Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
  • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
  • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

• the present invention relates to a resin composition having excellent flexibility and excellent long-term storage stability.
• Vinyl alcohol-based resins are emulsifiers, suspending agents, and surfactants by utilizing the excellent film properties (mechanical strength, oil resistance, film-forming property, oxygen gas barrier property, etc.) or hydrophilicity due to high crystallinity.
• vinyl alcohol-based resins usually have a glass transition temperature higher than room temperature and are highly crystallized, which poses a major problem depending on the application, such as low flexibility, weak bending resistance, and low reactivity. Has physical defects. The low flexibility can be solved by combining the plasticizer, but in that case, the mechanical properties and the barrier property are inevitably lowered due to the bleed-out of the plasticizer or the marked decrease in crystallinity.
• Patent Document 1 exemplifies a polymer in which a diene polymer having a modified functional group introduced at the terminal is reacted in a dimethyl sulfoxide solution of a vinyl alcohol resin, and the diene polymer is introduced via a reactive group. There is.
• Patent Documents 2 and 3 disclose a method for producing a copolymer by generating radicals in a vinyl alcohol-based resin using ionizing radiation and bringing the vinyl alcohol-based resin into contact with butadiene.
• the present invention has been made to solve the above problems, and an object of the present invention is to provide a resin composition having excellent flexibility and excellent long-term storage stability.
• the present inventors have found that when a copolymer containing a vinyl alcohol-based polymer unit and a diene-based polymer unit is stored in a wet state for a long period of time under atmospheric exposure, the diene-based polymer is used. It was discovered that a phenomenon occurs in which the polymer gradually decomposes and desorbs. As a result of examining the factors, it was found that the desorption phenomenon of the diene-based polymer changes in stability in relation to the type of trace radicals contained in the resin composition. From this finding, it was found that the above-mentioned problems can be solved by controlling the structure of radicals contained in the resin composition, and the present invention has been completed.
• the present invention includes the following inventions.
• a copolymer (B) composed of a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) unit is contained, and the g value of the ESR spectrum is 2.031 to 2. 0050, a resin composition.
• the method for producing a resin composition according to any one of [1] to [10], which comprises a step of heat treatment and the heat treatment temperature is 30 to 150 ° C.
• the present invention it is possible to provide a resin composition having excellent flexibility and excellent long-term storage stability.
• the resin composition of the present invention can be used even when the obtained copolymer is stored in a wet state for a certain period of time, such as when a copolymer is produced in a plant, from the viewpoint of industrial practicality. In the meantime, deterioration due to moisture absorption can be suppressed, and long-term storage stability is excellent.
• the resin composition of the present invention contains a copolymer (B) composed of a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) unit, and has a g value of 2 in the ESR spectrum. It is characterized in that it is .0031 to 2.050.
• the g value obtained by measuring the ESR spectrum is a parameter represented by the following formula (Q).
• h Planck's constant
• ⁇ the resonance frequency
• ⁇ the Bohr magneton
• H the resonance magnetic field (the intersection of the ESR signal and the baseline).
• the g value is obtained by measuring the ESR spectrum.
• the measurement of the ESR spectrum can be performed using a known electron spin resonance apparatus.
• the electron spin resonance device include JES-X3 manufactured by JEOL Ltd., EMXplus manufactured by Bruker Japan Co., Ltd. (accessory device: Cryostat ESR910 manufactured by Oxford Instruments Co., Ltd.) and the like.
• the present inventors have discovered that the decomposition reaction of the resin proceeds remarkably in a wet state such as a state in which the resin composition contains moisture in the atmosphere or some solvent.
• the resin composition is plasticized in a wet state to facilitate molecular motion of the polymer, and as a result, a substance that promotes the reaction or decomposition between molecular chains (for example, oxygen or water). It is thought that this is due to the promotion of penetration of.
• radicals are detected in an extremely small amount regardless of the production method. Therefore, it is considered that the amount of radicals affects the stability against the decomposition reaction. It was discovered that its stability is greatly influenced by the type and structure of radicals, not by the amount of radicals.
• the g value of the resin composition of the present invention is preferably 2.0035 to 2.0049, more preferably 2.0036 to 2.0048, from the viewpoint of being excellent in flexibility and long-term storage stability. .0037 to 2.0047 are more preferable.
• the amount of radicals in the resin composition of the present invention is preferably 15 ⁇ 10 -3 mmol / kg or less, preferably 10 ⁇ 10 -3 mmol / kg or less, from the viewpoint of excellent flexibility and long-term storage stability. Is more preferable, and 8.5 ⁇ 10 -3 mmol / kg or less is further preferable.
• the amount of radical can be calculated from the signal intensity obtained by measuring the ESR spectrum, for example, as described in Examples described later.
• the ultrafine coupling constant (A value) of the ESR spectrum is preferably less than 20 gauss, more preferably less than 19 gauss, and even more preferably less than 18 gauss.
• the copolymer (B) contained in the resin composition of the present invention is chemically stable in a dry state, but the A value calculated from the ESR spectrum changes depending on the radical structure, and thus the resin composition.
• the structural species of radicals in which can exist stably can be defined within the range of A value. If the A value is less than 20 gauss, the decomposition reaction is unlikely to occur even when the amount of radicals is large, which is preferable. Further, the A value of the resin composition having excellent stability is preferably 10 gauss or more. When the A value exceeds 20 gauss, the above-mentioned decomposition reaction is promoted.
• the resin composition of the present invention contains a copolymer (B) composed of a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) unit.
• the vinyl alcohol polymer (A) may be contained.
• the types of the vinyl alcohol-based polymer (A) and the vinyl alcohol-based polymer (B-1) are not particularly limited, but for example, the following polyvinyl alcohol or ethylene-vinyl alcohol copolymers are preferably used.
• the vinyl alcohol-based polymer (A) and the vinyl alcohol-based polymer (B-1) may have the same structural unit constituting each polymer, the viscosity average degree of polymerization of each polymer, the degree of saponification, and the like. , May be different.
• the vinyl alcohol-based polymer (A) and the vinyl alcohol-based polymer (B-1) preferably have a vinyl alcohol unit content of 40 mol% or more, and even if the content is 50 mol% or more, it is 55 mol% or more. You may. Further, in each of the vinyl alcohol-based polymer (A) and the vinyl alcohol-based polymer (B-1), a single polyvinyl alcohol or an ethylene-vinyl alcohol copolymer may be used, or a plurality of polyvinyl alcohols and / Alternatively, an ethylene-vinyl alcohol copolymer may be used in combination.
• the structural unit in the polymer means a repeating unit constituting the polymer. For example, an ethylene unit or a vinyl alcohol unit is also a structural unit.
• the viscosity average degree of polymerization of the polyvinyl alcohol is not particularly limited, and is preferably 100 to 10,000, more preferably 200 to 7,000, and further preferably 300 to 5. It is 000. When the viscosity average degree of polymerization is within the above range, the mechanical properties of the obtained resin composition are excellent.
• the viscosity average degree of polymerization may be adjusted according to the desired number average molecular weight of the copolymer (B).
• the saponification degree of the polyvinyl alcohol is not particularly limited, but from the viewpoint of excellent mechanical properties, 50 mol% or more is preferable, 80 mol% or more is more preferable, and 95 mol% or more is further preferable. Preferably, it may be 100 mol%.
• the content of the ethylene unit in the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, from the viewpoint of excellent mechanical properties and easy production.
• the content of ethylene units in the ethylene-vinyl alcohol copolymer can be determined from 1 1 H-NMR measurement.
• the saponification degree of the ethylene-vinyl alcohol copolymer is not particularly limited, but from the viewpoint of excellent moldability and mechanical properties, 80 mol% or more is preferable, 95 mol% or more is more preferable, 99 mol% or more is further preferable, and 100 mol% is preferable. There may be.
• the saponification degree of the ethylene-vinyl alcohol copolymer can be measured according to JIS K 6726 (1994).
• the melt flow rate (MFR) (210 ° C., load 2160 g) of the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 0.1 g / 10 minutes or more, and more preferably 0.5 g / 10 minutes or more. When the melt flow rate is 0.1 g / 10 minutes or more, the water resistance and mechanical properties are excellent.
• the upper limit of the melt flow rate may be a value usually used, for example, 25 g / 10 minutes or less.
• the melt flow rate indicates a value obtained by measuring with a melt indexer at 210 ° C. and a load of 2160 g in accordance with ASTM D1238.
• the above ethylene-vinyl alcohol copolymer may contain structural units derived from unsaturated monomers other than ethylene units and vinyl alcohol units, as long as the effects of the present invention are not impaired.
• the content of structural units derived from the unsaturated monomer in the ethylene-vinyl alcohol copolymer is preferably 10 mol% or less with respect to all the structural units constituting the ethylene-vinyl alcohol copolymer. More preferably, it is 5 mol% or less.
• the polyvinyl alcohol and the ethylene-vinyl alcohol copolymer may contain a structural unit (c) other than the vinyl alcohol unit, the vinyl ester monomer and the ethylene unit as long as the effects of the present invention are not impaired.
• Examples of the structural unit (c) include ⁇ -olefins such as propylene, n-butyl, isobutylene, and 1-hexene (including ethylene in the case of polyvinyl alcohol); acrylate; methyl acrylate, ethyl acrylate, and the like.
• Acrylic acid ester groups such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
• Unsaturated monomers having a methacrylate ester group such as 2-ethylhexyl, dodecyl methacrylate, octadecyl methacrylate
• methacrylicamides such as methacrylamide, N-methylmethacrylate, N-ethylmethacrylate, methacrylicamide propanesulfonic acid and methacrylateprop
• resin compositions include a vinyl alcohol polymer (B-1) unit comprising an ethylene-vinyl alcohol copolymer unit.
• the copolymer (B) is composed of a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) unit.
• the copolymer (B) is not particularly limited as long as it is a copolymer having at least one vinyl alcohol-based polymer (B-1) unit and at least one diene-based polymer (B-2) unit.
• the copolymer (B) is, for example, a graft copolymer (B1) or a block copolymer (B2).
• the copolymer (B) is preferably a graft copolymer (B1).
• the structure of the graft copolymer (B1) is not particularly limited, but is composed of a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) unit.
• the graft copolymer (B1) is preferably composed of a main chain composed of vinyl alcohol-based polymer (B-1) units and a side chain composed of diene-based polymer (B-2) units. That is, it is preferable that the main chain composed of the vinyl alcohol polymer (B-1) is introduced with the side chain composed of the diene polymer (B-2) unit.
• one in which a plurality of diene-based polymer (B-2) units are bonded to one vinyl alcohol-based polymer (B-1) unit is particularly preferable.
• the type of the vinyl alcohol-based polymer (B-1) is not particularly limited, but for example, the above-mentioned polyvinyl alcohol or ethylene-vinyl alcohol copolymer is preferable.
• the vinyl alcohol-based polymer (B-1) preferably has a vinyl alcohol unit content of 40 mol% or more, and may be 50 mol% or more or 55 mol% or more.
• one type of polyvinyl alcohol or ethylene-vinyl alcohol copolymer may be used alone, or a plurality of polyvinyl alcohols and / or ethylene-vinyl alcohol copolymers may be used in combination. You may.
• Block copolymer (B2) When the copolymer (B) is a block copolymer (B2), it has a vinyl alcohol-based polymer (B-1) unit as a polymer block (b1) and is a diene-based polymer (B-2). It has a unit as a polymer block (b2).
• the block copolymer (B2) may have one polymer block (b1) and one polymer block (b2), or the polymer block (b1) and / or the polymer block (b2). ) May have two or more.
• b1-b2 type diblock copolymer As the binding mode of the block copolymer, b1-b2 type diblock copolymer, b1-b2-b1 type triblock copolymer, b2-b1-b2 type triblock copolymer, b1-b2-b1 Linear multi-block copolymers typified by -b2-type tetrablock copolymers or b2-b1-b2-b1-type tetrablock copolymers, (b2-b1-) n, (b1-b2-) n and the like. Examples thereof include a star-shaped (radial star-shaped) block copolymer represented by. n is a value greater than 2.
• the copolymer (B) contains a diene-based polymer (B-2).
• the structure of the diene-based polymer (B-2) is not particularly limited, but it is preferable that the diene-based polymer (B-2) has an olefin structure. Since the diene polymer (B-2) has an olefin structure, the resin composition of the present invention can be crosslinked or vulcanized by high energy rays.
• the diene polymer (B-2) include polybutadiene, polyisoprene, polyisobutylene, polychloroprene, polyfarnesene and the like. These may be used alone or in combination of two or more.
• the diene-based polymer (B-2) may be two or more kinds of copolymers selected from the group consisting of butadiene, isoprene, isobutylene, chloroprene and farnesene. Of these, polybutadiene, polyisoprene, and polyisobutylene are preferable, and polyisoprene is more preferable, from the viewpoint of reactivity and flexibility.
• the copolymer (B) may contain structural units other than the vinyl alcohol-based polymer (B-1) and the diene-based polymer (B-2) as long as the effects of the present invention are not impaired. ..
• the side chain of the graft copolymer (B1) contains structural units other than the vinyl alcohol polymer (B-1) and the diene polymer (B-2) as long as the effects of the present invention are not impaired. You may be.
• the content of the diene polymer (B-2) unit with respect to the total mass of the vinyl alcohol polymer (B-1) unit and the diene polymer (B-2) unit in the copolymer (B) is particularly limited. However, 10% by mass or more is preferable, 15% by mass or more is more preferable, and 20% by mass or more is further preferable.
• the content of the diene polymer (B-2) unit is preferably 80% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
• the content is 10% by mass or more, the desired flexibility and reactivity can be easily obtained in the copolymer (B) (particularly the graft copolymer (B1)), and when the content is 80% by mass or less, it is vinyl alcohol-based.
• the polymer (A) and the copolymer (B) have excellent compatibility, and it is easy to suppress deterioration of transparency and various physical properties due to the formation of coarse phase separation.
• the method for measuring the content of the diene polymer (B-2) unit is as described in Examples described later.
• the content of the copolymer (B) is preferably 10 to 85% by mass, more preferably 15 to 75% by mass, and even more preferably 20 to 70% by mass with respect to 100 parts by mass of the resin composition.
• the side chain composed of the diene polymer (B-2) unit has a molecular weight distribution.
• the side chain composed of the diene polymer (B-2) unit has a molecular weight distribution, in the embodiment containing the vinyl alcohol polymer (A), the vinyl alcohol polymer (A) and the graft copolymer (B1) ) Is likely to improve compatibility and transparency after molding is likely to increase.
• the total amount of modification of the polymer composition (P) of the present invention is preferably 1.0 to 30 mol%, more preferably 5.0 to 25 mol%, and preferably 8.0 to 20 mol% from the viewpoint of being more flexible. More preferred.
• the polymer composition (P) means a polymer composition composed of a vinyl alcohol-based polymer (A) and a copolymer (B), and the total modification amount of the polymer composition (P). Means the content of the graft-polymerized monomer with respect to all the monomer units. Specifically, the total amount of modification of the polymer composition (P) is calculated by the method described in Examples.
• the crystal melting temperature of the polymer composition (P) of the present invention is preferably 140 ° C. or higher. When the crystal melting temperature is 140 ° C. or higher, excellent mechanical properties are likely to be exhibited. On the other hand, the crystal melting temperature of the polymer composition (P) is preferably 200 ° C. or lower. When the crystal melting temperature is 200 ° C. or lower, it is not necessary to raise the temperature during molding, and it is easy to suppress thermal deterioration of the resin.
• the method for producing the polymer composition (P) of the present invention is not particularly limited, but when the copolymer (B) is a graft copolymer (B1), for example, various generally known graft polymerization methods are used.
• a graft copolymer (B1) was produced by generating a radical on the main chain of the vinyl alcohol-based polymer and introducing a graft chain, and the obtained graft copolymer (B1) and the vinyl alcohol-based polymer (B1) were produced. Examples thereof include a method of mixing A) with a desired composition.
• Examples of the graft polymerization method include a method of graft polymerization using radical polymerization using a polymerization initiator; a graft polymerization method using active energy rays (hereinafter referred to as an active energy ray graft polymerization method);
• the active energy ray graft polymerization method is preferably used.
• a method for producing the polymer composition (P) using the active energy ray graft polymerization method a step of irradiating the vinyl alcohol-based polymer (B-1) with active energy rays in advance in order to generate radicals.
• a step of dispersing the vinyl alcohol-based polymer (B-1) in a monomer as a raw material of the diene-based polymer (B-2) or in a solution containing the monomer and performing graft polymerization is performed.
• the manufacturing method is preferable.
• the product obtained by using such a method is a mixture of an unreacted vinyl alcohol polymer (B-1) and a graft copolymer (B1), and the unreacted vinyl alcohol polymer (B-1) is obtained. 1) corresponds to the vinyl alcohol-based polymer (A). Therefore, if this method is used, the polymer composition (P) of the present invention can be produced in only one step.
• the molecular weight of the side chain of the graft copolymer (B1) obtained by such a method is not homogenized and has a molecular weight distribution.
• the vinyl alcohol-based polymer (A) may be added to the polymer composition obtained by the method for producing the polymer composition (P) using the above active energy ray graft polymerization method, if necessary. ..
• the ethylene-vinyl alcohol copolymer when the ethylene-vinyl alcohol copolymer is irradiated with active energy rays, it is considered that radicals are also generated at the carbon atom of the methylene group of the ethylene unit. Therefore, the monomer that is the raw material of the diene polymer (B-2) undergoes radical polymerization starting from the carbon atom of the methylene group, so that the side chain composed of the diene polymer (B-2) is formed. It is presumed that a graft copolymer (B1) directly bonded to the secondary carbon atom of the main chain composed of the vinyl alcohol polymer (B-1) is produced.
• the vinyl alcohol-based polymer (B-1) having a water content of 15% by mass or less with active energy rays.
• the water content is more preferably 5% by mass or less, further preferably 3% by mass or less.
• the radicals generated in the vinyl alcohol polymer (B-1) are less likely to disappear, and the vinyl alcohol with respect to the monomer which is the raw material of the diene polymer (B-2) is vinyl alcohol.
• the reactivity of the radical polymer (B-1) tends to be sufficient.
• the vinyl alcohol-based polymer (B-1) having a water content of 0.001% by mass or more with active energy rays.
• the water content is more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more.
• Examples of the active energy rays to irradiate the vinyl alcohol-based polymer (B-1) include ionizing radiation such as ⁇ -rays, ⁇ -rays, ⁇ -rays, electron rays, and ultraviolet rays; Among them, ionizing radiation is preferable, electron beams and ⁇ -rays are more preferable in practical use, and electron beams having a high processing speed and easy equipment are further preferable.
• the dose of irradiating the vinyl alcohol polymer (B-1) with active energy rays is preferably 5 to 200 kGy, more preferably 10 to 150 kGy, further preferably 20 to 100 kGy, and particularly preferably 30 to 90 kGy.
• the irradiation dose is 5 kGy or more, it becomes easy to introduce a sufficient amount of side chains.
• the irradiation dose is 200 kGy or less, it tends to be advantageous in terms of cost, and it becomes easy to suppress deterioration of the vinyl alcohol polymer (B-1) due to irradiation with active energy rays.
• the shape of the vinyl alcohol-based polymer (B-1) is not particularly limited, but it is preferably in the form of a powder or pellet having an average particle size of 50 to 4000 ⁇ m.
• the contact efficiency with the monomer for example, butadiene, isoprene, isobutylene, chloroprene, farnesene, etc.
• the monomer for example, butadiene, isoprene, isobutylene, chloroprene, farnesene, etc.
• the average particle size is more preferably 60 to 3500 ⁇ m, still more preferably 80 to 3000 ⁇ m.
• a measurement method using a laser diffractometer "LA-950V2" manufactured by HORIBA, Ltd. can be mentioned.
• the dispersion solvent used must be one that dissolves the monomer that is the raw material of the diene-based polymer (B-2), but does not dissolve the vinyl alcohol-based polymer (B-1) that has been irradiated with active energy rays. There is.
• the progress of graft polymerization and the deactivation of radicals generated in the vinyl alcohol polymer (B-1) occur at the same time. As it progresses, it is difficult to control the amount of monomer added.
• the dispersion solvent used for the graft polymerization include water; lower alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran, dioxane and diethyl ether; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide.
• a surfactant or the like may be used in combination to disperse the monomer, if necessary. Moreover, you may use these solvents in combination of 2 or more types.
• the vinyl alcohol-based polymer (B-1) irradiated with active energy rays swells, so that the monomer that is the raw material of the diene-based polymer (B-2) becomes the vinyl alcohol. It can penetrate into the inside of the system polymer (B-1) and introduce a large amount of side chains composed of the diene polymer (B-2). Therefore, it is preferable to select the dispersion solvent to be used in consideration of the affinity with the vinyl alcohol-based polymer irradiated with the active energy rays.
• lower alcohols such as methanol, ethanol, and isopropanol have high affinity with the vinyl alcohol polymer (B-1) irradiated with active energy rays, and are therefore suitable for the production method of the present invention. Used. Further, it is also effective to use the mixture of the above dispersion solvents as a liquid medium as long as the vinyl alcohol polymer (B-1) irradiated with the active energy rays is not dissolved, for the same reason as described above.
• the amount of the monomer used as the raw material of the diene polymer (B-2) in the graft polymerization is appropriately adjusted according to the reactivity of the monomer. As described above, the reactivity changes depending on the ease of penetration of the monomer into the vinyl alcohol-based polymer and the like. Therefore, the appropriate amount of the above-mentioned monomer added varies depending on the type or amount of the dispersion solvent, the degree of polymerization or the degree of saponification of the vinyl alcohol-based polymer (B-1), etc. 1 to 1000 parts by mass is preferable with respect to 100 parts by mass of the irradiated vinyl alcohol-based polymer (B-1).
• the graft copolymer (B1) has a vinyl alcohol-based polymer (B-1) and a diene-based weight. It is easy to control the ratio of coalescence (B-2) within the above range.
• the amount of the monomer used is more preferably 2 to 900 parts by mass, further preferably 5 to 800 parts by mass.
• the amount of the liquid medium used in the graft polymerization is preferably 100 to 4000 parts by mass, more preferably 200 to 2000 parts by mass, based on 100 parts by mass of the vinyl alcohol polymer (B-1) irradiated with active energy rays. More preferably, it is 300 to 1500 parts by mass.
• the reaction temperature in the graft polymerization is preferably 20 ° C. to 150 ° C., more preferably 30 ° C. to 120 ° C., and further preferably 40 ° C. to 100 ° C.
• the reaction temperature is 20 ° C. or higher, the graft polymerization reaction tends to proceed.
• the reaction temperature is 150 ° C. or lower, thermal melting of the vinyl alcohol polymer (B-1) is unlikely to occur.
• the reaction can be carried out under pressure in a pressure-resistant container such as an autoclave.
• the reaction time in the graft polymerization is preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less. When the reaction time is 10 hours or less, it is easy to suppress the homopolymerization of the monomer which is the raw material of the diene polymer (B-2).
• the reaction time in the graft polymerization is preferably 0.5 hours or more, more preferably 1 hour or more.
• a production method comprising a step of heat-treating the polymer composition (P) containing the coalescence (B) and having a heat treatment temperature of 30 to 150 ° C., (ii) a vinyl alcohol-based polymer (B-1) unit.
• a step of washing the polymer composition (P) containing the copolymer (B) composed of the diene polymer (B-2) unit with a washing liquid is included, and the washing liquid contains an antioxidant (C). Examples include a manufacturing method.
• the solution may contain an antioxidant (C).
• an antioxidant (C) used in these production methods, those described later can be used.
• the content of the antioxidant (C) in the production method (i) is preferably 10 to 1000 ppm, more preferably 20 to 800 ppm, still more preferably 30 to 500 ppm, based on the total amount of the solution.
• the content of the antioxidant (C) in the production method (ii) is preferably 10 to 1000 ppm, more preferably 20 to 800 ppm, still more preferably 30 to 500 ppm, based on the total amount of the cleaning liquid.
• the heat treatment temperature is preferably 35 to 120 ° C, more preferably 40 to 100 ° C, and even more preferably 50 to 90 ° C.
• the solvent used for the solution of the production method (i) is preferably a solvent having a high affinity with the resin composition and capable of swelling the resin composition.
• Preferable examples include alcohols such as water and methanol.
• Examples of the solvent used for the cleaning solution of the production method (ii) include hydrocarbon solvents such as hexane and heptane; and organic solvents containing ethers such as tetrahydrofuran, dioxane and diethyl ether.
• the resin composition of the present invention exhibits excellent storage stability by controlling the g value of the ESR spectrum within a predetermined range, but contains an antioxidant (C) for the purpose of further improving the stability. You may.
• the antioxidant (C) preferably contains at least one selected from the group consisting of a phenolic compound (C1), an amine compound (C2) and a phosphorus compound (C3).
• the content of the antioxidant (C) in the resin composition of the present invention is preferably less than 1.0% by mass, more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.
• the molecular weight of the phenolic compound (C1) is preferably 100 or more and 2000 or less, more preferably 150 or more and 1500 or less, and further preferably 160 or more and 1200 or less, from the viewpoint of thermal stability and flexibility of the resin composition.
• R 1 to R 7 independently represent a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms or a hydroxyl group
• X represents a divalent hydrocarbon group having 1 to 15 carbon atoms
• Y represents a vinyloxy group, or (meth) acryloyloxy group, said hydrocarbon group R 1 ⁇ R 7 and X, -O -, - S -, - NH -, - N (R 8) -, - It may contain at least one atom selected from the group consisting of O (CO)-and-CO-.
• R 8 represents a hydrocarbon group having 1 to 6 carbon atoms.
• the hydrocarbon group having 1 to 15 carbon atoms of R 1 to R 7 may be linear or branched, and for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl.
• Examples of the substituent contained in the substituted phenyl group include a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like.
• a linear or branched alkyl group is preferable from the viewpoint of more excellent thermal stability and flexibility of the resin composition.
• the number of carbon atoms of the hydrocarbon groups of R 1 to R 7 is preferably 1 to 10, and more preferably 1 to 6 from the viewpoint of more excellent thermal stability and flexibility of the resin composition.
• Examples of the hydrocarbon group of R 8 include those described above as R 1 to R 7 having 1 to 6 carbon atoms of the hydrocarbon group.
• the divalent hydrocarbon group having 1 to 15 carbon atoms of X may be a linear or branched chain, for example, a methylene group, a methylmethylene group, an ethylene group, an n-propylene group or an isopropylene group.
• the number of carbon atoms of the hydrocarbon group of X is preferably 1 to 10, more preferably 1 to 6 and even more preferably 1 to 4 from the viewpoint of more excellent thermal stability and flexibility of the resin composition.
• Y a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable, from the viewpoint of more excellent thermal stability and flexibility of the resin composition.
• the hydrocarbon groups of R 1 to R 7 and X are -O-, -S-, -NH-, -N (R 8 )-, -O (CO)-, and. Examples thereof include phenolic compounds containing no -CO-. Further, in another preferred embodiment, the phenolic compounds wherein R 3 is a hydroxyl group.
• examples of the phenolic compound (C1) of the other embodiment include compounds represented by the following general formula [III].
• R 9 and R 10 each independently represent a hydrocarbon group having 1 to 15 carbon atoms
• Z represents a divalent hydrocarbon group having 1 to 15 carbon atoms
• R 9 and R 10 respectively.
• Z hydrocarbon groups are at least one group selected from the group consisting of -O-, -S-, -NH-, -N (R 11 )-, -O (CO)-, and -CO-.
• R 11 represents a hydrocarbon group having 1 to 6 carbon atoms.
• Examples of the hydrocarbon groups of R 9 and R 10 are the same as those of R 1 to R 7 .
• Examples of the hydrocarbon group of R 11 are the same as those of R 8 .
• R 9 and R 10 are hydrocarbon groups having 1 to 6 carbon atoms
• Z is a divalent hydrocarbon group having 1 to 10 carbon atoms. At least one group selected from the group in which the valent hydrocarbon group consists of -O-, -S-, -NH-, -N (R 11 )-, -O (CO)-, and -CO- Compounds containing are preferred.
• the phenolic compound (C1) of a preferred embodiment has the general formula [I] because it is more excellent in thermal stability and flexibility of the resin composition, and is also more excellent in the effect of suppressing the formation of bleeding and the effect of preventing discoloration.
• a compound represented by, R 1, R 2, and R 3 may be mentioned phenolic compounds is a hydrocarbon group having 1 to 6 carbon atoms.
• the phenolic compound (C1) of another suitable embodiment it is represented by the general formula [II] because the resin composition is more excellent in thermal stability and flexibility and is more excellent in the effect of preventing discoloration.
• R 4 , R 5 , R 6 and R 7 are hydrocarbon groups having 1 to 6 carbon atoms
• X is a divalent hydrocarbon group having 1 to 6 carbon atoms
• Y is acryloyl. Examples thereof include phenolic compounds which are oxy groups.
• Examples of the phenolic compound (C1) include dibutylhydroxytoluene, hydroquinone, mono ( ⁇ -methylbenzyl) phenol, di ( ⁇ -methylbenzyl) phenol, tri ( ⁇ -methylbenzyl) phenol, and 2,5-di-.
• the phenolic compound (C1) one type may be used alone, or two or more types may be used in combination.
• phenolic compounds (C1) dibutylhydroxytoluene, hydroquinone and 2- [1- (2-hydroxy-3,5-di-t) are selected from the viewpoint of excellent thermal stability and flexibility of the resin composition.
• -Pentylphenyl) ethyl] -4,6-di-t-At least one selected from the group consisting of pentylphenyl acrylate is more preferable.
• the content of the phenolic compound (C1) is preferably 0.001 to 15 parts by mass, preferably 0.005 parts by mass, based on 100 parts by mass of the polymer composition (P), from the viewpoint of thermal stability and flexibility of the resin composition. To 10 parts by mass is more preferable, and 0.008 to 8 parts by mass is further preferable from the viewpoint of being more excellent in the effect of suppressing the formation of bleed and the effect of preventing discoloration.
• the molecular weight of the amine compound (C2) is preferably 100 or more and 2000 or less, more preferably 150 or more and 1500 or less, and further preferably 160 or more and 1200 or less, from the viewpoint of thermal stability and flexibility of the resin composition.
• the oxidation reaction of the diene polymer (B-2) unit of the copolymer (B) can be specifically suppressed, that is, of the copolymer (B).
• the formation of a carbonyl group in the diene-based polymer (B-2) unit can be suppressed.
• the reaction between the carbonyl group generated in the diene polymer (B-2) unit of the copolymer (B) and the hydroxyl group of the vinyl alcohol polymer (B-1) does not occur, and the thermal stability is excellent. ..
• the amine compound (C2) and the copolymer (B) appropriate flexibility can be imparted to the resin composition. Further, the amine compound (C2) can suppress the formation of the carbonyl group even in a small amount, and can enhance the thermal stability and flexibility of the resin composition.
• the amine compound (C2) is an amine having an aromatic group (however, a benzimidazole compound having a benzimidazole skeleton (for example, 2-mercaptobenzimidazole, etc.)) from the viewpoint of thermal stability and flexibility of the resin composition. ) Is preferable.
• the aromatic group include aryl groups such as a phenyl group, a substituted phenyl group and a naphthyl group, and a phenyl group is preferable.
• Examples of the substituent contained in the substituted phenyl group include a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like.
• a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom
• the amine having an aromatic group a secondary amine containing two or more aromatic rings or a tertiary amine containing two or more aromatic rings is preferable from the viewpoint of being excellent in thermal stability and flexibility of the resin composition.
• the number of aromatic rings contained in the amine having an aromatic group is not particularly limited, but may be 2 to 6, 2 to 4, or 2 to 3.
• Examples of the secondary amine containing two or more aromatic rings include compounds represented by the following general formula [IV].
• R 12 to R 21 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms
• W 1 and W 2 are divalent hydrocarbon groups having 1 to 15 carbon atoms.
• M and n are independently 0 or 1, respectively, and the hydrocarbon groups of R 12 to R 21 and W 1 and W 2 are -O-, -S-, -NH-, and -N (R). 22
• It may contain at least one group selected from the group consisting of-, -O (CO)-, and -CO-.
• R 12 to R 21 together form a ring.
• R 22 represents a hydrocarbon group having 1 to 6 carbon atoms.
• Examples of the hydrocarbon group having 1 to 15 carbon atoms of R 12 to R 21 are the same as those of R 1 to R 7 .
• Examples of the divalent hydrocarbon group having 1 to 15 carbon atoms of W 1 and W 2 are the same as those of X.
• the ring formed by combining R 12 to R 21 may be an aromatic ring or a heterocycle containing an oxygen atom or a sulfur atom.
• R 12 and R 17 may be combined to form a heterocycle containing a sulfur atom and a nitrogen atom via —S—.
• an amine having a diarylamine skeleton in which m and n are 0 is preferable.
• R 12 to R 21 are all hydrogen atoms, m and n are 0, a combination of R 12 and R 17 and / or R 16 and R 21. Also included are compounds in which the combination of is forming a heterocycle via —S—.
• Examples of the amine compound (C2) include N-phenyl-1-naphthylamine, di (4-butylphenyl) amine, di (4-pentylphenyl) amine, di (4-hexylphenyl) amine, and di (4-hexylphenyl) amine.
• Heptylphenyl) amine di (4-octylphenyl) amine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamide) diphenylamine, N, N'di-2-naphthyl -P-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N'-(3) -Methacryloxy-2-hydroxypropyl) -p-phenylenediamine, 2,3: 5,6-dibenzo-1,4-thiadin, N, N, N', N'-tetramethyl-p-diaminodiphenylmethane, diphenylamine Examples of amines having a diarylamine,
• amine compound (C2) one type may be used alone, or two or more types may be used in combination.
• the content of the amine compound (C2) is preferably 0.05 to 15 parts by mass, preferably 0.1 parts by mass, in 100 parts by mass of the polymer composition (P) from the viewpoint of thermal stability and flexibility of the resin composition. To 8 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable from the viewpoint of being more excellent in thermal stability of the resin composition even when used in a small amount.
• the molecular weight of the phosphorus compound (C3) is preferably 100 or more and 2000 or less, more preferably 150 or more and 1500 or less, and further preferably 160 or more and 1200 or less, from the viewpoint of thermal stability and flexibility of the resin composition.
• the oxidation reaction of the diene-based polymer (B-2) unit of the copolymer (B) can be specifically suppressed. That is, the formation of a carbonyl group in the copolymer (B) can be suppressed.
• the reaction between the carbonyl group generated in the diene polymer (B-2) unit of the copolymer (B) and the hydroxyl group of the vinyl alcohol polymer does not occur, and the thermal stability is excellent.
• the phosphorus compound (C3) and the copolymer (B) appropriate flexibility can be imparted to the resin composition. Further, the phosphorus compound (C3) can suppress the formation of the carbonyl group even in a small amount, and can enhance the thermal stability and flexibility of the resin composition.
• a trivalent phosphite ester is preferable.
• the trivalent phosphite ester include compounds represented by the following general formulas [V], [VI] or [VII].
• R 23 , R 24 , R 28 and R 29 each independently represent a hydrocarbon group having 1 to 25 carbon atoms, and R 25 to R 27 each independently represent 1 to 25 carbon atoms. Representing a divalent hydrocarbon group, a plurality of R 23s may be combined to form a ring.
• the hydrocarbon groups having 1 to 25 carbon atoms of R 23 , R 24 , R 28 and R 29 may be linear or branched, and are alkyl groups having 1 to 25 carbon atoms and 2 to 25 carbon atoms.
• Aliphatic groups such as 25 alkenyl groups; aromatic groups having 6 to 25 carbon atoms can be mentioned.
• an alkyl group having 3 to 20 carbon atoms is preferable, and an alkyl group having 4 to 19 carbon atoms is more preferable.
• the aromatic group include aryl groups such as a phenyl group, a substituted phenyl group and a naphthyl group, and a phenyl group and a substituted phenyl group are preferable.
• Examples of the substituent contained in the substituted phenyl group include a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like.
• the plurality of R 23 , R 24 , R 28 and R 29 may be the same or different from each other.
• the divalent hydrocarbon group having 1 to 25 carbon atoms of R 25 to R 27 may be linear or branched, and may be an alkylene group having 1 to 25 carbon atoms and an alkenylene having 2 to 25 carbon atoms.
• Divalent aliphatic groups such as groups; divalent aromatic groups having 6 to 25 carbon atoms can be mentioned.
• an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable.
• the alkylene group include a methylene group, a methylmethylene group, an ethylene group, an n-propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group and a decylene group.
• the divalent aromatic group include an arylene group such as a phenylene group, a substituted phenylene group, and a naphthylene group.
• Examples of the substituent contained in the substituted phenylene group include those similar to those of the substituted phenyl group.
• the plurality of R 25 to R 27 may be the same or different.
• the phosphorus-based compound (C3) is, R 23 is a linear or branched substituted phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, all three R 23 It is the same compound represented by the general formula [V].
• Examples of the phosphorus compound (C3) include tris (nonylphenyl) phosphine, triphenylphosphine, tristearyl phosphite, tricresylphosphite, and tris (2,4-di-tert-butylphenyl) phosphite.
• a preferred embodiment of the resin composition of the present invention may contain a phenolic compound (C1) and an amine compound (C2) as long as the effects of the present invention can be obtained, and the phenolic compound (C1) and phosphorus may be contained. It may contain a system compound (C3), may contain an amine compound (C2) and a phosphorus compound (C3), and may contain a phenol compound (C1), an amine compound (C2) and a phosphorus compound (C3). It may be.
• a resin composition containing a phenolic compound (C1) and a phosphorus compound (C3) or a resin composition containing an amine compound (C2) and a phosphorus compound (C3) is effective, and particularly an amine compound (C2).
• the total content of the phenolic compound (C1), the amine compound (C2) and the phosphorus compound (C3) is preferably 0.001 to 15 parts by mass, and 0. More preferably, 005 to 10 parts by mass.
• the mixing ratio when at least one compound selected from the group consisting of the phenolic compound (C1) and the amine compound (C2) and the phosphorus compound (C3) is contained is not particularly limited.
• X / W Y ) is preferably 90/10 to 50/50. When the mass ratio is in this range, the effect when two kinds of compounds are contained in combination is likely to appear.
• the mass ratio (W X / W Y ) is preferably 85/15 to 55/45, and more preferably 80/20 to 60/40.
• the resin composition of the present invention may contain other components other than the above as long as the effects of the present invention are not impaired.
• the other components include colorants, light stabilizers, vulcanizing agents and vulcanization accelerators, and inorganic additives (silica and the like).
• the resin composition of the present invention comprises a molded body (film, sheet, board, fiber, etc.), a multilayer structure, an additive, a compatibilizer, a coating agent, a barrier material, a sealing agent (metal sealant, etc.), an adhesive, etc. Can be used for a wide range of purposes.
• the present invention includes embodiments in which the above configurations are variously combined within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.
• the upper limit value and the lower limit value of the numerical range can be appropriately combined.
• Wb-Wq is the mass of the main chain composed of the vinyl alcohol polymer (B-1) unit
• Wq is the mass of the side chain composed of the diene polymer (B-2) unit.
• the content of the side chain consisting of the diene polymer (B-2) unit with respect to the total mass of the main chain consisting of the unit (B-1) and the side chain consisting of the diene polymer (B-2) unit was calculated.
• the ethylene unit of the raw material ethylene-vinyl alcohol copolymer is a 2 % by mass, and the vinyl alcohol unit is b 2 % by mass.
• the total amount of modification content of graft-polymerized monomer with respect to all monomer units of the resin composition was calculated according to the following formula.
• Degeneration amount [mol%] Z 2 / (X 2 + Y 2 + Z 2 ) ⁇ 100
• X 2 , Y 2 , and Z 2 are values calculated by the following formula.
• X 2 ⁇ (a raw material for an ethylene - vinyl alcohol copolymer (parts by weight)) ⁇ (a 2/100 ) ⁇ / 28
• Y 2 ⁇ (a raw material for an ethylene - vinyl alcohol copolymer (parts by weight)) ⁇ (b 2/100 ) ⁇ / 44
• Z 2 ⁇ (resin composition after reaction (parts by mass))-(raw material ethylene-vinyl alcohol copolymer (parts by mass)) ⁇ / (molecular weight of monomer to be graft-polymerized)
• the elastic modulus and elongation at break were measured (load cell 1 kN, tensile speed 500 mm / min, distance between chucks 70 mm). As the value of elongation at break shown in the table, the average value of 5 measurements was adopted.
• Example 1 Commercially available ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., E105, ethylene unit content 44 mol%, ethylene mass fraction 33.3 mass%, vinyl alcohol mass fraction 66.7 mass%, MFR (210 ° C., After crushing (load 2160 g) 13.0 g / 10 minutes), particles trapped between both sieves were collected and classified using a sieve with a mesh size of 75 ⁇ m and a sieve with a mesh size of 212 ⁇ m. Obtained particles.
• Example 2 In the same manner as in Example 1, ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained. Next, 100 parts by mass of an ethylene-vinyl alcohol copolymer irradiated with an electron beam is added to an autoclave equipped with a stirrer, a nitrogen introduction tube and a particle addition port, and nitrogen is sealed and depressurized in the system. The system was replaced with nitrogen by repeating 5 times. 250 parts by mass of liquefied butadiene was charged therein, the autoclave was sealed and heated until the internal temperature reached 65 ° C., and heating and stirring were continued for 4 hours as it was, and graft polymerization was carried out.
• Example 3 Ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained in the same manner as in Example 1, and graft polymerization was carried out in the same manner as in Example 1. Then, after cooling to room temperature, 0.02 parts by mass of dibutylhydroxytoluene (hereinafter referred to as BHT) was added, and then the particles were separated by filtration to recover the particles. Then, it was added to heptane containing 50 ppm of BHT, washed with stirring for 15 minutes, and the washing operation of filtering the particles was repeated 10 times.
• BHT dibutylhydroxytoluene
• Example 4 Ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained in the same manner as in Example 1, and graft polymerization was carried out in the same manner as in Example 1. Then, after cooling to room temperature, 0.1 parts by mass of dibutylhydroxytoluene (hereinafter referred to as BHT) was added, and then the particles were separated by filtration to recover the particles. Then, it was added to heptane containing 200 ppm of BHT, washed with stirring for 15 minutes, and the washing operation of filtering the particles was repeated 10 times.
• BHT dibutylhydroxytoluene
• Example 5 Ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained in the same manner as in Example 1, and graft polymerization was carried out in the same manner as in Example 1. Then, after cooling to room temperature, the particles were collected by filtration, added to heptane, washed with stirring for 15 minutes, and the washing operation of separating the particles was repeated 10 times. In this operation, it was confirmed from 1 H-NMR analysis of the extract that a trace amount of polyisoprene produced as a by-product was extracted and removed, and no extract was confirmed after the 7th washing operation. That is, polyisoprene did not remain in the particles.
• washed particles were added to deionized water containing 200 ppm of hydroquinone (hereinafter referred to as HQ), treated at 80 ° C. for 1 hour, filtered again, and the obtained particles were filtered at 40 ° C. overnight.
• Vacuum drying was performed to obtain a desired resin composition containing an ethylene-vinyl alcohol copolymer and a graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.
• Example 6 After crushing commercially available polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval 5-74, saponification degree 74 mol%, vinyl acetate mass fraction 40.7 mass%, vinyl alcohol mass fraction 59.3 mass%), the opening is 75 ⁇ m. Using a sieve and a sieve having a mesh size of 212 ⁇ m, the particles trapped between the two sieves when shaken were collected to obtain classified particles. 100 parts by mass (water content 0.5% by mass) of the obtained particles was irradiated with an electron beam (30 kGy) under a nitrogen atmosphere to obtain ethylene-vinyl alcohol copolymer particles irradiated with the electron beam.
• an electron beam (30 kGy
• Example 7 Commercially available ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., F101, ethylene unit content 32 mol%, ethylene mass fraction 23.0 mass%, vinyl alcohol mass fraction 77.0 mass%, MFR (210 ° C., After crushing (load 2160 g) 3.8 g / 10 minutes), particles trapped between both sieves were collected and classified using a sieve with a mesh size of 75 ⁇ m and a sieve with a mesh size of 212 ⁇ m. Obtained particles.
• 100 parts by mass (water content 0.5% by mass) of the obtained particles was irradiated with an electron beam (20 kGy) under a nitrogen atmosphere to obtain ethylene-vinyl alcohol copolymer particles irradiated with the electron beam.
• 240 parts by mass of isoprene and 245 parts by mass of isopropanol are charged in an autoclave equipped with a stirrer, a nitrogen introduction tube and a particle addition port, and the pressure is reduced to 300 Torr in an ice-cooled state and then returned to normal pressure with nitrogen. was carried out 3 times, and the inside of the system was replaced with nitrogen.
• Example 2 Ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained in the same manner as in Example 1, and graft polymerization was carried out in the same manner as in Example 1. Then, after cooling to room temperature, the particles were collected by filtration, added to heptane, washed with stirring for 15 minutes, and the washing operation of separating the particles was repeated 10 times. In this operation, it was confirmed from 1 H-NMR analysis of the extract that a trace amount of polyisoprene produced as a by-product was extracted and removed, and no extract was confirmed after the 7th washing operation. That is, polyisoprene did not remain in the particles. The obtained particles were vacuum dried at 40 ° C. overnight to obtain a desired resin composition containing an ethylene-vinyl alcohol copolymer and a graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.
• Example 3 Ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained in the same manner as in Example 2, and graft polymerization was carried out in the same manner as in Example 2. Then, after cooling to room temperature, residual butadiene was removed while depressurizing. The obtained particles after the reaction were added to heptane, washed with stirring for 15 minutes, and the washing operation for filtering the particles was repeated 10 times. In this operation, it was confirmed from 1 H-NMR analysis of the extract that a trace amount of by-produced polybutadiene was extracted and removed, and no extract was confirmed after the 4th washing operation. That is, no polybutadiene remained in the particles. The obtained particles were vacuum dried at 40 ° C. overnight to obtain a desired resin composition containing an ethylene-vinyl alcohol copolymer and a graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.
• Comparative Example 4 As a comparative example corresponding to Tokukousho 41-021994, the following Comparative Example 4 was performed. In the same manner as in Example 1, ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained. Next, 100 parts by mass of an ethylene-vinyl alcohol copolymer and 99 parts by mass of methanol irradiated with an electron beam were added to an autoclave equipped with a stirrer, a nitrogen introduction tube and a particle addition port, and nitrogen was sealed in the system. The depressurization operation was repeated 5 times to replace the nitrogen in the system.
• the obtained kneaded product was freeze-milled to obtain a desired resin composition containing an ethylene-vinyl alcohol copolymer and a graft copolymer.
• the results of physical characteristic evaluation are shown in Table 1.
• an analysis was attempted according to the above method, but it was difficult to separate the components due to the difference in solubility in the extraction solvent, and the details of the structure could not be identified, but the mass of the particles before and after graft polymerization. From the change, a mass increase of 4% was confirmed.
• the resin composition of the present invention has higher flexibility than the vinyl alcohol-based resin, is also excellent in storage stability, and is less likely to cause decomposition products even in a long-term storage environment. You can see that. Therefore, it is expected to form a molded product that is more supple and less likely to crack than the conventional vinyl alcohol polymer.
• the unmodified vinyl alcohol-based resin has a high elastic modulus and has a drawback of being hard and brittle.
• Comparative Examples 2 and 3 in the resin composition whose A value deviates from the range of the present invention even when the amount of radicals is small, the diene-based polymer portion is easily decomposed with time in the atmosphere.
• the resin composition in the state where the decomposed product is generated tends to have defects such as cracks after thermoforming, and the films of Comparative Examples 2 and 3 are softened and the tensile elastic modulus is lowered, but the film is easily broken and stretched. The degree has decreased.

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