TW202110917A - Resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a resin composition having excellent flexibility and excellent storage stability. The present invention relates to a resin composition which includes a copolymer (B) composed of a vinyl alcohol-based polymer (B-1) region and a diene-based polymer (B-2) region, and which has a g value of 2.0031-2.0050 in the ESR spectrum.

Description

Resin composition

The present invention relates to a resin composition having excellent flexibility and excellent long-term storage stability.

Vinyl alcohol resins utilize excellent film properties (mechanical strength, oil resistance, film forming properties, oxygen gas barrier properties, etc.) due to high crystallinity, or hydrophilic properties, and are widely used in emulsifiers, suspending agents, and interfacial activity. Agents, fiber processing agents, various adhesives, paper processing agents, adhesives, various packaging bodies, sheets, containers, etc. On the other hand, vinyl alcohol-based resin glass usually has a higher transition temperature than normal temperature and is highly crystalline. Therefore, it has low flexibility, weak bending resistance, low reactivity, etc., depending on the application. The physical shortcomings of the subject. The low degree of flexibility can be solved by a compound plasticizer, but in this case, the overflow of the plasticizer or the decrease in mechanical properties and barrier properties caused by the obvious decrease in crystallinity cannot be avoided.

On the other hand, a method of chemically introducing a specific structure into a vinyl alcohol-based resin has been proposed. In Patent Document 1, there is an example in which a diene polymer with modified functional groups introduced at the end is reacted in a dimethyl sulfide solution of a vinyl alcohol resin, and the diene polymer is introduced via the reactive group.物的polymers.

In addition, Patent Documents 2 and 3 disclose a method of producing a copolymer by using ionizing radiation to generate radicals in a vinyl alcohol-based resin, and contacting the vinyl alcohol-based resin with butadiene. [Prior Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2015/190029 Patent Document 2: Japanese Patent Publication No. 39-6386 Patent Document 3: Japanese Patent Publication No. 41-21994

[The problem to be solved by the invention]

However, these patent documents have not reviewed the long-term storage stability of the copolymer. In fact, the copolymer is extremely prone to deterioration when exposed to the atmosphere, so there is a problem in terms of storage stability in actual use.

The present invention was accomplished in order to solve the above-mentioned problems, and its object is to provide a resin composition having excellent flexibility and excellent long-term storage stability. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention conducted a careful review and found that when a copolymer containing vinyl alcohol polymer units and diene polymer units is directly stored in a wet state under air exposure for a long period of time , It will cause the phenomenon that the diene polymer slowly decomposes and detaches. After reviewing and verifying the main cause, it was found that the detachment phenomenon of the diene polymer is related to the types of trace free radicals in the resin composition, and the stability will change. From this knowledge, it can be seen that the above-mentioned problems can be solved by controlling the radical structure of the resin composition, and the present invention has been completed.

That is, the present invention includes the following inventions. [1] A resin composition containing a copolymer (B) composed of vinyl alcohol polymer (B-1) units and diene polymer (B-2) units, and the g value of the ESR spectrum 2.0031～2.0050. [2] The resin composition according to [1], wherein the amount of radicals is 15×10 ^-3 mmol/kg or less. [3] The resin composition of [1] or [2], wherein the ultrafine binding constant (A value) of the ESR spectrum is less than 20 Gauss. [4] The resin composition according to any one of [1] to [3], wherein the copolymer (B) is a graft copolymer (B1). [5] The resin composition according to any one of [1] to [4], which further contains a vinyl alcohol-based polymer (A). [6] The resin composition according to any one of [1] to [5], wherein the vinyl alcohol-based polymer (B-1) unit contains an ethylene-vinyl alcohol copolymer unit. [7] The resin composition according to any one of [1] to [6], wherein the diene polymer (B-2) is selected from the group consisting of polybutadiene, polyisoprene and polyisobutylene One or more types of groups. [8] The resin composition according to any one of [1] to [7], which further contains an antioxidant (C). [9] The resin composition according to [8], wherein the content of antioxidant (C) is less than 0.1% by mass. [10] The resin composition according to any one of [1] to [9], which contains 10 to 85% by mass of the copolymer (B) with respect to 100 parts by mass of the resin composition. [11] A method for producing the resin composition according to any one of [1] to [10], which comprises dispersing in a solution containing a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer The step of heat-treating the polymer composition (P) of the copolymer (B) composed of the polymer (B-2) unit; the temperature of the heat-treating is 30-150°C. [12] The method for producing a resin composition according to [11], wherein the solution contains an antioxidant (C). [13] A method for producing a resin composition as described in any one of [1] to [10], which comprises combining a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer with a cleaning solution (B-2) A step of washing the polymer composition (P) of the copolymer (B) constituted by the unit; the washing liquid contains an antioxidant (C). [Effects of Invention]

According to the present invention, it is possible to provide a resin composition having excellent flexibility and excellent long-term storage stability. In particular, from the viewpoint of industrial applicability, the resin composition of the present invention can suppress the intervening factors even when the copolymer is stored in a wet state for a certain period of time, such as when a copolymer is produced in a factory. Deterioration caused by moisture absorption, excellent long-term storage stability.

[Form to implement the invention]

The resin composition of the present invention is characterized by containing a copolymer (B) composed of vinyl alcohol polymer (B-1) units and diene polymer (B-2) units, and the g value of the ESR spectrum is 2.0031 ~2.0050.

The so-called g value obtained by the measurement of the ESR spectrum is a parameter represented by the following formula (Q). g=hν/βH (Q) (In the formula, h represents the Planck constant, ν represents the resonance frequency, β represents the Bohr magneton (Bohr magneton), and H represents the resonance magnetic field (the intersection point of the ESR signal and the baseline)).

The g value can be obtained from the measurement of the ESR spectrum. The measurement of the ESR spectrum can be performed using a well-known electronic rotation resonance device. As an electronic rotation resonance device, JES-X3 manufactured by JEOL Ltd., EMXplus manufactured by BRUKER JAPAN Co., Ltd. (attachment device: Cryostat ESR910 manufactured by Oxford Instruments Co., Ltd.), etc. are mentioned.

The inventors of the present invention have discovered that the decomposition reaction of the resin proceeds violently when the resin composition is in a wet state such as a state containing moisture in the atmosphere or a certain solvent. It is believed that this decomposition reaction is due to the fact that the resin composition is plasticized in a wet state, and the polymer becomes a state where molecular motion is easy to proceed. As a result, the reaction between the molecular chains or the substance that promotes decomposition (for example, oxygen or Water, etc.). It is considered that the resin composition system of the present invention can detect a very small amount of free radicals regardless of the production method, and the amount of free radicals affects the stability of the decomposition reaction, but it can be found from the results of the review by the inventors. The stability is not affected by the amount of free radicals, but greatly affected by the type and structure of free radicals. It was found that a resin composition system whose g value is set in a specific range as a spectrum that reflects anisotropy can suppress the decomposition of the diene polymer even in a wet state. The g value of the resin composition of the present invention is preferably 2.0035 to 2.0049, preferably 2.0036 to 2.0048, and more preferably 2.0037 to 2.0047 from the viewpoint of superior flexibility and long-term storage stability.

The amount of free radicals of the resin composition of the present invention is based on the viewpoint that flexibility and long-term storage stability are more excellent, preferably 15×10 ^-3 mmol/kg or less, preferably 10×10 ^-3 mmol/kg or less 8.5×10 ^-3 mmol/kg or less is more preferable. The amount of free radicals is, for example, described in the following examples, and can be calculated from the signal intensity obtained by the measurement of the ESR spectrum.

The ultrafine binding constant (A value) of the ESR spectrum of the resin composition of the present invention is preferably less than 20 Gauss, preferably less than 19 Gauss, and 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 according to the free radical structure, so the resin composition can exist stably The structure type of the free radical can be specified by the range of A value. If the A value is less than 20 Gauss, even in a state where there are many radicals, the decomposition reaction will not easily occur, which is preferable. In addition, the A value of the resin composition having excellent stability is preferably 10 Gauss or more. If the A value exceeds 20 Gauss, the above decomposition reaction will be 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. Moreover, in addition to this, a vinyl alcohol-based polymer (A) may also be contained.

(Vinyl alcohol polymer (A) and (B-1)) The types of the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1) are not particularly limited. For example, the following polyvinyl alcohol or ethylene-vinyl alcohol copolymer can be suitably used. The vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1) constitute the structural unit of each polymer, and the viscosity, average polymerization degree, saponification degree, etc. of each polymer may be the same or different. The vinyl alcohol unit content of the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1) is preferably 40 mol% or more, may be 50 mol% or more, or may be 55 mol% or more. In addition, for each of the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1), a single polyvinyl alcohol or an ethylene-vinyl alcohol copolymer may be used, or plural polyvinyl alcohol copolymers may be used in combination. Vinyl alcohol and/or ethylene-vinyl alcohol copolymer. In addition, in the present invention, the so-called structural unit in the polymer means the repeating unit constituting the polymer. For example, ethylene units or vinyl alcohol units are also structural units.

The viscosity average polymerization degree of the polyvinyl alcohol (measured in accordance with JIS K 6726 (1994)) is not particularly limited, and is preferably 100 to 10,000, preferably 200 to 7,000, and more preferably 300 to 5,000. When the viscosity average degree of polymerization is within the above range, the resulting resin composition has excellent mechanical properties. Regarding the vinyl alcohol polymer (B-1), the viscosity average degree of polymerization can be adjusted in accordance with the desired number average molecular weight of the copolymer (B).

The degree of saponification of polyvinyl alcohol (measured in accordance with JIS K 6726 (1994)) is not particularly limited. From the viewpoint of excellent mechanical properties, it is preferably 50 mol% or more, preferably 80 mol% or more, and more preferably 95 mol% or more , Can also be 100mol%.

The content rate of the ethylene unit in the ethylene-vinyl alcohol copolymer is not particularly limited. From the viewpoint of excellent mechanical properties and easy production, it is preferably 10 to 60 mol%, and more preferably 20 to 50 mol%. The content of the ethylene unit of the ethylene-vinyl alcohol copolymer can be ^{determined from 1} H-NMR measurement.

The degree of saponification of the ethylene-vinyl alcohol copolymer is not particularly limited. From the viewpoint of formability and mechanical properties, it is preferably 80 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more, or 100 mol% . The saponification degree of the ethylene-vinyl alcohol copolymer can be measured in accordance with JIS K 6726 (1994).

The melt flow rate (MFR) (210°C, 2160 g of the load) of the above-mentioned ethylene-vinyl alcohol copolymer is not particularly limited, and is preferably 0.1 g/10 minutes or more, and 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. In addition, the upper limit of the melt flow rate may be a value generally used, and for example, it may be 25 g/10 minutes or less. The melt flow rate is a value obtained by measuring under the conditions of 210°C and a load of 2160 g using a melt index meter in accordance with ASTM D1238.

The above-mentioned ethylene-vinyl alcohol copolymer may contain structural units derived from unsaturated monomers other than ethylene units and vinyl alcohol units within a range that does not impair the effects of the present invention. The content of the structural unit derived from the unsaturated monomer in the ethylene-vinyl alcohol copolymer is preferably 10 mol% or less, preferably 5 mol, relative to all the structural units constituting the ethylene-vinyl alcohol copolymer %the following.

The above-mentioned polyvinyl alcohol and ethylene-vinyl alcohol copolymer may contain structural units (c) other than vinyl alcohol units, vinyl ester monomers, and ethylene units within a range that does not impair the effects of the present invention.

Examples of the structural unit (c) include structural units derived from α-olefins such as propylene, n-butene, isobutylene, 1-hexene, etc. (in the case of polyvinyl alcohol, ethylene is included) ; Acrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, Unsaturated monomers with acrylate groups such as octadecyl acrylate; methacrylic acid; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate Butyl ester, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, octadecyl methacrylate, etc. with methacrylate groups Unsaturated monomers; acrylamide, N-methacrylamide, N-ethacrylamide, N,N-dimethylacrylamide, diacetone acrylamide, acrylamide propane sulfonic acid, propylene Acrylic amines such as amide propyl dimethylamine; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid, Methacrylamides such as methacrylamide, propyldimethylamine, etc.; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl ethylene Base ether, isobutyl vinyl ether, tertiary butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diethoxy-1-vinyloxypropane, etc. Vinyl ethers; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; Halogenated vinyls such as vinyl chloride and vinyl fluoride; Halogenated vinylenes such as vinylidene chloride and vinylidene fluoride; Allyl acetate Allyl compounds such as esters, 2,3-diethoxy-1-allyloxypropane, allyl chloride, etc.; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid Acids and their salts or esters; vinyl silicon compounds such as vinyl trimethoxysilane; isopropenyl acetate, etc. The content of the structural unit (c) is preferably less than 10 mol% with respect to all structural units constituting the polyvinyl alcohol or the ethylene-vinyl alcohol copolymer.

As the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1), in particular, an ethylene-vinyl alcohol copolymer can be suitably used. A certain preferred embodiment includes a resin composition in which the vinyl alcohol polymer (B-1) unit contains an ethylene-vinyl alcohol copolymer unit. By using ethylene-vinyl alcohol copolymer, the thermoformability of the resin composition of the present invention can be easily improved.

(Copolymer (B)) 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) and a block copolymer (B2).

(Graft copolymer (B1)) The copolymer (B) is preferably a graft copolymer (B1). The structure of the graft copolymer (B1) is not particularly limited, and may be 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 containing a vinyl alcohol polymer (B-1) unit and a side chain containing a diene polymer (B-2) unit. That is, it is preferable to introduce a side chain containing a unit of a diene polymer (B-2) with respect to a main chain containing a unit of a vinyl alcohol polymer (B-1). Particularly preferred is one having a plurality of diene polymer (B-2) units bonded to one vinyl alcohol polymer (B-1) unit. The type of vinyl alcohol polymer (B-1) is not particularly limited, and for example, it is preferably the above-mentioned polyvinyl alcohol or ethylene-vinyl alcohol copolymer. The vinyl alcohol-based polymer (B-1)-based vinyl alcohol unit content is preferably 40 mol% or more, may be 50 mol% or more, or may be 55 mol% or more. Regarding the vinyl alcohol polymer (B-1), polyvinyl alcohol or ethylene-vinyl alcohol copolymer may be used alone, or plural polyvinyl alcohol and/or ethylene-vinyl alcohol copolymers may be used in combination.

(Block copolymer (B2)) When the copolymer (B) is a block copolymer (B2), it has a vinyl alcohol polymer (B-1) unit as the polymer block (b1) and has a diene as the polymer block (b2) It is a unit of polymer (B-2). The block copolymer (B2) may each have one polymer block (b1) and polymer block (b2), or it may have two or more polymer blocks (b1) and/or polymers Block (b2). Examples of the bonding pattern of the block copolymer include: b1-b2 type diblock copolymer, b1-b2-b1 type triblock copolymer, b2-b1-b2 type triblock copolymer, The linear multi-block copolymer represented by b1-b2-b1-b2 type tetrablock copolymer or b2-b1-b2-b1 type tetrablock copolymer, consisting of (b2-b1-)n, (b1- b2-) Star-shaped (radial star-shaped) block copolymers and the like represented by n and others. n is a value greater than 2.

(Diene polymer (B-2)) The copolymer (B) contains a diene polymer (B-2). The structure of the diene polymer (B-2) is not particularly limited, but the diene polymer (B-2) preferably 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. As the diene polymer (B-2), for example, polybutadiene, polyisoprene, polyisobutylene, polychloroprene, polybacterolene, etc. can be cited. These systems may be used singly or in combination of two or more. In addition, the diene polymer (B-2) may be a copolymer of two or more types selected from the group including butadiene, isoprene, isobutylene, chloroprene, and bacteriogreen. Among them, from the viewpoint of reactivity and flexibility, polybutadiene, polyisoprene, and polyisobutylene are preferred, and polyisoprene is preferred. In addition, the copolymer (B) may contain structural units other than the vinyl alcohol-based polymer (B-1) and the diene-based polymer (B-2) in a range that does not impair the effects of the present invention. In addition, the side chain of the graft copolymer (B1) is within a range that does not impair the effect of the present invention, and may include other than vinyl alcohol polymer (B-1) and diene polymer (B-2) Structural units.

The content of the diene polymer (B-2) unit in the copolymer (B) relative to the total mass of the vinyl alcohol polymer (B-1) unit and the diene polymer (B-2) unit It is not particularly limited, but it is preferably 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more. The content of the diene polymer (B-2) unit is preferably 80% by mass or less, preferably 60% by mass or less, and more preferably 50% by mass or less. When the above content is 10% by mass or more, the copolymer (B) (especially the graft copolymer (B1)) can easily obtain the desired flexibility and reactivity. When the content is below 80% by mass, the vinyl alcohol polymer (A) has excellent compatibility with the copolymer (B), and can suppress the deterioration of transparency and various physical properties caused by the formation of coarse phase separation. The method for measuring the content of the diene polymer (B-2) unit is as described in the following Examples.

The content of the copolymer (B) is preferably 10 to 85% by mass relative to 100 parts by mass of the resin composition, preferably 15 to 75% by mass, and more preferably 20 to 70% by mass.

In the graft copolymer (B1), the side chain system containing the unit of the diene polymer (B-2) preferably has a molecular weight distribution. When the side chain containing the diene polymer (B-2) unit has a molecular weight distribution, in the embodiment containing the vinyl alcohol polymer (A), it is easy to improve the graft copolymerization of the vinyl alcohol polymer (A) The compatibility of the material (B1), and the transparency after molding tends to increase.

The total modified mass of the polymer composition (P) of the present invention is based on the viewpoint of better flexibility, and is preferably 1.0-30 mol%, preferably 5.0-25 mol%, and more preferably 8.0-20 mol%. In this specification, the so-called polymer composition (P) means a polymer composition comprising a vinyl alcohol-based polymer (A) and a copolymer (B). The so-called polymer composition (P) is a total modification The quality refers to the content of the monomer grafted and polymerized relative to all of its monomer units. Specifically, the total modified amount of the polymer composition (P) can be calculated using the method described in the 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 above 140°C, excellent mechanical properties are easily expressed. 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 below 200°C, it is not necessary to set it to a high temperature during molding, and it is easy to suppress thermal degradation of the resin.

(Manufacturing method of polymer composition (P)) The method for producing the polymer composition (P) of the present invention is not particularly limited. When the copolymer (B) is a graft copolymer (B1), for example, it can be exemplified by the use of various commonly known graft polymerization methods. , The free radicals are generated on the main chain of the vinyl alcohol polymer, the graft chain is introduced to produce the graft copolymer (B1), and the graft copolymer (B1) obtained is combined with ethylene according to the desired composition A method of mixing the alcohol-based polymer (A). The graft polymerization method includes, for example, a method of graft polymerization using radical polymerization using a polymerization initiator; a graft polymerization method using active energy rays (hereinafter referred to as active energy ray graft polymerization method). ); Preferably, an active energy ray graft polymerization method is used. In particular, as a method for producing the polymer composition (P) by the active energy ray graft polymerization method, a production method including the following steps is preferred: in order to generate free radicals, an active energy ray is irradiated on the vinyl alcohol system in advance. The step of polymer (B-1); and dispersing the vinyl alcohol polymer (B-1) in a monomer that is a raw material of the diene polymer (B-2) or a solution containing the monomer, To carry out the graft polymerization step. The product obtained by this method becomes a mixture of unreacted vinyl alcohol polymer (B-1) and graft copolymer (B1), and the above unreacted vinyl alcohol polymer (B-1) corresponds to Vinyl alcohol polymer (A). Therefore, if this method is adopted, the polymer composition (P) of the present invention can be produced in a single step. In addition, the molecular weight of the side chain of the graft copolymer (B1) obtained by this method is not homogenized but has a molecular weight distribution. Furthermore, for the polymer composition obtained by the method of producing the polymer composition (P) using the above-mentioned active energy ray graft polymerization method, a vinyl alcohol-based polymer (A) may be added as needed.

When the vinyl alcohol polymer (B-1) was irradiated with active energy rays, it was confirmed that radicals were generated at least on the carbon atoms of the methine of the vinyl alcohol unit. Therefore, the single system belonging to the raw material of the diene polymer (B-2) undergoes radical polymerization starting from the carbon atom of the above-mentioned methine group to produce a diene polymer (B- 2) A graft copolymer (B1) in which the side chain of the vinyl alcohol polymer (B-1) is directly bonded to the tertiary carbon atom of the main chain. In addition, it is considered that when an ethylene-vinyl alcohol copolymer is irradiated with active energy rays, radicals are also generated on the carbon atoms of the methylene group of the ethylene unit. Therefore, it can be inferred that the single system belonging to the raw material of the diene polymer (B-2) undergoes radical polymerization with the carbon atom of the methylene group as the starting end, and the formation will contain the diene polymer A graft copolymer (B1) in which the side chain of the substance (B-2) is directly bonded to the secondary carbon atom of the main chain of the vinyl alcohol-based polymer (B-1).

In the production method of the present invention, it is preferable to irradiate active energy rays to the vinyl alcohol polymer (B-1) with a water content of 15% by mass or less. The moisture content is preferably 5% by mass or less, and more preferably 3% by mass or less. When the moisture content is 15% by mass or less, the free radicals generated on the vinyl alcohol polymer (B-1) are less likely to disappear, and the vinyl alcohol polymer (B-1) is relatively diene polymer The monomer of the raw material of (B-2) tends to have sufficient reactivity. In addition, in the production method of the present invention, it is preferable to irradiate an active energy ray to a vinyl alcohol polymer (B-1) having a water content of 0.001% by mass or more. The moisture content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more.

Examples of the active energy rays irradiated on the vinyl alcohol polymer (B-1) include ionizing radiation such as α rays, β rays, γ rays, electron rays, and ultraviolet rays; X rays, g rays, i rays, and collimated rays. Molecular lasers and the like, among them, ionizing radiation is preferred, electron beams and γ-rays are more practical in practice, and electron beams with fast processing speed and simple equipment are more preferred.

The dose of active energy rays irradiated to the vinyl alcohol polymer (B-1) is preferably 5 to 200 kGy, preferably 10 to 150 kGy, more preferably 20 to 100 kGy, and particularly preferably 30 to 90 kGy. When the radiation dose is 5 kGy or more, it becomes easy to introduce a sufficient amount of side chains. On the other hand, when the radiation dose is 200kGy or less, it will be advantageous in terms of cost, and it will also become easier to suppress the deterioration of the vinyl alcohol polymer (B-1) caused by the irradiation of active energy rays. .

The shape of the vinyl alcohol-based polymer (B-1) is not particularly limited, but it is preferably a powder or particle shape having an average particle diameter of 50 to 4000 μm. By making this shape, it can be combined with the monomers (for example, butadiene, isoprene, isobutylene, chloroprene, bacteriochloroprene, etc.) which are the raw materials of the diene polymer (B-2) or include The contact efficiency of the monomer solution is improved, so it is easy to obtain a high reaction rate. When the average particle size is 50 μm or more, there is a tendency that powder scattering is easily suppressed. When it is 4000 μm or less, the reaction rate tends to increase. The above-mentioned average particle size is preferably 60-3500 μm, preferably 80-3000 μm. The measurement method using the laser diffraction device "LA-950V2" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

烷、二乙基醚等之醚；丙酮、甲基乙基酮等之酮；二甲基甲醯胺、二甲基乙醯胺等之醯胺；甲苯、己烷等。另外，在使用水時，因應需要，可合併使用用以使單體分散之界面活性劑等。又，該等溶媒係也可組合使用2種以上。In the case where the vinyl alcohol polymer (B-1) irradiated with active energy rays is dispersed in a solution containing monomers belonging to the raw material of the diene polymer (B-2) to carry out graft polymerization It is necessary that the dispersing solvent used will dissolve the monomers that are the raw material of the diene polymer (B-2), but will not cause the vinyl alcohol polymer (B-1) irradiated with active energy rays Dissolve. In the case of using a solvent that will dissolve the vinyl alcohol polymer (B-1) irradiated with active energy rays, the graft polymerization proceeds with the radicals generated on the vinyl alcohol polymer (B-1) The deactivation will proceed at the same time, so it is difficult to suppress the amount of monomer added. As the dispersing solvent used in the graft polymerization, for example, water; lower alcohols such as methanol, ethanol, and isopropanol; tetrahydrofuran, two

Ethers such as alkanes and diethyl ether; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide; toluene, hexane, etc. In addition, when water is used, a surfactant for dispersing monomers, etc. can be used in combination as needed. Moreover, these solvent systems can also be used in combination of 2 or more types.

In the step of graft polymerization, the vinyl alcohol polymer (B-1) irradiated by active energy rays swells, and the monomers belonging to the raw material of the diene polymer (B-2) penetrate to A large amount of side chains containing the diene polymer (B-2) can be introduced into the inside of the vinyl alcohol polymer (B-1). Therefore, the dispersion solvent used should be selected in consideration of the affinity with the vinyl alcohol-based polymer irradiated with active energy rays. Among the above-mentioned dispersing solvents, lower alcohols such as methanol, ethanol, isopropanol, etc., have high affinity with the vinyl alcohol polymer (B-1) irradiated with active energy rays, and therefore can be suitably used in the present invention. Production method. In addition, in the range in which the vinyl alcohol polymer (B-1) irradiated with active energy rays is insoluble, using the mixture of the dispersion solvent as a liquid medium is also effective for the same reason as described above. On the other hand, when the affinity between the liquid medium and the vinyl alcohol polymer is too high, the resin after the reaction is greatly swollen, and it is difficult to isolate by filtration. It is a diene polymer (B-2 ) The monomer of the raw material becomes easy to homopolymerize. Therefore, it is preferable that the dispersing solvent system can be appropriately selected in accordance with the affinity with the vinyl alcohol-based polymer used and the swelling property at the reaction temperature described later.

The amount of monomer used as the raw material of the diene polymer (B-2) in the graft polymerization can be adjusted appropriately according to the reactivity of the monomer. The above-mentioned reactivity system changes as described above, depending on the ease of penetration of the monomer into the vinyl alcohol-based polymer, etc. Therefore, the appropriate addition amount of the above-mentioned monomers varies depending on the type or amount of the dispersing solvent, or the degree of polymerization or saponification of the vinyl alcohol polymer (B-1), and is relative to the amount irradiated by active energy rays. 100 parts by mass of vinyl alcohol polymer (B-1), preferably 1 to 1000 parts by mass. When the amount of monomers belonging to the raw material of the diene polymer (B-2) is within the above range, it is easy to polymerize the vinyl alcohol polymer (B-1) of the graft copolymer (B1) with the diene polymer The ratio of material (B-2) is controlled within this range. The amount of the above monomer used is preferably 2 to 900 parts by mass, 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, and more preferably 200 parts by mass relative to 100 parts by mass of the vinyl alcohol polymer (B-1) irradiated with active energy rays. ~2000 parts by mass, more preferably 300-1500 parts by mass.

The reaction temperature of the graft polymerization is preferably 20°C to 150°C, preferably 30°C to 120°C, more preferably 40°C to 100°C. When the reaction temperature is 20°C or higher, the graft polymerization reaction easily proceeds. When the reaction temperature is 150°C or lower, it is difficult to cause thermal melting of the vinyl alcohol polymer (B-1). In addition, when the boiling point of the monomer that is the raw material of the diene polymer (B-2) or the boiling point of the liquid medium is lower than the above reaction temperature, it can be placed in a pressure vessel such as an autoclave under pressure. Carry out the reaction.

The reaction time of graft polymerization is preferably within 10 hours, preferably within 8 hours, and more preferably within 6 hours. When the above-mentioned reaction time is 10 hours or less, it is easy to suppress homopolymerization of monomers that are raw materials of the diene polymer (B-2). The reaction time of graft polymerization is preferably 0.5 hour or more, preferably 1 hour or more.

(Manufacturing method of resin composition) Examples of the method for producing the resin composition of the present invention include: (i) including a vinyl alcohol-based polymer (B-1) unit dispersed in a solution and a diene-based polymer (B-2). ) The step of heat-treating the polymer composition (P) of the copolymer (B) composed of units, and the heat-treating temperature is 30-150°C; (ii) The method includes using a cleaning solution to contain vinyl alcohol The step of washing the polymer composition (P) of the copolymer (B) composed of the polymer (B-1) unit and the diene polymer (B-2) unit, and the washing liquid contains The manufacturing method of oxidant (C), etc. In the production method (i), the solution system may contain an antioxidant (C). The antioxidant (C) used in these manufacturing methods can be those described later. The content of the antioxidant (C) in the production method (i) is preferably 10 to 1000 ppm, preferably 20 to 800 ppm, and more preferably 30 to 500 ppm relative to the total amount of the solution. The content of the antioxidant (C) in the production method (ii) is preferably 10 to 1000 ppm, preferably 20 to 800 ppm, and more preferably 30 to 500 ppm relative to the total amount of the solution.

烷、二乙基醚等之醚類的有機溶媒。In the manufacturing method (i), the temperature of the heat treatment is preferably 35 to 120°C, preferably 40 to 100°C, more preferably 50 to 90°C. The solvent used in the solution of the manufacturing method (i) is preferably a solvent that has high affinity with the resin composition and can swell the resin composition. Preferably, alcohols such as water and methanol can be cited. The solvent system used in the cleaning solution of the manufacturing method (ii) includes: hydrocarbon solvents such as hexane and heptane; tetrahydrofuran, two

Ether organic solvents such as alkane and diethyl ether.

(Antioxidant (C)) The resin composition of the present invention can control the g value of the ESR spectrum within a predetermined range, thereby exhibiting excellent storage stability, but for the purpose of improving the stability, it may further contain an antioxidant (C). As the antioxidant (C), it is preferable to include at least one selected from the group consisting of a phenol-based compound (C1), an amine-based compound (C2), and a phosphorus-based compound (C3). The content of antioxidant (C) in the resin composition of the present invention is preferably less than 1.0% by mass, preferably less than 0.5% by mass, and more preferably less than 0.1% by mass.

(Phenolic compound (C1)) The molecular weight of the phenolic compound (C1) is preferably 100 or more and 2000 or less. From the viewpoint of thermal stability and flexibility of the resin composition, it is preferably 150 or more and 1500 or less, and more preferably 160 or more and 1200 or less.

(式中，R¹ ～R⁷ 係分別獨立表示氫原子、碳數1～15之烴基或羥基，X係表示碳數1～15之二價烴基，Y係表示乙烯基氧基或(甲基)丙烯醯氧基，R¹ ～R⁷ 及X之該烴基係可由包含 -O-、-S-、-NH-、-N(R⁸ )-、-O(CO)-及-CO-之群組所選出之至少1種原子。R⁸ 係表示碳數1～6之烴基)。The phenolic compound (C1) is preferably a compound represented by the following general formula [I] or [II].

(In the formula, R ¹ to R ⁷ each independently represent a hydrogen atom, a hydrocarbon group with 1 to 15 carbons or a hydroxyl group, X represents a divalent hydrocarbon group with 1 to 15 carbons, and Y represents a vinyloxy group or (methyl ) Allyloxy, R ¹ ～R ⁷ and the hydrocarbon group of X may include -O-, -S-, -NH-, -N(R ⁸ )-, -O(CO)- and -CO- At least one atom selected from the group. R ⁸ represents a hydrocarbon group with 1 to 6 carbon atoms).

The hydrocarbon group of R ¹ to R ^{7 having} 1 to 15 carbon atoms may be linear or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. Butyl, 2-methylpropyl, tertiary butyl, n-pentyl, isopentyl, secondary pentyl, neopentyl, 1-ethylpropyl, 1,1-dimethyl Propyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl (isohexyl), 1- Ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl Base, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-2-methyl-propyl, 1,1,2 -Trimethylpropyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl , 1-methylnonyl, n-undecyl, n-dodecyl and other alkyl groups; vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2 -Butenyl, 3-butenyl, 1,3-butadienyl, 2-pentenyl and other alkenyl groups; phenyl, substituted phenyl, naphthyl and other aryl groups. Examples of the substituent possessed by the substituted phenyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, and iodine atom). As ^{the hydrocarbon group having 1 to 15 carbon atoms of R 1} to R ⁷ , from the viewpoint that the thermal stability and flexibility of the resin composition are more excellent, it is preferably a linear or branched chain alkyl group. The carbon number of the hydrocarbon group of R ¹ to R ⁷ is preferably 1 to 10, and it is preferably 1 to 6 from the viewpoint that the thermal stability and flexibility of the resin composition are more excellent. Examples of the hydrocarbon group of R ⁸ include those having 1 to 6 carbon atoms as the above-mentioned hydrocarbon groups of ^{R 1} to R ^7. The divalent hydrocarbon group having 1 to 15 carbon atoms of X may be linear or branched, and examples include methylene, methylmethylene, ethylene, n-propyl, and isopropyl , Butylene, pentyl, hexylene, heptyl, octyl, nonyl, decylene, etc. The carbon number of the hydrocarbon group of X is preferably 1-10, and from the viewpoint that the thermal stability and flexibility of the resin composition are more excellent, it is preferably 1-6, more preferably 1-4. As Y, from the viewpoint that the thermal stability and flexibility of the resin composition are more excellent, the (meth)acryloxy group is preferable, and the acryloxy group is more preferable. In addition, in a preferred embodiment, ^{the hydrocarbon groups of R 1} to R ⁷ and X may be exemplified without -O-, -S-, -NH-, -N(R ⁸ )-, -O(CO) -And -CO- phenolic compounds. Furthermore, in other preferred embodiments, ^{phenolic compounds in which R 3} is a hydroxyl group can be cited.

(式中，R⁹ 及R¹⁰ 係分別獨立表示碳數1～15之烴基，Z係表示碳數1～15之二價烴基，R⁹ 、R¹⁰ 及Z之烴基係可包含：由包含-O-、-S-、-NH-、-N(R¹¹ )-、-O(CO)-及-CO-之群組所選出之至少1種基。R¹¹ 係表示碳數1～6之烴基)。Moreover, as a phenolic compound (C1) of another embodiment, the compound represented by the following general formula [III] can be mentioned.

(In the formula, 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, and the hydrocarbon group of ^{R 9} , R ^{10 and Z may include:} At least one group selected from the group of O-, -S-, -NH-, -N(R ¹¹ )-, -O(CO)- and -CO-. R ¹¹ represents a group with 1 to 6 carbon atoms Hydrocarbyl).

Examples of the hydrocarbon group 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.} As the compound represented by the general formula [III], it is preferable that R ⁹ and R ¹⁰ are a hydrocarbon group with 1 to 6 carbons, Z is a divalent hydrocarbon group with 1 to 10 carbons, and the divalent hydrocarbon group includes -O-, -S-, -NH-, -N(R ¹¹ )-, -O(CO)- and -CO- group selected from at least one group of compounds.

The phenolic compound (C1) of a preferred embodiment is more excellent in thermal stability and flexibility based on the resin composition, and at the same time, the effect of inhibiting the generation of bleeding and the effect of preventing discoloration are more excellent, including In the compound represented by the general formula [I], R ¹ , R ² and R ³ are phenolic compounds having a hydrocarbon group having 1 to 6 carbon atoms.

In addition, as the phenolic compound (C1) of another preferred embodiment, the resin composition is more excellent in thermal stability and flexibility, and at the same time the discoloration prevention effect is more excellent, as represented by the general formula [II] Among the compounds, 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, and Y is a phenolic compound having an acryloxy group.

As the phenolic compound (C1), for example, dibutylhydroxytoluene, hydroquinone, mono(α-methylbenzyl)phenol, bis(α-methylbenzyl)phenol, tri(α-methyl) Benzyl)phenol, 2,5-di-tertiary butyl hydroquinone, 2,5-di-tertiary pentyl hydroquinone, 2-[1-(2-hydroxy-3,5-di-tertiary pentyl (Phenyl) ethyl)-4,6-di-tertiary pentyl phenyl acrylate, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methylbenzyl) )-4-methylphenyl acrylate, 4,6-bis[(octylthio)methyl]-o-cresol, pentaerythritol 4[3-(3,5-di-tertiarybutyl-4-hydroxyl) Phenyl) propionate), 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6-tri Butyl phenol), 4,4'-butylene bis (3-methyl-6-tertiary butyl phenol), octadecyl-3-(3,5-di-tertiary butyl-4-hydroxy Phenyl) propionate, etc., based on the viewpoint that the resin composition is more excellent in thermal stability and flexibility, dibutylhydroxytoluene, hydroquinone, 2-[1-(2-hydroxy-3,5- Di-tertiary pentyl phenyl) ethyl)-4,6-di-tertiary pentyl phenyl acrylate, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5 -Methylbenzyl)-4-methylphenyl acrylate, 2-tertiarybutyl-6-(3-tertiarybutyl-2-hydroxy-5-methylbenzyl)-4-methylbenzene Base acrylate. The phenolic compound (C1) may be used singly, or two or more of them may be used in combination.

Based on the viewpoint that the resin composition is more excellent in thermal stability and flexibility, the phenolic compound (C1) is preferably composed of dibutylhydroxytoluene, hydroquinone and 2-[1-(2-hydroxyl At least one selected from the group of -3,5-di-tertiary pentylphenyl) ethyl]-4,6-di-tertiary pentyl phenyl acrylate.

The content of the phenolic compound (C1) is based on 100 parts by mass of the polymer composition (P). Based on the thermal stability and flexibility of the resin composition, the content is preferably 0.001-15 parts by mass, more preferably 0.005- 10 parts by mass, based on the viewpoint that the effect of preventing the generation of leakage and the effect of preventing discoloration is more excellent, it is more preferably 0.008-8 parts by mass.

(Amine compound (C2)) The molecular weight of the amine compound (C2) is preferably 100 or more and 2000 or less. From the viewpoint of thermal stability and flexibility of the resin composition, it is preferably 150 or more and 1500 or less, and more preferably 160 or more and 1200 or less. By using the amine compound (C2), the oxidation reaction of the diene polymer (B-2) unit of the copolymer (B) can be particularly suppressed, that is, the diene polymerization of the copolymer (B) can be suppressed The carbonyl group in the unit (B-2) is formed. Therefore, 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. In addition, by using the amine compound (C2) and the copolymer (B), appropriate flexibility can be imparted to the resin composition. Furthermore, even if the amine compound (C2) is a small amount, the generation of the carbonyl group can be suppressed, and the thermal stability and flexibility of the resin composition can be improved.

As the amine compound (C2), based on the thermal stability and flexibility of the resin composition, an amine having an aromatic group (but a benzimidazole compound having a benzimidazole skeleton (for example, 2-mercaptobenzo (Except imidazole, etc.)). Examples of the aromatic group include aryl groups such as a phenyl group, a substituted phenyl group, and a naphthyl group, and a phenyl group is preferred. Examples of the substituent possessed by the substituted phenyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), and the like. The amine having an aromatic group is preferably a secondary amine containing two or more aromatic rings or a tertiary amine containing two or more aromatic rings based on the viewpoint that the resin composition is more excellent in thermal stability and flexibility. The number of aromatic rings contained in the amine having an aromatic group is not particularly limited, and it may be 2 to 6, or 2 to 4, or 2 to 3.

(式中，R¹² ～R²¹ 係分別獨立表示氫原子或碳數1～15之烴基，W¹ 及W² 係表示碳數1～15之二價烴基，m及n係分別獨立表示0或1，R¹² ～R²¹ 以及W¹ 及W² 之烴基係可包含：由包含-O-、-S-、-NH-、-N(R²² )-、-O(CO)-及-CO-之群組所選出之至少1種基。R¹² ～R²¹ 係可一起形成環。R²² 係表示碳數1～6之烴基)。Examples of secondary amines containing two or more aromatic rings include compounds represented by the following general formula [IV].

(In the formula, R ¹² to R ²¹ each independently represent a hydrogen atom or a hydrocarbon group with 1 to 15 carbons, W ¹ and W ² represent a divalent hydrocarbon group with 1 to 15 carbons, and m and n each independently represent 0 or 1. ^{The hydrocarbon group of R 12} ～R ²¹ and W ¹ and W ² may include: -O-, -S-, -NH-, -N(R ²² )-, -O(CO)- and -CO -At least one group selected from the group. R ¹² to R ²¹ can form a ring together. R ²² represents a hydrocarbon group with 1 to 6 carbon atoms).

The hydrocarbon groups of R ¹² to R ^{21 having} 1 to 15 carbon atoms are the same as those of ^{R 1} to R ^7. Examples of the divalent hydrocarbon groups having 1 to 15 carbon atoms of W ¹ and W ^{2 are the same as those of X.} The ring system formed by R ¹² to R ²¹ together may be an aromatic ring or a heterocyclic ring containing an oxygen atom or a sulfur atom. For example, R ¹² and R ^{17 may} form a heterocyclic ring containing a sulfur atom and a nitrogen atom via -S- together.

As the compound represented by the general formula [IV], an amine having a diarylamine skeleton in which m and n are 0 is preferred. Furthermore, as the compound represented by the general formula [IV], all of R ¹² to R ²¹ are hydrogen atoms, m and n are 0, ^{the combination of R 12} and R ¹⁷ and/or the combination of R ¹⁶ and R ²¹ are interposed therebetween -S- to form heterocyclic compounds.

、N,N,N’,N’-四甲基-對二胺基二苯基甲烷、二苯基胺等之具有二芳基胺骨架之胺，基於樹脂組成物之熱安定性及柔軟性的觀點，較佳為包含：由包含4,4’-雙(α,α-二甲基苄基)二苯基胺、N-苯基-N’-異丙基-對伸苯基二胺、N-苯基-N’-(1,3-二甲基丁基)-對伸苯基二胺、2,3:5,6-二苯并-1,4-噻

、及N,N,N’,N’-四甲基-對二胺基二苯基甲烷之群組所選出之至少1種以上。胺系化合物(C2)係可單獨使用1種，也可合併使用2種以上。As the amine compound (C2), for example, N-phenyl-1-naphthylamine, bis(4-butylphenyl)amine, bis(4-pentylphenyl)amine, and bis(4- Hexylphenyl)amine, bis(4-heptylphenyl)amine, bis(4-octylphenyl)amine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, P-(p-toluenesulfonamide) 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-thio

, N,N,N',N'-Tetramethyl-p-diaminodiphenylmethane, diphenylamine and other amines with diarylamine skeleton, based on the thermal stability and flexibility of the resin composition It is preferable to include: 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N-phenyl-N'-isopropyl-p-phenylene diamine , N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, 2,3:5,6-dibenzo-1,4-thiol

, And at least one selected from the group of N,N,N',N'-tetramethyl-p-diaminodiphenylmethane. The amine compound (C2) system may be used individually by 1 type, and may use 2 or more types together.

The content of the amine compound (C2) is based on 100 parts by mass of the polymer composition (P). Based on the thermal stability and flexibility of the resin composition, it is preferably 0.05-15 parts by mass, more preferably 0.1- 8 parts by mass, based on the viewpoint that the thermal stability of the resin composition is more excellent even when used in a small amount, and it is more preferably 1 to 5 parts by mass.

(Phosphorus compound (C3)) The molecular weight of the phosphorus compound (C3) is preferably 100 or more and 2000 or less. From the viewpoint of thermal stability and flexibility of the resin composition, it is preferably 150 or more and 1500 or less, and more preferably 160 or more and 1200 or less. By using the phosphorus compound (C3), the oxidation reaction of the diene polymer (B-2) unit of the copolymer (B) can be particularly suppressed. That is, the formation of carbonyl groups in the copolymer (B) can be suppressed. Therefore, 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. In addition, by using the phosphorus compound (C3) and the copolymer (B), appropriate flexibility can be imparted to the resin composition. Furthermore, even if the phosphorus compound (C3) is a small amount, the formation of the aforementioned carbonyl group can be suppressed, and the thermal stability and flexibility of the resin composition can be improved.

(式中，R²³ 、R²⁴ 、R²⁸ 及R²⁹ 係分別獨立表示碳數1～25之烴基，R²⁵ ～R²⁷ 係分別獨立表示碳數1～25之二價烴基，複數個R²³ 可一起形成環)。The phosphorus compound (C3) is preferably a trivalent phosphite. Examples of trivalent phosphites include compounds represented by the following general formulas [V], [VI], or [VII].

(In the formula, R ²³ , R ²⁴ , R ²⁸ and R ²⁹ each independently represent a hydrocarbon group with 1 to 25 carbons, R ²⁵ to R ²⁷ each independently represent a divalent hydrocarbon group with 1 to 25 carbons, and a plurality of R ²³ Can form a ring together).

The hydrocarbon groups having 1 to 25 carbons for R ²³ , R ²⁴ , R ²⁸ and R ²⁹ may be linear or branched, and examples include alkyl groups having 1 to 25 carbons, and alkyl groups having 2 to 25 carbons. Aliphatic groups such as alkenyl groups; aromatic groups with 6 to 25 carbon atoms. As the aliphatic group, an alkyl group having 3 to 20 carbon atoms is preferred, and an alkyl group having 4 to 19 carbon atoms is preferred. Examples of the aromatic group include aryl groups such as phenyl, substituted phenyl, and naphthyl, and phenyl and substituted phenyl are preferred. Examples of the substituent possessed by the substituted phenyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, halogen atoms (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. The ^{divalent hydrocarbon group of R 25} to R ^{27 having} 1 to 25 carbons may be linear or branched, and examples include: alkylene having 1 to 25 carbons, and alkenylene having 2 to 25 carbons. Divalent aliphatic groups such as those; divalent aromatic groups with 6 to 25 carbon atoms. As the aliphatic group, an alkylene group having 1 to 20 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is preferred. Examples of the alkylene group include: methylene, methylmethylene, ethylidene, n-propylidene, isopropylidene, butylene, pentylene, hexylene, heptylene, and octylene. Base, nonyl, decyl, etc. Examples of the divalent aromatic group include phenylene groups, substituted phenylene groups, and naphthylene groups. As the substituent possessed by the substituted phenylene group, the same as the substituted phenyl group can be mentioned. The plural R ²⁵ to R ²⁷ systems are the same or different. In a preferred embodiment, the phosphorus-based compound (C3) based R ²³ is a linear or branched chain of carbon atoms are replaced by an alkyl group having 1 to 10 substituents of the phenyl group, three R ²³ are all the same, And a compound represented by the general formula [V].

As the phosphorus compound (C3), for example, tris(nonylphenyl) phosphite, triphenyl phosphite, tristearyl phosphite, tricresolyl phosphite, tris(2, 4-di-tertiary butylphenyl) phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecanyl) phosphite , Trioleic acid-based phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, 2,2 '-Methylene bis(4,6-di-tertiary butylphenyl) 2-ethylhexyl phosphite, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite Salt, distearyl pentaerythritol diphosphite, etc., preferably tris(nonylphenyl) phosphite. The phosphorus compound (C3) system may be used individually by 1 type, and may use 2 or more types together.

As a preferred embodiment of the resin composition of the present invention, as long as the effects of the present invention can be obtained, it may contain a phenolic compound (C1) and an amine compound (C2), or may contain a phenolic compound (C1) In addition to the phosphorus compound (C3), an amine compound (C2) and a phosphorus compound (C3) may be contained, and a phenol compound (C1), an amine compound (C2), and a phosphorus compound (C3) may also be contained. A resin composition containing a phenol-based compound (C1) and a phosphorus-based compound (C3), or a resin composition containing an amine-based compound (C2) and a phosphorus-based compound (C3) is effective, especially those containing an amine-based compound (C2) The resin composition of) and phosphorus compound (C3) is effective. In 100 parts by mass of the polymer composition (P), the total content of the phenol-based compound (C1), the amine-based compound (C2), and the phosphorus-based compound (C3) is preferably 0.001-15 parts by mass, preferably 0.005-10 Mass parts. In the resin composition of the present invention, the mixing ratio when containing at least one compound selected from the group consisting of a phenol-based compound (C1) and an amine-based compound (C2) and a phosphorus-based compound (C3) is not particularly _{Subject to limitations, it is preferable that the mass (W X} ) of at least one compound selected from the group containing the phenol-based compound (C1) and the amine-based compound (C2) and the mass (W X) of the phosphorus-based compound (C3) _Y) mass ratio (W _X / W _Y) is 90/10 ~ 50/50. When the mass ratio is in this range, the effect of using two compounds in combination and containing them is easy to show. The mass ratio (W _X /W _Y ) is preferably 85/15 to 55/45, preferably 80/20 to 60/40.

The resin composition of the present invention may contain other components than the above in a range that does not impair the effects of the present invention. Examples of the above-mentioned other components include colorants, light stabilizers, vulcanizing agents and vulcanization accelerators, and inorganic additives (silicon dioxide, etc.).

The resin composition of the present invention can be used for molded products (films, sheets, plates, fibers, etc.), multilayer structures, additives, compatibilizers, coating agents, barrier materials, sealants (metal sealants, etc.), and adhesives And so on a wide range of uses.

The present invention is based on the premise of achieving the effects of the present invention, and within the scope of the technical idea of the present invention, includes embodiments in which the above-mentioned constitutions are combined in various ways. In addition, in this specification, the upper limit and lower limit of the numerical range (the content of each component, the value calculated from each component, and each physical property, etc.) can be appropriately combined. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited by these examples in any way. Within the scope of the technical idea of the present invention, many changes can be made by those with ordinary knowledge in the field. get on. In addition, the "%" and "parts" in the examples and comparative examples indicate "% by mass" and "parts by mass", unless otherwise specified.

[Calculation of the mass ratio of the vinyl alcohol polymer (A) and the copolymer (B) of the resin composition] The resin composition obtained by the graft polymerization reaction of the following Examples and Comparative Examples was added to the extraction solvent ( In the case of polyvinyl alcohol: water, in the case of ethylene-vinyl alcohol copolymer: water/isopropanol=4/6 (mixed by mass ratio), extraction treatment was performed at 80°C for 3 hours. The extract is concentrated, and the quality of the obtained extract and the unextracted residue are measured respectively. The mass of the extract is the mass of the vinyl alcohol polymer (A) contained in the resin composition (set as Wa), and the mass of the unextracted residue is the graft copolymer (B1) contained in the resin composition ) Quality (set as Wb). Calculate the mass ratio of (A)/(B1) from these masses. In addition, from ¹ H-NMR analysis of the extract, it was confirmed that the extract in this treatment did not contain the graft copolymer (B1), but only the vinyl alcohol polymer (A).

[Calculation of the content rate of the diene polymer (B-2) unit relative to the total mass of the vinyl alcohol polymer (B-1) unit and the diene polymer (B-2) unit] The mass of the resin composition obtained in each of the Examples and Comparative Examples is referred to as "Wab", and the difference between the mass of Wab and the vinyl alcohol polymer (B-1) used in the reaction is referred to as "Wq". The mass of the vinyl alcohol polymer (A) in the resin composition calculated according to the above method is referred to as "Wa", and Wab-Wa is referred to as the mass "Wb" of the graft copolymer (B1). Then, set Wb-Wq as the mass of the main chain containing the vinyl alcohol polymer (B-1) unit, and Wq as the mass of the side chain containing the diene polymer (B-2) unit, and calculate The side chain containing the diene polymer (B-2) unit is the sum of the main chain containing the vinyl alcohol polymer (B-1) unit and the side chain containing the diene polymer (B-2) unit The content of mass.

[Calculation of total modified mass] (When the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1) are polyvinyl alcohol) Set the vinyl acetate unit of the polyvinyl alcohol as the raw material to a ¹ mass %, let the vinyl alcohol unit be b ¹ % by mass. According to the following calculation formula, the total modified mass (the content of the graft-polymerized monomer relative to the total monomer unit of the resin composition) is calculated. Change the mass [mol%]=Z ¹ /(X ¹ +Y ¹ +Z ¹ )×100 In the above formula, X ¹ , Y ¹ , and Z ¹ are the values calculated by the following mathematical formula. X ¹ = {(Polyvinyl alcohol of raw material (parts by mass))×(a ¹ /100))/86 Y ¹ ={(Polyvinyl alcohol of raw material (parts by mass))×(b ¹ /100)}/44 Z ¹ ={(resin composition after reaction (parts by mass))-(polyvinyl alcohol of raw materials (parts by mass)))/(molecular weight of graft polymerized monomer)

(When the vinyl alcohol polymer (A) and the vinyl alcohol polymer (B-1) are ethylene-vinyl alcohol copolymers) The ethylene unit of the ethylene-vinyl alcohol copolymer of the raw material is set to a ² % by mass, and The vinyl alcohol unit is set to b ² % by mass. According to the following calculation formula, the total modified mass (the content of the graft-polymerized monomer relative to the total monomer unit of the resin composition) is calculated. Change the mass [mol%]=Z ² /(X ² +Y ² +Z ² )×100 In the above formula, X ² , Y ² , and Z ² are the values calculated by the following mathematical formula. X ² ={(Ethylene-vinyl alcohol copolymer of raw material (parts by mass))×(a ² /100))/28 Y ² ={(Ethylene-vinyl alcohol copolymer of raw material (parts by mass))×(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 graft polymerized monomer)

[Calculation of antioxidant (C) content in resin composition] For the resin composition obtained in each of the Examples and Comparative Examples, a thermal pyrolysis gas chromatography device (GC/MS Agilent 7890A/5975C manufactured by Agilent Technologies Co., Ltd., PYROLYZER: Double Shot Pyrolyzer manufactured by FRONTIER-LAB Co., Ltd.) was used. The content of antioxidant (C) in the resin composition was calculated based on the following conditions. Thermal desorption temperature: 100℃/0min-10℃/min-320℃/0.1min String: HP-5ms GC injection temperature: 290℃ Split ratio: 50/1 GC furnace temperature: 50℃/1min-10℃/min-290℃/15min Carrier gas: helium (1.0mL/min) Mass range: m/z　29-600

[Calculation of the amount of free radicals measured by ESR, g value, and ultra-fine binding constant (A value)] The resin composition obtained in each Example and Comparative Example was put into a glass tube for ESR measurement, and an electronic rotation resonance device (EMXplus manufactured by BRUKER JAPAN Co., Ltd., accessory device: Cryostat ESR910 manufactured by Oxford Instruments Co., Ltd.) was used according to the following Under the conditions, the ESR measurement was performed, and the g value and A value were calculated from the obtained ESR spectrum. In addition, the amount of free radicals (mmol/kg) is a value obtained by dividing the number of free radicals obtained from the signal intensity of the obtained ESR spectrum by the mass of the measured sample (pieces/kg), and the Avogadro constant is used to give the mole Calculated by conversion. Temperature: room temperature Central magnetic field: around 3360～3390G Magnetic field scanning range: 400G Modulation: 100kHz, 5G Microwave: 9.5GHz, 0.016mW Scan time: 83.89s×8 times Time constant: 163.84ms

[Stability Evaluation] For 70 parts by mass of the resin composition of each example and comparative example, 30 parts by mass of heptane was mixed, and the resulting mixture in a wet state was spread on an aluminum pad, and the surface was covered with aluminum foil at 20°C, 50% Let it stand in the RH environment. The mixture after 10 days of standing was sampled, and the mass was measured (W1). After drying this at 40°C overnight, the mass (W2) is measured again, and the solid content concentration (A, %) of the sampled mixture is calculated from the following formula. Solid content concentration (A)=W2/W1×100 In addition, a part of the mixture sampled during the mass measurement of W1 is additionally taken, and the mass is measured (W3). After stirring this in tetrahydrofuran at 60°C for 30 minutes, the operation of filtering and separating the resin composition was repeated 6 times. All the filtrate (containing the decomposed product) obtained by the 6 operations was mixed, and after the solvent was distilled off under reduced pressure, it was vacuum dried at 40°C overnight. Measure the mass (W4) of the extracted dried product, and calculate the amount of decomposition product (%) contained in the sampled mixture from the following formula. Amount of decomposition products (%)=W4/W3×{(A/100)}×100 The larger the value of the amount of decomposition products, the greater the amount of time-dependent decomposition products, indicating poor stability.

[Evaluation of tensile elasticity and elongation] The resin compositions of the respective Examples and Comparative Examples provided after the above-mentioned stability evaluation were press-formed at 200° C. for 120 seconds to produce a pressed film with a thickness of 100 μm, and irradiated with electron beams of 150 kGy in a nitrogen atmosphere. Cut the irradiated film into a dumbbell shape with a width of 10mm, and adjust the humidity for 1 week under a storage environment of 20°C and 70%RH, and then use an autoclave ("AG-5000B" manufactured by Shimadzu Corporation). Determine the coefficient of tensile elasticity and elongation at break (force measuring device 1kN, tensile speed 500mm/min, distance between clamps 70mm). The elongation at break value in the table is the average value of 5 measurements.

[Example 1] A commercially available ethylene-vinyl alcohol copolymer (manufactured by KURARAY Co., Ltd., E105, 44 mol% of ethylene unit content, 33.3 mass% of ethylene, 66.7 mass% of vinyl alcohol, MFR (210 ℃, load 2160g) 13.0g/10 minutes) After crushing, use 75μm mesh sieve and 212μm mesh sieve. During vibration, the particles sandwiched between the two sieves are recovered to obtain classified particles . 100 parts by mass (water content of 0.5% by mass) of the obtained particles were irradiated with electron beams (30 kGy) in a nitrogen atmosphere to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. In addition, to an autoclave equipped with a stirrer, a nitrogen inlet pipe, and a particle addition port, 485 parts by mass of isoprene was added, and it was carried out three times under the condition of ice storage and cooling. After the pressure was reduced to 300 Torr, the nitrogen was used Return to normal pressure operation and replace the system with nitrogen. Add 100 parts by mass of ethylene-vinyl alcohol copolymer particles that have been irradiated with electron beams to the autoclave, seal the autoclave, and cool it in ice again for three times. After decompression to 300 Torr, it is restored with nitrogen. To operate at normal pressure, replace the system with nitrogen. After that, heating was performed until the internal temperature became 68°C. With the copolymer particles dispersed in isoprene, continue heating and stirring at 68°C for 4 hours to perform graft polymerization. Thereafter, after cooling to normal temperature, filtration was performed to collect particles, and the washing operation of adding to heptane, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the seventh washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The washed particles were further added to deionized water, treated at 80°C for 1 hour, and the particles were filtered again, and the resulting particles were vacuum dried at 40°C overnight to obtain a copolymer containing ethylene-vinyl alcohol and The resin composition of the target of the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 2] The same operation as in Example 1 was carried out to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. Next, to an autoclave equipped with a stirrer, a nitrogen introduction tube, and a particle addition port, 100 parts by mass of the ethylene-vinyl alcohol copolymer irradiated with electron beams were added, and the operation of sealing nitrogen in the system and depressurizing was repeated 5 times. Replace the system with nitrogen. 250 parts by mass of liquefied butadiene was added here, the autoclave was sealed, heated until the internal temperature became 65°C, and heating and stirring were continued as it was for 4 hours to perform graft polymerization. Thereafter, after cooling to normal temperature, the remaining butadiene was removed while decompressing. The washing operation of adding the obtained reacted particles to heptane, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a trace amount of by-product polybutadiene was extracted and removed. After the fourth washing operation, no extract was confirmed. That is, polybutadiene does not remain in the particles. The washed particles were further added to deionized water, treated at 80°C for 1 hour, and the particles were filtered again, and the resulting particles were vacuum dried at 40°C overnight to obtain a copolymer containing ethylene-vinyl alcohol and The resin composition of the target of the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 3] In the same manner as in Example 1, electron beam irradiated ethylene-vinyl alcohol copolymer particles were obtained. In the same manner as in Example 1, graft polymerization was performed. Thereafter, after cooling to normal temperature, 0.02 parts by mass of dibutylhydroxytoluene (hereinafter referred to as BHT) was added, followed by filtration to collect particles. Thereafter, the washing operation of adding to heptane containing 50 ppm of BHT, stirring and washing for 15 minutes, and filtering particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the seventh washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 4] In the same manner as in Example 1, ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained. In the same manner as in Example 1, graft polymerization was performed. Thereafter, after cooling to normal temperature, 0.1 parts by mass of dibutylhydroxytoluene (hereinafter referred to as BHT) was added, followed by filtration to collect particles. Thereafter, the washing operation of adding to heptane containing 200 ppm of BHT, stirring and washing for 15 minutes, and filtering particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the seventh washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 5] In the same manner as in Example 1, ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained. In the same manner as in Example 1, graft polymerization was performed. Thereafter, after cooling to normal temperature, filtration was performed and particles were recovered, and the washing operation of adding to heptane, stirring and washing for 15 minutes, and filtering particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the seventh washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The washed particles were further added to deionized water containing 200 ppm of hydroquinone (hereinafter referred to as HQ), treated at 80°C for 1 hour, then the particles were filtered again, and the resulting particles were vacuum dried at 40°C Overnight, a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the graft copolymer was obtained. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 6] After pulverizing commercially available polyvinyl alcohol (manufactured by KURARAY Co., Ltd., Poval 5-74, saponification degree 74 mol%, vinyl acetate mass fraction 40.7 mass%, and vinyl alcohol mass fraction 59.3 mass%) , Use 75μm mesh sieve and 212μm mesh sieve, when vibrating, the particles caught between the two sieves are recovered to obtain classified particles. 100 parts by mass (water content of 0.5% by mass) of the obtained particles were irradiated with electron beams (30 kGy) in a nitrogen atmosphere to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. In addition, to an autoclave equipped with a stirrer, a nitrogen inlet pipe, and a particle addition port, 485 parts by mass of isoprene was added, and it was carried out three times under the condition of ice storage and cooling. After the pressure was reduced to 300 Torr, the nitrogen was used Return to normal pressure operation and replace the system with nitrogen. Add 100 parts by mass of ethylene-vinyl alcohol copolymer particles that have been irradiated with electron beams to the autoclave, seal the autoclave, and cool it in ice again for three times. After decompression to 300 Torr, it is restored with nitrogen. To operate at normal pressure, replace the system with nitrogen. After that, heating was performed until the internal temperature became 68°C. With the copolymer particles dispersed in isoprene, continue heating and stirring at 68°C for 4 hours to perform graft polymerization. Thereafter, after cooling to normal temperature, after adding 0.02 parts by mass of BHT, filtration was performed to recover particles. Thereafter, the washing operation of adding to heptane containing 50 ppm of BHT, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the fifth washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing polyvinyl alcohol and the target substance of the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Example 7] A 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 ℃, load 2160g) 3.8g/10 minutes) After crushing, use 75μm sieve and 212μm sieve. During vibration, the particles sandwiched between the two sieves are recovered to obtain classified particles. . 100 parts by mass (water content of 0.5% by mass) of the obtained particles were irradiated with electron beams (20 kGy) in a nitrogen atmosphere to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. In addition, to an autoclave equipped with a stirrer, a nitrogen inlet pipe, and a particle addition port, 240 parts by mass of isoprene and 245 parts by mass of isopropanol were added, and the reaction was carried out three times under the condition of ice storage and cooling. After the pressure is reduced to 300 Torr, the operation of returning to normal pressure with nitrogen is used to replace the system with nitrogen. Add 100 parts by mass of ethylene-vinyl alcohol copolymer particles that have been irradiated with electron beams to the autoclave, seal the autoclave, and cool it in ice again for three times. After decompression to 300 Torr, it is restored with nitrogen. To operate at normal pressure, replace the system with nitrogen. After that, heating was performed until the internal temperature became 68°C. With the copolymer particles dispersed in isoprene, continue heating and stirring at 68°C for 4 hours to perform graft polymerization. Thereafter, after cooling to normal temperature, 0.02 parts by mass of BHT was added, followed by filtration to collect particles. Thereafter, the washing operation of adding to heptane containing 50 ppm of BHT, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the fifth washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing polyvinyl alcohol and the target substance of the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Comparative Example 1] The commercially available ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., E105) was evaluated. Table 1 shows the evaluation results of physical properties.

[Comparative Example 2] The same operation as in Example 1 was carried out to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. In the same manner as in Example 1, graft polymerization was performed. Thereafter, after cooling to normal temperature, filtration was performed and particles were recovered, and the washing operation of adding to heptane, stirring and washing for 15 minutes, and filtering particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a small amount of by-product polyisoprene was extracted and removed. After the seventh washing operation, no extract was confirmed. That is, polyisoprene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the graft copolymer. Table 1 shows the analysis results and physical property evaluation results of the resin composition.

[Comparative Example 3] In the same manner as in Example 2, ethylene-vinyl alcohol copolymer particles irradiated with an electron beam were obtained. In the same manner as in Example 2, graft polymerization was performed. Thereafter, after cooling to normal temperature, the remaining butadiene was removed while decompressing. The washing operation of adding the obtained reacted particles to heptane, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. In this operation, ¹ H-NMR analysis of the extract confirmed that a trace amount of by-product polybutadiene was extracted and removed. After the fourth washing operation, no extract was confirmed. That is, polybutadiene does not remain in the particles. The obtained particles were vacuum dried at 40° C. overnight to obtain a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the 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 Japanese Patent Publication No. 41-021994, the following comparative example 4 was performed. The operation was carried out in the same manner as in Example 1 to obtain electron beam-irradiated ethylene-vinyl alcohol copolymer particles. Next, to an autoclave equipped with a stirrer, a nitrogen introduction tube, and a particle addition port, 100 parts by mass of ethylene-vinyl alcohol copolymer irradiated with electron beams and 99 parts by mass of methanol were added, and the nitrogen was sealed in the system by repeating 5 times. The depressurization operation replaces the system with nitrogen. 149 parts by mass of liquefied butadiene was added here, the autoclave was sealed, and stirring was continued at room temperature for 19 hours to perform graft polymerization. After that, the remaining butadiene was removed while decompressing. After filtering the obtained reaction content and separating the particles, the operation of adding the particles to methanol, stirring and washing for 15 minutes, and filtering the particles was repeated 10 times. After the obtained particles were vacuum dried at 40°C overnight, the particles were placed in a batch mixer and kneaded at 175°C for 15 minutes. The obtained kneaded product is frozen and crushed to obtain a resin composition containing the target substance of the ethylene-vinyl alcohol copolymer and the graft copolymer. Table 1 shows the evaluation results of physical properties. In addition, in the analysis of the resin composition, although the analysis was attempted according to the above method, it is difficult to separate the components caused by the poor solubility of the extraction solvent, and it is impossible to identify the details of the structure. However, the quality of the particles before and after the graft polymerization changes. A 4% increase in quality has been confirmed.

[Table 1] Vinyl alcohol polymer (A) Copolymer (B) Resin composition Property evaluation results Type of polymer Vinyl alcohol polymer (B-1) Type of polymer Diene polymer (B-2) Type of synthetic rubber The content rate of the diene polymer (B-2) unit (the content rate relative to the total mass of (B-1) and (B-2)) [mass%] (A)/(B) Mass ratio Antioxidant (C) content rate [mass%] Total modified mass of polymer composition (P) Free radical amount g value A value Tensile elasticity coefficient Elongation at break Decomposition amount [mol%] [×10 ^-3 mmol/kg] [Gauss] [kgf/mm ² ] [%] [quality%] Example 1 EVOH EVOH Polyisoprene 29.9 50.1/49.9 - 18.8 1.1 2.0038 11.6 80 94 0.21 Example 2 EVOH EVOH Polybutadiene 33.3 35.0/65.0 - 25.5 0.9 2.0038 11.4 39 101 0.40 Example 3 EVOH EVOH Polyisoprene 30.1 50.0/50.0 0.01 19.0 1.5 2.0037 10.6 78 86 0.07 Example 4 EVOH EVOH Polyisoprene 29.7 50.3/49.7 0.04 18.7 8.1 2.0040 10.6 75 92 0.04 Example 5 EVOH EVOH Polyisoprene 33.3 49.8/50.2 0.01 19.0 2.3 2.0038 11.7 81 95 0.08 Example 6 PVOH PVOH Polyisoprene 24.9 52.2/47.8 0.01 21.1 3.1 2.0042 17.5 54 100 0.07 Example 7 EVOH EVOH Polyisoprene 13.9 90.9/9.1 0.01 8.6 0.3 2.0040 11.4 126 27 0.04 Comparative example 1 EVOH - - - - - - Not detected Not detected Not detected 325 6 0.0 Comparative example 2 EVOH EVOH Polyisoprene 29.0 51.7/48.3 - 18.2 0.8 2.0026 34.0 64 11 15.6 Comparative example 3 EVOH EVOH Polybutadiene 36.7 31.2/68.8 - 28.4 0.5 2.0028 32.6 31 9 14.2 Comparative example 4 EVOH EVOH Polybutadiene - - - 6.0 Not detected Not detected Not detected 259 3 3.1 In the table, EVOH series means ethylene-vinyl alcohol copolymer, and PVOH series means polyvinyl alcohol. In the table, "not detected" means that there are no peaks that can be clearly distinguished from the baseline in the ESR spectrum.

It can be seen from the above examples that the resin composition of the present invention has higher flexibility than vinyl alcohol-based resins, and is also excellent in storage stability. Even in a long-term storage environment, decomposition products are not easily generated. Therefore, it can be expected to form a molded body that is more flexible than conventional vinyl alcohol-based polymers and is not easily cracked.

As in Comparative Example 1, the unmodified vinyl alcohol-based resin has a high elastic modulus and has the disadvantage of being hard and brittle. As in Comparative Examples 2 and 3, even when the amount of radicals is small, a resin composition having an A value outside the scope of the present invention is likely to decompose a part of the diene polymer under the atmosphere. The resin composition in a state where decomposition products have been produced is likely to cause defects such as cracks after thermoforming. The films of Comparative Examples 2 and 3 are softened and the tensile elasticity coefficient is reduced. On the other hand, because the film is easy to The elongation decreases due to breakage. It is believed that this phenomenon of decomposition over time will further progress in accordance with the period of standing. Therefore, a resin composition having an A value outside the scope of the present invention cannot exhibit stable physical properties after being molded. In Comparative Example 4, the resin composition system has a high coefficient of elasticity, and not only has the disadvantage of being hard and brittle, but also a phenomenon of decomposition with time can be seen.

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Claims (13)

A resin composition containing a vinyl alcohol polymer (B-1 The g value of the ESR spectrum of the copolymer (B) composed of) unit and diene polymer (B-2) unit is 2.0031 to 2.0050. The resin composition of claim 1, wherein the amount of radicals is 15×10 ^-3 mmol/kg or less. The resin composition of claim 1 or 2, wherein the ultrafine binding constant (A value) of the ESR spectrum is less than 20 Gauss. The resin composition according to any one of claims 1 to 3, wherein the copolymer (B) is a graft copolymer (B1). The resin composition according to any one of claims 1 to 4, which further contains a vinyl alcohol-based polymer (A). The resin composition according to any one of claims 1 to 5, wherein the vinyl alcohol-based polymer (B-1) unit contains an ethylene-vinyl alcohol copolymer unit. The resin composition according to any one of claims 1 to 6, wherein the diene polymer (B-2) is one selected from the group consisting of polybutadiene, polyisoprene, and polyisobutylene the above. The resin composition according to any one of claims 1 to 7, which further contains an antioxidant (C). The resin composition of claim 8, wherein the content of antioxidant (C) is less than 0.1% by mass. The resin composition according to any one of claims 1 to 9, which contains 10 to 85% by mass of the copolymer (B) with respect to 100 parts by mass of the resin composition. A method for producing a resin composition according to any one of claims 1 to 10, which comprises dispersing in a solution containing a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B- 2) The step of heat-treating the polymer composition (P) of the copolymer (B) composed of units; the heat-treating temperature is 30-150°C. The method for producing a resin composition according to claim 11, wherein the solution contains an antioxidant (C). A method for producing a resin composition according to any one of claims 1 to 10, which comprises using a cleaning solution to contain a vinyl alcohol-based polymer (B-1) unit and a diene-based polymer (B-2) The step of washing the polymer composition (P) of the copolymer (B) composed of units; the washing liquid contains an antioxidant (C).