JP6067193B2 - Tube laminate and tube container - Google Patents

Description

  The present invention relates to a laminate or the like for forming a tube container.

  Conventionally, in order to improve the visibility or appearance of a tube container, it is known to incorporate a base material and an ink layer in the tube body. In general, a polyethylene terephthalate (PET) film is used as a substrate in consideration of dimensional stability and ease of printing. In addition, the ink layer formed on the PET film and the layer on the front side of the ink layer are bonded together via an adhesive.

  Furthermore, on the front side of the body portion of the tube, functionality such as antistatic property, matte property, light resistance, light absorption property, and blocking resistance may be required.

  Specifically, in Patent Document 1, from the front side to the back side, a low density polyethylene (LDPE) film containing an antistatic agent / polyethylene (PE) adhesive layer / LDPE film / PE adhesive layer / aluminum oxide vapor deposited PET film / A laminate for a tube having a layer configuration of: / ink layer-PET film / milk white LDPE film / linear low density polyethylene (LLDPE) layer has been proposed. The symbol “/” represents an extrusion laminate, and the symbol “//” represents a dry laminate adhesive.

  In Patent Document 1, an aluminum oxide-deposited PET film and a PET film provided with an ink layer are dry-laminated through a two-component polyester adhesive (paragraphs [0025] and [0031] in Patent Document 1). The outermost layer of the tube laminate is formed of an LDPE film kneaded with an antistatic agent (paragraphs [0015] and [0017] in Patent Document 1). Therefore, as shown in FIG. 1 of the present application, the tube laminate (1) described in Patent Document 1 includes a layer structure of PET film // ink layer / PET film from the front side to the back side, In addition, antistatic properties are imparted to the front side.

  Moreover, in patent document 2, the extrusion laminated body (9) which has a layer structure as shown to Fig.2 (a) of this application, and the dry laminate body which has a layer structure as shown in FIG.2 (b) of this application (10) is described. Further, a PE molten resin layer is used as an adhesive layer to be extrusion laminated, and a urethane-based adhesive is used as an adhesive for dry lamination.

  In Patent Document 2, since the PET film is a surface layer, and the printed surface of the PET film and the sealant film are laminated via a laminating adhesive, the obtained extruded laminate has a surface layer / adhesive layer / ink layer / On the other hand, the obtained dry laminate has a layer structure of surface layer // ink layer / sealant layer.

  Furthermore, Patent Document 2 describes that a practical level is reached when the laminate strength between the surface layer and the ink layer is 1.0 N / 15 mm or more.

JP 2001-38861 A JP 2012-136582 A

  The tube laminate described in Patent Document 1 has a problem that, when stress is applied at the time of forming the shoulder portion of the tube, the ink layer is agglomerated and peeled off, and the PET film on the front side is rolled. Moreover, since this laminated body for tubes always requires a dry laminate of an aluminum oxide-deposited PET film and a PET film provided with an ink layer, there is still room for studying handling properties and economy.

  Patent Document 2 does not describe the use of the tube container. Even if a tube container is formed using the packaging material described in Patent Document 2, if the laminate strength between the surface layer and the ink layer is 1.0 N / 15 mm, the stress generated during the molding of the shoulder portion of the tube Since it cannot withstand, the surface layer is expected to peel off.

  In Patent Document 2, the functionality on the front side of the extruded laminate or the dry laminate is not specifically studied.

  Therefore, an object of the present invention is to provide a tube laminate that solves at least one of the above-described problems, and a tube container using the same.

As a result of intensive studies in view of the above-mentioned problems, the present inventors have completed the following invention.
[1] A laminate for a tube in which a functional layer, a functional layer support layer, an adhesive layer, an ink layer, and a substrate laminate are laminated in this order from the front side to the back side.
[2] The laminated body for a tube according to [1], wherein the functional layer is formed of an extruded resin containing a functional material.
[3] The laminated body for a tube according to [1], wherein the functional layer is formed by subjecting an extruded resin not containing a functional material or an extruded resin containing a functional material to a functional treatment.
[4] The laminated body for a tube according to [3], wherein the functionality imparting treatment is roughening.
[5] The laminate for a tube according to any one of [2] to [4], wherein the functional material is an antistatic agent and / or a matting agent.
[6] The adhesive layer is formed of a two-component adhesive of a polyol having an ester portion and a polyisocyanate, the ink layer is formed of UV ink, and The laminated body for tubes according to any one of [1] to [5], wherein a surface in contact with the ink layer is formed of polyolefin.
[7] The laminate for a tube according to any one of [1] to [6], wherein an initial laminate strength between the functional layer support layer and the ink layer is 3.0 N / 15 mm or more.
[8] The tube laminate according to any one of [1] to [7], wherein the ink layer is disposed at a position corresponding to a seal portion on a surface of the substrate laminate.
[9] The tube laminate according to any one of [1] to [8], wherein the ink layer is disposed on the entire surface of the substrate laminate.
[10]
The functional layer includes a polyolefin, and the adhesive layer is formed of a two-component adhesive of a polyol having an ester portion and a polyisocyanate, and the surface of the substrate laminate that is in contact with the ink layer is: Any one of [1] to [9], wherein the ink layer is formed of a polyolefin, and is formed of UV ink, and is disposed at a position corresponding to a seal portion on the surface of the substrate laminate. The laminated body for tubes of Claim 1.
[11] A tube container having a body portion formed of the laminated body for a tube according to any one of [1] to [10].

  According to the present invention, the functional layer, the functional layer support layer, and the adhesive layer are laminated in this order from the front side to the back side, so that the functionality by the migration of the functional material from the functional layer to the adhesive layer is achieved. Loss or decrease in laminate strength can be prevented, and functionality can be imparted to the front side of the tube laminate.

FIG. 1 is a schematic cross-sectional view of a tube laminate described in Patent Document 1. As shown in FIG. FIG. 2A is a schematic cross-sectional view of the extruded laminate described in Patent Document 2, and FIG. 2B is a schematic cross-sectional view of the dry laminate described in Patent Document 2. FIG. 3 is a schematic cross-sectional view of a tube laminate according to an embodiment of the present invention. FIG. 4 is a schematic view of an extrusion line for forming a tube laminate according to an embodiment of the present invention.

<Constituent elements of tube laminate>
The laminated body for tubes is a laminated body in which a functional layer, a functional layer support layer, an adhesive layer, an ink layer, and a base material laminated body are laminated in this order from the front side to the back side.

  The tube laminate has a front side that faces outward when the tube is formed, and a back side that faces inward or faces the contents when the tube is formed. The exposed portion of the functional layer can form the front side. The exposed portion of the substrate laminate can form the back side.

  In FIG. 3, an example of the typical cross section of the laminated body for tubes which concerns on embodiment of this invention is shown. As shown in FIG. 3, the functional layer (15), the functional layer support layer (16), the adhesive layer (4), the ink layer (5), and the base material laminate (17) are formed into a laminate for a tube (14). ) From the front side (2) to the back side (3). The substrate laminate (17) may include a polyolefin surface (17a) and a portion (17b) other than the polyolefin surface.

  Hereinafter, the “functional layer”, “functional layer support layer”, “adhesive layer”, “ink layer”, and “base material laminate”, which are components of the laminate for a tube, will be described.

<Functional layer>
The functional layer is a layer for imparting functionality to the front side of the tube laminate and is formed by extruding a resin containing a functional material, or an extruded resin or functionality that does not contain a functional material. It is formed by subjecting an extruded resin containing a material to a functional treatment. The functional layer may be used as a surface layer.

  As FIG. 3 shows, a functional layer (15) forms the front side (2) of the laminated body (14) for tubes.

  Examples of the functionality imparted to the front side of the tube laminate include antistatic properties, matte properties, light resistance, abrasion resistance, lubricity, and blocking resistance. Among these, antistatic properties and / or matte properties are preferable. For example, when antistatic properties are provided, static electricity is suppressed during packing, transportation, or display, and dust attracted to the tube container is reduced, so that the appearance of the tube container can be ensured. Further, when matte properties are given, the tube container can have a high-grade appearance such as a matte feeling. Furthermore, when antistatic properties and matte properties are imparted, it is possible to achieve both aesthetics and matte feeling in the tube container.

  For example, in order to form a functional layer, a resin that contains a functional material in advance is extruded into the functional layer support layer, or a resin that does not contain a functional material is extruded into the functional layer support layer, and then the functional application treatment is performed. Functionality may be imparted to the extruded resin layer. Further, by extruding a resin containing a functional material in advance to the functional layer support layer to form the functional layer, by further subjecting the functional layer to a functionality imparting treatment, the functionality of the functional layer is improved, Or you may provide another functionality to a functional layer.

  The extruded resin in the functional layer can be selected according to heat sealability for forming the tube, dispersibility of the functional material, suppression of excessive bleed out of the functional material, and the like. Examples of the extruded resin include polyolefins such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and polypropylene (PP); and ethylene-vinyl acetate. Mention may be made of copolymers.

  Examples of the functional material include an antistatic agent, a matting agent, a lubricant, and an antiblocking agent. Among these, an antistatic agent and / or a matting agent are preferable.

  Examples of the antistatic agent include anionic surfactants such as carboxylates and sulfonates; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols and polyhydric alcohols. Surfactant; Conductive fine powder such as carbon black and metal powder; Polymer type antistatic agent such as polyether-polyolefin block copolymer, polythiophene and ionomer; Betaine and the like. The low-molecular-type antistatic agent is easy to migrate and has a fast effect, but may easily overbleed, cause a setback or adhesion failure, and may be attracted to the adhesive during dry lamination, resulting in poor performance. Therefore, considering not only the fast-acting properties of low-molecular antistatic agents, but also the possibility of poor adhesion or poor performance, materials for low-molecular antistatic agents are selected and processing conditions for low-molecular antistatic agents Or it is preferable to determine storage conditions.

  Examples of the functionality imparting process include roughening. An embossing process etc. are mentioned as a process for roughening.

  In FIG. 4, the schematic of the extrusion line which replaced the cooling roll with the roughening apparatus is shown. The extrusion resin (22) can be roughened by the roughening device (23) to impart matte properties to the extrusion resin (22). The roughening device (23) may be, for example, a mat roll or a semi mat roll.

<Functional layer support layer>
The functional layer support layer is disposed between the functional layer and the adhesive layer.

  As shown in FIG. 3, the functional layer support layer (16) is closer to the back side (3) of the tube laminate (14) than the functional layer (15).

  The functional layer support layer may be a single layer or a laminate in which a plurality of layers are laminated, and may include a plurality of the same kind of layers. The functional layer support layer may comprise at least one film and optionally a printed layer, a foil stamping layer, an anchor coat layer, an adhesive layer, a barrier layer, a sealant layer, and combinations thereof.

  The functional layer support layer preferably includes a polyethylene terephthalate (PET) film, a stretched polypropylene (OPP) film, and the like in order to improve the waist of the tube laminate.

  The influence of the functional layer on the adhesive layer that bonds the functional layer support layer and the ink layer will be described below.

[Influence of functional layer on adhesive layer]
In order to improve the laminate strength between the functional layer support layer and the ink layer, the influence of the functional layer on the adhesive layer that bonds the functional layer support layer and the ink layer is suppressed, and the adhesive strength of the adhesive layer is secured. It is preferable.

  As a means for suppressing the influence of the functional layer on the adhesive layer, for example, a means for imparting functionality by applying physical processing such as roughening treatment to the extruded resin without using a functional material, or bonding the functional layer Means for disposing away from the agent layer or means for selecting a functional material to be mixed with the extruded resin may be used.

  In the case of means for imparting functionality by subjecting extruded resin to physical processing such as roughening treatment without using functional material, the functional layer support layer and the ink layer are provided on the functional material provided on the functional layer support layer. Since a material that lowers the adhesive strength is not used for the adhesive layer that bonds the functional layer, there is no influence of the functional layer on the adhesive layer that bonds the functional layer support layer and the ink layer.

  Specifically, as shown in FIG. 4, a functional layer can be formed on the functional layer support layer without using a functional material by using a roughening device as the functionality imparting device.

  Examples of means for disposing the functional layer away from the adhesive layer include adjustment of the thickness of the functional layer support layer and multilayering of the functional layer support layer. By such means, the functional layer and the adhesive layer can be prevented from contacting each other.

  Furthermore, in order to suppress migration of the functional material to the adhesive layer, it is also preferable to incorporate a barrier layer in the functional layer support layer and provide a barrier layer between the functional layer and the adhesive layer. For example, a film obtained by coextrusion laminating HDPE or the like having a relatively high density can be incorporated into the functional layer support layer.

  Examples of means for selecting a functional material to be mixed with the extruded resin include use of a functional material that does not migrate. The functional material having a low tendency to migrate is preferably a polymer material having functionality.

  For example, as the antistatic agent that does not migrate, a polymer type antistatic agent is preferable, and an ionomer is more preferable. Ionomer causes a dielectric relaxation phenomenon that relaxes the surface charge of the base material by ionic conduction of ionic groups present in the molecular chain, so it does not migrate and has a stable antistatic function compared to low molecular weight antistatic agents. Is expressed.

  The polymer portion of the ionomer is preferably a copolymer of olefin and acrylic acid or methacrylic acid, and the ionomer cationic species is preferably zinc ion, potassium ion or the like.

<Adhesive layer>
The adhesive layer is a layer for bonding the functional layer support layer and the ink layer. The adhesive layer may be formed of an adhesive known in the field of packaging materials or tube containers, but is preferably formed of a two-component adhesive.

The application amount of the two-component adhesive is preferably about 3 g / m ² or more in order to secure adhesive strength and prevent peeling of the laminate during tubing and to obtain predetermined content resistance. On the other hand, the application amount of the two-component adhesive is preferably about 5 g / m ² or less in order to prevent generation of bad odor due to poor drying and residual solvent in consideration of economics and upper limit of adhesive strength. .

  The two-component adhesive is preferably a combination of a polyol having an ester moiety and a polyisocyanate. In such an embodiment, the adhesive layer strongly bonds the surface layer and the UV ink layer to improve the laminate strength, thereby preventing the surface layer from being lifted by the stress generated strongly in the seal portion of the tube. Can do. Thereby, a print pattern can be formed even on the seam portion of the tube, and in particular, a continuous print pattern can be formed on the entire surface of the base material laminate to ensure the design of the tube container. The “polyol having an ester moiety” and “polyisocyanate” will be described below.

[Polyol having an ester moiety]
The polyol having an ester moiety has heat resistance, strong initial tack, and excellent content resistance. Note that the initial tack is a property of exhibiting adhesive force by forming a bond immediately after contact with the adherend, and is also referred to as initial adhesiveness.

  Since the polyol having an ester portion is superior in content resistance as compared with the polyol having an ether portion, the tube container can be prevented from being broken from the side seam after the tube container is filled with the content.

  Although not restricted by the mechanism of action, the adhesive strength of the two-component adhesive before the crosslinking with the polyisocyanate proceeds depends on the cohesive energy of the main agent, and thus has a higher cohesive strength than the polyol having an ether moiety. Polyols having ester moieties are considered advantageous in initial adhesion.

  The polyol having an ester moiety is preferably a polyester polyol from the viewpoint of crosslinking with isocyanate.

[Polyisocyanate]
A polyisocyanate is a compound having at least two isocyanate groups, and is crosslinked with a polyol to form an oligomer or polymer.

  As the polyisocyanate, for example, in the case of producing a laminate for a tube that exhibits a high-class feeling by utilizing design properties, it is preferable to use an aliphatic polyisocyanate having excellent light resistance.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, methyl 2,6-diisocyanatohexanoate; 2,6-diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1, -Aliphatic triisocyanates such as diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane It is done. As the aliphatic polyisocyanate, hexamethylene diisocyanate is preferable.

  In order to ensure content resistance, it is also preferable to use an aromatic polyisocyanate.

  Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate, or 2,6-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2, Aromatic triisocyanates such as 4,6-triisocyanatotoluene; aromatic tetraisocyanates such as 4,4′-diphenylmethane-2,2 ′, 5,5′-tetraisocyanate and the like.

<Ink layer>
The ink layer is a layer formed of ink, and is disposed on the front side of the substrate laminate. As an ink layer, a printing layer etc. are mentioned, for example. The ink layer may be disposed at a location corresponding to the seal portion on the surface of the substrate laminate, and may be disposed on the entire surface of the substrate laminate. Here, the location corresponding to the seal portion refers to a region of the laminate that becomes a seal portion when the laminate is sealed in a cylindrical shape and formed into a tube. In a specific embodiment of the present invention, the ink layer is arranged at a position corresponding to the seal portion on the surface of the base material laminate, so that a printed pattern is formed even on the seam portion of the tube. A continuous print pattern can be formed on the entire surface of the material laminate to ensure the design of the tube container.

  An ink layer may be formed by covering the printed surface of the substrate laminate with a single ink, and printing a single ink or a plurality of inks on the printed surface of the substrate laminate, An ink layer having gradation or the like may be formed.

  The ink may be oil-based ink or UV ink, but is preferably UV ink.

  The UV ink is an ultraviolet curable ink, and generally does not contain an organic volatile compound such as an organic solvent. Therefore, the UV ink is environmentally friendly, can be instantaneously cured, and does not easily fade. Therefore, UV ink contributes to improvement of productivity and shortening of production time, and is energy saving as compared with heat drying ink.

  In general, UV inks contain a photopolymerizable polymer, optionally monomers, a photopolymerization initiator, and a colorant. Examples of the colorant include pigments and dyes.

  The UV ink preferably has light resistance and heat resistance, and is a UV flexo ink in order to ensure printing reproducibility with respect to a substrate having various surface characteristics, for example, against a polyolefin substrate. It is more preferable.

  In order to improve the adhesion of the UV ink to the substrate laminate and the cohesive strength of the ink, it is also preferable to add polyisocyanate to the UV ink. It is preferable to add polyisocyanate to the UV ink because a crosslinked structure can be formed between the ink layer and the base material laminate or between the ink layer and the adhesive layer. The polyisocyanate contained in the UV ink may be the same as that contained in the two-component adhesive as described above.

  Furthermore, in order to prevent the laminate from floating when an external force is applied to the tube laminate, the initial laminate strength between the functional layer support layer and the ink layer is preferably about 3.0 N / 15 mm or more, and about 6. More preferably, it is 0 N / 15 mm or more. In this specification, the initial laminate strength refers to the laminate strength measured 30 minutes after the completion of lamination.

  Ink printing on the substrate laminate can be performed by any printing method such as letterpress printing, planographic printing, intaglio printing, and ink jet printing. Among these, letterpress printing is preferable, and flexographic printing is more preferable.

<Base material laminate>
The substrate laminate is a layer on which ink is printed. The substrate laminate may be a laminate in which a plurality of layers are laminated, and may include a plurality of the same type of layers.

  For example, the substrate laminate may include at least one film and optionally an adhesive layer, a resin layer, a barrier layer, a sealant layer, and combinations thereof.

  In order to improve the adhesion of the substrate laminate to the ink, the surface of the substrate laminate in contact with the ink layer is preferably formed of polyolefin. In such an aspect, since the laminate strength is improved between the surface layer and the UV ink layer, it is possible to prevent the surface layer from being lifted by a stress that is strongly generated in the seal portion of the tube. Thereby, a print pattern can be formed even on the seam portion of the tube, and in particular, a continuous print pattern can be formed on the entire surface of the base material laminate to ensure the design of the tube container.

  The substrate laminate may be formed of one or a plurality of polyolefin films. Furthermore, it is more preferable that the base material laminate includes a polyolefin film so that the polyolefin film becomes the innermost layer when a tube is formed from the tube laminate. The polyolefin film may be the same as that contained in the functional layer support layer as described above.

  In order to ensure the strength of the tube laminate, the substrate laminate preferably includes a PET film in a portion excluding the surface in contact with the ink layer and the innermost layer.

  Examples of the barrier layer included in the substrate laminate include a metal foil layer and a metal / inorganic vapor deposition layer.

  The sealant layer included in the substrate laminate may be formed of a polyolefin such as LDPE or LLDPE, for example.

<Method for producing laminated body for tube>
The tube laminate can be manufactured by a method comprising the following steps:
An extrusion process of forming a functional layer by extruding a resin containing a functional material to the functional layer support layer;
A printing process in which ink is printed on the substrate laminate to form an ink layer;
A laminating step of bonding the ink layer side of the base material laminate and the side of the functional layer support layer where the functional layer is not formed to obtain a laminate for the tube; and aging for aging the tube laminate as desired Process.

The tube laminate can also be produced by a method comprising the following steps:
An extrusion process in which a resin not containing a functional material is extruded into a functional layer support layer to form an extruded resin layer, or a resin containing a functional material is extruded into a functional layer support layer to form a functional layer;
Functionality imparting step for subjecting the surface of the extruded resin layer or functional layer to a functionality imparting treatment;
A printing process in which ink is printed on the substrate laminate to form an ink layer;
A laminating step of bonding the ink layer side of the base material laminate and the side of the functional layer support layer where the functional layer is not formed to obtain a laminate for the tube; and aging for aging the tube laminate as desired Process.

  In order to improve the adhesion strength of the substrate laminate with the ink, it is preferable to prepare a substrate laminate having a polyolefin surface. Ink may be printed at a location corresponding to the seal portion on the polyolefin surface, and in particular, the ink may be printed on the entire polyolefin surface. Although a printing process may be performed by arbitrary printing systems, it is preferable to be performed by flexographic printing using UV flexographic ink.

  The extrusion process can be performed using an extrusion apparatus. In order to improve the adhesion between the functional layer support layer and the extruded resin or the functional extruded resin, the functional layer support layer is subjected to corona treatment and / or an anchor coating agent is applied to the functional layer support layer before the extrusion process. It is preferable to do.

  The extruder may be a single extruder and a single extruder with a T die. In the extrusion process, a plurality of resins may be extruded to the functional layer support layer using a co-extrusion apparatus.

  A functionality provision process can be performed by roughening apparatuses, such as an embossing apparatus, for example.

  Specifically, the extrusion step and the functionality imparting step can be performed by an extrusion line shown in FIG. If desired, the order of the extrusion step and the functionality providing step may be interchanged. Further, the functional application process may be performed separately from the extrusion process or may be performed as an inline process of the extrusion process.

  The lamination step can be performed by dry lamination using a two-component adhesive of a polyol having an ester moiety and a polyisocyanate.

  The aging step may be continued until the laminate strength between the functional layer support layer and the ink layer does not substantially fluctuate, and can be performed, for example, at 40 ° C. for 6 days.

  The laminated body for a tube of the present invention not only can improve the laminate strength between the functional layer support layer and the ink layer to prevent the ink layer from aggregating and peeling, but also has a printed pattern even on the seam portion of the tube. In particular, a continuous printing pattern can be formed on the entire surface of the base material laminate to ensure the design of the tube container. Therefore, provision of the tube container provided with a full print in a trunk | drum can be achieved.

<Tube container>
A tube container is a container which has the trunk | drum formed with the laminated body for tubes.

  The tube container can be filled with contents such as medicines, cosmetics, and foods. Examples of the contents include toothpaste, moisturizing cream, sunscreen, shampoo, hair conditioner and the like.

The tube container can be manufactured by a method comprising the following steps:
A process of obtaining a body part by overlapping and sealing the end parts of the laminated body while rolling the laminated body for a tube so that the non-ink-printed portion of the base material laminated body faces the back side; and an opening part of the body part A step of joining a head portion having a shoulder portion and a cap portion to the periphery of the tube to obtain a tube container.

<Preparation of tube laminate>
For Examples 1 to 3 and Comparative Example 1, materials shown in Table 1 below were prepared.

Explanation of terms in Table 1 Extruded LLDPE: “SP1071C” (thickness: 60 μm), Prime Polymer Co., Ltd. Extruded LDPE containing antistatic agent (ionomer): 80 parts by weight of LDPE and 20 parts by weight of “ENTILA (registered trademark)” Dry blend with MK440 (Mitsui / DuPont Polychemical Co., Ltd.) AC agent: Anchor coating agent (application amount: 0.5 g / m ² )
PET film: “E5200” (thickness: 12 μm), Toyobo Co., Ltd. L-103: Product name of LLDPE film (thickness: 90 μm, Aicello Co., Ltd.)
TM-277: Trade name of ester main agent (Toyo Morton Co., Ltd.)
cat-RT86: Trade name of aliphatic curing agent (Toyo Morton Co., Ltd.)
FDFL: UV curable flexo ink trade name (Toyo Ink Co., Ltd.)
Additive: Hexamethylene diisocyanate EAA: Ethylene-acrylic acid copolymer EMAA: Ethylene-methacrylic acid copolymer AL: Aluminum foil layer Numbers in parentheses in layer structure: Thickness in μm Cooling roll: Extruded resin layer or functional extruded resin layer A semi-matt roll (Ra: 1.7 μm, Rmax: 12.5 μm, Rz: 17.0 μm) is used when a semi-matt process is performed on the surface, and a mirror roll (Ra: 0.0. 25 μm, Rmax: 2.63 μm, Rz: 1.78 μm).

  The ink layer was formed by flexographic printing of UV ink on the front side of the substrate laminate.

  In Examples 1 to 3, an AC agent was applied to a PET film. In Comparative Example 1, an LLDPE film was used instead of the PET film.

  In Examples 1 and 3, a functional layer having a thickness of 70 μm was formed by extruding a functional extruded resin onto the AC agent-coated surface of the PET film using an extrusion laminator. In Example 2, using an extrusion laminator, the extruded resin was extruded onto the AC agent-coated surface of the PET film to form an extruded resin layer having a thickness of 60 μm. In Comparative Example 1, no resin was extruded onto the LLDPE film.

  In Example 2, the extruded resin layer was semi-matted to form a functional layer. In Example 3, the functional layer was further semi-matted.

Using a dry laminating apparatus, according to the following production conditions, in Examples 1 to 3, the side on which the functional layer of the PET film was not formed and the ink layer side of the base material laminate were compared with the LLDPE film and the base in Comparative Example 1. The ink layer side of the material laminate was dry laminated via an adhesive to obtain a laminate for a tube.
(Production conditions)
Line speed: 30 m / min Adhesive coating amount: 3.5 g / m ²

  In the tube laminate obtained in Example 1, the antistatic agent-containing extruded LDPE (70) / AC agent / PET (12) // ink layer-LLDPE (50) / LDPE (in order from the front side to the back side) 80) / EAA (20) / AL (12) / EMAA (30) / PET (12) // LLDPE (100).

  The laminated body for a tube obtained in Example 2 was semi-matt processed-extruded LLDPE (60) / AC agent / PET (12) // ink layer-LLDPE (50) / LDPE (80 in order from the front side to the back side. ) / EAA (20) / AL (12) / EMAA (30) / PET (12) // LLDPE (100).

  The laminated body for a tube obtained in Example 3 was semi-matt processed-antistatic agent-containing extruded LDPE (70) / AC agent / PET (12) // ink layer-LLDPE (50) in order from the front side to the back side. It had a layer configuration of / LDPE (80) / EAA (20) / AL (12) / EMAA (30) / PET (12) // LLDPE (100).

  The laminated body for tubes obtained in Comparative Example 1 was LLDPE (90) // ink layer-LLDPE (50) / LDPE (80) / EAA (20) / AL (12) / in order from the front side to the back side. EMAA (30) / PET (12) // LLDPE (100) ”.

  In the above layer structure, the semi-matting process-extruded LLDPE (60) of Example 2 indicates that a matte feeling is imparted to the front side of the extruded resin layer by the semi-matting process. The inhibitor-containing extruded LDPE (70) indicates that a matte feeling is imparted to the front side of the antistatic extruded resin layer by semi-matting, and the ink layers of Examples 1 to 3 and Comparative Example 1-LLDPE (50) Represents that the UV ink is printed on the front side of the substrate laminate.

Moreover, as Comparative Example 2, a commercially available laminate for a tube having a gravure printing layer was prepared. This laminated body for tubes is, in order from the front side to the back side, LLDPE (35) / LLDPE / LDPE (20) / PET-ink layer / LDPE (25) / white LDPE (100) / PETSiO _x (12) / EMAA. / LLDPE (80). In addition, a PET-ink layer represents that the ink is printed on the back side of PET base material.

Experiment 1. Examination of functional layer and functional layer support layer <Evaluation method of tube laminate>
1. Measurement of initial laminate strength between functional layer support layer and ink layer 30 minutes after producing the tube laminates of Examples 1 to 3 and Comparative Example 1, the tube laminate was cut into a width of 15 mm and a length of 150 mm. A test piece was obtained.

About each of the test pieces, the initial lamination strength between a functional layer support layer and an ink layer was measured according to the following measurement conditions using the Toyo Seiki Co., Ltd. strograph (for EL).
(Measurement condition)
Between gripping tools: 50mm
Tensile speed: 150 mm / min Peeling type: T-peeling

2. Measurement of laminate strength after aging The tube laminates of Examples 1 to 3 and Comparative Examples 1 and 2 were aged at 40 ° C. for 6 days. The tube laminate after aging was cut into a width of 15 mm and a length of 150 mm to obtain a test piece.

  Using the Toyo Seiki Co., Ltd. strograph (for E-L), according to the same measurement conditions as initial lamination strength, about the test piece of Examples 1-3 and the comparative example 1, it is between a functional layer support layer and an ink layer. The laminate strength after aging was measured, and for the test piece of Comparative Example 2, the laminate strength after aging between the printed surface of the “PET-ink layer” and the LDPE layer below it was measured.

3. Evaluation of charge removal A tube body was produced from the tube laminate. According to the half-life measurement method (JIS L 1094), the charge half-life of the trunk was measured as follows.

  The trunk was left to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Then, using a static Honest meter ("S-5109" manufactured by Sisid Electrostatic Co., Ltd.), measure the time from applying a voltage of 10 kV to the body until the voltage on the body decays to 1/2. did.

The body neutralization was evaluated according to the following criteria:
(Standard)
◯: Time until the charged voltage of the body part is attenuated to ½ is less than 10 seconds.
X: Time until the charged voltage of the trunk part is attenuated to ½ is 10 seconds or more.

4). Dirt Adhesion Test A tube body was prepared from the tube laminate. The trunk was left to stand for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the barrel was placed in a toner-type dirt chamber tester, and the fan was rotated to allow dirt to adhere to the barrel over 5 minutes. The torso was then removed and the level of dirt on the torso was observed and evaluated according to the following criteria:
(Standard)
○: There is no noticeable dirt on the body.
X: Remarkably dirty on the trunk.

5. Glossiness Measurement According to JIS K 7105, the glossiness of the front side of the tube laminate was measured using “GROSS METER GM-3D” manufactured by Murakami Color Research Laboratory Co., Ltd.

6). Sensory evaluation of touch and gloss Touch the front side of the tube laminate with the hand and visually observe under a fluorescent lamp and evaluate according to the following criteria:
(Standard)
A: Moist touch and no reflection of fluorescent light.
○: A light touch and a fluorescent light is reflected in the light.
X: It is a smooth hand and the outline of the reflected fluorescent lamp can be seen.

  The evaluation results of the tube laminate are shown in Table 2 below.

[About Tables 1 and 2]
From the comparison between Examples 1 to 3 and Comparative Example 1, when the functional layer is arranged on the front side of the functional layer support layer, the functional material does not affect the adhesive layer, and between the functional layer support layer and the ink layer. It can be seen that the laminate strength can be ensured and antistatic properties and / or matte feeling can be imparted to the tube laminate.

  Moreover, Examples 1-3 which surface-printed UV ink on the polyolefin (LLDPE) surface of a base-material laminated body are compared with the gravure original fabric (comparative example 2) which is printed on the PET base material, It can be seen that since the ink application surface is flexible, cohesive peeling or surface peeling does not occur due to stress relaxation, and a sufficient laminate strength can be secured even after aging.

  In Comparative Example 2, after aging, aggregation peeling of the ink layer or surface cleavage of the PET layer was observed. Accordingly, the tube laminate of Comparative Example 2 is expected to cause surface layer peeling when an external force is applied to the end face during molding of the shoulder or the like.

Experiment 2. Reference examination of tube laminate having polyolefin film as surface layer instead of functional layer and functional layer support layer <Preparation of tube laminate>
For Reference Examples 1 to 4 and Comparative Reference Example 1, UV ink, adhesive, and surface layer were prepared as shown in Table 3 below.

Explanation of terms in Table 3 FDFL: trade name of UV curable flexo ink (manufactured by Toyo Ink Co., Ltd.)
Additive: Hexamethylene diisocyanate TM-277: Trade name of ester main agent (manufactured by Toyo Morton Co., Ltd.)
A-310: Trade name of ester-based main agent (Mitsui Chemicals, Inc.)
A-620: Trade name of ester-based main agent (Mitsui Chemicals)
A-969V: Trade name of ether-based main agent (manufactured by Mitsui Chemicals, Inc.)
cat-RT86: Trade name of aliphatic curing agent (manufactured by Toyo Morton Co., Ltd.)
cat-10L: Trade name of aromatic curing agent (manufactured by Toyo Morton Co., Ltd.)
A-3: Trade name of aromatic curing agent (Mitsui Chemicals)
A-65: Trade name of aliphatic curing agent (Mitsui Chemicals)
A-8: Trade name of aromatic curing agent (Mitsui Chemicals)
L-103: Trade name of LLDPE film (Aisero Chemical Co., Ltd .: thickness 90 μm)

  Layer structure of LLDPE (50) / LDPE (80) / EAA (20) / AL (12) / EMAA (30) / PET (12) // LLDPE (100) in order from the front side to the back side (in parentheses) (A number represents a thickness in μm) and a substrate having a width of 200 mm and a length of 800 m was prepared.

  A UV ink was flexographically printed on the front side of the substrate to form a printed layer.

Using a dry laminating apparatus, the printed layer and the surface layer were dry laminated via an adhesive in accordance with the following production conditions to obtain a laminated body for a tube.
(Production conditions)
Line speed: 30 m / min Adhesive coating amount: 3.5 g / m ²

  For Reference Examples 1 to 4 and Comparative Reference Example 1, the tube laminate was LLDPE (90) // printed layer-LLDPE (50) / LDPE (80) / EAA (20) in order from the front side to the back side. It had a layer structure of / AL (12) / EMAA (30) / PET (12) // LLDPE (100).

Moreover, as Comparative Reference Example 2, a commercially available laminate for a tube having a gravure printing layer was prepared. Commercially available laminates for tubes are LLDPE (35) / LLDPE / LDPE (20) / PET-printed layer / LDPE (25) / white LDPE (100) / PETSiO _x (12) / in order from the front side to the back side. It had a layer configuration of EMAA / LLDPE (80).

<Evaluation method of laminate for tube>
1. Measurement of initial laminate strength between surface layer (polyolefin) and UV ink layer 30 minutes after producing the tube laminates of Reference Examples 1 to 4 and Comparative Reference Example 1, the tube laminates were 15 mm wide and 150 mm long. To obtain a test piece.

About each of the test pieces, the initial laminate strength between the surface layer and the UV ink layer was measured according to the following measurement conditions using a strograph (for EL) manufactured by Toyo Seiki Co., Ltd.
(Measurement condition)
Between gripping tools: 50mm
Tensile speed: 150 mm / min Peeling type: T-peeling

  The measurement results of the initial laminate strength are shown in Table 2 below.

2. Measurement of laminate strength after aging The tube laminates of Reference Examples 1 to 4 and Reference Examples 1 and 2 were aged at 40 ° C. for 6 days.

  The tube laminate after aging was cut into a width of 15 mm and a length of 150 mm to obtain a test piece.

  Aging between the surface layer and the UV ink layer for the test specimens of Reference Examples 1 to 4 and Comparative Example 1 using a Toyo Seiki Co., Ltd. strograph (for EL) according to the same measurement conditions as the initial laminate strength. The subsequent laminate strength was measured, and for the test piece of Comparative Reference Example 2, the laminate strength after aging between the printed surface of the PET-printed layer and the underlying LDPE layer was measured.

  The measurement results of the laminate strength after aging are shown in Table 4 below.

[Initial laminate strength]
From Table 4, it can be seen that in Reference Examples 1 to 4 using a polyester-based main agent, a sufficient laminate strength can be obtained even immediately after lamination.

  On the other hand, in Comparative Reference Example 1 using an ether-based main agent, since the initial laminate strength was insufficient, laminate lifting occurred when stress was applied to the original fabric. Therefore, the tube laminate of Comparative Reference Example 1 has insufficient handling properties.

[About laminate strength after aging]
From Table 4, Reference Examples 1 to 4 in which UV ink is printed on the polyolefin (LLDPE) surface of the substrate are compared with the gravure raw material (Comparative Reference Example 2) that is printed on the PET substrate. It can be seen that since the ink application surface is flexible, cohesive peeling or surface peeling does not occur due to stress relaxation, and a sufficient laminate strength can be secured even after aging.

  In Comparative Reference Example 2, ink layer aggregation peeling or PET surface layer peeling was observed after aging. Therefore, the tube laminate of Comparative Reference Example 2 is expected to cause surface layer peeling when an external force is applied to the end face during molding of the shoulder portion or the like.

DESCRIPTION OF SYMBOLS 1 Laminate for tubes 2 Front side 3 Back side 4 Adhesive layer 5 Ink layer 6 Polyethylene terephthalate layer 7 Low density polyethylene film containing antistatic agent 8 Other layers or laminates 9 Extruded laminate 10 Dry laminate 11 Anchor agent layer 12 Polyethylene layer 13 Polypropylene layer 14 Tube laminate 15 Functional layer 16 Functional layer support layer 17 Base material laminate 17a Polyolefin surface 17b Portions other than the polyolefin surface 18 Extrusion line 19 Die 20 Pressure roll 21 Functional layer support layer base material 22 Extrusion Resin 23 Roughening device x Flow direction

Claims (9)

The functional layer, the functional layer support layer, the adhesive layer, the ink layer, and the base material laminate are laminated in this order from the front side to the back side, and the adhesive layer includes a polyol having an ester portion and a polyisocyanate. To provide a tube container containing a two-component adhesive, the ink layer containing UV ink, the surface of the substrate laminate in contact with the ink layer containing polyolefin, and having a full print on the body. A laminated body for tubes. The functional layer comprises an extruded resin containing a functional material, a tube for laminate according to claim 1. The functional layer comprises an extruded resin or functional material containing no functional material is roughened, the tube for laminate according to 請 Motomeko 1. The laminate for a tube according to claim 2 or 3 , wherein the functional material is an antistatic agent and / or a matting agent. The laminated body for tubes according to any one of claims 1 to 4 , wherein an initial laminate strength between the functional layer support layer and the ink layer is 3.0 N / 15 mm or more. The said ink layer is a laminated body for tubes of any one of Claims 1-5 arrange | positioned in the location corresponding to the seal part of the surface of the said base material laminated body. The said ink layer is a laminated body for tubes of any one of Claims 1-6 arrange | positioned at all the surfaces of the said base material laminated body. The functional layer comprises a polyolefin, prior Symbol ink layer, before being arranged in the portion corresponding to the sealing portion of the surface of the Kimotozai laminate according to any one of claims 1-7 Tube Laminated body. The tube container which has a trunk | drum formed with the laminated body for tubes of any one of Claims 1-8 .

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