added to the PVA-based resin as a mixture of dipentaerythritol and pentaerythritol in advance (or dipentaerythritol containing pentaerythritol as a by-product).
• the melt-molded body of the resin composition and its manufacturing method The resin composition of the present invention can be melt-molded based on the characteristics of the side chain primary hydroxyl group-containing PVA-based resin which is the main component. From the relationship between the melting point of the side chain primary hydroxyl group PV resin and the thermal decomposition temperature, a melt extrusion molding method generally used for thermoplastic resins can be adopted. Therefore, the resin composition of the present invention is used for melt-molded bodies that are required to have gas barrier properties, especially for melt-molded films, stretched films, bags made of sheets, and containers and lids made of cups, trays, tubes, bottles, and the like. Can be used.
• the film or container may be a film or container made of the resin composition of the present invention alone (single layer), or may be used as a multilayer structure in which two or more layers of other thermoplastic resins, papers, etc. are laminated. good.
• the resin composition layer of the present invention has a role as a gas barrier layer.
• Examples of the multilayer structure including the resin composition layer of the present invention as a gas barrier layer include food packaging materials such as coffee capsules and shrink films, chemical packaging materials, cosmetic packaging materials such as cosmetic water and foundation cases, and metals.
• melt molding method examples include injection molding and extrusion molding.
• Extrusion molding is particularly suitable as a method for molding a film or a sheet, and examples thereof include a T-die molding method and an inflation molding method (blown method). Not only single-layer extrusion but also multi-layer extrusion may be used.
• Multi-layer extrusion co-extrusion molding is suitable for producing a multi-layer structure in which films are laminated.
• the obtained film or sheet may be subjected to secondary processing such as uniaxial or biaxial stretching. Since the resin composition of the present invention is excellent in stretchability, it is preferable to perform a stretching treatment in order to further improve the film strength and the gas barrier property.
• Oxygen permeation amount (cc / m 2 , day, atm) Using the MOCON oxygen permeability measuring device OX-TRAN2-21 (Hitachi High-Tech Science Co., Ltd.), the oxygen permeation amount (per 20 ⁇ m) of the created single-layer film was measured under the conditions of humidity 65% RH and temperature 23 ° C. It was measured.
• Components of resin composition 1.
• PVA-based resin As the side-chain primary hydroxyl group-containing PVA-based resin, a side-chain 1,2-diol-containing PVA-based resin having a structural unit represented by the formula (3a) was used.
• the side chain 1,2-diol-containing PVA-based resin used had a degree of modification (content of 1,2-diol units in the side chain) of 6 mol%, a saponification degree of 99 mol% measured in accordance with JIS K6726, and JIS.
• the degree of polymerization measured according to K6726 is 450.
• Resin composition No. 1-8 Frm molding and evaluation by T-die method
• TEX30 ⁇ twin-screw extruder
• Diameter (D) 15 mm L / D 60 Screw rotation speed: 200 rpm
• Set temperature: C1 / C2 / C3 / C4 / C5 / C6 / C7 / C8 / D 120/150/180/195/200/200/210/210/210 ° C.
• the obtained resin composition pellets were extruded using a single-screw extruder GT-40 (Plastic Engineering Laboratory Co., Ltd.) and a T-die under the following conditions to prepare a single-layer film having a thickness of 20 ⁇ m.
• the oxygen permeation amount (cc / m2 ⁇ day ⁇ atm) per 20 ⁇ m thickness of the obtained film was measured.
• the long-running properties of 2 and 4 were measured based on the above measuring method.
• Diameter (D) 15 mm, L / D 60 Screw rotation speed: 200 rpm
• Set temperature: C1 / C2 / C3 / C4 / C5 / C6 / C7 / C8 / D 150/180/190/195/200/210/210/210/210 ° C.
• the composition containing dipentaerythritol and pentaerythritol contains glycerin as a plasticizer in the case of the side chain 1,2-diol PVA-based resin alone (No. 1). It was superior to the case of (No. 8).
• Resin composition No. 11-18 Frm molding and evaluation by inflation method
• No. Pellets were prepared in the same manner as in No. 1, and a film was formed using an inflation film forming machine (manufactured by PLACO Co., Ltd.) under the following conditions.
• the oxygen permeation amount (cc / m2 ⁇ day ⁇ atm) per 20 ⁇ m thickness was measured according to the above evaluation method.
• No. for 11, 12, 14, and 15 the stretchability was also evaluated based on the above-mentioned measuring method.
• Cooling Air cooling ⁇ L / D: 26 ⁇ Screw: Full flight ⁇ Compression ratio: 3.0 -Mesh: 90/120/90 ⁇ Die diameter: 75mm ⁇ ⁇ Gap: 1 mm ⁇ Blow ratio: 1.2 -Film folding width: 130 mm ⁇ Temperature setting: Cylinder 210 °C, Die 210 °C
• the resin composition of the present invention can be melt-molded and has an excellent gas barrier property, it is suitable as various packaging materials, especially a packaging film. Further, as a multilayer structure film containing a gas barrier layer of the resin composition of the present invention, it is suitably used in the field of food packaging and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=80247881

Family Applications (1)

Country Status (5)

Families Citing this family (1)

Citations (16)

Family Cites Families (6)

• 2021
  • 2021-08-10 JP JP2022542850A patent/JPWO2022034876A1/ja active Pending
  • 2021-08-10 WO PCT/JP2021/029493 patent/WO2022034876A1/ja not_active Ceased
  • 2021-08-10 EP EP21855955.7A patent/EP4198084A4/en active Pending
  • 2021-08-10 JP JP2021130447A patent/JP7667944B2/ja active Active
  • 2021-08-10 CN CN202180055662.7A patent/CN116056894B/zh active Active
• 2023
  • 2023-02-01 US US18/104,491 patent/US20230174765A1/en active Pending

Patent Citations (16)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events