JP7246169B2 - Blow-molded container, and fuel container and bottle container comprising the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a blow-molded container, and a fuel container and a bottle container having the same.

Ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as "EVOH") is a polymeric material with excellent gas barrier properties, oil resistance, antistatic properties, mechanical strength, etc., and is widely used as various packaging materials. ing.

A blow-molded container having an EVOH layer is known as one of containers using EVOH (see Patent Document 1). Blow-molded containers widely employ a multilayer structure comprising an EVOH layer and another thermoplastic resin layer having excellent moisture resistance, impact resistance, and the like. Blow-molded containers having an EVOH layer are used in various fields such as fuel containers and various bottles because of their excellent gas barrier properties.

On the other hand, when EVOH is used as various packaging materials, EVOH resin compositions which are relatively easy to melt and mold have been proposed. In Patent Document 2, in producing a resin composition containing specific amounts of EVOH and a boron compound, EVOH having a water content of 20 to 80% by mass is brought into contact with an aqueous boron compound solution, and the content of the boron compound in the aqueous boron compound solution is is 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the total amount of water contained in the EVOH and the water contained in the boron compound aqueous solution. It is described that an EVOH resin composition that can suppress the occurrence of fish eyes and the like in some cases and has good long-run moldability can be obtained.

In Patent Document 3, the boron compound is 100 to 5000 ppm in terms of orthoboric acid (H ₃ BO ₃ ), the carboxylic acid and/or its salt is 100 to 1000 ppm in terms of carboxylic acid, and the alkali metal salt is 50 to 300 ppm in terms of metal. Disclosed is a multilayer structure obtained by co-extrusion of a molten multilayer body consisting of an EVOH resin composition layer and a carboxylic acid-modified polyolefin resin layer adjacent thereto, and has thermal stability (long-run property) and coexistence during high-temperature production. It is stated that extrusion film-forming stability is improved.

JP-A-2005-089482 JP-A-11-293078 WO 2000/020211

However, when the above-mentioned conventional EVOH resin composition is continuously subjected to multi-layer blow molding for a long period of time, the resulting blow-molded container may have appearance defects such as streaks and lumps. A streak is a transparent streak-like defect, and is considered to be caused by layer disorder or partial cross-linking. In addition, a lump is a granular defect, and is said to be caused by gelation due to partial cross-linking.

These defects such as streaks and pimples cause not only deterioration in appearance but also deterioration in performance such as gas barrier properties. For example, in order to store and transport food, fuel, etc. at low temperatures, blow-molded containers are required to be impact resistant and maintain gas barrier properties even in low-temperature environments. However, a blow-molded container including an EVOH layer tends to harden at a low temperature, so cracks and the like are likely to occur due to impact, and the gas barrier property tends to decrease. Here, if there are many streaks and bumps as described above, cracks or the like tend to occur from these starting points when receiving an impact, and the gas barrier property is lowered.

The present invention has been made based on the above circumstances, and an object of the present invention is to provide a blow-molded container having few streaks and bumps and excellent impact resistance at low temperatures, and a fuel provided with such a blow-molded container. To provide a container and a bottle container.

That is, the present invention provides [1] an ethylene-vinyl alcohol copolymer (A) having an ethylene unit content of 20 to 60 mol% (hereinafter sometimes abbreviated as "EVOH (A)") and a boron compound (B). A blow-molded container comprising a layer formed from a resin composition (α) containing, wherein the boron compound (B) contains free boric acid (C), and boron relative to EVOH (A) in the resin composition (α) The content of the compound (B) is 100 ppm or more and 5000 ppm or less in terms of orthoboric acid, and the ratio of free boric acid (C) in the boron compound (B) is 0.1 mass% or more and 10 mass% or less in terms of orthoboric acid. a blow molded container;
[2] The blow-molded container of [1], wherein the resin composition (α) contains a phosphoric acid compound of 1 ppm or more and 500 ppm or less in terms of phosphate radical.
[3] The blow-molded container of [1] or [2], wherein the resin composition (α) contains 0.01 μmol/g or more and 20 μmol/g or less of carboxylic acid and/or carboxylic acid ion in terms of carboxylic acid radical;
[4] The blow of any one of [1] to [3], wherein the resin composition (α) has a melt index measured according to ASTM D1238 at 190° C. under a load of 2160 g of 0.1 to 15 g/10 minutes. molded container;
[5] A fuel container comprising the blow-molded container according to any one of [1] to [4];
[6] A bottle container comprising the blow-molded container according to any one of [1] to [4];
This is achieved by providing

According to the present invention, it is possible to provide a blow-molded container that has few streaks and bumps and is excellent in impact resistance at low temperatures, as well as a fuel container and a bottle container that are provided with such a blow-molded container.

It is a side see-through explanatory view showing a hot cutter used in Examples.

<Blow molded container>
The blow-molded container of the present invention is a blow-molded container comprising a layer formed from a resin composition (α) containing EVOH (A) and a boron compound (B), wherein the boron compound (B) is free boric acid (C), the content of the boron compound (B) with respect to EVOH (A) in the resin composition (α) is 100 ppm or more and 5000 ppm or less in terms of orthoboric acid, and the free boric acid (C ) is 0.1% by mass or more and 10% by mass or less in terms of orthoboric acid.

The blow-molded container of the present invention is provided with a layer formed from a resin composition (α) containing a predetermined amount of boron compound (B) and a predetermined proportion of free boric acid (C). and has excellent impact resistance at low temperatures. In addition, "impact resistance at low temperature" refers to resistance to impact in a low temperature environment. Therefore, the blow-molded container of the present invention has a good appearance and maintains a good gas barrier property even when impact is applied at low temperatures. Furthermore, by using the resin composition (α), even when continuous multi-layer blow molding is performed at a relatively high temperature and high speed for a long period of time, streaks and lumps are suppressed, so the blow-molded container of the present invention has high productivity. is also expensive. The blow-molded container of the present invention is used for various purposes such as fuel containers and various bottles.

The blow-molded container of the present invention may include a layer formed from the resin composition (α) (hereinafter sometimes abbreviated as “layer (1)”), but the layer structure further includes other layers. can be a body. Other layers include, for example, a layer containing a thermoplastic resin other than EVOH (A) as a main component (hereinafter sometimes abbreviated as "layer (2)"), a layer containing an adhesive resin as a main component (" hereinafter sometimes abbreviated as "layer (3)"), recovery layer (hereinafter sometimes abbreviated as "layer (4)"), and the like. The blow-molded container of the present invention preferably comprises layer (1), layer (2) and layer (3).

Specifically, the blow-molded container includes, for example, layer (2), layer (3), layer (1), layer (3), layer (4), layer (2) from the inner surface of the container toward the outer surface of the container. (hereinafter, expressed as (inner) 2/3/1/3/4/2 (outer)), (inner) 2/3/1/3/2 (outer), (inner) 2/4 Layer structures such as /3/1/3/4/2 (outer), (inner) 4/3/1/3/4 (outer), etc. can be employed. The layer (4) may be provided instead of the layer (2), and in the case of an arrangement in which a plurality of layers (1) to (4) are used, the resins constituting each layer may be the same or different. may

The overall average thickness of the blow-molded container of the present invention is preferably 300 to 10,000 μm, more preferably 500 to 8,000 μm, even more preferably 1,000 to 5,000 μm. Incidentally, these overall average thicknesses refer to the average thickness of the body of the blow-molded container. If the overall average thickness is too large, the weight increases, which adversely affects fuel consumption when used as a fuel container for automobiles, etc., and increases the cost of the container. On the other hand, if the overall average thickness is too small, the rigidity cannot be maintained, and there is a risk of being easily destroyed. Therefore, it is important to set the thickness corresponding to the capacity and usage. Each layer will be described in detail below.

[Layer (1)]
Layer (1) is a layer formed from the resin composition (α). The resin composition (α) contains EVOH (A) and a boron compound (B), and the boron compound (B) contains free boric acid (C). Each component will be described below.

(EVOH (A))
EVOH (A) is a copolymer having ethylene units and vinyl alcohol units and an ethylene unit content of 20 to 60 mol %. EVOH (A) is usually obtained by saponifying an ethylene-vinyl ester copolymer, and the production and saponification of the ethylene-vinyl ester copolymer can be carried out by known methods. Vinyl esters are typically vinyl acetate, but other aliphatic esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl pivalate and vinyl versatate. It may be a carboxylic acid vinyl ester.

The ethylene unit content of EVOH (A) is 20 mol % or more, preferably 25 mol % or more, and more preferably 27 mol % or more. The ethylene unit content of EVOH (A) is 60 mol % or less, preferably 55 mol % or less, more preferably 50 mol % or less. If the ethylene unit content is less than 20 mol %, the thermal stability during melt extrusion is lowered, gelation tends to occur, and streaks and lumps tend to occur. This is especially noticeable when running for long periods of time at higher temperatures or higher speeds than under normal conditions. When the ethylene unit content exceeds 60 mol %, the gas barrier properties tend to deteriorate.

The degree of saponification of EVOH (A) is preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 99 mol% or more. When the degree of saponification of EVOH (A) is 90 mol % or more, gas barrier properties, thermal stability, and moisture resistance of the resin composition and blow-molded container tend to be good. The degree of saponification may be 100 mol % or less, 99.97 mol % or less, or 99.94 mol % or less.

In addition, EVOH (A) may have units derived from monomers other than ethylene, vinyl esters and saponified products thereof as long as the object of the present invention is not hindered. When EVOH (A) has units derived from the other monomer, the content of units derived from the other monomer relative to the total structural units of EVOH (A) is preferably 30 mol% or less, and 20 mol%. The following is more preferable, 10 mol % or less is more preferable, 5 mol % or less is even more preferable, and 1 mol % or less is even more preferable. When EVOH (A) has units derived from the other monomers, the content thereof may be 0.05 mol % or more, or 0.10 mol % or more. The other monomers include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid, or their anhydrides, salts, or mono- or dialkyl esters; nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide and methacrylamide; olefin sulfonic acids such as vinylsulfonic acid, allylsulfonic acid and methallylsulfonic acid, or salts thereof; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy)silane, γ -vinylsilane compounds such as methacryloxypropylmethoxysilane; alkyl vinyl ethers, vinyl ketones, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride and the like.

Further, the unit derived from the other monomer is represented by the structural unit (I) represented by the following formula (I), the structural unit (II) represented by the following formula (II), and the following formula (III). may be at least one of the structural units (III).

In structural unit (I), structural unit (II) and structural unit (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and Each R ¹¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a hydroxyl group. represents Also, pairs of R ¹ , R ² and R ³ , R ⁴ and R ⁵ , R ⁶ and R ⁷ may be bonded. Some or all of the hydrogen atoms of the aliphatic hydrocarbon group having 1 to 10 carbon atoms, the alicyclic hydrocarbon group having 3 to 10 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms are hydroxyl groups, It may be substituted with an alkoxy group, a carboxyl group or a halogen atom. In structural unit (III), R ¹² and R ¹³ each independently represent a hydrogen atom, a formyl group or an alkanoyl group having 2 to 10 carbon atoms.

When EVOH (A) has the structural unit (I), (II) or (III), the flexibility and processability of the resin composition are improved, and the moldability of the resin composition tends to be improved. .

In the structural unit (I), (II) or (III), the aliphatic hydrocarbon group having 1 to 10 carbon atoms includes an alkyl group, an alkenyl group, and the like. Hydrogen groups include cycloalkyl groups, cycloalkenyl groups and the like, and aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl groups and the like.

In the structural unit (I), R ¹ , R ² and R ³ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group, a hydroxymethyl group and a hydroxyethyl group. A hydrogen atom, a methyl group, a hydroxyl group and a hydroxymethyl group are more preferable from the viewpoint of being able to further improve the moldability of the product.

The method for incorporating the structural unit (I) into EVOH (A) is not particularly limited. methods and the like. Examples of monomers derived from the structural unit (I) include alkenes such as propylene, butylene, pentene, and hexene; 3-hydroxy-1-propene, 3-acyloxy-1-propene, 3-acyloxy-1-butene; , 4-acyloxy-1-butene, 3,4-diacyloxy-1-butene, 3-acyloxy-4-hydroxy-1-butene, 4-acyloxy-3-hydroxy-1-butene, 3-acyloxy-4-methyl -1-butene, 4-acyloxy-2-methyl-1-butene, 4-acyloxy-3-methyl-1-butene, 3,4-diacyloxy-2-methyl-1-butene, 4-hydroxy-1-pentene , 5-hydroxy-1-pentene, 4,5-dihydroxy-1-pentene, 4-acyloxy-1-pentene, 5-acyloxy-1-pentene, 4,5-diacyloxy-1-pentene, 4-hydroxy-3 -methyl-1-pentene, 5-hydroxy-3-methyl-1-pentene, 4,5-dihydroxy-3-methyl-1-pentene, 5,6-dihydroxy-1-hexene, 4-hydroxy-1-hexene , 5-hydroxy-1-hexene, 6-hydroxy-1-hexene, 4-acyloxy-1-hexene, 5-acyloxy-1-hexene, 6-acyloxy-1-hexene, 5,6-diacyloxy-1-hexene Examples include alkenes having a hydroxyl group or an ester group such as Among them, propylene, 3-acyloxy-1-propene, 3-acyloxy-1-butene, 4-acyloxy-1-butene, 3,4-diacyloxy-1-butene is preferred. Incidentally, "acyloxy" is preferably acetoxy, specifically 3-acetoxy-1-propene, 3-acetoxy-1-butene, 4-acetoxy-1-butene and 3,4-diacetoxy-1-butene is preferred. In the case of an alkene having an ester, it is derived to the structural unit (I) during the saponification reaction.

In the structural unit (II), both ^R4 and ^R5 are preferably hydrogen atoms. More preferably, both R ⁴ and R ⁵ are hydrogen atoms, one of R ⁶ and R ⁷ is a C 1-10 aliphatic hydrocarbon group, and the other is a hydrogen atom. This aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group. From the viewpoint of placing particular importance on the gas barrier properties of the resulting blow-molded container, it is more preferable that one of R ⁶ and R ⁷ is a methyl group or an ethyl group, and the other is a hydrogen atom. It is more preferable that one of R ⁶ and R ⁷ is a substituent represented by (CH ₂ ) _h OH (where h is an integer of 1 to 8) and the other is a hydrogen atom. In the substituent represented by (CH ₂ ) _h OH, h is preferably an integer of 1 to 4, more preferably 1 or 2, even more preferably 1.

The method of incorporating the structural unit (II) into EVOH (A) is not particularly limited, and for example, a method of incorporating by reacting EVOH (A) obtained by a saponification reaction with a monovalent epoxy compound. Used. As the monovalent epoxy compound, compounds represented by the following formulas (IV) to (X) are preferably used.

In the above formulas (IV) to (X), R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (alkyl group, alkenyl group, etc.), an alicyclic hydrocarbon group having 3 to 10 carbon atoms (cycloalkyl group, cycloalkenyl group, etc.), or an aliphatic hydrocarbon group having 6 to 10 carbon atoms (phenyl group, etc.). i, j, k, p and q each independently represents an integer of 1 to 8; However, when R ¹⁷ is a hydrogen atom, R ¹⁸ has a substituent other than a hydrogen atom.

Examples of monovalent epoxy compounds represented by formula (IV) include epoxyethane (ethylene oxide), epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl-1,2-epoxy, Butane, 1,2-epoxypentane, 3-methyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxy Hexane, 3-methyl-1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 1,2-epoxynonane, 2,3-epoxy nonane, 1,2-epoxydecane, 1,2-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-epoxypropane, 3-phenyl-1,2-epoxypropane and the like. Examples of the monovalent epoxy compound represented by the formula (V) include various alkyl glycidyl ethers. Examples of the monovalent epoxy compound represented by formula (VI) include various alkylene glycol monoglycidyl ethers. Examples of the monovalent epoxy compound represented by the formula (VII) include various alkenyl glycidyl ethers. Examples of the monovalent epoxy compound represented by the formula (VIII) include various epoxy alkanols such as glycidol. Examples of the monovalent epoxy compound represented by the formula (IX) include various epoxycycloalkanes. Examples of the monovalent epoxy compound represented by the formula (X) include various epoxycycloalkenes.

Among the monovalent epoxy compounds, epoxy compounds having 2 to 8 carbon atoms are preferred. In particular, from the viewpoints of ease of handling and reactivity of the compound, the number of carbon atoms in the monovalent epoxy compound is more preferably 2-6, more preferably 2-4. Moreover, it is particularly preferable that the monovalent epoxy compound is a compound represented by the formula (IV) or (V). Specifically, from the viewpoint of reactivity with EVOH (A), workability of the resin composition, gas barrier properties, etc., 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane, or Glycidol is preferred, with epoxypropane or glycidol being more preferred.

In the structural unit (III), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are preferably hydrogen atoms or aliphatic hydrocarbon groups having 1 to 5 carbon atoms, and such aliphatic hydrocarbon groups are methyl groups. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or n-pentyl are preferred.

The method for incorporating the structural unit (III) into EVOH (A) is not particularly limited, and examples thereof include the method described in JP-A-2014-034647.

EVOH (A) may be used alone or in combination of two or more. From the viewpoint of gas barrier properties, etc., the proportion of EVOH (A) in the resin composition (α) is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. On the other hand, the proportion of EVOH (A) in the resin composition (α) may be, for example, 99.9% by mass or less, or may be 99% by mass or less.

(Boron compound (B))
The resin composition (α) contains 100 ppm or more and 5000 ppm or less of a boron compound (B) containing free boric acid (C) described below in terms of orthoboric acid (H ₃ BO ₃ ). The orthoboric acid conversion content of the boron compound (B) is synonymous with the orthoboric acid conversion content of all the boron atoms contained in the resin composition (α). The boron compound (B) can be quantified by a known method such as ICP emission spectrometry, and specifically by the method described in Examples. In addition, ppm is a mass standard.

Examples of the boron compound (B) include boric acids such as orthoboric acid (H ₃ BO ₃ ), metaboric acid, and tetraboric acid; sodium metaborate, sodium tetraborate, sodium pentaborate, borax, lithium borate, boric acid salts such as potassium borate; borate esters such as triethyl borate and trimethyl borate; The compound obtained by the above is also included in the boron compound (B). Among them, orthoboric acid, borax and derivatives thereof are preferably used from the viewpoint of cost and improvement of melt moldability. In addition, the derivative means a compound obtained by reacting with orthoboric acid or the like, such as its ester or amide.

The content of the boron compound (B) with respect to EVOH (A) is 100 ppm or more, preferably 500 ppm or more, more preferably 700 ppm or more, and more preferably 1000 ppm or more in terms of orthoboric acid. When the content of the boron compound (B) is less than 100 ppm, streaks due to layer disturbance increase during long-term blow molding. If there are many streaks in the blow-molded container, cracks or the like tend to occur starting from these streaks, and the low-temperature impact resistance and gas barrier properties tend to deteriorate.

On the other hand, the content of the boron compound (B) is 5000 ppm or less, preferably 2500 ppm or less, more preferably 1500 ppm or less in terms of orthoboric acid. When the content of the boron compound (B) exceeds 5000 ppm, streaks and bumps increase during long-term blow molding, resulting in a decrease in impact resistance at low temperatures. The reason why streaks and pimples increase when the content of the boron compound (B) exceeds 5000 ppm is not clear, but the high content of the boron compound (B) reduces the viscosity of the resin composition. It is presumed that the presence of

(Free boric acid (C))
The boron compound (B) contains free boric acid (C) which is "unreacted boric acid or its salt". Generally, most of the boron compound (B) other than the free boric acid (C) is crosslinked boric acid. On the other hand, free boric acid (C) exists in the resin composition (α) in a non-crosslinked state. The amount of free boric acid (C) in the resin composition (α) is determined using a coordinating compound capable of forming a complex ion with boric acid, such as 2-ethyl-1,3-hexanediol and free boric acid (C ), the reaction product can be quantified and calculated. Specifically, it can be quantified by the method described in Examples.

The ratio of free boric acid (C) in the boron compound (B) is 0.1% by mass or more, preferably 0.3% by mass or more, and 0.5% by mass in terms of orthoboric acid with respect to the boron compound (B). % or more by mass is more preferable. If the ratio of free boric acid (C) to the boron compound (B) is less than 0.1% by mass, streaks increase during long-term blow molding. In addition, when the content of the boron compound (B) is relatively large and the content of the free boric acid (C) is low, it means that the cross-linking is progressing, and the number of pimples tends to increase during long-term blow molding. . When the ratio of free boric acid (C) to the boron compound (B) is less than 0.1% by mass, these streaks and bumps occur, resulting in low-temperature impact resistance and gas barrier properties.

Further, the proportion of free boric acid (C) in the boron compound (B) is 10% by mass or less in terms of orthoboric acid with respect to the boron compound (B), preferably 7% by mass or less, and 3% by mass or less. More preferably, 1.5% by mass or less or 1% by mass or less may be even more preferable. If the ratio of the free boric acid (C) to the boron compound (B) is more than 10% by mass, a local crosslinking reaction caused by the free boric acid (C) proceeds during blow molding for a long period of time. Increases streaks, etc. As a result, the impact resistance at low temperatures is lowered, and the gas barrier properties are lowered. In addition, the ratio of the free boric acid (C) in the boron compound (B) can be adjusted by the manufacturing method described later.

The upper limit of the content of free boric acid (C) with respect to EVOH (A) is 500 ppm (10% of 5000 ppm) in terms of orthoboric acid, but 200 ppm is preferable, 100 ppm is more preferable, and 20 ppm or 10 ppm may be even more preferable. . By setting the content of the free boric acid (C) to the above upper limit or less, it is possible to suppress the generation of pimples and the like and improve the impact resistance at low temperatures. On the other hand, the lower limit of the content of free boric acid (C) is 0.1 ppm (0.1% of 100 ppm) in terms of orthoboric acid, preferably 0.5 ppm, more preferably 1 ppm, and further preferably 3 ppm or 5 ppm. Sometimes. By making the content of free boric acid (C) equal to or higher than the above lower limit, the occurrence of streaks and the like can be suppressed, and impact resistance at low temperatures can be enhanced.

(Other optional ingredients)
The resin composition (α) may contain, as other components, resins other than EVOH (A) and additives other than the boron compound (B) to the extent that the effects of the present invention are not impaired. good. Other resins include, for example, thermoplastic resins such as polyolefins. When the resin composition (α) contains another resin, the content of the other resin relative to the resin composition (α) is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. .

Other additives include known additives such as antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, fillers, antiblocking agents, and desiccants. The method for incorporating these additives into the resin composition (α) is not particularly limited. A method of melt blending an agent, a resin composition (α) powder, granular, spherical, cylindrical chip-shaped pellets, etc., and a solid, liquid or solution of these additives are mixed to form a resin composition ( Examples include a method of impregnating or spreading α). These methods can be appropriately selected in consideration of the physical properties of the additive and the permeability to the resin composition (α). When other additives are contained, the content thereof is preferably 5% by mass or less, more preferably 3% by mass or less, relative to the resin composition (α).

Antioxidants include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis-(6-t-butylphenol, 2,2'methylene -bis(4-methyl-6-t-butylphenol, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, octadecyl-3-(3′ ,5'-di-t-butyl-4'-hydroxyphenyl)propionate, 4,4'-thiobis-(6-t-butylphenol), etc. Ultraviolet absorbers include ethyl-2-cyano-3 , 3-diphenyl acrylate, 2-(2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5 -chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. Plasticizers include dimethyl phthalate and phthalate. diethyl acid, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc. Antistatic agents include pentaerythrityl monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbowax, and the like. Lubricants include ethylene bisstearylamide, butyl stearate, calcium stearate, zinc stearate, etc. Colorants include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc. Fillers include glass fiber, mica, ballastonite, and the like.

Moreover, the resin composition (α) may contain various acids, metal salts, and the like from the viewpoint of thermal stability or viscosity adjustment. Examples of the various acids include carboxylic acids and phosphoric compounds, and examples of the various metal salts include alkali metal salts and alkaline earth metal salts. These acids, metal salts and the like may be mixed with EVOH (A) in advance before use.

(Carboxylic acid and/or carboxylic acid ion)
When the resin composition (α) contains carboxylic acid and/or carboxylic acid ions, there is a tendency to improve coloration resistance during melt molding. Carboxylic acids are compounds with one or more carboxy groups in the molecule. A carboxylate ion is a hydrogen ion released from a carboxy group of a carboxylic acid. The carboxylic acid may be a monocarboxylic acid, a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule, or a combination thereof. In addition, a polymer is not contained in this polyhydric carboxylic acid. Moreover, the polyvalent carboxylic acid ion is obtained by desorption of at least one of the hydrogen ions of the carboxy group of the polyvalent carboxylic acid. The carboxy group of the carboxylic acid may have an ester structure, and the carboxylate ion may form a salt with a metal.

The monocarboxylic acid is not particularly limited, and examples include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, capric acid, acrylic acid, methacrylic acid, benzoic acid, 2-naphthoic acid and the like. These carboxylic acids may have a hydroxy group or a halogen atom. Carboxylic acid ions include those obtained by desorption of hydrogen ions from the carboxy group of each carboxylic acid. The pKa of this monocarboxylic acid (including a monocarboxylic acid that gives a monocarboxylic acid ion) is preferably 3.5 or more, more preferably 4 or more, from the viewpoint of pH adjustment ability and melt moldability of the resin composition (α). preferable. Such monocarboxylic acids include formic acid (pKa = 3.68), acetic acid (pKa = 4.74), propionic acid (pKa = 4.85), butyric acid (pKa = 4.80) and the like. Acetic acid is preferred from the viewpoint of ease of use.

The polyvalent carboxylic acid is not particularly limited as long as it has two or more carboxy groups in the molecule. Examples include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, and adipine. acids, aliphatic dicarboxylic acids such as pimelic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; tricarboxylic acids such as aconitic acid; 1,2,3,4-butanetetracarboxylic acid, ethylenediaminetetraacetic acid and the like hydroxycarboxylic acids such as tartaric acid, citric acid, isocitric acid, malic acid, mucic acid, tartronic acid, citramaric acid; oxaloacetic acid, mesooxalic acid, 2-ketoglutaric acid, 3-ketoglutarate ketocarboxylic acids such as acids; amino acids such as glutamic acid, aspartic acid and 2-aminoadipic acid; In addition, these anions are mentioned as polyvalent carboxylic acid ion. Among them, succinic acid, malic acid, tartaric acid, and citric acid are particularly preferred because they are readily available.

When the resin composition (α) contains a carboxylic acid and/or a carboxylic acid ion, the content of the carboxylic acid ion in the resin composition (α) should be 0.00 in terms of carboxylic acid group from the viewpoint of color resistance during melt molding. 01 μmol/g or more is preferable, 0.05 μmol/g or more is more preferable, and 0.5 μmol/g or more is still more preferable. Also, it is preferably 20 μmol/g or less, more preferably 15 μmol/g or less, and even more preferably 10 μmol/g or less in terms of carboxylic acid radical.

(Phosphate compound)
When the resin composition (α) contains a phosphoric acid compound, it tends to improve long-run properties during melt molding.

The phosphoric acid compound is not particularly limited, and examples thereof include various phosphorus oxyacids such as phosphoric acid and phosphorous acid, and salts thereof. The phosphate may be contained, for example, in any form of primary phosphate, secondary phosphate, or tertiary phosphate, and its counter-cation species is not particularly limited. Alternatively, alkaline earth metal salts may be mentioned, with alkali metal salts being preferred. Specifically, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate are preferred from the viewpoint of improving long-run properties during melt molding.

When the resin composition (α) contains a phosphoric acid compound, the content is preferably 1 ppm or more, more preferably 5 ppm or more, and even more preferably 8 ppm or more in terms of phosphate radical. In addition, it is preferably 500 ppm or less, more preferably 200 ppm or less, and even more preferably 50 ppm or less in terms of phosphate radical. When the content of the phosphoric acid compound is within the above range, it is possible to further improve long-run properties during melt molding.

(alkali metal salt)
When the resin composition (α) contains an alkali metal salt, the long-run property and the interlaminar adhesion strength when formed into a multilayer structure are improved. Alkali metals constituting the alkali metal salt include lithium, sodium, potassium, rubidium, cesium and the like, but sodium and potassium are more preferable from the viewpoint of industrial availability.

The alkali metal salt is not particularly limited, and examples thereof include aliphatic carboxylates of lithium, sodium, potassium, etc., aromatic carboxylates, phosphates included in the phosphoric acid compounds described above, metal complexes, and the like. be done. Specifically, sodium acetate, potassium acetate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, lithium dihydrogen phosphate , trilithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, and the like. Among these, sodium acetate, potassium acetate and sodium dihydrogen phosphate are particularly preferred from the viewpoint of easy availability.

When the resin composition (α) contains an alkali metal salt, the content of the alkali metal salt in the resin composition is preferably 2.5 μmol/g or more, more preferably 3.5 μmol/g or more, and 4.5 μmol/g. g or more is more preferable. Also, the content of the alkali metal salt is preferably 22 μmol/g or less, more preferably 16 μmol/g or less, even more preferably 10 μmol/g or less. When the content of the alkali metal salt is 2.5 μmol/g or more, the interlayer adhesion of the obtained multilayer sheet tends to be more excellent. Moreover, when the content of the alkali metal salt is 22 μmol/g or less, the appearance of the blow-molded container tends to be better.

(alkaline earth metal salt)
When the resin composition (α) contains an alkaline earth metal salt, scrap recoverability of multilayer sheets containing the resin composition (α) is improved. Alkaline earth metals constituting the alkaline earth metal salt include beryllium, magnesium, calcium, strontium, barium, etc. From the viewpoint of industrial availability, magnesium or calcium is preferred.

The resin composition (α) has a melt index (hereinafter sometimes abbreviated as “MI”) measured according to ASTM D1238 under a load of 2160 g at 190° C. of 0.1 to 15 g/10 min. is preferred. By setting the MI within the above range, it is possible to suppress the occurrence of streaks due to layer disturbance in long-term blow molding and the occurrence of pimples due to local cross-linking. In addition, this can improve the impact resistance of the blow-molded container at low temperatures. In order to enhance the effect, the MI at 190° C. under a load of 2160 g is preferably 15 g/10 min or less, more preferably 10 g/10 min or less, still more preferably 6.6 g/10 min or less, and 6 g/10 min or less. Even more preferably, 2 g/10 minutes or less is particularly preferable. Moreover, MI at 190° C. under a load of 2160 g is preferably 0.2 g/10 minutes or more, more preferably 0.5 g/10 minutes or more.

The lower limit of the average thickness of layer (1) is not particularly limited, and from the viewpoint of barrier properties, mechanical strength, etc., it is preferably 0.5%, more preferably 1%, and even more preferably 2% of the average thickness of all layers. . The upper limit of the average thickness of layer (1) is not particularly limited, and from the viewpoint of barrier properties, mechanical strength, etc., it is preferably 20%, more preferably 10%, and even more preferably 5% of the average thickness of all layers.

(Method for producing resin composition (α))
The resin composition (α) can be produced, for example, by the following steps.
(1) Copolymerization of ethylene and vinyl ester to obtain an ethylene-vinyl ester copolymer (EVAc) (polymerization step)
(2) A step of saponifying the EVAc to obtain EVOH (A) (saponification step)
(3) A step of obtaining pellets containing EVOH (A) from the solution or paste containing EVOH (A) (pelletizing step)
(4) A step of washing the pellet (washing step)
(5) Step of dehydrating the pellet (dehydration step)
(6) Drying the pellet (drying step)
The pellets subjected to the dehydration step contain the boron compound (B). That is, the pellet containing EVOH (A), the boron compound (B) and water to be subjected to the dehydration step is an example of the water-containing composition.

(1) Polymerization Process The method of copolymerizing ethylene and vinyl ester is not particularly limited, and may be solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, or the like, and may be continuous or batchwise.

Vinyl esters used in the polymerization include those mentioned above. Moreover, when copolymerizing monomers other than ethylene and vinyl ester, the other monomers include those mentioned above.

The solvent used for polymerization is not particularly limited as long as it is an organic solvent capable of dissolving ethylene, vinyl ester and ethylene-vinyl ester copolymer. Alcohol; dimethylsulfoxide and the like can be used. Among them, methanol is preferable because it is easy to remove and separate after the reaction.

Catalysts used for polymerization include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobis-(4-methoxy- 2,4-dimethylvaleronitrile), 2,2′-azobis-(2-cyclopropylpropionitrile) and other azonitrile initiators; isobutyryl peroxide, cumyl peroxyneodecanoate, diisopropyl peroxycarbonate, Organic peroxide initiators such as di-n-propylperoxydicarbonate, t-butylperoxyneodecanoate, lauroyl peroxide, benzoylperoxide, t-butylhydroperoxide and the like are included.

The polymerization temperature is preferably 20 to 90°C, more preferably 40 to 70°C. The polymerization time is, for example, preferably 2 to 15 hours, more preferably 3 to 11 hours. The polymerization rate is preferably 10 to 90%, more preferably 30 to 80%, based on the charged vinyl ester. The resin content in the solution after polymerization is preferably 5 to 85% by mass, more preferably 20 to 70% by mass.

Usually, after polymerization for a predetermined time or after reaching a predetermined rate of polymerization, a polymerization inhibitor is added as necessary, unreacted ethylene is removed, and then unreacted vinyl ester is removed. As a method for removing the unreacted vinyl ester, for example, the reaction liquid is continuously supplied at a constant rate from the top of a column filled with a filler such as Raschig ring, and an organic solvent such as methanol is blown in as vapor from the bottom of the column. For example, a mixed vapor of an organic solvent such as methanol and unreacted vinyl ester is distilled from the top of the tower, and a copolymer solution from which the unreacted vinyl ester is removed is taken out from the bottom of the tower.

(2) Saponification step Next, the EVAc obtained in the above step is saponified. The saponification method can be either continuous or batchwise. The saponification catalyst is not particularly limited, and alkali catalysts such as sodium hydroxide, potassium hydroxide, and alkali metal alcoholates are preferably used.

As for the saponification conditions, for example, in the case of a batch system, the concentration in the EVAc solution is preferably 10 to 50% by mass, the reaction temperature is preferably 30 to 60° C., and the amount of catalyst used is 0.5% per 1 mol of the vinyl ester structural unit. 02 to 0.6 mol is preferred, and the saponification time is preferably 1 to 6 hours. In the case of the continuous method, methyl acetate produced by saponification can be removed more efficiently, so a resin with a high degree of saponification can be obtained with a smaller amount of catalyst than in the case of the batch method. In order to prevent precipitation of (A), it is necessary to saponify at a higher temperature. Therefore, in the case of the continuous type, for example, the concentration in the EVAc solution is 10% by mass or more and 50% by mass or less, the reaction temperature is 70°C or more and 150°C or less, and the amount of catalyst used is 0.005 mol or more per 1 mol of the vinyl ester structural unit. .1 mol or less, and the saponification time can be 1 hour or more and 6 hours or less.

The saponification process yields a solution or paste containing EVOH (A). The EVOH (A) after the saponification reaction contains alkali catalysts, by-product salts such as sodium acetate and potassium acetate, and other impurities, so these should be removed by neutralization and washing as necessary. good too. Here, when the EVOH (A) after the saponification reaction is washed with ion-exchanged water or the like containing almost no metal ions, chloride ions, etc., a portion of sodium acetate, potassium acetate, etc. is allowed to remain in the EVOH (A). may

(3) Pelletizing Step and (4) Washing Step Next, the obtained EVOH (A) solution or paste is pelletized. The method of pelletization is not particularly limited, and examples include a method of cooling and solidifying a solution of EVOH (A) and cutting, and a method of melting and kneading EVOH (A) with an extruder and then discharging and cutting. As a method for cutting EVOH (A), a method (method (i)) in which EVOH (A) is extruded into a strand and then cut with a pelletizer (method (i)), or a center hot cut method or an underwater cut method is used to cut EVOH (A) discharged from a die. A specific example is a method of cutting by a method (method (ii)).

method (i)
When the EVOH (A) solution is extruded into strands and pelletized, water or a water/alcohol mixed solvent, aromatic hydrocarbons such as benzene, ketones such as acetone and methyl ethyl ketone can be used as the solidifying liquid for precipitating EVOH (A). , ethers such as dipropyl ether, organic acid esters such as methyl acetate, ethyl acetate and methyl propionate, etc., but water or a water/alcohol mixed solvent is preferable from the viewpoint of ease of handling. Alcohols such as methanol, ethanol and propanol are used as the alcohol, and methanol is industrially preferred. The mass ratio of the coagulating liquid to the EVOH (A) strands in the coagulating liquid (coagulating liquid/strands of EVOH (A)) is preferably 50 to 10,000. By setting the mass ratio within the above range, EVOH (A) pellets having a uniform size distribution can be obtained.

The temperature at which the EVOH (A) solution is brought into contact with the coagulation liquid (bath temperature during pelletizing) is preferably −10° C. or higher, more preferably 0° C. or higher. The bath temperature during pelletizing is preferably 40° C. or lower, more preferably 20° C. or lower, still more preferably 15° C. or lower, and particularly preferably 10° C. or lower. If the bath temperature during pelletizing is -10°C or higher, precipitation of low molecular weight components tends to be suppressed, and if it is 40°C or lower, thermal deterioration of EVOH (A) tends to be suppressed.

The EVOH (A) solution is extruded in strands into the coagulation liquid through a nozzle having an arbitrary shape. The shape of such a nozzle is not particularly limited, and, for example, a cylindrical shape is preferred. The number of strands does not necessarily have to be one, and any number between several to several hundred can be extruded.

After the EVOH (A) extruded in the form of a strand is sufficiently solidified, it is cut, pelletized, and then washed with water. The size of such a pellet can be, for example, a diameter of 1 mm or more and 10 mm or less and a length of 1 mm or more and 10 mm or less in the case of a cylindrical shape, and a diameter of 1 mm or more and 10 mm or less in the case of a spherical shape.

Subsequently, a washing step is performed in which the EVOH (A) pellets are washed with water in a water tank. Oligomers and impurities in the EVOH (A) pellets are removed by such washing treatment. The water temperature during washing is preferably 5°C or higher, and preferably 80°C or lower. An acetic acid aqueous solution or ion-exchanged water can be used for washing, but it is preferable to finally wash with ion-exchanged water. Washing with ion-exchanged water is preferably performed twice or more for one hour or longer. The temperature of ion-exchanged water at this time is preferably in the range of 5 to 60° C., and the bath ratio of ion-exchanged water to EVOH (A) pellets is preferably 2 or more.

After the washing step, the pellets are immersed in a solution containing the boron compound (B) (hereinafter sometimes abbreviated as "immersion solution") to incorporate the boron compound (B) into the pellets. At this time, other components (for example, an acid component and a metal salt) may be included in the solution so that the pellets contain the other components.

The concentration of the boron compound (B) in the immersion solution is 0.01 to 2 g/L in terms of orthoboric acid, and an appropriate amount of the boron compound (B) is contained in the dry EVOH (A) pellets. It is possible and suitable. The lower limit of the concentration of the boron compound (B) in the immersion solution is more preferably 0.05 g/L, still more preferably 0.2 g/L. When it is 0.01 g/L or more, the MI of the resin composition (α) becomes sufficient due to a sufficient cross-linking effect, and the occurrence of streaks tends to be further suppressed. The upper limit of the concentration of the boron compound (B) is more preferably 1.5 g/L, still more preferably 0.8 g/L. When the amount is 2 g/L or less, gelation of the resin composition (α) is suppressed, and the occurrence of pimples tends to be further suppressed.

method (ii)
When pelletizing by melt kneading using an extruder, the shape of the EVOH (A) before being put into the extruder is not particularly limited, and pellets obtained by cutting the molten resin extruded into the air are used. Alternatively, a precipitate on crumbs obtained by solidifying a solution or paste of EVOH (A) in an irregular shape after polymerization and saponification can also be used.

The water content of EVOH (A) before being fed into the extruder is preferably 0.5% by mass or more, more preferably 5% by mass or more, and preferably 7% by mass or more. Also, the water content of EVOH (A) before being fed into the extruder is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

In pelletization by melt-kneading using an extruder, the boron compound (B) can be added to EVOH (A) within the extruder. When adding the boron compound (B) to the EVOH (A) in the extruder, the feed position of the boron compound (B) is preferably added at a position in the extruder in which the EVOH (A) is in a molten state. It is more preferable to add at In particular, it is preferable to add the boron compound (B) to the water-containing and molten EVOH (A). The boron compound (B) can be added into the extruder from one or two or more places, and other components (eg, acid component and metal salt) may be added at the same time.

When the boron compound (B) is added within the extruder, the amount supplied within the extruder is the content in the resin composition (α). The form of addition of the boron compound (B) is not particularly limited, and a method of adding it as a dry powder in the extruder, a method of adding it as a paste impregnated with a solvent, a method of adding it in a state of being suspended in a liquid, and a solvent A method of dissolving and adding as a solution is exemplified. A method of adding as a solution is particularly preferred. Such a solvent is not particularly limited, and water is preferable from the viewpoints of the solubility of the boron compound (B), economic efficiency, ease of handling, safety in the working environment, and the like.

When the boron compound (B) is added as a solution to EVOH (A), the amount of the solution added is preferably 1 part by mass or more, and 3 parts by mass with respect to 100 parts by mass of the dry mass of EVOH (A). 1 part or more is more preferable, and 5 parts by mass or more is particularly preferable. The amount of the solution added is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less per 100 parts by mass of the dry mass of EVOH (A). When the amount of the solution added is less than 1 part by mass, the concentration of the solution generally increases, and the dispersibility of the boron compound (B) tends to decrease. On the other hand, if it exceeds 50 parts by mass, it tends to be difficult to control the water content of EVOH (A), and the resin and the water contained in the resin tend to undergo phase separation in the extruder. Further, the orthoboric acid concentration of the solution is in the range of 0.2 g/L to 57 g/L, and is appropriately adjusted by the amount of orthoboric acid to be contained in the dry mass of EVOH (A) and the addition amount of the solution.

The resin temperature in the extruder is preferably 70 to 170°C. If the resin temperature is lower than 70° C., the EVOH (A) may not melt completely, and the boron compound (B) to be added may not be sufficiently dispersed. The resin temperature is more preferably 80° C. or higher, more preferably 90° C. or higher. Also, when the resin temperature exceeds 170° C., EVOH (A) tends to be susceptible to thermal deterioration. Furthermore, when the boron compound (B) is added as an aqueous solution, it is difficult to mix EVOH (A) and the aqueous solution at a suitable aqueous solution concentration because the evaporation of water will be intense if the resin temperature exceeds 170 ° C. tends to be The resin temperature in the extruder is more preferably 150° C. or lower, more preferably 130° C. or lower. A method of adjusting the resin temperature is not particularly limited, and a method of suitably setting the temperature of the cylinder in the extruder is particularly preferable. In the present invention, the resin temperature refers to the temperature detected by a temperature sensor installed in the cylinder inside the extruder, and the detection point indicates the temperature near the discharge port at the tip of the extruder.

The water content of the resin composition (α) immediately after being discharged from the extruder is preferably 5 to 40% by mass, more preferably 5 to 35% by mass. If the water content of the resin composition (α) immediately after discharge from the extruder exceeds 40% by mass, the resin and water contained in the resin tend to undergo phase separation, and as a result, after discharge from the extruder Strands tend to foam easily. In addition, when the water content of the resin composition (α) immediately after extruder discharge is less than 5% by mass, there is a tendency that the suppression of deterioration due to heating of EVOH (A) is insufficient, and the obtained pellets are resistant to coloration. tend to be inferior.

The method of pelletizing the resin composition (α) discharged from the extruder is not particularly limited, and a method of extruding the resin composition (α) from a die into the air and cutting it to an appropriate length is exemplified. From the viewpoint of easy handling of the pellets, the diameter of the die is preferably 2 to 5 mmφ (φ is the diameter; the same shall apply hereinafter), and the strand is preferably cut into lengths of about 1 to 5 mm.

When pelletization is performed by melt-kneading using an extruder, the washing step may be the same step as in method (i), but a step of washing within the extruder may be provided. When washing is performed in the extruder, a method of injecting a washing liquid into the extruder to wash the resin and then discharging the washing liquid from the downstream side of the extruder can be used.

(5) Dehydration step The ratio of free boric acid (C) in the boron compound (B) in the resin composition (α) can be determined by physical It can be adjusted by drying after removing the moisture by appropriate means. Examples of the method for removing water include centrifugal dehydration (separation), vacuum sieving (hydro sieve), gas flow, etc., and it is preferable to preferentially remove water adhering to the pellets. A centrifugal dehydration method is industrially preferably used.

Such a centrifugal dehydration method may be either a batch type or a continuous type, and the continuous type is preferably used industrially. Both the batch type and the continuous type have a bucket-shaped rotating body with perforated holes or slits, and the continuous type has a structure that allows continuous discharge without changing the shape of the pellets. equipment) is not limited. The amount of water to be removed is adjusted by the perforated hole diameter, rotation speed, treatment amount (treatment time), etc. The perforated hole diameter may be smaller than the pellet diameter, preferably about 0.1 to 3 mm. If the perforated hole diameter is less than 0.1 mm, the water removal capacity is insufficient, and clogging due to fine powder tends to occur. Although the number of revolutions varies depending on the apparatus, it is preferably 500 to 20000 rpm, and the treatment time is preferably 10 seconds or more and 15 minutes or less. If the rotational speed is too low, the proportion of residual free boric acid (C) tends to increase. On the other hand, if the rotational speed is too high, the proportion of remaining free boric acid (C) tends to be low. Similarly, if the treatment time is less than 10 seconds, it causes an increase in the proportion of free boric acid (C) remaining in the resulting resin composition (α). The treatment time is preferably 45 seconds or longer, more preferably 1 minute or longer. If the treatment time exceeds 15 minutes, the proportion of free boric acid (C) in the resulting resin composition (α) tends to decrease. The treatment time is preferably 13 minutes or less, more preferably 10 minutes or less.

(6) Drying process After the dehydration process, the pellets are subjected to a drying process. Drying is preferably performed so that the moisture content of the EVOH (A) pellets after drying is 0.08% by mass or less. If the water content exceeds 0.08% by mass, the amount of crosslinked boric acid tends to decrease and the amount of free boric acid (C) tends to increase. The water content is preferably 0.05% by mass or less. The drying method is not particularly limited, and the content of free boric acid (C) may increase or decrease depending on the drying means and drying temperature. Static drying combined with air drying or nitrogen drying, fluidized drying, or vacuum drying may be mentioned, but multi-stage drying combining several drying methods is preferred, and multi-stage drying comprising pre-drying and main drying. is more preferable. Here, preliminary drying is used for drying from a relatively high water content to a water content of about 10% by mass in order to suppress heat fusion between resin compositions (α) having a high water content during drying. It means drying performed at a lower temperature than main drying. On the other hand, the main drying is used for lowering the water content of the resin composition (α) having a relatively low water content after pre-drying, and means drying performed at a higher temperature than pre-drying. Pre-drying can use heated gas (such as hot air), infrared rays, microwaves, and the like. The temperature and time of the pre-drying are not particularly limited, and the resin composition (α) having the desired moisture content can be obtained by subjecting it to a drying time of 1 hour or more and 12 hours or less, for example, at 60° C. or more and 100° C. or less. can be done. For the main drying, the general drying means described above can be used, but among them, vacuum drying is suitable for making free boric acid (C) into a specific amount. Methods other than vacuum drying tend to make it somewhat difficult to control the amount of free boric acid (C) to a specific amount.

The lower limit of the main drying temperature (ambient temperature) is preferably 70°C, more preferably 100°C, still more preferably 110°C, and particularly preferably 120°C. On the other hand, the upper limit is preferably 160°C, more preferably 150°C, and even more preferably 130°C. When the main drying temperature is equal to or higher than the above lower limit, the main drying can be performed efficiently and sufficiently, and the main drying time can be shortened. On the other hand, if the main drying temperature is set to the above upper limit or less, thermal deterioration of EVOH (A) can be suppressed. Moreover, when the temperature of the main drying is within the above range, it tends to be easy to adjust the amount of free boric acid (C) to an appropriate amount. For example, lowering the main drying temperature tends to lower the proportion of free boric acid (C). In addition, the drying time at a specific main drying temperature is not particularly limited. Then, a resin composition (α) having a desired moisture content is obtained.

[Layer (2)]
Layer (2) is a layer containing a thermoplastic resin other than EVOH (A) as a main component. Thermoplastic resins other than EVOH (A) include, for example, polyolefin, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, vinyl ester resin, polyamide resin, polyester resin, polyurethane elastomer, polycarbonate, chlorinated polyethylene, Chlorinated polypropylene, ionomers, and the like. When the layer (2) is laminated on the layer (1) with the layer (3) interposed therebetween, the solubility parameter of the layer (2) calculated from the Fedors formula is 11 (cal/cm ³ ) ^1/ It is preferable that the layer is mainly composed of a thermoplastic resin having a thickness of ² or less. A thermoplastic resin having a solubility parameter of 11 (cal/cm ³ ) ^1/2 or less calculated by this formula is excellent in moisture resistance. The solubility parameter calculated from the Fedors formula is a value represented by (E/V) ^1/2 . In the above formula, E is molecular cohesive energy (cal/mol) and is represented by E=Σei. Note that ei is evaporation energy. Also, V is the molecular volume (cm ³ /mol) and is represented by V=Σvi (vi: molar volume). Layer (2) is preferably arranged on the inner and outer surface sides of layer (1).

Examples of the thermoplastic resin having a solubility parameter of 11 (cal/cm ³ ) ^1/2 or less include polyolefin, polystyrene, polyvinyl chloride, polyvinylidene chloride, acrylic resin, vinyl ester resin, polyurethane elastomer, polycarbonate, Examples include chlorinated polyethylene and chlorinated polypropylene. Polyolefins include polyethylene (linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, etc.), ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, propylene and 4 or more carbon atoms. Examples include copolymers with α-olefins of No. 20, and homopolymers or copolymers of olefins such as polybutene and polypentene. Among them, polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polypropylene, and polystyrene are preferable, and high-density polyethylene is more preferable.

The lower limit of the MI of the thermoplastic resin at 190° C. under a load of 2,160 g is preferably 0.01 g/10 minutes, more preferably 0.02 g/10 minutes. On the other hand, the upper limit of the MI is preferably 0.5 g/10 minutes, more preferably 0.1 g/10 minutes, and even more preferably 0.05 g/10 minutes.

In addition, the said thermoplastic resin can be suitably selected and used from a normal commercial item. Moreover, the layer (2) may contain other optional components similar to those of the layer (1) as long as the effects of the present invention are not impaired.

The lower limit of the average thickness of layer (2) is not particularly limited, and is preferably 10%, more preferably 30%, and even more preferably 50%, 70% or 80% of the average thickness of all layers. The upper limit of the average thickness of the layer (2) is not particularly limited, and is preferably 95%, more preferably 90% of the average thickness of all layers.

[Layer (3)]
Layer (3) may be placed between layer (1) and layer (2), and is a layer whose main component is an adhesive resin. Layer (3) can act as an adhesive layer between layer (1) and other layers such as layer (2). Examples of adhesive resins include carboxylic acid-modified polyolefins. The carboxylic acid-modified polyolefin has a carboxy group or an anhydride group obtained by chemically bonding an ethylenically unsaturated carboxylic acid or its anhydride to an olefin polymer by an addition reaction, a graft reaction, or the like. Refers to olefinic polymers.

The lower limit of MI of the adhesive resin under a load of 2,160 g at 190° C. is preferably 0.1 g/10 minutes, more preferably 0.2 g/10 minutes, and even more preferably 0.3 g/10 minutes. On the other hand, the upper limit of the MI is preferably 15 g/10 minutes, more preferably 10 g/10 minutes, even more preferably 5 g/10 minutes. In addition, such an adhesive resin can be an industrially manufactured commercial product, for example, used in the examples described later, both trade names "ADMER NF642E" and "ADMER AT2235E" manufactured by Mitsui Chemicals, Inc. "ADMER NF408E" etc. are mentioned.

In addition, the layer (3) may contain other arbitrary components similar to those of the layer (1) in addition to the adhesive resin within a range that does not impair the effects of the present invention.

The lower limit of the average thickness of the layer (3) is not particularly limited, and is preferably 0.5%, more preferably 2% of the average thickness of all layers. (3) The upper limit of the average thickness of the layer is not particularly limited, and is preferably 20%, more preferably 12%, of the average thickness of all layers. If the average thickness of the layer (3) as the adhesive resin layer is less than the above lower limit, the adhesiveness may deteriorate. Moreover, when the average thickness of the layer (3) exceeds the upper limit, the cost may increase.

[Layer (4)]
Layer (4) is a layer containing, for example, EVOH (A), the thermoplastic resin, and the adhesive resin. Moreover, the layer (4) is preferably formed using the recovered layers (1), (2) and (3) in the manufacturing process of the blow-molded container. Examples of collected materials include burrs generated in the manufacturing process of blow-molded containers, products that have not passed inspection, and the like.

The layer (4) can be used as a substitute for the layer (2) described above, but generally the mechanical strength of the layer (4) is often lower than that of the layer (2). It is preferable to laminate (2) and layer (4) for use. When the blow-molded container of the present invention receives an impact from the outside, stress concentration occurs in the container, and compressive stress against the impact acts on the inner layer side of the container at the stress concentration portion, which may cause breakage. It is preferable that the layer (4) which is vulnerable to corrosion is arranged on the outer layer side of the layer (1). In addition, when it is necessary to recycle a large amount of resin, such as when a large amount of burrs are generated, layer (4), which is a recovery layer, can be arranged on both sides of layer (1).

[Method for manufacturing blow-molded container]
The blow-molded container of the present invention is preferably produced by a production method comprising a step of blow-molding using the resin composition (α). Blow molding can be performed by known methods such as direct blow molding, injection blow molding, sheet blow molding, and free blow molding.

Specifically, for example, using a resin composition (α) pellet that forms the layer (1) and, if necessary, each resin that forms other layers, a blow molding machine is used at a temperature of 100 ° C. to 400 ° C. It is blow-molded and cooled at a temperature of 10° C. to 30° C. in the mold for 10 seconds to 30 minutes. Thereby, a blow-molded hollow container can be formed. The heating temperature during blow molding may be 150° C. or higher, 180° C. or 200° C. or higher. Also, the heating temperature may be equal to or higher than the melting point of EVOH (A). On the other hand, the upper limit of this heating temperature may be 350°C, and may be 300°C or 250°C.

<Fuel container>
The blow-molded container of the present invention can be used as a fuel container. The fuel container of the present invention may include filters, fuel gauges, baffle plates, and the like. The fuel container of the present invention, which includes the blow-molded container of the present invention, is suitable for use as a fuel container because it has few streaks and bumps, excellent impact resistance at low temperatures, and excellent gas barrier properties. Here, the fuel container means a fuel container mounted on automobiles, motorcycles, ships, aircraft, generators, industrial or agricultural equipment, etc., or a portable fuel container for refueling these fuel containers, and further means a container for storing fuel. Typical examples of the fuel include gasoline, particularly oxygenated gasoline blended with methanol, ethanol, MTBE, etc., but heavy oil, light oil, kerosene, etc. are also included. Among these, the fuel container of the present invention is particularly suitably used as a fuel container for oxygen-containing gasoline.

<Bottle container>
The blow-molded container of the present invention can be used as a bottle container. The bottle container of the present invention may further include components other than the blow-molded container of the present invention, such as a cover film and a cap. Examples of the method for molding the bottle container of the present invention include direct blow molding and injection blow molding. The blow-molded container of the present invention molded in the shape of a bottle is excellent in appearance, impact resistance at low temperatures, gas barrier properties, etc., and thus is suitable for use as a bottle container for foods, cosmetics, and the like.

EXAMPLES The present invention will be described in detail below with reference to Examples, etc., but the present invention is not limited to these Examples. In addition, evaluation of the obtained resin composition was performed as follows.

(1) Quantification of Boron Compound (B) in Resin Composition The dry resin composition pellets obtained in Production Example were pulverized by freeze pulverization. 5 mL of nitric acid for precision analysis manufactured by Wako Pure Chemical Industries, Ltd. was added to 0.5 g of the obtained powder, and wet decomposition was performed using Speedwave MWS-2 (manufactured by BERGHOF). The resulting liquid was diluted with ion-exchanged water to a total liquid volume of 50 mL to prepare a sample solution, and the boron element was quantified using an ICP emission spectrometer ("Optima 4300 DV", manufactured by PerkinElmer Japan Co., Ltd.). Analysis was performed, and the amount of the boron compound (B) was calculated as an orthoboric acid conversion value (B1). In the determination, a calibration curve prepared using a boron standard undiluted solution (1000 ppm) (manufactured by Kanto Kagaku Co., Ltd.) for atomic absorption spectrometry was used.

(2) Quantification of Free Boric Acid (C) in Resin Composition (i) Preparation of Sample Solution Dry resin composition pellets obtained in Production Example were pulverized by freeze pulverization. The obtained powder was sieved through a sieve with a nominal size of 1 mm (in accordance with standard sieve standard JIS Z-8801), and a measurement sample of 1000 mg of the resin composition powder that passed through the sieve was subjected to 2-ethyl-1,3- The mixture was mixed with 3.5 mL of a hexanediol/chloroform mixed solution (volume ratio: 10/90), allowed to stand at room temperature for 24 hours, and then filtered using a 0.2 μm filter to obtain a filtrate.
(ii) Method for quantifying free boric acid (C) Apparatus name: ICP emission spectrometer iCAP6300 (manufactured by Thermo Fisher Scientific)
Measurement wavelength: 208.893 nm, 208.959 nm, 249.773 nm
Calibration curve: for atomic absorption analysis: Boron standard undiluted solution (1000 ppm) manufactured by Kanto Kagaku Co., Ltd. Measurement sample: 0.6 g of the filtrate was weighed out and adjusted to 10 mL with ethanol.
All of the obtained boron contents were assumed to be derived from free boric acid (C), and were calculated as orthoboric acid conversion values (B2).
(iii) Calculation of the ratio of free boric acid (C) Calculated by the following formula using the measurement result (B1) of the boron compound (B) and the measurement result (B2) of the free boric acid (C) obtained by the above measurement bottom.
Percentage of free boric acid (C) (% by mass) = measurement result of free boric acid (C) (B2) / measurement result of boron compound (B) (B1) × 100

(3) Melt index (MI) of resin composition
According to ASTM-D1238, using a melt indexer, the measurement was performed under conditions of a temperature of 190° C. and a load of 2160 g.

(4) Determination of metal salt and acid component in resin composition (determination of phosphoric acid compound/metal ion)
A sample solution is prepared in the same manner as in (1), and quantitatively analyzed at the following observation wavelengths using an ICP emission spectrometer Optima 4300 DV manufactured by PerkinElmer Japan Co., Ltd. to quantify the amount of metal ions and phosphate compounds. bottom. The amount of the phosphoric acid compound was calculated by quantifying the elemental phosphorus and converting it to a phosphate equivalent. For quantification, a calibration curve prepared by diluting various standard solutions was used.
Na: 589.592 nm
K: 766.490 nm
P: 214.914 nm
(Quantitative determination of carboxylic acid and carboxylic acid ion)
The dry resin composition obtained in Production Example was pulverized by freeze pulverization. The resulting pulverized resin composition is sieved through a sieve with a nominal size of 1 mm (standard sieve standard JIS Z8801-1 to 3 compliant), and 10 g of the resin composition powder that has passed through the sieve and 50 mL of ion-exchanged water are added to 100 mL with a common stopper. The mixture was put into an Erlenmeyer flask, attached with a cooling condenser, and stirred at 95° C. for 10 hours. 2 mL of the resulting solution was taken and diluted with 8 mL of deionized water. Using the ion chromatography "ICS-1500" manufactured by Yokogawa Electric Corporation, the diluted solution was quantified for carboxylic acid and carboxylic acid ions according to the following measurement conditions. A calibration curve prepared using monocarboxylic acid or polyvalent carboxylic acid was used for quantification.
Measurement conditions column: "IonPAC ICE-AS1 (9φ × 250 mm, electrical conductivity detector)" manufactured by DIONEX
Eluent: 1.0 mmol/L octanesulfonic acid aqueous solution Measurement temperature: 35°C
Eluent flow rate: 1 mL/min Analysis volume: 50 μL

Production example 1
19,600 parts of vinyl acetate, 2,180 parts of methanol, and 7.5 parts of AIBN (2,2′-azobisisobutyronitrile) were placed in a polymerization tank with a pressure resistance of 100 kg/cm ² , and after nitrogen substitution with stirring, the temperature was raised and the pressure was increased. The inside temperature was adjusted to 60°C and the ethylene pressure was adjusted to 35.5 kg/cm ² . After polymerization was carried out while maintaining the temperature and pressure for 3.5 hours, 5 parts of hydroquinone was added, the pressure in the polymerization tank was returned to normal pressure, and ethylene was removed by evaporation. Subsequently, this methanol solution is continuously flowed down from the upper part of a stripping tower packed with Raschig rings, while methanol vapor is blown in from the bottom of the tower to discharge unreacted vinyl acetate monomer together with the methanol vapor from the top of the tower into a condenser. A 45% methanol solution of ethylene-vinyl acetate copolymer containing 0.01% or less of unreacted vinyl acetate was obtained. At this time, the polymerization rate was 47% with respect to the charged vinyl acetate, and the ethylene content was 32 mol %. Next, a methanol solution of an ethylene-vinyl acetate copolymer is charged into a saponification reactor, and a sodium hydroxide/methanol solution (80 g/L) is added in an amount of 0.4 equivalent to the vinyl acetate component in the copolymer. and methanol was added to adjust the copolymer concentration to 20%. The temperature was raised to 60° C., and the reaction was carried out for about 4 hours while nitrogen gas was blown into the reactor. Then, it was neutralized with acetic acid to stop the reaction, extruded into water through a metal plate having a circular opening to precipitate, and was cut to obtain pellets having a diameter of about 3 mm and a length of about 5 mm. The obtained pellets were deliquored in a centrifuge, and a large amount of water was added to repeat washing and deliquoring operations to obtain washed hydrous pellets. The degree of saponification of the obtained EVOH was 99.7 mol%. 300 g of the washed hydrous pellets were dispersed in 0.5 L of immersion liquid to which 0.06 g/L of orthoboric acid, 0.1 g/L of acetic acid and 0.3 g/L of potassium dihydrogen phosphate were added, and stirred for 4 hours. After that, the obtained pellet was taken out and dehydrated with a centrifuge (diameter of perforated plate 1 mm, number of rotations 4000 rpm, treatment time 15 minutes), and then using a hot air dryer for preliminary drying at 80 ° C. in an air atmosphere. and dried for 3 hours. The moisture content of the pellet before centrifugation was 200% by weight based on the dry weight, the moisture content after centrifugal dehydration for 15 minutes was 78% by weight, and the moisture content after preliminary air drying was 10% by weight. After that, using a vacuum dryer for main drying, drying was performed at 80° C. for 142 hours under vacuum conditions. Vacuum drying was carried out until the moisture content in the pellets after main drying was 0.08% by mass or less, and a resin composition 1 was obtained. Regarding the resin composition 1, the metal component and the acid component were quantified according to the method described in (4) above. As a result of measurement, the resin composition contained 600 ppm (10 μmol/g) of acetic acid and its salt in terms of acetic acid radical, 150 ppm of alkali metal salt in terms of metal, and 35 ppm of phosphate compound in terms of phosphate radical.

Production Examples 2 to 24, Production Examples C1 to C14
The ethylene unit content (Et) of the EVOH used, the orthoboric acid concentration of the immersion liquid in which the washed hydrous pellets are immersed, the centrifugal dehydration conditions (treatment time and moisture content after centrifugal dehydration), and the treatment temperature for main drying are shown. Resin compositions 2 to 24 and resin compositions C1 to C14 were produced in the same manner as in Production Example 1 except for the changes shown in 1. In all production examples, main drying was performed for the treatment time shown in Table 1 until the water content in the pellets became 0.08% by mass or less. In addition, in the production examples in which centrifugal dehydration was not performed, the value described in the column of moisture content after centrifugal dehydration is the moisture content before pre-drying (hereinafter the same).

Production Examples C15-C17
The orthoboric acid concentration of the immersion liquid in which the washed hydrous pellets are immersed, and the centrifugal dehydration conditions (treatment time and moisture content after centrifugal dehydration) are as shown in Table 2, and the main drying is a hot air dryer in an air atmosphere. Resin compositions C15 to C17 were produced in the same manner as in Production Example 1 except that the pellets were air-dried under the temperature conditions shown in Table 2 until the water content in the pellets became 0.08% by mass or less.

Production Examples C18-C20
The orthoboric acid concentration of the immersion liquid in which the washed hydrous pellets are immersed, and the centrifugal dehydration conditions (treatment time and moisture content after centrifugal dehydration) are as shown in Table 3, and the main drying is a hot air dryer under a nitrogen atmosphere ( Resin compositions C18 to C20 were prepared in the same manner as in Production Example 1, except that the temperature was dried under the conditions shown in Table 3 under the conditions shown in Table 3 until the water content in the pellets became 0.08% by mass or less. manufactured.

Production example 25
The steps up to the saponification step were the same as in Production Example 1 to obtain a methanol solution of EVOH with a concentration of 20%. Subsequently, a methanol solution of EVOH was introduced from the top of the tower-type trayed reaction vessel, steam was introduced from the bottom of the reaction vessel, and methanol was mixed with water under the conditions of a tower temperature of 130°C and a tower pressure of 3 kg/cm ² . By substituting, an EVOH hydrous composition having a concentration of 50% was obtained from the bottom of the column. Subsequently, the obtained water-containing composition was introduced into an extruder having a slit for water discharge, extruded at a die temperature of 118° C., and cut and granulated with a center hot cutter to obtain pellet-like EVOH. The obtained pellets are introduced from the top of a tower-type countercurrent washing device, and pure water at 50 ° C. is introduced from the bottom to wash the pellets countercurrently. EVOH having a yield of 32 mol %, a degree of saponification of 99.7 mol % and a water content of 35% by mass was obtained. The obtained EVOH is put into a twin-screw extruder, the resin temperature at the outlet is set to 100 ° C., and an aqueous solution of acetic acid / orthoboric acid / sodium acetate / potassium dihydrogen phosphate is added from the minor component addition section at the tip of the outlet side. Processing solutions were added. The input amount of EVOH per unit time was 10 kg/hr (including the mass of water contained), and the input amount of the treatment liquid per unit time was 0.65 L/hr. It was an aqueous solution containing 3 g/L, 5.3 g/L of orthoboric acid, 4.6 g/L of sodium acetate, and 1.4 g/L of potassium dihydrogen phosphate.
Type Twin screw extruder L/D 45.5
Diameter 30mmφ
Screw: Same direction full mesh type Rotation speed: 300 rpm
Motor capacity DC22KW
Heater 13 division type Number of die holes 5 holes (3mmφ)
Resin temperature in die 105°C
The resin composition extruded from the outlet of the twin-screw extruder was cut into pellets by a hot cutter 10 having the configuration shown in FIG. Specifically, in the hot cutter 10 of FIG. 1, the resin composition discharged from the discharge port 11 of the twin-screw extruder is extruded from the die 12 and cut by the rotary blade 13 . The rotary blade 13 rotates together with a rotary shaft 14 directly connected to the rotary blade 13 . Cooling water 17 is supplied from a cooling water supply port 16 into the cutter box 15 . The pellets immediately after being cut are cooled by the water film 18 formed by the cooling water 17 , and the cooling water and the pellets 20 are discharged from the pellet discharge port 19 . The ejected pellets were flat spherical and had a moisture content of 80% by mass. The obtained pellets were taken out and dehydrated in a centrifuge (diameter of perforated plate 1 mm, number of rotations 4000 rpm, treatment time 2 minutes), and then pre-drying was carried out using a hot air dryer in an air atmosphere at 80° C. and 11 minutes. Time drying was performed to reduce the moisture content to 4.2% by mass. Subsequently, as main drying, drying was performed under vacuum conditions at 120° C. for 16 hours to obtain Resin Composition 25 with a water content of 0.08% by mass or less. The metal component and acid component of resin composition 25 were quantified according to the method described in (4) above. The content of acetic acid and its salts is 300 ppm (5 μmol/g) in terms of acetic acid radicals, the content of phosphoric acid compounds is 100 ppm in terms of phosphate radicals, and the content of alkali metal salts is 40 ppm in terms of potassium and sodium in terms of metals. was 130 ppm.

Production Examples 26-30, Production Examples C21 and C22
A resin composition was produced in the same manner as in Production Example 25 except that the concentration of orthoboric acid added to the extruder, the centrifugal dehydration conditions (treatment time and moisture content after centrifugal dehydration), and the treatment temperature for main drying were changed as shown in Table 4. 26-30, resin compositions C21 and C22 were prepared. In all production examples, main drying was performed for the treatment time shown in Table 4 until the moisture content in the pellets became 0.08% by mass or less.

Production Examples 31-34
The resin was prepared in the same manner as in Production Example 1, except that the orthoboric acid concentration of the immersion liquid, the centrifugal dehydration conditions (treatment time, and the moisture content after centrifugal dehydration), and the atmosphere, temperature, and time of the main drying were changed as shown in Table 5. Compositions 31-34 were made.

Production example C23
A resin composition C23 was produced in the same manner as in Production Example C2, except that the components of the immersion liquid were changed to 0.5 L of the immersion liquid to which 1.66 g/L of orthoboric acid and 0.11 g/L of potassium hydroxide were added. . The metal component and the acid component were quantified according to the method described in (4) above. Acetic acid and its salts were found to be 0 ppm in terms of acetic acid radicals, alkali metal salts were found to be 160 ppm in terms of metals, and phosphate compounds were found to be 0 ppm in terms of phosphate radicals.

<Examples 1 to 34, Comparative Examples 1 to 23>
(Manufacture of blow-molded containers)
Using the resin composition obtained in the production example, high-density polyethylene (Prime Polymer HI-ZEX8200B, 190 ° C., 2160 g MI = 0.03 g / 10 minutes), and the following adhesive resin, Suzuki Iron Works blow At 210° C. with a molding machine TB-ST-6P, a blow-molded container of 3 types and 5 layers of (inner) high-density polyethylene/adhesive resin/resin composition/adhesive resin layer/high-density polyethylene (outer) was produced. In the production of the blow-molded container, the inside of the mold is cooled at a temperature of 15 ° C. for 20 seconds, and the total thickness of the body is 1000 μm ((inside) high density polyethylene / adhesive resin / resin composition / adhesive resin / high density polyethylene (outside) ) = (inner) 430/50/40/50/430 μm (outer)). The tank had an average bottom diameter of 100 mm and an average height of 400 mm. In order to enable blow molding, an adhesive resin was selected and used according to the MI of the obtained resin composition.
(adhesive resin)
A-1: ADMER NF642E (manufactured by Mitsui Chemicals, Inc., 190 ° C., MI 4.0 g / 10 minutes at 2160 g)
A-2: ADMER AT2235E (manufactured by Mitsui Chemicals, Inc., 190 ° C., MI 0.3 g / 10 minutes at 2160 g)
A-3: ADMER NF408E (manufactured by Mitsui Chemicals, Inc., 190 ° C., MI 1.6 g / 10 minutes at 2160 g)

(a) Appearance Immediately after starting up the blow molding machine, after 48 hours of continuous operation, and after 96 hours of continuous operation, 3L tanks (blow-molded containers) were cut along the longitudinal direction, held up to the illumination of a fluorescent lamp, and visually observed. to confirm the presence of streaks and lumps, and evaluated according to the following criteria. In cases A to C, it was judged that streaks or bumps were suppressed.
(Streak evaluation criteria)
A: No streaks are observed B: Two or less thin streaks are confirmed C: Many thin streaks are confirmed D: Clear streaks are confirmed (evaluation criteria for products)
A: No spots are observed B: Small spots are seen C: 2 or less clear spots are seen per container D: 3 or more clear spots are seen per container

(b) Impact resistance at low temperature (gas barrier property)
After continuous operation for 96 hours, a 3 L tank (blow molded container) was filled with 2.5 L of propylene glycol, and the opening was heat-sealed with a film of polyethylene 40 µm/aluminum foil 12 µm/polyethylene terephthalate 12 µm and the lid was closed. The tank was stored at -40°C for 8 weeks.
A flat plate of 10 cm square was cut out from the part of the body of the blow-molded container after storage that was close to the flat shape below the liquid surface, and the surface was washed. After that, the inner surface of the tank was fixed to the jig connecting the metal plate and the copper pipe with an epoxy adhesive so as to be in contact with the metal plate, and MOCON OX-TRAN2/20 manufactured by Modern Control (detection limit 0.01 mL / (m ² · day · atm)) and the oxygen permeability was measured. The measurement conditions were 23° C. and 65% RH on both the carrier gas side and the oxygen gas side, with an oxygen pressure of 1 atm and a carrier gas pressure of 1 atm.
In addition, the container stored at -40°C was dropped from a height of 6 m while maintaining the temperature at -40°C, and the oxygen permeability of the unbroken container was measured in the same manner as before the drop test. Based on the oxygen permeability before and after the drop test, evaluation was made according to the following criteria. When the evaluation after the drop test was A to C, it was judged that the impact resistance at low temperatures was excellent.
A: less than 0.1 mL / (m ² · day · atm) B: 0.1 mL / (m ² · day · atm) or more and less than 1.0 mL / (m ² · day · atm) C: 1.0 mL / ( m ² · day · atm) or more and less than 10 mL / (m ² · day · atm) D: 10 mL / (m ² · day · atm) or more

For each example and comparative example using resin compositions 1 to 34 and resin compositions C1 to C23, the boron compound (B ) and free boric acid (C), measurement of MI, and evaluation were performed. The results are shown in Tables 6-11.

For example, from the comparison of Production Examples 3, 9, 10, 19, C2 and C9 (Examples 3, 9, 10, 19, Comparative Examples 2 and 9) in which boron was added by immersion, the treatment time of centrifugal dehydration was increased, Further, by lowering the temperature during the main drying, even if the concentration of the boron compound (B) is the same, the result is that the ratio of the free boric acid (C) is lowered. When boric acid was added by an extruder, a similar trend can be seen from a comparison of Production Examples 26-29, C21 and C22 (Examples 26-29, Comparative Examples 21 and 22).

Focusing on the content of the boron compound (B), in Comparative Example 5, in which the content of the boron compound (B) is small, streaks increase in long-term blow molding. This is presumed to be due to the fact that the MI is too high and layer disturbance is likely to occur. In Comparative Example 5, since a large amount of streaks act as crack initiation points, it is considered that the low-temperature impact resistance (gas barrier properties after the drop test) is low. On the other hand, Comparative Example 6, which has a large content of the boron compound (B), has many streaks and bumps. It is presumed that this is influenced by the fact that the MI is low and the viscosity is high. In Comparative Example 6, since a large amount of streaks and lumps act as crack initiation points, it is considered that the impact resistance at low temperatures (gas barrier properties after the drop test) is low.

Focusing on the content of free boron (C), Comparative Examples 1 to 4, 13, 15, 17, 18, 21 and 23, which have a low content of free boron (C), have no layer disturbance in long-term blow molding. Happens and streaks are happening. These streaks are the origin of cracks, so it is considered that the low-temperature impact resistance (gas barrier properties after the drop test) is low. In addition, Comparative Examples 7 to 12, 14, 16, 19, 20 and 22, which have a high content of free boron (C), tend to have many pimples because the free boron (C) causes local cross-linking. It is thought that the impact resistance at low temperatures (gas barrier properties after the drop test) is low because these bumps act as starting points for cracks. Furthermore, from the comparison between Comparative Example 4 and Example 16, when the content of the boron compound (B) is large and the content of free boron (C) is low (Comparative Example 4), it is likely that crosslinking is progressing. , it can be seen that the number of bumps increases.

On the other hand, Examples 1 to 34 in which the content of the boron compound (B) and the content of the free boric acid (C) are within the predetermined ranges have few streaks and pimples, and have good impact resistance at low temperatures. Good results were obtained.

Further, from the comparison of Examples 10, 33 and 34 (Production Examples 10, 33, 34), when the treatment temperature of main drying is the same, vacuum drying is performed, even if the concentration of the boron compound (B) is the same , resulting in a lower proportion of free boric acid (C). Further, from the comparison between Comparative Example 2 and Comparative Example 23 (manufacturing examples C2 and C23), it can be read that the presence of acid components such as acetic acid and phosphoric acid can suppress the occurrence of pimples.

According to the present invention, it is possible to provide a blow-molded container that has few streaks and small spots and is excellent in impact resistance at low temperatures.

10 hot cutter 11 discharge port 12 die 13 rotary blade 14 rotating shaft 15 cutter box 16 cooling water supply port 17 cooling water 18 water film 19 pellet discharge port 20 cooling water and pellets

Claims (6)

A resin composition containing an ethylene unit content of 27 mol% or more and 50 mol% or less and an ethylene-vinyl alcohol copolymer (A) having a saponification degree of 99 mol% or more and a boron compound (B) ( A blow-molded container comprising a layer formed from α),
The boron compound (B) contains free boric acid (C),
The content of the boron compound (B) with respect to the ethylene-vinyl alcohol copolymer (A) in the resin composition (α) is 100 ppm or more and 5000 ppm or less in terms of orthoboric acid, and the free boric acid (C ) is 0.1% by mass or more and 10% by mass or less in terms of orthoboric acid. The blow-molded container according to claim 1, wherein the resin composition (α) contains a phosphoric acid compound of 1 ppm or more and 500 ppm or less in terms of phosphate radical. 3. The blow-molded container according to claim 1, wherein the resin composition (α) contains 0.01 μmol/g or more and 20 μmol/g or less of carboxylic acid and/or carboxylic acid ion in terms of carboxylic acid radical. The blow-molded container according to any one of claims 1 to 3, wherein the resin composition has a melt index of 0.1 to 15 g/10 minutes measured according to ASTM D1238 at 190°C under a load of 2160 g. A fuel container comprising the blow-molded container according to any one of claims 1 to 4. A bottle container comprising the blow-molded container according to any one of claims 1 to 4.

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