JP2006281480A - Laminated film, its manufacturing method, lamination treatment method and printed matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated film capable of fundamentally obtaining a sufficient blocking preventing function in a preserved state of printed matter subjected to lamination treatment, realizing sufficient glossiness in an obtained product even in a case that lamination treatment is performed at a relatively low temperature, obtaining sufficient transmittance in the laminated layer of the product and enhancing the image quality of the product by those effects. <P>SOLUTION: In the laminated film, which is constituted by laminating a protective layer having a surface layer and an adhesive layer on a heat-resistant base material in a peelable manner, used in a laminator of which the fixing temperature is 110-140°C, the adhesive layer contains an adhesive resin material and beads, the glass transition point (Tg) of the adhesive layer is 35°C or below and the melting point of the beads is 70-135°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate film for covering the surface of a member to be protected (for example, a recording member obtained by forming an image) with a protective layer. In particular, after a protective layer formed on a heat-resistant substrate is thermally fixed to a member to be protected (recording member), only the heat-resistant substrate is peeled off to form a protective layer on the recording member. The present invention relates to a laminate film that can be produced, a method for producing the laminate film, a laminate processing method using the laminate film, and a printed matter in which the laminate film is fixed on the image surface.

  Conventionally, in a printed matter obtained by various image forming methods such as an inkjet method, an offset method, a gravure method, and an electrophotographic method, a surface on which an image is formed (image receiving media surface) is covered with a laminate film (so-called laminate). Processing) has been done. And, by laminating, image fastness such as light resistance, water resistance, gas resistance and friction resistance is improved, and further, the glossiness, smoothness and image density of the image surface are increased, and the image quality is improved. It is widely known (see, for example, Patent Document 1).

  Among the image forming methods described above, the laminating treatment is particularly effective for a printed matter obtained by an ink jet method. In other words, for recording devices that use the inkjet method, a method of printing dyes and pigments dissolved in water on a recording member with high moisture absorption is adopted due to restrictions on the printing method that ink ejects from fine ejection openings. Is widely spread. In general, printed matter formed by an inkjet method using a water-based ink containing a water-soluble dye is often poor in weather resistance due to light, gas, water, etc. The printed matter formed in 1 is particularly inferior in scratch resistance and often causes uneven gloss, etc. In order to make these images highly durable, it is effective to perform the laminating process described above.

  Here, in the laminating process, the protective layer supported by the heat-resistant substrate is thermally fixed on the image surface of the printed material, and then only the heat-resistant substrate is peeled off from the protective layer so that the protective layer is placed on the image surface. There are a method of obtaining a finished print by leaving it, and a method of obtaining a finished print by leaving it on the image surface as it is without peeling off the heat-resistant substrate. Among these, the laminating method of the type in which the heat-resistant substrate is peeled off is not affected by the haze of the heat-resistant substrate, so that a high-density image is obtained.

  Laminate films used for these laminating processes are laminated films in order to prevent blocking between the adhesive layer and the heat-resistant substrate before one winding in contact with the adhesive layer, which occurs when stored in a roll state. Often, a release agent is added to the adhesive layer. And as a mold release agent, the fillers which consist of an inorganic or organic compound, a polysiloxane type material, a fatty acid ester type material, etc. are used. Among these, the polysiloxane-based material has an advantage that, when laminating to a recording member having a silica-based ink receiving layer, the adhesive layer can easily wrap around the silica-based ink receiving layer, resulting in an increase in the density of the printed matter. It is known that there is.

  In addition, in the laminate film, it is also widely known that a back coat layer is further provided on a surface different from the surface on which the protective layer is provided on the heat-resistant substrate in order to prevent blocking. Furthermore, it is also known to form irregularities on the surface of the adhesive layer by mixing organic or inorganic beads in the adhesive layer of the laminate film. And by forming such irregularities, not only the anti-blocking action is exhibited, but a fine air gap is formed, and adhesion of films and generation of wrinkles during lamination processing or film processing, It is also known that displacement is prevented. In addition, when the adhesive layer is made of a material having a low Tg, fluidity may occur in the material constituting the adhesive layer after long-term storage. This may cause loss of uniformity on the surface of the adhesive layer, and It often happens that the image is uneven. In order to deal with such problems, surface properties with fine and uniform irregularities can be obtained by mixing an appropriate amount of organic or inorganic beads. As a result, good image quality can be obtained in the finished product (printed product) after lamination. (See, for example, Patent Document 2 and Patent Document 3).

  On the other hand, beads having a suitable melting point are used for the laminate film, and they are completely melted by heating at the time of lamination, and are completely taken into the range of the thickness of the adhesive layer, and have a smooth surface property. It has been achieved (see, for example, Patent Document 4).

JP 2001-121609 A JP 2003-231217 A JP-A-9-66677 JP-A-9-175054

  However, for example, when a laminate film having an adhesive layer containing beads having a relatively high melting point such as acrylic is laminated with heat and pressure on the recording member, the beads are not completely dissolved and the particles are not dissolved. In some cases, all or part of the shape is maintained. For this reason, even if a smooth surface property is obtained immediately after fixing, if the laminated print (hereinafter also referred to as a product) is left in a storage environment such as high temperature and humidity, the material constituting the adhesive layer flows. By doing so, there is a problem that the beads whose shape is gradually maintained protrude from the surface layer into a convex shape and the image quality (glossiness, smoothness, etc.) of the resulting product is lowered.

  In addition, when laminating is performed at such a high temperature that high melting point beads can be dissolved, a heat-resistant substrate constituting the laminate film (generally, PET, PP, or vinyl chloride is often used). ) Or the recording member shrinks and melts due to heat, and deformation such as wrinkles occurs. On the other hand, in laminated films using beads with an excessively low melting point, the shape of the beads gradually changes due to long-term storage at normal temperature and humidity, and the anti-blocking effect cannot be obtained sufficiently. There is a manufacturing problem in that it can be processed only at a low temperature in the process (for example, when the resin is coated and dried).

  In addition, in a product obtained using a laminate film using beads having an appropriate melting point as described in Patent Document 4, even if sufficient glossiness is obtained due to the smooth surface property, Sufficient transmittance is not always obtained, and there is a possibility that white turbidity, unevenness, dust and the like may occur. Such a lack of transparency may make it difficult to achieve the desired image quality, particularly when an image formed by the inkjet method is laminated to achieve high image quality.

  The present invention has been made in consideration of these circumstances, and the first object of the present invention is to provide a sufficient anti-blocking function in the storage state of the laminated printed matter. Even when laminating at a relatively low temperature, sufficient gloss is achieved in the resulting product, and sufficient transparency is obtained in the laminate layer of the product, resulting in these results. An object of the present invention is to provide a laminate film that can improve the quality of an object.

The second object of the present invention is to provide a method for producing a laminate film from which the above laminate film can be obtained.
The third object of the present invention is to provide a laminating method for laminating using the above laminating film.
Furthermore, a fourth object of the present invention is to provide a printed matter in which the image surface is laminated with the above laminate film.

  The above object is achieved by the present invention described below. That is, the present invention is a laminate film obtained by laminating a protective layer having a surface layer and an adhesive layer on a heat-resistant substrate, which is used in a laminating apparatus having a fixing temperature of 110 ° C. to 140 ° C. The adhesive layer contains an adhesive resin material and beads, the glass transition point (Tg) of the adhesive layer is 35 ° C. or lower, and the melting point of the beads is 70 to 135 ° C. This is a laminate film.

  In addition, preferred embodiments of the laminate film according to the present invention include the following [1] to [12]. [1] A laminate film in which the content of beads in the adhesive layer is 0.1 to 5% by mass with respect to 100% by mass of all materials constituting the adhesive layer. [2] A laminate film in which the number average particle diameter of beads in the adhesive layer is (layer thickness of adhesive layer × 0.6) to (layer thickness of adhesive layer × 2).

[3] A laminated film in which the beads in the adhesive layer are composed of a group of beads that satisfy the following condition (1).
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5).
[4] A laminate film in which the beads in the adhesive layer are constituted by a group of beads that satisfy both the above condition (1) and the following condition (2).
Condition (2): Containing less than 10% by number of beads having a particle diameter equal to or greater than (layer thickness of the adhesive layer × 3.5).
[5] A laminated film in which the beads in the adhesive layer are composed of a group of beads that satisfy both the above condition (1) and the following condition (3).
Condition (3): Containing less than 10% by number of beads having a particle size of (adhesive layer thickness × 0.3) or less.
[6] A laminated film in which the beads in the adhesive layer are constituted by a group of beads that satisfy all of the above conditions (1), (2), and (3).

  [7] A laminated film in which the beads in the adhesive layer are formed of low-density polyethylene.

  [8] A laminate film in which the adhesive resin material that is the main component of the adhesive layer is a polymer material selected from the group consisting of acrylic resins, vinyl acetate resins, ethylene / vinyl acetate copolymer resins, polyester resins, and polyurethane resins . [9] A laminate film in which an ultraviolet absorbent is mixed with an adhesive resin material that is a main component of an adhesive layer. [10] A laminate film in which the adhesive resin material that is the main component of the adhesive layer contains a resin material having an ultraviolet absorbing group in the molecular chain.

  [11] A laminate film in which the main component of the surface layer is a resin material, and an ultraviolet absorber is mixed with the resin material. [12] A laminate film in which the main component of the surface layer is a resin material, and the resin material contains a polymer substance having an ultraviolet absorbing group in the molecular chain.

  According to another embodiment of the present invention, there is provided a manufacturing method for manufacturing a laminate film according to any one of the above, wherein a surface layer and an adhesive layer are sequentially laminated on a heat resistant substrate. A method for producing a laminate film, comprising a step of forming an adhesive layer by applying a coating solution containing the above by a coating method.

  In another embodiment of the present invention, in the laminating method in which the laminate film described above is used and the protective layer of the laminate film is fixed to the recording member by heating, the heating means is a heat roller. And a recording member laminating method.

  Another embodiment of the present invention is a printed matter, wherein the surface of the recording member is laminated with a protective layer constituting any one of the laminated films described above.

  As a preferred embodiment of the printed matter according to the present invention, the recording member is a printed matter having an image formed by an ink jet recording method, or the recording member comprises a substrate and an ink receiving layer. The printed matter which is a thing is mentioned.

  According to the laminate film of the present invention, basically, the adhesive layer having a Tg within a specific range has a configuration in which beads having a melting point within a specific range are contained. In this case, a sufficient anti-blocking function is exhibited. At the same time, since the beads in the adhesive layer have an appropriate melting point, even when the laminating process is performed at a relatively low temperature, the beads soften or dissolve and are taken into the adhesive layer. The adhesive layer after the lamination process is completely melted and is completely taken into the adhesive layer to achieve a smooth surface, so that the product obtained using the laminate film has sufficient gloss Is realized. Moreover, as described above, the laminate film of the present invention is formed by using an adhesive resin material that can provide an adhesive layer having a specific Tg with respect to beads having a specific melting point. The mixed state of the beads formed by the heating of the treatment with respect to the adhesive resin material becomes a completely compatible state or an extremely high dispersion / diffusion state. As a result, white turbidity, unevenness, dust, etc., which are considered to occur due to the difference between the refractive index of light inherent to each of the adhesive resin material and the beads, or the difference in crystallinity between the two, are practically used. Sufficient permeability is obtained in the laminate layer in the resulting product, which is suppressed to an unproblematic level. By using the laminate film according to the present invention having the above-described actions and effects, the resulting product can have high image quality.

Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a laminate film of the present invention. This laminate film is an example of the simplest layer structure, and includes a surface layer (B) on one surface of the heat-resistant substrate (A), and on the surface of the surface layer (B), a recording member. An adhesive layer (C) containing an adhesive resin material that can be bonded to the adhesive layer (C) is provided, and beads (D) are contained in the adhesive layer (C).

Next, each layer and each material which comprise the laminate film of this invention are demonstrated.
1: Heat-resistant substrate (A)
As the heat-resistant substrate (A), the self-holding property required for the production stage of the laminate film, the use of heating the laminate film to the recording member, and applying the pressure in some cases is stable. Any material can be used as long as it can be maintained and can be easily peeled off when the protective layer is coated on the recording layer of the recording member. For example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyethersulfone, polyetherketone, polypropylene, polycarbonate, polystyrene, polyamide, polyimide, polyamideimide, polyethylene, polyvinyl chloride, polyvinylidene chloride, cellulose acetate, A film or sheet made of a single layer or a laminate made of materials such as cellulose acetate and polymethylpentene, or a mixture of two or more kinds of materials can be used.

  Moreover, what is necessary is just to let the thickness of a heat resistant base material (A) be a thickness suitable for a lamination process, for example, it is preferable that it is the range of about 5-200 micrometers. Moreover, you may use what gave the process which improves adhesiveness, such as a corona treatment, to the surface of these heat resistant base materials, or the thing which gave the mold release process conversely.

  The heat-resistant substrate may have a surface roughened by embossing, sandblasting, or laminating a resin layer containing powder particles on the surface on which the protective layer is formed. When a laminate film using such a heat-resistant substrate that has been roughened is used, the printed matter obtained after the laminate treatment is a protective layer such as semi-glossy, matte, or silky. It will have. On the other hand, when a heat-resistant substrate that has not been subjected to a roughening treatment is used, after the laminate film is bonded to the recording member and the heat-resistant substrate is peeled off, a glossy protective layer is formed. A printed matter having the above is obtained.

2: Surface layer (B)
The surface layer (B) is a layer that becomes the outermost surface of the protective layer when the laminate film is laminated on the recording member. In the present invention, the surface layer (B) from the viewpoints of imparting heat resistance to the printed material, bending property (flexibility), and preventing blocking on the image surface laminated in various environments. It is desirable to use a resin material having a glass transition point (Tg) of 60 ° C. or more as a resin material which is a main component of the forming material (60% by mass or more of all materials constituting the surface layer). Examples of such materials include resin materials containing polymer substances such as acrylic resins, styrene resins, vinyl chloride resins, and vinyl acetate resins. The layer thickness of the surface layer (B) can be selected from the range of 0.5 to 20 μm, for example.

3: Adhesive layer (C)
The adhesive layer (C) constitutes a protective layer together with the above-described surface layer. The adhesive layer (C) is in a cured state at room temperature, and is softened by heating during the laminating process, has fluidity, and soaks into the recording member, thereby adhering (fixing) the laminate film to the recording member. It has an action. In the present invention, the glass transition point (Tg) of the adhesive layer (C) is set to 35 ° C. or lower. Specifically, a material having a glass transition point (Tg) of 35 ° C. or lower may be used as an adhesive resin material that is a main forming material of the adhesive layer. The adhesive layer (C) includes beads (D) contained in such an adhesive resin material, and the beads have a melting point of 70 to 135 ° C. Hereinafter, these materials constituting the adhesive layer (C) will be described.

a) Beads (D)
As the beads (D) contained in the adhesive layer (C), those having a melting point of 70 to 135 ° C. are used. Further, the melting point is more preferably 120 ° C. or lower. The beads (D) made of such a material are a roll of the adhesive layer and the adhesive layer that may be generated when the laminate film according to the present invention is stored in a roll and placed in a high temperature environment. It is contained in the adhesive layer (C) for the purpose of preventing blocking with the previous heat resistant substrate. Therefore, it is preferable that the material is composed of a material that exhibits hardly deformability at an appropriately set storage environment temperature and that can form irregularities on the surface of the adhesive layer (C).

  In order to achieve the above object, the number average particle diameter of the beads (D) contained in the adhesive layer (C) is (layer thickness of the adhesive layer × 0.6) to (layer thickness of the adhesive layer × 2). Furthermore, it is more preferable that they are (layer thickness of the adhesive layer × 0.8) to (layer thickness of the adhesive layer × 1.4).

  Furthermore, in the form in which beads are contained in the adhesive layer of the laminate film, the beads are present in the adhesive layer between the recording member and the surface layer in the laminated print product. Depending on the storage environmental conditions of the processed printed matter and the type of adhesive resin material, the surface layer laminated on the bead may be deformed along the shape of the bead, affecting the gloss of the printed matter. There may be a problem in a printed matter in which a printed matter such as an image is laminated. Therefore, in order to obtain glossiness and smoothness equivalent to a print obtained by using a laminate film not containing beads with respect to a print obtained by laminating, in the adhesive layer The beads to be contained are preferably materials that are deformed and dissolved by heating during the laminating process and taken into the range of the thickness of the adhesive layer.

  Examples of such a bead material include low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer resin, and higher fatty acid calcium. Among these, the bead material that can be particularly preferably used in the present invention is low-density polyethylene. As described above, the physical properties require that the melting point of the beads be 70 ° C. or more and 135 ° C. or less, and it is particularly preferable that the melting point be 120 ° C. or less.

  In addition, the beads (D) made of the above-described materials constituting the laminate film according to the present invention cause a decrease in the light transmittance of the protective layer of the resulting laminate film when the amount added to the adhesive layer is large. Let If the light transmittance is significantly reduced, it gives false recognition in the film detection using, for example, a light detection element in the laminating apparatus used when laminating the surface of the recording member. Process control may not be performed. Therefore, the content of the beads in the adhesive layer is preferably 0.1 to 5% by mass, particularly 0.25 to 1% by mass, with respect to 100% by mass of all the materials constituting the adhesive layer. It is preferable to make it.

  Further, when beads having a large particle diameter are used, the beads contained in the adhesive layer are not dissolved during the laminating process, and there is a risk of causing the above-described problems in the obtained product. . In this case, the beads having a large particle diameter are caught by a bar or the like used when the adhesive layer forming coating solution containing beads is applied and formed on the surface protective layer (FIG. 1B). A uniform adhesive layer surface may not be obtained, for example, streaks may be formed on the surface of the adhesive layer formed thereafter. Furthermore, the above-described coating liquid is stirred and circulated and applied onto the surface protective layer (FIG. 1B). However, a large amount of mesh is applied to the mesh on the circulation path, for example, to remove dust. It may cause clogging.

Therefore, the beads (D) used in the present invention are constituted by a group of beads satisfying at least the condition (1) of the following conditions (1) to (3), and further include the condition (1) 2 More preferably, the beads are composed of a group of beads satisfying the above conditions.
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5).
Condition (2): Containing less than 10% by number of beads having a particle diameter equal to or greater than (layer thickness of the adhesive layer × 3.5).
Condition (3): Containing less than 10% by number of beads having a particle size of (adhesive layer thickness × 0.3) or less.

  Moreover, it is also preferable that the beads (D) used in the present invention have a shape closer to a true sphere. That is, by including beads with a shape close to a true sphere, even when laminating at a relatively low temperature of about 110 to 140 ° C., the beads are uniformly softened and denatured. The occurrence of defects can be suppressed, and a printed matter having a uniform surface shape can be obtained. Furthermore, when beads having a shape close to a true sphere are included in the coating solution for forming the adhesive layer, the dispersibility of the beads is increased, and the occurrence of aggregation of the beads in the coating solution for forming the adhesive layer is caused. As a result, it is possible to obtain a good image quality in the recording member (product) after the lamination process.

b) Adhesive resin material The adhesive resin material that is the main component of the adhesive layer (C) (60% by mass or more of the total material constituting the adhesive layer) is in a cured state at room temperature and softened by heating. What has fluidity | liquidity and what makes | forms the effect | action which adhere | attaches a laminate film to a recording member by using a recording member is used. Since the heating time for laminating the laminate film according to the present invention on the recording member using a heat roller or a thermal head as the heating means is very short, the adhesive resin material is used within the slight heating time. In addition, it is preferable to use a material that softens and flows instantaneously and exhibits adhesiveness.

  In the case of a laminate film in which the beads (D) having an appropriate melting point described in the above a) are contained in the adhesive resin material as described above, the beads are dissolved by heating in the laminating process, and the adhesive layer High glossiness due to the smooth surface property can be obtained in a product obtained by being taken in the range of the film thickness and laminated. However, depending on the adhesive resin material, sufficient transmittance may not always be obtained, and the difference in the refractive index of light inherent to each of the adhesive resin material and the beads, or the crystal of each of the two materials. Due to the difference in sex, there is a risk of white turbidity, unevenness, dust and the like. This lack of transparency of the laminate layer is particularly difficult when the desired image quality cannot be achieved when trying to achieve high image quality in a product obtained by laminating an image formed by the inkjet method. There is.

  Therefore, in order to suppress white turbidity, unevenness and dust to such an extent that there is no practical problem, to achieve sufficient transparency in the laminate layer of the resulting product, and to achieve a high image quality of the product, laminate At the time of processing, the mixed state of the adhesive resin material and the beads is required to be in a completely compatible state or an extremely high dispersion / diffusion state. On the other hand, in this invention, it is comprised so that the glass transition point (Tg) of an contact bonding layer may be 35 degrees C or less.

  Examples of the adhesive resin material that can be used in the present invention include acrylic resins, styrene-acrylic resins, vinyl acetate resins, vinyl chloride resins, vinyl chloride-vinyl acetate resins, styrene-butadiene resins, styrene- Examples thereof include vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate resin, polyester resin, polyethylene resin, polyamide resin, chlorinated rubber resin, polypropylene resin, and urethane resin. These can be used alone or as an emulsion-based resin or an organic solvent-based resin mainly composed of a mixture of two or more thereof.

  In order to obtain better penetration into the recording member, a low molecular weight crystalline resin such as wax can be added to such an adhesive resin material. As the wax, a material that exhibits a sharp melting property upon heating is preferable. Specific examples of such wax include carnauba wax, paraffin wax, microcrystalline wax, candelilla wax, Fischer-Tropsch wax, and synthetic polyethylene wax. The thickness of the adhesive layer made of the material as described above may be a thickness suitable for laminating, and is preferably selected from a range of about 5 to 50 μm, for example.

  The laminate film according to the present invention is a surface of the heat-resistant substrate layer (A) opposite to the surface on which the surface layer (B) and the adhesive layer (C) are formed (the lower surface in FIG. 1). Further, a back coat layer may be provided. Examples of the material used for forming the back coat layer include silicone resins, polyolefins, ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, nitrocellulose, and other cellulose resins, polyvinyl alcohol, and polyvinyl acetate. , Vinyl resins such as polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymer, acrylic-silicone resin, polyamide resin, polyvinyl toluene Resin, coumarone indene resin, polyester resin, polyester-silicone resin, polyurethane resin, silicone modified or fluorine modified Resin material such as urethane and the like. These can be used alone or in admixture of two or more.

  Further, a heat-resistant slip property may be imparted by adding a solid or liquid release agent or lubricant to the material for forming the back coat layer. The release agent or lubricant is not particularly limited, and examples thereof include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, anionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants, fluorosurfactants, organic carboxylic acids and derivatives thereof, fluororesins, silicone resins, fine particles of inorganic compounds such as talc and silica, and the like can be used.

  In particular, in order to increase the surface strength and scratch resistance of the backcoat layer, among the above resin materials, the resin having adhesion to the heat-resistant substrate and the slipperiness / peeling (non-adhesion) required for the backcoat It is preferable to use a resin which is reactively bonded to a material having a property (for example, silicone).

  Furthermore, in order to improve the heat resistance in the back coat layer, a resin having a reactive group among the above resin materials is added by adding polyisocyanate or the like as a cross-linking agent to be cross-linked. It is preferable to use it.

  The laminate film according to the present invention includes any one of the surface layer (B), the adhesive layer (C), and the back coat layer formed as necessary, or a plurality selected from these layers. The resin material constituting the layer may be mixed with an ultraviolet absorber. Examples of the ultraviolet absorber used at this time include non-reactive ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, substituted acrylonitrile, hindered amine and nickel chelate. These may be used alone or in admixture of two or more and mixed with an emulsion resin or organic solvent resin material as a main component.

  Further, in the above-described form, in order to prevent bleeding of the contained UV absorber and prevent the UV absorption performance from being deteriorated, the resin material containing a high molecular substance having an UV absorbing group in the molecular chain is used. Each layer may be formed. Examples of such a resin material include those in which a reactive ultraviolet absorber and a resin as a main component are preliminarily bonded, or those that are crosslinked in a coating and drying stage for being laminated on the heat-resistant substrate (A). Can be mentioned.

  Examples of the ultraviolet absorber that can be suitably used for the above purpose include 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5). '-(Meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2 ' And benzotriazole compounds such as -hydroxy-5 '-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole. In addition, as a thermoplastic resin in which a compound having an ultraviolet absorption performance is chemically bonded, a resin obtained by synthesis by a known method or a commercially available product can be used.

  The surface layer (B), the adhesive layer (C), and the back coat layer to be formed as needed are a step of applying a coating solution prepared with a suitable material for each layer onto a heat resistant substrate and drying it. It can be formed by repeatedly laminating. As a coating method used at this time, for example, a roll coating method, a rod bar coating method, a slot die coating method, a micro gravure coating method, a pawn tent method, or the like can be used.

  In addition, each said layer provided on the heat resistant base material may be transparent or opaque in the state provided on the heat resistant base material. What is necessary is just to be a transparent film in the state coat | covered on the image surface of the recording member by the lamination process.

  Next, the lamination process using the laminate film according to the present invention will be described. The laminate film according to the present invention can be applied to various recording members. In particular, the laminate film can be suitably applied to a printed product obtained by laminating an image surface formed by an inkjet recording method and covered with a laminate film. . FIG. 2 shows a cross-sectional view of an example of a recording member obtained by laminating the laminate film on a recording member used in the ink jet recording method. The recording member used at this time is preferably one in which the ink receiving layer (F) is coated on the substrate (E) that supports the ink receiving layer.

  For the ink receiving layer (F) at this time, for example, one having a configuration in which porous inorganic particles and a binder as necessary are mixed is used. Examples of the porous inorganic particles include silica, alumina, magnesium carbonate, calcium carbonate, silica alumina mixed crystal and silica magnesium mixed crystal. In particular, silica or alumina is preferably used from the viewpoint of good image quality and economy.

  As a form of the laminate film according to the present invention suitable for the ink-receiving layer containing silica, a laminate film in which a polysiloxane-based antiblocking agent is added to the adhesive layer can be mentioned. When the laminate film is used for lamination, for example, the adhesive layer of the laminate film sufficiently wraps around the ink receiving layer containing silica, so that a high-quality printed product can be formed.

  FIG. 3 shows an example of an apparatus for performing a forming process of a laminate film-attached print (laminated print) in which the laminate film is applied to the image surface using the laminate film according to the present invention. The apparatus of FIG. 3 includes an image receiving medium supply unit 1, and the inside of the apparatus is in order from the front upper part to the front middle part, the film attachment part 2, the laminate film (G) attached to the film attachment part 2, the supply port 4 and A supply roller pair 5 serving as a supply means, a guide roller 6 and a fixing roller pair 7 at a substantially center, and a conveyance roller pair 8, a discharge roller pair 9, and a discharge port 10 are arranged in order from the lower rear to the lower front. Yes. The supply roller pair 5 includes a supply lower roller 5a and a supply upper roller 5b, and the fixing roller pair 7 includes a fixing upper roller 7a and a fixing lower roller 7b. Further, the transport roller pair 8 includes a transport main roller 8a and a transport sub-roller 8b, and the discharge roller pair 9 includes a discharge upper roller 9a and a discharge lower roller 9b.

  The recording member (H) is fed from the supply port 4 in a state in which the stamp screen (ink receiving layer surface) faces the adhesive layer surface of the laminate film (G) drawn out from the rolled state. Then, it passes between the fixing roller pair 7 and is heated and pressurized to 110 ° C. to 140 ° C. as necessary. After the lamination treatment, only the heat-resistant substrate is peeled off to obtain a laminate printed matter having a protective layer on the image surface.

  Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

Example 1
The laminate film of this example was produced according to the following procedure. Furthermore, using the obtained laminate film, the image surface of a recording member (inkjet print product) on which an image was formed by an ink jet recording method was laminated to prepare a laminate print product.

<Formation of surface layer>
In this example, a polyethylene terephthalate film (layer thickness: 25 μm) was used as the heat resistant substrate. Then, on one surface of the heat-resistant substrate, an ultraviolet absorbing polymer (PUVA-30M, manufactured by Otsuka Chemical Co., Ltd.), which is a high molecular substance having an ultraviolet absorbing group in the molecular chain, has a dry layer thickness of 5 μm. And dried to obtain a coating film in which a thin film to be the surface layer of the laminate film was formed on the surface of the heat-resistant substrate.

<Formation of adhesive layer>
On the surface layer of the coating film obtained above, a thin film to be an adhesive layer of the laminate film was formed by the following method to obtain a laminate film of this example. First, 100 parts of Viniblanc 2706E (Nissin Chemical Industry Co., Ltd., solid content 40%, Tg 30 ° C.), which is an acrylic emulsion, and 2 parts of a water-based surface conditioner (BYK-333, Big Chemie Japan Co., Ltd.) In addition, as anti-blocking beads, 0.5 parts of true spherical low density polyethylene beads (flow beads SS-1, manufactured by Sumitomo Seika Co., Ltd.) having a number average particle diameter of 16.3 μm and a melting point of 107 ° C. were mixed. A coating solution for forming an adhesive layer was prepared. Next, the coating solution is applied on the surface layer of the coating film by a fountain method using a doctor bar so as to have a dry layer thickness of 15 μm, and dried to form an adhesive layer. A laminate film was obtained. The beads contained in the adhesive layer of the laminate film have a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer) × 3. 5 = 27% by number of beads having a particle size of less than 52.5 μm, and 0.2% by number of beads having a particle size of 15 μm (adhesive layer thickness) × 3.5 = 52.5 μm or more. It was confirmed that less than 1.2% by number of beads having a particle diameter of 15 μm (adhesive layer thickness) × 0.3 = 1.5 μm or less was further contained.

<Creation of recording member (inkjet print)>
A glossy paper dedicated to inkjet printers (Professional Photo Paper PR101, manufactured by Canon Inc.) is used as the recording member, and a solid black image is formed on the recording member using an inkjet printer (PIXUS 990 Canon Inc.). Obtained.

<Making laminate prints>
Using the apparatus shown in FIG. 3, the inkjet print obtained above was laminated with the laminate film of this example to obtain a laminate print. The printed surface of the black solid print obtained above was overlaid with the adhesive layer surface of the previously produced laminate film, and a steel roller with a diameter of 80 mm and a rubber roller with a diameter of 50 mm heated to 120 ° C. were nipped with a load of 120 N. Lamination was performed on the pair of fixing rollers by thermocompression bonding at a feed rate of 8 mm / sec so that the laminate film was on the steel roller side. After the treatment, only the polyethylene terephthalate film, which is a heat-resistant substrate, was peeled off to obtain a laminate print having a laminate film on the printing surface.

(Example 2)
For forming an adhesive layer by mixing 4 parts of anti-blocking true spherical low-density polyethylene beads (Flow Bead SS-1, manufactured by Sumitomo Seika Co., Ltd.) used in producing a laminate film in Example 1. A laminate print was obtained in the same manner as in Example 1 except that the coating solution was prepared.

(Example 3)
The anti-blocking beads contained in the coating solution for forming the adhesive layer used in preparing the laminate film in Example 1 were a low density polyethylene emulsion (A110, Gifu Shellac) having a number average particle diameter of 10 μm and a melting point of 117 ° C. A laminate film of this example was produced in the same manner as in Example 1 except that 1.25 parts (0.5% in terms of dry solid content) was used. Further, a laminate printed matter was obtained by carrying out the same laminating treatment as in Example 1 except that the laminate film obtained above was used. The beads contained in the adhesive layer of the laminate film of this example had a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer). × 22 = 22% by number or more of beads having a particle size of less than 3.5 = 52.5 μm, and 15 μm (layer thickness of the adhesive layer) × 3.5 = 52.5 μm or more of beads having a particle size of 0. It was confirmed that less than 3.5% by number of beads having a particle diameter of less than 1% by number and further having a particle diameter of 15 μm (layer thickness of the adhesive layer) × 0.3 = 1.5 μm or less.

Example 4
The anti-blocking beads contained in the coating solution for forming the adhesive layer used in preparing the laminate film in Example 1 were true spherical high density polyethylene beads having a number average particle diameter of 12 μm and a melting point of 130 ° C. (flow beads). A laminate film of this example was produced in the same manner as in Example 1 except that 0.5 part (HE-3040, manufactured by Sumitomo Seika Co., Ltd.) was used. Further, a laminate printed matter was obtained by carrying out the same laminating treatment as in Example 1 except that the laminate film obtained above was used. The beads contained in the adhesive layer of the laminate film of this example had a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer). X 28 = 28% by number or more of beads having a particle diameter of less than 52.5 μm, and 15 μm (adhesive layer thickness) x 3.5 = beads having a particle diameter of 52.5 μm or more are 0. It was confirmed that less than 1.7% by number of beads having a particle diameter of less than 1% by number and further having a particle diameter of 15 μm (layer thickness of the adhesive layer) × 0.3 = 1.5 μm or less.

(Example 5)
Anti-blocking beads contained in the coating liquid for forming the adhesive layer used in preparing the laminate film in Example 1 were 0.5 parts of low-density polyethylene beads having a number average particle diameter of 25 μm and a melting point of 107 ° C. A laminated film of this example was produced in the same manner as in Example 1 except that. Further, a laminate print was obtained by carrying out the same laminating treatment as in Example 1 except that the laminate film obtained above was used. The beads contained in the adhesive layer of the laminate film of this example had a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer). X 30 = 30% by number or more of beads having a particle diameter of less than 52.5 μm, and 12 beads having a particle diameter of 15 μm (adhesive layer) x 3.5 = 52.5 μm or more It was confirmed that beads having a particle diameter of 15 μm (adhesive layer thickness) × 0.3 = 1.5 μm or less were contained in an amount of less than 0.6% by number.

(Example 6)
The anti-blocking beads contained in the coating liquid for forming the adhesive layer used in preparing the laminate film in Example 1 were fine powder low-density polyethylene beads having a number average particle diameter of 15 μm and a melting point of 107 ° C. (Flocene UF A laminate film of this example was produced in the same manner as in Example 1 except that the amount was 0.5 part (-1.5, manufactured by Sumitomo Seika Co., Ltd.). Further, a laminate printed matter was obtained by carrying out the same laminating treatment as in Example 1 except that the laminate film obtained above was used. The beads contained in the adhesive layer of the laminate film of this example had a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer). X Beads having a particle diameter of less than 3.5 = 52.5 μm are contained in 38% by number or more, and further beads having a particle diameter of 15 μm (layer thickness of the adhesive layer) × 3.5 = 52.5 μm or more. It was confirmed that less than 5% by number of beads having a particle diameter of 15 μm (adhesive layer thickness) × 0.3 = 1.5 μm or less was contained in less than 2.5% by number.

(Comparative Example 1)
The coating liquid for forming the adhesive layer used in preparing the laminate film in Example 1 was 100 parts of Viniblanc 2647 (Nissin Chemical Industry Co., Ltd., solid content 40%, Tg 78 ° C.) that is an acrylic emulsion. And 2 parts of a water-based surface conditioner (BYK-333, Big Chemie Japan Co., Ltd.), and further as anti-blocking beads, true spherical low density polyethylene beads (flow beads having a number average particle diameter of 16.3 μm and a melting point of 107 ° C. SS-1 (manufactured by Sumitomo Seika Co., Ltd.) was mixed with 0.5 part, and the laminate film of this comparative example was prepared in the same manner as in Example 1 except that a coating liquid for forming an adhesive layer was prepared. Produced. Further, a laminate printed matter was obtained by carrying out the same laminating treatment as in Example 1 except that the laminate film obtained above was used. The beads contained in the adhesive layer of the laminate film have a particle size distribution of 15 μm (layer thickness of the adhesive layer) × 1.3 = 19.5 μm or more and 15 μm (layer thickness of the adhesive layer) × 3. 5 = 27% by number of beads having a particle size of less than 52.5 μm, and 0.2% by number of beads having a particle size of 15 μm (adhesive layer thickness) × 3.5 = 52.5 μm or more. It was confirmed that less than 1.2% by number of beads having a particle diameter of 15 μm (adhesive layer thickness) × 0.3 = 1.5 μm or less was further contained.

(Comparative Example 2)
In Example 1, 0.5 parts of spherical low density polyethylene beads (Chemical V100, Mitsui Chemicals) having a number average particle size of 12 μm and a melting point of 40 ° C. were mixed as anti-blocking beads to be used when producing a laminate film. A laminate print was obtained in the same manner as in Example 1 except that the coating liquid for forming the adhesive layer was prepared.

(Comparative Example 3)
In Example 1, 0.5 parts of acrylic beads having a number average particle diameter of 20 μm and a melting point of 140 ° C. or higher (Chemino-MX2000, Soken Chemical Co., Ltd.) were mixed as an anti-blocking bead used for producing a laminate film. A laminate print was obtained in the same manner as in Example 1 except that the forming coating solution was prepared.

(Evaluation test)
Each laminate film and laminate print obtained above were evaluated for the following items by the following methods and standards. The evaluation results are shown in Table 2.

a) Evaluation of blocking resistance Two laminate films of each Example and Comparative Example were cut into A4 size, and were laminated so that the adhesive layer and a polyethylene terephthalate film as a heat-resistant substrate were in contact with each other. Then, the upper and lower surfaces of this laminated film were sandwiched between 20 sheets of PPC paper, and in that state, a load of 25 kg / cm ² was applied and left in an environment of temperature 50 ° C. and humidity 80% for 10 days. After leaving, the laminate film is taken out, and the two laminated films are peeled off and the blocking between the adhesive layer and the heat-resistant substrate is visually observed according to the following evaluation criteria, and evaluated according to the following criteria. did.
〔Evaluation criteria〕
A: No blocking at all.
○: Almost no blocking.
Δ: There is a part that is slightly blocked.
X: Completely blocking.

b) Evaluation of adhesive layer surface state after distribution environment preservation The surface state of the adhesive layer used in blocking resistance evaluation was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
(Double-circle): The width | variety of the unevenness | corrugation of the surface is very fine (within 4 mm), and has spread uniformly.
○: The width of the unevenness on the surface is fine (within 8 mm) and spreads uniformly.
X: The width | variety of the unevenness | corrugation of the surface is wide (10 mm or more), and is non-uniform | heterogenous.

c) Evaluation 1 of the image after laminating
The image quality of the laminate prints produced in the above Examples and Comparative Examples was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
(Double-circle): The form of the bead added to the contact bonding layer is not visible at all.
○: The form of beads added to the adhesive layer is hardly visible.
(Triangle | delta): The form of the bead added to the contact bonding layer can be seen slightly.
X: The form of the beads added to the adhesive layer is clearly visible.

d) Evaluation of image after laminating process 2
The image transparency of the laminate prints produced in the above examples and comparative examples was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
(Double-circle): The image after a lamination process is very clear.
○: The image after lamination is almost clear.
Δ: Slightly cloudy, uneven, or cloudy is observed in the image after lamination.
X: One of white turbidity, unevenness, and cloudiness is observed in the image after the lamination treatment.

e) Laminate suitability of laminate film to printed matter The laminate suitability of the laminate films prepared in the above Examples and Comparative Examples was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
○: The laminate film is laminated on the printed material and the image is clear.
X: The laminate film is not laminated on the printed material and the image is not clear.

  As shown in Examples 1 to 4, the laminate film of the present invention produced by containing a specific adhesive resin material and specific beads in the adhesive layer has anti-blocking properties, surface properties of the adhesive layer, and the laminate. The image quality and image transparency of the printed material with the film fixed were good.

It is sectional drawing which shows the structure of the laminate film of this invention. It is sectional drawing of the product which laminated the protective layer on the recording member using the laminate film of this invention. It is sectional drawing which shows the apparatus main body internal structure used as the principal part of the lamination apparatus which concerns on the Example of this invention.

Explanation of symbols

(A): heat-resistant substrate (B): surface layer (C): adhesive layer (D): anti-blocking beads (E): substrate (F): ink receiving layer (G): laminate film (H): Recording member 1: Image receiving medium supply unit 2: Film mounting unit 4: Supply port 5: Supply roller (5a: supply lower roller, 5b: supply upper roller)
6: Guide roller 7: Fixing roller pair (7a: fixing upper roller, 7b: fixing lower roller)
8: Transport roller pair (8a: transport main roller, 8b: transport sub-roller)
9: discharge roller pair (9a: discharge upper roller, 9b: discharge lower roller)
10: Discharge port

Claims (18)

  A laminate film formed by laminating a protective layer having a surface layer and an adhesive layer on a heat-resistant substrate for use in a laminating apparatus having a fixing temperature of 110 ° C. to 140 ° C. Is a laminate comprising an adhesive resin material and beads, wherein the glass transition point (Tg) of the adhesive layer is 35 ° C. or less, and the melting point of the beads is 70 to 135 ° C. the film.   The laminate film according to claim 1, wherein the content of the beads is 0.1 to 5% by mass with respect to 100% by mass of all materials constituting the adhesive layer.   The laminate film according to claim 1, wherein the number average particle diameter of the beads is (layer thickness of the adhesive layer × 0.6) to (layer thickness of the adhesive layer × 2). The laminate film according to any one of claims 1 to 3, wherein the beads are constituted by a group of beads satisfying the following condition (1).
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5). The said bead is a laminated film of any one of Claims 1-3 comprised by the bead group which satisfy | fills both the following conditions (1) and conditions (2).
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5).
Condition (2): Containing less than 10% by number of beads having a particle size of (adhesive layer thickness × 3.5) or more. The said bead is a laminated film of any one of Claims 1-3 comprised by the bead group which satisfy | fills both the following conditions (1) and conditions (3).
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5).
Condition (3): Containing less than 10% by number of beads having a particle size of (adhesive layer thickness × 0.3) or less. The said bead is a laminated film of any one of Claims 1-3 comprised by the bead group which satisfy | fills all the following conditions (1), conditions (2), and conditions (3).
Condition (1): 20% by number or more of beads having a particle diameter of (adhesive layer thickness × 1.3) or more and less than (adhesive layer thickness × 3.5).
Condition (2): Containing less than 10% by number of beads having a particle diameter equal to or greater than (layer thickness of the adhesive layer × 3.5).
Condition (3): Containing less than 10% by number of beads having a particle size of (adhesive layer thickness × 0.3) or less.   The laminate film according to claim 1, wherein the beads are formed of low-density polyethylene.   The adhesive resin material that is a main component of the adhesive layer is a polymer substance selected from the group consisting of acrylic resin, vinyl acetate resin, ethylene / vinyl acetate copolymer resin, polyester resin, and polyurethane resin. 9. The laminate film according to any one of 8 above.   The laminate film according to any one of claims 1 to 9, wherein an ultraviolet absorbent is mixed in an adhesive resin material that is a main component of the adhesive layer.   The laminate film according to any one of claims 1 to 10, wherein the adhesive resin material that is a main component of the adhesive layer includes a resin material having an ultraviolet absorbing group in a molecular chain.   The laminate film according to any one of claims 1 to 11, wherein a main component of the surface layer is a resin material, and an ultraviolet absorber is mixed with the resin material.   The laminate film according to any one of claims 1 to 12, wherein a main component of the surface layer is a resin material, and the resin material includes a polymer substance having an ultraviolet absorbing group in a molecular chain.   A surface layer and an adhesive layer are laminated on a heat resistant substrate in order, and in the production method for producing a laminate film according to any one of claims 1 to 13, the adhesive resin material and beads are contained. A method for producing a laminate film, comprising a step of coating a coating liquid by a coating method to form an adhesive layer.   A laminate method using the laminate film according to any one of claims 1 to 13 and fixing the protective layer of the laminate film to a recording member by heating, wherein the heating means is a heat roller. Recording member laminating method.   A printed material, wherein the surface of the recording member is laminated by a protective layer constituting the laminate film according to claim 1.   The printed matter according to claim 16, wherein the recording member has an image formed by an inkjet recording method. The printed matter according to claim 16 or 17, wherein the recording member comprises a substrate and an ink receiving layer.

Images