JP2010167639A - Graphic receptive article and graphic structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a graphic receptive article which hardly causes a shift of an ink to a blocking and the rear surface of printing base material (support ), and the fall-down of a microsphere (power fall) from a resin layer when the article is used for inkjet printing, and a graphic structure. <P>SOLUTION: The graphic receptive article includes a support layer, a back surface resin layer which is laminated on the first surface of the support layer and contains a microsphere with a volume average particle diameter of 18 to 40 μm and resin, and shows a mass ratio of the microsphere to the resin of 45 to 180:100, and furthermore, a receptor layer laminated on the second surface of the support layer. The graphic structure is formed of a printing layer and a pressure-sensitive adhesive layer included in the receptor layer of the graphics receptive article in this order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to graphics receptive articles. Specifically, the present invention relates to a graphics receptive article including a support layer, a back resin layer laminated on a first surface of the support layer, and a receptor layer laminated on a second surface of the support layer. Furthermore, the present invention relates to a graphics structure that further includes a printed layer and a white pressure-sensitive adhesive layer on the graphics-receptive article.

  A technique for printing a high-quality image at a high speed on a smooth substrate such as a film by an ink jet printer has been widespread. In such printing, it is a normal process to wind up the substrate or stack the substrate immediately after printing a high-quality image on the substrate by inkjet. However, when the printing surface and the back surface of the base material come into contact immediately after printing, blocking occurs on the printing surface or ink moves to the back surface of the base material.

  For example, Patent Document 1 discloses a printing substrate (A) made of an acrylic resin film laminated on a releasable carrier, and a white color for lamination on a printing surface formed by printing the acrylic resin film. An adhesive film in which an adhesive substrate (B) in which a pigment is dispersed is laminated is disclosed. The present invention provides a printed material laminate having good durability such as scratch resistance and weather resistance and easy incineration disposal.

  For example, in Patent Document 2, in a transparent inkjet recording sheet in which at least a transparent inkjet image-receiving layer is provided on a transparent substrate and a back layer is provided on the opposite surface, the substrate is a transparent resin film, and the back layer is formed from a binder and spherical particles. A transparent ink jet recording sheet is disclosed. The spherical particles are monodisperse particles having an average particle diameter D in the range of 1 to 15 μm and a variation in the particle diameter of the spherical particles in the range of D ± 0.3 Dμm. Further, it is essential that the relationship between the thickness T of the back layer and the average particle diameter D of the spherical particles is DT = 0.9 to 14 μm and the total light transmittance of the recording sheet is 85% or more. This is a requirement.

For example, in Patent Document 3, in an ink jet recording sheet in which an ink receiving layer and a backcoat layer are provided on the front and back surfaces of a support, the support has a center line average roughness of 0.4 μm or less according to JIS-B0601. A polyolefin resin-coated paper or a polyester film having a surface, comprising 5 to 100 mg / m ² of a spherical fine particle polymer having an average particle size of 5 to 15 μm in a dry weight in the backing layer, and An ink jet recording sheet having a thickness smaller than the average particle size of the spherical fine particle polymer is disclosed.

JP 2002-366040 A JP 2007-313837 A JP-A-7-179025

  A graphics-receptive article and a graphics structure in which blocking, ink transfer to the back surface of a printing substrate (support), and microspheres do not fall off (powder off) when used for inkjet printing. The purpose is to provide.

  That is, the present invention includes a support layer, a microsphere having a volume average particle diameter of 18 μm to 40 μm and a resin laminated on the first surface of the support layer, and the mass ratio of the microsphere to the resin is A graphics-receptive article is provided that includes a back resin layer that is 45-180: 100 and a receptor layer laminated to the second side of the support layer.

  Furthermore, the present invention provides a graphics structure including a printed layer and an adhesive layer in this order in the receptor layer of the graphics-receiving article.

  The graphics receiving material and graphics structure of the present invention can prevent blocking and ink transfer to the back of the printing substrate (support) by the resin layer containing microspheres, and the microspheres in the resin layer Does not fall off (powder off) from the resin layer.

It is sectional drawing which shows an example of the graphic receptive article of this invention. It is sectional drawing which shows an example of the graphics structure of this invention.

  The graphics receptive article of the present invention includes a support layer, a back resin layer laminated on the first surface of the support layer, and a receptor layer laminated on the second surface of the support layer.

  The support layer of the present invention serves as a substrate for the receptor layer and protects the surface of the receptor layer. As such a support layer, a film having strength (rigidity) satisfying the above role, or a resin layer coated with a resin on the surface of the receptor layer and dried can be used.

  As the film, for example, a film made of polyester such as polyethylene terephthalate (PET), polyvinyl chloride, polyolefin such as polyethylene or polypropylene (PP), acrylic polymer, urethane polymer, or fluorine polymer can be used. . Among these, PET and PP can be mentioned as preferable from the viewpoint of rigidity. Moreover, as said resin, resin, such as polyolefin, such as polyester, polyvinyl chloride, polyethylene, a polypropylene, an acrylic polymer, a urethane type polymer, or a fluorine-type polymer, can be used, for example.

  Moreover, the film or resin used here may be transparent or opaque, and may or may not be colored.

  The thickness of the support layer can be appropriately selected and is not limited. For example, it can be about 5 μm to about 300 μm.

  The back surface resin layer of the present invention contains microspheres and resin. In such a back resin layer, it is preferable that the microspheres are substantially included in the resin constituting the back resin layer (for example, the embodiment shown in FIG. 1 or 2) in order to prevent the microspheres from falling off (powder off). .

  The microspheres are spherical fine particles made of an organic material or an inorganic material, and are preferably non-adhesive. Specifically, for example, spherical fine particles made of polyester resin, polystyrene resin, acrylic resin, urethane resin, silica, or glass can be used. The shape is preferably spherical from the viewpoint of blocking and ink transfer prevention. From the viewpoint of solvent resistance, the microspheres are preferably crosslinked particles. Hollow particles can also be used.

  The volume average particle diameter (D) of the microspheres is about 18 μm to about 40 μm. Alternatively, it can be about 18 μm to about 30 μm. In the present specification, the volume average particle diameter is measured using a laser diffraction / scattering particle diameter measuring apparatus LS-230 manufactured by Coulter, Inc.

  The resin of the back resin layer is not particularly limited as long as it is a non-adhesive resin. It is preferable to use a resin having good wettability with the microspheres and excellent film strength and solvent resistance. Moreover, it is preferable to use a cross-linked resin from the viewpoint of solvent resistance. Specific examples include silicone resins, epoxy resins, melamine resins, alkyd resins, alkyd melamine resins, and the like. The viscosity of the resin can be about 100 to about 5000 centipoise.

  The mass ratio of the microspheres to the resin is preferably about 45 to about 180: about 100. If the addition amount of the microsphere is less than this, when the graphics-receiving article or graphics structure of the present invention is wound up, the projection due to the microsphere tends to bite into the printing surface and there is a risk of generating an impression or dropping the printing layer. . On the other hand, if the amount of microspheres added is larger than the above, the contact ratio with the printing layer (printing surface) becomes large, and there is a risk of the printing layer falling off or the gloss being lowered.

The weight of the back resin layer applied to the receptor layer can be about 10 g / m ² to about 30 g / m ² .

  The back resin layer can be obtained by adding and mixing the microspheres to the resin and then applying and drying the first surface of the support layer by a conventionally known method such as knife coating. At this time, it is preferable for the microspheres to be applied discretely in a single layer without agglomerating or overlapping.

  The thickness of the back resin layer is not particularly limited. For example, when the thickness (T) is from the first surface of the support layer to the top of the convex portion of the back resin layer, T can be about 10 μm to about 50 μm. The thickness (H) of only the resin portion excluding the thickness due to the fine particles can be about 5 to about 40 μm.

  Further, in the back resin layer, about 40% to about 90% of the microspheres can be embedded in the resin. That is, about 40% to about 90% of the volume average particle diameter (D) of the microspheres can be embedded in the resin portion having the thickness H.

  The receptor layer of the present invention is a layer made of a known resin conventionally used as a receptor layer for various printing. Such a resin should just be a thermoplastic resin, and can be suitably selected according to the printing method applied to the surface and the ink to be used. Examples thereof include acrylic resins, acrylic urethane resins, urethane resins, polyester resins such as polyethylene terephthalate, vinyl acetate resins, polyvinyl chloride resins, and polystyrene resins. The receptor layer can be formed by applying and drying these resins at a desired thickness on a substrate or a release agent.

  The thickness of the receptor layer is not particularly limited, and can be, for example, about 1 μm to about 80 μm. This thickness can be appropriately adjusted according to the usage mode of the graphics-receptive article, the type of printing applied to the receptor layer, and the like.

  The graphics receptive article of the present invention can be produced by appropriately selecting a conventionally known method. An example of the production method is shown below. First, a resin mixed with microspheres is applied to a film to be a support and dried to provide a back resin layer. Subsequently, on the surface of the support opposite to the back surface resin layer, a resin is applied and dried to provide a receptor layer to obtain a graphics-receptive article.

  The graphics structure of the present invention further includes a printing layer and a white adhesive layer in this order in the receptor layer of the graphics-receiving article.

  The printing layer of the present invention is applied to the receptor layer by various ink jet printing using an aqueous solvent-based ink, an organic solvent-based ink, or a UV ink.

  The pressure-sensitive adhesive layer of the present invention includes a pressure-sensitive adhesive made of a conventionally known pressure-sensitive polymer such as acrylic, urethane, polyester, or silicone. Further, if desired, a white pigment may be included. Such a tacky polymer and white pigment can be appropriately selected from conventionally known ones and are not limited. When the graphics structure of the present invention is used under various conditions, it is preferable to use a pressure-sensitive adhesive having an appropriate concealing property so as not to cause a difference in the color density of graphics.

In order to have concealment, for example,
Carboxyl group-containing (meth) acrylic polymer,
About 5 to about 150 parts by mass of white pigment with respect to 100 parts by mass of the carboxyl group-containing (meth) acrylic polymer, and an acrylic white adhesive containing an amino group-containing (meth) acrylic polymer that does not contain an aromatic vinyl monomer Agents can be used.

In this specification, “(meth) acryl” means “acryl or methacryl”,
“Carboxyl group-containing (meth) acrylic polymer” means “carboxyl group-containing polymer”, and “amino group-containing (meth) acrylic polymer not containing aromatic vinyl monomer” means “amino group-containing polymer”. It may mean.

  The white pressure-sensitive adhesive is about 5 parts by weight to about 150 parts by weight with respect to (i) carboxyl group-containing (meth) acrylic pressure-sensitive adhesive polymer and (ii) 100 parts by weight of the carboxyl group-containing (meth) acrylic polymer. A white pigment and a colorant comprising an amino group-containing (meth) acrylic polymer not containing an aromatic vinyl monomer may be included.

  By including the colorant, that is, by dispersing the white pigment in the polymer in advance, more white pigment can be stably dispersed in the pressure-sensitive adhesive.

  Further, the white pressure-sensitive adhesive may contain a crosslinking agent.

  The white pressure-sensitive adhesive mixes a carboxyl group-containing polymer which is a polymer obtained by polymerizing a monomer containing a carboxyl group as a constituent component and an amino group-containing polymer which is a polymer obtained by polymerizing a monomer containing an amino group as a constituent component. Thus, the dispersibility of the white pigment in the pressure-sensitive adhesive can be improved, and the white pigment can be stably held in the pressure-sensitive adhesive. Therefore, a white pressure-sensitive adhesive containing more pigment can be provided. And by using the white adhesive as the adhesive layer of the graphics structure of the present invention, an image with little difference in color density of graphics can be obtained even when used under various environments such as internal lighting and external lighting. It becomes possible to provide.

Carboxyl group-containing (meth) acrylic polymer The carboxyl group-containing (meth) acrylic polymer is a polymer mainly composed of a monoethylenically unsaturated monomer, and a monoethylenic polymer containing a carboxyl group in a part thereof. It contains a saturated monomer (carboxyl group-containing monoethylenically unsaturated monomer). The monoethylenically unsaturated monomer is the main component of the polymer and generally has the formula CH ₂ = CR ¹ COOR ² (wherein R ¹ is hydrogen or a methyl group, R ² is a straight chain, A cyclic or branched alkyl group, a phenyl group, an alkoxyalkyl group, a phenoxyalkyl group, a hydroxyalkyl group, or a cyclic ether group). Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, or alkyl (meth) acrylate such as dodecyl (meth) acrylate, cyclohexyl (meth) acrylate; phenoxyalkyl (such as phenoxyethyl (meth) acrylate) (Meth) acrylate; alkoxyalkyl (meth) acrylate such as methoxypropyl (meth) acrylate and 2-methoxybutyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, Examples include hydroxyalkyl (meth) acrylates such as loxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; cyclic ether-containing (meth) acrylates such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate. Can do. If necessary, one or more monoethylenically unsaturated monomers can be used.

  Examples of the carboxyl group-containing monoethylenically unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, citraconic acid, and maleic acid; ω-carboxypoly Examples include caprolactone monoacrylate, β-carboxyethyl acrylate, 2- (meth) acryloyloxyethyl succinic acid, and the like.

  The carboxyl group-containing (meth) acrylic polymer is, for example, a ratio of 80 to 99.5 parts by mass of the monoethylenically unsaturated monomer and 0.5 to 20 parts by mass of the carboxyl group-containing monoethylenically unsaturated monomer. Can be obtained by copolymerization with Alternatively, the monoethylenically unsaturated monomer can be 90 to 99 parts by mass, and the carboxyl group-containing monoethylenically unsaturated monomer can be 1 to 10 parts by mass.

  The mass average molecular weight of the carboxyl group-containing (meth) acrylic polymer is not particularly limited, and may be, for example, about 100,000 to about 2,000,000, or about 300,000 to about 1,000,000. it can.

  The carboxyl group-containing (meth) acrylic polymer can be used as a main component of the white pressure-sensitive adhesive, and the blending amount thereof is about 35 parts by weight to about 35 parts by weight when the whole white pressure-sensitive adhesive is 100 parts by weight. The amount can be 80 parts by mass.

Amino group-containing (meth) acrylic polymer not containing an aromatic vinyl monomer The amino group-containing (meth) acrylic polymer not containing an aromatic vinyl monomer is a polymer mainly composed of a monoethylenically unsaturated monomer. In addition, some of them contain an amino group-containing unsaturated monomer and do not contain an aromatic vinyl monomer as a constituent component of the polymer. The monoethylenically unsaturated monomer is the same as that of the acrylic polymer in the carboxyl group-containing (meth) agent, and the aromatic vinyl monomer is styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, vinylanthracene. , Vinyl anthraquinone, (meth) acrylamide of an aromatic amine, or (meth) acrylate of a hydroxyl group-containing aromatic compound. Examples of the aromatic amine include aniline, benzylamine, naphthylamine, aminoanthracene, aminoanthraquinone, and derivatives thereof. Examples of the hydroxyl group-containing aromatic compound include a hydroxyl group-containing compound corresponding to the aromatic amine. As a method for obtaining the amino group-containing (meth) acrylic polymer, copolymerization of a monoethylenically unsaturated monomer and an unsaturated monomer containing an amino group can be mentioned.

  Examples of the amino group-containing unsaturated monomer include dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl acrylate (DMAEA) and N, N-dimethylaminoethyl methacrylate (DMAEMA); N, N-dimethylaminopropyl Dialkylaminoalkyl (meth) acrylamides such as acrylamide (DMAPAA), N, N-dimethylaminopropyl methacrylamide; dialkylaminoalkyl vinyl ethers such as N, N-dimethylaminoethyl vinyl ether, N, N-diethylaminoethyl vinyl ether; Mention may be made of mixtures.

  The amino group-containing polymer is, for example, copolymerized in a proportion of about 80 to about 99.5 parts by mass of the monoethylenically unsaturated monomer and about 0.5 to about 20 parts by mass of the amino group-containing unsaturated monomer. Can be obtained. Alternatively, the monoethylenically unsaturated monomer can be about 90 to about 99 parts by mass, and the amino group-containing unsaturated monomer can be about 1 to about 10 parts by mass.

  Although the mass average molecular weight of the amino group-containing polymer is not particularly limited, for example, about 1,000 to about 500,000, about 5,000 to about 200,000, or about 10,000 to about 100,000 Can do.

  The compounding amount of the amino group-containing polymer can be about 1 part by mass to about 20 parts by mass when the total amount of the white pressure-sensitive adhesive is 100 parts by mass. Moreover, when the said white adhesive contains a coloring agent, it can be used as one component of the said coloring agent.

  Copolymerization of these polymers can be performed by radical polymerization. In this case, a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization can be used. Initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2,2 ′. -Azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methylpropionic acid) dimethyl, azobis-2,4-dimethylvaleronitrile (AVN), etc. An azo polymerization initiator is used. As a usage-amount of this initiator, it can be set as 0.05-5 mass parts per 100 mass parts of monomer mixtures.

White Pigment Examples of the white pigment include conventionally known white pigments such as zinc carbonate, zinc oxide, zinc sulfide, and titanium oxide (titanium dioxide). Moreover, you may contain a talc, a kaolin, and a calcium carbonate as an additive. These white pigments can be used alone or in admixture of two or more. These white pigments may be in any form, or may have been subjected to various dispersion treatments by a conventionally known method.

  The white pigment may be about 5 parts by mass to about 150 parts by mass, or about 25 parts by mass to about 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing (meth) acrylic polymer.

Colorant The colorant contains a white pigment and an amino group-containing (meth) acrylic polymer that does not contain an aromatic vinyl monomer. Here, the white pigment and the amino group-containing (meth) acrylic polymer not containing the aromatic vinyl monomer are as described above.

  In the present specification, an amino group-containing (meth) acrylic polymer that does not contain an aromatic vinyl monomer in the colorant may be referred to as a “colorant polymer”. In addition, a polymer that is used as a main component of the white pressure-sensitive adhesive of the present invention and is not derived from a colorant may be referred to as a “pressure-sensitive adhesive polymer”.

  The colorant polymer is preferably compatible with the pressure-sensitive adhesive polymer from the viewpoint of maintaining long-term stability.

  The colorant can be obtained by mixing the white pigment and the polymer of the colorant by a conventionally known method. For example, it can be obtained by mixing using a paint shaker, a sand grind mill, a ball mill, an attritor mill, or a three-roll mill. At this time, an aqueous or organic solvent may be added as necessary.

  The colorant can maintain a well-dispersed state in which the pigment particles do not aggregate as well as immediately after the preparation, as well as after the preparation for a long time (for example, about 1 month). . This is not only the case when using a device with a relatively strong mixing force such as a sand grind mill, a ball mill, an attritor mill, or a three roll mill, but also a device with a relatively low mixing force such as a paint shaker. The same applies to the case of using only the above. Furthermore, when using this relatively weak mixing device, the pigment particles do not aggregate and disperse well immediately after preparation and after a long period of time by mixing for a relatively short time (for example, about 10 minutes). A colorant can be obtained.

Crosslinking agent The white pressure-sensitive adhesive may contain a crosslinking agent. Examples of such cross-linking agents include bisamide-based cross-linking agents (for example, 1,1′-isophthaloyl-bis (2-methylaziridine)), aziridine-based cross-linking agents (for example, Nippon Shokubai Chemite PZ33, Avisia NeoCryl CX-100). , Carbodiimide-based crosslinking agents (for example, Nisshinbo Carbodilite V-03, V-05, V-07), epoxy-based crosslinking agents (for example, E-AX, E-5XM, E5C manufactured by Soken Chemical), isocyanate-based crosslinking agents (for example, , Nippon Polyurethane Coronate L, Coronate HK, Bayer Death Module H, Death Module W, Death Module I) and the like can be used.

  The addition amount of the crosslinking agent can be 0.01 to 0.5 equivalents relative to the carboxyl group in the polymer containing a carboxyl group or the amino group in the polymer containing an amino group.

  The white pressure-sensitive adhesive is obtained by mixing the carboxyl group-containing (meth) acrylic polymer, the white pigment, and the amino group-containing (meth) acrylic polymer not containing the aromatic vinyl monomer by a conventionally known method. can get.

  For example, it can be obtained by putting each component in a mixing container almost simultaneously and mixing them using a paint shaker, sand grind mill, ball mill, attritor mill, or three roll mill. At this time, the cross-linking agent or a known aqueous or organic solvent can be used as necessary. Alternatively, the white pigment can be mixed with an aqueous or organic solvent and then mixed with other components.

  Moreover, when the said white adhesive contains a coloring agent, it is obtained by mixing the said carboxyl group-containing acrylic polymer and the said coloring agent by a conventionally well-known method.

  Moreover, the graphics structure of this invention can provide a liner (peeling layer) on the opposite side to the said printing layer of the said white adhesive layer. Such a liner may be one generally used in the field such as an adhesive tape, and is not limited to a specific member. Suitable liners include, for example, paper, for example, plastic materials such as polyethylene, polypropylene, polyester, or cellulose acetate, or paper or other materials coated or laminated with such plastic materials. it can. These liners may be used as they are, but they can be used after being treated with a silicone treatment or other methods to improve the release characteristics.

  The graphics structure of the present invention may further have a layer having another function such as a primer layer, if necessary.

  The graphics structure of the present invention can be manufactured by appropriately selecting a conventionally known method. An example of the production method is shown below. The receptor layer of the graphics-receiving article of the present invention is printed by a solvent-based inkjet printer to form a printed layer. For example, a solution in which the acrylic white pressure-sensitive adhesive is dissolved in an organic solvent is applied and dried on a liner with a knife coater or a bar coater to obtain a pressure-sensitive adhesive layer. The graphics structure of the present invention is obtained by sticking the pressure-sensitive adhesive surface of the laminate of the obtained pressure-sensitive adhesive layer and liner to the printed layer.

  In the graphics structure of the present invention, (i) a second pressure-sensitive adhesive layer is laminated on the pressure-sensitive adhesive layer, or (ii) a metal layer such as an aluminum layer or a layer such as a film serving as a core material and Two adhesive layers can also be laminated. The second pressure-sensitive adhesive layer can have the same configuration as the pressure-sensitive adhesive layer, and may be transparent, white, milky white, or other colored. Such a graphics structure can be manufactured as follows, for example.

In the case of (i) A second pressure-sensitive adhesive layer is laminated on the release-treated liner. The pressure-sensitive adhesive surface of the obtained laminate is affixed to the printed surface of the printed layer formed on the receptor layer of the graphics-receiving article of the present invention to obtain a graphics structure.

In the case of (ii) First, a second pressure-sensitive adhesive layer is provided on the release-treated liner, and further a metal layer such as an aluminum foil is laminated, and then the pressure-sensitive adhesive layer and the release-treated liner are laminated in order. Manufacturing films. Subsequently, the liner on the pressure-sensitive adhesive layer side of the mounting film is peeled off and laminated on the printing surface of the printing layer formed on the receptor layer of the graphics-receiving article of the present invention.

  The graphics structure of the present invention can be used by being attached to indoor and outdoor vehicles, buildings (walls, pillars), traffic signs, packaging materials, signs, and the like. Or it can be used as an internal lighting graphic by attaching to the surface of an internal lighting signboard.

In the present specification, the following abbreviations may be used.
BA: Butyl acrylate 2EHA: 2-ethylhexyl acrylate AA: Acrylic acid MMA: Methyl methacrylate BMA: Butyl methacrylate DMAEMA: Dimethylaminoethyl methacrylate VAc: Vinyl acetate EtAc: Ethyl acetate MIBK: Methyl isobutyl ketone Mw: Weight average molecular weight Dv: Volume average particle diameter (volume average diameter)

  Hereinafter, the materials shown in Table 1 were used.

Example 1
Production of Graphics Receiving Article 100 parts by weight of hard polymer 1 and 50 parts by weight of soft polymer 1 were mixed. Furthermore, 3 parts by mass (solid content ratio) of the crosslinking agent 2 was added to 100 parts by mass of the soft polymer 1 to obtain a polymer composition. The compatibility between the polymers was good. A 50 μm thick transparent receptor layer was applied to the release treated surface of a 50 μm-thick release polyester film (support) by knife coating, dried and crosslinked at 95 ° C. for 3 minutes and 155 ° C. for 2 minutes. Got.

Next, 100 parts by mass of the backside treatment resin 1 and 35 parts by mass of the backside treatment resin 2 (solid content ratio) were mixed to prepare a backside treatment resin solution. 50 parts by mass of microspheres 1 were added to 100 parts by mass of the resin solution for backside treatment and mixed to obtain a non-adhesive microsphere-containing solution. The obtained non-adhesive microsphere-containing solution was applied to the surface of the support opposite to the transparent receptor layer by knife coating so that the coating weight was 15 g / m ^2, and the coating was performed at 95 ° C. for 3 minutes and 155 Drying and cross-linking at 3 ° C. for 3 minutes gave a back resin layer.

Examples 2-9
Samples were prepared according to Table 2 in the same manner as in Example 1.

Example 10
40 parts by mass of methyl isobutyl ketone (MIBK) is added to 10 parts by mass of hard polymer 1 and 50 parts by mass of titanium oxide 1, and the mixture is stirred for 10 minutes with a paint shaker (ARE250 manufactured by Thinky Co., Ltd.). A solution was obtained.

  Next, the pressure-sensitive adhesive component and the pigment premix are mixed so that the pressure-sensitive adhesive polymer 1 is 100 parts by weight, the titanium oxide 1 is 50 parts by weight, and the hard polymer 1 is 10 parts by weight. Prepared. 0.2 parts by mass (solid content ratio) of the crosslinking agent 1 was added to 100 parts by mass of the adhesive polymer 1. The compatibility between the pressure-sensitive adhesive and the pigment was good, and it was easily dispersible. The white pressure-sensitive adhesive composition solution is applied onto a paper-based double-sided polyethylene laminate release paper by knife coating so that the thickness after drying becomes 30 μm, heated at 90 ° C. for 5 minutes, dried and crosslinked to form a white pressure-sensitive adhesive layer. Obtained.

  A printed image (printing layer) was formed on the graphics-receptive article prepared in Example 1 using a solvent-based inkjet printer (XC540 manufactured by Roland). The white pressure-sensitive adhesive layer obtained above was laminated on this printed layer by dry lamination to obtain a sample.

Comparative Examples 1-14
Samples were prepared according to Table 2 in the same manner as in Example 1.

Example 11
Production of Film for Mounting 0.2 parts by mass (solid content ratio) of the crosslinking agent 1 was added to 100 parts by mass of the adhesive polymer 1. The pressure-sensitive adhesive composition solution was applied onto a paper-based double-sided polyethylene laminate release paper by knife coating so that the thickness after drying was 45 μm, heated at 90 ° C. for 5 minutes, dried and crosslinked to obtain a pressure-sensitive adhesive layer. . A 50 μm aluminum foil was laminated on the air side of the pressure-sensitive adhesive layer to form an aluminum layer. Further, a white pressure-sensitive adhesive layer was formed on the aluminum layer in the same manner as in Example 10. The thickness of the white pressure-sensitive adhesive layer was 30 μm. Thereafter, a 25 μm polyester film having been subjected to silicone release treatment was laminated on the white pressure-sensitive adhesive layer to obtain a film for mounting.

Production of Graphics Structure In the same manner as in Example 10, a printed image (printing layer) was formed on the graphics-receptive article produced in Example 1 using a solvent-based inkjet printer (Roland XC540). The polyester film after the silicone release treatment was removed from the mounting film obtained above, and a white pressure-sensitive adhesive layer and the printed layer were dry laminated to obtain a graphics structure sample.

Example 12
A sample was prepared in the same manner as in Example 1 except that the microsphere 6 (3M glass bubble S60HS) was used.

Ink transfer test Print images (printing layers) were formed on the receptor layers of the samples obtained in Examples 1 to 9, and Comparative Examples 1 to 14 using a solvent-based ink jet printer (Roland XC540). As the ink, ECO-SOL MAX manufactured by Roland was used. The printing conditions were 6 colors (cyan, magenta, yellow, black, light cyan, light magenta), bidirectional printing, high image quality mode (720 dpi × 1440 dpi), variable dots, and solid printing at 300% ink density. The feed rate was about 3 m / hour, and the platen temperature was about 40 ° C.

  The obtained sample was wound up so that the printed layer and the back resin layer were in contact with each other and allowed to stand for 24 hours, and then the printed layer and the back resin layer were peeled off. When ink transfer was observed on the back resin layer, it was determined that ink transfer was “present”, and when there was no ink transfer, ink transfer was “not present”. The results are shown in Table 3.

Observation of appearance after winding The surface of the printed layer of the sample after the ink transfer test was visually observed. “Bad” was determined when surface impressions and gross spots were observed, “Poor” when minor surface impressions and gross spots were observed, and “Good” when surface impressions and gross spots were not observed. . The results are shown in Table 3.

Measurement of surface gloss The 60 ° gloss value of the surface of the printed layer of the sample after the ink transfer test was measured. The 60 ° surface glossiness was measured with a portable gloss meter (GMX-202 manufactured by Murakami Color Research Laboratory). The formula for calculating the surface gloss retention is as follows.
[Surface gloss retention (%)] = {[surface gloss after irradiation] / [surface gloss before irradiation]} × 100
The measurement was performed at N = 3, and the average value was used as a representative value. The results are shown in Table 3.

DESCRIPTION OF SYMBOLS 1 Graphics receptive article 2 Graphics structure 100,200 Support layer 102,202 Receptor layer 104,204 Back surface resin layer 106,206 Microsphere 208 Printing layer 210 Adhesive layer 212 Liner D Volume average particle diameter of microsphere H Thickness of only the resin part of the back resin layer T Thickness of the back resin layer

Claims (5)

Support layer,
A back surface resin that is laminated on the first surface of the support layer and includes a microsphere having a volume average particle diameter of 18 μm to 40 μm and a resin, and a mass ratio of the microsphere to the resin is 45 to 180: 100. A graphics receptive article comprising: a layer; and a receptor layer laminated to the second side of the support layer. The graphics-receptive article according to claim 1, wherein the coating weight of the back layer is 10 to 30 g / m ² .   The graphics receptive article according to claim 1 or 2, wherein the microsphere has a true spherical shape.   The graphics structure which further contains a printing layer and an adhesive layer in this order in the receptor layer of the graphics receptive article as described in any one of Claims 1-3. The pressure-sensitive adhesive layer is
Carboxyl group-containing (meth) acrylic polymer,
An acrylic white pressure-sensitive adhesive containing 5 to 150 parts by weight of a white pigment and an amino group-containing (meth) acrylic polymer not containing an aromatic vinyl monomer with respect to 100 parts by weight of the carboxyl group-containing (meth) acrylic polymer. The graphics structure according to claim 4, comprising:

Images