JP4883281B2 - Laminated structure - Google Patents

Laminated structure Download PDF

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JP4883281B2
JP4883281B2 JP2006103982A JP2006103982A JP4883281B2 JP 4883281 B2 JP4883281 B2 JP 4883281B2 JP 2006103982 A JP2006103982 A JP 2006103982A JP 2006103982 A JP2006103982 A JP 2006103982A JP 4883281 B2 JP4883281 B2 JP 4883281B2
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resin
laminated structure
polyvinyl alcohol
structure according
acid
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JP2006312313A (en
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光夫 渋谷
新治 湯野
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日本合成化学工業株式会社
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Description

  The present invention relates to a laminated structure having a layer containing a polyvinyl alcohol-based resin (A) and a layer containing a thermoplastic resin (B), more specifically, excellent long-run moldability during production by coextrusion molding, The present invention relates to a laminated structure excellent in interlayer adhesion, stretchability, gas barrier properties, and bending resistance.

  Conventionally, resin films made of polyamide-based resins, polyester-based resins, polyolefin-based resins, etc. have been used as packaging materials, but in the case of articles whose quality deteriorates due to oxygen, such as food and drink, pharmaceuticals, chemicals, Since a single film of the above resin cannot provide a sufficient oxygen gas barrier property, a laminated structure in which a material having an oxygen gas barrier property is combined by coating, laminating, coextrusion molding or the like is widely used.

  As a material having such an oxygen gas barrier property, a polyvinyl alcohol-based resin (hereinafter, polyvinyl alcohol is abbreviated as PVA) is known. For example, a saponification degree of 90 mol% is formed on at least one surface of a base film. As described above, a multilayer film in which an oxygen gas barrier layer mainly composed of a mixture of a PVA resin having a polymerization degree of 200 to 2600 and a PVA resin having a saponification degree of less than 90 mol% and a polymerization degree of 1500 to 3800 is formed (for example, a patent Reference 1) has been proposed.

Moreover, as a manufacturing method of the laminated structure, a coextrusion molding method that can be formed and laminated in one step is preferable, and it is necessary that the PVA-based resin used for this can also be hot-melt molded, A normal PVA resin has a melting point close to the decomposition point (230 ° C. or higher), so that hot melt molding is difficult. Therefore, the applicant of the present invention is a PVA resin that can be hot-melt molded and contains 2 to 10 mol% of 1,2-glycol bond in the side chain and has a saponification degree of 96 mol% or more. Based resin (for example, refer to Patent Document 2).
JP 2004-082619 A JP 2004-075866 A

  However, the PVA-based resin used in the multilayer film described in Patent Document 1 has a high melting point and is difficult to be melt-molded, so it must be manufactured by a solution coating method. A complicated process is required. The PVA-based resin described in Patent Document 2 can be co-extruded with a thermoplastic resin, but is not sufficiently adhesive with an adjacent layer, such as a thermoplastic resin layer or an adhesive resin, and stretched. Under severe conditions such as bending and repeated bending, cracks, voids, stretching unevenness or delamination may occur, and there may be problems such as deterioration of the appearance due to whitening and deterioration of gas barrier properties, and there is still room for improvement Met.

  That is, there is a demand for a laminated structure having excellent long-run moldability during production by coextrusion molding and excellent interlayer adhesion, stretchability, gas barrier properties, and flex resistance.

However, as a result of intensive studies in view of such circumstances, the present inventor has obtained 1,2 in the side chain obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the following general formula (1). -It discovered that the laminated structure which has a layer containing the PVA-type resin (A) containing a diol structure, and a layer containing a thermoplastic resin (B) matched the said objective, and completed this invention.

In the formula, R 1 , R 2 , and R 3 each independently represent hydrogen or an organic group, and X is a single bond, that is, a carbon of a vinyl structure portion and a carbon of a 1,2-diol structure portion are directly bonded. Or R 4 , R 5 , and R 6 each independently represents a hydrogen atom or an organic group, and R 7 and R 8 each independently represent a hydrogen atom or R 9 —CO— ( Wherein R 9 is an alkyl group).

The greatest feature of the present invention is a PVA having a 1,2-diol structure in the side chain obtained by saponifying a copolymer of a compound represented by the general formula (1) and a vinyl ester monomer as a PVA resin. This is because the resin (A) is used, and thereby the effects specific to the present invention are obtained.
That is, the crystallinity of the PVA resin is hindered by the 1,2-diol structure of the side chain, and by lowering the melting point, it becomes possible to stably perform melt molding at a temperature much lower than the thermal decomposition temperature. By using the compound represented by the general formula (1) as a comonomer for introducing a 2-diol structure, adhesion to an adjacent layer is improved when a laminated structure is formed. A delamination due to repeated bending does not occur, and a laminated structure having an excellent appearance and gas barrier properties is obtained.

  The laminated structure of the present invention can be co-extruded, has good long-run moldability, has excellent gas barrier properties and stretchability, and has good interlayer adhesion, so there are no cracks, voids, or stretching unevenness due to stretching. Since it is excellent in bending resistance, it is suitable as a packaging material for articles whose quality deteriorates due to oxygen.

Hereinafter, the present invention will be described in detail.
The PVA resin (A) containing a 1,2-diol structure in the side chain used in the present invention is obtained by saponifying a copolymer of a vinyl ester monomer and a compound represented by the following general formula (1). Obtained PVA-based resin.

In the formula, R 1 , R 2 , and R 3 each independently represent hydrogen or an organic group, and X is a single bond, that is, a carbon of a vinyl structure portion and a carbon of a 1,2-diol structure portion are directly bonded. Or R 4 , R 5 , and R 6 each independently represents a hydrogen atom or an organic group, and R 7 and R 8 each independently represent a hydrogen atom or R 9 —CO— ( Wherein R 9 is an alkyl group).
In the compound represented by the general formula (1), R 1 , R 2 , R 3 , and R 4 , R 5 , R 6 are typically hydrogen and may be in a range that does not inhibit the effects of the present invention. For example, an organic group such as an alkyl group may be used.

X in the compound represented by the general formula (1) is typically a single bond, that is, a carbon having a vinyl structure part and a carbon having a 1,2-diol structure part directly bonded. A bond chain may be used as long as it does not inhibit the effect, and the bond chain is not particularly limited, but hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene, naphthylene (these hydrocarbons are fluorine, chlorine, bromine). also it) chain and optionally, -CO substituted by halogen or the like etc. -, - COCO -, - CO (CH 2) m CO -, - CO (C 6 H 4) CO -, - S -, - CS -, - SO -, - SO 2 -, - NR -, - CONR -, - NRCO -, - CSNR -, - NRCS -, - NRNR -, - HPO 4 -, - Si (OR) 2 -, - OSi (OR) 2 -, - OSi (O ) 2 O -, - Ti ( OR) 2 -, - OTi (OR) 2 -, - OTi (OR) 2 O -, - Al (OR) -, - OAl (OR) -, - OAl (OR) O (Wherein R is each independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is a natural number). Among them, carbon is preferable in terms of stability during production or use. An alkylene group having a number of 6 or less is preferred. Those having an ether bond in such a bond chain may be insufficient in thermal stability, and may be thermally decomposed at the time of melt molding or after being made into a laminated structure, which is not preferable.

  Specific examples of the compound represented by the formula (1) include 3,4-dihydroxy-1-butene, 3,4-diasiloxy-1-butene, and 3-acyloxy-4-hydroxy-1-, in which X is a single bond. Butene, 4-acyloxy-3-hydroxy-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4,5-dihydroxy-1-pentene, wherein X is an alkylene group, 4,5-diacyloxy- 1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 4,5-diacyloxy-3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, 5,6-diacyloxy-1- Hexene, etc.

Among them, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen, X is a single bond, R 7 and R 8 are R in that they are excellent in copolymerization reactivity and industrial handling. 3,4-Diacyl-1-butene, which is 9- CO- and R 9 is an alkyl group, is preferred, and 3,4-diacetoxy-1-butene in which R 9 is a methyl group is particularly preferred. The reactivity ratio of each monomer when vinyl acetate and 3,4-diacetoxy-1-butene were copolymerized was r (vinyl acetate) = 0.710, r (3,4-diacetoxy-1-butene) = 0.701, which is compared to r (vinyl acetate) = 0.85 and r (vinyl ethylene carbonate) = 5.4 in the case of vinyl ethylene carbonate, 3,4-diacetoxy-1- This shows that butene is excellent in copolymerization reactivity with vinyl acetate.

  As for 3,4-diacetoxy-1-butene, products from Eastman Chemical Company for industrial production and Acros Company at the reagent level can be obtained from the market. Further, 3,4-diacetoxy-1-butene obtained as a by-product during the production process of 1,4-butanediol can also be used.

  Vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, versatic acid. Vinyl etc. are mentioned. Of these, vinyl acetate is preferably used from the economical viewpoint.

Moreover, the PVA-type resin (A) used for this invention can use what copolymerized various unsaturated monomers in the range which does not inhibit the objective of this invention, for example, the range of 0.5-10 mol%. The introduction amount of the unsaturated monomer cannot be generally specified, but if the introduction amount is too large, the thermal stability may be impaired or the gas barrier property may be deteriorated.
Examples of the unsaturated monomer include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid and the like. Unsaturated acids, their salts, monoesters or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as diacetone acrylamide, acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, etc. Olefin sulfonic acids or salts thereof, alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl compounds such as vinyl chloride, substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate. Le ethers, vinylidene chloride, 1,4-diacetoxy-2-butene ,, vinyl ethylene carbonate, glycerin monoallyl ether, vinylene carbonate, acetoacetyl group-containing monomers.

Furthermore, polyoxyethylene (meth) allyl ether, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polyoxyethylene (1- ( Poly) alkylene groups such as (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, polyoxypropylene vinylamine Containing monomer, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylic Amidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3- Examples also include cation group-containing monomers such as butenetrimethylammonium chloride, dimethyldiallylammonium chloride, and diethyldiallylammonium chloride.
In addition, by setting the polymerization temperature to 100 ° C. or higher, it is possible to use a PVA main chain having about 1.6 to 3.5 mol% of 1,2-diol bonds.

There are no particular limitations on the copolymerization of the above-mentioned vinyl ester monomer and the compound represented by the general formula (1) (and other monomers). Bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion polymerization Although known methods such as the above can be employed, solution polymerization is usually performed.
The charging method of the monomer component at the time of copolymerization is not particularly limited, and any method such as batch charging, split charging, continuous charging, etc. is adopted, but the structural unit derived from the compound represented by the general formula (1) is polyvinyl. Drop polymerization is preferred from the viewpoint of being uniformly distributed in the molecular chain of the ester-based polymer and reducing the residual unreacted monomer in the polymer as much as possible, and a polymerization method based on the HANNA method is particularly preferred.

Examples of the solvent used in such copolymerization usually include lower alcohols such as methanol, ethanol, isopropyl alcohol, n-propanol and butanol, and ketones such as acetone and methyl ethyl ketone, and methanol is preferably used industrially. Is done.
The amount of the solvent used may be appropriately selected in consideration of the chain transfer constant of the solvent in accordance with the degree of polymerization of the target copolymer. For example, when the solvent is methanol, S (solvent) / M (monomer) = 0.01 to 10 (weight ratio), preferably selected from the range of about 0.05 to 3 (weight ratio).

In the copolymerization, a polymerization catalyst is used. Examples of the polymerization catalyst include known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauryl peroxide, azobisdimethylvaleronitrile, azobis. Examples include low-temperature active radical polymerization catalysts such as methoxydimethylvaleronitrile, and the amount of polymerization catalyst used varies depending on the type of catalyst and cannot be determined unconditionally, but is arbitrarily selected according to the polymerization rate. For example, when azoisobutyronitrile or acetyl peroxide is used, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0.15 mol% is particularly preferable.
The reaction temperature of the copolymerization reaction is about 30 ° C. to the boiling point depending on the solvent and pressure used, more specifically 35 to 150 ° C., preferably 40 to 75 ° C.

  In the present invention, the copolymerization ratio of the compound represented by the formula (1) is not particularly limited, and the copolymerization ratio may be determined in accordance with the amount of 1,2-diol bond introduced later.

  The obtained copolymer is then saponified. In such saponification, the copolymer obtained above is dissolved in an alcohol or a hydrous alcohol, and the reaction is carried out using an alkali catalyst or an acid catalyst. Examples of the alcohol include methanol, ethanol, propanol, tert-butanol and the like, and methanol is particularly preferably used. The concentration of the copolymer in the alcohol is appropriately selected depending on the viscosity of the system, but is usually selected from the range of 10 to 60% by weight. Catalysts used for saponification include alkali catalysts such as hydroxides and alcoholates of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, alcoholates, sulfuric acid, hydrochloric acid Acid catalysts such as nitric acid, metasulfonic acid, zeolite, and cation exchange resin.

The amount of the saponification catalyst used is appropriately selected depending on the saponification method, the target degree of saponification, and the like. When an alkali catalyst is used, it is usually represented by the vinyl ester monomer and the general formula (1). 0.1 to 30 mmol, preferably 2 to 17 mmol is suitable for 1 mol of the total amount of the compound. If the amount of the saponification catalyst used is too small, it may take a long time for the saponification reaction. Conversely, if it is too much, a large amount will remain in the product, and neutralization may be necessary. Absent.
Moreover, although the reaction temperature of saponification reaction is not specifically limited, 10-60 degreeC is preferable, More preferably, it is 20-50 degreeC.
The PVA resin (A) of the present invention is produced by simultaneously converting the ester moiety of the vinyl ester monomer and the acyloxy moiety of the compound represented by the formula (1) into a hydroxyl group during saponification.

  Thus, a PVA resin (A) having a 1,2-diol structure in the side chain is obtained, but the 1,2-diol structure content in the PVA resin is not particularly limited. It is preferable that it is 4-20 mol% with respect to all the vinyl structural units of resin (A), Furthermore, 4-15 mol%, Especially 5-12 mol% is preferable. If the content of the 1,2-diol structure is too small, the interlayer adhesion of the laminate may be lowered or the stretchability may be lowered. On the other hand, if the content is too large, the polymerization degree of the PVA resin is lowered. Since there exists a possibility that the intensity | strength etc. of the molding obtained using PVA-type resin may fall, it is not preferable. In addition, the all vinyl structural unit in PVA-type resin (A) is a structural unit derived from the vinyl ester, the compound represented by General formula (1), and another copolymerization monomer.

In addition, the saponification degree of the PVA resin is preferably 95 mol% or more, more preferably 97 mol% or more, and particularly preferably 99.5 mol% or more. If the saponification degree is too low, the gas barrier property is lowered. Or an acetic acid odor may remain in the resulting laminated structure.
In addition, the saponification degree in this invention is the change rate (mol%) to the hydroxyl group of the total amount of the ester part of a vinyl ester monomer, and the acyloxy part in the structural unit derived from the compound shown by General formula (1). Is displayed.

  In the present invention, the average degree of polymerization (measured in accordance with JIS K6726) of the PVA resin (A) is 200 to 3000, more preferably 200 to 1800, particularly 300 to 1700, and particularly 300 to 1500. If the degree of polymerization is too small, the strength of the resulting laminated structure tends to decrease. Conversely, if the degree of polymerization is too large, the melt viscosity at the time of molding becomes too high, and shear heat generation becomes large during molding. There is a risk of decomposition, which is not preferable.

  As a means for introducing the 1,2-diol structure into the PVA-based resin, the polymerization is carried out at a high temperature as described above, and the ratio of head-to-head bonds is increased as described above. There is a method of introducing into the main chain, but the latter method has a limit in the amount of introduction, and introduction of 3 mol% or more is practically impossible. However, the PVA resin (A) of the present invention is 1, The content of the 2-diol structure can be arbitrarily controlled within the above range.

  In addition, the PVA resin (A) used in the present invention may be a mixture with other different PVA resins, and as such other PVA resins, 1, represented by the general formula (1) Examples include those having different 2-diol structure contents, those having different saponification degrees, those having different polymerization degrees, and those having different other copolymerization components.

  Moreover, it is preferable that melting | fusing point of this PVA-type resin (A) is 200 degrees C or less, Furthermore, it is preferable that it is 195 degrees C or less, When melting | fusing point exceeds 200 degreeC, a melt molding temperature must be made high according to it, Therefore The PVA-based resin (A) is not preferable because it tends to be thermally deteriorated and may cause long-run moldability, fish eyes and the like, and may cause foaming of the film due to decomposition of the PVA-based resin. The melting point is measured by differential scanning calorimetry (hereinafter abbreviated as DSC) of JIS K7121. Further, when the amount of the side chain containing the 1,2-diol structure in the PVA resin (A) is increased, the polymer becomes an amorphous polymer, a clear melting peak cannot be obtained by the DSC method, and it is difficult to specify the melting point. However, the PVA resin (A) which is such an amorphous polymer can also be preferably used in the present invention. The melting point can be adjusted by the content of the 1,2-diol structure in the side chain and the degree of saponification.

  Further, in the present invention, the PVA resin (A) is saturated aliphatic amide (for example, stearic acid amide), unsaturated fatty acid amide (for example, oleic acid amide), bis-fatty acid as long as the object of the present invention is not impaired. Lubricants such as amides (for example, ethylene bis-stearic acid amide), oxygen absorbers [(for example, reduced iron powders as inorganic oxygen absorbents, water-absorbing substances and electrolytes added thereto, aluminum powder, sulfurous acid Potassium, photocatalytic titanium oxide and the like are ascorbic acid as an organic compound-based oxygen absorber, fatty acid esters and metal salts thereof, hydroquinone, gallic acid, polyhydric phenols such as hydroxyl group-containing phenol aldehyde resin, bis-salicylic aldehyde-imine Cobalt, tetraethylenepentamine cobalt, cobalt-Schiff salt Complexes, porphyrins, macrocyclic polyamine complexes, polyethyleneimine-cobalt complexes and other nitrogen-containing compounds and transition metal coordination complexes, terpene compounds, reaction products of amino acids and hydroxyl group-containing reducing substances, triphenylmethyl compounds And the like, as a polymer-based oxygen absorber, a coordinated combination of a nitrogen-containing resin and a transition metal (for example, a combination of MXD nylon and cobalt), a blend of a tertiary hydrogen-containing resin and a transition metal (for example, polypropylene and cobalt). Combination), a blend of a carbon-carbon unsaturated bond-containing resin and a transition metal (for example, a combination of polybutadiene and cobalt), a photo-oxidative decay resin (for example, polyketone), an anthraquinone polymer (for example, polyvinyl anthraquinone), and the like These compounds can contain photoinitiators (such as benzophenone) and peroxide supplements. Additives (such as commercially available antioxidants) and deodorants (such as activated carbon)], heat stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, colorants, antistatic agents, interfaces You may mix | blend an active agent, an antibacterial agent, etc.

  In particular, it is preferable to contain an alkali metal salt and / or an alkaline earth metal salt from the viewpoint of further improving melt moldability. Examples of the alkali metal salt include acetic acid such as potassium and sodium, propionic acid, butyric acid, and lauric acid. , Organic acid such as stearic acid, oleic acid and behenic acid, and metal salts of inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid and phosphoric acid, and alkaline earth metal salts include acetic acid such as calcium and magnesium. And organic acid such as propionic acid, butyric acid, lauric acid, stearic acid, oleic acid and behenic acid, and metal salts of inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid and phosphoric acid.

  The content of these metal salts is preferably 5 to 3000 ppm (more preferably 20 to 2500 ppm, particularly 50 to 2000 ppm) in terms of metal relative to the PVA resin (A), and when the content is less than 5 ppm, The effect of improving melt moldability, for example, the effect of suppressing gel and eyes, is poor, and conversely, if it exceeds 3000 ppm, decomposition is likely to occur at the time of melt molding, foaming and odor are likely to occur, and the degree of coloring becomes unfavorable. In addition, when 2 or more types of alkali metal and / or alkaline-earth metal salt are contained, it is preferable that the sum total is in the range of the above contents.

  The method for containing the alkali metal salt or alkaline earth metal salt in the PVA resin (A) is not particularly limited, but once the PVA resin (A) is obtained, alkali metal ions or alkaline earth metal ions are contained. A method of adding a compound before extrusion molding, using an alkaline substance containing an alkali metal ion as a saponification catalyst at the time of production (saponification) of a PVA resin (A), and adding a saponified PVA resin (A) A method for controlling the amount of alkali metal ions contained in the resin by washing is exemplified. The content of alkali metal or alkaline earth metal in the PVA resin (A) can be determined by atomic absorption analysis.

  The PVA-based resin (A) of the present invention can obtain good coextrusion moldability without blending a plasticizer, but it is also possible to blend a plasticizer if necessary, and as such a plasticizer Is an aliphatic polyhydric alcohol (for example, ethylene glycol, hexanediol, glycerin, trimethylolpropane, diglycerin, etc.), a compound obtained by adding ethylene oxide to a polyhydric alcohol such as glycerin, various alkylene oxides (ethylene oxide, propylene oxide, Mixed adducts of ethylene oxide and propylene oxide, etc.), sugars (eg, sorbitol, mannitol, pentaerythritol, xylol, arabinose, ribulose, etc.), phenol derivatives such as bisphenol A and bisphenol S, and amide compounds such as N-methylpyrrolidone , Glucosides such as α- methyl -D- glucoside, water and the like. The blending amount is preferably 100 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less with respect to 100 parts by weight of the PVA resin (A).

  Also, thermoplastic resins (eg polyethylene, polypropylene, polyester in the presence of compatibilizers), fragrances, foaming agents, deodorants, extenders, fillers (talc, clay, montmorillonite, calcium carbonate, glass beads, glass fibers , Silica, mica, alumina, hydrotalcite, titanium oxide, zirconium oxide, boron nitride, aluminum nitride and other inorganic fillers, melamine-formalin-based organic fillers, etc.), release agents, UV absorbers, antioxidants In addition, additives such as processing stabilizers, weather resistance stabilizers, fungicides, and preservatives can be appropriately blended.

  The PVA resin (A) containing a 1,2-diol structure in the side chain obtained as described above or a composition thereof can be used for coextrusion molding as it is. In consideration of stability, it is preferable to knead once in a molten state and then cool and solidify to form a pellet.

  As such means, for example, known kneaders such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer, a blast mill can be used, but usually a single-screw or twin-screw extruder is used. It is industrially preferable, and it is also preferable to provide a vent suction device, a gear pump device, a screen device, a strand support belt, a dry fog generator, and the like as necessary. In particular, in order to remove moisture and by-products (pyrolysis low molecular weight products, etc.), one or more vent holes are provided in the extruder, and suction is performed under reduced pressure, and mixing of oxygen into the extruder is prevented. In order to achieve this, by supplying an inert gas such as nitrogen continuously into the hopper, the PVA resin (A) with excellent quality, which is reduced in thermal coloring and thermal deterioration, or a pellet of the composition is provided. Obtainable.

  The laminated structure of the present invention has a layer containing a PVA resin (A) containing a 1,2-diol structure in the side chain and a layer containing a thermoplastic resin (B). In manufacturing the structure, a layer containing the thermoplastic resin (B) may be laminated on one or both sides of the layer containing the PVA resin (A). A method of melt extrusion laminating a thermoplastic resin (B) on a film or sheet containing a resin (A), and conversely, a PVA resin (A) or a PVA system on a substrate containing a thermoplastic resin (B) or the like Method of melt extrusion laminating resin composition containing resin (A), co-extrusion of PVA resin (A) or resin composition containing PVA resin (A) and thermoplastic resin (B) Method, and further, the PVA resin ( ) Containing a film or sheet and a thermoplastic resin (B), a sheet and a method of dry laminating using a known adhesive resin such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, etc. Can be mentioned. In particular, a co-extrusion method is preferably used because it is not necessary to provide a separate lamination step and a laminated structure can be obtained in one step. The molding temperature when the layer containing the PVA resin (A) is produced by melt molding must be determined by appropriately determining the melting point based on the content of the 1,2-diol structure of the side chain. However, a range of 120 to 200 ° C. (further, a range of 185 to 200 ° C. is preferably used.

  Examples of the thermoplastic resin (B) include polyolefin resins, polyester resins, polyamide resins, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride, acrylic resins, vinyl ester resins, polyester elastomers, polyurethanes. Elastomers, chlorinated polyethylene, chlorinated polypropylene, aromatic and aliphatic polyketones, aliphatic polyalcohols and the like can be mentioned, and polyolefin resins, polyester resins, and polyamide resins are preferably used. When applying, it is preferable to use a polyester-based resin, and when applying to a packaging film or the like, it is preferable to use a polyolefin-based resin.

  Specific examples of such polyolefin resins include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and ethylene. -Vinyl acetate copolymer (EVA), ionomer, ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene -Methacrylic acid ester copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene, polypentene, polymethylpentene or other olefin homo- or copolymer, or these Olefin homo- or copolymerization Examples thereof include polyolefin resins in a broad sense such as those obtained by graft modification with unsaturated carboxylic acids or esters thereof, and blends thereof, among which linear low density polyethylene (LLDPE), low density polyethylene (LDPE). ), Very low density polyethylene (VLDPE), ethylene-vinyl acetate copolymer (EVA), and ionomer are preferable in that they are excellent in bending fatigue resistance, vibration fatigue resistance, and the like of the resulting laminated packaging material.

In particular, linear low-density polyethylene made of an ethylene-α-olefin copolymer having a density of 0.86 to 0.95 g / cm 3 is preferably used, and when the density is smaller than the above range, the mechanical properties of the laminated packaging material Various physical properties are insufficient or blocking occurs. On the other hand, if it is large, the bending fatigue resistance, vibration fatigue resistance, etc. may be insufficient, such being undesirable. Here, the density is a value measured by JIS K6760 at 20 ° C., and ethylene-α-olefin is ethylene and butene-1, pentene-1,4-methylpentene-1, hexene-1. , Octene-1, etc., and a copolymer having 18 or less carbon atoms. Among these, an ethylene-α-olefin copolymer using an olefin having 4 to 8 carbon atoms is preferably used.

  In the above-mentioned linear low density polyethylene, an ethylene-α-olefin copolymer produced in the presence of a single site catalyst is further preferred in that the effects of the present invention can be further expressed. A single-site catalyst is a catalyst that has the characteristics that the active sites are uniform (single site), whereas the current Ziegler catalyst and Philips catalyst are called multi-site catalysts with non-uniform active sites. Typical examples include metallocene catalysts. Specific product names include “Kernel” (Nippon Polychem), “Evolue” (Mitsui Chemicals), “Exact” (Exxon Chemical), “Affinity” (Dow Chemical) It is done.

  Specific examples of such polyamide resins include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylauryl. Lactam (nylon 12), polyethylenediamine adipamide (nylon 26), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), poly Hexamethylene dodecamide (nylon 612), polyoctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 108), caprolactam / lauryl lactam copolymer (nylon 6/12), caprolactam / ω-aminononane Acid copolymer (Nai 6/9), caprolactam / hexamethylene diammonium adipate copolymer (nylon 6/66), lauryl lactam / hexamethylene diammonium adipate copolymer (nylon 12/66), ethylenediamine adipamide / hexamethylene diammonium Adipate copolymer (nylon 26/66), caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 66/610), ethyleneammonium adipate / hexamethylenediammonium adipate / hexamethylenediammonium seba Kate copolymer (nylon 6/66/610), polyhexamethylene isophthalamide, polyhexamethylene terephthalamide, hexamethylene isophthalamide / te Examples include phthalamide copolymers or those obtained by modifying these polyamide resins with aromatic amines such as methylenebenzylamine and metaxylenediamine, and metaxylylenediamine adipate. In the present invention, one or two of these are used. The above blend can be used.

  In addition, a polyamide resin having a carboxyl group and / or amino group at the molecular end adjusted (modified) with an alkyl monocarboxylic acid, an alkyl dicarboxylic acid, an alkyl monoamine, an alkyl diamine, or the like can also be used.

  Specific examples of such polyester resins include condensation polymers containing aromatic dicarboxylic acids or their alkyl esters and glycols as main components, and those having ethylene terephthalate as the main repeating unit are preferred. Furthermore, it is possible to contain a copolymer component within a range that does not significantly impair processability, strength, etc., and as such a copolymer component, as an acid component, isophthalic acid, diphenyl-4,4′-dicarboxylic acid , Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and ester-forming derivatives thereof, fats such as adipic acid, sebacic acid, azelaic acid, succinic acid, etc. Dicarboxylic acids and ester-forming derivatives thereof, cycloaliphatic dicarboxylic acids, alicyclic dicarboxylic acids such as hexahydroterephthalic acid and ester-forming derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid, and the like Other than ester-forming derivatives, trimellitic acid, pyromellitic acid, etc. Rukoto can.

  The glycol component includes aliphatic glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol, alicyclic glycols such as 1,4-cyclohexanedimethanol, bisphenol A and alkylene oxide adducts of bisphenol A. In addition to aromatic glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, glycerin, 1,3-propanediol, pentaerythritol, and the like can be given.

  The content of the ethylene terephthalate unit is 75 to 100 mol%, preferably about 85 to 100 mol%. The preferable intrinsic viscosity (measured in a mixed solvent of 50% by weight / 50% by weight of phenol and tetrachloroethane at a temperature of 30 ° C.) is 0.5 to 1.3 dl / g, more preferably 0.65 to 1. .2 dl / g.

  Next, typical examples include those having ethylene telenaphthalate as the main repeating unit. It is possible to contain the same copolymerization component as described above, and the content of ethylene telenaphthalate is about 75 to 100 mol%, preferably about 85 to 98 mol%. Moreover, preferable intrinsic viscosity is 0.4-1.2 dl / g, Furthermore, 0.55-1.0 dl / g.

In addition, it is also preferable to blend the ethylene terephthalate-based polyester resin and the ethylene terephthalate-based resin in terms of improving gas barrier properties, ultraviolet ray blocking properties, and melt moldability. In that case, the blend ratio is ethylene terephthalate-based. The polyester resin is 5 to 90% by weight, more preferably 15 to 85% by weight, and the ethylene terephthalate-based polyester resin is 95 to 10% by weight, and further 85 to 15% by weight.
Furthermore, other thermoplastic resins and additives can be blended within a range that does not significantly impair various properties. Examples of the thermoplastic resin include MXD-6 nylon, polycarbonate, polyarylate, and liquid crystal polymer. .

  As a layer structure of the laminated structure of the present invention, a layer containing a PVA resin (A) is a (a1, a2,...), And a layer containing a thermoplastic resin (B) is b (b1, b2). ,...), Not only a / b two-layer structure but also b / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / Arbitrary combinations such as b1 / b2, b1 / b2 / a / b3 / b4, a1 / b1 / a2 / b2 are possible, and a layer structure of b / a / b or b2 / b1 / a / b1 / b2 is particularly preferable. .

  In the above layer structure, an adhesive resin layer can be provided between the respective layers as required, and various types of such adhesive resins can be used, depending on the type of the resin b. Although it cannot be generally stated, a modification containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or its anhydride to an olefin polymer (the above-mentioned polyolefin resin in the broad sense) by an addition reaction or a graft reaction. Examples of the olefin polymer include maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block or random) copolymer, maleic anhydride graft. Modified ethylene-ethyl acrylate copolymer, maleic anhydride graft modified Len - one or a mixture of two or more species selected from vinyl acetate copolymers and the like as preferred. The amount of the unsaturated carboxylic acid or anhydride thereof contained in the olefin polymer at this time is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, particularly preferably 0.00. 03 to 0.5% by weight. If the amount of modification in the modified product is small, the adhesiveness may be insufficient. On the other hand, if the amount is too large, a crosslinking reaction may occur and the moldability may be deteriorated. These adhesive resins can be blended with a rubber / elastomer component such as polyisobutylene or ethylene-propylene rubber, and further a resin of layer b. In particular, blending a polyolefin resin different from the base polyolefin resin of the adhesive resin is useful because the adhesiveness may be improved.

The thickness of each layer of the laminated structure cannot be generally stated depending on the layer structure, the type of the thermoplastic resin (B), the application and container form, the required physical properties, etc., but usually contains the PVA resin (A). The layer is 5 to 500 μm, more preferably 10 to 200 μm, the layer containing the thermoplastic resin (B) is 5 to 5000 μm, more preferably 30 to 1000 μm, and the adhesive resin layer is about 5 to 400 μm, more preferably about 10 to 150 μm. Selected from. If the a layer is less than 5 μm, the gas barrier property is insufficient, and the thickness control becomes unstable. On the other hand, if it exceeds 500 μm, the bending fatigue resistance is inferior, and it is not economical and increases in weight. If the layer is less than 5 μm, the rigidity is insufficient. Conversely, if the layer exceeds 5000 μm, the bending fatigue resistance is inferior and the weight increases, which is not preferable. If the adhesive resin layer is less than 5 μm, the interlayer adhesion is insufficient, and the thickness is controlled. However, if the thickness exceeds 400 μm, the weight increases, and it is not economical and not preferable.
In addition, in each layer of the laminated structure of the present invention, the above-mentioned various additives, modifiers, fillers, other resins, and the like are not hindered by the effects of the present invention in order to improve molding processability and various physical properties. Can also be added.

  Such a laminated structure is used in various shapes as it is, but it is also preferable to perform a heat stretching treatment in order to further improve the physical properties or to form a desired arbitrary container shape. Here, the heat stretching treatment refers to an operation in which a film is heated to a temperature below the melting point and mechanically stretched to orient the molecules in parallel to the pulling direction. Such stretching is either uniaxial stretching or biaxial stretching. It is possible to obtain a stretched molded article having better physical properties by stretching as high a magnification as possible, and excellent in strength, toughness, gas barrier properties and the like.

As the stretching method, a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, a vacuum forming method, a pressure forming method, a vacuum pressure forming method, and the like having a high drawing ratio can be employed. In the case of biaxial stretching, both a simultaneous biaxial stretching method and a sequential biaxial stretching method can be employed. The stretching temperature is selected from the range of about 60 to 170 ° C, preferably about 80 to 160 ° C.
It is also preferable to perform heat setting after the completion of stretching. The heat setting can be performed by a known means, and the heat treatment is performed at 50 to 170 ° C., preferably 70 to 160 ° C. for about 2 to 600 seconds while keeping the stretched film in a tension state.

  Moreover, it is also possible to give shrink property to the laminated structure of this invention by this heat-stretching process, and it is useful for the shrink packaging or skin pack packaging use in food packaging, such as raw meat, processed meat, and cheese.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to the description of the examples unless it exceeds the gist.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.

Example 1
[Production of PVA resin (A1)]
A reaction vessel (1 m 3 ) equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 250 kg of vinyl acetate, 250 kg of methanol, 23.76 kg of 3,4-diacetoxy-1-butene, and 0% of azobisisobutyronitrile. 0.09 mol% (vs. charged vinyl acetate) was added, and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. Thereafter, a 20% methanol solution of 3,4-diacetoxy-1-butene was added in 33.10 over 10 hours according to the HANNA method. When kg of vinyl acetate was dropped and the polymerization rate of vinyl acetate reached 95%, 10 ppm of m-dinitrobenzene (as opposed to vinyl acetate charged) was added as a polymerization inhibitor to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. Saponification was carried out by adding 8 mmol per 1 mol of the total amount of diacetoxy-1-butene. As saponification progressed, saponified material precipitated and became particulate, and then filtered, washed well with methanol and dried in a hot air dryer to obtain PVA resin (A1).
The saponification degree of the obtained PVA-based resin (A1) was 99.0 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butene. The average degree of polymerization was 500 when analyzed according to JIS K6726. The amount of the side chain introduced containing the 1,2-diol structure was 6 mol% when calculated by 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6), melting point Was 185 ° C.

[Pelletization]
The obtained PVA-based resin (A1) was supplied to a biaxial co-directional extruder and pelletized under the following conditions.
Screw inner diameter 30mm
L / D 30
Screw rotation speed 100rpm
Extrusion temperature C1: 185 ° C
C2: 195 ° C
C3: 195 ° C
C4: 190 ° C
H (head): 190 ° C
D (die): 190 ° C

[Manufacture of laminated structure]
The obtained PVA-based resin (A1) pellets, and linear low density polyethylene (MFR 1.5 g / 10 min (190 ° C., 2160 g), density 0.920 g / cm 3 ) and adhesive properties as the thermoplastic resin (B) Maleic anhydride modified linear low density polyethylene (MFR) as resin
2.0 g / 10 min (190 ° C., 2160 g)), and these are supplied to a multi-layer extrusion apparatus equipped with a multi-layer T-die of 5 layers, and a thermoplastic resin (B) layer / adhesive resin layer / PVA system Resin (A1
) Layer / adhesive resin layer / thermoplastic resin (B) layer (thickness 80/20/40/20/80 μm)
A laminated structure having the following layer structure was obtained. The molding conditions are as follows.
Screw inner diameter 40 mm [thermoplastic resin (B), PVA resin (A1)]
30mm [adhesive resin]
L / D 25
Screw compression ratio 3.2
Screw rotation speed 40rpm [Thermoplastic resin (B)]
20 rpm [PVA resin (A1), adhesive resin]
Die T-die with 5 layers combining adapter Die width 450mm
Extrusion temperature C1: 180 ° C. [PVA resin (A1)]
C2: 198 ° C [〃]
C3: 198 ° C [〃]
C4: 198 ° C [〃]
C1: 190 ° C. [thermoplastic resin (B), adhesive resin]
C2: 200 ° C. [〃]
C3: 210 ° C. [〃]
C4: 210 ° C. [〃]
A (adapter): 200 ° C
D (die): 200 ° C

[Long run formability]
Long run molding was performed under the above conditions, and the appearance of the obtained laminated structure and the situation in the vicinity of the die lip were visually observed and evaluated according to the following criteria. The results are shown in Table 1.
(appearance)
◎ ・ ・ ・ No gel formation is observed even after molding for 2 days or more ○ ・ ・ ・ Generation of gel was observed after molding for 1 day or more and less than 2 days △ ・ ・ ・ 3 hours or more, 1 day Generation of gel was observed when molding was less than x ... Generation of gel was observed after molding for less than 3 hours (in the eyes)
◎ ・ ・ ・ No eyes or eyes are observed even after molding for 3 days or more ○ ・ ・ ・ Eyes or eyes are recognized for molding for 2 days or more and less than 3 days △ ・ ・ ・ For 3 hours or more and less than 2 days Eyes and eyes were observed × ... Eyes and eyes were observed after molding for less than 3 hours

[Interlayer adhesion]
A strip-shaped test piece (width 15 mm, length 150 mm) was cut out parallel to the flow direction (MD) of the obtained laminated structure, and “Autograph IS” manufactured by Shimadzu Corporation under an atmosphere of 23 ° C. and 50% RH. −5000 ”, the delamination strength (g / 15 mm) between the PVA-based resin (A1) layer and the adhesive resin layer was measured by the T peel method (peeling speed 200 mm / min). The results are shown in Table 1.

[Extensible]
The obtained laminated structure was preheated at 100 ° C. for 5 minutes, and at the same temperature, simultaneous biaxial stretching was performed at a stretching speed of 100 mm / second, in the longitudinal direction 6 times, and in the transverse direction 6 times. Heat-fixing for a minute was performed, and the multilayer stretched film was obtained. The appearance of the obtained multilayer stretched film was visually observed and evaluated according to the following criteria. The results are shown in Table 1.
(appearance)
◎ ・ ・ ・ Smooth and transparent × ・ ・ ・ Whitening or fibrillation is observed (uneven drawing)
◎ ・ ・ ・ No streaks recognized ○ ・ ・ ・ One or two streaks recognized ×× Three or more streaks recognized

[Gas barrier properties]
The oxygen permeability of the obtained multilayer stretched film was measured using “OXTRAN 2/20” manufactured by MOCON under the conditions of 20 ° C. and 65% RH. The results are shown in Table 1.

[Flexibility]
50 pieces of 21 cm × 30 cm test pieces were cut out from the obtained multilayer stretched film, conditioned for 5 days at 20 ° C. and 65% RH, and then subjected to oxygen test after bending test using “Gelbo Flex Tester” manufactured by Rigaku Corporation. The number of times until the transmittance rapidly increased was measured and evaluated according to the following criteria. The results are shown in Table 1.
◎ ... 2000 times or more ○ ... 1000 times or more, less than 2000 times × ... less than 1000 times

Example 2
A reaction vessel (1 m 3 ) equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 400 kg of vinyl acetate, 20 kg of methanol, and 38.02 kg of 3,4-diacetoxy-1-butene, and 0% of azobisisobutyronitrile was added. 0.04 mol% (vs. vinyl acetate charged) was added, and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. Thereafter, 52.83 kg of a 20% methanol solution of 3,4-diacetoxy-1-butene was dropped over 11 hours according to the HANNA method, and when the polymerization rate of vinyl acetate reached 95%, m- Dinitrobenzene 10 ppm (vs. vinyl acetate) was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. Saponification was carried out by adding 9 mmol per 1 mol of the total amount of diacetoxy-1-butene. As saponification progressed, saponified material precipitated and became particulate, and then filtered, washed well with methanol and dried in a hot air dryer to obtain a PVA resin (A2).
The saponification degree of the obtained PVA-based resin (A2) was 99.5 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butene. The average degree of polymerization was 1100 when analyzed according to JIS K6726. The amount of the side chain introduced containing the 1,2-diol structure was 6 mol% when calculated by 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6), melting point Was 190 ° C.
Using this PVA resin (A2), a laminated structure was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 3
A reaction vessel (1 m 3 ) equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 260 kg of vinyl acetate, 52 kg of methanol, and 15.08 kg of 3,4-diacetoxy-1-butene, and 0% of azobisisobutyronitrile was added. 0.06 mol% (vs. vinyl acetate charged) was added, and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. Thereafter, 28.7 kg of a 20% methanol solution of 3,4-diacetoxy-1-butene was added dropwise over 11 hours according to the HANNA method. When the polymerization rate of vinyl acetate reached 95%, m- Dinitrobenzene 10 ppm (vs. vinyl acetate) was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. Saponification was carried out by adding 8 mmol per 1 mol of the total amount of diacetoxy-1-butene. As the saponification progressed, the saponified product precipitated and became particulate, and then filtered, washed well with methanol, and dried in a hot air dryer to obtain a PVA resin (A3).
The saponification degree of the obtained PVA-based resin (A3) was 97.2 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butene. The average degree of polymerization was 1000 when analyzed according to JIS K6726. The amount of side chain introduced containing a 1,2-diol structure was 4.0 mol% as calculated by measurement with 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6). The melting point was 182 ° C.
Using this PVA resin (A3), a laminated structure was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 4
A reaction vessel (1 m 3 ) equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 260 kg of vinyl acetate, 78.0 kg of methanol, and 20.81 kg of 3,4-diacetoxy-1-butene, and azobisisobutyronitrile. Was added in an amount of 0.06 mol% (compared with vinyl acetate), and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. Thereafter, 31.75 kg of a 20% methanol solution of 3,4-diacetoxy-1-butene was added dropwise over 11 hours according to the HANNA method, and when the polymerization rate of vinyl acetate reached 95%, m- Dinitrobenzene 10 ppm (vs. vinyl acetate) was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. Saponification was carried out by adding 9 mmol per 1 mol of the total amount of diacetoxy-1-butene. As saponification progressed, saponified substances precipitated and became particulate, and then filtered, washed well with methanol, and dried in a hot air dryer to obtain a PVA resin (A4).
The saponification degree of the obtained PVA-based resin (A4) was 99.6 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butene. The average degree of polymerization was 800 when analyzed according to JIS K6726. In addition, the amount of side chain introduced containing a 1,2-diol structure was 5 mol% when calculated by 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6), melting point Was 192 ° C.
Using this PVA resin (A4), a laminated structure was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 5
In the production of the PVA-based resin (A3) of Example 3, the amount of sodium hydroxide added in a 2% methanol solution during saponification was determined by adding vinyl acetate and 3,4-diacetoxy-1-butene in the copolymer. A PVA resin (A5) was obtained in the same manner as in Example 3 except that the amount was 5 mmol per 1 mol.
The saponification degree of the obtained PVA-based resin (A5) was 90 mol% when analyzed with the alkali consumption required for hydrolysis of the residual vinyl acetate and the residual 3,4-diacetoxy-1-butene, and the average The degree of polymerization was 1000 when analyzed according to JIS K6726. In addition, the amount of side chain introduced containing a 1,2-diol structure was 4 mol% when calculated by 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6), melting point Was 163 ° C.
Using this PVA resin (A5), a laminated structure was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 6
A reaction vessel (1 m 3 ) equipped with a reflux condenser, a dropping funnel and a stirrer was charged with 260 kg of vinyl acetate, 10.4 kg of methanol, and 59.59 kg of 3,4-diacetoxy-1-butene, and azobisisobutyronitrile. Was added in an amount of 0.10 mol% (compared with vinyl acetate), and the temperature was raised under a nitrogen stream while stirring to initiate polymerization. Thereafter, 87.58 kg of a 20% methanol solution of 3,4-diacetoxy-1-butene was added dropwise over 12 hours according to the HANNA method, and when the polymerization rate of vinyl acetate reached 95%, m- Dinitrobenzene 10 ppm (vs. vinyl acetate) was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. Saponification was carried out by adding 8 mmol per 1 mol of the total amount of diacetoxy-1-butene. As saponification progressed, saponified substances precipitated and became particulate, and then filtered, washed well with methanol, and dried in a hot air dryer to obtain a PVA resin (A4).
The saponification degree of the obtained PVA-based resin (A4) was 99.8 mol% when analyzed by the alkali consumption required for hydrolysis of residual vinyl acetate and residual 3,4-diacetoxy-1-butene. The average degree of polymerization was 500 when analyzed according to JIS K6726. In addition, the amount of side chain introduced containing a 1,2-diol structure was 12 mol% when calculated by 1 H-NMR (internal standard: tetramethylsilane, solvent: DMSO-d6) and DSC. There is no melting point peak due to the second run.
Using this PVA resin (A4), a laminated structure was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Example 7
To PVA resin (A2), 150 ppm dibasic potassium phosphate and 150 ppm potassium acetate were added, pelletized in the same manner as in Example 1, and a laminated structure was similarly obtained for evaluation. The results are shown in Table 1.

Comparative Example 1
In Example 1, an unmodified PVA having a saponification degree of 99.0 mol%, an average polymerization degree of 1100, and a melting point of 230 ° C. was used in place of the PVA resin (A1), and a laminated structure was obtained in the same manner as in Example 1. The same evaluation was performed. The results are shown in Table 1.
However, gas barrier properties were not measurable because cracks occurred during stretching.
In addition, the extrusion temperature conditions in manufacture of a pelletization and a laminated structure were performed by changing conditions as follows according to melting | fusing point of PVA-type resin.
[Pelletization]
Extrusion temperature C1: 220 ° C
C2: 225 ° C
C3: 230 ° C
C4: 230 ° C
H (head): 220 ° C
D (die): 220 ° C
[Manufacture of laminated structure]
Extrusion temperature C1: 220 ° C. [PVA resin (A5)]
C2: 198 ° C [〃]
C3: 198 ° C [〃]
C4: 198 ° C [〃]
A (adapter): 200 ° C
D (die): 200 ° C

The laminated structure of the present invention can be co-extruded, has excellent long-run moldability at the time of molding, has excellent gas barrier properties and stretchability, and has good interlayer adhesion, so that delamination, cracks, voids, stretching due to stretching Since unevenness does not occur and bending resistance is good, it is suitable as a packaging material for articles whose quality can be deteriorated by oxygen such as foods and drinks, pharmaceuticals and chemicals.


Claims (12)

  1. In a laminated structure having a layer containing a polyvinyl alcohol resin (A) and a layer containing a thermoplastic resin (B), the polyvinyl alcohol resin (A) is a vinyl ester monomer and the following general formula (1): A laminate structure, which is a polyvinyl alcohol resin (A) containing a 1,2-diol structure in the side chain, obtained by saponifying a copolymer with the compound shown.

    [Wherein, R 1 , R 2 and R 3 each independently represent hydrogen or an organic group, X represents a single bond or a bond chain, and R 4 , R 5 and R 6 each independently represent hydrogen. An atom or an organic group, R 7 and R 8 each independently represent a hydrogen atom or R 9 —CO— (wherein R 9 is an alkyl group)]
  2. The laminated structure according to claim 1, wherein the compound represented by the general formula (1) is 3,4-diasiloxy-1-butene.
  3. The laminated structure according to claim 1, wherein the polyvinyl alcohol resin (A) has a melting point of 200 ° C. or less or is amorphous.
  4. The content of the structural unit containing a 1,2-diol structure in the polyvinyl alcohol-based resin (A) is 4 to 15 mol% with respect to all vinyl structural units. A laminated structure according to any one of the above.
  5. The laminated structure according to any one of claims 1 to 4, wherein the degree of saponification of the polyvinyl alcohol-based resin (A) is 95 mol% or more.
  6. The layered structure according to any one of claims 1 to 5, wherein the layer containing the polyvinyl alcohol-based resin (A) further contains an alkali metal salt and / or an alkaline earth metal salt.
  7. The laminated structure according to claim 6, wherein the content of the alkali metal salt and / or alkaline earth metal salt is 5 to 3000 ppm with respect to the polyvinyl alcohol resin (A).
  8. The laminated structure according to any one of claims 1 to 7, wherein the thermoplastic resin (B) is at least one selected from the group consisting of a polyolefin resin, a polyamide resin, and a polyester resin.
  9. The laminated structure according to any one of claims 1 to 8, wherein the intermediate layer is a layer containing a polyvinyl alcohol-based resin (A), and both outer layers are layers containing a thermoplastic resin (B).
  10. The laminate according to any one of claims 1 to 9, wherein an adhesive resin layer is provided between the layer containing the polyvinyl alcohol resin (A) and the layer containing the thermoplastic resin (B). Structure.
  11. The laminated structure according to any one of claims 1 to 10, which is obtained by coextrusion molding.
  12. The laminated structure according to any one of claims 1 to 11, wherein the laminated structure is stretched in at least a uniaxial direction.







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