WO2017110676A1 - エチレン-ビニルエステル系共重合体ケン化物組成物及びその製造方法 - Google Patents
エチレン-ビニルエステル系共重合体ケン化物組成物及びその製造方法 Download PDFInfo
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- WO2017110676A1 WO2017110676A1 PCT/JP2016/087551 JP2016087551W WO2017110676A1 WO 2017110676 A1 WO2017110676 A1 WO 2017110676A1 JP 2016087551 W JP2016087551 W JP 2016087551W WO 2017110676 A1 WO2017110676 A1 WO 2017110676A1
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
Definitions
- the present invention relates to an ethylene-vinyl ester copolymer saponified product (EVOH resin) composition having an increased elongation viscosity while reducing the boron content, and in particular, an EVOH resin composition excellent in molding processability and its It relates to a manufacturing method.
- EVOH resin ethylene-vinyl ester copolymer saponified product
- EVOH resin has excellent gas barrier properties, including oxygen barrier properties, because hydroxyl groups contained in molecular chains form strong hydrogen bonds to form crystal parts, and these crystal parts prevent oxygen from entering from the outside. Can be shown. Taking advantage of these characteristics, EVOH-based resins are used after being molded into films and sheets of food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, agricultural chemical packaging materials, or packaging containers such as bottles. .
- EVOH-based resin When molding EVOH-based resin, it is usually melt-molded and molded and processed into a film shape, a sheet shape, a bottle shape, a cup shape, a tube shape, a pipe shape, etc., and provided for practical use. Therefore, the moldability and processability of the EVOH resin are important.
- EVOH resin can increase melt viscosity by blending boric acids.
- Patent Document 1 proposes that melt molding as a resin composition containing boric acids is effective from the viewpoint of melt moldability of an EVOH-based resin, in particular, prevention of surging during film formation.
- EVOH resin pellets are added to a boric acid aqueous solution to contain boric acid, and then dried to a moisture content of 0.001 to 2% by weight. It has been proposed to reduce boric acid concentration by adjusting and further washing with water. It is disclosed that the generation of fish eyes can be suppressed by performing the water washing treatment as compared with the case where the water washing treatment is not performed (Example, Table 1).
- the pellets after drying are washed with water, the pellets absorb moisture, so that drying is necessary again.
- the resin may be colored by heat history due to repeated moisture absorption and drying. Further, from the viewpoint of production economy, it is preferable that there are few washing and drying steps.
- the present invention has been made in view of such circumstances, and the object of the present invention is to ensure the desired melt viscosity without increasing the boron content, and to effectively prevent surging. It is providing the resin composition (pellet) and its manufacturing method.
- boric acids act as a cross-linking agent, and the hydroxyl groups and boron of EVOH-based resins form hydrogen bonds or covalent bonds to form polymer chains. It is thought to be due to concatenating. As shown in FIG. 1, the crosslinking with boron may be based on boron tricoordinate (planar tricoordinate) or tetracoordinate (tetrahedral tetracoordinate). As a result of intensive studies on EVOH resin compositions containing boric acids, the present inventors have found that the presence of tetracoordinate boron is advantageous in increasing the viscosity of EVOH resins.
- Boric acid is usually present in a resin composition in a tricoordinate structure of boron, but the present inventors have incorporated a tricoordinate boron in a tetracoordinate structure.
- the present invention has been completed by finding a method that can be converted into
- the EVOH resin composition of the present invention is a resin composition containing a saponified ethylene-vinyl ester copolymer and boric acid, wherein the boric acid contains boron having a four-coordinate structure. It is characterized by.
- the content of the boric acid is preferably 1 to 350 ppm in terms of boron per saponified ethylene-vinyl ester copolymer. Further, the proportion of boron in a tetracoordinate structure in boron in the boric acids is preferably 10 to 99 mol%.
- the alkali metal salt is preferably contained in an amount of 300 to 1000 ppm in terms of metal per saponified ethylene-vinyl ester copolymer.
- the alkali metal salt is preferably a sodium salt.
- the content of the alkali metal salt relative to the boric acid is preferably 0.8 to 10.0 as a weight ratio (alkali metal equivalent of alkali metal salt / boron equivalent of boric acid).
- the elongational viscosity at 210 ° C. at an elongation strain rate of 100 sec ⁇ 1 is preferably 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 Pa ⁇ s.
- the method for producing an EVOH-based resin composition of the present invention is a method for producing an ethylene-vinyl ester copolymer saponified composition containing boron having a tetracoordinate structure, By bringing a paste of a saponified ethylene-vinyl ester copolymer containing boric acid into contact with an aqueous solution containing boric acid and an alkali metal salt under heating and pressurization, the boric acid contained in the paste Converting at least a portion of the boron of the compound to a tetracoordinate structure,
- the aqueous solution has a boric acid content per ethylene-vinyl ester copolymer in the saponified ethylene-vinyl ester copolymer composition of 1 to 350 ppm in terms of boron, and the ethylene-vinyl ester
- the aqueous solution contains boric acids and alkali metal salts so that the content of alkali metal salts per copolymer is 300
- the heating / pressurization is preferably performed at 50 to 150 ° C. as the temperature in the system where the conversion treatment step is performed, and 0.01 to 1 MPaG as the difference between the pressure in the system and atmospheric pressure.
- the contact is preferably performed while the paste of the saponified ethylene-vinyl ester copolymer is kneaded with the aqueous solution.
- the paste of the saponified ethylene-vinyl ester copolymer comprises 1 to 350 ppm of boric acid or a metal salt thereof in terms of boron and 1000 alkali metal salt in terms of metal per saponified ethylene-vinyl ester copolymer. It is preferable to contain ⁇ 4000 ppm.
- the concentration of boric acids in the aqueous solution is preferably 1 to 50 ppm in terms of boron, and the alkali metal salt concentration is preferably 50 to 1500 ppm in terms of metal.
- the EVOH-based resin composition of the present invention contains tetracoordinate boron, it has excellent melt moldability despite the fact that the content of boric acids is reduced as compared with the prior art.
- the method for producing an EVOH resin composition of the present invention can cope with the conventional production method only by changing the composition of the treatment solution of the EVOH resin paste, which is advantageous in production.
- EVOH resin composition (1) EVOH-based resin
- the EVOH-based resin used in the EVOH-based resin composition of the present invention is usually a saponification of a copolymer of ethylene and a vinyl ester monomer (ethylene-vinyl ester copolymer). And is a water-insoluble thermoplastic resin.
- the copolymerization of the monomer can be carried out using any known polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization, but generally a lower alcohol such as methanol, particularly preferably methanol as a solvent. Solution polymerization is used. Saponification of the obtained ethylene-vinyl ester copolymer can also be performed by a known method.
- the EVOH-based resin produced in this manner is mainly composed of ethylene-derived structural units and vinyl alcohol structural units, and in some cases, contains a slight amount of vinyl ester structural units that remain without being saponified.
- vinyl ester-based monomer vinyl acetate is typically used because it is easily available from the market and has high efficiency in treating impurities during production.
- examples of other vinyl ester monomers include, for example, fats such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate.
- Aromatic vinyl esters such as aromatic vinyl esters and vinyl benzoates, and the like.
- aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms are used. It can. These are usually used alone, but a plurality of them may be used simultaneously as necessary.
- Copolymerization of ethylene and a vinyl ester monomer can be carried out using any known polymerization method such as solution polymerization, suspension polymerization, and emulsion polymerization.
- the solvent used for such copolymerization include usually lower alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, and methanol is preferably used industrially.
- Saponification of the obtained ethylene-vinyl ester copolymer can also be performed by a known method.
- the catalyst used for saponification include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, and the like,
- alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, and the like
- acid catalysts such as sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, zeolite, and cation exchange resin.
- the content of the ethylene structural unit in the EVOH-based resin is a value measured based on ISO 14663, and is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 45 mol%.
- the content is too low, the gas barrier property and melt moldability under high humidity tend to be lowered, and when it is too high, the gas barrier property tends to be lowered.
- the saponification degree of the vinyl ester component in the EVOH resin is a value measured based on JIS K6726 (however, water / methanol is used as a solvent), and is usually 90 to 100 mol%, preferably 95 to 100 mol%, particularly Preferably, it is 99 to 100 mol%.
- degree of saponification is too low, gas barrier properties, thermal stability, moisture resistance and the like tend to decrease.
- the melt flow rate (MFR) (210 ° C., load 2,160 g) of the EVOH resin is usually 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 3 to 35 g. / 10 minutes.
- MFR melt flow rate
- the EVOH-based resin used in the present invention may further contain structural units derived from the following comonomer within a range that does not inhibit the effects of the present invention (for example, 10 mol% or less).
- the comonomer include olefins such as propylene, 1-butene and isobutene, 3-buten-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, and 5-hexene-1,2.
- hydroxy group-containing ⁇ -olefins such as diols, esterified products and acylated products thereof; hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; Hydroxyalkyl vinylidene diacetates such as 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane; acrylic acid, methacrylic acid Acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc.
- Vinyl silanes such as trimethoxyvinyl silane; allyl halide compounds such as allyl acetate and allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; trimethyl- (3-acrylamido-3-dimethyl) And a comonomer such as propyl) -ammonium chloride and acrylamido-2-methylpropanesulfonic acid.
- post-modified EVOH-based resins such as urethanization, acetalization, cyanoethylation, oxyalkyleneation and the like can also be used.
- EVOH-based resins containing hydroxyl groups in the side chain are preferred from the viewpoint of good secondary moldability.
- EVOH-based resins having a primary hydroxyl group in the side chain particularly a 1,2-diol structure on the side.
- An EVOH resin having a chain is preferred.
- Such an EVOH resin having a 1,2-diol structure in the side chain contains a 1,2-diol structural unit in the side chain.
- the 1,2-diol structural unit is specifically a structural unit represented by the following general formula (1).
- R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an organic group
- X represents a single bond or a bond chain
- R 4 , R 5 , and R 6 each independently Represents a hydrogen atom or an organic group.
- Examples of the organic group in the 1,2-diol structural unit represented by the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
- a saturated hydrocarbon group such as phenyl group and benzyl group, a halogen atom, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, a carboxyl group, and a sulfonic acid group.
- R 1 to R 3 are preferably a saturated hydrocarbon group or a hydrogen atom usually having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably a hydrogen atom.
- R 4 to R 6 are preferably an alkyl group having 1 to 30 carbon atoms, particularly 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms, or a hydrogen atom, and most preferably a hydrogen atom. In particular, it is most preferable that R 1 to R 6 are all hydrogen.
- X in the structural unit represented by the general formula (1) is typically a single bond.
- a bond chain may be used as long as the effect of the present invention is not inhibited.
- hydrocarbon chains such as alkylene, alkenylene, alkynylene, phenylene, naphthylene (these hydrocarbons may be substituted by halogens, such as fluorine, chlorine, bromine, etc.)
- Other structures including an ether bond site such as —O—, — (CH 2 O) m—, — (OCH 2 ) m—, — (CH 2 O) mCH 2 —, etc .; —CO—, —COCO—, — A structure containing a carbonyl group such as CO (CH 2 ) mCO— or —CO (C 6 H 4 ) CO—; a structure containing a sulfur atom such as —S—, —CS—, —SO—
- R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is a natural number, usually 1 to 30, preferably 1 to 15, and more preferably 1 to 10.
- —CH 2 OCH 2 — and a hydrocarbon chain having 1 to 10 carbon atoms are preferable from the viewpoint of stability during production or use, and further a hydrocarbon chain having 1 to 6 carbon atoms, particularly 1 carbon atom. It is preferable that
- the most preferred structure in the 1,2-diol structural unit represented by the general formula (1) is one in which R 1 to R 6 are all hydrogen atoms and X is a single bond. That is, the structural unit represented by the following structural formula (1a) is most preferable.
- the content is usually 0.1 to 20 mol%, further 0.1 to 15 mol%, particularly 0.1 to 0.1 mol%.
- the thing of 10 mol% is preferable.
- boric acids that is, boric acid or a salt thereof.
- the borate include calcium borate, cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), aluminum borate / potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate, Ammonium pentaborate, ammonium octaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, Potassium octaborate), silver borate (silver metaborate, silver tetraborate, etc.), copper borate (cupric borate, copper metaborate, copper tetraborate, etc.), sodium borate (sodium metaborate
- Lead borate (lead metaborate, lead hexaborate, etc.), nickel borate (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), barium borate (barium orthoborate, metaborate) Barium acid, barium diborate, barium tetraborate, etc.), bismuth borate, magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, etc.), In addition to manganese borate (manganese borate, manganese metaborate, manganese tetraborate, etc.), lithium borate (lithium metaborate, lithium tetraborate, lithium pentaborate, etc.), borax, carnite, Examples include borate minerals such as inyoite, agate stone, suianite, and zaiberite. Borax, boric acid, sodium
- the boric acid content in the resin composition is preferably 1 to 350 ppm, more preferably 10 to 330 ppm, still more preferably 30 to 300 ppm, and particularly preferably 100 to 300 ppm in terms of boron per EVOH resin. is there. From the viewpoint of moldability of the resin composition and prevention of surging, boric acids are added. However, if the boric acid content is too high, cross-linked products are localized, and fish eyes are likely to occur. Tend to be.
- the resin composition of the present invention is characterized in that even if the content of boric acids is reduced as compared with the conventional one, it is excellent in moldability and can suppress the generation of fish eyes.
- boric acid has a tricoordinate structure (FIG. 1A) and a tetracoordinate structure (FIG. 1B).
- boric acid contained in the EVOH-based resin exists in a three-coordinate structure.
- the resin composition of the present invention is characterized in that it includes a tetracoordinate boron. The presence of tetracoordinated boron increases the elongational viscosity of the resin composition even if the boron content is the same.
- the content of boron in a four-coordinate structure in boric acids (in terms of boron) contained in the resin composition is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, Especially preferably, it is 50 mol% or more. If the content is too low, the effect of improving the moldability tends not to be seen. In addition, an upper limit is 99 mol% normally from a viewpoint of productivity, Preferably it is 95 mol%.
- Such a content can be calculated by the following formula from each area by analyzing the spectrum of tricoordinate boron and tetracoordinate boron by measuring the structure of the boron nucleus using solid-state NMR.
- the method for converting to a four-coordinate structure is not particularly limited.
- the method used in the production method of the present invention described later that is, the boric acid-containing EVOH-based resin composition is heated and pressurized in a boric acid-containing treatment.
- a method of contacting with a liquid is preferably employed. Since this method can be carried out during the production process of the EVOH resin composition pellets, it is simple and excellent in productivity.
- the resin composition of the present invention preferably contains an alkali metal salt.
- the alkali metal salt is usually contained in the resin composition conventionally by being added as a residue of the alkali catalyst used in the saponification reaction or as a heat stabilizer.
- boric acids are known as crosslinking agents for EVOH-based resins. And it turned out that the coordination structure of the boron in EVOH type-resin composition is influenced by the content rate of the coexisting alkali metal.
- the alkali metal salt is contained at such a concentration that boron of boric acids can stably exist in a four-coordinate structure.
- the resin composition of the present invention can produce the composition of the present invention described later.
- the alkali metal salt is added by a content treatment such that the content of the alkali metal salt becomes a predetermined concentration.
- alkali metal salts include inorganic acid salts such as phosphates, monohydrogen phosphates, dihydrogen phosphates, sulfates, sulfites and carbonates; acetates, stearates, propionic acids and butyric acids.
- Carboxylic acid salts having 2 to 16 carbon atoms such as lauric acid, stearic acid, oleic acid, and behenic acid.
- an alkali metal salt of acetic acid is preferable from the viewpoint that it is the same as a byproduct generated in the saponification step.
- a sodium salt and potassium salt are used preferably, More preferably, it is a sodium salt.
- metal salts are not limited to one type, and may be a combination of different types of metal salts.
- sodium salts such as sodium acetate, sodium propionate, sodium phosphate, and sodium hydrogen phosphate may be used in combination.
- the content of the alkali metal salt in the resin composition refers to the total sodium equivalent of these metal salts.
- the content of the alkali metal salt in the EVOH-based resin composition is not particularly limited, but is preferably 300 ppm or more, more preferably 300 to 1000 ppm, still more preferably 310 to 1000 ppm, particularly preferably in terms of metal per EVOH-based resin. Is 320 to 800 ppm.
- the alkali metal salt is a sodium salt
- the content of the sodium salt is not particularly limited, but is preferably 300 ppm or more, more preferably 300 to 1000 ppm, still more preferably 310 to 1000 ppm in terms of sodium per EVOH resin. 1000 ppm, particularly preferably 320 to 800 ppm.
- the cross-linked structure with boric acids is affected by alkali metals such as sodium and potassium or alkaline earth metals such as calcium and magnesium.
- alkali metals such as sodium and potassium or alkaline earth metals such as calcium and magnesium.
- metal salts boron is easy to form a tetracoordinate structure when an alkali metal having a strong basicity is used, and boron is easy to form a tetracoordinate structure particularly when it is a sodium salt, so that it is preferably used.
- the content ratio of the alkali metal equivalent in the alkali metal salt and the boron equivalent in the boric acid is important.
- the content weight ratio of the alkali metal to boron is preferably 0.8 to 10, more preferably 0.9 to 5, and still more preferably. Is 1.0-3.
- the resin composition of the present invention contains a compounding agent or the like generally blended with an EVOH-based resin within a range that does not impair the effects of the present invention (usually 5% by weight or less in the resin composition). May be.
- the compounding agent examples include heat stabilizers other than alkali metal salts, antioxidants, antistatic agents, colorants, ultraviolet absorbers, lubricants, plasticizers, light stabilizers, surfactants, antibacterial agents, and desiccants. , Antiblocking agents, flame retardants, crosslinking agents, curing agents, foaming agents, crystal nucleating agents, antifogging agents, biodegradable additives, silane coupling agents, oxygen absorbers and the like.
- the EVOH-based resin composition containing boron having a tetracoordinate structure as described above has a tetracoordinate structure at a corresponding boron equivalent concentration even though the amount of boric acid is reduced as compared with the conventional case.
- a conventional EVOH resin composition containing no boron it has a high elongational viscosity.
- the elongational viscosity is expressed as the viscosity under the constant deformation rate and the constant temperature of the molten resin, and the flow of the resin where the flow rate of the resin accelerates or decelerates, such as the reduced part of the flow path or the multi-layer joint part. Dominated.
- the extensional viscosity can be used as an evaluation index for melt formability and workability such as melt spinning, film forming, and blow molding. The higher the elongation viscosity, the better the moldability.
- the elongational viscosity at 210 ° C. of the composition at a general elongation strain rate of 100 sec ⁇ 1 at the time of film formation.
- 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 Pa ⁇ s preferably about 5.0 ⁇ 10 2 to 5.0 ⁇ 10 5 Pa ⁇ s.
- the resin composition of the present invention that is, the EVOH-based resin composition containing tetracoordinate boron
- the method for producing an EVOH-based resin composition of the present invention comprises a paste of an EVOH-based resin composition containing boric acids (hereinafter referred to as “boric acid-containing EVOH-based resin paste (II)”) under heating and pressure, A step of converting at least a part of boron in the boric acids contained in the paste into a four-coordinate structure by contacting with an aqueous solution (treatment solution) containing boric acids and alkali metal salts (hereinafter referred to as “four-coordinated structure”).
- the 4-coordination treatment step which may be referred to as a “coordination treatment step”.
- a combination of two or more selected from (1) to (7) above can be converted into a 4-coordination structure.
- the boric acid-containing EVOH resin paste (II) is prepared by treating the EVOH resin water-containing paste (I) with a boric acid-containing treatment.
- EVOH-based resin water-containing paste (I) is a paste-like EVOH-based resin (or EVOH-based resin composition) subjected to boric acid-containing treatment and is 4-coordinated. It is distinguished from the EVOH resin paste used for the chemical treatment step.
- the EVOH-based resin hydrous paste (I) is usually an EVOH-based resin hydrous composition in a rubbery or jelly-like soft and fluid state containing water and alcohol.
- the EVOH-based resin after the saponification reaction is an alcohol solvent or a water / alcohol mixed solvent solution (hereinafter collectively referred to as an “EVOH-based resin alcohol solution” unless otherwise specified). Derived from the reaction system at high temperature and high pressure. By replacing part of the alcohol in the alcohol solution of the EVOH resin obtained after saponification with water, the EVOH resin water-containing paste (I) having a reduced alcohol content can be prepared.
- the alcohol solution of EVOH resin obtained by saponification usually has a concentration of 10 to 70% by weight, preferably 20 to 65% by weight, more preferably 30 to 60% by weight of the EVOH resin.
- the alcohol solution of EVOH resin used for the preparation of EVOH resin-containing water-containing paste (I) usually has a residual monomer (vinyl ester monomer) removed when the ethylene-vinyl ester copolymer is synthesized. Yes. A part of the carboxylic acid produced by saponification remains. For this reason, when a saponification catalyst is an alkali catalyst, it may become a by-product by becoming a carboxylic acid metal salt. For example, when vinyl acetate is used as the vinyl ester and sodium hydroxide is used as a catalyst, sodium acetate, which is an alkali metal salt, can be contained in the EVOH resin hydrous paste (I) as a by-product.
- the content of the alkali metal salt that can be contained in the EVOH resin-containing water-containing paste (I) is usually 1000 to 4000 ppm in terms of alkali metal per EVOH resin.
- alcohol / water replacement The operation of replacing alcohol with water (abbreviated as “alcohol / water replacement”) is usually obtained by bringing an EVOH resin alcohol solution into contact with water or steam (hydrous treatment).
- the temperature of water and water vapor used for the contact treatment is usually 30 to 200 ° C, preferably 80 to 180 ° C, more preferably 100 to 150 ° C. From the viewpoint of substitution efficiency, it is particularly preferable that the water vapor be introduced into the container.
- the amount of the water vapor is usually 0.01 to 30 times (weight ratio) relative to the amount of the EVOH resin alcohol solution introduced, preferably 0.1 to 10 times, more preferably 0.5 to 5 times.
- the contact treatment between the alcohol solution of EVOH resin and water or water vapor can be usually carried out using a tower-type container such as a perforated plate tower or a bubble tower, or a packed tower.
- a tower-type container such as a perforated plate tower or a bubble tower, or a packed tower.
- the number of theoretical plates is usually 2 to 20 plates, preferably 5 to 15 plates.
- the packed tower type the amount of packing is set in accordance therewith.
- an alcohol solution of EVOH resin and water vapor and / or water are introduced, and by contacting both, a part of the alcohol in the EVOH resin solution is replaced with water, and the EVOH resin A hydrous paste (I) is derived.
- the contact between the alcohol solution of the EVOH-based resin and water or water vapor may be either counter-current or co-current, but is preferably made counter-current from the viewpoint of substitution efficiency.
- an alcohol solution of EVOH resin is introduced from the upper part of the tower, water vapor is introduced from the lower part of the tower and brought into countercurrent contact, and the alcohol vapor is led out together with the water vapor from the upper part of the tower. Is preferably derived from the bottom of the column.
- the water content, alcohol content, and EVOH resin fraction of the EVOH resin water-containing paste (I) are the amount of water (and / or water vapor) introduced into the alcohol solution of the EVOH resin introduced into the container, and the temperature in the tower. It can be controlled by pressure and pressure. Also, depending on the specifications of the tower-type container to be used, for example, the number of shelves, the ratio of the cross-sectional area to the tower length, the number of shelves, the hole diameter and number of the perforated plate, alcohol in the alcohol solution of the EVOH resin You may adjust a content rate, a resin fraction, etc. suitably.
- the pressure in the tower-shaped container is not particularly limited, but is preferably 0 to 0.5 MPaG, more preferably 0.1 to 0.3 MPaG as a difference from the atmospheric pressure. If the applied pressure becomes too high, the temperature in the container rises and the EVOH resin tends to be thermally deteriorated.
- the EVOH resin hydrous paste (I) obtained as described above has an alcohol content of usually 10 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight based on 100 parts by weight of the EVOH resin. Parts by weight.
- the EVOH resin content in the EVOH resin hydrous paste (I) is usually 20 to 60% by weight, preferably 30 to 50% by weight.
- the water content is usually 20 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the EVOH resin.
- the water / alcohol ratio in the EVOH resin hydrous paste (I) is usually (1/99) to (80/20), preferably (10/90) to (75) in terms of the weight ratio of (water / alcohol). / 25), more preferably (30/70) to (70/30).
- the polarity of the solution tends to be too low and the compatibility with the EVOH resin tends to be reduced. If the alcohol content is too low, the polarity of the solution becomes too high and the EVOH is still too high. There is a tendency that compatibility with a resin is reduced.
- boric acid-containing EVOH resin paste (II) is prepared by adding boric acids to the EVOH resin water-containing paste (I) prepared above.
- the EVOH-based resin hydrous paste (I) does not contain boric acids and therefore needs to be added.
- the amount of boric acid at a concentration corresponding to the composition of the EVOH resin composition to be finally obtained is subjected to 4-coordination treatment. It is usually difficult to contain in the process. It also causes a decrease in boron tetracoordinate conversion efficiency. Therefore, it is preferable to add boric acids to a certain concentration prior to the 4-coordination treatment step.
- boric acid-containing liquid an aqueous solution of boric acids
- EVOH resin hydrous paste (I) aqueous solution of boric acids
- concentration of boric acids in the boric acid-containing liquid is appropriately selected depending on the concentration of the EVOH resin composition to be finally obtained.
- the content of boric acid with respect to water is preferably 1 to 350 ppm in terms of boron, more preferably 10 to 330 ppm, and still more preferably 15 to 300 ppm.
- compounding agent mix blended as needed in the boric acid containing liquid to be used.
- compounding agents include heat stabilizers other than alkali metal salts, antioxidants, antistatic agents, colorants, ultraviolet absorbers, lubricants, plasticizers, light stabilizers, surfactants, antibacterial agents, and desiccants.
- Examples of the contact method include a method in which the EVOH resin hydrous paste (I) is exposed to a boric acid aqueous solution, and the EVOH resin hydrous paste (I) is immersed in a boric acid aqueous solution. You may make it contact with boric acid aqueous solution countercurrently using the tower-type washing
- the boric acid-containing EVOH resin paste (II) thus obtained depends on the composition of the boric acid-containing liquid used in the treatment and the composition of the EVOH resin-containing water-containing paste (I).
- the alcohol content relative to parts by weight is usually 10 to 200 parts by weight, preferably 20 to 150 parts by weight, and more preferably 30 to 120 parts by weight.
- the EVOH resin content in the boric acid-containing EVOH resin paste (II) is usually 20 to 60% by weight, preferably 30 to 50% by weight.
- the water content is usually 50 to 400 parts by weight, preferably 80 to 360 parts by weight, and more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the EVOH resin.
- the boric acid is preferably adjusted to about 1 to 350 ppm, preferably 10 to 330 ppm, more preferably 30 to 300 ppm in terms of boron per EVOH resin.
- the alkali metal salt can usually remain at 1000 to 4000 ppm in terms of alkali metal per EVOH resin.
- the boric acid-containing EVOH resin paste (II) by adjusting the boric acid concentration and the alkali metal salt concentration within the above ranges, the next boron 4-coordination conversion can be efficiently performed.
- the tetracoordinate transformation of boron is achieved by contacting with a predetermined concentration of boric acid-containing treatment solution under heating and pressure in the presence of a specific amount of alkali metal salt. Even when the boric acid-containing treatment solution having the same composition is used, 4-coordination is unlikely to occur in contact at normal temperature and normal pressure. In addition, even when the boric acid-containing treatment solution and the boric acid-containing EVOH resin paste (II) are brought into contact with each other under heating and pressurization, four-coordination is achieved unless a predetermined amount of alkali metal salt coexists. Is unlikely to occur.
- the boric acid concentration and sodium concentration in the boric acid-containing EVOH resin paste (II) are In addition to changing, the state of the EVOH resin may also change. Accordingly, it is preferable that the boric acid-containing EVOH resin paste (II) is brought into contact with the treatment liquid under heating and pressure under conditions and conditions that allow a specific amount of alkali metal salt to coexist.
- the contact treatment with the treatment liquid is preferably performed while applying a shearing force to the boric acid-containing EVOH resin paste (II), and specifically, it is preferably performed by liquid phase kneading with the treatment liquid.
- Treatment liquid The composition of the treatment liquid is appropriately set depending on the composition of the EVOH resin composition to be finally obtained and the composition of the boric acid-containing EVOH resin paste (II) to be used. . That is, the treatment liquid used for the four-coordination treatment is the composition of the EVOH resin composition to finally obtain the boric acid and alkali metal salt contents of the boric acid-containing EVOH resin paste (II) ( Boric acid concentration, alkali metal salt concentration).
- the composition of the EVOH-based resin composition to be finally obtained is a composition in which boron can stably maintain a four-coordinate structure, and is preferably 1 to 350 ppm in terms of boron per EVOH-based resin. More preferably, it is 10 to 330 ppm, more preferably 30 to 300 ppm, and the content of the alkali metal salt in the EVOH resin composition is preferably 300 ppm or more in terms of metal per EVOH resin, more preferably It is 300 to 1000 ppm, more preferably 310 to 1000 ppm, particularly preferably 320 to 800 ppm or more.
- the boric acid content of the treatment liquid used for the contact treatment is 1 to 50 ppm in terms of boron with respect to the water of the treatment liquid. More preferred is 5 to 40 ppm, still more preferred is 10 to 30 ppm.
- the treatment liquid contains an alkali metal salt such as sodium.
- an alkali metal salt such as sodium. This is because the cross-linked structure of boric acid is affected by the alkali metal salt, and the boron 4-coordination treatment needs to be performed in a state where 300 ppm or more of the alkali metal salt coexists. If the content of the alkali metal salt in the boric acid-containing EVOH-based resin paste (II) used in the 4-coordination treatment step is too small, 4-coordination is unlikely to occur.
- the alkali metal salt When a treatment liquid having an alkali metal salt concentration that is too low is used, the alkali metal salt is eluted from the boric acid-containing EVOH-based resin paste (II) by liquid phase kneading, and tricoordinate boron is tetracoordinated. It becomes difficult to change the position.
- the concentration of the alkali metal salt contained in the boric acid-containing EVOH resin paste (II) is increased by the liquid phase kneading treatment, and thus the EVOH
- the quality of the finally obtained EVOH-based resin composition may be deteriorated, for example, the resin composition may be colored.
- the content of the alkali metal salt in the treatment liquid is preferably 50 to 1500 ppm in terms of metal with respect to the water of the treatment liquid. More preferred is 70 to 1200 ppm, and still more preferred is 100 to 1000 ppm.
- the content of carboxylic acid in the tetracoordinate boron-containing EVOH resin paste (III) obtained after the treatment is usually 10 to 10,000 ppm, preferably 50 to 3000 ppm with respect to the EVOH resin.
- the concentration of the carboxylic acid in the treatment liquid is usually 10 to 3000 ppm, preferably 20 to 1000 ppm, and more preferably 30 to 500 ppm.
- the content of the phosphate compound in the tetracoordinate boron-containing EVOH resin paste (III) obtained after the treatment is expressed in terms of phosphate groups relative to the EVOH resin paste (ion chromatography). In general, it is 1 to 1000 ppm in terms of phosphate radical. If the content is too small, it tends to be colored easily at the time of melt molding. Conversely, if the content is too large, gels and fish eyes of the molded product may be easily generated. Therefore, the concentration of the phosphoric acid compound in the treatment liquid is usually 1 to 3000 ppm, preferably 10 to 1000 ppm, more preferably 20 to 500 ppm.
- the contact treatment with the boric acid-containing EVOH resin paste (II) with the treatment liquid under heating / pressurization either continuous treatment or batch treatment can be adopted, but from the viewpoint of production efficiency, preferably Continuous processing type.
- the continuous treatment method a method of continuously supplying and exposing the boric acid-containing EVOH resin paste (II) to the boric acid-containing EVOH resin paste (II); The method of introducing; a method of introducing both the treatment liquid and boric acid-containing EVOH resin paste (II) into the container, and the like.
- the treatment liquid and the boric acid-containing EVOH resin paste (II) are continuously contacted using a container having a paste inlet, a paste outlet, a washing water inlet, and a drain outlet at arbitrary positions. Is preferably performed.
- a washing machine is preferably a horizontal type in terms of productivity.
- the temperature at the time of the contact treatment is the temperature in the container, usually 50 to 150 ° C., preferably 60 to 140 ° C., more preferably 70 to 130 ° C. If the temperature is too high, the resin tends to deteriorate due to heat and the EVOH-based resin tends to be colored. On the other hand, when too low, a viscosity may rise and handling may become difficult.
- the temperature of the boric acid-containing EVOH resin paste (II) to be introduced is usually 50 to 120 ° C., preferably 60 to 120 ° C.
- the pressurizing pressure is generally 0.01 to 1 MPaG, preferably 0.05 to 0.5 MPaG, more preferably 0.1 to 0.3 MPaG, as a differential pressure between the pressure in the system and atmospheric pressure. If the pressurizing pressure is too high, it tends to be difficult to maintain the airtightness of the equipment, and if it is too low, moisture in the system tends to boil. Contact between the introduced paste and the concentration-adjusting treatment liquid may be countercurrent or cocurrent, but is preferably made countercurrent in view of replacement efficiency.
- a tetracoordinate boron-containing EVOH resin paste (III) in which the content of alkali metal salt and boric acid is adjusted to a predetermined amount and at least a part of boron has a tetracoordinate structure is derived. Is done.
- the contact treatment between the treatment liquid and the boric acid-containing EVOH resin paste (II) is preferably performed while applying a shearing force. Specifically, it is preferable to bring the boric acid-containing EVOH resin paste (II) into contact with the boric acid-containing EVOH resin paste (II) in the treatment liquid.
- Such an operation may be referred to as liquid phase kneading.
- the liquid phase kneading involves renewing the surface of the boric acid-containing EVOH resin paste (II) while kneading with a screw or the like, and continuously supplying the treatment liquid to the inside of the EVOH resin paste (II). The liquid is uniformly brought into contact with the treatment liquid.
- the liquid phase kneading treatment can be performed using a container provided with a kneading device for applying a shearing force to the paste in the above-described container.
- a kneader-equipped container is preferably a horizontal type in terms of productivity.
- the kneading apparatus examples include a kneading apparatus having screws, gears, paddles, and the like.
- the shearing force applied to the paste by these kneading devices is preferably perpendicular to the direction of paste travel in the container, and preferably includes a temperature control means such as a jacket, a coil, or a heater built-in screw shaft. .
- a temperature control means such as a jacket, a coil, or a heater built-in screw shaft.
- the shearing force is preferably in the vertical direction.
- a double-arm kneader type, a kneader type, a botata type, or the like may be used.
- Horizontal types such as ribbon type, screw type, paddle type, muller type, radial rod type mixers, pin mixers, cutter mixers, rod mixers, internal mixers, etc., ball rod mills, pug mills, etc. It is also possible to use a kneading apparatus having a single axis or multiple axes.
- a container with a large clearance type kneading device in which a large gap (clearance) is provided between the screw and the container tank main body is preferable.
- the screw rotates in the treatment liquid, and liquid phase kneading is performed in the treatment liquid introduced from the washing water introduction port while applying a shearing force to the boric acid-containing EVOH resin paste (II) introduced from the paste introduction port. Therefore, the treatment liquid can be efficiently brought into contact with the paste.
- the above “clearance” indicates the closest distance between the tip of the screw blade and the inner wall of the container.
- the clearance is usually 1 to 20 mm, preferably 5 to 15 mm, more preferably 5 to 10 mm.
- the paste surface renewal efficiency tends to decrease, and when it is too narrow, the paste transfer efficiency tends to decrease.
- a contact opportunity with a process liquid reduces somewhat, it can be used also with a general kneader.
- the bath ratio (treatment liquid amount / prepared EVOH resin amount) with respect to the EVOH resin content in the boric acid-containing EVOH resin paste (II) charged into the container is usually 0.5 to 10 , Preferably 1-8, more preferably 3-5. If the bath ratio is too high, the economy tends to decrease, and if it is too low, the tetracoordinate conversion efficiency tends to decrease.
- the residence time of the paste in the container varies depending on the characteristics of the target EVOH resin, but is usually 0.5 to 10 hours, preferably 1 to 8 hours, more preferably 1 to 5 hours. is there. If the contact time with the treatment liquid becomes too long or the liquid phase kneaded state becomes too long, the carboxyl group (—COOH) which is the polymerization terminal of the EVOH resin reacts with the adjacent hydroxyl group to form a lactone, There exists a tendency for the retention strength of the alkali metal salt by the said carboxyl group to fall. As a result, the alkali metal salt concentration necessary for tetracoordination cannot be ensured, and once the tetracoordination is performed, the tricoordinate structure may be restored.
- the amount of the boric acid-containing EVOH resin paste (II) introduced into the washing tank varies depending on the bath ratio, but is usually 10 to 90% by volume / hour, preferably 10 to 50 volumes with respect to the internal volume of the horizontal washing tank. % / Hour, more preferably 10 to 25% by volume / hour. If the amount is too small, the tetracoordination efficiency tends to be reduced. Conversely, if the amount is too large, sufficient tetracoordination tends not to be performed.
- the residence time of the treated water is usually 0.5 to 20 hours, preferably 0.5 to 15 hours.
- boron contained in boric acids contained in the EVOH resin composition can be converted into a tetracoordinate structure.
- the tetracoordinate boron-containing EVOH-based resin paste (III) thus obtained becomes a paste having a higher viscosity as the tetracoordination of boron is achieved.
- the proportion of boron having a tetracoordinate structure in the boron contained in the EVOH resin composition is based on the boric acid-containing EVOH resin paste (II) to be used and the four coordination treatment conditions (treatment liquid composition, heating Depending on pressure conditions, liquid phase kneading conditions, treatment time, etc.), usually 10 to 95% by weight, preferably 20 to 90% by weight of boron can be tetracoordinated.
- the tetracoordinate boron-containing EVOH resin paste (III) usually has a resin content of 40 to 70% by weight, the alcohol content is usually 0 to 5 parts by weight, and the water content is usually 40 to 70% by weight with respect to 100 parts by weight of the EVOH resin. 100 parts by weight.
- the amount of acetic acid based on the EVOH resin is usually 500 to 3000 ppm, preferably 800 to 2000 ppm, boric acids are usually 1 to 350 ppm, preferably 30 to 300 ppm in terms of boron, and alkali metal salts are usually 300 to 3000 in terms of alkali metal. 1000 ppm, preferably 320 to 800 ppm.
- the method of pelletizing the tetracoordinate boron-containing EVOH resin paste (III) is not particularly limited, but is preferably performed by the following method.
- a tetracoordinate boron-containing EVOH resin paste (III) is extruded through holes or slits and cut to obtain pellets (for example, hot cut or underwater cut), or extruded into a sheet or strand to cool and solidify. And a method of cutting the obtained strand or sheet to obtain pellets. What is necessary is just to dry the obtained pellet by various well-known drying methods.
- the shape of the pellet is not particularly limited.
- the shape may be any of a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, a strip shape, and the like, and usually depends on a pellet manufacturing method.
- the pellet size has a diameter of usually 1 to 6 mm, preferably 2 to 5 mm, and a height of usually 1 to 6 mm, preferably 2 to 5 mm.
- the EVOH-based resin composition pellets obtained in this manner depend on the composition of the resin composition and the production method, but 10 to 95 mol% of boron contained in the boric acid is present in a four-coordinate structure. ing. Therefore, the EVOH-based resin pellet obtained by the production method of the present invention is an EVOH-based resin composition containing a corresponding boron-converted concentration in terms of boron, although the amount of boric acids is reduced as compared with the prior art. Compared to, it has a high extensional viscosity.
- the elongational viscosity dominates the resin flow at locations where the flow rate of the resin accelerates and decelerates, such as the reduced portion of the flow path and the multi-layered merged portion, and it is possible to evaluate the difference in moldability that cannot be understood by conventional melt viscosity evaluation.
- the elongational viscosity of the composition at 210 ° C. at a general elongation strain rate of 100 sec ⁇ 1 during film formation is It is about 1.0 ⁇ 10 2 to 1.0 ⁇ 10 6 Pa ⁇ s.
- Elongation viscosity (Pa ⁇ s) About 35 g of pellets were packed in a barrel, preheated at a barrel temperature of 210 ° C. for 5 minutes, the molten resin was extruded, and the extensional viscosity at an elongation strain rate of 100 sec ⁇ 1 was measured.
- a twin capillary rheometer “RG20” manufactured by GOTTFERT was used for measurement of elongational viscosity.
- Example 1 (1) Synthesis of EVOH-based resin A polymerization vessel equipped with a cooling coil was charged with 420 parts by weight of vinyl acetate, 90 parts by weight of methanol, and 180 ppm of acetyl peroxide (vs. vinyl acetate), and the system was replaced with nitrogen gas. Next, the system was replaced with ethylene, and ethylene was injected until the ethylene pressure reached 4.7 MPaG. Then, it heated up to 67 degreeC, stirring, and started the copolymerization reaction of vinyl acetate and ethylene. After 6 hours, the polymerization reaction was stopped.
- acetyl peroxide vs. vinyl acetate
- the polymerization rate of vinyl acetate was 63% by weight relative to the charged amount of vinyl acetate, and an ethylene-vinyl acetate copolymer having an ethylene content of 38 mol% was obtained.
- the obtained ethylene-vinyl acetate copolymer solution was supplied to a distillation column, and methanol vapor was introduced from the bottom of the column to remove unreacted vinyl acetate, and the ethylene-vinyl acetate copolymer methanol solution ( Resin concentration 48% by weight) was obtained.
- the methanol solution of this ethylene-vinyl acetate copolymer was supplied from the top of the tower column at a rate of 30 parts by weight / hour, and methanol was supplied from the bottom of the tower at 60 parts by weight / hour. Simultaneously, saponification was performed by supplying a methanol solution containing 6 mmol equivalent of sodium hydroxide to the acetyl group in the ethylene-vinyl acetate copolymer from the top of the column.
- a methanol solution of saponified ethylene-vinyl acetate copolymer (EVOH resin) was derived from the bottom of the column.
- the produced EVOH-based resin had an ethylene content of 38 mol% and a saponification degree of 99.7 mol%.
- the saponification temperature in the tower was 100 to 105 ° C., and the tower pressure was 0.25 MPaG.
- the prepared EVOH-based resin hydrous paste (I) was 92 parts by weight of methanol and 40 parts by weight of water with respect to 100 parts by weight of the EVOH-based resin.
- the EVOH resin content relative to the entire hydrous paste (I) was 43% by weight, and 3460 ppm (8050 ppm relative to the EVOH resin content) of sodium acetate was contained in the EVOH resin hydrous paste.
- boric acid-containing EVOH resin paste (II) Treatment with boric acid (preparation of boric acid-containing EVOH resin paste (II)) An aqueous solution containing boric acid (1200 ppm) and acetic acid (3000 ppm) was added to the EVOH resin-containing water-containing paste (I), and a boric acid-containing EVOH resin paste (II) was prepared using a line mixer. .
- the obtained boric acid-containing EVOH resin paste (II) had a resin content of 24% by weight, and was 92 parts by weight of methanol and 220 parts by weight of water with respect to 100 parts by weight of the EVOH resin. Moreover, they were 3000 ppm of acetic acid, 8050 ppm of sodium acetate, and 1200 ppm of boric acid (210 ppm of boron conversion) with respect to EVOH type-resin content.
- This tetracoordinate boron-containing EVOH resin paste (III) had an EVOH resin content of 60% by weight, and was 67 parts by weight of water and 0 parts by weight of methanol with respect to 100 parts by weight of the EVOH resin.
- the obtained boric acid-containing EVOH resin paste (II ′) had a resin content of 42% by weight, and was 95 parts by weight of methanol and 41 parts by weight of water with respect to 100 parts by weight of the EVOH resin. Moreover, they were 3000 ppm of acetic acid, 8050 ppm of sodium acetate, and 1200 ppm of boric acid (210 ppm of boron conversion) with respect to EVOH type-resin content.
- the pellet after the washing treatment has an EVOH resin content of 60% by weight, with respect to 100 parts by weight of the EVOH resin, 67 parts by weight of water, 0 parts by weight of methanol, 2400 ppm of acetic acid, 1546 ppm of boric acid (270 ppm in terms of boron), sodium
- the minute content was 210 ppm
- the phosphoric acid content was 110 ppm
- the calcium content was 10 ppm.
- boric acid-containing EVOH resin paste (II ′′) has an EVOH resin content of 60% by weight, with respect to 100 parts by weight of EVOH resin, 67 parts by weight of water, 0 part by weight of methanol, and acetic acid with respect to the EVOH resin. It was 580 ppm, boric acid 1290 ppm (225 ppm in terms of boron), sodium content 105 ppm, phosphoric acid content 56 ppm, calcium content 11 ppm.
- Example 1 As can be seen from Table 1, in Example 1 where the liquid phase kneading treatment was performed under heating and pressurization as the boric acid concentration adjusting treatment, tetracoordination of boron occurred, and the obtained EVOH resin pellets The elongational viscosity of was high. On the other hand, even when a treatment liquid having the same composition as that of Example 1 is used as a washing liquid, the conventional method for washing EVOH-based resin pellets (Comparative Example 1) does not cause tetracoordination of boron and causes elongation. The viscosity was about 60% of Example 1.
- the concentration of boric acids in the EVOH-based resin composition is adjusted using the cleaning treatment of the composition, and the boron contained in the boric acids is converted into a four-coordinate structure.
- EVOH resin compositions paste, pellets
- tetracoordinate boron are excellent in moldability even when the boric acid content is reduced, and the pellets are washed and dried for concentration adjustment. Since the number of repeated operations can be reduced, it is useful from the viewpoint of the productivity of EVOH resin pellets and the quality of EVOH resin pellets.
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Abstract
Description
水洗処理を施すことにより、水洗処理を施さない場合と比べて、フィッシュアイの発生が抑制できたことが開示されている(実施例、表1)。
ホウ素による架橋は、図1に示すように、ホウ素の3配位(平面3配位)による場合と4配位(4面体型4配位)による場合とがある。
本発明者らは、ホウ酸類を含有するEVOH系樹脂組成物について鋭意検討した結果、4配位構造のホウ素が存在することが、EVOH系樹脂の粘度上昇に有利であることを見出した。ホウ酸は、通常、樹脂組成物中において、ホウ素が3配位構造の状態で存在しているが、本発明者らは、3配位の状態で含有されているホウ素を、4配位構造に変換できる方法を見出し、本発明を完成した。
伸長歪速度が100sec-1での210℃における伸長粘度は、1.0×102~1.0×106Pa・sであることが好ましい。
ホウ酸類を含有するエチレン-ビニルエステル系共重合体ケン化物のペーストを、加温・加圧下で、ホウ酸類及びアルカリ金属塩を含有する水溶液と接触させることにより、前記ペーストに含まれるホウ酸類中のホウ素の少なくとも一部を4配位構造に変換させる工程を含み、
前記水溶液は、前記エチレン-ビニルエステル系共重合体ケン化物組成物中の該エチレン-ビニルエステル系共重合体あたりのホウ酸類の含有量がホウ素換算で1~350ppmで、該エチレン-ビニルエステル系共重合体あたりのアルカリ金属塩の含有量が金属換算で300~1000ppmとなるように、ホウ酸類及びアルカリ金属塩を含有している水溶液である。
また、前記接触は、前記エチレン-ビニルエステル系共重合体ケン化物のペーストを、前記水溶液と混錬しながら行うことが好ましい。
また、前記水溶液中のホウ酸類の濃度は、ホウ素換算で1~50ppm、アルカリ金属塩濃度は金属換算で50~1500ppmであることが好ましい。
また、本発明のEVOH系樹脂組成物の製造方法は、従来の製造方法において、EVOH系樹脂ペーストの処理液の組成を変えるだけで対応可能であり、生産上、有利である。
(1)EVOH系樹脂
本発明のEVOH系樹脂組成物に用いられるEVOH系樹脂は、通常、エチレンとビニルエステル系モノマーとの共重合体(エチレン-ビニルエステル系共重合体)をケン化させることにより得られる樹脂であり、非水溶性の熱可塑性樹脂である。上記モノマーの共重合は、公知の任意の重合法、例えば、溶液重合、懸濁重合、エマルジョン重合を用いて行うことができるが、一般的にはメタノール等の低級アルコール、特に好ましくはメタノールを溶媒とする溶液重合が用いられる。得られたエチレン-ビニルエステル系共重合体のケン化も公知の方法で行い得る。
このようにして製造されるEVOH系樹脂は、エチレン由来の構造単位とビニルアルコール構造単位を主とし、場合によっては、ケン化されずに残存した若干量のビニルエステル構造単位を含む。
かかる共重合に用いられる溶媒としては、通常、メタノール、エタノール、プロパノール、ブタノール等の低級アルコールやアセトン、メチルエチルケトン等のケトン類等が挙げられ、工業的には、メタノールが好適に使用される。
ケン化に使用される触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、ナトリウムエチラート、カリウムメチラート、リチウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒、硫酸、塩酸、硝酸、メタンスルフォン酸、ゼオライト、カチオン交換樹脂等の酸触媒が挙げられる。
前記コモノマーとしては、プロピレン、1-ブテン、イソブテン等のオレフィン類、3-ブテン-1-オール、3-ブテン-1,2-ジオール、4-ペンテン-1-オール、5-ヘキセン-1,2-ジオール等のヒドロキシ基含有α-オレフィン類やそのエステル化物、アシル化物などの誘導体;2-メチレンプロパン-1,3-ジオール、3-メチレンペンタン-1,5-ジオール等のヒドロキシアルキルビニリデン類;1,3-ジアセトキシ-2-メチレンプロパン、1,3-ジプロピオニルオキシ-2-メチレンプロパン、1,3-ジブチロニルオキシ-2-メチレンプロパン等のヒドロキシアルキルビニリデンジアセテート類;アクリル酸、メタクリル酸、クロトン酸、(無水)フタル酸、(無水)マレイン酸、(無水)イタコン酸等の不飽和酸類あるいはその塩あるいは炭素数1~18のモノまたはジアルキルエステル類;アクリルアミド、炭素数1~18のN-アルキルアクリルアミド、N,N-ジメチルアクリルアミド、2-アクリルアミドプロパンスルホン酸あるいはその塩、アクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のアクリルアミド類;メタアクリルアミド、炭素数1~18のN-アルキルメタクリルアミド、N,N-ジメチルメタクリルアミド、2-メタクリルアミドプロパンスルホン酸あるいはその塩、メタクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のメタクリルアミド類;N-ビニルピロリドン、N-ビニルホルムアミド、N-ビニルアセトアミド等のN-ビニルアミド類;アクリルニトリル、メタクリルニトリル等のシアン化ビニル類;炭素数1~18のアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルコキシアルキルビニルエーテル等のビニルエーテル類;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化ビニル等のハロゲン化ビニル化合物類;トリメトキシビニルシラン等のビニルシラン類;酢酸アリル、塩化アリル等のハロゲン化アリル化合物類;アリルアルコール、ジメトキシアリルアルコール等のアリルアルコール類;トリメチル-(3-アクリルアミド-3-ジメチルプロピル)-アンモニウムクロリド、アクリルアミド-2-メチルプロパンスルホン酸等のコモノマーが挙げられる。
かかる1,2-ジオール構造を側鎖に有するEVOH系樹脂は、側鎖に1,2-ジオール構造単位を含むものである。かかる1,2-ジオール構造単位とは、具体的には下記一般式(1)で示される構造単位である。
R1~R3は、通常炭素数1~30、特には炭素数1~15、さらには炭素数1~4の飽和炭化水素基または水素原子が好ましく、水素原子が最も好ましい。R4~R6は、通常炭素数1~30、特には炭素数1~15、さらには炭素数1~4のアルキル基または水素原子が好ましく、水素原子が最も好ましい。特に、R1~R6がすべて水素であるものが最も好ましい。
なお、本発明の効果を阻害しない範囲であれば結合鎖であってもよい。かかる結合鎖としては特に限定されないが、例えば、アルキレン、アルケニレン、アルキニレン、フェニレン、ナフチレン等の炭化水素鎖(これらの炭化水素はフッ素、塩素、臭素等のハロゲン等で置換されていても良い)の他、-O-、-(CH2O)m-、-(OCH2)m-、-(CH2O)mCH2-等のエーテル結合部位を含む構造;-CO-、-COCO-、-CO(CH2)mCO-、-CO(C6H4)CO-等のカルボニル基を含む構造;-S-、-CS-、-SO-、-SO2-等の硫黄原子を含む構造;-NR-、-CONR-、-NRCO-、-CSNR-、-NRCS-、-NRNR-等の窒素原子を含む構造;-HPO4-等のリン原子を含む構造などのヘテロ原子を含む構造;-Si(OR)2-、-OSi(OR)2-、-OSi(OR)2O-等の珪素原子を含む構造;-Ti(OR)2-、-OTi(OR)2-、-OTi(OR)2O-等のチタン原子を含む構造;-Al(OR)-、-OAl(OR)-、-OAl(OR)O-等のアルミニウム原子を含む構造などの金属原子を含む構造等が挙げられる。なお、Rは各々独立して任意の置換基であり、水素原子、アルキル基が好ましく、またmは自然数であり、通常1~30、好ましくは1~15、さらに好ましくは1~10である。その中でも製造時あるいは使用時の安定性の点で-CH2OCH2-、および炭素数1~10の炭化水素鎖が好ましく、さらには炭素数1~6の炭化水素鎖、特には炭素数1であることが好ましい。
本発明のEVOH系樹脂組成物に含有されるホウ素は、通常、ホウ酸類、すなわちホウ酸又はその塩として含有されている。かかるホウ酸塩としては、例えばホウ酸カルシウム、ホウ酸コバルト、ホウ酸亜鉛(四ホウ酸亜鉛,メタホウ酸亜鉛等)、ホウ酸アルミニウム・カリウム、ホウ酸アンモニウム(メタホウ酸アンモニウム、四ホウ酸アンモニウム、五ホウ酸アンモニウム、八ホウ酸アンモニウム等)、ホウ酸カドミウム(オルトホウ酸カドミウム、四ホウ酸カドミウム等)、ホウ酸カリウム(メタホウ酸カリウム、四ホウ酸カリウム、五ホウ酸カリウム、六ホウ酸カリウム、八ホウ酸カリウム等)、ホウ酸銀(メタホウ酸銀、四ホウ酸銀等)、ホウ酸銅(ホウ酸第2銅、メタホウ酸銅、四ホウ酸銅等)、ホウ酸ナトリウム(メタホウ酸ナトリウム、二ホウ酸ナトリウム、四ホウ酸ナトリウム、五ホウ酸ナトリウム、六ホウ酸ナトリウム、八ホウ酸ナトリウム等)、ホウ酸鉛(メタホウ酸鉛、六ホウ酸鉛等)、ホウ酸ニッケル(オルトホウ酸ニッケル、二ホウ酸ニッケル、四ホウ酸ニッケル、八ホウ酸ニッケル等)、ホウ酸バリウム(オルトホウ酸バリウム、メタホウ酸バリウム、二ホウ酸バリウム、四ホウ酸バリウム等)、ホウ酸ビスマス、ホウ酸マグネシウム(オルトホウ酸マグネシウム、二ホウ酸マグネシウム、メタホウ酸マグネシウム、四ホウ酸三マグネシウム、四ホウ酸五マグネシウム等)、ホウ酸マンガン(ホウ酸第1マンガン、メタホウ酸マンガン、四ホウ酸マンガン等)、ホウ酸リチウム(メタホウ酸リチウム、四ホウ酸リチウム、五ホウ酸リチウム等)などの他、ホウ砂、カーナイト、インヨーアイト、コトウ石、スイアン石、ザイベリ石等のホウ酸塩鉱物などが挙げられ、好適にはホウ砂、ホウ酸、ホウ酸ナトリウム(メタホウ酸ナトリウム、二ホウ酸ナトリウム、四ホウ酸ナトリウム、五ホウ酸ナトリウム、六ホウ酸ナトリウム、八ホウ酸ナトリウム等)が挙げられる。
本発明の樹脂組成物は、アルカリ金属塩を含有することが好ましい。アルカリ金属塩は、ケン化反応時に用いたアルカリ触媒の残存物として、あるいは、熱安定化剤として添加されることにより、従来より、通常、樹脂組成物中に含有されている。一方、ホウ酸類は、EVOH系樹脂の架橋剤として知られている。そして、EVOH系樹脂組成物におけるホウ素の配位構造は、共存するアルカリ金属の含有比率の影響を受けることが判明した。本発明の樹脂組成物においては、ホウ酸類のホウ素が安定的に4配位構造で存在できるような濃度で、アルカリ金属塩が含有されていることが好ましい。よって、アルカリ触媒を用いない場合、熱安定化剤としてアルカリ金属塩以外の熱安定化剤が用いられた場合であっても、本発明の樹脂組成物では、後述する本発明の組成物の製造方法において、アルカリ金属塩の含有量が所定濃度となるような含有処理により、添加されることが好ましい。
これらのうち、ケン化工程で発生する副生物と同じであるとの観点から、酢酸のアルカリ金属塩が好ましい。また、金属の種類としては、ナトリウム塩、カリウム塩が好ましく用いられ、より好ましくはナトリウム塩である。
また、アルカリ金属塩がナトリウム塩の場合、ナトリウム塩の含有量は特に限定しないが、EVOH系樹脂あたり、ナトリウム換算で300ppm以上とすることが好ましく、より好ましくは300~1000ppm、さらに好ましくは310~1000ppm、特に好ましくは320~800ppmである。
ホウ酸類による架橋構造は、ナトリウムやカリウムのようなアルカリ金属又はカルシウムやマグネシウム等のアルカリ土類金属の影響をうける。これらの金属塩のうち、塩基性が強いアルカリ金属を用いる場合にホウ素が4配位構造を形成しやすく、特にナトリウム塩である場合にホウ素が4配位構造を形成しやすいので、好ましく用いられる。
本発明の樹脂組成物は、本発明の効果を阻害しない範囲(通常、樹脂組成物中の5重量%以下)において、一般にEVOH系樹脂に配合する配合剤などを含有してもよい。
伸長粘度は、一定の歪速度、一定温度下での粘度を溶融樹脂の進行変形下の粘度で表され、流路の縮小部や多層合流部など、樹脂の流速が加減速する箇所の樹脂流動を支配している。従って、伸長粘度は、溶融紡糸、フィルム成形、ブロー成型などの溶融成形性、加工性の評価指標として用いることができる。伸長粘度が高いほど、成形加工性は良好である。
本発明の樹脂組成物、すなわち、4配位構造のホウ素を含有するEVOH系樹脂組成物は、以下のようにして製造できる。
本発明のEVOH系樹脂組成物の製造方法は、ホウ酸類を含有するEVOH系樹脂組成物のペースト(以下「ホウ酸類含有EVOH系樹脂ペースト(II)」という)を、加温・加圧下で、ホウ酸類及びアルカリ金属塩を含有する水溶液(処理液)と接触させることにより、前記ペーストに含有されるホウ酸類中のホウ素の少なくとも一部を4配位構造に変換させる工程(以下、「4配位化処理工程」と称することがある)を含むところに特徴があり、前記4配位化処理工程における、
(1)4配位化処理前EVOH系樹脂ペーストの組成;
(2)4配位化処理前EVOH系樹脂ペーストの温度;
(3)4配位化処理液の組成;
(4)4配位化処理液の温度;
(5)4配位化処理容器内の圧力;
(6)4配位化処理時間;
(7)4配位化処理後EVOHペーストのアルカリ金属含有量;又は
(8)上記(1)~(7)から選ばれる2以上の組み合わせ
により、4配位構造に変換させることができる。
EVOH系樹脂含水ペースト(I)は、ホウ酸類含有処理に供されるペースト状のEVOH系樹脂(又はEVOH系樹脂組成物)で、4配位化処理工程に供されるEVOH系樹脂ペーストとは区別される。
EVOH系樹脂含水ペースト(I)は、通常、水及びアルコールを含有したゴム状またはゼリー状の、柔らかく流動性がある状態のEVOH系樹脂含水組成物である。
ケン化により生じたカルボン酸の一部は残存している。このため、ケン化触媒がアルカリ触媒の場合、カルボン酸金属塩となって副生される場合がある。例えば、上記ビニルエステルとして酢酸ビニルを用い、水酸化ナトリウムを触媒として用いた場合、アルカリ金属塩である酢酸ナトリウムが副生物として、EVOH系樹脂含水ペースト(I)中に含まれ得る。
かかるEVOH系樹脂含水ペースト(I)中に含まれ得るアルカリ金属塩の含有量は、EVOH系樹脂あたりのアルカリ金属換算で、通常1000~4000ppm残存し得る。
上記棚段塔式では、その理論段数は通常2~20段であり、好ましくは5~15段である。また、充填塔式でも、それに準じて充填物量が設定される。このような塔型容器に、EVOH系樹脂のアルコール溶液と水蒸気および/または水とが導入され、両者が接触することによってEVOH系樹脂溶液中のアルコールの一部が水に置換され、EVOH系樹脂含水ペースト(I)が導出される。
ホウ酸類含有EVOH系樹脂ペースト(II)は、上記で調製したEVOH系樹脂含水ペースト(I)にホウ酸類を含有させることにより調製される。
ホウ酸類含有液におけるホウ酸類の濃度は、最終的に得ようとするEVOH系樹脂組成物の濃度により適宜選択される。通常、水に対するホウ酸類の含有量は、ホウ素換算にて、1~350ppmとすることが好ましく、より好ましくは10~330ppm、さらに好ましくは15~300ppmである。
かかる配合剤としては、例えば、アルカリ金属塩以外の熱安定剤、酸化防止剤、帯電防止剤、着色剤、紫外線吸収剤、滑剤、可塑剤、光安定剤、界面活性剤、抗菌剤、乾燥剤、アンチブロッキング剤、難燃剤、架橋剤、硬化剤、発泡剤、結晶核剤、防曇剤、生分解用添加剤、シランカップリング剤、酸素吸収剤などが挙げられる。
ホウ酸類含有EVOH系樹脂ペースト(II)において、ホウ酸類濃度、アルカリ金属塩濃度を上記範囲に調節しておくことにより、次に行うホウ素4配位化変換が効率的に行うことができる。
ホウ酸類含有EVOH系樹脂ペースト(II)を、加温・加圧下で、処理液と接触させることにより、含有されているホウ素を4配位化する。4配位化処理を行うと同時に、ホウ酸類濃度、及びアルカリ金属塩濃度を、最終的に得ようとするEVOH系樹脂組成物におけるこれらの濃度への調節を行うことが好ましい。
処理液の組成は、最終的に得ようとするEVOH系樹脂組成物の組成、使用するホウ酸類含有EVOH系樹脂ペースト(II)の組成に応じて、適宜設定される。すなわち、4配位化処理に用いる処理液は、ホウ酸類含有EVOH系樹脂ペースト(II)のホウ酸類及びアルカリ金属塩の含有量を、最終的に得ようとするEVOH系樹脂組成物の組成(ホウ酸類濃度、アルカリ金属塩濃度)に調節するために用いられる水溶液である。
また、リン酸化合物を添加する場合、処理後に得られる4配位ホウ素含有EVOH系樹脂ペースト(III)中のリン酸化合物の含有量は、EVOH系樹脂ペーストに対してリン酸根換算で(イオンクロマトグラフィーにて分析)で通常、リン酸根換算で1~1000ppmである。上記含有量が少なすぎると溶融成形時が着色しやすくなる傾向が見られ、逆に多すぎると成形物のゲルやフィッシュアイが発生しやすくなる場合がある。従って、処理液におけるリン酸化合物の濃度は、通常1~3000ppmであり、好ましくは10~1000ppm、さらに好ましくは20~500ppmである。
上記4配位化処理液との接触は、加温・加圧下で行う。さらにはせん断力を付与した状態で、行うことが好ましい。
連続処理方法としては、ホウ酸類含有EVOH系樹脂ペースト(II)に連続的に処理液を供給して晒す方法;処理液中に連続的にホウ酸類含有EVOH系樹脂ペースト(II)を容器内に導入する方法;容器内に処理液、ホウ酸類含有EVOH系樹脂ペースト(II)の双方を導入する方法などが挙げられる。
また、導入されるホウ酸類含有EVOH系樹脂ペースト(II)の温度は、通常50~120℃であり、好ましくは60~120℃である。
上記導入されたペーストと濃度調整処理液との接触は向流、並流のいずれでも可能であるが、置換効率の観点から向流で接触させることが好ましい。
処理液とホウ酸類含有EVOH系樹脂ペースト(II)との接触処理は、せん断力を付与しながら行うことが好ましい。具体的には、処理液中でホウ酸類含有EVOH系樹脂ペースト(II)にせん断力を付与しながら接触させることが好ましい。以下、かかる操作を液相混錬と称することがある。
上記液相混錬は、ホウ酸類含有EVOH系樹脂ペースト(II)をスクリュー等により混錬しながら表面更新し、かつ処理液を連続的に供給し、当該EVOH系樹脂ペースト(II)内部まで、均一に処理液と接触させるものである。
また、処理水の滞留時間は、通常0.5~20時間であり、好ましくは0.5~15時間である。
4配位ホウ素含有EVOH系樹脂ペースト(III)のペレット化方法は、特に限定しないが、以下の方法で行うことが好ましい。
4配位ホウ素含有EVOH系樹脂ペースト(III)を、孔又はスリットを通して押出し、カットしてペレットを得る方法(例えばホットカットやアンダーウォーターカット等)や、シート状またはストランド状に押し出して冷却固化し、得られたストランドまたはシートをカットしてペレットを得る方法があげられる。得られたペレットを各種の公知の乾燥方法にて乾燥すればよい。
従って、本発明の製造方法により得られるEVOH系樹脂ペレットは、ホウ素換算で、ホウ酸類の量が従来よりも低減しているにもかかわらず、対応するホウ素換算濃度を含有するEVOH系樹脂組成物と比べて、高い伸長粘度を有する。
伸長粘度は、流路の縮小部や多層合流部など、樹脂の流速が加減速する箇所の樹脂流動を支配しており、従来の溶融粘度評価ではわからない成形性の違いを評価できる。
尚、例中「部」とあるのは、重量基準を意味する。また、単位「MPaG」は、ゲージ値における単位であり、絶対圧と大気圧の差を示すものである。
(1)EVOH系樹脂組成物中のホウ酸類量(ホウ素換算)
EVOH系樹脂組成物(ペレット)0.1gを濃硝酸と共にマイクロウェーブ分解法にて処理して得られる溶液を純水にて定容(0.75mg/ml)したものを検液とし、ICP発光分析法(ICP-AES)(測定器:アジレント・テクノロジー社の720-ES型を使用)で測定した。当該測定されるホウ素含有量は、ホウ酸類に由来するホウ素量に該当する。
固体NMRを使用してホウ素核の構造を測定した。サンプルを液体窒素雰囲気下で冷凍粉砕にて細かく粉砕し、それを外径4mmのジルコニアローターに充填した。図3に示すパルスシーケンスにより、下記測定条件にて室温で測定した。
得られたスペクトルを図4に示す。2次元スペクトルはEVOH系樹脂が有するホウ酸類のホウ素部分の構造で3配位と4配位の構造が存在している。上側の1次元スペクトルはMAS軸のスペクトル、左側の四角で囲んだスペクトルは等方軸スペクトルである。4配位ホウ素は等方軸スペクトルをガウス関数にて波形分離し、各々の面積から、下記式により算出した。
11B (B0=128MHz; I=3/2)
観測核種(主なパラメータ)
11Bパルス HP1 : 4.15μs, HP2 : 1.38μs, SP1 : 30.00μs
FID信号取込時間:10ms
デカップルシーケンス:tppm15
積算回数(×FID):840×12
観測中心:0ppm
観測幅:232ppm
待ち時間:5sec
EVOH系樹脂の含溶剤試料を乾燥し、硫酸を加え炭化・灰化した後、硝酸を加えて加熱溶解し、得られた溶液に含有されるナトリウム量を原子吸光分光光度計(日立製作所製、Z-5310)を用いて原子吸光分析法により分析した。
ペレット約35gをバレルに詰め、バレル温度210℃にて5分間予熱を行った後に溶融樹脂を押し出し、伸長歪速度が100sec-1での伸長粘度を測定した。
なお、伸長粘度の測定には、GOTTFERT製ツインキャピラリーレオメーター「RG20」を用いた。
(1)EVOH系樹脂の合成
冷却コイルを備えた重合容器に酢酸ビニル420重量部、メタノール90重量部、アセチルパーオキシド180ppm(対酢酸ビニル)を仕込み、系内を窒素ガスで置換した。次に、系内をエチレンで置換し、エチレン圧が4.7MPaGとなるまで、エチレンを圧入した。
その後、撹拌しながら、67℃まで昇温し、酢酸ビニルとエチレンの共重合反応を開始させた。6時間後、重合反応を停止した。酢酸ビニルの重合率は、酢酸ビニルの仕込む量に対して63重量%であり、エチレン含有量38モル%のエチレン-酢酸ビニル共重合体が得られた。得られたエチレン-酢酸ビニル共重合体の溶液を蒸留塔に供給し、塔下部からメタノール蒸気を導入することにより、未反応の酢酸ビニルを除去し、エチレン-酢酸ビニル共重合体のメタノール溶液(樹脂分濃度48重量%)を得た。
上記で得られたEVOH系樹脂のメタノール溶液を、80重量部/時間で、塔型洗浄容器(10段の棚段塔)の塔頂から2段目の棚板に供給し、130℃の水蒸気を20重量部/時間で最下段の棚板から連続的に供給することにより、EVOH系樹脂のメタノール溶液と水蒸気とを、棚段塔内で向流で接触させ、塔型洗浄容器底部のペースト導出口より、EVOH系樹脂含水ペースト(I)を導出した。EVOH系樹脂の含水処理時の塔型洗浄容器内の温度は100~105℃で、該容器内の圧力は0.15MPaGであった。
調製したEVOH系樹脂含水ペースト(I)は、EVOH系樹脂100重量部に対し、メタノール92重量部、水40重量部であった。含水ペースト(I)全体に対するEVOH系樹脂分は43重量%であり、EVOH系樹脂含水ペースト中に3460ppm(EVOH系樹脂分に対して8050ppm)の酢酸ナトリウムが含有されていた。
EVOH系樹脂含水ペースト(I)に対して、ホウ酸(1200ppm)及び酢酸(3000ppm)を含有する水溶液を添加して、ラインミキサーを用いて、ホウ酸類含有EVOH系樹脂ペースト(II)を調製した。
得られたホウ酸類含有EVOH系樹脂ペースト(II)は、樹脂分24重量%であり、EVOH系樹脂100重量部に対して、メタノール92重量部、水220重量部であった。また、EVOH系樹脂分に対して、酢酸3000ppm、酢酸ナトリウム8050ppm、ホウ酸1200ppm(ホウ素換算210ppm)であった。
ホウ酸類含有EVOH系樹脂ペースト(II)を、混錬装置を備えた横型容器の上流部から供給し、下流部から下記組成を有する処理液を供給して、処理液との接触処理を行った。
スクリュー回転数:60rpm
スクリューと槽内壁との間のクリアランス:8mm
槽内温度(排出口前の水温):120℃
酢酸:230ppm
酢酸ナトリウム:400ppm
ホウ酸:122ppm(ホウ素換算:21ppm)
リン酸2水素ナトリウム:190ppm
リン酸カルシウム:28ppm
EVOH系樹脂ペースト(II)の導入量:26重量部/時間
導入時のEVOH系樹脂ペースト(II)の温度:80℃
EVOH系樹脂ペースト(II)滞留時間:4時間
処理液導入量:30重量部/時間
導出量:10重量部/時間
圧力:0.20MPaG
浴比(処理液重量/仕込みEVOH系樹脂分):4.8
この4配位ホウ素含有EVOH系樹脂ペースト(III)は、EVOH系樹脂分60重量%であり、EVOH系樹脂100重量部に対して、水67重量部、メタノール0重量部であった。また、EVOH系樹脂に対する酢酸1220ppm、ホウ酸1546ppm(ホウ素換算270ppm)、ナトリウム分435ppm、リン酸分55ppm、カルシウム分8ppmであった。
得られた4配位ホウ素含有EVOH系樹脂ペースト(III)を、スリットから溶融押出し、冷却固化して、EVOH系樹脂ペーストのシートを得た。このシートを短冊状に裁断後、乾燥して、EVOH系樹脂ペレットを得た。
こうして得られたペレットを、上記方法にて伸長粘度及びホウ素配位構造を測定した。結果を表1に示す。
(1)ホウ酸類含有EVOH系樹脂ペースト(II)の調製
実施例1と同様にして、EVOH系樹脂を合成し、EVOH系樹脂含水ペースト(I)を調製した。
EVOH系樹脂含水ペースト(I)に対して、ホウ酸(1200ppm)及び酢酸(3000ppm)を含有する水/メタノール溶液(水/メタノール=30/70:重量比)を添加して、ラインミキサーを用いて、ホウ酸類含有EVOH系樹脂ペースト(II’)を調製した。
得られたホウ酸類含有EVOH系樹脂ペースト(II’)は、樹脂分42重量%であり、EVOH系樹脂100重量部に対して、メタノール95重量部、水41重量部であった。また、EVOH系樹脂分に対して、酢酸3000ppm、酢酸ナトリウム8050ppm、ホウ酸1200ppm(ホウ素換算210ppm)であった。
含水率を調整したホウ酸類含有EVOH系樹脂ペースト(II’)を、5℃の冷却水中にストランド状に押出し、カッティングして、EVOH系樹脂ペレットを製造した。
上記で製造したEVOH系樹脂ペレットを、塔型洗浄槽の上部から、下記条件で供給し、実施例1で用いた処理液と同様の組成を有する洗浄液を用いて、以下の条件で洗浄処理を行い、洗浄槽の底部から、ペレットを連続的に抜き取った。
撹拌なし
塔内温度(排出口前の水温):30℃
実施例1と同じ
EVOH系樹脂ペレットの導入量:12重量部/時間
導入されるEVOH系樹脂ペレットの温度:30℃
EVOH系樹脂ペレットの滞留時間:4時間
洗浄液の導入量:24重量部/時間
ペレット導出量:12重量部/時間
圧力:常圧
浴比(洗浄水重量/仕込みEVOH系樹脂分):4.8
(1)ホウ素含有EVOH系樹脂ペースト(II)の調製
実施例1と同様にして、EVOH系樹脂を合成し、EVOH系樹脂含水ペースト(I)を調製後、ホウ酸含有処理を行って、実施例1と同様のホウ酸類含有EVOH系樹脂ペースト(II)を調製した。
ホウ酸類含有EVOH系樹脂ペースト(II)を、横型洗浄槽の上流部から供給し、下流部から下記組成を有する洗浄液を供給して、液相混錬による洗浄処理を行った。
スクリュー回転数:60rpm
スクリューと槽内壁との間のクリアランス:8mm
槽内温度(排出口前の水温):120℃
実施例1と同じ
EVOH系樹脂ペースト導入量:26重量部/時間
導入時のEVOH系樹脂ペーストの温度:120℃
EVOH系樹脂ペースト滞留時間:16時間
洗浄液導入量:30重量部/時間
導出量:10重量部/時間
圧力:0.2MPa
浴比(洗浄液重量/仕込みEVOH系樹脂分):4.8
このホウ酸類含有EVOH系樹脂ペースト(II”)は、EVOH系樹脂分60重量%であり、EVOH系樹脂100重量部に対して、水67重量部、メタノール0重量部、EVOH系樹脂分に対する酢酸580ppm、ホウ酸1290ppm(ホウ素換算225ppm)、ナトリウム分105ppm、リン酸分56ppm、カルシウム分11ppmであった。
洗浄されたホウ酸類含有EVOH系樹脂ペースト(II”)を、実施例1と同様の方法でペレット化して、短冊状のEVOH系樹脂ペレットを得た。
こうして得られたペレットを、上記方法にて伸長粘度及びホウ素配位構造を測定した。結果を表1に示す。
一方、実施例1と同じ組成を有する処理液を洗浄液として用いても、従来のように、EVOH系樹脂ペレットを洗浄する方法(比較例1)では、ホウ素の4配位化は生じず、伸長粘度は、実施例1の60%程度であった。
尚、比較例2で使用した処理液の組成は実施例1と同じであったが、処理時間が長すぎたために、共存するナトリウム濃度が下がりすぎて、3配位構造に戻ってしまったと考えられる。
Claims (12)
- エチレン-ビニルエステル系共重合体ケン化物とホウ酸類を含有する樹脂組成物において、
前記ホウ酸類は、4配位構造のホウ素を含有していることを特徴とする樹脂組成物。 - 前記ホウ酸類の含有量は、前記エチレン-ビニルエステル系共重合体ケン化物あたり、ホウ素換算で1~350ppmであることを特徴とする請求項1に記載の樹脂組成物。
- 前記ホウ酸類中のホウ素における4配位構造のホウ素の割合は、10~99モル%であることを特徴とする請求項1又は2に記載の樹脂組成物。
- アルカリ金属塩を、エチレン-ビニルエステル系共重合体ケン化物あたり、金属換算で、300~1000ppm含有することを特徴とする請求項1~3のいずれかに記載の樹脂組成物。
- 前記アルカリ金属塩は、ナトリウム塩であることを特徴とする請求項4に記載の樹脂組成物。
- 前記ホウ酸類に対する前記アルカリ金属塩の含有量は、重量比率(アルカリ金属塩のアルカリ金属換算量/ホウ酸類のホウ素換算量)として、0.8~10であることを特徴とする請求項1~5のいずれかに記載の樹脂組成物。
- 伸長歪速度が100sec-1での210℃における伸長粘度が1.0×102~1.0×106Pa・sであることを特徴とする請求項1~6のいずれかに記載の樹脂組成物。
- 4配位構造のホウ素を含有するエチレン-ビニルエステル系共重合体ケン化物組成物の製造方法であって、
ホウ酸類を含有するエチレン-ビニルエステル系共重合体ケン化物のペーストを、加温・加圧下で、ホウ酸類及びアルカリ金属塩を含有する水溶液と接触させることにより、前記ペーストに含まれるホウ酸類中のホウ素の少なくとも一部を4配位構造に変換させる工程を含み、
前記水溶液は、前記エチレン-ビニルエステル系共重合体ケン化物組成物中の該エチレン-ビニルエステル系共重合体あたりのホウ酸類の含有量がホウ素換算で1~350ppmで、該エチレン-ビニルエステル系共重合体あたりのアルカリ金属塩の含有量が金属換算で300~1000ppmとなるように、ホウ酸類及びアルカリ金属塩を含有している水溶液であることを特徴とするエチレン-ビニルエステル系共重合体ケン化物組成物の製造方法。 - 前記加温・加圧は、前記変換処理工程が行われる系内の温度として、50~150℃であり、該系内の圧力と大気圧の差として0.01~1MPaGであることを特徴とする請求項8に記載の製造方法。
- 前記接触は、前記エチレン-ビニルエステル系共重合体ケン化物のペーストを、前記水溶液と混錬しながら行う請求項8又は9に記載の製造方法。
- 前記エチレン-ビニルエステル系共重合体ケン化物のペーストは、エチレン-ビニルエステル系共重合体ケン化物あたり、ホウ酸類をホウ素換算で1~350ppm、前記アルカリ金属塩を金属換算で1000~4000ppm含有していることを特徴とする請求項8~10のいずれかに記載の製造方法。
- 前記水溶液中のホウ酸類の濃度は、ホウ素換算で1~50ppm、アルカリ金属塩濃度は金属換算で50~1500ppmであることを特徴とする請求項8~11のいずれかに記載の製造方法。
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Publication number | Publication date |
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EP3395890A1 (en) | 2018-10-31 |
US20180371229A1 (en) | 2018-12-27 |
JPWO2017110676A1 (ja) | 2018-10-11 |
EP3395890A4 (en) | 2019-08-07 |
TWI802532B (zh) | 2023-05-21 |
TW201736480A (zh) | 2017-10-16 |
CN108473746B (zh) | 2023-06-02 |
US11161970B2 (en) | 2021-11-02 |
CN108473746A (zh) | 2018-08-31 |
EP3395890B1 (en) | 2024-04-24 |
JP6848856B2 (ja) | 2021-03-24 |
SG11201804928QA (en) | 2018-07-30 |
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