JP2012101478A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that prevents a printing layer from being peeled out of a base material by a receiving layer, and can form the receiving layer in a short time.SOLUTION: The laminate is formed by laminating on a base material 11 which includes polyvinyl chloride, a receiving layer 12 for ultraviolet curing mold acrylic ink, and a printing layer 13 formed from ultraviolet curing mold acrylic ink in this order, and by carrying out pressurization and heat treatment. The laminate 1 is characterized in that the receiving layer 12 is formed from a composition combined with: an aqueous emulsion having an ultraviolet curing mold urethane acrylate as a principal component; aqueous emulsion which makes polyurethane principal component; and a photopolymerization initiator.

Description

  The present invention relates to a laminate in which peeling of a printed layer from a substrate made of polyvinyl chloride is suppressed and excellent in production suitability.

  Various laminates in which a printed layer is provided on a resin base material via a receiving layer are used in various fields including cards and decorative materials. Examples thereof include those using polyvinyl chloride and an ultraviolet curable resin as a receiving layer (see, for example, Patent Document 1). The receiving layer is necessary for strengthening the fixing of the printed layer to the substrate and suppressing peeling from the substrate.

For example, in a conventional laminate (print card) in which characters and designs are printed on a base material, a receiving layer is provided on the base material by a screen printing method, and offset printing is performed on the receiving layer to form a printing layer. It can be manufactured by a method of providing. And as a composition for receiving layers applied to screen printing, what contains resin, a silica, and a solvent can be illustrated, and when a non-target thing contacts silica on a receiving layer, these adhesion (blocking) is carried out. Functions as a blocking inhibitor to prevent. Since blocking causes a feed trouble at the time of forming a printing layer using a sheet-fed printing press, for example, it is necessary to use a blocking inhibitor.
The receiving layer can also be provided by a UV offset printing technique. Examples of the receiving layer composition to be applied in this case include those containing a pigment and a vehicle.

JP-A-8-80596

However, the screen printing method has a problem that printing itself and drying take time, and the receiving layer cannot be formed in a short time.
Further, in the UV offset printing method, the composition is transferred onto the substrate to form a receiving layer, so that the receiving layer can be formed in a shorter time than in the case of screen printing, but the composition has poor fixability. There is a problem that the receiving layer is easily peeled off from the substrate, and peeling of the printed layer from the substrate cannot be sufficiently suppressed.
Thus, conventionally, there has not been known a laminate in which peeling of a printed layer from a substrate is suppressed and a receptor layer can be formed in a short time.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the laminated body by which peeling of the printing layer from a base material is suppressed by the receiving layer, and the said receiving layer can be formed in a short time. .

To solve the above problem,
In the present invention, a UV-curable acrylic ink receiving layer and a UV-curable acrylic ink receiving layer are laminated in this order on a substrate made of polyvinyl chloride, and subjected to pressure and heat treatment. In the laminate, the receiving layer is formed from a composition in which an aqueous emulsion mainly composed of an ultraviolet curable urethane acrylate, an aqueous emulsion mainly composed of polyurethane, and a photopolymerization initiator are blended. Provided is a laminated body characterized by being
In the laminate of the present invention, when the urethane acrylate is obtained using an aliphatic isocyanate monomer, the blending amount of the polyurethane per 1 part by mass of the urethane acrylate is 0. When the urethane acrylate is obtained by using an aromatic isocyanate monomer, the blending amount of the polyurethane per 1 part by weight of the urethane acrylate is 0. It is preferably 8 parts by mass or more.
In the laminate of the present invention, a protective layer is further laminated on the printed layer and subjected to pressure and heat treatment, and is preferably card-shaped.

  ADVANTAGE OF THE INVENTION According to this invention, peeling of the printing layer from a base material can be suppressed by the receiving layer, and the laminated body which can form the said receiving layer in a short time can be provided. Such a laminate is particularly suitable as a print card in which characters and designs are printed on a substrate.

It is a schematic sectional drawing which illustrates the structure in the stage before pressurization heat processing before making it the layered product of the present invention. It is a schematic sectional drawing which illustrates the laminated body of this invention obtained by pressurizing and heating the structure shown in FIG.

<Laminated body>
The laminate of the present invention was formed from a receiving layer for ultraviolet curable acrylic ink (hereinafter simply referred to as “receiving layer”) and an ultraviolet curable acrylic ink on a substrate made of polyvinyl chloride. A laminate in which printing layers are laminated in this order and subjected to pressure and heat treatment, and the receiving layer is an aqueous emulsion mainly composed of an ultraviolet curable urethane acrylate (hereinafter abbreviated as urethane acrylate emulsion), From a composition (hereinafter, simply referred to as a composition for a receiving layer or simply “composition”) in which an aqueous emulsion containing polyurethane as a main component (hereinafter abbreviated as polyurethane emulsion) and a photopolymerization initiator are blended. It is formed.

[Base material]
Polyvinyl chloride, which is the material of the base material, may be a well-known material, and may be one in which a plasticizer or a stabilizer is blended.
The substrate may be a single layer or a plurality of layers. In the case of a plurality of layers, all the layers may be the same or different, and some layers may be different.
The thickness of the substrate may be set as appropriate according to the use of the laminate, and is not particularly limited. For example, when a printing card is used, a thickness of about 0.1 to 1 mm is suitable.

[Composition for receiving layer]
The said receiving layer suppresses peeling from the base material of a printing layer by fixing firmly the printing layer formed from an ultraviolet curable acrylic ink with respect to a base material.
It is considered that the receiving layer is formed from a composition for a receiving layer in which the urethane acrylate emulsion, the polyurethane emulsion, and a photopolymerization initiator are blended, and the urethane acrylate is polymerized.

In the urethane acrylate emulsion, “based on UV curable urethane acrylate” means that the aqueous emulsion contains an amount of UV curable urethane acrylate that does not hinder the effects of the present invention. Specifically, it means that the content of the urethane acrylate in the total amount of components other than water is preferably 65% by mass or more, more preferably 70% by mass or more.
The urethane acrylate emulsion preferably has a solid content of 10 to 70% by mass or more, and more preferably 20 to 60% by mass or more. By being in such a range, the handleability of the emulsion becomes better. And it is preferable that the ratio of the said urethane acrylate which occupies for this solid content is 70 mass% or more.

Similarly, in the polyurethane emulsion, “based on polyurethane” means that the aqueous emulsion contains an amount of polyurethane that does not hinder the effects of the present invention. Means that the polyurethane content in the total amount of components other than water is preferably 65% by mass or more, more preferably 70% by mass or more.
The polyurethane emulsion preferably has a solid content of 10 to 70% by mass or more, and more preferably 20 to 60% by mass or more. By being in such a range, the handleability of the emulsion becomes better. And it is preferable that the ratio of the said polyurethane to this solid content is 70 mass% or more.

(UV curable urethane acrylate)
The urethane acrylate is obtained by polymerizing an isocyanate monomer and an alcohol monomer, and may be a known one.
In the urethane acrylate, for example, both an aliphatic isocyanate monomer and an aromatic isocyanate monomer can be used as the isocyanate monomer. Here, the aliphatic isocyanate monomer means an isocyanate monomer having no aromatic group, and the aromatic isocyanate monomer means an isocyanate monomer having an aromatic group regardless of the presence or absence of an aliphatic group. .

  In the urethane acrylate, the isocyanate monomer and the alcohol monomer may be one kind or two or more kinds. When one or both of the isocyanate monomer and the alcohol monomer are two or more, the combination and ratio can be arbitrarily adjusted according to the purpose.

  Moreover, the urethane acrylate in the composition may be one kind or two or more kinds. In the case of two or more kinds, the combination and ratio can be arbitrarily adjusted according to the purpose.

  The said receiving layer exists in the tendency for the peeling suppression effect of the more excellent printing layer to be acquired by using what was obtained using the aliphatic isocyanate monomer as said urethane acrylate.

(Polyurethane)
The polyurethane may be a known one and is not particularly limited. Preferred examples of the polyurethane include polycarbonate / polyether type polyurethane, polycarbonate type polyurethane, polyester type polyurethane, and polycarbonate diol type polyurethane. These polyurethanes have a structure such as carbonate, ether, ester, diol, etc. in the alcohol monomer constituting them. Low molecular weight alcohol monomers are thought to make polyurethane hard (rigid). Moreover, it is thought that the polymeric alcohol monomer which has structures, such as a polycarbonate, polyether, and polyester, makes a polyurethane soft structure (soft).
On the other hand, the isocyanate monomer constituting the polyurethane is considered to have a hard structure, but the aliphatic isocyanate monomer is considered to impart heat softening properties to the polyurethane. Here, the aliphatic isocyanate monomer means an isocyanate monomer having no aromatic group, as in the case of the urethane acrylate.

  The polyurethane in the composition may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio can be arbitrarily adjusted according to the purpose.

The blending amount of the polyurethane in the composition is not particularly limited, and may be appropriately adjusted according to, for example, the type of the urethane acrylate used in combination. Usually, it is preferable that the compounding quantity of the said polyurethane per 1 mass part of compounding quantities of the said urethane acrylate is 0.1-9 mass parts.
For example, when the urethane acrylate is obtained using an aliphatic isocyanate monomer, the amount of the polyurethane per 1 part by mass of the urethane acrylate is 0.1 parts by mass. It is preferable that it is above, and it is more preferable that it is 0.2 parts by mass or more. Although the upper limit of the blending amount of the polyurethane is not particularly limited, it is preferable that the blending amount of the polyurethane per 1 part by weight of the urethane acrylate is 3 parts by weight or less.
When the urethane acrylate is obtained using an aromatic isocyanate monomer, the amount of the polyurethane per 1 part by mass of the urethane acrylate is 0.8 parts by mass or more. It is preferable that it is 1.1 parts by mass or more. Although the upper limit of the blending amount of the polyurethane is not particularly limited, it is preferable that the blending amount of the polyurethane per 1 part by weight of the urethane acrylate is 4 parts by weight or less.
By setting the blending amount of the polyurethane within the above range, peeling of the printed layer from the substrate is further suppressed. Moreover, the blocking in a receiving layer is suppressed more by making it below an upper limit.
In addition, when providing the contact bonding layer mentioned later on a printing layer, peeling of a protective layer is suppressed more, so that there are many compounding quantities of the said polyurethane.

(Photopolymerization initiator)
The photopolymerization initiator may be a known one such as an organic peroxide or an azo compound, and is not particularly limited.
The blending amount of the photopolymerization initiator in the composition may be appropriately adjusted. For example, the polymerization reaction proceeds more favorably by setting the content to 5 to 20% by mass with respect to the solid content of the urethane acrylate emulsion. Can be made.

(Other ingredients)
In addition to the urethane acrylate emulsion, the polyurethane emulsion, and the photopolymerization initiator, the composition may contain other components. Preferred examples of the other components include other resins not corresponding to the urethane acrylate and polyurethane, crosslinking agents, thickeners, antifoaming agents, leveling agents, dispersing agents, fillers, pH adjusting agents, and the like.

The other resin may be appropriately selected depending on the purpose and is not particularly limited, but a preferable example is a vinyl chloride vinyl acetate copolymer.
For example, when the other resin is in a powder form, it is preferably blended into the composition as an emulsion dispersed in water or the like in advance. Alternatively, it may be blended directly into the composition.
By blending the other resin, for example, the hardness of the receptor layer can be adjusted, or the surface of the receptor layer can be made into a mat to adjust the surface state to facilitate the formation of the printed layer.

As said crosslinking agent, what has a crosslinking action with respect to the said polyurethane is preferable, and a carbodiimide type crosslinking agent and an isocyanate type crosslinking agent can be illustrated. By using such a crosslinking agent in combination, the polyurethane can be crosslinked and the hardness of the receiving layer can be adjusted.
Moreover, as said thickener, what has a thickening effect | action with respect to the said polyurethane is preferable. By using such a thickener together, the viscosity of the composition can be adjusted.

What is necessary is just to adjust the compounding quantity of the other component in the said composition suitably according to the kind.
For example, the blending amount of the other resin is preferably 5 to 60% by mass and more preferably 10 to 45% by mass with respect to the total solid content of the urethane acrylate emulsion and the polyurethane emulsion.
Further, the blending amount of the crosslinking agent is preferably 0.1 to 5% by mass, and preferably 0.3 to 3.5% by mass with respect to the total solid content of the urethane acrylate emulsion and the polyurethane emulsion. More preferred.
Moreover, it is preferable that it is 0.08-4 mass% with respect to the solid content total amount of the said urethane acrylate emulsion and a polyurethane emulsion, and the compounding quantity of the said thickener is 0.1-1.5 mass%. Is more preferable.

  The said composition can be prepared by mix | blending the said urethane acrylate emulsion, the said polyurethane emulsion, a photoinitiator, and another component as needed, and fully stirring these compounding components.

  Each component may be blended together at once, may be blended sequentially for each component, or only some components may be blended together. The blending order of each component is not particularly limited. If a thickener is blended, the thickener is difficult to dissolve in the solvent component. For example, after mixing the urethane acrylate emulsion and polyurethane emulsion, the photopolymerization initiator and, if necessary, a crosslinking agent. Is preferably blended with other components such as the above-mentioned other resins (excluding the thickener) if necessary, and finally a thickener dissolved in water is blended.

The temperature at the time of blending is not particularly limited, and may be appropriately adjusted according to the type of blending component, but is preferably 15 to 30 ° C.
Stirring may be performed by a known method for preparing a dispersion, such as a method of rotating a stirring bar or a stirring blade, a method of using a mixer, or a method of applying ultrasonic waves. What is necessary is just to adjust stirring time suitably according to the quantity of the composition to prepare, the stirring method, etc.

[Receptive layer]
The receptor layer can be formed by applying the composition onto a substrate and curing it with ultraviolet light. The composition after application is preferably dried to remove moisture.
The method for applying the composition is not particularly limited, and any method may be used as long as it can apply a liquid material. Specifically, screen printing; offset printing; dip method; inkjet method; dispenser method; air knife coater, curtain coater, die coater, blade coater, roll coater, gate roll coater, bar coater, rod coater, gravure coater, spin Examples include a method using various coaters such as a coater; and a known method using a device such as a wire bar. Among these, it is preferable to select a method that can form the receptor layer in a short time, such as a method that can be applied and dried quickly and a method that can be applied, dried and cured continuously. For example, if a method using a roll coater is applied, coating, drying and curing can be performed continuously.

  The coating amount of the composition may be appropriately adjusted in consideration of the solid content concentration of the composition, the desired thickness of the receiving layer, and the like.

The thickness of the receiving layer may be appropriately adjusted in consideration of, for example, the blending components of the composition, the thickness of the printing layer described later, and the like. Usually, the lower limit is preferably 0.5 μm. . Although an upper limit is not specifically limited, It is preferable that it is 7 micrometers.
On the other hand, for example, when using a conventional composition containing silica as a blocking inhibitor, considering the average particle diameter of silica (for example, about 8 μm), in order to express the silica blocking inhibitory effect, It is necessary to make the thickness of the receiving layer excluding silica (for example, about 6 to 7 μm) relatively thick, making it difficult to reduce the thickness of the receiving layer and limiting the use of the laminate. Furthermore, when the average particle diameter of the silica is large, adhesion of each layer constituting the laminate is hindered during pressurizing and heat treatment described later, and the strength of the laminate is reduced. On the other hand, in the present invention, since the receiving layer has a blocking inhibitory effect without using silica, it is easy to make the receiving layer thin, and a laminate having sufficient strength is obtained. As described above, from the viewpoint of obtaining a thin laminate having sufficient strength and an effect of suppressing peeling of the printed layer, the thickness of the receiving layer is preferably 0.5 to 5 μm. And when making a receptor layer thin, since the drying time of the composition after application | coating can further be reduced, a receptor layer can be formed in a shorter time.

  The composition is considered to be in a state in which the urethane acrylate and polyurethane are freely mixed when applied on the substrate. Then, when urethane acrylate is polymerized by ultraviolet curing to form a three-dimensional skeleton of the urethane acrylate polymer, it is considered that a receiving layer in which polyurethane exists in the voids of this skeleton is formed. The skeleton of the urethane acrylate polymer has high affinity with an ultraviolet curable acrylic ink for forming a printing layer described later, and is considered suitable for ink transfer. Furthermore, this receptor layer is thought to have a three-dimensional skeleton in which particles formed by entangled molecular chains of urethane acrylate polymer are connected to each other, but the outside of this skeleton is strong and stable. Therefore, even if a laminate is present on the receptor layer, this skeleton suppresses contact with the polyurethane laminate, and as a result, blocking is considered to be suppressed. On the other hand, since the inside of the skeleton is increased in flexibility by heating, the three-dimensional skeleton of the urethane acrylate polymer is crushed in the thickness direction of the receiving layer during the pressure heat treatment described later, and changes to a more planar skeleton. Conceivable.

[Print layer]
The printing layer is formed from an ultraviolet curable acrylic ink, and the acrylic ink may be appropriately selected from known ones.
The thickness of the printing layer may be adjusted as appropriate. For example, when the thickness of the receiving layer is within the above range, it is preferably 0.5 to 5 μm, and more preferably 2 to 4 μm. . By setting it as such a range, the more stable peeling inhibitory effect from a base material is acquired.
The printing layer may be formed by, for example, screen printing, offset printing, ink jet method, etc., and is preferably formed by offset printing.

[Other layers]
In the laminated body of this invention, other layers may be further laminated | stacked on the said base material before a pressure heating process other than the said receiving layer and a printing layer.
Examples of preferable other layers include a protective layer for protecting the printed layer.

(Protective layer)
The protective layer is provided on the printing layer, and the material may be appropriately selected according to the material of the printing layer, and is not particularly limited, but is used for protective films for various printed materials. Can be illustrated. Among these, a thermoplastic resin is preferable, and polyvinyl chloride (PVC), polycarbonate (PC), polyethylene terephthalate (PET), and amorphous polyethylene terephthalate (PET-G) are more preferable.
The protective layer may be composed of a single layer or may be composed of a plurality of layers. In the case of a plurality of layers, all the layers may be the same or different, and some layers may be different.
The thickness of the protective layer may be appropriately adjusted according to the use of the laminate, but is preferably 25 to 200 μm, and more preferably 50 to 120 μm.
As a protective layer, what was formed by laminating | stacking what is a film form or a sheet form is preferable.

(Adhesive layer)
The protective layer may be laminated on the printed layer via an adhesive layer, for example, when the adhesiveness is insufficient, such as being easily peeled off from the printed layer even if subjected to pressure and heat treatment.
What is necessary is just to select the material of the adhesive agent which forms the said contact bonding layer suitably in consideration of the material of the said protective layer and printing layer. Examples of known ones include acrylate resins, polyimides, epoxy resins, polyurethanes, and polyolefins. For example, when the material of the protective layer is polyvinyl chloride, a composition for forming the receiving layer may be used as the adhesive. However, in this case, for example, it is preferable to reduce the blending amount of the cross-linking agent or not so that the adhesive layer to be formed does not become too hard (has appropriate flexibility). By doing in this way, the higher effect which suppresses the crack of a printing layer is acquired. Usually, it is preferable to adjust the compounding components of the composition so that the flexibility is improved as compared with the receiving layer formed simultaneously.

The thickness of the adhesive layer is preferably 2 to 8 μm.
What is necessary is just to apply | coat the said adhesive agent by the method similar to the said composition, for example.

[Pressurized heat treatment]
The laminate of the present invention is obtained by sequentially laminating the receiving layer, the printed layer, and, if necessary, the other layers on the substrate, and the obtained structure (hereinafter simply referred to as “structure”). ) Under pressure and heat treatment. By the pressure heat treatment, a laminate having sufficient strength is obtained.

  FIG. 1 is a schematic cross-sectional view illustrating the structure. The structure 1 ′ shown here is obtained by laminating a receiving layer 12 ′, a printing layer 13 ′, an adhesive layer 14 ′, and a protective layer 15 ′ in this order on a base material 11 ′. As described above, the adhesive layer 14 ′ and the protective layer 15 ′ have an arbitrary layer configuration, and may not be provided depending on the purpose, or other layers may be laminated instead of these two layers, In addition to these two layers, other layers may be further laminated.

The conditions for the pressure and heat treatment may be appropriately adjusted according to the structure of the structure, and are not particularly limited. However, the pressure is 0.1 to 1.0 kg / cm ² from the viewpoint of obtaining a strong laminate. It is preferable that the temperature is 100 to 200 ° C. Further, after the pressure and heat treatment, the temperature may be lowered while the pressure is maintained, and a low temperature of 10 to 30 ° C. may be maintained for a predetermined time (pressure cooling treatment). The time for the pressure heating treatment and the pressure cooling treatment may be appropriately set in consideration of the temperature and the like, but is preferably 5 to 60 minutes.
What is necessary is just to perform a pressurization heat processing using a well-known hot press machine.

  You may adjust the magnitude | size of the obtained laminated body suitably using known apparatuses, such as a cutter and a punching machine, after a pressurization heat processing as needed.

In the structure, as described above, it is considered that polyurethane exists in the voids of the strong three-dimensional skeleton of the urethane acrylate polymer. It is considered that the polyurethane is crushed in the thickness direction of the layer to change to a more planar skeleton, and a part of the polyurethane existing in the void is pushed out of the skeleton of the urethane acrylate polymer. And it is thought that the extruded polyurethane functions as an adhesive and suppresses peeling of the printed layer from the receiving layer and peeling of the receiving layer from the base material.
In addition, when a crosslinking agent having a crosslinking action on polyurethane is blended in the composition, the crosslinking of the polyurethane proceeds by pressure and heat treatment, so that the hardness of the receiving layer is improved (flexibility) Can be reduced).
Thus, in the present invention, the receiving layer has a blocking suppression effect (adhesion suppression effect) at the stage before the pressure heat treatment, whereas it has an adhesive effect after the pressure heat treatment, thereby printing. Separation of the layers is suppressed, and a laminate having excellent handleability during production is obtained.
Moreover, in this invention, it is excellent in the handleability at the time of laminated body manufacture also because the said composition is aqueous.
Furthermore, in general, when the printed layer is formed up to the end of the receiving layer, such as when the printed layer is formed on the entire surface of the receiving layer, the end of the laminate repeatedly contacts the object. Or the protective layer formed on the printed layer may peel off due to strong contact. However, since the laminate of the present invention has sufficient strength, the peeling of the protective layer from the printing layer and the peeling from the receiving layer in which the protective layer and the printing layer are integrated are suppressed.

  FIG. 2 is a schematic cross-sectional view illustrating the laminate of the present invention obtained by pressurizing and heating the structure shown in FIG. In the laminated body 1 shown here, the base material 11, the receiving layer 12, the printing layer 13, the adhesive layer 14 and the protective layer 15 are respectively the base material 11 ′, the receiving layer 12 ′, the printing layer 13 ′, the adhesive layer 14 ′ and The protective layer 15 ′ has been subjected to pressure and heat treatment. In the present invention, it does not necessarily mean that the characteristics of all of the base material 11 ′ to the protective layer 15 ′ are changed by the pressure heat treatment.

  The laminate of the present invention is particularly suitable for thin sheets such as a sheet or a card, and a laminate in which a receiving layer, a printing layer and a protective layer are laminated on a substrate is used for various printing cards. Is particularly suitable.

The laminate of the present invention is one in which peeling of the printing layer from the substrate is remarkably suppressed by using a composition containing a specific component as the composition for the receiving layer. In addition, by selecting such a composition, it is possible to select a method capable of forming the receiving layer in a short time, such as a method using a roll coater, in applying the composition at the time of forming the receiving layer. Furthermore, even if silica is not used, since it has a blocking inhibiting effect, it is easy to thin the receiving layer, that is, to thin the laminate. In this case, since the drying time of the composition can be further reduced, the receiving layer can be formed in a shorter time.
As described above, the laminate of the present invention is excellent in the effect of suppressing the peeling of the printed layer from the substrate, and in the production process, the receiving layer can be formed in a short time. It is excellent in manufacturing suitability, for example, without damaging various properties.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

<Raw materials>
The raw materials used are shown below.
[Urethane acrylate emulsion]
Radiation curing Laromargins LR8949 (made by BASF, water 60 mass%, urethane acrylate emulsion obtained using aliphatic isocyanate monomer)
Radiation curing Laromargins LR8983 (BASF, urethane 60 acrylate obtained by using an aromatic isocyanate monomer, 60% by weight of water)
[Polyurethane emulsion]
Rezamin D-4080 (manufactured by Dainichi Seika Kogyo Co., Ltd., non-volatile content 35% by mass, polycarbonate / polyether type polyurethane dispersion)
Rezamin D-6030 (manufactured by Dainichi Seika Kogyo Co., Ltd., nonvolatile content 30% by mass, polycarbonate / polyether type polyurethane dispersion)
Rezamin D-6031 (manufactured by Dainichi Seika Kogyo Co., Ltd., non-volatile content 30% by mass, polycarbonate type polyurethane dispersion)
Rezamin D-6300 (manufactured by Dainichi Seika Kogyo Co., Ltd., non-volatile content 30% by mass, polycarbonate type polyurethane dispersion)
UW-3100-E (manufactured by Ube Industries, non-volatile content 30% by mass, polycarbonate diol type polyurethane dispersion)
UW-5034-E (manufactured by Ube Industries, nonvolatile content 30% by mass, polycarbonate diol type polyurethane dispersion)
UW-5101-E (manufactured by Ube Industries, nonvolatile content 30% by mass, polycarbonate diol type polyurethane dispersion)
Hydran HW-311 (manufactured by DIC, nonvolatile content 45 mass%, polyester type polyurethane dispersion)
Hydran HW-337 (manufactured by DIC, nonvolatile content 38% by mass, polyester type polyurethane dispersion)
Superflex (Daiichi Kogyo Seiyaku Co., Ltd., 40% by weight, water-soluble urethane resin aqueous dispersion)
[Photopolymerization initiator]
Irgacure 500 (manufactured by Chiba)
[Polyvinyl chloride / vinyl acetate emulsion]
VINYBRAN 603SA (manufactured by Nissin Chemical Co., Ltd., vinyl chloride / vinyl acetate composition ratio (molar ratio): 70/30, solid content 50% by mass)
VINIBRAN 603 (Nisshin Chemical Co., Ltd., vinyl chloride / vinyl acetate composition ratio (molar ratio): 70/30, solid content 50 mass%)
[Polyvinyl chloride emulsion]
VINYBRAN 271 (manufactured by Nissin Chemical Co., Ltd., solid content 43% by mass, vinyl chloride / acrylic system: 50/50)
[Crosslinking agent]
Rezamin D-52 (manufactured by Dainichi Seika Kogyo Co., Ltd., solid content concentration 40% by mass, polycarbodiimide-based crosslinking agent)
CR-60N (manufactured by DIC, polyisocyanate crosslinking agent)
[Thickener (viscoelastic preparation agent)]
Rezamin D-28 (manufactured by Dainichi Seika Kogyo Co., Ltd., solid content concentration: 17.5% by mass)
SN thickener 612 (San Nopco, solid concentration 40% by mass)

<Manufacture of printing cards>
[Example 1]
(Preparation of composition for receiving layer)
In a 200 mL beaker, 2.5 g of a photopolymerization initiator (Irgacure 500, manufactured by Chiba), 2.5 g of a crosslinking agent (Rezamin D-52, manufactured by Dainichi Seika Kogyo Co., Ltd.), an ultraviolet curable aliphatic urethane acrylate emulsion (LR8949, 50 g of BASF), 50 g of polyurethane emulsion (Resamine D-4080, manufactured by Dainichi Seika Kogyo Co., Ltd.), and 1 g of thickener (Rezamin D-28, manufactured by Dainichi Seika Kogyo Co., Ltd.) were placed on an electronic balance (TOLED PL3000, METTTLER). The mixture was measured using a three-one motor stirrer (manufactured by Three-One Motor Co., Ltd.) at 300 rpm for 10 minutes at room temperature to obtain a composition for a receiving layer (coating agent). Table 1 shows the compounding components of the obtained composition and the compounding amounts of the effective components (for example, in the case of an emulsion, this corresponds to the compounding amount of the solid content excluding the dispersion medium).

(Coating of composition for receiving layer on substrate)
The composition is charged into a predetermined portion of a coating machine ((Micro Roller Coater MRC-450, Speed 2 m / min, Thermotronics Trading Co., Ltd.), (Gravure Roll NA1223, manufactured by Pilot Seiko Co., Ltd.)) A sheet made by Mitsubishi Plastics Co., Ltd. (size: 330 mm × 580 mm × 0.56 mm) was poured from a conveyor belt to a gravure roll, and coated on the sheet with the composition. At this time, the blade pressing pressure of the gravure roll was set to 1.5 scale, and the sheet pressing pressure was set to 0.1 mm.

(Formation of receiving layer)
Using a hair dryer (National TURROBO DRY1200), the coated sheet is dried for several minutes until there is no moisture, and a conveyor belt-type UV curing device (power supply unit UB041-5 for eye ultraviolet curing (lamp output 80 W / cm) The conveyor acrylate was polymerized using a conveyor speed of 15 m / min, a high-pressure mercury lamp lamp output of 4 kW, manufactured by iGraphics, Inc., to form a receiving layer. The thickness of the receiving layer was 1-2 μm.

(Formation of printing layer)
Using a sheet-fed printing machine (waterless ink: manufactured by T & K TOKA), lamp output: “200 W / cm × 3 lights” + “160 W / cm × 4 lights”, operation speed: 6400 sheets / hour, metal halide lamp : Under the printing conditions of “15 kW × 3” + “12 kW × 4”, the sheet on which the receiving layer is formed is offset printed with process ink (CMYK), and the thickness is 4 on the receiving layer.
A μm printed layer was formed.

(Formation of adhesive layer)
Using a sheet-fed silk printing machine, on the sheet on which the printed layer was formed under the printing conditions of 300 mesh, squeegee hardness 80 °, drying conditions: “45 ° C. × 25 minutes, normal temperature (25 ° C.) × 25 minutes” On the other hand, an adhesive (solvent ink, manufactured by Toyo Ink Co., Ltd.) was printed, and an adhesive layer having a thickness of 7 μm was formed on the printed layer.

(Formation of protective layer)
A transparent polyvinyl chloride sheet (thickness: 0.1 mm, Mitsubishi Plastics Co., Ltd.) is stacked on the adhesive layer on the sheet on which the adhesive layer has been formed, and the pressure is 0.5 kg / cm ² using a laminator. Then, hot pressing was performed under conditions of hot 150 ° C. × 22 minutes and cool 15 ° C. × 22 minutes to form a protective layer having a thickness of 100 μm on the adhesive layer.

(Card)
The sheet in which the receiving layer, the printing layer, the adhesive layer, and the protective layer were laminated in this order was cut into a card size of 85 mm × 54 mm to obtain a printed card.

[Examples 2 to 6]
A printing card was produced in the same manner as in Example 1 except that the compounding components and the effective components thereof at the time of preparing the receiving layer composition were as shown in Table 1.

[Example 7]
In a 200 mL beaker, 1.9 g of photopolymerization initiator (Irgacure 500, manufactured by Chiba), 26.5 g of urethane acrylate emulsion (LR8949, manufactured by BASF), 15.6 g of polyurethane emulsion (Hydran HW-311, manufactured by DIC), 10.6 g of polyvinyl chloride / vinyl acetate emulsion (Vinyl Blanc 603SA, manufactured by Nissin Chemical Co., Ltd.) was weighed with an upper plate electronic balance (TOLED PL3000, manufactured by METLER), and these mixtures were mixed with a three-one motor agitator (three-one motor company). The mixture was stirred at 300 rpm at room temperature for 10 minutes to obtain a mixed solution.
Next, 0.3 g of a viscoelasticity adjusting agent (SN thickener 612, manufactured by San Nopco) is dissolved in 32 g of ion-exchanged water in a 100 mL beaker, and the total amount thereof is combined with the above mixed solution to adjust the viscosity. did. Table 1 shows the compounding components of the obtained composition and the compounding amounts of the effective components (for example, in the case of an emulsion, this corresponds to the compounding amount of the solid content excluding the dispersion medium).
Thereafter, a printing card was produced in the same manner as in Example 1.

[Examples 8 to 12]
A printed card is produced in the same manner as in Example 7 except that the composition of the receiving layer composition, the blending amount of the effective component, and the thickness of the receiving layer are as shown in Table 1. did. The thickness of the receiving layer was adjusted by changing the number of coatings with the same coating amount per time of the composition. That is, in Examples 1 to 7, the thickness of the receiving layer was set to 1 to 2 μm after one coating, whereas the thickness of the receiving layer was set to two coatings. The thickness of the receiving layer was set to 5 to 6 μm by setting the number of coatings to 3 to 4 μm and the number of coatings to three.

[Examples 13 to 46]
The printing card was prepared in the same manner as in Example 7 except that the compounding component at the time of preparing the receiving layer composition, the blending amount of the effective component, and the thickness of the receiving layer were as shown in Tables 2 to 3, respectively. Manufactured. The thickness of the receiving layer was adjusted in the same manner as in Examples 7-12.

[Comparative Examples 1-8]
A printed card is produced in the same manner as in Example 7 except that the composition of the receiving layer composition, the blending amount of the effective component, and the thickness of the receiving layer are as shown in Table 4. did.

<Evaluation of effect of suppressing peeling of printed layer in printing card>
About the printing card manufactured in Examples 1-46 and Comparative Examples 1-8, the peeling inhibitory effect from the base material of a printing layer was evaluated with the following procedure.
First, on the surface on the protective layer side of the printing card, a cut was made with a cutter so as to draw a diagonal line. That is, the formed cut line intersects at almost the center of the card surface. At this time, the blade of the cutter is not perpendicular to the surface of the printing card, but is slightly inclined to make a cut so that at least the protective layer is cut over the entire thickness direction.
Subsequently, the protective layer was peeled off from the printed card body starting from the intersecting portion of the cut.
And the state of the printing layer in a printing card | curd main body was confirmed visually, and the peeling suppression effect of the printing layer was evaluated together with the degree of resistance felt when the protective layer was peeled off. The evaluation criteria are as follows. “◎” and “◯” indicate that the effect of suppressing the peeling of the printed layer is high and is acceptable, and “△”, “×”, and “XX” indicate that the effect of suppressing the peeling of the printed layer is low and are not satisfactory. Indicates an acceptable level. The evaluation results are shown in Table 5.

(Evaluation criteria)
A great resistance was felt, only the protective layer was peeled off from the card body, and the printed layer was completely left on the card body.
A large resistance was felt, only the protective layer was peeled off from the card body, and the printed layer was almost completely left on the card body.
Δ: A moderate resistance was felt, but the protective layer was peeled off from the card body together with at least a part of the printed layer.
X: The protective layer was easily peeled from the card body together with at least a part of the printed layer without feeling great resistance.
XX: The protective layer was easily peeled off from the card body together with at least a part of the printed layer with almost no resistance.

As is clear from Tables 1 to 5, it was confirmed that peeling of the printed layer from the substrate can be sufficiently suppressed according to the present invention.
For example, when the polyurethane is a polycarbonate / polyether type (Resamine D-4080) or a polycarbonate type (Resamine D-6031, Resamine D-6300), the smaller the blending amount with respect to the urethane acrylate, the more the peeling of the printed layer is. The tendency which was excellent by the inhibitory effect was seen (for example, Example 41 and 43, Example 13 and 15, Example 17 and 19, etc.).
On the other hand, when the polyurethane is a polycarbonate diol type (particularly UW-5034-E, UW-5101-E) and a polyester type (particularly Hydran HW-311), the printing layer having a larger blending amount with respect to urethane acrylate is preferred. The tendency which was excellent by the peeling inhibitory effect of (for example, Example 24 and 26, Example 28 and 29, Example 31 and 33 etc.) was seen.
In addition, for example, when the polyurethane is a polycarbonate type (Resamine D-6031), a tendency to be more excellent in the effect of suppressing the peeling of the printed layer was observed by using a crosslinking agent in the composition (for example, Example 13). And 36 etc.).
However, in Comparative Examples 1 to 8 in which urethane acrylate and polyurethane were not used in combination, peeling of the printed layer from the substrate could not be suppressed.

<Formation of receiving layer>
[Production Examples 1 to 10]
The composition of the receiving layer, the compounding amount of the effective component, and the thickness of the receiving layer are as shown in Table 6, respectively, and the pressure heating treatment is performed without forming the printed layer, the adhesive layer and the protective layer. A receiving layer was formed on the substrate in the same manner as in Example 7 except that the step was not performed. The thickness of the receiving layer was adjusted in the same manner as in Examples 7-12.

[Production Examples 11 to 16]
A receiving layer was formed on the substrate in the same manner as in Examples 1 to 6 except that the printing layer, the adhesive layer, and the protective layer were not formed and the pressure heat treatment was not performed. That is, in the production examples 11, 12, 13, 14, 15, and 16, the laminated structure in which the receiving layer is formed on the base material is the production of the printing cards of the above-described Examples 1, 2, 3, 4, 5, and 6, respectively. Same as in time.

<Evaluation of blocking effect of receptor layer>
About the receiving layer of each said manufacture example, the blocking suppression effect was evaluated with the following procedure.
First, a sheet made of hard polyvinyl chloride (Mitsubishi Resin Co., Ltd., thickness: 0.56 mm) not coated with the above composition was layered on the surface of each receiving layer, and a blanket was stuck on the surface. The sample was sandwiched between mirror plates and placed on a flat surface. Further, three 4 kg weights were placed on the mirror plate, pressure was applied to the receiving layer and the uncoated hard polyvinyl chloride sheet, and this state was maintained and allowed to stand at room temperature for 12 hours.
Next, the mirror plate was tilted as it was, and the presence or absence of sliding (sliding down) of the uncoated hard polyvinyl chloride sheet was confirmed, and the blocking inhibitory effect of the receiving layer was evaluated according to the following evaluation criteria. “◎” and “◯” both indicate a pass level, and “×” indicates a fail level. Table 7 shows the evaluation results.
(Evaluation criteria)
A: A high blocking inhibitory effect is recognized, and there is no problem in practical use.
○: Blocking suppression effect is recognized and there is no practical problem.
X: The blocking inhibiting effect is low or not recognized at all, and there is a problem in practical use.

  As is clear from Table 7, when the urethane acrylate and the polyurethane are used in combination, a blocking inhibitory effect is recognized. Further, from the results of Production Examples 11 to 16, the printing card of the present invention has a blocking inhibition effect in the production process. It was confirmed that the basic characteristic of the effect was not impaired.

  INDUSTRIAL APPLICATION This invention can be utilized as various laminated bodies, such as a card | curd with which a printing layer was provided on the base material which consists of polyvinyl chloride, and a decorative material.

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 1 '... Structure, 11, 11' ... Base material, 12, 12 '... Receiving layer, 13, 13' ... Printed layer, 14, 14 ' ..Adhesive layer, 15, 15 '... protective layer

Claims (3)

On the base material made of polyvinyl chloride, a receiving layer for ultraviolet curable acrylic ink and a printing layer formed from ultraviolet curable acrylic ink are laminated in this order and subjected to pressure heating treatment. And
The receiving layer is formed from a composition in which an aqueous emulsion mainly composed of an ultraviolet curable urethane acrylate, an aqueous emulsion mainly composed of polyurethane, and a photopolymerization initiator are blended. A featured laminate. When the urethane acrylate is obtained using an aliphatic isocyanate monomer, the blending amount of the polyurethane per 1 part by weight of the urethane acrylate is 0.1 part by weight or more,
When the urethane acrylate is obtained using an aromatic isocyanate monomer, the blending amount of the polyurethane per 1 part by weight of the urethane acrylate is 0.8 part by weight or more. The laminate according to claim 1.   The laminate according to claim 1 or 2, wherein a protective layer is further laminated on the printed layer and subjected to pressure and heat treatment to form a card shape.

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