JP7119357B2 - Ethylene-vinyl alcohol copolymer resin composition and multilayer structure - Google Patents

Description

The present invention relates to an ethylene-vinyl alcohol copolymer resin composition. It relates to the multilayer structure used.

Ethylene-vinyl alcohol copolymers (hereinafter sometimes abbreviated as "EVOH"), especially saponified ethylene-vinyl acetate copolymers, are excellent in various properties such as gas barrier properties and mechanical strength. Therefore, it is widely used in various applications such as films, sheets, containers, and fibers.
The saponified product is produced by copolymerizing ethylene and vinyl acetate, removing unreacted vinyl acetate, and then saponifying the obtained ethylene-vinyl acetate copolymer.

In order to manufacture various molded articles using such EVOH, melt molding such as extrusion molding and injection molding is performed. Therefore, thermal deterioration is likely to occur, and the quality of the molded product may be deteriorated, such as the occurrence of fish eyes and gel-like lumps (bubs).

As a method for improving such thermal deterioration at high temperatures, for example, the ratio of the total number of carboxylic acid units and lactone ring units at the polymer end of EVOH to the total number of ethylene units, vinyl alcohol units, and vinyl ester units in EVOH. is 0.12 mol % or less (see, for example, Patent Document 1).

International publication WO2004/092234

However, although the technology disclosed in Patent Document 1 has some improvement effect on heat deterioration, the evaluation method is to sample the film after 50 hours and visually confirm gel-like lumps (bubs) in the film. However, with the advancement of technology in recent years, there is a demand for further improvement. For example, there is a demand for an EVOH that is excellent in suppressing thermal decomposition even at high temperatures and that does not cause offensive odors or coloration even when processed at high temperatures.

Therefore, in order to meet such demands, the present invention provides an EVOH resin composition that has excellent thermal stability, such as excellent suppression of thermal decomposition even at high temperatures, and does not have an offensive odor or color even when processed at high temperatures, and this EVOH. A multilayer structure using a resin composition is provided.

In view of the above circumstances, the present inventors have conducted intensive research and found that the terminal structure of EVOH contains a conjugated polyene compound in a very small proportion with respect to an EVOH resin composition containing more lactone rings than carboxylic acids. It is possible to obtain an EVOH resin composition that can be used as a raw material that has excellent thermal stability, has no odor or coloration even when processed at high temperatures, and is particularly resistant to color change due to long-term retention. I found

From the above, the present invention provides a terminal structure of EVOH in which the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) is 55. A first aspect of the present invention is an EVOH resin composition containing EVOH in an amount of mol % or more and a conjugated polyene compound, wherein the content of the conjugated polyene compound in the resin composition is 800 ppm or less on a weight basis. .

A second aspect of the present invention is a multilayer structure having at least one layer containing the EVOH resin composition.

In the EVOH resin composition of the present invention, in the EVOH terminal structure, the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) is 55. It contains EVOH in an amount of mol % or more, and a conjugated polyene compound is contained in a proportion of 800 ppm or less (ppm is weight basis, the same shall apply hereinafter) to the resin composition. According to this constitution, the EVOH has excellent thermal stability even at high temperatures, and even if the EVOH resin composition is processed at high temperatures, no foul odor or coloration occurs. In particular, since the change in coloration of specks derived from long-term retention is small, a molded product with a good appearance can be obtained.

Further, when the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) is 0.01 to 0.3 mol% with respect to the total amount of the EVOH monomer units, Thermal stability is further improved.

Furthermore, when the content (Y) of the lactone ring is 0.01 to 0.3 mol % with respect to the total amount of the EVOH monomer units, the thermal stability is further improved.

Further, when the content (X) of the carboxylic acid is 0.01 to 0.3 mol % with respect to the total amount of the EVOH monomer units, the thermal stability is further improved.

In addition, since the multilayer structure of the present invention has at least one layer containing the EVOH resin composition of the present invention, which has excellent thermal stability, it has excellent thermal stability, and in particular, color change is suppressed, and has the advantage that its quality is less susceptible to heat.

1 is a chart of ¹ H-NMR measurement of a typical EVOH in DMSO-D6 solvent. FIG. 1 is a chart of ¹ H-NMR measurement of a typical EVOH in heavy water/ethanol-D6 solvent. FIG.

Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

In the EVOH resin composition of the present invention, the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the EVOH terminal structure is 55. A first feature is that it contains EVOH in an amount of mol % or more. A second feature is that the resin composition contains a conjugated polyene compound, and the content ratio of the conjugated polyene compound to the resin composition is 800 ppm or less.

That is, since the lactone ring is chemically more stable than carboxylic acids, it is presumed that the decomposition reaction that occurs during heating hardly progresses and that the lactone ring is excellent in thermal stability at high temperatures. The conjugated polyene structure of the conjugated polyene compound has an effect of trapping radicals generated during high-temperature heating, and is therefore considered to contribute to thermal stability at high temperatures. However, it has been found that if the content of the conjugated polyene compound is too large, and when the resin is formed with lumps derived from long-term retention in extrusion molding or the like, the lumps tend to change color at high temperatures. As a result of further studies, the inventors of the present invention have found that when the conjugated polyene compound is contained in the EVOH resin composition in an amount of 800 ppm or less, the thermal stability at high temperatures is further improved, and furthermore, high-temperature heating is achieved. It was found that the change in coloration of the time-consuming matter can be suppressed to a range that poses no practical problem.

First, the EVOH used in the EVOH resin composition of the present invention is usually a resin obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying it. It is a water-insoluble thermoplastic resin called coalescence or saponified ethylene-vinyl ester copolymer. Any polymerization method known in the art, such as solution polymerization, suspension polymerization, and emulsion polymerization, can be used. In general, solution polymerization using a lower alcohol such as methanol or ethanol, preferably methanol as a solvent, is used. Used. Saponification of the resulting ethylene-vinyl ester copolymer can also be carried out by a known method.
That is, the EVOH is mainly composed of ethylene structural units and vinyl alcohol structural units, and if necessary, usually contains a small amount of residual vinyl ester structural units that have not been saponified.

As the vinyl ester-based monomer, vinyl acetate is typically used because of its easy availability on the market and good efficiency in removing impurities during production. In addition, for example, aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate, and benzoin. Examples thereof include aromatic vinyl esters such as vinyl acid, and aliphatic vinyl esters usually having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, particularly preferably 4 to 7 carbon atoms. These are usually used alone, but if necessary, multiple types may be used at the same time.

The content of ethylene structural units in the EVOH is a value measured based on ISO14663, and is usually 20 to 60 mol%, preferably 25 to 50 mol%, particularly preferably 25 to 35 mol%. If the content is too small, gas barrier properties and melt moldability at high humidity will tend to deteriorate in the case of gas barrier properties, and conversely, if it is too large, gas barrier properties will tend to decline.

The degree of saponification of the vinyl ester component in the EVOH is a value measured based on JIS K6726 (however, EVOH is used as a solution uniformly dissolved in a water/methanol solvent), usually 90 to 100 mol%, preferably 95 to 100 mol %, particularly preferably 99 to 100 mol %. If the degree of saponification is too low, gas barrier properties, thermal stability, moisture resistance, etc. tend to deteriorate.

The melt flow rate (MFR) of the EVOH (210° C., load 2160 g) is usually 0.5 to 100 g/10 minutes, preferably 1 to 50 g/10 minutes, particularly preferably 2 to 35 g/10 minutes. is. If the MFR is too large, the film-forming property tends to be unstable, and if it is too small, the viscosity tends to be too high, making melt extrusion difficult.

In addition, the EVOH may further contain a structural unit derived from the following comonomer within a range (for example, 10 mol % or less) that does not impair the effects of the present invention.

The comonomers include, for example, olefins such as propylene, 1-butene and isobutene; , 3,4-dihydroxy-1-butene, 5-hexene-1,2-diol and other hydroxyl group-containing α-olefins, and their esters, 3,4-diacyloxy-1-butene (especially 3, 4-diacetoxy-1-butene, etc.), 2,3-diacetoxy-1-allyloxypropane, 2-acetoxy-1-allyloxy-3-hydroxypropane, 3-acetoxy-1-allyloxy-2-hydroxypropane, glycerin mono Vinyl ether, glycerin monoisopropenyl ether, derivatives such as acylated products, hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1,3-diacetoxy-2 Vinylidene diacetates such as -methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, 1,3-dibutyronyloxy-2-methylenepropane, acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalate acids, unsaturated acids such as (anhydrous) maleic acid and (anhydrous) itaconic acid, salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkylacrylamides having 1 to 18 carbon atoms, N,N -Acrylamides such as dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salts, acrylamidopropyldimethylamine or its acid salts or its quaternary salts, methacrylamides, N-alkylmethacrylamides having 1 to 18 carbon atoms, N,N -Methacrylamides such as dimethylmethacrylamide, 2-methacrylamide propanesulfonic acid or its salts, methacrylamidopropyldimethylamine or its acid salts or its quaternary salts, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide Vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, and alkoxyalkyl vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride, vinyl halide compounds such as vinyl bromide, vinyl compounds such as trimethoxyvinylsilane lusilanes, allyl halide compounds such as allyl acetate and allyl chloride, allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol, trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride, acrylamido-2-methylpropane Examples include comonomers such as sulfonic acid. These can be used alone or in combination of two or more.

Further, as the EVOH of the present invention, "post-modified" EVOH such as urethanized, acetalized, cyanoethylated, and oxyalkylenated EVOH can also be used.

In particular, EVOH obtained by copolymerizing hydroxyl group-containing α-olefins is preferable in terms of good secondary moldability. EVOH having chains is preferred.

The EVOH having a 1,2-diol structure in the side chain contains a 1,2-diol structural unit in the side chain, and the most preferred structure is an EVOH containing a structural unit represented by the following structural formula (1). is.

In particular, when it contains a 1,2-diol structural unit, its content is usually 0.1 to 20 mol %, preferably 0.5 to 15 mol %, particularly preferably 1 to 10 mol %.

Here, common EVOH usually has a terminal structure of a lactone ring or a carboxylic acid. As described above, the EVOH used in the EVOH resin composition of the present invention contains lactone rings relative to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure. The first characteristic is that the ratio (Y/Z) is 55 mol % or more.

That is, in the present invention, by containing more lactone rings than carboxylic acids in the terminal structure of EVOH, the EVOH is excellent in thermal stability at high temperatures and has no offensive odor or coloration even when processed at high temperatures. You can get it.

In the present invention, the lactone ring content ratio (Y/Z) is 55 mol % or more, more preferably 56 to 90 mol %, from the viewpoint of thermal stability at high temperatures. And, it is preferably 57 to 80 mol %, especially 58 to 70 mol %, further preferably 60 to 70 mol %. If the content ratio (Y/Z) is too small, the thermal stability will decrease. In addition, when the content is too large, there is a tendency that the adhesiveness with the adhesive resin layer is lowered when the multilayer structure is formed.

In the present invention, from the viewpoint of thermal stability, the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure of EVOH is equal to the total amount of the EVOH monomer units. is preferably 0.01 to 0.3 mol %, particularly 0.03 to 0.28 mol %, further 0.05 to 0.25 mol %, especially 0.1 to 0.25 mol %. 24 mol %, particularly 0.17 to 0.23 mol % are preferred. If the content is too small, the adhesion to the adhesive resin layer of the multilayer structure tends to be lowered, and if it is too large, the thermal stability tends to be lowered.

Here, the monomer unit refers to an ethylene unit represented by the following chemical formula (2), a vinyl alcohol unit represented by the following chemical formula (3), a vinyl acetate unit represented by the following chemical formula (4), and other copolymerized monomer units. refers to the total number of moles of each unit.

The content (X) of the carboxylic acid relative to the total amount of the monomer units of such EVOH is preferably 0.01 to 0.3 mol%, particularly 0.02 to 0.25 mol, in terms of thermal stability. %, more preferably 0.03 to 0.2 mol %, especially 0.05 to 0.1 mol %, especially 0.05 to 0.08 mol %. If the content is too small, the adhesion to the adhesive resin layer of the multilayer structure tends to be lowered, and if it is too large, the thermal stability tends to be lowered.

Also, the content (Y) of the lactone ring with respect to the total amount of monomer units of such EVOH is preferably 0.01 to 0.3 mol %, particularly 0.02 to 0.3 mol %, in terms of thermal stability. 25 mol %, more preferably 0.03 to 0.2 mol %, especially 0.05 to 0.15 mol %, especially 0.13 to 0.15 mol %. If the content is too small, the adhesion to the adhesive resin layer of the multilayer structure tends to be lowered, and if it is too large, the thermal stability tends to be lowered.

The carboxylic acid content (X), the lactone ring content (Y), and the lactone ring content ratio (Y/Z) are measured by NMR measurement. The carboxylic acids include carboxylic acids and carboxylic acid salts, and the content (X) of the carboxylic acids is measured as the total content thereof.
The NMR measurement is performed, for example, as follows.
<Measurement conditions>
Device name: (manufactured by AVANCE III Bruker)
Observation frequency: 400MHz
Solvent: heavy water / ethanol-D6 (weight ratio = heavy water 35: ethanol-D6 65), DMSO (dimethyl sulfoxide) -D6
Polymer concentration: 5% by weight
Measurement temperature: heavy water/ethanol-D6 70°C, DMSO-D6 50°C
Accumulation times: 16 times Pulse repetition time: 4 seconds Sample rotation speed: 20 Hz
Additive: trifluoroacetic acid

<Analysis method>
(1-1) Measurement of Terminal Methyl Amount The terminal methyl amount is calculated using ¹ H-NMR measurement (DMSO-D6, measured at 50° C.). That is, as shown in the chart of FIG. 1, the integrated value (I _Me-1 ) of terminal methyl at 0.7 to 0.95 ppm, methylene other than terminal groups at 0.95 to 1.85 ppm (ethylene unit, vinyl alcohol unit, methylene of vinyl acetate unit) integrated value (I _CH2 ), integrated value (I _OAc ) of terminal methyl in vinyl acetate unit from 1.9 to 2 ppm, vinyl alcohol from 3.1 to 4.3 ppm Using the integrated value (I _CH ) of methine in the unit, the amount of terminal methyl is calculated by the following (formula 1).

(Formula 1)
Amount of terminal methyl (mol%)
=( _IMe-1 /3)/[( _IMe-1 /3)+( _IOAc /3)+ _ICH
+{I _CH2 −2×I _CH −2×(I _OAc /3)−2×(I _Me−1 /3)}/4]

(1-2) Measurement of carboxylic acid content (X) and lactone ring content (Y) The content of carboxylic acids and lactone rings at the end of the polymer is the amount of terminal methyl obtained in (1-1). (% by mole), it is calculated using ¹ H-NMR measurement (heavy water/ethanol-D6 solvent, measured at 70°C). That is, as shown in the chart of FIG. 2, the integrated value of the terminal methyl (I _Me-2 ) from 0.7 to 1 ppm, the integrated value of the peak from 2.15 to 2.32 ppm (I _X ), 2.5 Using the integrated value (I _Y ) of the peak at ~2.7 ppm, the content (X) of carboxylic acids (mol%) and the content of lactone ring (Y) are obtained from the following (Equation 2) and (Equation 3): (mol%) are calculated respectively.

(Formula 2)
Carboxylic acid content (X) (mol%)
= Amount of terminal methyl (mol%) x ( _IX /2)/( _IMe-2 /3)

(Formula 3)
Lactone ring content (Y) (mol%)
= Terminal methyl amount (mol%) x (I _Y /2) / (I _Me-2 /3)

(1-3) Calculation of the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure The lactone ring content ratio (Y/Z) is calculated from the acid content (X) and the lactone ring content (Y) according to the following (formula 4).

(Formula 4)
Lactone ring content ratio (Y/Z) with respect to total amount (Z) of carboxylic acid content (X) and lactone ring content (Y) (mol%)
= {Y/(X + Y)} x 100

In the present invention, the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure of EVOH is 55 mol% or more. For example, the saponification step [I] of saponifying an ethylene-vinyl ester copolymer to obtain an EVOH intermediate, the chemical treatment step [II] of chemically treating the EVOH intermediate with a chemical treatment liquid, In the EVOH production method including the drying step [III] for drying the chemically treated EVOH intermediate, (1) the drying temperature in the drying step [III] is increased, and (2) the drying time in the drying step [III] is increased. and (3) increasing the concentration of carboxylic acid in the chemical treatment solution in the chemical treatment step [II]. These methods (1) to (3) may be employed singly or in combination as appropriate.

In particular, in the method (3), the saponification step [I] for saponifying an ethylene-vinyl ester copolymer to obtain an EVOH intermediate, and the chemical treatment step [I] for chemically treating the EVOH intermediate with a chemical treatment liquid. II], preferably including a drying step [III] for drying the chemically treated EVOH intermediate, and further, in the chemical treatment step [II], the carboxylic acid concentration in the chemical treatment solution is increased as described later, Specifically, a carboxylic acid and a carboxylic acid metal salt are used in combination as a chemical treating agent used in a chemical treatment solution, and the concentration of the carboxylic acid in the chemical treatment solution is increased. A method in which the weight ratio of the carboxylic acid concentration (concentration of carboxylic acid/concentration of metal ions) is 3.7 or more is preferable from the viewpoint of thermal stability at high temperatures.

The steps for obtaining the EVOH used in the present invention are described in detail below.

First, the saponification step [I] is a step of saponifying an ethylene-vinyl ester copolymer obtained by copolymerizing ethylene and a vinyl ester monomer by a conventionally known method.
At that stage, the saponified ethylene-vinyl ester copolymer (EVOH intermediate) can be formed into pellets and subjected to the following chemical treatment step [II] and drying step [III]. can.

As a method for pelletizing the EVOH intermediate, a conventionally known method can be adopted. For example, a hot EVOH intermediate in a molten state is extruded from an outlet, cut in a molten state, and then solidified by cooling to produce pellets. Examples include a cutting method and a strand cutting method in which a resin solution or slurry of an EVOH intermediate (aqueous EVOH composition) is extruded into a coagulating bath, and the EVOH strands obtained by cooling and solidifying are cut.

The shape of the pellets usually depends on the pellet manufacturing method, and may be cylindrical, spherical, rugby ball-shaped, cubic, rectangular parallelepiped, amorphous, and various other shapes. Moreover, the size of the pellets can be appropriately adjusted depending on the diameter of the nozzle of the extruder to be used, the number of cutter blades, the rotation speed of the cutter blades, and the like.

Next, the chemical treatment step [II] is a step of chemically treating the EVOH intermediate with a chemical treatment liquid containing a chemical treatment agent, and this step is performed for the purpose of imparting thermal stability and adhesiveness. It is something to do. Various compounds can be used as such chemical treatment agents, including carboxylic acids, inorganic acids such as boric acid and phosphoric acid, and esters and metal salts of these carboxylic acids and inorganic acids. It is generally a water-soluble compound. The chemical treatment liquid is an aqueous solution containing these.

Specific examples of the chemical treatment agents include carboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid, and do not include conjugated polyene compounds described later. From the viewpoint of thermal stability, aliphatic carboxylic acids having 1 to 4 carbon atoms are preferred, aliphatic monovalent carboxylic acids having 1 to 4 carbon atoms are more preferred, and acetic acid is particularly preferred. Inorganic acids include boric acid, phosphoric acid, carbonic acid, sulfuric acid, and the like.

Examples of the metal salts of carboxylic acids and inorganic acids include alkali metal salts, alkaline earth metal salts, and d-block metal salts of the fourth period of the periodic table. Examples of alkali metals include sodium and potassium, examples of alkaline earth metals include calcium and magnesium, and examples of d-block metals in the fourth period of the periodic table include titanium, manganese, copper, cobalt, and zinc. can give. Alkali metal salts are preferable, and sodium salts and potassium salts are particularly preferable.

Examples of the carboxylic acid metal salt include alkali metal acetate salts such as sodium acetate and potassium acetate; alkali metal propionate salts such as sodium propionate and potassium propionate; and alkali metal stearates such as sodium stearate and potassium stearate. alkali metal salts of carboxylates, alkaline earth metal acetates such as magnesium acetate and calcium acetate, alkaline earth metal propionates such as magnesium propionate and calcium propionate, alkaline earth stearates such as magnesium stearate and calcium stearate Alkaline earth metal salts of carboxylic acids such as metal salts can be mentioned.

Examples of metal salts of inorganic acids include alkali metal salts of inorganic acids, such as alkali metal borates such as sodium borate and potassium borate, and alkali metal phosphates such as sodium phosphate and potassium phosphate. be done. Examples of inorganic acid alkaline earth metal salts include alkaline earth metal borates such as magnesium borate and calcium borate, and alkaline earth metal phosphates such as magnesium phosphate and calcium phosphate. Phosphate also includes hydrogen phosphate. These can be used alone or in combination of two or more.

As the chemical treatment agent, carboxylic acid and carboxylic acid metal salt are preferably used from the viewpoint of thermal stability, and carboxylic acid, carboxylic acid metal salt, inorganic acid, and inorganic acid metal salt are more preferably used. . More specifically, acetic acid, metal acetate, boric acid, and phosphate are preferably used.

It is preferable to use an EVOH intermediate having a water content of 20 to 80% by weight in order to uniformly and rapidly incorporate the compounds used as the chemical treatment agent. In adjusting the content of such a compound, in the contact treatment between the chemical treatment solution and the EVOH intermediate, the concentration of the aqueous solution of the compound, the contact treatment time, the contact treatment temperature, the stirring speed during the contact treatment, and the treatment It is possible to control the water content of the EVOH intermediate, etc.

In the chemical treatment step [II], from the viewpoint of thermal stability at high temperatures, the weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the chemical treatment solution (carboxylic acid concentration/metal ion concentration) is 3. It is preferably 0.7 or more, more preferably 13 or more, more preferably 22 or more. If the ratio is too small, thermal stability tends to decrease. The upper limit of this ratio is usually 100, preferably 50.

The chemical treatment step [II] for chemically treating the EVOH intermediate with a chemical treatment solution may be a one-step chemical treatment step using a chemical treatment solution containing a high concentration of carboxylic acid, or It may be a multi-step chemical treatment process in which a plurality of chemical treatment solutions having different concentrations are used in each chemical treatment process. In the chemical treatment step [II] described above, "the weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the chemical treatment liquid (carboxylic acid concentration/metal ion concentration) is 3.7 or more." In the above one-step chemical treatment process, the weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the chemical treatment solution containing a high concentration of carboxylic acid used (concentration of carboxylic acid / metal ion concentration) is 3.7 or more. In addition, in the multi-stage chemical treatment process, as described later, the carboxylic acid concentration relative to the metal ion concentration of the carboxylic acid metal salt in the chemical treatment solution having the highest carboxylic acid concentration among the plurality of chemical treatment solutions used is This means that the weight ratio (carboxylic acid concentration/metal ion concentration) is 3.7 or more.

From the viewpoint of efficiently producing EVOH with excellent thermal stability, it is preferable to use a multi-step chemical treatment process in which a plurality of chemical treatment solutions having different carboxylic acid concentrations are used in each chemical treatment process. . In the chemical treatment step [II] in which the EVOH intermediate is chemically treated with the chemical treatment liquid, the multi-step chemical treatment step is carried out as follows. First, a plurality of chemical treatment solutions having different carboxylic acid concentrations are prepared. Then, a multi-step chemical treatment process is performed in which the plurality of chemical treatment solutions are used in each chemical treatment process (multi-step chemical treatment process) to chemically treat the EVOH intermediate in stages. In this case, the weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the chemical treatment solution having the highest carboxylic acid concentration among the plurality of chemical treatment solutions (concentration of carboxylic acid/concentration of metal ions) is 3.7. It is preferable that it is above.

Further, in the present invention, the carboxylic acid concentration in the chemical treatment liquid is 1 to 50000 ppm, particularly 10 to 10000 ppm, particularly 400 to 5000 ppm, and the metal ion concentration of the carboxylic acid metal salt is 1 to 50000 ppm, particularly 10 to 10,000 ppm is preferable in terms of treatment efficiency and cost.

In the present invention, the "concentration of carboxylic acid" refers to the concentration of carboxylic acid in the chemical treatment solution of the carboxylic acid used as the chemical treatment agent. means the concentration of acetic acid. In addition, "the metal ion concentration of the carboxylate metal salt" means the metal ion concentration of the carboxylate metal salt used as the chemical treatment agent in the chemical treatment solution. For example, when the chemical treatment solution contains sodium acetate, means the concentration of sodium ions. Even when a carboxylic acid and a carboxylic acid metal salt are used together as a chemical treatment agent, the carboxyl ion contained in the carboxylic acid metal salt is not considered in the "concentration of carboxylic acid". That is, when acetic acid and a metal acetate salt are used together as a chemical treatment agent, the acetate ion contained in such sodium acetate is not included in the above "concentration of carboxylic acid".

The treatment temperature in the chemical treatment step [II] is generally 10 to 100°C, preferably 15 to 80°C, more preferably 20 to 60°C. If the treatment temperature is too low, it tends to be difficult to incorporate a predetermined amount of the acid or its salt into the EVOH intermediate, and if it is too high, the solution tends to be difficult to handle, which tends to be disadvantageous in terms of production.

The treatment time in the chemical treatment step [II] is usually 1 hour or more, preferably 1.5 to 48 hours, more preferably 2 to 24 hours. If the treatment time is too short, the EVOH intermediate tends to be uneven in color and has reduced thermal stability. If the treatment time is too long, the EVOH intermediate tends to be colored.

Next, the drying step [III] is a step of drying the chemically treated EVOH intermediate, and the drying temperature is preferably 80 to 150° C., more preferably 90 to 140° C., particularly It is preferably 100 to 130°C. If the drying temperature is too low, the drying time tends to be long, and if it is too high, coloration tends to occur. The drying time is preferably 3 hours or longer, more preferably 5 hours or longer, particularly preferably 8 hours or longer. If the drying time is too short, the drying tends to be insufficient. Incidentally, the upper limit of the drying time is usually 1000 hours.

Various drying methods can be employed as the drying method. For example, fluidized drying in which a substantially pellet-like chemically treated EVOH intermediate is dried while being stirred and dispersed mechanically or by hot air, or motion such as stirring and dispersing a substantially pellet-like chemically treated EVOH intermediate. Stationary drying, which dries without giving a strong effect, can be mentioned. Dryers for fluidized drying include cylindrical/groove stirring dryers, circular tube dryers, rotary dryers, fluidized bed dryers, vibrating fluidized bed dryers, conical rotary dryers, and the like. In addition, as a dryer for static drying, a batch-type box-type dryer can be mentioned as a material stationary type, and a band dryer, a tunnel dryer, a vertical dryer, etc. can be mentioned as a material transfer type. can. Fluidized drying and stationary drying can be combined. In the present invention, it is preferable to perform stationary drying after fluidizing drying from the viewpoint of suppressing fusion of chemically treated EVOH intermediates.

The drying method will be described in more detail.
Air or an inert gas (nitrogen gas, helium gas, argon gas, etc.) is used as the heating gas used during the fluidized drying process, and the temperature of the heating gas varies depending on the volatile content of the chemically treated EVOH intermediate. Any temperature from 40 to 150° C. can be selected, but 40 to 100° C., more preferably 40 to 90° C. is preferable considering that the chemically treated EVOH intermediates are fused at high temperatures. The speed of the heating gas in the dryer is preferably 0.7 to 10 m/sec, more preferably 0.7 to 5 m/sec, particularly 1 to 3 m/sec. Fusion of the treated EVOH intermediate tends to occur, and conversely, if the speed is too high, chipping and fine powdering of the chemically treated EVOH intermediate tend to occur. The fluidized drying time is usually 5 minutes to 36 hours, preferably 10 minutes to 24 hours, although it depends on the amount of the chemically treated EVOH intermediate treated. Under the above conditions, the chemically treated EVOH intermediate is fluidized and dried, and the volatile content of the EVOH after the drying is preferably 5 to 60% by weight, more preferably 10 to 55% by weight. If the volatile content is too high, fusion of the chemically treated EVOH intermediate tends to occur during the subsequent static drying treatment, and if it is too low, energy loss tends to increase, which is not industrially preferable. In addition, in such a fluidized drying treatment, it is preferable to lower the volatile content by 5% by weight or more, more preferably 10 to 45% by weight, than before the treatment. There is a tendency for micro fisheyes to occur when

The chemically treated EVOH intermediate is dried under the above conditions, and the water content of the EVOH intermediate after the drying is preferably 0.001 to 5% by weight, particularly 0.01 to 2%. % by weight, more preferably 0.1 to 1% by weight. If the water content is too low, the long-run moldability tends to deteriorate, and if it is too high, foaming tends to occur during extrusion molding.

The melt flow rate (MFR) (210° C., load 2160 g) of the chemically treated EVOH intermediate obtained in this manner is usually 0.1 to 100 g/10 min, particularly preferably 0.5 to 50 g/10 min. 10 minutes, more preferably 1 to 30 g/10 minutes. If the melt flow rate is too small, the inside of the extruder tends to be in a high torque state during molding, making extrusion processing difficult.
The MFR can be adjusted by adjusting the degree of polymerization of the EVOH intermediate, and can be adjusted by adding a cross-linking agent or a plasticizer.

The EVOH resin composition of the present invention is prepared by adding a conjugated polyene compound to the EVOH resin composition thus obtained (not containing a conjugated polyene compound), or by preparing the above EVOH resin composition. In the process, a conjugated polyene compound is included in the EVOH resin composition. The second feature is that the conjugated polyene compound is contained in the entire EVOH resin composition at a rate of 800 ppm or less on a weight basis. As described above, the content of the conjugated polyene compound is in a very small range of 800 ppm or less, and the effect of trapping radicals generated during high-temperature heating works extremely effectively. However, if it is added in excess of 800 ppm, the change in coloration of specks derived from long-term retentive substances may become large, which may lead to deterioration in quality due to coloration.

Therefore, the content of the conjugated polyene compound is preferably 700 ppm or less, particularly preferably 500 ppm or less. The lower limit of the content is usually 5 ppm, preferably 50 ppm, and more preferably 150 ppm from the viewpoint of excellent effect of suppressing coloring after heating.

The EVOH resin composition, which serves as the standard for the content of the conjugated polyene compound, is an EVOH resin as a final product that contains a conjugated polyene compound or various additives that are optionally blended together with the conjugated polyene compound. composition.

Methods for obtaining an EVOH resin composition containing the conjugated polyene compound in a specific proportion include, for example, (1) the content of carboxylic acids (X) and the content of lactone rings in the terminal structure of EVOH, as described above; The conjugated polyene compound powder is directly added to the EVOH intermediate (pellet) prepared so that the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the amount (Y) is 55 mol% or more, and shaken uniformly. (2) a method of adding a conjugated polyene compound as a polymerization inhibitor after the polymerization reaction of the ethylene-vinyl ester copolymer before saponification of EVOH; (3) a solution containing a conjugated polyene compound (e.g., aqueous solution, methanol and (4) adding a conjugated polyene compound to the EVOH intermediate (pellet) and melting it with an extruder or the like. be done. Among these, the method (2) of adding a conjugated polyene compound as a polymerization inhibitor after the polymerization reaction of the ethylene-vinyl ester copolymer before saponification of EVOH is particularly preferred.

The conjugated polyene compound used in the present invention has a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, and the number of carbon-carbon double bonds is two or more, so-called It is a compound with a conjugated double bond. A conjugated polyene compound is a conjugated diene compound having a structure in which two carbon-carbon double bonds and one carbon-carbon single bond are alternately connected, three carbon-carbon double bonds and two carbons. - a conjugated triene compound having a structure in which carbon single bonds are alternately connected, or a conjugated polyene compound having a structure in which a greater number of carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, good too.

However, if the number of conjugated carbon-carbon double bonds is 8 or more, there is a concern that the molded product may be colored due to the color of the conjugated polyene compound itself, so the number of conjugated carbon-carbon double bonds should be 7 or less. It is preferred to have a certain polyene structure. In addition, a plurality of pairs of the above conjugated double bonds consisting of two or more carbon-carbon double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated trienes in the same molecule, such as tung oil, is also included in the conjugated polyene compound.

Examples of such conjugated polyene compounds include isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1 ,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene , 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2 ,4-hexadiene, 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-diphenyl-1,3-butadiene, 1-methoxy -1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3-butadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene, chloroprene, 1 -chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1,3-butadiene, fulvene, tropone, ocimene, phellandrene, myrcene, farnesene, cembrene, sorbic acid, sorbate , sorbic acids such as sorbate, ascorbic acid, ascorbic acid esters, ascorbic acid metal salts and other ascorbic acids, and abietic acid, conjugated diene compounds having a conjugated structure of two carbon-carbon double bonds; Conjugated triene compounds having a conjugated structure with three carbon-carbon double bonds, such as 5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, and cholecalciferol; Conjugated polyene compounds having a conjugated structure with 4 or more carbon-carbon double bonds such as tetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoic acid, terpene compounds, and the like can be mentioned. Any of those having multiple stereoisomers such as 1,3-pentadiene, myrcene and farnesene may be used. Two or more kinds of such polyene compounds can be used in combination.

Among these conjugated polyene compounds, those having a carboxyl group are preferable because of their high affinity with water, and more preferably chain compounds having a carboxyl group. Acids are preferred.

The molecular weight of the conjugated polyene compound is generally 30 to 500, preferably 50 to 400, particularly preferably 100 to 300, from the viewpoint of productivity and handleability. The number of carbon atoms in one molecule of the conjugated polyene compound is usually 4 to 30, preferably 4 to 20, particularly preferably 4 to 10, from the viewpoint of productivity and handling.

In the present invention, the content of the conjugated polyene compound in the EVOH resin composition is determined, for example, by subjecting the EVOH resin composition of interest to solvent extraction, and measuring the amount of the conjugated polyene compound in the extract by liquid chromatography. It can be obtained by converting from the value measured using.

In addition, in the present invention, the effect of improving the thermal stability by the conjugated polyene compound is, in particular, the lactone with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure of EVOH. A ring content ratio (Y/Z) of 62 mol % or more is preferable because a remarkable effect can be obtained. This is because the higher the lactone ring content, the more effective the radical trapping action of the conjugated polyene structure of the conjugated polyene compound against the decomposition reaction of the lactone ring at high temperatures, and the more the conjugated polyene compound content is very small. It is considered that even if there is, it can greatly contribute to the thermal stability.

The EVOH resin composition of the present invention may contain saturated fatty acid amides (eg, stearic acid amide, etc.), unsaturated fatty acid amides (eg, oleic acid amide, etc.), bis-fatty acid amides (eg, bis-fatty acid amides, etc.), as long as they do not hinder the object of the present invention. Lubricants such as ethylene bis stearamide, etc.), fatty acid metal salts (eg calcium stearate, magnesium stearate, etc.), low molecular weight polyolefins (eg, low molecular weight polyethylene with a molecular weight of about 500 to 10,000, or low molecular weight polypropylene, etc.), inorganic salts (e.g. hydrotalcite, etc.), plasticizers (e.g., ethylene glycol, glycerin, aliphatic polyhydric alcohols such as hexanediol, etc.), oxygen absorbers [e.g., reduced iron powders, and water-absorbing substances, electrolytes, etc. Inorganic oxygen absorbers such as iron, aluminum powder, potassium sulfite, photocatalyst titanium oxide; polyhydric phenols such as hydroquinone, gallic acid, hydroxyl group-containing phenol aldehyde resin, bis-salicylaldehyde-imine cobalt, tetraethylenepentamine cobalt , cobalt-Schiff base complexes, porphyrins, macrocyclic polyamine complexes, coordination bonds of nitrogen-containing compounds and transition metals such as polyethyleneimine-cobalt complexes, reaction products of amino acids and hydroxyl group-containing reducing substances, triphenylmethyl Organic compound-based oxygen absorbers such as compounds; coordination bonds of nitrogen-containing resins and transition metals (e.g., a combination of MXD nylon and cobalt), blends of tertiary hydrogen-containing resins and transition metals (e.g., polypropylene and cobalt combination), blends of carbon-carbon unsaturated bond-containing resins and transition metals (for example, a combination of polybutadiene and cobalt), photooxidatively degradable resins (for example, polyketones), anthraquinone polymers (for example, polyvinylanthraquinone), etc., and furthermore these Photoinitiators (benzophenone, etc.), peroxide scavengers (commercially available antioxidants, etc.), and deodorants (activated carbon, etc.) added to the formulation of polymeric oxygen absorbers], heat stabilizers , light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants, antibacterial agents, antiblocking agents, slip agents, fillers (such as inorganic fillers), other resins (such as polyolefins, polyamides, etc.), etc. May be blended. These compounds can be used alone or in combination of two or more.

The EVOH resin composition of the present invention thus obtained is prepared as pellets as it is, or as resin compositions in various forms such as powder and liquid, and provided as molding materials for various moldings. . Pellets for melt molding are preferable because the effects of the present invention can be obtained more effectively.
The EVOH resin composition of the present invention also includes resin compositions obtained by mixing resins other than the EVOH used in the EVOH resin composition of the present invention. Examples of such molded products include single-layer films molded using the EVOH resin composition of the present invention, and multilayer structures having at least one layer molded using the EVOH resin composition of the present invention. It can be put to practical use as

Such a multilayer structure will be described below.
In manufacturing the multilayer structure of the present invention, another base material (thermoplastic resin, etc.) is laminated on one or both sides of the layer molded using the EVOH resin composition of the present invention. As a method, for example, a method of melt-extrusion laminating another substrate onto a film, sheet, or the like formed using the EVOH resin composition of the present invention, etc., or conversely, the EVOH resin composition of the present invention is laminated onto another substrate. etc., a method of co-extrusion of the EVOH resin composition etc. of the present invention and other substrates, a film, sheet etc. (layer) using the EVOH resin composition etc. of the present invention and other A method of dry laminating the substrate (layer) with a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, a polyurethane compound, or the like can be mentioned. The melt molding temperature during melt extrusion is often selected from the range of 150 to 300°C.

Specific examples of such other base materials include various polyethylenes such as linear low density polyethylene, low density polyethylene, ultra-low density polyethylene, medium density polyethylene, and high density polyethylene, ethylene-vinyl acetate copolymers, and ionomers. , ethylene-propylene (block or random) copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer Widely defined polyolefin resins, polyester resins, homopolymers of olefins such as polybutene, polypentene, etc., or homopolymers or copolymers of these olefins graft-modified with unsaturated carboxylic acids or esters thereof, Polyamide resin (including copolyamide), polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, chlorinated polyethylene, chlorinated polypropylene, aromatic or aliphatic group polyketones, polyalcohols obtained by reducing these polyketones, and EVOH other than the EVOH used in the present invention. From the viewpoint of practicality such as physical properties (especially strength) of multilayer structures, polyolefin resins, polyamide resins, polystyrene resins, polyester resins are preferable, and polypropylene, ethylene-propylene (block or random) copolymer Coalescing, polyamide resin, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN) are preferably used.

Furthermore, moldings such as films and sheets formed using the EVOH resin composition of the present invention may be extrusion-coated with other substrates, or films, sheets, etc. of other substrates may be coated with an adhesive. In addition to the above thermoplastic resins, the base material may be any base material (paper, metal foil, uniaxially or biaxially oriented plastic film or sheet and its inorganic deposit, woven fabric, nonwoven fabric, etc.). , metallic cotton strips, wood, etc.) can also be used.

The layer structure of the multilayer structure of the present invention is such that the layers molded using the EVOH resin composition of the present invention are a (a1, a2, . b1, b2, . Any combination of a, a1/a2/b, a/b1/b2, a1/b1/a2/b2, a1/b1/b2/a2/b2/b1, etc. is possible, and at least the EVOH of the present invention When the regrind layer made of a mixture of a resin composition or the like and a thermoplastic resin is R, for example, a/R/b, a/R/a/b, a/b/R/a/R/b, a /b/a/R/a/b, a/b/R/a/R/a/R/b, etc. are also possible.

In addition, in the layer structure described above, an adhesive resin layer can be provided between each layer, if necessary. Various adhesive resins can be used, but from the point of view of obtaining a multilayer structure with excellent stretchability, for example, an unsaturated carboxylic acid or its anhydride is used as an olefinic polymer (in the broad sense of the above-mentioned modified olefin-based polymers containing carboxyl groups, which are obtained by chemically bonding to the polyolefin-based resins of (1) through addition reaction, graft reaction, or the like.

Specifically, maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymer, maleic anhydride graft-modified ethylene-ethyl acrylate copolymer, anhydrous Preferred examples include one or a mixture of two or more selected from maleic acid graft-modified ethylene-vinyl acetate copolymers and the like. At this time, the amount of unsaturated carboxylic acid or its anhydride contained in the thermoplastic resin is preferably 0.001 to 3% by weight, more preferably 0.01 to 1% by weight, and particularly preferably 0.03%. ~0.5% by weight. If the amount of modification in the modified product is too small, the adhesiveness tends to decrease, and conversely, if it is too large, a cross-linking reaction tends to occur and the moldability tends to decrease.

In addition, these adhesive resins are blended with EVOH derived from the EVOH resin composition of the present invention, other EVOH, polyisobutylene, rubber/elastomer components such as ethylene-propylene rubber, and resins of layer b. is also possible. In particular, it is useful to blend a polyolefin-based resin different from the base polyolefin-based resin of the adhesive resin, since the adhesiveness may be improved.

The thickness of each layer of the multilayer structure cannot be determined unconditionally depending on the layer structure, the type of the b layer, the application, the form of the molded product, the required physical properties, etc., but the a layer is usually 5 to 500 μm, preferably 10 to 500 μm. 200 μm, b layer 10 to 5000 μm, preferably 30 to 1000 μm, adhesive resin layer 5 to 400 μm, preferably 10 to 150 μm.

The multilayer structure can be used in various shapes as it is, but it is also preferable to subject the multilayer structure to heat drawing treatment in order to improve the physical properties of the multilayer structure. Here, the term “heating and stretching” means that a film, sheet, or parison-like laminate that has been uniformly thermally heated is subjected to molding means such as a chuck, plug, vacuum force, pneumatic force, or blow to form a cup, tray, or It means an operation to uniformly form a tube or film. Such stretching may be either uniaxial stretching or biaxial stretching, and it is better to stretch at a magnification as high as possible in terms of physical properties. It is possible to obtain a stretched molded article excellent in gas barrier properties without causing delamination or the like.

As the method for stretching the multilayer structure, a method with a high stretching ratio among roll stretching, tenter stretching, tubular stretching, stretch blowing, and vacuum pressure molding can be used. In the case of biaxial stretching, either a simultaneous biaxial stretching system or a sequential biaxial stretching system can be employed. The stretching temperature is selected from the range of 60 to 170°C, preferably 80 to 160°C. It is also preferable to perform heat setting after the drawing is completed. Heat setting can be performed by a well-known means, and heat setting can be performed by heat-treating the stretched film at 80 to 170° C., preferably 100 to 160° C., for about 2 to 600 seconds while maintaining a tensioned state. can.

In addition, when used for heat-shrink packaging of raw meat, processed meat, cheese, etc., it is used as a product film without heat setting after stretching, and after housing the raw meat, processed meat, cheese, etc. in the film, Heat treatment is performed at 50 to 130° C., preferably 70 to 120° C., for about 2 to 300 seconds to thermally shrink the film and tightly wrap it.

The shape of the multilayer structure thus obtained may be arbitrary, and examples thereof include films, sheets, tapes, extrudates with irregular cross-sections, and the like. In addition, the multilayer structure may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, split processing, as necessary. etc.

Containers such as cups, trays, and tubes obtained from the multilayer structure, and bags and lids made of the stretched film obtained from the multilayer structure can be used for foods, beverages, pharmaceuticals, cosmetics, industrial chemicals, detergents, It is useful as various packaging materials for packaging agricultural chemicals, fuels, and the like.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following description, "parts", "%" and "ppm" all mean weight standards. However, "mol%" shows "mol%" as it is.
Moreover, each physical property was measured as follows.

(1) Quantification of terminal structure of EVOH: NMR method <measurement conditions>
Device name: (manufactured by AVANCE III Bruker)
Observation frequency: 400MHz
Solvent: heavy water / ethanol-D6 (weight ratio = heavy water 35: ethanol-D6 65), DMSO-D6
Polymer concentration: 5%
Measurement temperature: heavy water/ethanol-D6 70°C, DMSO-D6 50°C
Accumulation times: 16 times Pulse repetition time: 4 seconds Sample rotation speed: 20 Hz
Additive: trifluoroacetic acid

<Analysis method>
(1-1) Measurement of Terminal Methyl Amount The terminal methyl amount was calculated using ¹ H-NMR measurement (DMSO-D6, measured at 50° C.) (the chemical shift value is based on the DMSO peak: 2.50 ppm). did). As shown in the chart of FIG. 1, the integrated value of terminal methyl (I _Me-1 ) from 0.7 to 0.95 ppm, methylene other than terminal groups from 0.95 to 1.85 ppm (ethylene unit, vinyl alcohol unit , total methylene of vinyl acetate unit), integrated value (I _CH2 ), integrated value (I _OAc ) of terminal methyl in vinyl acetate unit from 1.9 to 2 ppm, vinyl alcohol unit from 3.1 to 4.3 ppm Using the integrated value (I _CH ) of methine, the amount of terminal methyl was calculated according to the following (formula 1). Here, integral values (I _Me-1 ), (I _CH2 ), (I _OAc ), and (I _CH ) are respectively terminal methyl, methylene other than the terminal group, terminal methyl in the vinyl acetate unit, and It relates to the peak derived from methine.

(Formula 1)
Amount of terminal methyl (mol%)
=( _IMe-1 /3)/[( _IMe-1 /3)+( _IOAc /3)+ _ICH
+{I _CH2 −2×I _CH −2×(I _OAc /3)−2×(I _Me−1 /3)}/4]

(1-2) Measurement of carboxylic acid content (X) and lactone ring content (Y) The content of carboxylic acids and lactone rings at the end of the polymer is the amount of terminal methyl obtained in (1-1). (% by mole), it was calculated using ¹ H-NMR measurement (heavy water/ethanol-D6 solvent, measured at 70° C.) (chemical shift values were based on TMS peak: 0 ppm).
That is, as shown in the chart of FIG. 2, the integrated value of the terminal methyl (I _Me-2 ) from 0.7 to 1 ppm, the integrated value of the peak from 2.15 to 2.32 ppm (I _X ), 2.5 Using the integrated value (I _Y ) of the peak at ~2.7 ppm, the content (X) of carboxylic acids (mol%) and the content of lactone ring (Y) are obtained from the following (Equation 2) and (Equation 3): (mol%) were calculated respectively. Here, the integrated values (I _Me-2 ), (I _X ), and (I _Y ) relate to peaks derived from terminal methyl, carboxylic acids, and terminal lactone rings, respectively.

(Formula 2)
Carboxylic acid content (X) (mol%)
= Amount of terminal methyl (mol%) x ( _IX /2)/( _IMe-2 /3)

(Formula 3)
Lactone ring content (Y) (mol%)
= Terminal methyl amount (mol%) x (I _Y /2) / (I _Me-2 /3)

(1-3) Calculation of the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure The lactone ring content ratio (Y/Z) was calculated from the acid content (X) and the lactone ring content (Y) according to the following (formula 4).
If the above calculation is impossible due to additives, impurities, etc. different from EVOH, the sample may be washed as appropriate. For example, the following method can be used for washing the sample. That is, the sample is frozen and pulverized, then immersed in water for ultrasonic cleaning, filtered, and the filter residue is dried. After drying, the NMR measurement is performed.

(Formula 4)
Lactone ring content ratio (Y/Z) with respect to total amount (Z) of carboxylic acid content (X) and lactone ring content (Y) (mol%)
= {Y/(X + Y)} x 100

(2) Content (ppm) of sorbic acid (conjugated polyene compound): liquid chromatography mass spectrometry To 1 g of the EVOH resin composition, 8 mL of an extraction solvent of methanol/water = 1/1 (volume ratio) was added. . This solution was subjected to ultrasonic treatment for 1 hour at a temperature of 20° C. in a stationary state to extract sorbic acid in the resin. After cooling, the volume was adjusted to 10 mL with an extraction solvent. After filtering this solution, the amount of sorbic acid in the extracted solution was quantified with a liquid chromatograph-ultraviolet spectroscopic detector, and converted to the amount of sorbic acid in the EVOH resin composition.
[HPLC measurement conditions]
LC system: Agilent 1260/1290 [manufactured by Agilent Technologies]
Detector: Agilent 1260 infinity diode array detector [manufactured by Agilent Technologies]
Column: Cadenza CD-C18 (100 × 3.0 mm, 3 μm) [manufactured by Imtakt]
Column temperature: 40 degrees Mobile phase A: Aqueous solution of 5 vol% acetonitrile containing 0.05% formic acid Mobile phase B: Aqueous solution of 95 vol% acetonitrile containing 0.05% formic acid Time program: 0.0 → 5.0 min B% = 30%
5.0→8.0min B%=30%→50%
8.0→10.0min B%=50%
10.0→13.0min B%=50%→30%
13.0→15.0min B%=30%
Flow rate: 0.2mL/min
UV detection wavelength: 190-400 nm
Quantification wavelength: 262 nm

(3) Evaluation of thermal stability Thermal stability is measured using 5 mg of the EVOH resin composition with a thermogravimetry device (Pyris 1 TGA, manufactured by Perkin Elmer), and the weight is up to 95% of the original weight. It was evaluated based on the temperature when it decreased. Here, the measurement by TGA was performed under the conditions of a nitrogen atmosphere, an airflow rate of 20 mL/min, a temperature rise rate of 10°C/min, and a temperature range of 30 to 550°C.

(4) Coloring degree evaluation after heating Coloring evaluation of the EVOH resin composition after heating was performed using a visual analyzer (IRIS, manufactured by Alpha Moss Japan Co., Ltd.), and the EVOH resin composition heated at 240 ° C. for 10 minutes. It was carried out by measuring the occupied area ratio (%) of the portion where a remarkable color (R: 232, G: 216, B: 168) appeared when the object was thermally colored.

[Example 1]
After polymerizing ethylene and vinyl acetate, a methanol solution of sorbic acid, which is a conjugated polyene compound, was added to the methanol paste of the ethylene-vinyl acetate copolymer resin so that the content was as shown in Table 1 below. This resin paste containing sorbic acid was saponified to obtain an EVOH intermediate having an ethylene content of 32 mol %, a degree of saponification of 99.5 mol % and an MFR of 12 g/10 min (210° C., load of 2160 g). Then, this EVOH intermediate was dissolved in a water/methanol mixed solution (water 35/methanol 65, weight ratio), and the obtained EVOH intermediate solution (EVOH resin concentration 40%) was placed in a water tank containing cold water. After being extruded into a strand and solidified, it was cut with a cutter to obtain cylindrical EVOH intermediate pellets (containing 100 parts of water per 100 parts of EVOH intermediate).

Then, the EVOH intermediate pellets are put into an aqueous solution containing 350 ppm acetic acid, 370 ppm sodium acetate, 15 ppm calcium dihydrogen phosphate, and 57 ppm boric acid, and stirred at 30 to 35 ° C. for 1 hour. , the aqueous solution was replaced, and the stirring treatment was similarly performed a total of 5 times (first chemical treatment step). The weight ratio of the carboxylic acid concentration to the metal ion concentration (concentration of carboxylic acid/concentration of metal ion) of the carboxylic acid metal salt in the aqueous solution used in the first-stage chemical treatment was 3.0.

The resulting EVOH intermediate pellets are then placed in an aqueous solution containing 2450 ppm acetic acid, 370 ppm sodium acetate, 15 ppm calcium dihydrogen phosphate, and 57 ppm boric acid, and heated at 30-35° C. for 4 hours. The amount of acetic acid in the EVOH intermediate pellets was adjusted by stirring (second chemical treatment step). The weight ratio of the carboxylic acid concentration to the metal ion concentration (concentration of carboxylic acid/concentration of metal ions) of the carboxylic acid metal salt in the aqueous solution used in the second-stage chemical treatment was 23.6.

Then, the EVOH intermediate pellets were dried at 121° C. for 10 hours to obtain the EVOH resin composition of the present invention (in the form of pellets with a diameter of 2.3 mm and a length of 2.4 mm). Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

[Example 2]
The amount of sorbic acid in the EVOH resin composition was adjusted to the content shown in Table 1 below, and the drying temperature in the drying step of the EVOH intermediate pellets was changed to 150°C. Otherwise, the procedure was the same as in Example 1 to obtain an EVOH resin composition. Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

[Example 3]
The amount of sorbic acid in the EVOH resin composition was adjusted to the content shown in Table 1 below, and the amount of acetic acid in the aqueous solution in the second-stage chemical treatment process was changed to 3500 ppm. The weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the aqueous solution (concentration of carboxylic acid/metal ion concentration) was set to 33.7. Otherwise, the procedure was the same as in Example 1 to obtain an EVOH resin composition. Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

[Example 4]
The amount of sorbic acid in the EVOH resin composition was adjusted to the content shown in Table 1 below, and the amount of acetic acid in the aqueous solution in the second-stage chemical treatment process was changed to 3500 ppm. The weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the aqueous solution (concentration of carboxylic acid/metal ion concentration) was set to 33.7. Also, the drying temperature in the drying step of the EVOH intermediate pellets was changed to 150°C. Otherwise, the same procedure as in Example 1 was carried out to obtain an EVOH resin composition. Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

[Comparative Example 1]
The amount of sorbic acid in the EVOH resin composition was adjusted to the content shown in Table 1 below, and the amount of acetic acid in the aqueous solution in the second-stage chemical treatment process) was changed to 350 ppm, and the second-stage chemical treatment process was performed. The weight ratio of the carboxylic acid concentration to the metal ion concentration of the carboxylic acid metal salt in the aqueous solution (concentration of carboxylic acid/concentration of metal ion) was set to 3.4. Also, the drying temperature in the drying step of the EVOH intermediate pellets was changed to 118°C. Otherwise, the same procedure as in Example 1 was carried out to obtain an EVOH resin composition. Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

[Comparative Example 2]
An EVOH resin composition was obtained in the same manner as in Example 3, except that the amount of sorbic acid in the EVOH resin composition was adjusted to the content shown in Table 1 below. Various measurement results of the obtained EVOH resin composition are shown in Table 1 below.

From the above results, the lactone ring content ratio (Y/Z) with respect to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure of EVOH, and the sorbic acid (conjugated The polyene compound) content satisfies the requirements of the present invention, and the examples have excellent thermal stability at high temperatures and exhibit no or greatly reduced coloration after heating. On the other hand, Comparative Example 1, which does not satisfy the lactone ring content ratio (Y/Z), is inferior in thermal stability, and Comparative Example 2, which does not satisfy the sorbic acid content, shows remarkable coloration after heating. In the evaluation of thermal stability, the temperature was 362 to 363°C in Examples 1 to 4, and 332°C in Comparative Example 1, the difference being about 30°C. Oxidative deterioration and thermal decomposition of resins are chemical reactions, and the reaction rate of chemical reactions usually increases exponentially as the temperature rises. From the point of view of reaction kinetics, this is a very large difference.

The EVOH resin composition of the present invention contains EVOH in which the ratio of the lactone ring content to the total amount of the carboxylic acid content and the lactone ring content is set within a specific range, and further comprises a conjugated polyene compound However, since it is contained in a very small amount within a specific range, it has excellent thermal stability such as excellent suppression of thermal decomposition at high temperatures, and in particular, the coloration of particles derived from long-term retention is remarkably suppressed. Even after processing, there is no offensive odor or coloration. Therefore, the EVOH resin composition of the present invention can be molded into containers such as cups, trays and tubes, and bags and lids made of stretched film. , fuel, etc., as various packaging materials.

Claims (2)

The molar ratio of the lactone ring content ratio (Y/Z) to the total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) in the terminal structure of the ethylene-vinyl alcohol copolymer. A resin composition containing an ethylene-vinyl alcohol-based copolymer of 64 to 90% and a conjugated polyene compound,
The total amount (Z) of the carboxylic acid content (X) and the lactone ring content (Y) is 0.01 to 0.3 with respect to the total amount of the monomer units of the ethylene-vinyl alcohol copolymer. is mol %,
The content (X) of the carboxylic acid is 0.01 to 0.25 mol% with respect to the total amount of the monomer units of the ethylene-vinyl alcohol copolymer,
The content (Y) of the lactone ring is 0.01 to 0.25 mol% with respect to the total amount of the monomer units of the ethylene-vinyl alcohol copolymer,
An ethylene-vinyl alcohol copolymer resin composition, characterized in that the content of the conjugated polyene compound in the resin composition is 800 ppm or less on a weight basis. A multilayer structure comprising at least one layer containing the ethylene-vinyl alcohol copolymer resin composition according to claim 1 .

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