JP6977499B2 - Resin composition and laminate - Google Patents

Description

The present invention comprises a resin composition which is excellent in gas barrier property, impact resistance, and moldability, and also has excellent adhesiveness to an adhesive resin layer, and is suitable as a resin composition for forming a gas barrier layer of a gas barrier laminated body. The present invention relates to a laminate using a resin composition.

Ethylene-vinyl ester-based copolymer saken product (EVOH) is widely used as a packaging material because it has excellent transparency, gas barrier properties, and aroma retention properties. Furthermore, since the ethylene-vinyl ester copolymer saken product has excellent antistatic properties, oil resistance, and solvent resistance, containers for solutions containing volatile substances such as fuels and pesticides, tanks, drums, and the like. It is also useful as a material for hoses and the like that transport them.

However, the ethylene-vinyl ester-based copolymer saken product exhibits a high degree of gas barrier property due to the abundance of hydroxyl groups, but at the same time, it tends to have high crystallinity and low impact resistance, and has a drawback that cracks and the like are likely to occur. be.

In Patent Document 1, as a solution to this problem, a thermoplastic resin composition in which a modified polyester-based thermoplastic elastomer obtained by modifying a polyester-based thermoplastic elastomer with an unsaturated carboxylic acid or a derivative thereof is blended with EVOH is described. Proposed.
Further, Patent Document 2 proposes a resin composition in which EVOH is blended with a polymer having a rubbery graft polymer and a polyalkylene ether unit. In Patent Document 2, a polyalkylene ether is used as a rubbery graft polymer obtained by graft-polymerizing styrene and methyl methacrylate in the presence of a rubbery polymer containing butadiene as a main component. As the polymer having a unit, a block copolymer of polybutylene terephthalate and polytetramethylene ether glycol corresponding to the modified aromatic polyester-based thermoplastic elastomer used in the present invention is modified with maleic anhydride. Further, there is a description that a (meth) acrylic acid ester polymer having a glycidyl group may be blended.

Gas barrier resins such as ethylene-vinyl ester copolymer saponified products are usually used in laminated sheets such as a base material layer / adhesive resin layer / gas barrier layer / adhesive resin layer / base material layer in applications such as packaging materials. It is used as a molding material for gas barrier layers. Therefore, it is an important requirement for the gas barrier resin to be excellent not only in gas barrier property but also in adhesiveness with the adhesive resin layer. Usually, as the resin of the base material layer, a polyolefin-based resin is used from the viewpoint of mechanical strength, moldability, etc., and as the adhesive resin of the adhesive resin layer, a modified polyolefin-based resin such as maleic anhydride-modified polyethylene is used. Since a resin is used, the gas barrier resin is required to have excellent adhesion to an adhesive resin such as this modified polyolefin resin.

Japanese Unexamined Patent Publication No. 2004-2791 Japanese Unexamined Patent Publication No. 2011-208134

When a modified polyester-based thermoplastic elastomer is blended with EVOH as in Patent Document 1, the impact resistance and moldability are improved, but the adhesiveness with an adhesive resin such as a modified polyolefin-based resin is significantly impaired.

Even if the rubbery graft polymer and the modified aromatic polyester-based thermoplastic elastomer are blended as in Patent Document 2, the problem of the deterioration of the adhesiveness cannot be solved, and further, it has a glycidyl group. Even if the (meth) acrylic acid ester polymer is blended, the problem of deterioration of adhesiveness cannot be solved.

The present invention solves the above-mentioned conventional problems, and is a resin containing a modified aromatic polyester-based thermoplastic elastomer in order to improve the impact resistance and moldability of the ethylene / vinyl ester-based copolymer saponified product. An object of the present invention is to provide a resin composition that solves the problem of deterioration of adhesiveness with a modified polyolefin resin such as maleic anhydride-modified polyethylene.

As a result of diligent studies to solve the above problems, the present inventor has added ethylene / vinyl by blending an epoxy functional styrene / (meth) acrylate compound having a specific molecular weight and having a styrene unit and a glycidyl group. It is possible to solve the problem of deterioration of the adhesiveness to the adhesive resin by blending the modified aromatic polyester-based thermoplastic elastomer with the ester-based copolymer saponified compound, and this epoxy functional styrene / (meth) acrylate. It has been found that by blending the system compound as a master batch, it is possible to suppress the deterioration of the appearance due to the compounding of the epoxy functional styrene / (meth) acrylate compound.
That is, the gist of the present invention is as follows.

[1] Ethylene-vinyl ester-based copolymer saken compound (A) and modified aromatic polyester-based thermoplastic elastomer (B) graft-modified with α, β-ethylenically unsaturated carboxylic acid and / or a derivative thereof. , A resin composition containing an epoxy-functional styrene (meth) acrylate-based compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000.

[2] The epoxy functional styrene / (meth) acrylate compound (C) has a styrene unit represented by the following formula (c1) and a glycidyl (meth) acrylate unit represented by the following formula (c2). , [1].

(In the formula, R ^{1 to} R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

[3] The epoxy functional styrene / (meth) acrylate compound (C) has a styrene unit represented by the following formula (c1), a glycidyl (meth) acrylate unit represented by the following formula (c2), and the following. The resin composition according to [2], which comprises a (meth) acrylate unit represented by the formula (c3).

(In the formula, R ^{1 to} R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ⁶ represents an alkyl group having 1 to 12 carbon atoms.)

[4] The resin composition according to any one of [1] to [3], wherein the content of the styrene unit of the epoxy functional styrene / (meth) acrylate compound (C) is 0.001 to 10% by mass. thing.

[5] The epoxy equivalent of the epoxy functional styrene / (meth) acrylate compound (C) is 10 to 1000 g / eq. The resin composition according to any one of [1] to [4].

[6] The modification rate (graft amount) of the modified aromatic polyester-based thermoplastic elastomer (B) is 0.01 to 10% by mass, and the melt flow rate (temperature 230 ° C., load 2.16 kg) is 0.1 to 100 g. The resin composition according to any one of [1] to [5], which is / 10 minutes.

[7] The ethylene-vinyl ester copolymer saken product (A) has an ethylene unit content of 20 to 60 mol%, a saponification degree of 90 to 100 mol%, and a melt flow rate (temperature 210 ° C., load 2). The resin composition according to any one of [1] to [6], wherein .16 kg) is 0.1 to 100 g / 10 minutes.

[8] The ethylene / vinyl ester-based copolymer saken product (A) is contained in a total of 100 parts by mass of the ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B). 40 to 99 parts by mass, 60 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B), and the ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B). The resin composition according to any one of [1] to [7], which contains 0.05 to 10 parts by mass of the epoxy-functional styrene / (meth) acrylate-based compound (C) with respect to 100 parts by mass in total. ..

[9] The resin composition according to any one of [1] to [8], which is a gas barrier resin composition.

[10] A laminate having a layer made of the resin composition according to any one of [1] to [9].

[11] The laminate according to [10], which has a gas barrier layer made of the resin composition and an adhesive resin layer made of a maleic acid-modified polyolefin resin adjacent to the gas barrier layer.

[12] Ethylene-vinyl ester-based copolymer saken compound (A) and modified aromatic polyester-based thermoplastic elastomer (B) graft-modified with α, β-ethylenically unsaturated carboxylic acid and / or a derivative thereof. A master batch for improving the appearance to be blended in a resin composition containing styrene, which comprises an epoxy-functional styrene / (meth) acrylate compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000. , Master batch for appearance improvement made into master batch with olefin resin (D).

The resin composition of the present invention has the original gas barrier properties of an ethylene / vinyl ester-based copolymer saponified product, impact resistance and moldability due to a modified aromatic polyester-based thermoplastic elastomer, and an epoxy having a specific molecular weight. By blending a functional styrene / (meth) acrylate compound, it has excellent adhesion to modified polyolefin resins such as maleic anhydride-modified polyethylene, and is a laminate with excellent interlayer adhesion in applications such as packaging materials. Can be provided.
Further, by using this epoxy functional styrene / (meth) acrylate compound as a masterbatch, it is possible to suppress the deterioration of the appearance due to the blending of the epoxy functional styrene / (meth) acrylate compound.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and carried out without departing from the gist of the present invention. In this specification, when a numerical value or a physical property value is inserted before and after using "~", it is used as including the values before and after that.

[Resin composition]
The resin composition of the present invention is a modified aromatic polyester-based thermoplastic graft-modified with an ethylene / vinyl ester-based copolymer saponide (A) and an α, β-ethylenically unsaturated carboxylic acid and / or a derivative thereof. It is characterized by containing an elastomer (B) and an epoxy-functional styrene- (meth) acrylate-based compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000.

<Mechanism>
In the present invention, by containing an epoxy functional styrene (meth) acrylate compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000, an effect of improving adhesiveness can be obtained. Details are not clear, but it is estimated as follows.

The epoxy functional styrene / (meth) acrylate-based compound (C) used in the present invention has a styrene unit, and the benzene ring of the styrene unit and the benzene ring of the modified aromatic polyester-based thermoplastic elastomer (B). Due to the high compatibility, the epoxy-functional styrene / (meth) acrylate-based compound (C) increases the viscosity of the modified aromatic polyester-based thermoplastic elastomer (B) in the ethylene / vinyl ester-based copolymer saponified product (A). By preventing the modified aromatic polyester-based thermoplastic elastomer (B) from migrating to the bonding interface, the ethylene-vinyl ester-based copolymer saken product (A) originally has good adhesion at the bonding interface. You will be able to get it.
That is, the epoxy-functional styrene / (meth) acrylate-based compound (C) used in the present invention not only has a chain extension effect of connecting a polar resin with a glycidyl group, but also has a styrene-unit benzene ring and a modified aromatic polyester-based thermoplastic elastomer. The compatibility effect between the benzene rings of (B) strengthens the entanglement of molecules and achieves high viscosity of the modified aromatic polyester-based thermoplastic elastomer (B), thereby achieving modified aromatic polyester-based heat. Prevents adhesion inhibition due to the plastic elastomer (B).

On the other hand, in Patent Document 2, a glycidyl group is used in order to improve the compatibility between the ken product of the ethylene / vinyl ester-based copolymer and the rubbery polymer, and to improve the impact resistance and the gas barrier property. It contains a (meth) acrylic acid ester polymer that has (meth) acrylic acid that does not have a styrene unit, has only a chain extension effect, and has this glycidyl group that has migrated to the adhesive interface. Since the ester polymer itself is a factor that inhibits the adhesiveness, the adhesiveness is low as in Comparative Example 2 described later.

<Ethylene-vinyl ester copolymer saken product (A)>
The ethylene-vinyl ester-based copolymer saken product (hereinafter, may be referred to as “EVOH”) is a known resin and is a water-insoluble thermoplastic resin. EVOH (A) is usually obtained by copolymerizing a vinyl ester-based monomer (for example, fatty acid vinyl ester) with ethylene to obtain an ethylene-vinyl ester-based copolymer, which is saponified. That is, it mainly contains an ethylene structural unit and a vinyl alcohol structural unit, and contains a small amount of vinyl ester structural unit remaining after saponification. For the above copolymerization, a known polymerization method such as a solution polymerization method can be adopted.

As the vinyl ester-based monomer, vinyl acetate is usually used from an economical point of view. In addition, for example, aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatic acid, and benzoate Examples thereof include aromatic vinyl esters such as acid vinyl, and usually, aliphatic vinyl esters having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms are used. These are usually used alone, but a plurality of types may be used if necessary.

Further, the content of the ethylene unit of EVOH (A) is determined at the time of polymerization of ethylene and the vinyl ester-based monomer, and does not change before and after saponification. For EVOH (A), the content of ethylene units (structural units derived from ethylene) measured based on ISO14663 is usually 20 to 60 mol%, preferably 20 to 55 mol%, and particularly preferably 25 to 50 mol%. be. If the content of ethylene unit is too low, the impact resistance and processability tend to decrease, and if it is too high, the gas barrier property and solvent resistance tend to decrease.

Further, the degree of saponification of EVOH (A) is a value measured by a titration method (JIS K6726) (however, EVOH is measured with a solution uniformly dissolved in a water / methanol solvent), and is usually 90 to 100 mol%, preferably 90 to 100 mol%. It is 95 to 100 mol%, particularly preferably 98 to 100 mol%. If the degree of saponification is too low, the oxygen barrier property tends to decrease.

The melt flow rate (MFR) of EVOH (A) is usually 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly 1 to 50 g / 10 minutes, as measured at a temperature of 210 ° C. and a load of 2.16 kg according to JIS K7210. It is preferably 2 to 40 g / 10 minutes. When the MFR is in the above range, the workability is excellent.

In the present invention, in addition to ethylene and the fatty acid vinyl ester, an ethylenically unsaturated monomer copolymerizable within a range that does not impair the characteristics required for EVOH (A) may be copolymerized, and the above-mentioned simple monomer may be copolymerized. Examples of the metric include the following. For example, olefins such as propylene, 1-butene and isobutene, 2-propene-1-ol, 3-butene-1-ol, 4-pentene-1-ol, 5-hexene-1-ol, 3,4. Hydroxy group-containing α-olefins such as −dihydroxy-1-butene and 5-hexene-1,2-diol, and their esterified products, 3,4-diasiloxy-1-butene, particularly 3,4-diacetoxy. -1-Butene and the like can be mentioned. In addition, unsaturated α, β-ethylenically unsaturated carboxylic acid components such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (maleic anhydride) maleic acid, and (anhydrous) itaconic acid or salts thereof, and carbon. Examples thereof include mono or dialkyl esters of the number 1-18. In addition, acrylamide, N-alkylacrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamide propanesulfonic acid or a salt thereof, and acrylamide such as acrylamidepropyldimethylamine or an acid salt thereof or a quaternary salt thereof. Kind, methacrylic amide, N-alkyl methacrylic amide having 1 to 18 carbon atoms, N, N-dimethyl methacrylic acid, 2-methacrylic amide propanesulfonic acid or a salt thereof, methacrylamide propyl dimethylamine or its acid salt, and its fourth grade. Examples thereof include methacrylic amides such as salts. In addition, N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, and N-vinylacetamide, vinyl cyanide such as acrylicnitrile and methacrylnitrile, alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, and alkoxys. Vinyl ethers such as alkyl vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halides such as vinyl bromide, vinyl silanes such as trimethoxyvinylsilane, and allyl acetate, allyl chloride, trimethyl- (allyl acetate, allyl chloride, trimethyl- ( Examples thereof include 3-acrylamide-3-dimethylpropyl) -ammonium chloride, acrylamide-2-methylpropanesulfonic acid, vinylethylene carbonate, and glycerin monoallyl ether. Further, it may be "post-denatured" such as urethanization, acetalization, cyanoethylation, and oxyalkyleneization.
In particular, EVOH (A), which is a copolymer of hydroxy group-containing α-olefins, is preferable in that it improves secondary formability such as stretching and vacuum / pneumatic molding, and among them, 1,2-diol is contained in the side chain. EVOH (A) is preferred.

The EVOH (A) used in the present invention includes a compounding agent generally blended with EVOH, for example, a heat stabilizer, an antioxidant, an antistatic agent, a colorant, and an ultraviolet absorber, as long as the effect of the present invention is not impaired. , Lubricants, plasticizers, light stabilizers, surfactants, antibacterial agents, desiccants, antiblocking agents, flame retardants, cross-linking agents, hardening agents, foaming agents, crystal nucleating agents, anti-fog agents, biodegrading additives, A silane coupling agent, an oxygen absorber, or the like may be contained.

The heat stabilizer includes organic α, β-ethylene such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, and behenic acid for the purpose of improving various physical properties such as thermal stability during melt molding. Sexual unsaturated carboxylic acid components or salts such as alkali metal salts (sodium, potassium, etc.) and alkaline earth metal salts (calcium, magnesium, etc.); or inorganic substances such as sulfuric acid, sulfite, carbonic acid, phosphoric acid, boric acid, etc. Add additives such as α, β-ethylenic unsaturated carboxylic acid components, or salts such as alkali metal salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), zinc salts, etc. May be good. Of these, it is particularly preferable to add acetic acid, a boron compound containing boric acid and a salt thereof, an acetate salt, and a phosphate salt.

When acetic acid is added, the amount of acetic acid added is usually 0.001 to 1 part by mass, preferably 0.005 to 0.2 parts by mass, and particularly preferably 0.010 to 0, based on 100 parts by mass of EVOH (A). .1 part by mass. If the amount of acetic acid added is too small, the effect of containing acetic acid tends to be insufficient, and conversely, if the amount of acetic acid is too large, it tends to be difficult to obtain a uniform film.

When a boron compound is added, the amount added is usually 0.001 to 1 part by mass in terms of boron (analyzed by ICP emission analysis method after incineration) with respect to 100 parts by mass of EVOH (A). It is preferably 0.002 to 0.2 parts by mass, and particularly preferably 0.005 to 0.1 parts by mass. If the amount of the boron compound added is too small, the effect of adding the boron compound may not be sufficient, and conversely, if the amount of the boron compound is too large, it tends to be difficult to obtain a uniform film.

The amount of acetate and phosphate (including hydrogen phosphate) added is usually 0 in terms of metal (analyzed by ICP emission analysis method after incineration) with respect to 100 parts by mass of EVOH (A). It is 0005 to 0.1 parts by mass, preferably 0.001 to 0.05 parts by mass, and particularly preferably 0.002 to 0.03 parts by mass. If the amount added is too small, the effect of the content may not be sufficiently obtained, and conversely, if the amount added is too large, it tends to be difficult to obtain a uniform film. When two or more kinds of salts are added to EVOH (A), it is preferable that the total amount thereof is within the range of the above-mentioned addition amount.

The method for adding acetic acid, boron compound, acetate, phosphate, or alkali metal salt to EVOH (A) is not particularly limited, and i) porous precipitation of EVOH (A) having a water content of 20 to 80% by mass. A method in which an object is brought into contact with an aqueous solution of the additive to contain the additive and then dried; ii) After the additive is contained in a uniform solution of EVOH (A) (water / alcohol solution, etc.), a coagulation liquid is used. A method of extruding into a strand shape and then cutting the obtained strand into pellets for further drying treatment; iii) EVOH (A) and additives are mixed together and then melt-kneaded with an extruder or the like. Method; iv) In the production of EVOH (A), the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step was neutralized with an organic α, β-ethylenically unsaturated carboxylic acid component such as acetic acid. Further, a method of adjusting the amount of the residual organic α, β-ethylenically unsaturated carboxylic acid component such as acetate and the amount of the by-produced salt by washing with water can be mentioned.
In order to obtain the effect of the present invention more remarkably, the methods i) and ii), which have excellent dispersibility of additives, and the method iv) when an organic acid and a salt thereof are contained are preferable.

Only one type of EVOH (A) may be used, or two or more types having different ethylene unit contents, saponification degrees, other physical properties and the like may be used in combination.

<Modified aromatic polyester-based thermoplastic elastomer (B)>
The modified aromatic polyester-based thermoplastic elastomer (B) used in the present invention is an aromatic polyester-based thermoplastic elastomer graft-modified with an α, β-ethylenically unsaturated carboxylic acid and / or a derivative thereof.

As the aromatic polyester-based thermoplastic elastomer before modification of the modified aromatic polyester-based thermoplastic elastomer (B), a block copolymer having an aromatic polyester unit and a polyalkylene ether unit is preferable, and the polyalkylene ether unit is preferable. Is a polytetramethylene ether glycol unit.

The lower limit of the content of the polyalkylene ether unit in the block copolymer having the polyalkylene ether unit is not limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. When the content of the polyalkylene ether unit is less than the above lower limit value, the dispersibility tends to decrease when blending with EVOH (A). The upper limit of the content of the polyalkylene ether unit is not limited, but is usually 90% by mass or less, preferably 80% by mass or less. The content of the polyalkylene ether unit in the block copolymer having the polyalkylene ether unit is calculated based on the chemical shift of the hydrogen atom and its content by using the nuclear magnetic resonance spectroscopy (NMR). be able to.

The number average molecular weight of the polyalkylene ether unit is usually 600 to 4000, more preferably 800 to 2500, and particularly preferably 900 to 2100. If the number average molecular weight is too low, the melting point tends to be high and the dispersibility tends to decrease when blending with EVOH (A), and conversely, if the number average molecular weight is too high, the melting point decreases and EVOH (A) tends to decrease. ) May adhere to the hopper when blended with. As these polyalkylene ether units, one kind or two or more kinds having different number average molecular weights can be used. Here, the number average molecular weight of the polyalkylene ether unit means that measured by gel permeation chromatography (GPC).

The polyester polyether block copolymer having the above aromatic polyester unit and polyalkylene ether unit has an aliphatic and / or alicyclic diol having 2 to 12 carbon atoms and an aromatic dicarboxylic acid or an alkyl ester thereof. It can be obtained by polycondensation of an oligomer obtained by an esterification reaction or an ester exchange reaction using a polyalkylene ether having a number average molecular weight of 600 to 4000 as a raw material.

As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those usually used as a raw material for polyester can be used. For example, examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, and 1,6-hexanediol. Examples of the alicyclic diol include 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. For these diols, one kind or a mixture of two or more kinds can be used. Of these, aliphatic diols having 2 to 12 carbon atoms are preferable, and 1,4-butanediol is particularly preferable.

As the aromatic dicarboxylic acid, those generally used as a raw material for polyester can be used, for example, terephthalic acid and its lower (for example, 4 or less carbon atoms) alkyl ester, isophthalic acid, phthalic acid, 2,5-norrate. Examples thereof include bonandicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid, 2,6-naphthalenedicarboxylic acid and lower alkyl esters thereof. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is particularly preferable. In addition, these aromatic dicarboxylic acids may be used alone or in combination of two or more.

That is, the polyester polyether block copolymer having an aromatic polyester and a polyalkylene ether is preferably a polyester unit containing terephthalic acid and an aliphatic diol having 2 to 12 carbon atoms, and a block having a polytetramethylene ether glycol unit. It is a polymer.

In addition to the above components, the polyester polyether block copolymer may be copolymerized with one or more of a trifunctional alcohol, a tricarboxylic acid and / or an ester thereof in a small amount, and further, such as adipic acid. An aliphatic dicarboxylic acid or a dialkyl ester thereof may also be introduced as a copolymerization component.

The melting point of the polyester polyether block copolymer is not limited, but is usually 125 ° C. or higher, preferably 140 ° C. or higher, and more preferably 160 ° C. or higher. When the melting point of the polyester polyether block copolymer is less than the above lower limit, the heat resistance of the obtained resin composition tends to decrease. The upper limit of the melting point of the polyester polyether block copolymer is not limited, but is usually 300 ° C. or lower, preferably 260 ° C. or lower. Here, the method for measuring the melting point of the polyester polyether block copolymer is the temperature of the melting peak when the temperature is raised at a heating rate of 10 ° C./min using a differential scanning calorimeter.

The above-mentioned polyester polyether block copolymers include "Polyester" (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), "Primaloy" (manufactured by Mitsubishi Chemical Corporation), "Perprene" (manufactured by Toyobo Co., Ltd.), and "Hytrel" (Dupont). Commercial products such as (manufactured by the company) can be mentioned.

Examples of the α, β-ethylenic unsaturated carboxylic acid used for the modification of the above aromatic polyester-based thermoplastic elastomer include acrylic acid, methacrylic acid, etacrilic acid, maleic acid, fumaric acid, itaconic acid, citrus acid, and tetrahydrophthalic acid. , Crotonic acid, isocrotonic acid and the like. Examples of the derivative include acid anhydrides, esters, acid halides, amides, and imides. Acid anhydrides are preferred as these derivatives. For example, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned. Of these, acid anhydride is preferable, and maleic anhydride is particularly preferable. These α, β-ethylenically unsaturated carboxylic acids and / or derivatives thereof are not limited to the case where one kind is used alone, and two or more kinds may be used in combination.

The method for graft-modifying the aromatic polyester-based thermoplastic elastomer is not limited, and it can be obtained by a reaction using only heat, but a radical generator may be added during the reaction. Further, as a method for reacting, a method such as a solution modification method in which the reaction is carried out in a solvent, a melt modification method in which no solvent is used, or a suspension dispersion reaction method may be used. Above all, the melt modification method is preferable.

As the melt modification method, an aromatic polyester-based thermoplastic elastomer and an α, β-ethylenically unsaturated carboxylic acid and / or a derivative thereof (hereinafter, may be referred to as “α, β-ethylenically unsaturated carboxylic acid component””. ), And if necessary, a radical generator described later is mixed in advance and then melt-kneaded in a kneader to react, or the aromatic polyester-based thermoplastic elastomer melted in the kneader is dissolved in a solvent or the like. A method of adding a mixture of an α, β-ethylenically unsaturated carboxylic acid component and a radical generator from the inlet and reacting them can be used. A Henschel mixer, ribbon blender, V-type blender or the like is usually used for mixing, and a single-screw or twin-screw extruder, a roll, a Banbury mixer, a kneader, a lavender mixer or the like can be usually used for melt kneading. .. The temperature of melt-kneading may be appropriately set within a temperature range in which the aromatic polyester-based thermoplastic elastomer does not thermally deteriorate.

The amount of the α, β-ethylenically unsaturated carboxylic acid component used for the modification is usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.05 part by mass with respect to 100 parts by mass of the aromatic polyester-based thermoplastic elastomer. It is preferably 0.1 part by mass or more, usually 30 parts by mass or less, preferably 5 parts by mass or less, and more preferably 1 part by mass or less. If the amount of the α, β-ethylenically unsaturated carboxylic acid component used is too small, sufficient modification cannot be performed and the number of functional groups is too small, so that the dispersibility tends to decrease when blending with EVOH (A). If the amount used is too large, the compound that has not undergone the graft reaction remains, which tends to cause poor appearance or the like.

Radical generators are not limited, but are, for example, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis. (T-Butyloxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxybenzoate, benzoyl peroxide, m-tol oil peroxide, dicumyl peroxide, 1,3-bis (t) -Butylperoxyisopropyl) Organic and inorganic radicals such as benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide; 2,2'-azobisisobutyronitrile, 2,2'- Azobis (isobutylamide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], azo compounds such as azodi-t-butane; carbon radical generators such as dicumyl, etc. Be done.

The above radical generator can be appropriately selected depending on the type of aromatic polyester-based thermoplastic elastomer to be subjected to the graft modification reaction, the type of α, β-ethylenically unsaturated carboxylic acid component, and the modification conditions. May be used alone or in combination of two or more.

The amount of the radical generator used is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and usually, with respect to 100 parts by mass of the aromatic polyester-based thermoplastic elastomer. It is 3 parts by mass or less, preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, and particularly preferably 0.1 part by mass or less. If the amount of the radical generator used is too small, denaturation tends not to occur sufficiently, and if it is too large, the molecular weight of the aromatic polyester-based thermoplastic elastomer is reduced (viscosity is lowered), and the material strength tends to be lowered. be.

The modification rate (graft amount) of the modified aromatic polyester-based thermoplastic elastomer (B) is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and is usually used. It is 10% by mass or less, preferably 7% by mass or less, and more preferably 5% by mass or less. If the amount of graft is too small, the dispersibility tends to decrease when blending with EVOH (A) because there are too few functional groups, and if it is too large, the material strength tends to be reduced due to the low molecular weight in the process of denaturation. Tends to decline. Here, the denaturation rate (graft amount) can be obtained from the spectrum obtained by ^{1 H-NMR measurement.}

The melt flow rate (MFR) of the modified aromatic polyester-based thermoplastic elastomer (B) was 0.1 to 100 g / 10 minutes at a temperature of 230 ° C. and a load of 2.16 kg according to JIS K7210, particularly 1 It is preferably ~ 80 g / 10 minutes, particularly 5 to 70 g / 10 minutes. Even if the MFR is at least the above upper limit value or at least the above lower limit value, the moldability is deteriorated.

As such a modified aromatic polyester-based thermoplastic elastomer (B), a commercially available product can also be used, and examples of the carboxyl group-containing polyester polyether block copolymer include "Primaloy" (manufactured by Mitsubishi Chemical Corporation).

Only one type of modified aromatic polyester-based thermoplastic elastomer (B) may be used, and the composition and physical characteristics of the aromatic polyester-based thermoplastic elastomer before modification may be different, or α, β-ethylene used for modification may be used. Two or more kinds of sex unsaturated carboxylic acid components, those having different modification rates (graft amount) and physical properties may be used in combination.

<Epoxy functional styrene / (meth) acrylate compound (C)>
The epoxy-functional styrene / (meth) acrylate-based compound (C) used in the present invention is an epoxy-functional styrene / (meth) acrylate-based compound having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000. It is preferably an epoxy-functional, styrene-(meth) acrylate-based polymer having a styrene unit represented by the following formula (c1) and a glycidyl (meth) acrylate unit represented by the following formula (c2). It is preferably a polymer containing a styrene unit represented by the following formula (c1), a glycidyl (meth) acrylate unit represented by the following formula (c2), and a (meth) acrylate unit represented by the following formula (c3). ..

(In the formula, R ^{1 to} R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)

(In the formula, R ^{1 to} R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ⁶ represents an alkyl group having 1 to 12 carbon atoms.)

In the formulas (c1) to (c3), R ^{1 to} R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, but when R ^{1 to} R ⁵ are alkyl groups, the number of carbon atoms is high. It is 1 to 12, preferably 1 to 6, and may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group and the like, and a methyl group is particularly preferable.
Further, R ⁶ represents an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group and the like, and a methyl group is particularly preferable.
^{Among them, when R 4} in the formula (c2) is a methyl group and when R ⁵ in the formula (c3) is a methyl group, the resin composition of the present invention is excellent in transparency. Especially preferable.

The weight average molecular weight (Mw) of the epoxy functional styrene / (meth) acrylate compound (C) is 250 to 9000. When the Mw of the epoxy functional styrene / (meth) acrylate compound (C) is less than 250, the productivity is lowered, and when it exceeds 9000, the effect of suppressing the deterioration of the adhesiveness is lowered. The Mw of the epoxy functional styrene / (meth) acrylate compound (C) is preferably 300 to 8900, more preferably 400 to 8800. Here, Mw of the epoxy functional styrene / (meth) acrylate compound (C) is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

Within the range of the above weight average molecular weight, the number x of the styrene units represented by the above formula (c1) and the above formula (c2) contained in the epoxy functional styrene / (meth) acrylate compound (C). The number y of the represented glycidyl (meth) acrylate unit is 1 to 35 independently, and y is preferably 2 to 30 and more preferably 4 to 25 from the viewpoint of transparency. x + y is preferably 10 to 70, more preferably 15 to 60.
When having the (meth) acrylate unit represented by the formula (c3), the number x of the styrene units represented by the formula (c1) and the glycidyl (meth) acrylate unit represented by the formula (c2). The number y and the number z of the (meth) acrylate unit represented by the above formula (c3) are independently 1 to 20, and y is preferably 2 to 20 and more preferably 3 from the viewpoint of transparency. It is -10. x + z is preferably greater than 10.
Each structural unit can be bonded in any order, and the epoxy-functional styrene / (meth) acrylate-based compound (C) may be a block copolymer or a random copolymer.

Further, the ratio of the styrene unit represented by the above formula (c1) in the epoxy functional styrene / (meth) acrylate compound (C) is preferably 0.001 to 10% by mass, preferably 0.005 to 10. It is preferably 5% by mass. When the styrene unit represented by the formula (c1) is 0.001% by mass or more, the above-mentioned effect due to having a benzene ring can be sufficiently obtained, and when it is 10% by mass or less, the moldability is affected. Do not give.

The epoxy equivalent of the epoxy functional styrene / (meth) acrylate compound (C) is 10 to 1000 g / eq. Especially 50-700 g / eq. Is preferable. When the epoxy equivalent of the epoxy functional styrene / (meth) acrylate compound (C) is not more than the above upper limit, the effect of improving the adhesiveness of the epoxy functional styrene / (meth) acrylate compound (C) can be sufficiently obtained. If it is equal to or higher than the above lower limit, the moldability is not affected.

As the epoxy functional styrene / (meth) acrylate compound (C), a commercially available product can be used, and examples thereof include "Joncryl ADR" (trade name) manufactured by BASF.

As the epoxy functional styrene / (meth) acrylate compound (C), only one type may be used, or two or more types having different types, compositions, physical properties, etc. of the constituent units may be used in combination.

<Content ratio>
The resin composition of the present invention contains the ethylene / vinyl ester-based copolymer with respect to a total of 100 parts by mass of the above-mentioned ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B). Containing 40 to 99 parts by mass of the polymer saponified product (A) and 60 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B) in terms of both gas barrier property, impact resistance and moldability. This ratio is more preferably 60 to 99 parts by mass of the ethylene / vinyl ester-based copolymer saponified product (A), 40 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B), and further preferably ethylene. 70 to 99 parts by mass of the vinyl ester-based copolymer saken product (A) and 30 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B).

Further, in order to effectively obtain the effect of improving the adhesiveness of the epoxy-functional styrene / (meth) acrylate-based compound (C), the epoxy-functional styrene / (meth) acrylate-based compound (C) is an ethylene / vinyl ester-based compound. It is preferably contained in an amount of 0.05 to 10 parts by mass, preferably 0.08 to 8 parts by mass, based on a total of 100 parts by mass of the copolymer saponified product (A) and the modified aromatic polyester-based thermoplastic elastomer (B). It is more preferably contained in an amount of 0.1 to 7 parts by mass, and further preferably contained in an amount of 0.1 to 7 parts by mass. If the content of the epoxy-functional styrene / (meth) acrylate-based compound (C) is too small, the effect of improving the adhesiveness by using the epoxy-functional styrene / (meth) acrylate-based compound (C) can be sufficiently obtained. However, if the amount is too large, the formability becomes unstable and the appearance and transparency of the product are impaired.

<Other ingredients>
The resin composition of the present invention includes other than the ethylene / vinyl ester-based copolymer saken product (A), the modified aromatic polyester-based thermoplastic elastomer (B), and the epoxy functional styrene / (meth) acrylate-based compound (C). In addition, other thermoplastic resins, for example, the olefin resin (D) contained in the master batch for appearance improvement described later may be contained, as long as the effects of the present invention are not impaired. When the other thermoplastic resin is contained, the content of the other thermoplastic resin is usually preferably less than 30% by mass based on the entire resin composition.

Further, the resin composition of the present invention may contain other compounding agent components depending on the intended purpose, as long as the effects of the present invention are not impaired. The amount of these compounding agents added is usually less than 20% by mass with respect to the resin composition. The above-mentioned compounding agents include rubber components, talc, calcium carbonate, mica, fillers such as glass fibers, plasticizers such as paraffin oil, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, neutralizers, and lubricants. , Antifogging agent, Antiblocking agent, Slip agent, Crosslinking agent, Crosslinking aid, Coloring agent, Flame retardant, Dispersant, Antistatic agent, Antibacterial agent, Fluorescent whitening agent, etc. One kind or two or more kinds can be added.

In particular, in order to enhance the effect of the present invention and improve the melt stability and the like, hydrotalcite compounds, hindered phenols, hindered amine heat stabilizers, and metal salts of higher aliphatic carboxylic acids (for example, calcium stearate). , Magnesium stearate, etc.) is preferably added in an amount of 0.01 to 1% by mass based on the resin composition.

Further, it is also effective to enhance the effect of the present invention and to contain an alkali metal salt having alkali metal ions such as lithium ion, sodium ion and potassium ion in order to improve the interlayer adhesion and the compatibility of the resin composition. be. Specific examples of the alkali metal compound include lower aliphatic carboxylates having 2 to 7 carbon atoms such as sodium acetate and potassium acetate, and higher aliphatic carboxylates having 8 to 22 carbon atoms such as sodium stearate and potassium stearate. Examples thereof include aromatic carboxylates such as acid salts, sodium benzoate and potassium benzoate, metal complexes such as sodium phosphate ethylenediamine tetraacetate such as sodium phosphate and lithium phosphate, preferably sodium acetate, potassium acetate and the like. It is a lower aliphatic carboxylate having 2 to 7 carbon atoms, a higher aliphatic carboxylate having 8 to 22 carbon atoms such as sodium stearate and potassium stearate, and a phosphate such as sodium phosphate and lithium phosphate, more preferably. It is a higher aliphatic carboxylic acid salt having 8 to 22 carbon atoms such as sodium stearate and potassium stearate, and particularly preferably a potassium salt of the higher aliphatic carboxylic acid having 8 to 22 carbon atoms. These may be used alone or in combination of two or more.

The content of the alkali metal compound is usually 0.0001 to 1 part by mass, preferably 0.0003 to 0.5 part by mass, based on a metal conversion value (weight basis) with respect to 100 parts by mass of EVOH (A). It is more preferably 0.0005 to 0.1 parts by mass, still more preferably 0.001 to 0.05 parts by mass. When the alkali metal compound is contained in EVOH (A) in advance as described above, it is preferable that the total amount including the amount is within the above range.

<Manufacturing method>
Ethylene / vinyl ester-based copolymer kenide (A), modified aromatic polyester-based thermoplastic elastomer (B), epoxy-functional styrene / (meth) acrylate-based compound (C) and other components used as necessary. As a method for producing the resin composition of the present invention by mixing the above, a known method can be adopted. For example, a melt mixing method such as a method of dry blending all components and melting and mixing, a method of blending other components with EVOH (A) melted in advance, or a method of dissolving EVOH (A) in a solvent and applying the method. There is a method of blending other components with the solution and precipitating using a poor solvent of EVOH (A).

Above all, the melt mixing method is preferable because it has good industrial productivity and enables uniform mixing. A known machine can be used for melting and mixing. For example, it can be carried out by using a kneader ruder, a single-screw or twin-screw extruder, a mixing roll, a Banbury mixer, a kneading device such as a plast mill, etc., but it is industrially preferable to use a twin-screw extruder.

The resin composition of the present invention uses the masterbatch for improving the appearance described later of the present invention instead of the epoxy-functional styrene / (meth) acrylate-based compound (C), and the masterbatch for improving the appearance is used as an ethylene-vinyl ester. It can also be produced by melt-mixing the based copolymer saponified product (A) and the modified aromatic polyester-based thermoplastic elastomer (B) as described above.

The resin composition of the present invention may be formed into various molded products when melt-mixed in an extruder and then extruded, or resin composition pellets are once produced and various molded products are molded by a separately known processing method. You may. The latter method is preferable from the viewpoint of distribution and handleability of the resin composition.
Further, in the case of making pellets, the shape is usually spherical, cylindrical, cubic, rectangular parallelepiped or the like, and cylindrical pellets are preferable, and the diameter is usually 1 to 5 mm and the length is usually 1 to 5 mm.

[Laminate]
The resin composition of the present invention can be applied to various molded products as a single layer, but from the viewpoint of improving mechanical strength and the like, the resin composition layer of the present invention has a thermoplastic resin layer other than EVOH (A). It is preferable to provide various molded products as a multi-layer laminated body in which at least one layer is laminated.

Specific examples of the thermoplastic resin (hereinafter, may be referred to as “other thermoplastic resin”) constituting the thermoplastic resin layer other than EVOH (A) include linear low-density polyethylene and low-density polyethylene. , Polyethylene resin such as ultra-low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, etc., Polypropylene resin, ethylene-acetic acid Vinyl copolymers, ionomers, ethylene-propylene (block and random) copolymers, ethylene-acrylic acid copolymers, ethylene-acrylic acid ester copolymers, polybutenes, polypentenes and other olefins alone or copolymers, or Broadly defined polyolefin resins such as these olefins alone or copolymers graft-modified with unsaturated carboxylic acids or esters thereof; polyester resins; polyamide resins (including copolymerized polyamides); polyvinyl chloride; poly Examples thereof include vinylidene chloride; acrylic resin; polystyrene; vinyl ester resin; polyester elastomer; polyurethane elastomer; chlorinated polyethylene; chlorinated polypropylene; aromatic or aliphatic polyketone; and polyalcohols obtained by reducing these. These may be used alone or in combination of two or more.
Among them, it is preferable to use a hydrophobic resin from the viewpoint of suppressing deterioration of the gas barrier property of the resin composition of the present invention, specifically, a polyolefin-based resin is preferable, and a polyethylene-based resin and a polypropylene-based resin are particularly preferable.

The resin composition layer and the other thermoplastic resin layer of the present invention may each have two or more layers in the multilayer structure.
In the resin composition layer and other thermoplastic resin layer of the present invention, it is preferable that an adhesive resin layer is further interposed between the resin composition layer of the present invention and the other thermoplastic resin layer.

The adhesive resin layer contains, for example, a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to an olefin polymer (the above-mentioned polyolefin resin) by an addition reaction, a graft reaction, or the like. Examples thereof include modified olefin resins. Specifically, maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, maleic anhydride-modified ethylene-propylene (block and random) copolymer, maleic anhydride-grafted ethylene-ethylacrylate copolymer, anhydrous. One or a mixture of two or more selected from a maleic acid graft-modified ethylene-vinyl acetate copolymer and the like is preferable. The amount (modification amount) of the unsaturated carboxylic acid or its anhydride contained in the modified resin is usually 0.001 to 3% by mass, preferably 0.01 to 1% by mass, and particularly preferably 0.03 to 0.03. It is 0.5% by mass. If the modified amount of the modified resin is small, the adhesiveness tends to be insufficient, and conversely, if it is large, a crosslinking reaction occurs and the moldability tends to deteriorate.

These adhesive resins can be blended with rubber / elastomer components such as EVOH (A), polyisobutylene, and ethylene-propylene rubber, as well as resins of other thermoplastic resin layers, and are adhesive resins. It is also possible to blend a polyolefin resin different from the parent polyolefin resin of.

Even if the other thermoplastic resin layer or adhesive resin layer contains known antioxidants, antistatic agents, plasticizers, lubricants, nuclei, antiblocking agents, waxes, etc., which are usually blended. good.

The laminate having the multi-layer structure may include at least one layer of the resin composition of the present invention, and the composition thereof is not particularly limited, but the purpose is to prevent deterioration of the gas barrier performance of the resin composition of the present invention due to moisture. Therefore, it is preferable that the resin composition layer of the present invention is an intermediate layer.

The layer structure of the multilayer body is usually 3 when the resin composition layer is α (α1, α2, ...) And the other thermoplastic resin layer is β (β1, β2, ...). ~ 20 layers, preferably 3 to 15 layers, particularly preferably 3 to 10 layers. For example, specifically, β / α / β, α / β / α, α1 / α2 / β, α / β1 / β2, β2 / β1 / α / β1 / β2, β2 / β1 / α / β1 / α / Any combination such as β1 / β2 is possible.
Further, the laminated body is provided with a recycled layer containing a mixture of a resin composition and a thermoplastic resin other than EVOH, which is obtained by remelt molding the edges and defective products generated in the process of manufacturing the laminated body. It is possible. When the recycled layer is R, the layer structure of the multilayer laminate is, for example, β / α / R, R / β / α, β / R / α / β, β / R / α / R / β, β /. Examples thereof include α / R / α / β and β / R / α / R / α / R / β.
In particular, it is industrially preferable to provide a recycled layer in that a large amount of scrap generated during molding can be effectively utilized.

The layer structure of the multilayer structure in the laminated body of the present invention is preferably such that the resin composition layer of the present invention (hereinafter, may be referred to as “the present resin composition layer”) exists as a layer in contact with the inclusions. , It is preferable that the thermoplastic resin layer other than EVOH, preferably the polyolefin resin layer, is present in the layer outside the layer in contact with the inclusions. For example, (inside) this resin composition layer / adhesive resin layer / other thermoplastic resin layer (outside), (inside) this resin composition layer / adhesive resin layer / recycled layer / other thermoplastic resin layer (inside) Outside) (Inside) This resin composition layer / Adhesive resin layer / Other thermoplastic resin layer / Recycled layer / Other thermoplastic resin layer (Outside), (Inside) This resin composition layer / Adhesive resin layer / Examples thereof include other thermoplastic resin layer / adhesive resin layer / other thermoplastic resin layer (outside), but most preferably (inside) this resin composition layer / adhesive resin layer / other thermoplastic resin. The layer (outside).

The total thickness of the laminate is usually 20 to 50,000 μm, particularly preferably 100 to 20000 μm from the viewpoint of mechanical strength. If the total thickness of the laminate is too thin, impact resistance and gas barrier properties may decrease. If the total thickness of the laminate is too thick, the impact resistance and the gas barrier property will be excessive, and unnecessary raw materials will be used, which tends to be uneconomical.

The thickness of each layer in the multi-layer structure cannot be unequivocally determined depending on the layer structure, use, container form, required physical properties, etc., but is as follows, for example. The values below are the total thickness of the same type of layer when at least one of the resin composition layer, the adhesive resin layer, and the other thermoplastic resin layer is present in two or more layers. Is.

The thickness of the present resin composition layer is usually 0.1 to 500 μm, preferably 1 to 300 μm, and particularly preferably 5 to 100 μm. If the resin composition layer is too thin, the effect of the present invention tends to be difficult to obtain, and if the resin composition layer is too thick, the processability tends to decrease.
The other thermoplastic resin layer is usually 1 to 6000 μm, preferably 5 to 4000 μm, and particularly preferably 10 to 2000 μm. If the other thermoplastic resin layer is too thin, the impact resistance tends to decrease, and if the other thermoplastic resin layer is too thick, the workability tends to decrease.
The adhesive resin layer is usually 0.1 to 500 μm, preferably 0.5 to 300 μm, and particularly preferably 5 to 100 μm.

The thickness ratio of each layer is the thickness ratio of the present resin composition layer / the other thermoplastic resin layer = usually 0.001 or more and less than 1, preferably 0.005 or more and less than 1, and particularly preferably 0.05 to 0. The thickness ratio of the present resin composition layer / adhesive resin layer is usually 0.005 to 300, preferably 0.01 to 50, and particularly preferably 0.05 to 10.

The laminate may be further stretched by a known method.
The stretching treatment in this case may be a known stretching method, and examples thereof include uniaxial stretching and biaxial stretching. In the case of biaxial stretching, either the simultaneous biaxial stretching method or the sequential biaxial stretching method can be adopted. The stretching temperature is the temperature of the laminated body (temperature in the vicinity of the laminated body), and is usually selected from the range of about 60 to 300 ° C., preferably about 80 to 180 ° C. The draw ratio is usually 2 to 50 times, preferably 2 to 20 times in terms of area ratio.

The thickness of each layer in the stretched laminate is, for example, as follows. The resin composition layer is usually 0.1 to 1000 μm, preferably 1 to 500 μm. The other thermoplastic resin layer is usually 0.1 to 500 μm, preferably 1 to 100 μm. The adhesive resin layer is usually 0.1 to 250 μm, preferably 0.1 to 100 μm. The thickness ratio of each layer is the thickness ratio of the present resin composition layer / the other thermoplastic resin layer = usually 0.001 to less than 1, preferably 0.005 or more and less than 1, and particularly preferably 0.05 to 0. The thickness ratio of the present resin composition layer / adhesive resin layer is usually 0.005 to 300, preferably 0.01 to 50, and particularly preferably 0.05 to 10.

[Masterbatch for improving appearance]
The resin composition of the present invention containing an ethylene / vinyl ester-based copolymer kenide (A), a modified aromatic polyester-based thermoplastic elastomer (B), and an epoxy-functional styrene / (meth) acrylate-based compound (C). When the above-mentioned laminate is made into a sheet for producing the above-mentioned laminate, the appearance is deteriorated due to the epoxy functional styrene / (meth) acrylate compound (C) (for example, lumps on the sheet surface). May occur.
In order to suppress this deterioration of appearance, the epoxy functional styrene / (meth) acrylate-based compound (C) is mixed with another resin to form a masterbatch, and this masterbatch is used as an ethylene / vinyl ester-based copolymer Ken. The resin composition of the present invention may be obtained by melt-mixing with a compound (A), a modified aromatic polyester-based thermoplastic elastomer (B), and other components used as necessary.

The resin used for masterbatch of the epoxy functional styrene / (meth) acrylate compound (C) is not particularly limited, but the olefin resin (D) is used from the viewpoint of suppressing the appearance deterioration. preferable.

Examples of the olefin resin (D) include homopolymers of α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and 1-butene, their α-olefins, or their α-olefins and 3-methyl. Other α-olefins having about 2 to 20 carbon atoms such as -1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, vinyl acetate, (meth). Examples thereof include a copolymer with an acrylic acid, a (meth) acrylic acid ester, and the like.

More specifically, for example, low / medium / high density polyethylene or the like (branched or linear) ethylene homopolymer, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4- Methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) ) Ethylene resins such as ethyl acrylate copolymers; propylene homopolymers, propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-ethylene-1-butene copolymers, propylene-4-methyl Examples thereof include propylene-based resins such as 1-pentene copolymers; and 1-butene-based resins such as 1-butene homopolymers, 1-butene-ethylene copolymers, and 1-butene-propylene copolymers. These olefin resins may be used alone or in combination of two or more.
Here, the ethylene-based resin, the propylene-based resin, and the 1-butene-based resin each contain 50% by mass or more of a monomer unit based on ethylene, propylene, or 1-butene in all the constituent monomer units. Say resin.

Among these, the olefin resin (D) is preferably an ethylene resin. Among the ethylene-based resins, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-vinyl acetate copolymer are particularly preferable.

The olefin resin (D) such as an ethylene resin has an ethylene-based monomer unit content of 70 to 90% by mass and a 1-octene-based monomer unit content of 10 to 30% by mass (however). , Ethylene 1-octene copolymer (density: 0.902 g) of ethylene 1-octene copolymer (the total of the content of the monomer unit based on ethylene and the content of the monomer unit based on 1-octene is 100% by mass). / Cm ³ , tensile strength: 24.8 MPa, JIS-D hardness: 42) is preferable from the viewpoint of compatibility.

The masterbatch for improving the appearance of the present invention is a masterbatch in which an epoxy-functional styrene / (meth) acrylate-based compound (C) is melt-kneaded in advance using such an olefin-based resin (D). .. The masterbatch method is not particularly limited, and the masterbatch for improving the appearance of the present invention can be produced according to a conventional method.

The content of the epoxy-functional styrene / (meth) acrylate-based compound (C) in the master batch for improving the appearance of the present invention includes the olefin-based resin (D) and the epoxy-functional styrene / (meth) acrylate-based compound (C). It is preferable that the total amount is 0.05 to 60 parts by mass, particularly 1 to 40 parts by mass in 100 parts by mass. If the content of the epoxy-functional styrene / (meth) acrylate-based compound (C) in the master batch for improving the appearance is too large, the epoxy-functional styrene / (meth) acrylate-based compound (C) is made into a master batch. If the effect of suppressing appearance deterioration cannot be sufficiently obtained and the amount is too small, the amount of the master batch for blending a predetermined amount of the epoxy functional styrene / (meth) acrylate compound (C) becomes large, which is relative. In addition, the blending amount of the ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B) may be reduced, and the effect of the present invention may be impaired.

Hereinafter, the content of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable ranges are the values of the upper limit or the lower limit of the relations and the following. It may be in the range specified by the value of Examples or the combination of the values of Examples.

In the following, the ethylene-vinyl ester copolymer saken product (A) is referred to as "component (A)", the modified aromatic polyester-based thermoplastic elastomer (B) is referred to as "component (B)", and C is referred to as "component (C)". ".

[material]
<Ingredient (A)>
Ethylene-vinyl ester copolymer saponified product (EVOH resin): "EVAL H171B" manufactured by Kuraray Co., Ltd. (ethylene unit content: 38 mol%, saponification degree: 100 mol%, MFR (210 ° C, 2.16 kg) ): 3.5g / 10 minutes)

<Ingredient (B)>
B-1: Maleic anhydride-modified aromatic polyester-based thermoplastic elastomer: "Primaloy AP GQ430" manufactured by Mitsubishi Chemical Co., Ltd. (melting point of block copolymer before modification: 165 ° C, poly of block copolymer before modification Content of tetramethylene ether glycol unit: 60% by mass, number average molecular weight of polytetramethylene ether glycol unit: 1000, modification rate (graft amount): 0.5% by mass, MFR (230 ° C, 2.16 kg): 35 g / 10 minutes)
B-2: Maleic anhydride-modified aromatic polyester-based thermoplastic elastomer: "Primaloy AP" manufactured by Mitsubishi Chemical Co., Ltd. (melting point of block copolymer before modification: 197 ° C, polytetra of block copolymer before modification Content of methylene ether glycol unit: 64% by mass, number average molecular weight of polytetramethylene ether glycol unit: 1700, modification rate (graft amount): 0.1% by mass, MFR (230 ° C, 2.16 kg): 6 g / 10 minutes)

<Component (C)>
C-1; Epoxy functionality, styrene, (meth) acrylate polymer: BASF "Joncryl ADR-4368" (weight average molecular weight: 7700, epoxy equivalent: 281 g / eq, styrene unit content: 0.1- It has 0.5% by mass, at least the units represented by the above formulas (c1) to (c3), R ^{1 to} R ³ are hydrogen atoms, R ⁴ is a methyl group, x = 31 to 34, y =. 22-25)
C-2: Epoxy functionality, styrene, (meth) acrylate polymer: BASF "Joncryl ADR-4368" (weight average molecular weight: 7700, epoxy equivalent: 281 g / eq, styrene unit content: 0.1- It has 0.5% by mass, at least the units represented by the above formulas (c1) to (c3), R ^{1 to} R ³ are hydrogen atoms, R ⁴ is a methyl group, x = 31 to 34, y =. 22-25) 20 parts by mass of ethylene / α-olefin copolymer (content of ethylene-based monomer unit is 80% by mass, content of 1-octene-based monomer unit is 20% by mass). Ethylene 1-octene copolymer, density: 0.902 g / cm ³ , tensile strength: 24.8 MPa, JIS-D hardness: 42) 80 parts by mass in a master batch.

<Other ingredients>
Acrylic polymer with glycidyl group: "Metabrene P 1901" manufactured by Mitsubishi Rayon Co., Ltd. (weight average molecular weight: 68000, epoxy equivalent: 148q / eq.)

[Example 1]
<Manufacturing of gas barrier resin composition>
Component (A) Ethylene-vinyl ester-based copolymer saponified product 80 parts by mass, Component (B) Modified aromatic polyester-based thermoplastic elastomer (B-1: Primaloy AP GQ430) 20 parts by mass, Component (C) Epoxy functionality -Styrene (meth) acrylate polymer (C-1: Joncryl ADR-4368) 1.5 parts by mass is mixed in advance by dry blending, and the twin-screw extruder "TEX30α-52.5BW" (D = 30 mmφ, L / D = 52.5, manufactured by Nippon Steel Co., Ltd.), melt-kneaded at a temperature of 220 ° C., screw rotation speed of 400 rpm, extrusion rate of 40 kg / h, extruded into a string, cooled and then cut to create a gas barrier resin. Pellets of the composition were obtained.

<Molding of multi-layer sheet>
The pellets of the obtained gas barrier resin composition were used as a material for constituting the gas barrier layer, and a multilayer sheet (laminated body) was obtained by a 4-type 5-layer coextrusion multilayer sheet molding machine manufactured by Pura Giken Co., Ltd.
The layer structure was a five-layer structure consisting of a polyolefin resin layer / an adhesive resin layer / a gas barrier layer / an adhesive resin layer / a polyolefin resin layer from the side in contact with the cooling roll surface to the outside. The materials used for the polyolefin-based resin layer and the adhesive resin layer are as follows, and the thickness of each layer is 50 μm / 10 μm / 10 μm / 10 μm / 50 μm, the molding temperature is 220 ° C., and the molding speed is 20 m / min. I set it up and got a multi-layer sheet.
Polyolefin-based resin layer: Ethylene 1-hexene copolymer "SF8402" manufactured by Japan Polyethylene Corporation (MFR (190 ° C, 2.16 kg): 2.6 g / 10 minutes, density: 0.929 g / cm ³ )
Adhesive resin layer: Adhesive polyethylene "Modic L553" manufactured by Mitsubishi Chemical Corporation (MFR (190 ° C, 2.16 kg): 1.6 g / 10 minutes, density 0.920 g / cm ³ )

<Evaluation of adhesiveness>
A strip-shaped test piece having a width of 10 mm was cut out from the multilayer sheet obtained above, and a T-peel peeling test was conducted at a speed of 300 mm / min in an atmosphere of 23 ° C. to measure the peeling strength, and the peeling strength was measured. Relative evaluation was performed with the peel strength in the case of Example 1 as 1. The results are shown in Table 1. In this T-pee peeling test, peeling occurs between the adhesive resin layer and the gas barrier layer.

<Appearance evaluation of multi-layer sheet>
The appearance of the multilayer sheet obtained above was visually observed and evaluated by the following indexes. Relative evaluation was performed with the evaluation in the case of Reference Example 1 below as ⊚.
◎: No visible lumps 〇: A few small lumps are seen compared to Reference Example 1 △: Many small lumps are seen compared to Reference Example 1 ×: Large lumps are seen compared to Reference Example 1 Often seen

[Example 2]
Component (B) The type of modified aromatic polyester-based thermoplastic elastomer was changed from B-1 to B-2, the type of component (C) was changed from C-1 to C-2, and the formulation of C-2 was changed. The resin composition was produced, the multilayer sheet was molded, the adhesiveness and the appearance were evaluated in the same manner as in Example 1 except that the amount was changed to 0.4 parts by mass, and the results are shown in Table 1.

[Example 3]
The resin composition was produced and the multilayer sheet was prepared in the same manner as in Example 1 except that the type of the component (C) was changed from C-1 to C-2 and the blending amount of C-2 was changed to 1 part by mass. Molding, adhesiveness and appearance were evaluated, and the results are shown in Table-1.

[Comparative Example 1]
Component (A) ethylene / vinyl ester-based copolymer saken product is 80 parts by mass, component (B) modified aromatic polyester-based thermoplastic elastomer (B-1: Primaloy AP GQ430) is 20 parts by mass, and component (C) epoxy. Except for the fact that the functional styrene / (meth) acrylate compound was not used, the resin composition was produced, the multilayer sheet was formed, the adhesiveness and the appearance were evaluated in the same manner as in Example 1, and the results are shown in Table 1-1. It was shown to.

[Comparative Example 2]
Component (A) Ethylene-vinyl ester-based copolymer saken product is 80 parts by mass, component (B) Modified aromatic polyester-based thermoplastic elastomer (B-1: Primaloy AP GQ430) is 20 parts by mass, and acrylic having a glycidyl group. The resin composition was manufactured, the multilayer sheet was formed, the adhesiveness and the appearance were evaluated in the same manner as in Example 1 except that 0.5 part by mass of the system polymer (Metabrene P 1901) was used, and the results are shown in Table 1. Indicated.

[Reference Example 1]
Using only 100 parts by mass of the ethylene-vinyl ester copolymer saponified product, the multilayer sheet was formed and the adhesiveness was evaluated in the same manner as in Example 1, and the measured peel strength was set to "1". In addition, the appearance was evaluated, and it was confirmed that there were no bumps, and the evaluation result was marked as "◎".

The following can be seen from Table-1.
In Comparative Example 1, the adhesiveness with the adhesive resin layer is inhibited by adding the modified aromatic polyester-based thermoplastic elastomer to the EVOH resin.
As is clear from Comparative Example 2, the acrylic polymer having only a glycidyl group does not improve the adhesion inhibition by the modified aromatic polyester-based thermoplastic elastomer.
On the other hand, as in Example 1, the resin composition of the present invention containing an epoxy-functional styrene-(meth) acrylate-based compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000. If this is the case, the inhibition of adhesiveness by the modified aromatic polyester-based thermoplastic elastomer is improved, and almost the same adhesiveness as in the case of the EVOH resin alone can be obtained.
Further, as in Examples 2 and 3, an epoxy functional styrene / (meth) acrylate compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000 is blended as a master batch. Therefore, the inhibition of the adhesiveness due to the modified aromatic polyester-based thermoplastic elastomer can be improved, and the deterioration of the appearance when formed into a laminated body can be suppressed.

Claims (11)

Ethylene-vinyl ester copolymer saken product (A) and
Modified aromatic polyester-based thermoplastic elastomer (B) graft-modified with one or more of α, β-ethylenic unsaturated carboxylic acid and / or its derivative acid anhydride, ester, acid halide, amide, and imide. When,
A resin composition containing an epoxy functional styrene (meth) acrylate compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000 .
In a total of 100 parts by mass of the ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B), 40 to 40 to 40 parts of the ethylene / vinyl ester-based copolymer saken product (A) are added. 99 parts by mass, 60 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B), and the ethylene / vinyl ester-based copolymer saken product (A) and the modified aromatic polyester-based thermoplastic elastomer (B) A resin composition containing 0.05 to 10 parts by mass of an epoxy-functional styrene / (meth) acrylate-based compound (C) with respect to a total of 100 parts by mass. Claim 1 in which the epoxy-functional styrene / (meth) acrylate compound (C) has a styrene unit represented by the following formula (c1) and a glycidyl (meth) acrylate unit represented by the following formula (c2). The resin composition according to.

(In the formula, R ^{1 to} R ⁴ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.) The epoxy functional styrene / (meth) acrylate compound (C) has a styrene unit represented by the following formula (c1), a glycidyl (meth) acrylate unit represented by the following formula (c2), and the following formula (c3). The resin composition according to claim 2, which comprises a (meth) acrylate unit represented by).

(In the formula, R ^{1 to} R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ⁶ represents an alkyl group having 1 to 12 carbon atoms.) The resin composition according to any one of claims 1 to 3, wherein the content of the styrene unit of the epoxy functional styrene / (meth) acrylate compound (C) is 0.001 to 10% by mass. Epoxy functionality The epoxy equivalent of the (meth) acrylate compound (C) is 10 to 1000 g / eq. The resin composition according to any one of claims 1 to 4. The modification rate (graft amount) of the modified aromatic polyester-based thermoplastic elastomer (B) is 0.01 to 10% by mass, and the melt flow rate (temperature 230 ° C., load 2.16 kg) is 0.1 to 100 g / 10 minutes. The resin composition according to any one of claims 1 to 5. The ethylene-vinyl ester copolymer saponified product (A) has an ethylene unit content of 20 to 60 mol%, a saponification degree of 90 to 100 mol%, and a melt flow rate (temperature 210 ° C., load 2.16 kg). The resin composition according to any one of claims 1 to 6, wherein the amount is 0.1 to 100 g / 10 minutes. The resin composition according to any one of claims 1 to 7 , which is a gas barrier resin composition. A laminate having a layer made of the resin composition according to any one of claims 1 to 8. The laminate according to claim 9 , further comprising a gas barrier layer made of the resin composition and an adhesive resin layer made of a maleic acid-modified polyolefin resin adjacent to the gas barrier layer. Ethylene / vinyl ester-based copolymer kenide (A) and one or more of α, β-ethylenically unsaturated carboxylic acid and / or its derivative acid anhydride, ester, acid halide, amide, and imide. It is a resin composition containing a graft-modified modified aromatic polyester-based thermoplastic elastomer (B), and is an ethylene / vinyl ester-based copolymer saken product (A) and a modified aromatic polyester-based thermoplastic elastomer (B). In a total of 100 parts by mass, 40 to 99 parts by mass of the ethylene / vinyl ester-based copolymer saponified product (A) and 60 to 1 part by mass of the modified aromatic polyester-based thermoplastic elastomer (B) are contained. 0.05 parts by mass of the vinyl ester-based copolymer saponified product (A) and the modified aromatic polyester-based thermoplastic elastomer (B) with 0.05 parts by weight of the epoxy-functional styrene / (meth) acrylate-based compound (C). An epoxy functional styrene / (meth) acrylate-based compound (C) having a styrene unit and a glycidyl group and having a weight average molecular weight of 250 to 9000, which is a master batch for improving appearance to be blended in a resin composition containing 10 parts by mass. ) Is made into a master batch with an olefin resin (D) to improve the appearance.