JP6848218B2 - Laminates and flexible containers - Google Patents

Description

The present invention relates to a laminated body and a flexible container using the same, and more specifically, it is used for packaging, storage, and transportation of powders and granules such as salt, and has low transferability of additives to packaged contents. The present invention relates to a laminate suitable as a material for a flexible container and a flexible container using the same.

Flexible containers are widely used for packaging, storing, and transporting powders and granules. As such a flexible container, a fiber woven fabric made of synthetic resin fibers such as polyester, polyamide, polyolefin, vinylon, etc., and other fibers is used as a base cloth, and polyvinyl chloride or polyvinyl chloride is used on one or both sides of the base cloth. A tarpaulin on which a resin such as rubber is laminated is used as a base material to make a bag.

This tarpaulin using polyvinyl chloride can be subjected to high-frequency welder processing, which is one of the heat treatment processes for welding the material by vibrating the molecules of the material with high frequency, and has excellent flexibility and heat resistance. It is used for materials for materials, industrial materials, logistics materials, etc.

However, since polyvinyl chloride contains a large amount of plasticizer for the purpose of improving thermal stability, flexibility, etc., the plasticizer elutes (bleeds) in a flexible container formed by high-frequency welding of tarpaulin. There was a problem that it was easy to transfer to the contents or get dirty. In addition, the specific gravity of the resin itself is high and the workability is inferior, and since hydrogen chloride gas, which is the most toxic in the disposal / incineration process, is generated, there are concerns about hygiene, handling, and safety.

As a flexible container that attempts to suppress the transfer of additives to such packaging contents, 2-propylheptanol is mainly used, and a mixed alcohol of 4-methyl-2-propylheptanol and phthalic acid are used. A flexible container made of polyvinyl chloride obtained by blending the diester of the above has been proposed (Patent Document 1). However, even with the technique described in Patent Document 1, the transferability of the additive to the package contents cannot be sufficiently suppressed, and the plasticizer in the resin used for the flexible container is the content after long-term use. It was not able to withstand actual use because it moved to a product and the sheet became hard probably because of it.

Therefore, in recent years, as a material capable of high-frequency welder processing and having less problems as described above, ethylene-based weights such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-α olefin copolymer are used. The coalescence is used as a resin material for laminates for flexible containers. It is not necessary to add a large amount of plasticizer to these polymers, but on the other hand, in order to prevent blocking and improve calendar formability such as roll peelability, fatty acid amides, polyoxyethylene alkyl ethers and the like are usually used. It is necessary to add a phosphate ester-based lubricant containing a nonionic surfactant (Patent Documents 2 and 3).

Further, a technique for blending an elastomer such as an ethylene-propylene-diene copolymer or a styrene-ethylene-butylene-styrene block copolymer in order to impart flexibility, heat resistance, processability, coatability, etc. to a flexible container. Is also known (Patent Document 4).

Japanese Unexamined Patent Publication No. 8-301295 Japanese Unexamined Patent Publication No. 10-07661 Japanese Unexamined Patent Publication No. 2001-293831 Japanese Unexamined Patent Publication No. 2006-04415

Although such a lubricant is also added in a small amount, it has been clarified by the studies by the present inventors that, like the plasticizer described above, transfer to the contents when it is made into a flexible container becomes a problem. It was also clarified that there is a problem that components such as carboxylic acid metal salts contained in the elastomer are also transferred to the contents of the flexible container. Specifically, for example, when salt is stored in a flexible container for a long period of time, and then the salt is dissolved in water and stirred, white or yellow bubbles are formed in the dissolved salt water, and the bubbles remain without being extinguished even after a while. There was a problem that the quality of salt deteriorated, such as the state of being left as it was or the lye remaining.

An object of the present invention is a laminate which is used for packaging, storage, and transportation of powders and granules such as salt, and has low transferability of additives to the package contents, in view of the above-mentioned problems of the prior art. The purpose is to provide a flexible container using it.

As a result of repeating various studies in order to solve the above problems, the present inventors have a barrier layer made of a specific resin composition as a resin layer to be laminated on the base cloth, and when the package is made, this is used. It has been found that by using the barrier layer as the innermost layer, the transferability of the additive to the package contents is remarkably improved as compared with the conventional material. Furthermore, they have also found that when the SP value of the resin layer laminated on the base fabric satisfies a specific condition, the transferability of the additive to the package contents is remarkably improved as compared with the conventional material. It came to be completed.

The gist of the present invention is as follows.

[1] A coating layer composed of a base cloth, a resin composition (b) containing a resin (b-1) and an additive (b-2), which covers at least one surface of the base cloth, and a resin ( A laminate having the barrier layer having a first layer made of the resin composition (c) containing c-1), and the coating layer interposed between the barrier layer and the base cloth. The resin (c-1) contains at least one resin selected from the group consisting of an α-olefin-vinyl alcohol copolymer, a polyamide resin, a polyester resin, and a polyvinylidene chloride resin as a main component. A laminate characterized by being used for a package having the barrier layer as the innermost layer.

[2] In [1], the resin (b-1) is an α-olefin-vinyl acetate copolymer, a copolymer of α-olefin and an unsaturated carboxylic acid and / or a derivative thereof, a polyolefin resin, and a poly. A laminate characterized by containing at least one resin selected from the group consisting of vinyl chloride resins as a main component.

[3] In [1] or [2], the barrier layer is a resin composition (d-1) containing a resin (d-1) that overlaps the first layer and at least one surface of the first layer. A laminated body having a second layer made of).

[4] The laminate according to [3], wherein the resin (d-1) is a resin having an affinity with the resin (b-1).

[5] In [3] or [4], the resin (d-1) and the resin (b-1) are an α-olefin-vinyl acetate copolymer, an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof. A laminate characterized by containing at least one resin selected from the group consisting of a copolymer of the above and a polyolefin resin as a main component.

[6] The laminate according to [3] or [4], wherein the resin (d-1) and the resin (b-1) contain a polyvinyl chloride-based resin as a main component.

[7] A laminate according to any one of [1] to [6], wherein the additive (b-2) contains a surfactant.

[8] A laminate according to any one of [1] to [7], wherein the additive (b-2) contains a carboxylic acid metal salt.

[9] The laminate according to any one of [1] to [8], wherein the thickness of the first layer is 1 to 100 μm.

[10] The laminate according to any one of [3] to [9], wherein the thickness of the second layer is 3 to 150 μm.

[11] The laminate according to any one of [1] to [10], wherein the thickness of the barrier layer is 10 to 300 μm.

[12] A flexible container made of the laminate according to any one of [1] to [11].

[13] A packing body having the flexible container of [12] and the salt filled in the flexible container.

[14] A coating layer composed of a base cloth, a resin composition (b) containing a resin (b-1) and an additive (b-2), which covers at least one surface of the base cloth, and a resin ( A laminated body having a barrier layer having a first layer made of the resin composition (c) containing c-1) and having the coating layer interposed between the barrier layer and the base cloth is made into a bag. This is a method for suppressing the bleeding of the additive (b-2) from the flexible container, wherein the resin (c-1) is an α-olefin-vinyl alcohol copolymer, a polyamide resin, a polyester resin, and a resin. A bleed suppression method comprising at least one resin selected from the group consisting of polyvinylidene chloride resins as a main component and using the barrier layer as the innermost layer of the flexible container.

[15] A coating layer composed of a base cloth, a resin composition (b) containing a resin (b-1) and an additive (b-2), which covers at least one surface of the base cloth, and a resin ( A laminate having a barrier layer having a first layer made of the resin composition (c) containing c-1), and the coating layer interposed between the barrier layer and the base fabric. The SP value of the resin (b-1) (SP (b-1)), the SP value of the additive (b-2) (SP (b-2)), and the SP value of the resin (c-1) ( A laminated body in which SP (c-1)) satisfies the following relational expression and is used for a package having the barrier layer as the innermost layer.
| SP (c-1) -SP (b-2) |> | SP (b-1) -SP (b-2) |

Since the laminate of the present invention has a barrier layer including a first layer made of the resin composition (c) containing a specific resin (c-1), it is added to the resin composition used for the laminate. It has a remarkable effect of low transferability of the agent. Therefore, for example, in a packaging bag such as a flexible container in which this laminate is manufactured so that the barrier layer is the innermost layer, it is difficult for additives to transfer to the contents, and the quality of the contents is high. Can be maintained.

It is an enlarged sectional view of the laminated body which concerns on embodiment. It is a schematic enlarged sectional view of the joint part between laminated bodies.

Embodiments of the present invention will be described in detail below.
In the present invention, the "main component" refers to a component whose content is usually 50% by mass or more, preferably 70% by mass or more, and more preferably 80 to 100% by mass.

[Laminate]
The laminate of the present invention has a base cloth, a coating layer, and a barrier layer.

[Layer structure of laminated body]
1A to 1C are cross-sectional views showing a configuration example of the laminated body of the present invention. The laminate 1A of FIG. 1A is a coating layer 3 composed of a base cloth 2 and a resin composition (b) formed on one surface of the base cloth 2, and a resin composition covering the coating layer 3 ( It has a barrier layer 4 composed of c).

The laminate 1B of FIG. 1B includes a base cloth 2, a coating layer 3A formed on one surface of the base cloth 2, and a coating layer 3B formed on the other surface of the base cloth 2. It has a barrier layer 4 that covers the one coating layer 3A. The coating layer 3A is made of the resin composition (b). The coating layer 3B is preferably made of the resin composition (b) or the same resin composition as the resin composition (b) except that it does not contain the additive (b-2) described later. The barrier layer 4 is made of the resin composition (c) as a whole.

The laminate 1C of FIG. 1C includes a base cloth 2, a coating layer 3A formed on one surface of the base cloth 2, and a coating layer 3B formed on the other surface of the base cloth 2. It has a barrier layer 4'covering the one coating layer 3A. Similar to the laminate 1B of FIG. 1B, the coating layer 3A is made of the resin composition (b). Further, the coating layer 3B is preferably made of the resin composition (b) or the same resin composition as the resin composition (b) except that it does not contain the additive (b-2) described later.
In this laminated body 1C, the barrier layer 4'has a first layer 4-1 made of the resin composition (c) and a second layer 4-2 made of the resin composition (d). The second layer 4-2 is provided on both sides of the first layer 4-1 so as to sandwich the first layer 4-1. The covering layer 4'is [second layer / first layer]. / Second layer] has a three-layer structure.

The resin (d-1) in the resin composition (d) constituting the second layer 4-2 has an affinity with the resin (b-1) in the resin composition (b) constituting the coating layer 3A. High is preferable. As a result, the bondability between the second layer 4-2 of the barrier layer 4'and the coating layer 3A is improved. The definition of high affinity of the resin will be described later.
As the layer structure of the laminated body of the present invention, the layer structure of the laminated body 1C of FIG. 1C is suitable because the adhesiveness between the barrier layer and the coating layer is good.

Although not shown, the second layer 4-2 may be omitted in FIG. 1 (c). For example, the second layer 4-2 between the first layer 4-1 and the coating layer 3A may be omitted so that the coating layer 3A is in direct contact with the first layer 4-1. On the contrary, the second layer 4-2 on the opposite side of the coating layer 3A may be omitted.

[Base cloth]
The base cloth may be a woven cloth, a knitted cloth, or a resin-impregnated cloth thereof, but a knitted cloth is particularly preferable.

The fibers of the base fabric may be woven from synthetic fibers, naturally derived fibers, semi-synthetic fibers, inorganic fibers, or mixed fibers composed of two or more of these. Specifically, polyolefin fibers such as vinylon fibers, polyester fibers, polyamide fibers and polyethylene fibers, synthetic fibers such as aromatic polyamide fibers and acrylic fibers; naturally derived fibers such as cotton, cotton, rayon and hemp; glass fibers, Inorganic fibers such as silica fibers, alumina fibers, and carbon fibers can be mentioned, but synthetic fibers are preferable in consideration of processability and versatility, and polyester fibers, polyamide fibers, and vinylon fibers are particularly heat-resistant in the obtained laminate. It is preferable because it increases the strength. The fibers of the base cloth listed above may be used alone or in combination of two or more. These fibers can be used in any shape such as multifilament yarn, short fiber spun yarn, monofilament yarn, split yarn, tape yarn, etc., but the fiber yarn used in the present invention includes multifilament yarn and short yarn. Fiber-spun yarn is preferable because it has excellent strength and dimensional stability of the base fabric.

The fiber diameter of the base fabric is usually 139 to 2222 dtex (125 to 2000 denier), and particularly preferably 278 to 1111 dtex (250 to 1000 denier).
As such a base cloth, a commercially available product can be used as it is.

[Coating layer]
The coating layers 3 and 3A are made of a resin composition (b) containing a resin (b-1) and an additive (b-2). The coating layer 3B may be made of the resin composition (b) or the composition of the resin (b-1) containing no additive (b-2).

<Resin (b-1)>
The resin (b-1) is not particularly limited as long as it can be laminated with the barrier layer, but is an α-olefin-vinyl acetate copolymer, or a copolymer of an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof. , Polyolefin-based resins, and those containing at least one resin selected from the group consisting of polyvinyl chloride-based resins as a main component are preferable, and in particular, α-olefin-vinyl acetate copolymers capable of high-frequency welding and α-olefins are incompatible. A copolymer containing a saturated carboxylic acid and / or a derivative thereof, and a polyvinyl chloride resin as a main component are preferable.

● α-olefin-vinyl acetate copolymer As α-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, etc. Examples thereof include 1-decene and 1-dodecene. As the α-olefin-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, a propylene-vinyl acetate copolymer and the like are preferable, and an ethylene-vinyl acetate copolymer is more preferable.

The content of the vinyl acetate unit in the α-olefin-vinyl acetate copolymer is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and further preferably 10 to 20% by mass. preferable. When the content of the vinyl acetate unit is 5% by mass or more, the high-frequency welding processability tends to be good, while when the content of the vinyl acetate unit is 30% by mass or less, the heat resistance is good. Tend.

As the ethylene-vinyl acetate copolymer preferably used, one having a melt flow rate (MFR) of 0.05 to 20 g / 10 minutes is preferable, and one having a melt flow rate (MFR) of 0.1 to 10 g / 10 minutes is more preferable, and 0.3. The one of ~ 5 g / 10 minutes is more preferable, and the one of 0.5 to 3 g / 10 minutes is particularly preferable. When the MFR is 0.05 g / 10 minutes or more, the moldability tends to be good, while when the MFR is 20 g / 10 minutes or less, the deterioration of the physical properties of the obtained laminate tends to be easily suppressed, which is preferable. In particular, when a laminate is produced by a calender molding method, an MFR of 0.3 to 5 g / 10 minutes is preferable.

As the α-olefin-vinyl acetate copolymer, one produced by a conventionally known method can be used, and a commercially available product can be appropriately selected and used. Examples of commercially available products include "Novatec EVA" manufactured by Japan Polyethylene Corporation.

The MFR and vinyl acetate contents of the ethylene-vinyl acetate copolymer are as follows: JIS K6924-2: 1997 "Plastic-Ethylene / Vinyl Acetate (E / VAC) Molding and Extrusion Material-Part 2: Test Piece Measure in accordance with the annex "Ethylene-vinyl acetate resin test method" of "How to make and obtain various properties".

● Copolymers of α-olefins and unsaturated carboxylic acids and / or derivatives thereof (hereinafter sometimes referred to as “unsaturated carboxylic acids (derivatives)”) Examples of α-olefins include ethylene, propylene, 1-butene, and the like. Examples thereof include 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene and the like, and ethylene is preferable.

Examples of unsaturated carboxylic acids include α and β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Examples of the unsaturated carboxylic acid derivative include the following unsaturated carboxylic acid esters, maleic anhydride, α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride, N-phenylmaleimide, N-methylmaleimide, and N-t. Examples thereof include imide compounds of α, β-unsaturated dicarboxylic acid such as −butylmaleimide, preferably α, β-unsaturated carboxylic acid or an ester thereof, and more preferably acrylic acid, methacrylic acid or an ester thereof. is there.

Examples of the unsaturated carboxylic acid ester include the above-mentioned ester compounds of the unsaturated carboxylic acid, and among them, an alkyl ester or a glycol ester having 1 to 20 carbon atoms of the unsaturated carboxylic acid is preferable, and the (meth) acrylic acid has the carbon number of carbon atoms. 1 to 20 alkyl esters or glycol esters are preferred. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylate- (Meta) acrylic acid alkyl ester such as 2-ethylhexyl; (meth) acrylic acid cyclohexyl, (meth) acrylic acid methylcyclohexyl, (meth) acrylic acid boronyl, (meth) acrylic acid isobornyl, (meth) acrylic acid adamantyl, etc. (Meta) acrylic acid cycloalkyl ester; (meth) acrylic acid aryl ester such as (meth) acrylic acid phenyl, (meth) acrylic acid fluorophenyl, (meth) acrylic acid chlorophenyl, etc. or (meth) acrylic acid substituted aryl ester; ( (Meta) acrylic acid aryl-substituted alkyl esters such as (meth) acrylic acid benzyl, (meth) acrylic acid fluorobenzyl, (meth) acrylic acid chlorobenzyl, or (meth) acrylic acid halide aryl-substituted alkyl esters; (meth) acrylic acid (Meta) acrylic acid halogenated alkyl esters such as fluoromethyl, fluoroethyl (meth) acrylic acid; (meth) acrylic acid hydroxyalkyl esters, (meth) glycidyl acrylate, (meth) acrylic acid ethylene glycol esters, (meth) Acrylic acid polyethylene glycol ester and the like can be mentioned. Here, "(meth) acrylic acid" means methacrylic acid or acrylic acid.

Among these, (meth) acrylic acid alkyl esters having an alkyl group carbon of 1 to 4 such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable.

The α-olefin-unsaturated carboxylic acid (derivative) copolymer may contain only one kind of these unsaturated carboxylic acid (derivative) units, or may contain two or more kinds.

Specific examples of the α-olefin-unsaturated carboxylic acid (derivative) copolymer are preferably an ethylene- (meth) acrylic acid ester copolymer and an ethylene- (meth) acrylic acid copolymer, and more specifically, For example, ethylene-methyl acrylate copolymer (EMA, thermal decomposition temperature about 280 ° C.), ethylene-ethyl acrylate copolymer (EEA, thermal decomposition temperature about 280 ° C.), ethylene-butyl acrylate copolymer (EBA), ethylene. Examples thereof include a methyl methacrylate copolymer (EMMA, a thermal decomposition temperature of about 300 ° C.), an ethylene-acrylic acid copolymer, and an ethylene-methacrylic acid copolymer.

The method for producing the α-olefin-unsaturated carboxylic acid (derivative) copolymer is not particularly limited, and it is produced by a known radical polymerization method. For example, a radical catalyst such as a peroxide is added to either an α-olefin or an unsaturated carboxylic acid (derivative) to generate a free radical, which is reacted with another copolymerization component to polymerize.

The structure of the α-olefin-unsaturated carboxylic acid (derivative) copolymer may be any of a random copolymer, a graft copolymer, a block copolymer and the like, but (1) at a measurement temperature of 190 ° C. and a load of 21.18 N. The MFR value is preferably 0.05 to 20 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes, still more preferably 0.3 to 5 g / 10 minutes, 0.5. It is particularly preferably ~ 3 g / 10 minutes. Further, (2) the content ratio of the unsaturated carboxylic acid (derivative) unit in the total monomer unit in the copolymer is preferably 5 to 30% by mass, more preferably 7 to 25% by mass. It is preferably 10 to 20% by mass, more preferably 10 to 20% by mass. The α-olefin-unsaturated carboxylic acid (derivative) copolymer preferably satisfies both (1) and (2). When the MFR is 0.05 g / 10 minutes or more, the moldability tends to be good, and when it is 20 g / 10 minutes or less, deterioration of the physical properties of the obtained laminate is easily suppressed, which is preferable. In particular, when a laminate is produced by a calender molding method, an MFR of 0.3 to 5 g / 10 minutes is preferable.
Further, when the content ratio of the unsaturated carboxylic acid (derivative) in the α-olefin-unsaturated carboxylic acid (derivative) copolymer is 5% by mass or more, the high-frequency welding processability tends to be good, and is 30% by mass. The following is preferable because the heat resistance tends to be good.

● Polyolefin-based resin Examples of the polyolefin-based resin include polyethylene-based resin and polypropylene-based resin, and polyethylene-based resin is preferable.

Examples of polyethylene-based resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-pentene copolymer, and ethylene-1-. Ethylene-α olefins such as hexene copolymers, ethylene-propylene-hexene copolymers, ethylene-4-methyl-1-pentene copolymers, ethylene-1-heptene copolymers, and ethylene-1-octene copolymers. Examples thereof include copolymers. Among them, high-density polyethylene is preferable from the viewpoint of heat resistance, and low-density polyethylene is preferable from the viewpoint of softness and texture. A polyolefin resin having an appropriate density may be selected in consideration of the desired balance between heat resistance and texture.

The melt flow rate (MFR) of the polyolefin resin used in the present invention at 190 ° C. and a load of 21.18 N (JIS K7210: 2014) is preferably 0.05 to 20 g / 10 minutes, and is 0.1 to 0.1. It is more preferably 10 g / 10 minutes, further preferably 0.3 to 5 g / 10 minutes, and particularly preferably 0.5 to 3 g / 10 minutes. When the MFR of the polyolefin resin is 0.05 g / 10 minutes or more, the moldability tends to be good, and when it is 20 g / 10 minutes or less, the deterioration of the physical properties of the obtained laminate tends to be suppressed, which is preferable. In particular, when a laminate is produced by a calender molding method, an MFR of 0.3 to 5 g / 10 minutes is preferable.

● Polyvinyl chloride-based resin Polyvinyl chloride-based resins include, in addition to the homopolymer of vinyl chloride, random, graft and block copolymers with other copolymerizable comonomer containing vinyl chloride as the main component, chloride. Examples thereof include resins having vinyl as a main constituent unit.

Examples of the copolymerizable comonomer include olefin-based monomers such as ethylene, propylene and polybutene, saturated vinyl esters such as vinyl acetate, vinyl laurate, acrylic acid ester and methacrylic acid ester, unsaturated alkyl esters and alkyl vinyl ethers such as lauryl vinyl ether. , Maleic acid, acrylonitrile, styrene, methylstyrene, vinylidene chloride, vinylidene fluoride and the like.

Further, the polyvinyl chloride-based resin may be, for example, a polymer blend with a styrene-based resin such as an acrylonitrile-butadiene-styrene copolymer or a halogen-containing resin such as a post-chlorinated product.

The degree of polymerization of the polyvinyl chloride resin is preferably 500 to 2000, more preferably 700 to 1500, and even more preferably 800 to 1300. A polymer having a degree of polymerization in this range is preferable because it has moldability, heat resistance, fluidity, etc. necessary for molding a laminate, and is more flexible and hard to break.

The resin composition (b) is a resin (b-1) such as the above-mentioned α-olefin-vinyl acetate copolymer, a copolymer of an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof, a polyolefin resin, and a poly. It may contain only one kind of vinyl chloride resin, or may contain two or more kinds.
When the laminates are high-frequency welded to each other, the resin composition (b) is a resin (b-1) such as an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer (EMA), or an ethylene-. Ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), polyvinyl chloride resin (PVC), ethylene-methacrylic acid copolymer (EMAA) and ethylene-methyl methacrylate copolymer (EMMA) It is preferable to contain one or more of the above, and when the laminates are welded to each other by a dryer, one or two of EVA, EMA, EEA, EBA, polyethylene resin, PVC, EMAA, and EMMA should be included. Is preferable.

<Additive (b-2)>
Examples of the additive (b-2) include lubricants, elastomers, inorganic compounds, antioxidants (phenolic), pigments, dyes, light stabilizers, ultraviolet absorbers, flame retardants, and dispersants.

● Lubricants As lubricants, various paraffins such as phosphoric acid ester, carboxylic acid or metal salts thereof, liquid paraffin, paraffin wax, polyolefin wax, carboxylic acid ester, fatty acid amide, higher alcohols, natural waxes, kerosene, etc. can be used. .. Among them, a phosphoric acid ester is preferable from the viewpoints of calender forming processability such as releasability from a calendar roll, sustainability of lubricant activity, and less adversely affecting physical properties such as peel strength of the obtained laminate.

Examples of the phosphoric acid ester include monostearyl phosphate, monolauryl phosphate, monononyl phosphate, monooleyl phosphate, distearyl phosphate, dilauryl phosphate, dinonyl phosphate, diorail phosphate, and trickre. Examples thereof include dizyl phosphate, trixysilyl phosphate, tributyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, diphenyl cresil phosphate, tributoxyethyl phosphate and the like.

Examples of the carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the carboxylic acid also includes an alicyclic carboxylic acid. Among these, a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms is preferable, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable. Specific examples of such carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanic acid, montanic acid, and adipic acid. Examples include azelaic acid.

As the carboxylic acid metal salts, the metal salts of the above carboxylic acid are preferable, and specific examples thereof include carboxylic acid metal salts such as zinc stearate, barium stearate, and calcium stearate.

Examples of the polyolefin wax include low molecular weight polyethylene, low molecular weight polyethylene copolymer, and modified polyethylene wax in which a polar group is introduced by oxidatively modifying or acid-modifying them. The number average molecular weight may be appropriately selected and determined, but is usually less than 20,000, and more preferably 500 to 15,000, particularly 1,000 to 10,000.

Examples of the carboxylic acid ester include higher fatty acids such as stearic acid, oleic acid, octanoic acid, lauric acid, ricinolic acid and behenic acid, and octyl alcohol, myristyl alcohol, stearyl alcohol, behenic alcohol, glycols, glycerin and pentaerythritol. Esters with monohydric or polyhydric alcohols can be mentioned.

As the fatty acid amide, a compound obtained by a dehydration reaction between a higher fatty acid and / or a polybasic acid and a diamine is preferable. As the higher fatty acid, a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms, for example, 16 to 30 carbon atoms is preferable, and specific examples thereof include palmitic acid, stearic acid, behenic acid, and montanic acid. The polybasic acid is a carboxylic acid of dibasic acid or more, for example, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimeric acid, and azelaic acid, and aromatic acids such as phthalic acid and terephthalic acid. Examples thereof include dicarboxylic acids and alicyclic dicarboxylic acids such as cyclohexyldicarboxylic acid and cyclohexylsuccinic acid. Examples of the diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, m-xylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, isophoronediamine and the like. Specific examples thereof include stearic acid amide, behenic acid amide, montanic acid amide, methylene bisstearyl amide, and ethylene bisstearyl amide.
These lubricants may be used alone or in combination of two or more.

When the resin composition (b) contains the above-mentioned lubricant as the additive (b-2), the content thereof is the required amount of the lubricant according to the type of the lubricant used and the type of the resin (b-1). In the case of calendar molding, for example, the lubricant should be added without deteriorating the physical properties of the laminate such as peel strength, the high-frequency weldability between the laminates, and the hot air weldability. From the viewpoint of sufficiently obtaining the effect of improving the releasability of the calendar roll, the amount is preferably 0.1 to 10 parts by mass, and 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin (b-1). It is more preferable that the amount is 0.5 to 3 parts by mass.

● Elastomers Examples of elastomers include olefin rubbers such as ethylene-propylene-diene copolymer (EPDM) and ethylene-propine copolymer (EPR), styrene-butadiene-styrene copolymer (SBS), and styrene-ethylene-. Styrene-based rubbers such as butylene-styrene copolymer (SEBS) and thermoplastic modified polyolefin elastomers are suitable. Among them, olefin rubber having excellent heat resistance and affinity with the resin (b-1) is preferable, and EPDM is particularly preferable.
EPDM contains conjugated diene as a third component in addition to ethylene and propylene, and examples of conjugated diene include ethylidene norbornene, 1,4-cyclohexadiene, dicyclopentadiene, and cyclooctadiene.

As the thermoplastic modified polyolefin elastomer, the hard segment is composed of an α-olefin polymer such as polyethylene and polypropylene, and the soft segment is an olefin rubber such as EPDM and EPR or a diene rubber such as butyl rubber, NBR and hydrogenated SBR. Examples thereof include hydroxyl-modified products, carboxyl-group-modified products, acid anhydride-modified products, and ester-group-modified products of the constituent thermoplastic polyolefin elastomers. Further, the thermoplastic polyolefin elastomer may have two or more kinds of functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group and an ester group. There are two types of thermoplastic polyolefin elastomers, a partially crosslinked type and a fully crosslinked type, and either elastomer may be used. The modification method of the thermoplastic modified polyolefin elastomer may be modified by any known method, for example, a method of copolymerizing a vinyl monomer having a hydroxyl group, a carboxyl group, an acid anhydride group and / or an ester group. Can be mentioned. The copolymerization ratio of the vinyl monomer having a substituent is 0.1 to 80 mol%, preferably 0.1 to 40 mol% in the case of a vinyl monomer having a hydroxyl group or an ester group, and a carboxyl group or an acid anhydride group is used. In the case of the vinyl monomer having, it is often 0.1 to 40 mol%, preferably 0.1 to 20 mol%.

The elastomer has a melt flow rate (MFR) of 0.05 to 20 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes, at 230 ° C. and a load of 21.18 N (JIS K7210: 2014). It is more preferably 0.3 to 5 g / 10 minutes, and particularly preferably 0.5 to 3 g / 10 minutes. When the MFR of the elastomer is 0.05 g / 10 minutes or more, the kneadability with the resin (b-1) is likely to be improved, and when it is 20 g / 10 minutes or less, the kneadability is similarly deteriorated and the resin composition is similarly deteriorated. It is preferable that the decrease in strength and the decrease in heat resistance of the object (b) are easily suppressed.
These elastomers may be used alone or in combination of two or more.

When the resin composition (b) contains the above-mentioned elastomer as the additive (b-2), the content thereof is the required amount of the elastomer according to the type of the elastomer used and the type of the resin (b-1). However, from the viewpoint of sufficiently obtaining the effect of improving the flexibility by adding the elastomer without impairing the characteristics of the resin (b-1) and deteriorating the physical properties of the obtained laminate. The amount is preferably 0.5 to 49 parts by mass, more preferably 1 to 40 parts by mass, and further preferably 5 to 30 parts by mass with respect to 100 parts by mass of the resin (b-1).

● Inorganic compound As the inorganic compound, a water-containing inorganic compound which is an inorganic compound to which water is bonded is preferable, and typically, for example, silica gel [SiO ₂ · nH ₂ O], hydrated alumina [Al ₂ O ₃ ·. nH ₂ O], hydrous aluminum silicate [Al ₂ O ₃ , mSiO ₂ , nH ₂ O], calcium silicate [CaO, mSiO ₂ , nH ₂ O], hydrous magnesium silicate [MaO, mSiO ₂ , nH ₂ O] ] And the like, such as hydrous silicate. Moisture contained in these inorganic compounds contributes to heat generation during high-frequency welder processing, so that high-frequency welder workability can be greatly improved, such as by increasing heat welding strength.
These inorganic compounds may be used alone or in combination of two or more.

When the resin composition (b) contains the above-mentioned inorganic compound as the additive (b-2), the content thereof depends on the type of the inorganic compound used and the type of the resin (b-1). Although it depends on the required amount of the resin (b-1), the characteristics of the resin (b-1) are not impaired, the physical properties of the obtained laminate are not deteriorated, the high-frequency weldability is improved by adding an inorganic compound, and the calendar roll is released. From the viewpoint of improving the properties and sufficiently obtaining the effect of suppressing additive bleeding such as a lubricant, the amount is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the resin (b-1), and 1 to 25 parts by mass. It is more preferable that the amount is 3 to 20 parts by mass.

● Antioxidants As antioxidants, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-) One or more of the hindered phenolic antioxidants such as 4-hydroxyphenyl) propionate can be used. Specific examples thereof include BASF's product names (same below) "Irganox 1010" and "Irganox 1076", and ADEKA's "ADEKA STAB AO-50" and "ADEKA STAB AO-60".

When the resin composition (b) contains the above-mentioned antioxidant as the additive (b-2), the content thereof depends on the type of the antioxidant used and the type of the resin (b-1). Although it depends on the required amount of the antioxidant, the thermal stability, wet heat stability, and hue due to the addition of the antioxidant do not cause poor appearance due to gas generation during molding or deterioration of physical properties due to oxidative deterioration. From the viewpoint of sufficiently obtaining the effect of improving stability, the amount is preferably 0.01 to 1 part by mass, and 0.03 to 0.8 parts by mass with respect to 100 parts by mass of the resin (b-1). Is more preferable, and 0.06 to 0.5 parts by mass is further preferable.

● Pigments Pigments may be either inorganic or organic, but for example, inorganic pigments such as zinc oxide, titanium oxide (rutyl type, anatase type), antimony trioxide, iron oxide, and lead oxide. One or more of azo pigments, phthalocyanine pigments, anthraquinone pigments, perinone pigments, quinacridone pigments and the like can be used.

When the resin composition (b) contains the above-mentioned pigment as the additive (b-2), the content thereof is the required amount of the pigment according to the type of the pigment used and the type of the resin (b-1). However, the minimum amount for obtaining a desired color may be added as long as the physical properties of the obtained laminate are not impaired.

In the present invention, when the resin composition (b) contains a lubricant as an additive (b-2), the lubricant often contains a surfactant in order to suppress a decrease in the lubricant activity.
Examples of the surfactant contained in the lubricant include ionic surfactants such as anionic surfactants, cationic surfactants and amphoteric surfactants, and nonionic surfactants.

Examples of the anionic surfactant include sulfonates, sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl ether sulfate, and sulfates such as polyoxyethylene alkyl sulfate. Be done. Examples of the cationic surfactant include a quaternary ammonium salt type such as an amine salt type and an alkyltrimethylammonium salt. Examples of amphoteric surfactants include amino acid type and betaine type carboxylate types, and typical examples thereof include alkylaminofatty acid sodium and alkylbetaine.

Examples of the nonionic surfactant include an ester type, an ether type and an ester ether type. Specific examples include, for example, glycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, citrate mono (di or tri) stearyl ester, pentaeristol fatty acid ester, trimethylolpropane fatty acid ester, polyglycerin. Fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene glycol aliphatic alcohol ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, N , N-bis (2-hydroxyethylene) aliphatic amine, condensation product of fatty acid and diethanol, block copolymer of polyoxyethylene and polyoxypropylene, polyethylene glycol, polypropylene glycol and the like.
These surfactants may be used alone or in combination of two or more.

In particular, when the lubricant is a phosphoric acid ester-based lubricant, it often contains a nonionic surfactant typified by polyoxyethylene alkyl ether or the like. When the laminate of the present invention is used as a package, this nonionic surfactant bleeds out as itself or hydrolyzed polyethylene glycol and easily migrates to the contents. Therefore, the package contents according to the present invention. The effect of suppressing migration to an object can be obtained particularly remarkably. That is, the polyoxyethylene alkyl ether is usually contained in the lubricant as a surfactant of the above-mentioned lubricant and is contained in the resin composition (b), but it is easy to bleed out and is transferred to the package contents. The problem is big. According to the present invention, the transfer of such polyoxyethylene alkyl ether or polyethylene glycol to the packaged contents can be effectively suppressed.
The content of the polyoxyethylene alkyl ether and / or polyethylene glycol contained in the resin composition (b) contained in the phosphoric acid ester-based lubricant or the like is usually 100 parts by mass of the resin (b-1). It is about 0.1 to 1 part by mass, and often 0.2 to 0.6 part by mass.

Similarly, for example, when the additive (b-2) contained in the resin composition (b) contains an elastomer, a metal carboxylic acid salt such as calcium stearate may be contained in the elastomer as a blocking inhibitor. In this case, the effect of suppressing migration to the packaged contents according to the present invention can be obtained particularly remarkably. That is, the carboxylic acid metal salt is easy to bleed out, and there is a big problem of migration to the package contents. According to the present invention, the transfer of such a carboxylic acid metal salt to the packaged contents can be effectively suppressed.

In addition, the molecular weight of the additive (b-2) also affects the transferability to the packaged contents. For example, when an additive (b-2) having a molecular weight of 1000 or less, particularly 500 or less, is contained, the additive (b-2) tends to bleed out, and there is a big problem of migration to the package contents. According to the present invention, it is possible to effectively suppress the transfer of such a low molecular weight additive (b-2) to the packaged contents.

<Thickness of coating layer>
The thickness of the coating layer is determined by forming the coating layer on only one surface of the base fabric, such as the compounding composition of the resin composition (b) forming the coating layer and the required physical properties such as piercing strength, or both. Although it depends on whether it is formed on the surface of the surface, the thickness per layer is usually preferably 10 to 1000 μm, preferably 30 to 500 μm, and more preferably 50 to 400 μm.
When the thickness of the coating layer is equal to or greater than the above lower limit, when the laminate of the present invention is used as a package, physical properties such as piercing strength due to the formation of the coating layer, weldability between the laminates, and waterproofness When it is not more than the above upper limit, it becomes easy to suppress the occurrence of problems such as the laminated body becoming too hard and the texture being impaired, which is preferable.

<Method of forming the coating layer>
As a coating method for coating one surface or both sides of the base cloth 2 with the coating layer 3 or 3A, 3B,
(1) A method in which a thin film for a coating layer is previously formed from the resin composition (b) by a calendar molding method or the like, and one or both surfaces of the base cloth are pressure-coated with the thin film for the coating layer between rolls (2). ) Calendar molding method of forming a coating layer on the base cloth one side at a time while forming a thin film for the coating layer of the resin composition (b) with a calendar roll (3) A coating layer is formed on one or both sides of the base cloth. Method of melt-extruding and coating the resin composition to be coated (4) A thin film for the coating layer is formed in advance from the resin composition (b) by a calendar molding method or the like, and a thin film for the coating layer is formed on one or both surfaces of the base cloth. Examples include a method of adhesively coating the resin with an adhesive.
When the coating layers 3A and 3B are formed on both sides of the base cloth, they may be formed at the same time or sequentially.

[Barrier layer]
The barrier layer is a layer that becomes the innermost layer when the laminate of the present invention is used as a packaging body, and is a layer (first layer) made of a resin composition (c) containing a resin (c-1). Have. Further, the barrier layer may further have a second layer made of the resin composition (d) containing the resin (d-1), which is overlapped with the first layer. The barrier layer preferably has a three-layer structure in which a second layer 4-2 is laminated on both sides of the first layer 4-1 as shown in FIG. 1 (c).

<First layer>
(Resin (c-1))
The resin (c-1) of the resin composition (c) constituting the first layer 4-1 of the barrier layer includes an α-olefin-vinyl alcohol copolymer, a polyamide resin, a polyester resin, and polyvinylidene chloride. At least one of the based resins is suitable.

● Alpha-olefin-vinyl alcohol copolymer α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene. Examples thereof include 1-decene and 1-dodecene. As the α-olefin-vinyl alcohol copolymer, an ethylene-vinyl alcohol copolymer, a propylene-vinyl alcohol copolymer and the like are preferable, and an ethylene-vinyl alcohol copolymer is more preferable.

The content of the α-olefin unit in the α-olefin-vinyl alcohol copolymer is preferably 20 to 60 mol%, more preferably 25 to 50 mol%, and further preferably 30 to 45 mol%. preferable. When the content of the α-olefin unit is 20 mol% or more, it tends to be easy to maintain good molding processability such as water resistance and extrusion property, while the content of the α-olefin unit is 60 mol% or less. As a result, the bleed-out of the additive can be effectively suppressed, and when the package is formed, the transfer of the additive to the package contents tends to be effectively suppressed, which is preferable.

A preferably used ethylene-vinyl alcohol copolymer has a melt flow rate (MFR) of 1 to 20 g / 10 minutes measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K7210: 2014. Preferably, 1.5 to 10 g / 10 minutes is more preferable, and 2 to 7 g / 10 minutes is even more preferable. When the MFR is 1 g / 10 minutes or more, it tends to be easy to maintain good molding processability such as extrusion property, and when it is 20 g / 10 minutes or less, it tends to be easy to maintain good film formation stability. preferable.

As the α-olefin-vinyl alcohol copolymer, one produced by a conventionally known method can be used, and a commercially available product can be appropriately selected and used. As a commercially available product, for example, "Evar" manufactured by Kuraray Co., Ltd. can be exemplified.

● Polyamide-based resin Polyamide-based resin is a polyamide polymer that has an acid amide group (-CONH-) in its molecule and can be melted by heating. Specifically, various polyamide resins such as lactam polycondensate, diamine compound and dicarboxylic acid compound polycondensate, ω-aminocarboxylic acid polycondensate, or copolymerized polyamide resins and blends thereof. Things etc. can be mentioned.

Examples of lactam, which is a raw material for polycondensation of a polyamide resin, include ε-caprolactam and ω-laurolactam.
Examples of the diamine compound include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, and (2,2,4- or 2,4,4-) trimethylhexamethylenediamine. , 5-Methylnonamethylenediamine, Metaxylylene diamine (MXDA), Paraxylylene diamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) ) Examples thereof include aliphatic amines such as piperazine and aminoethyl piperazine, alicyclic and aromatic amines.
Examples of the dicarboxylic acid compound include adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-. Examples thereof include aliphatic, alicyclic, and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.
Examples of the ω-aminocarboxylic acid include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.

Specific examples of the polyamide-based resin obtained by polycondensing from these raw materials include polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, and polyhexamethylene terephthalamide (polyamide). 6T), polyhexamethylene isophthalamide (polyamide 6I), polymethoxylylene adipamide (polyamide MXD6), polymethoxylylend decamide, polyamide 9T, polyamide 9MT and the like. In the present invention, these polyamide homopolymers or copolymers can be used alone or in the form of a mixture, respectively.

Among the above-mentioned polyamide resins, xylylenedi obtained by polycondensation of polyamide 6, polyamide 66, or α, ω-linear aliphatic dibasic acid and xylylenediamine from the viewpoint of moldability and heat resistance. Amine-based polyamide-based resins are more preferably used. Among these, MX nylon is further preferable from the viewpoint of heat resistance and flame retardancy. When the polyamide resin is a mixture, for example, a mixture with an aliphatic polyamide resin such as polyamide 6 or polyamide 66, the ratio of MX nylon in the polyamide resin is preferably 50% by mass or more. More preferably, it is 80% by mass or more.

The number average molecular weight of the polyamide resin is preferably 6,000 to 40,000, more preferably 10,000 to 20,000. By setting the molecular weight to 6,000 or more, embrittlement of the resin composition (c) can be prevented, and by setting the molecular weight to 40,000 or less, the fluidity of the resin composition (c) during molding is good. This is preferable because the molding process can be facilitated.

The amino-terminal concentration of the polyamide resin is preferably 10 to 140 meq / kg, more preferably 30 to 100 meq / kg from the viewpoint of the molecular weight of the polymer. The terminal carboxyl group concentration of the polyamide resin is preferably 10 to 140 meq / kg, more preferably 30 to 100 meq / kg, from the viewpoint of the molecular weight of the polymer.

● Polyester-based resin The polyester-based resin is not particularly limited as long as it is a thermoplastic polyester-based resin. Usually, it is a thermoplastic polyester-based resin obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, or polycondensation of these compounds, and is either homopolyester or copolyester. May be good.

As the dicarboxylic acid compound constituting the polyester resin, an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably used.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, Biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulphon-4,4'-dicarboxylic acid , Diphenylisopropyridene-4,4'-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p -Terphenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid and the like can be mentioned, and terephthalic acid can be preferably used.

Two or more kinds of these aromatic dicarboxylic acids may be mixed and used. As is well known, dimethyl ester or the like can be used as an ester-forming derivative in the polycondensation reaction in addition to the free acid.
In addition, if it is a small amount, along with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecandioic acid and sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 , 4-Cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids can be mixed and used.

Examples of the dihydroxy compound constituting the polyester resin include aliphatic diols such as ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol and triethylene glycol. Examples thereof include alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.
In addition, aromatic diols such as hydroquinone, resorcin, naphthalene diol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.

In addition to the above-mentioned bifunctional monomers, trifunctional or higher functional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure and molecular weight regulation can be used. Therefore, a small amount of a monofunctional compound such as a fatty acid can be used in combination.

As the polyester-based resin, a resin mainly composed of a polycondensation of a dicarboxylic acid and a diol, that is, a resin in which 50% by mass, preferably 70% by mass or more of the total resin is composed of this polycondensate is used. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.

Of these, polyalkylene terephthalate in which 95 mol% or more of the acid component is terephthalic acid and 95 mol% or more of the alcohol component is an aliphatic diol is preferable. Typical examples are polybutylene terephthalate and polyethylene terephthalate. It is preferable that these are close to homopolyester, that is, 95 mol% or more of the whole resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.

The intrinsic viscosity of the polyester resin is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are more preferable. If an intrinsic viscosity of 0.5 dl / g or more is used, the obtained resin composition (c) tends to have high mechanical strength. Further, when the content is 2 dl / g or less, the fluidity of the resin composition (c) tends to be good and the moldability tends to be improved.
The intrinsic viscosity of the polyester resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The amount of the terminal carboxyl group of the polyester resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. When the amount of terminal carboxyl groups is 50 eq / ton or less, gas generation during melt molding of the resin composition (c) is suppressed. The lower limit of the amount of terminal carboxyl groups is not particularly specified, but is usually 10 eq / ton.

The amount of terminal carboxyl groups in the polyester resin is a value measured by dissolving 0.5 g of the polyester resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent is used. Just do it.

Among them, the polyester-based resin preferably contains a polybutylene terephthalate resin or a polyethylene terephthalate resin, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 90% by mass or more in the polyester-based resin. Most preferably, the total amount of the polyester-based resin is polybutylene terephthalate resin or polyethylene terephthalate resin.

The polybutylene terephthalate resin is a polyester-based resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded, and in addition to the polybutylene terephthalate resin (copolymer), a terephthalic acid unit and 1, It contains a polybutylene terephthalate copolymer containing other copolymerization components other than the 4-butanediol unit, and a mixture of a homopolymer and the copolymer.

The polybutylene terephthalate resin may contain a dicarboxylic acid unit other than terephthalic acid, but specific examples of other dicarboxylic acids include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, and 2,5-naphthalene. Dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis (4,4'-carboxyphenyl) ) Aromatic dicarboxylic acids such as methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyldicarboxylic acid, and Examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dimer acid.

The diol unit may contain other diol units in addition to 1,4-butanediol, but specific examples of the other diol units are aliphatic or alicyclic diols having 2 to 20 carbon atoms. , Bisphenol derivatives and the like. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4'-dicyclohexylhydroxymethane, 4 , 4'-Dicyclohexylhydroxypropane, ethylene oxide-added diol of bisphenol A and the like. Further, triols such as glycerin and trimethylolpropane can also be mentioned.

The polybutylene terephthalate resin is preferably a polybutylene terephthalate homopolymer obtained by polycondensing terephthalic acid and 1,4-butanediol, but the carboxylic acid unit includes one or more dicarboxylic acids other than the above-mentioned terephthalic acid. / Or, as a diol unit, it may be a polybutylene terephthalate copolymer containing one or more diols other than the above 1,4-butanediol. The proportion of terephthalic acid in the dicarboxylic acid unit of the polybutylene terephthalate resin is preferably 70 mol% or more, more preferably 90 mol% or more, from the viewpoint of mechanical properties and heat resistance. Similarly, the proportion of 1,4-butanediol in the diol unit is preferably 70 mol% or more, more preferably 90 mol% or more.

In addition to the above-mentioned bifunctional monomers, trifunctional or higher functional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane for introducing a branched structure and molecular weight regulation can be used. Therefore, a small amount of a monofunctional compound such as a fatty acid can be used in combination.

Polybutylene terephthalate resin is produced by melt-polymerizing a dicarboxylic acid component containing terephthalic acid as a main component or an ester derivative thereof and a diol component containing 1,4-butanediol as a main component by a batch method or a continuous method. can do. Further, the degree of polymerization (or molecular weight) can be increased to a desired value by producing a low molecular weight polybutylene telecturate resin by melt polymerization and then performing solid phase polymerization under a nitrogen stream or under reduced pressure.
The polybutylene terephthalate resin is preferably obtained by a production method in which a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component are continuously melt-polycondensed.

The catalyst used in carrying out the esterification reaction may be a conventionally known catalyst, and examples thereof include titanium compounds, tin compounds, magnesium compounds, and calcium compounds. Of these, particularly suitable ones are titanium compounds. Specific examples of the titanium compound as an esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

The polybutylene terephthalate resin may be a polybutylene terephthalate resin modified by copolymerization, and as a specific preferable copolymer thereof, polyalkylene glycols (particularly polytetramethylene glycol (PTMG)) are used together. Examples thereof include a polymerized polyester ether resin and a dimer acid copolymer polybutylene terephthalate resin, particularly an isophthalic acid copolymer polybutylene terephthalate resin.

When a polyester ether resin copolymerized with polyalkylene glycol is used as the modified polybutylene terephthalate resin, the proportion of the polyalkylene glycol component in the copolymer is preferably 3 to 40% by mass, preferably 5 to 30% by mass. Is more preferable, and 10 to 25% by mass is further preferable. Such a copolymerization ratio tends to have an excellent balance between mechanical properties and heat resistance, which is preferable.
When a dimer acid copolymerized polybutylene terephthalate resin is used as the modified polybutylene terephthalate resin, the ratio of the dimer acid component to the total carboxylic acid component is preferably 0.5 to 30 mol% as the carboxylic acid group. 1 to 20 mol% is more preferable, and 3 to 15 mol% is even more preferable. Such a copolymerization ratio tends to have an excellent balance between mechanical properties, long-term heat resistance, and toughness, which is preferable.
When an isophthalic acid copolymer polybutylene terephthalate resin is used as the modified polybutylene terephthalate resin, the ratio of the isophthalic acid component to the total carboxylic acid components is preferably 1 to 30 mol% as the carboxylic acid group, and 1 to 1 20 mol% is more preferable, and 3 to 15 mol% is even more preferable. Such a copolymerization ratio tends to have an excellent balance of mechanical properties, heat resistance and toughness, which is preferable.
Among the modified polybutylene terephthalate resins, polyester ether resin copolymerized with polytetramethylene glycol and isophthalic acid copolymerized polybutylene terephthalate resin are preferable.

The preferable content of these copolymers is 5 to 50% by mass, more 10 to 40% by mass, and particularly 15 to 30% by mass in the total amount of 100% by mass of the polybutylene terephthalate resin.

The ultimate viscosity ([η]) of the polybutylene terephthalate resin is preferably 0.6 dl / g or more, more preferably 0.7 dl / g or more, and further preferably 0.75 dl / g or more. preferable. When a resin composition having an ultimate viscosity of 0.6 dl / g or more is used, the obtained resin composition (c) tends to have excellent mechanical strength such as impact resistance. The ultimate viscosity is preferably 1.8 dl / g or less, more preferably 1.6 dl / g or less, and even more preferably 1.3 dl / g or less. If it is 1.8 dl / g or less, the fluidity and moldability of the resin composition (c) are good. Here, the ultimate viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The amount of the terminal carboxyl group of the polybutylene terephthalate resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. When the amount of terminal carboxyl groups is 50 eq / ton or less, gas generation during melt molding of the resin composition (c) is suppressed. The lower limit of the amount of the terminal carboxyl group is not particularly determined, but is usually 10 eq / ton in consideration of the productivity of producing the polybutylene terephthalate resin.

The amount of terminal carboxyl groups in the polybutylene terephthalate resin is obtained by dissolving 0.5 g of the polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. The value given. As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent can be used. Just do it.

The polyethylene terephthalate resin is a resin whose main constituent unit is an oxyethylene oxyterephthaloyl unit composed of terephthalic acid and ethylene glycol with respect to all constituent repeating units, and contains a constituent repeating unit other than the oxyethylene oxyterephthaloyl unit. May be good. The polyethylene terephthalate resin is produced by using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as a main raw material, but other acid components and / or other glycol components may be used together as a raw material.

Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-. Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

Examples of the diol component other than ethylene glycol include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, and cyclohexane. Examples thereof include alicyclic glycols such as dimethanol, aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S, and the like.

Further, the polyethylene terephthalate resin may be a branched component, such as a trifunctional acid such as tricarbaryl acid, trimeric acid, trimellitic acid or an acid having a tetrafunctional ester form performance such as pyromellitic acid, or a glycerin, trimethyl propane, Copolymerized with 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.3 mol% or less of an alcohol having a trifunctional or tetrafunctional ester-forming ability such as pentaerythrit. It may be.

The intrinsic viscosity of the polyethylene terephthalate resin may be appropriately selected and determined, but is usually 0.5 to 2 dl / g, particularly 0.6 to 1.5 dl / g, particularly 0.7 to 1.0 dl / g. It is preferable to have. By setting the intrinsic viscosity to 0.5 dl / g or more, particularly 0.7 dl / g or more, the mechanical properties, moldability, retention heat stability, chemical resistance, and moisture heat resistance of the resin composition (c) can be improved. It tends to improve and is preferable. On the contrary, when the intrinsic viscosity is 2 dl / g or less, particularly less than 1.0 dl / g, the fluidity of the resin composition (c) tends to be improved, which is preferable.
The intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The amount of the terminal carboxyl group of the polyethylene terephthalate resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. .. When the amount of terminal carboxyl groups is 50 eq / ton or less, gas generation during melt molding of the resin composition (c) is suppressed. The lower limit of the amount of the terminal carboxyl group is not particularly determined, but is usually 10 eq / ton in consideration of the productivity of manufacturing the polyethylene terephthalate resin.

The terminal carboxyl group concentration of the polyethylene terephthalate resin was obtained by dissolving 0.5 g of the polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. Is. As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method of adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, the depressurization method, and the method of reacting the terminal blocking agent can be used. Just do it.

● Polyvinylidene chloride-based resin The polyvinylidene chloride-based resin is not particularly limited as long as it contains a vinylidene chloride repeating unit, and in addition to the copolymer of vinylidene chloride, the vinylidene chloride repeating unit includes, for example, vinyl chloride, methyl acrylate, and the like. Acrylic acid esters such as butyl acrylate; methacrylic acid esters such as methyl methacrylate and butyl methacrylate; acrylonitrile; even if one or more monomers copolymerizable with vinylidene chloride such as vinyl acetate are copolymerized. Good.

When the polyvinylidene chloride-based resin is a copolymer resin, the ratio of vinylidene chloride repeating units is not particularly limited, but those containing 70 to 95% by mass of vinylidene chloride repeating units are preferable, and those containing 72 to 93% by mass are more preferable. It is preferable that it contains 75 to 92% by mass, more preferably 80 to 90% by mass, and particularly preferably 80 to 90% by mass. When the repeating unit of vinylidene chloride is 70% by mass or more, the glass transition temperature of the vinylidene chloride resin is low, the laminate tends to be soft, and tearing of the flexible container can be reduced even when used in a low temperature environment such as winter, which is preferable. On the other hand, when the repeating unit of vinylidene chloride is 95% by mass or less, a significant increase in crystallinity can be suppressed and deterioration of molding processability of the laminated body can be suppressed, which is preferable.

The ratio of the vinylidene chloride repeating unit of the polyvinylidene chloride resin can be measured by using a highly decomposed proton nuclear magnetic resonance measuring device. The ratio of vinylidene chloride repeat units is calculated using a unique chemical shift relative to tetramethylsilane in the resulting spectrum.
The polyvinylidene chloride resin is suitable for high frequency welding. Each of the above resins other than the polyvinylidene chloride resin can be applied to both high frequency welding and dryer welding.

Even if the resin composition (c) contains only one of the above-mentioned α-olefin-vinyl alcohol copolymer, polyamide-based resin, polyester-based resin, and polyvinylidene chloride-based resin as the resin (c-1). Well, it may contain two or more kinds.

The resin composition (c) contains the above-mentioned α-olefin-vinyl alcohol copolymer, polyamide resin, polyester resin, and polyvinylidene chloride as the resin (c-1) as long as the effects of the present invention are not impaired. Other resins other than the vinylidene resin may be contained, but the content in that case is preferably 5% by mass or less, more preferably 3% by mass or less in the resin (c-1). It is more preferably 1% by mass or less. From the viewpoint of the transferability of the additive, it is preferable that the resin (c-1) does not contain a resin other than the α-olefin-vinyl alcohol copolymer, the polyamide resin, the polyester resin and the polyvinylidene chloride resin.

(Other components of the resin composition (c))
In addition to the above resin (c-1), the resin composition (c) contains a heat stabilizer, a weather-resistant stabilizer, an antioxidant, and an antistatic agent to the extent normally used, as long as the effects of the present invention are not impaired. It may contain agents, nucleating agents, fillers, pigments, dyes, flame retardants, antiblocking agents and the like. However, it is preferable that the resin composition (c) does not contain the above-mentioned additive (b-2).

(Thickness of the first layer)
The thickness of the first layer 4-1 made of the resin composition (c) is 1 μm or more, particularly 3 μm or more, particularly 4 μm or more, particularly 5 μm or more, and 100 μm or less, particularly 50 μm or less, particularly 30 μm or less, especially 20 μm or less. Is preferable.
If the thickness of the first layer is too thick, it becomes hard, and there are disadvantages such as high cost. If it is too thin, the original function of the barrier layer that prevents the transfer of the additive bleeding out from the coating layer to the package contents is sufficient. It may not be able to be exhibited, and there are disadvantages such as being unable to withstand the load of the welding process and easily causing pinholes in the first layer.

<Second layer>
The preferred example of the resin (d-1) in the resin composition (d) constituting the second layer 4-2 of the barrier layer is the same as the preferred example of the resin (b-1).
In the present invention, it is preferable that the resin (d-1) and the resin (b-1) have an affinity.

The resin having affinity is a resin having the same skeleton, preferably a resin having a difference in SP value of 3 or less, more preferably 2 or less, which will be described later. The resin (d-1) has, for example, the same α-olefin skeleton, specifically, the same resin as the resin (b-1), polypropylene in which ethylene-propylene rubber such as EPR or EPDM is finely dispersed. Examples thereof include polyolefin-based elastomers, rubbers having an ethylene skeleton (EPR, CEBC (block copolymers of polyethylene segments and ethylene / butene copolymer rubber segments), SEBS, etc.).

(Other components of the resin composition (d))
In addition to the above resin (d-1), the resin composition (d) contains a heat stabilizer, a weather-resistant stabilizer, an antioxidant, and an antistatic agent to the extent normally used, as long as the effects of the present invention are not impaired. , Nucleating agent, filler, pigment, dye, flame retardant, antiblocking agent and the like may be contained. However, it is preferable that the resin composition (d) does not contain the above-mentioned additive (b-2).

(Thickness of the second layer)
The thickness of the second layer 4-2 made of the resin composition (d) is 3 μm or more, particularly 5 μm or more, particularly 10 μm or more, particularly 15 μm or more, and 500 μm or less, particularly 300 μm or less, especially 150 μm or less, especially 100 μm or less. Is preferable.
If the thickness of the second layer is too thick, the obtained laminate tends to be hard and the texture is likely to be impaired, and if it is too thin, the weldability in forming a flexible container tends to decrease and the bonding strength tends to decrease.

<Suitable barrier layer>
In the present invention, the barrier layer 4'of the laminated structure shown in FIG. 1 (c) is suitable as the barrier layer, and specifically, the ethylene-vinyl alcohol copolymer resin (EVOH) is used as the resin (c-1). A barrier layer having a three-layer laminated structure in which a second layer 4-2 made of a polyolefin resin as a resin (d-1) is provided on both sides of the first layer 4-1 made of the resin (d-1) is preferable. When a film in which the first layer and the second layer are bonded via an adhesive layer is used, this film is a second layer (surface layer) / adhesive layer / first layer / adhesive layer / second. It has a layer structure of a layer (surface layer). The adhesive may be any adhesive as long as it can bond the first layer and the second layer to each other. For example, an acid-modified polyolefin resin or an acid-modified polyolefin resin and EVOH are melt-mixed. be able to.

<Thickness of barrier layer>
The thickness of the barrier layer consisting of only the first layer, or consisting of the first layer and the second layer, preferably having the first layer of one layer interposed between the second layers of the two layers. Is usually 3 μm or more, preferably 10 μm or more, particularly 20 μm or more, particularly 33 μm or more, and 300 μm or less, particularly 200 μm or less, particularly 100 μm or less. If the thickness of the barrier layer is less than 3 μm, the original function of the barrier layer that prevents the transfer of the bleed-out additive from the coating layer to the package contents may not be fully exhibited, and if it exceeds 300 μm, it may not be fully exhibited. , The laminated body may become hard, the texture may be impaired, or the cost may increase, which is not preferable.

<Method of forming barrier layer>
The method for forming the barrier layer is not particularly limited, and is described above except that the resin composition (c) or the resin composition (c) and the resin composition (d) are used instead of the resin composition (b). It can be formed on the coating layer of the base cloth on which the coating layer is formed in advance in the same manner as the method for forming the coating layer of the above, but in particular, a separately formed film for forming a barrier layer can be formed on the base cloth. A method of welding to the coating layer is simple and preferable.
In this case, for example, when forming a layer having a three-layer laminated structure of a second layer / a first layer / a second layer as a barrier layer, as described above, the second layer (surface layer) / adhesive layer / A laminated film having a layer structure of a first layer / an adhesive layer / a second layer (surface layer) may be used and welded onto the coating layer.

<Relationship between SP values of resin (b-1), (c-1) and additive (b-2)>
In one aspect of the laminate of the present invention, the SP value (SP (b-1)) of the resin (b-1), the SP value (SP (b-2)) of the additive (b-2), and The SP value (SP (c-1)) of the resin (c-1) satisfies the following relational expression.
| SP (c-1) -SP (b-2) |> | SP (b-1) -SP (b-2) |

Further, in the present invention, it is preferable that the difference between the SP value of the resin (c-1) and the SP value of the additive is large. As a result, the resin (c-1) effectively suppresses the migration and bleeding of the additive (b-2).
In particular, | SP (c-1) -SP (b-2) | is preferably 1 or more larger than | SP (b-1) -SP (b-2) |, and more preferably 2 or more. It is more preferably 3 or more, and particularly preferably 3.5 or more. There is no particular limitation on the upper limit of the difference between | SP (c-1) -SP (b-2) | and | SP (b-1) -SP (b-2) |, but due to material selection restrictions, there is no particular limitation. It is usually 10 or less, preferably 8 or less.
Here, the SP value of the additive (b-2) is the SP value of the additive (b-2) whose bleeding is desired to be suppressed, and is, for example, polyoxyethylene alkyl ether or polyethylene glycol which is a decomposition product thereof. SP value of.

The SP value can be obtained by substituting the evaporation energy (Δei) and molar volume (Δvi) of atoms and atomic groups constituting the resin or additive into the following Fedors equation.
SP value (cal / cm ³ ) ^0.5 = (ΣΔei / ΣΔvi) ^0.5
Here, the constants proposed by Fedors can be used for Δei and Δvi.

[Flexible container]
The flexible container of the present invention is manufactured from the laminate of the present invention.
In order to produce a flexible container from the laminate of the present invention, the laminate of the present invention is cut into each size constituting each part of the flexible container, welded by a high frequency welder or a dryer, and JIS Z1651: 2008. A flexible container with a structure as specified in.

For example, when a flexible container is made into a bag using the laminates 1A, 1B or 1C shown in FIGS. 1A to 1C, a sheet having an appropriate size is cut out from the laminate 1A, 1B or 1C, and the edge of the sheet is cut out. The edges are overlapped and joined. FIG. 2 is a schematic cross-sectional view of a joint portion between laminated bodies (sheets). In FIG. 2, both end edges of the laminated body 1C are overlapped and joined by high-frequency welding, dryer welding, or the like. As shown in FIG. 2, the second layer 4-2 of the barrier layer 4'of the one (left side) laminate 1C is welded to the coating layer 3B of the other (right side) laminate 1C.
In the present invention, the affinity between the resin (d-1) in the resin composition (d) of the second layer 4-2 and the resin (b-1) in the resin composition of the coating layer 3B is high. preferable. As a result, in the joint portion, the joint strength between the second layer 4-2 and the coating layer 3B becomes high, and the bond strength between the laminated bodies 1C becomes high.

The flexible container is made so that the barrier layer 4 or 4'is the innermost layer, that is, forms the inner surface of the flexible container. This prevents the additives from bleeding from the coating layer 3 or 3A, 3B and contaminating the contents of the flexible container.
The container body is provided with an inlet, an outlet, a hanging metal fitting, a hanging belt, a hanging rope, and the like.

The flexible container having a barrier layer thus produced is suitably used for transporting and storing salts (particularly chloride salts, especially salt).

Next, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following description examples as long as the gist of the present invention is not exceeded.
The base fabric used in the following examples and comparative examples is a plain woven fabric in which 750 denier polyester fibers are driven in at 20 × 20 fibers / inch, and the layer structure of the produced laminate is as shown in FIG. 1 (c). is there.
The laminated film 4'for the barrier layer includes a second layer 4-2 (thickness 25 μm) made of high-density polyethylene as the resin (d-1) and ethylene-vinyl alcohol as the resin (c-1). With the first layer 4-1 (thickness 5 μm) made of a polymer (EVOH, ethylene unit content 38 mol%, 230 ° C., MFR 4.0 g / 10 min at a load of 21.18 N (JIS K7210: 2014)). , A coextruded non-stretched laminated film having three layers with a second layer 4-2 (thickness 25 μm) made of high-density polyethylene was used.

[Example 1]
100 parts by mass of EVA below as resin (b-1), 25 parts by mass of EPDM below, 12.5 parts by mass of silica gel, 2 parts by mass of lubricant and 0.2 parts by mass of hindered phenol-based antioxidant as additive (b-2). , 4 parts by mass of the pigment was kneaded with a pressure kneader and a Banbury mixer at a temperature of 160 ° C. to produce a resin composition (b) for a coating layer.
The obtained resin composition (b) is supplied to an inverted L-shaped calender roll machine, and while rolling using four rolls, a coating layer 3B having a thickness of 250 μm is laminated on one surface of a polyester plain weave base cloth. did. Next, a coating layer 3A having a thickness of 250 μm is laminated on the other surface of the polyester plain weave base fabric by the same operation, and the above-mentioned laminated film for the barrier layer is further pressure-welded onto the coating layer 3A. The barrier layer 4'with a thickness of 55 μm was formed by laminating and integrating.
EVA: Ethylene-vinyl acetate copolymer having a vinyl acetate content of 20% by mass, conforming to JIS K7210, and having an MFR of 2.5 g / 10 min measured under the conditions of a temperature of 190 ° C. and a load of 21.18 N (“EVA resin”). It is described as.)
EPDM: 5-ethylidene-2-norbornene content 4.5 mol%, ethylene content 67 mol%, Mooney viscosity 58 (ML (1 + 4) 125 ° C.), containing calcium stearate.
Lubricants: Organic phosphate ester lubricants, polyoxyethylene alkyl ether content 15% by mass

The laminate produced in this manner is cut out to a predetermined size, the edge portions are overlapped over a width of 50 mm so that the barrier layer 4'consists the inner surface of the flexible container, and welded by a high frequency welder to test a volume of 50 L. I made a flexible container for.
50 kg of salt was placed in this flexible container, covered, and stored in a warehouse for 120 days from June to September.
Then, the whole amount of salt was taken out and dissolved in 83 L of water (25 ° C.) by stirring with a mixer for 30 seconds. The dissolution state at this time and the state of the liquid after dissolution were visually observed.
As a result, bubbles were generated during stirring, but as shown in Table 1, it was confirmed that the bubbles were quickly extinguished.
In addition, 150 ml was collected from the above-mentioned saline solution, evaporated to dryness, the precipitate was extracted with ether, and the extract was subjected to NMR and IR analysis. Not detected.

[Comparative Example 1]
In Example 1, a coating layer 3C made of the resin composition (b) was further laminated on the barrier layer 4', and the thickness of each layer was 250 μm for the coating layer 3B, 150 μm for the coating layer 3A, and 55 μm for the barrier layer 4'. A flexible container was produced so that the innermost layer was the coating layer 3C in the same manner as in Example 1 except that the coating layer 3C was set to 100 μm. When the same salt storage and dissolution test as in Example 1 was carried out using this flexible container, it was found that yellow bubbles were formed when the salt was dissolved, and these bubbles remained without being defoamed for 15 minutes or more. It was. In addition, yellow precipitates were also observed.
150 ml of a salt solution was evaporated to dryness, the precipitate was extracted with ether, and this ether extract was subjected to NMR and IR analysis. As a result, polyoxy was used as a component other than the higher fatty acid ester contained in the salt as a defoaming agent. Ethylene alkyl ether was detected.
In addition, since a yellow precipitate adhered to the inner wall of the container containing the salt, it was found to be calcium stearate as a result of analysis by an IR and X-ray microanalyzer.
From these results, it was inferred that in Comparative Example 1, bleeding of the additive was generated from the coating layer 3C and the like.

[Comparative Example 2]
In Example 1, 80 parts by mass of EVA and 20 parts by mass of low-density polyethylene (PE) were used as the resin (b-1) of the coating layers 3A and 3B without forming the barrier layer, and the formulations shown in Table 1 were used. A flexible container was manufactured using a laminate having the same configuration as that of Example 1 except for these. When the same salt storage and dissolution test as in Example 1 was carried out using this flexible container, it was found that bubbles were formed when the salt was dissolved, and the bubbles remained without being defoamed for 15 minutes or more.
150 ml of this salt aqueous solution was evaporated to dryness, the precipitate was extracted with ether, and the precipitate was subjected to NMR and IR analysis. As a result, polyoxy was used as a component other than the higher fatty acid ester contained in the salt as a defoaming agent. Ethylene alkyl ether was detected.

The SP value of the ethylene-vinyl alcohol copolymer of the resin (c-1) used in Example 1 is 14.15, and the SP value of the ethylene-vinyl acetate copolymer of the resin (b-1) is 14. Since it is 9.95 and the SP value of the polyoxyethylene alkyl ether is 9.54, the polyoxyethylene alkyl ether has the above-mentioned relational expression: | SP (c-1) -SP (b-2) |>| SP (b-1) -SP (b-2) | is satisfied.

1A ~ 1C Laminated body 2 Base cloth 3,3A, 3B Coating layer 4,4'Barrier layer 4-1 First layer 4-2 Second layer

Claims (9)

With the base cloth
A coating layer composed of a resin composition (b) containing a resin (b-1) and an additive (b-2), which covers at least one surface of the base fabric, and a coating layer.
A barrier layer having a first layer made of the resin composition (c) containing the resin (c-1), and a barrier layer.
A laminate in which the coating layer is interposed between the barrier layer and the base fabric.
The resin (b-1) is an ethylene-vinyl acetate copolymer, and the resin (b-1) is an ethylene-vinyl acetate copolymer.
The additive (b-2) is a polyoxyethylene alkyl ether, and the additive (b-2) is a polyoxyethylene alkyl ether.
The resin (c-1) contains as a main component any one resin selected from the group consisting of an α-olefin-vinyl alcohol copolymer, a polyamide resin, a polyester resin, and a polyvinylidene chloride resin.
The SP value (SP (b-1)) of the resin (b-1), the SP value (SP (b-2)) of the additive (b-2), and the SP value (SP (c-1)) of the resin (c-1). SP (c-1)) satisfies the following relational expression,
A laminate characterized by being used for a packaging body having the barrier layer as the innermost layer.
| SP (c-1) -SP (b-2) |> | SP (b-1) -SP (b-2) |
Here, the SP value is the SP value (cal / cm ³ ) ^0.5 obtained by substituting into the Fedors equation. Oite to claim 1, wherein the barrier layer includes a first layer, overlaps at least one surface of the first layer, the second consisting of the resin (d-1) a resin composition comprising (d) is A laminate characterized by having a layer of. In claim 2 , the resin (d-1 ) is selected from the group consisting of an α-olefin-vinyl acetate copolymer, a copolymer of an α-olefin and an unsaturated carboxylic acid and / or a derivative thereof, and a polyolefin-based resin. A laminate characterized by containing any one of the resins as a main component. The laminate according to any one of claims 1 to 3 , wherein the thickness of the first layer is 1 to 100 μm. The laminate according to any one of claims 2 to 4 , wherein the thickness of the second layer is 3 to 150 μm. The laminated body according to any one of claims 1 to 5 , wherein the thickness of the barrier layer is 10 to 300 μm. A flexible container made of the laminate according to any one of claims 1 to 6. A packaging body having the flexible container of claim 7 and the salt filled in the flexible container. With the base cloth
A coating layer composed of a resin composition (b) containing a resin (b-1) and an additive (b-2), which covers at least one surface of the base fabric, and a coating layer.
A barrier layer having a first layer made of the resin composition (c) containing the resin (c-1), and a barrier layer.
A method of suppressing bleeding of an additive (b-2) from a flexible container formed by bag-making a laminate in which the coating layer is interposed between the barrier layer and the base cloth.
The resin (b-1) is an ethylene-vinyl acetate copolymer, and the resin (b-1) is an ethylene-vinyl acetate copolymer.
The additive (b-2) is a polyoxyethylene alkyl ether, and the additive (b-2) is a polyoxyethylene alkyl ether.
The resin (c-1) contains as a main component any one resin selected from the group consisting of an α-olefin-vinyl alcohol copolymer, a polyamide resin, a polyester resin, and a polyvinylidene chloride resin. A method for suppressing bleeding, wherein the barrier layer is the innermost layer of the flexible container.

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