JPWO2016021637A1 - Latex ink, foil image forming method using the same, laminate, and wallpaper - Google Patents

Abstract

The present invention is an ink for an adhesive layer used for foil transfer, having good adhesion between a coating film (adhesive layer) and the foil, good pattern reproducibility of the foil, and volatile organic compound It is an object to provide a latex ink that hardly discharges (VOC). In order to solve the above-described problems, an adhesive used in a method of forming a foil image by heat-pressing a transfer foil on an adhesive layer formed in a pattern on a substrate and forming a foil transfer layer on the adhesive layer It is a latex ink for forming a layer, and includes a solvent and core-shell type latex resin particles. The core-shell type latex resin particles have a core made of an elastic resin and a shell layer made of a molten resin. The latex ink has a storage elastic modulus G ′ (120) at 1 ° C. of 1 × 10 4 to 1 × 10 6 dyn / cm 2.

Description

  The present invention is a method for forming an adhesive layer, which is used in a method of heat-pressing a transfer foil on an adhesive layer formed in a pattern on a substrate and forming a foil transfer layer on the adhesive layer to form a foil image. The present invention relates to a latex ink, a foil image forming method using the latex ink, a laminate, and a wallpaper.

  In recent years, latex inks in which a resin or pigment is dispersed in a solvent have been developed. In the latex ink, the resin is melted and cured by heating or the like after the ink is applied to the substrate. As a result, a resin film is formed on the substrate and the image is fixed. In such a latex ink, since water is generally used as a solvent, the odor at the time of image formation is small, and the discharge amount of volatile organic compounds (VOC) is also small. Further, an image can be formed even if ink does not soak into the substrate. That is, it has the advantage that it can print on various base materials. In Patent Document 1, it is studied to apply such a latex ink by an inkjet method.

  On the other hand, in recent years, various kinds of wallpaper with enhanced decorativeness have been developed by foil stamping. As such a wallpaper, in addition to a printed wallpaper in which a pattern is formed by digital printing, a decorative wallpaper in which a foil is partially transferred as a pattern is known. As described above, a thermal transfer method (foil pressing) is known as a method for forming a foil image by transferring a foil as a pattern.

  In the thermal transfer method, a transfer foil having a support / foil layer / adhesive layer is brought into close contact so that the adhesive layer is in contact with a material to be transferred (base material). Next, the heated mold is pressed from above the transfer foil, the part of the adhesive layer corresponding to the mold is heated and melted, and the part of the foil layer corresponding to the mold is transferred onto the substrate. As an adhesive used for the thermal transfer method, an acrylic copolymer emulsion adhesive obtained by polymerizing a monomer containing a vinyl cyanide monomer and an alkyl (meth) acrylate in an aqueous medium is known. (For example, Patent Document 2).

  On the other hand, the thermal transfer method has a problem that it is necessary to prepare various types of molds in accordance with a pattern or a pattern, and foil transfer tends to be uneven due to variations in heating of the molds. Therefore, a foil image forming method that does not use a mold has been studied.

  As a foil image forming method that does not use a mold, there is a method of forming a pattern of an adhesive layer. In the method of forming an adhesive pattern, an adhesive layer is formed on a substrate. Next, the adhesive layer application surface of the substrate and the foil layer of the transfer foil are superposed and heat-pressed to transfer the portion of the foil layer corresponding to the adhesive layer. As such an adhesive, a latent image forming liquid containing microcapsules enclosing an adhesive material is known (for example, Patent Document 3).

  Here, according to the technique of patterning the adhesive, the time required for the foil transfer work is shortened, and the work efficiency can be improved. In such a foil transfer method, it is effective to digitally print a curable adhesive from the viewpoint of on-demand variable output, and it is expected to be put to practical use in wallpaper printing as well from design flexibility.

  And, it has been studied to use the latex ink as an adhesive for transferring the foil (hot-melt adhesive). However, when the latex ink is used, there is a problem in the transfer reproducibility of the foil. In recent years, latex ink is generally melted at a relatively low temperature from the viewpoint of productivity of printed matter and low energy at the time of fixing. On the other hand, foil transfer is generally performed at a temperature of 100 ° C. or higher. Therefore, when a general latex ink coating film is used as an adhesive layer and foil transfer is attempted, the adhesive layer is easily softened by heating during foil transfer. When the pressure for transfer was applied in this state, the shape of the adhesive layer could not be maintained. That is, it was difficult to transfer the foil into a desired pattern.

  For such a problem, it has been proposed to add a hard filler to the adhesive to suppress deformation of the adhesive layer during foil transfer (Patent Document 4). In addition, it has been proposed to reduce the transfer area of the foil by making the amount of the adhesive at the contour portion of the pattern smaller than the amount of the adhesive at the center of the pattern (Patent Document 5). On the other hand, it has also been proposed to use active energy ray-curable ink as an adhesive, and after applying the ink, temporarily cure it to enhance the shape retention of the adhesive layer and enhance the pattern reproducibility of the foil (patent) Reference 6).

Special table 2014-501636 gazette JP 2006-16513 A JP 2002-264495 A JP 2013-964 A JP 2009-279538 A JP 2009-226863 A

  However, in the technique of the above-mentioned Patent Document 4, the adhesion between the foil and the adhesive layer is hindered by the hard filler at the time of transferring the foil, the foil is torn at the time of transferring, or the hard filler is caused on the foil surface after the transfer. There were problems such as protrusions. This phenomenon is particularly noticeable when it is strongly pressed in the pasting process like wallpaper. The technique of Patent Document 5 can be applied to a large area pattern, but is difficult to apply to a fine line pattern or the like.

  Furthermore, in the technique of Patent Document 6, the curing process is required twice, and the image forming process is complicated. Furthermore, since the ultraviolet curable ink contains a large amount of volatile organic compounds (VOC), there is a problem that it is difficult to apply to the manufacture of products used indoors such as wallpaper.

  In addition, polyvinyl chloride resin, plastic, paper, and the like are used as a wallpaper base material. Recently, fleece wallpaper in which the backing paper is made of fleece material has been widely used due to its good workability. The fleece material is a material in which natural fibers and synthetic fibers are mixed.

  And with the adhesives as in Patent Documents 2 and 3, the adhesive strength between the transferred foil layer and the base material is likely to be uneven with respect to the base material combined with different materials such as fleece material, and the foil layer peels off. Or the scratch resistance of the foil layer is reduced.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is an ink for an adhesive layer used for foil transfer, having good adhesion between the coating film (adhesive layer) and the foil, having good foil pattern reproducibility, and It is an object of the present invention to provide a latex ink that hardly discharges volatile organic compounds (VOC). Another object of the present invention is to provide a latex ink capable of forming a foil image having good adhesive strength and scratch resistance even on a substrate composed of, for example, a fleece material, and a foil image forming method using the same. And

The first embodiment of the present invention relates to a latex ink, a foil image forming method, a laminate, and wallpaper as described below.
[1] For forming an adhesive layer used in a method of forming a foil image by heat-pressing a transfer foil on an adhesive layer formed in a pattern on a substrate and forming the foil transfer layer on the adhesive layer A latex ink comprising a solvent and core-shell type latex resin particles, wherein the core-shell type latex resin particles have a core made of an elastic resin and a shell layer made of a molten resin, and the elastic resin at 120 ° C. Latex ink having a storage modulus G ′ (120) of 1 × 10 ⁴ to 1 × 10 ⁶ dyn / cm ² .
[2] The latex ink according to [1], wherein the amount of the elastic resin is 2 to 10% by mass with respect to the total mass of the core-shell type latex resin particles.

[3] A step of applying the latex ink according to [1] or [2] in a pattern on a substrate to form an adhesive layer, and bringing the transfer surface of the transfer foil into contact with the adhesive layer Forming a foil layer on the adhesive layer by thermocompression bonding.
[4] The foil image forming method according to [3], wherein in the adhesive layer forming step, the latex ink is applied by an inkjet method.
[5] The material according to [3] or [4], wherein the substrate is a substrate selected from the group consisting of a natural pulp substrate, a fleece substrate obtained by mixing natural pulp and synthetic fibers, and a Japanese paper substrate. Foil image forming method.

[6] A base material, an adhesive layer formed in a pattern on the base material, and a foil layer formed in the same pattern as the adhesive layer on the adhesive layer, the adhesive layer comprising: A laminate that is a cured film of the latex ink according to [1] or [2].
[7] A wallpaper comprising the laminate according to [6].

The second embodiment of the present invention relates to the following latex ink, foil image forming method, laminate, and wallpaper.
[8] For heat-pressing the base material and the foil layer of the transfer foil through an adhesive layer formed in a pattern, to transfer the foil layer onto the base material layer to form a foil image, A latex ink for adhesive layer, comprising resin particles and an aqueous solvent in which the resin particles are dispersed, wherein the resin particles contain a resin having a crosslinkable group and a curing agent.
[9] The latex ink according to [8], wherein the resin particles have a core layer and a shell layer that covers the periphery of the core layer, and the core layer contains the curing agent.
[10] The latex ink according to [8] or [9], wherein the curing agent is a blocked isocyanate compound.
[11] The latex ink according to any one of [8] to [10], wherein the resin particles have a volume average particle diameter of 80 to 300 nm.
[12] The latex ink according to any one of [8] to [11], wherein the resin particles are produced by an emulsion polymerization method.

[13] A step of applying the latex ink according to any one of [8] to [12] in a pattern on a base material or a foil layer of a transfer foil to form an adhesive layer; A foil image including a step of heat-pressing the transfer foil layer through the adhesive layer formed in the pattern and transferring the foil layer of the transfer foil onto the substrate to obtain a foil image. Forming method.
[14] The foil image forming method according to [13], wherein the adhesive layer is formed by applying the latex ink by an inkjet method.
[15] The foil image forming method according to [13] or [14], wherein the substrate is a fleece substrate obtained by mixing natural fibers and synthetic fibers.

[16] The latex according to any one of [8] to [12], which is disposed between the substrate, the foil layer disposed in a pattern on the substrate, and the substrate and the foil layer. A laminate comprising a cured product layer of ink.
[17] A wallpaper comprising the laminate according to [16].

  The latex ink of the first embodiment of the present invention has good adhesion between the coating film (adhesive layer) and the foil and adhesion between the coating film and the substrate, and utilizes the adhesion of the coating film. Thus, the foil can be transferred to a desired pattern. Further, the latex ink has a small amount of volatile organic compounds (VOC) generated from the coating film. In addition, according to the latex ink of the second embodiment of the present invention, a foil image having good adhesive strength and scratch resistance can be formed even on a base material made of, for example, a fleece material.

FIG. 1A to FIG. 1D are process diagrams showing an example of a foil image forming method using the latex ink of the first embodiment of the present invention. FIG. 2A to FIG. 2D are schematic views illustrating an example of a method for forming a foil image using the latex ink according to the second embodiment of the present invention.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the invention.

A. First Embodiment First, a latex ink and foil image forming method according to a first embodiment of the present invention will be described.

A-1. Latex ink The latex ink of the first embodiment is an adhesive layer ink used for foil transfer. An example of a foil image forming method using the latex ink of this embodiment is shown in FIG. As shown in FIG. 1A, the latex ink 2 of the present embodiment is applied in a pattern on the substrate 1. Then, as shown in FIG. 1B, the latex ink 2 is fixed on the substrate 1 by heating or the like to form an adhesive layer 2 ′. Then, as shown in FIG.1 (c), the transfer surface (foil 12) of the transfer foil 10 containing the support material 11 and the foil 12 is contact | adhered on contact bonding layer 2 ', and it crimps | bonds by the heating roller 20 grade | etc.,. Then, as shown in FIG. 1D, the transfer foil 10 is removed. At this time, the foil 12 pressure-bonded to the adhesive layer 2 ′ remains on the adhesive layer 2 ′ and becomes the foil layer 12 ′. On the other hand, the foil 12 that has not been pressure-bonded to the adhesive layer 2 ′ is removed together with the support material 11. That is, the foil layer 12 ′ remains in the pattern of the adhesive layer 2 ′ on the substrate 1, and this becomes a foil image.

  Conventionally, when an attempt is made to transfer a foil using the adhesive property of the adhesive layer, the adhesive layer is softened by the heat during the foil transfer, and the shape cannot be maintained. For this reason, there is a problem that the pattern made of thin lines is crushed and the foil cannot be transferred into a desired pattern. Furthermore, when an adhesive layer is formed on a substrate having irregularities, there is a problem that the adhesive layer is pushed into the concave portion due to the pressure at the time of transfer, and this also makes it impossible to form a foil image in a desired pattern shape. .

  On the other hand, if an inorganic filler or the like is included in the adhesive layer in order to suppress deformation of the adhesive layer at the time of transferring the foil, the deformation of the adhesive layer is suppressed, but the inorganic filler breaks through the foil or on the foil surface after transfer. The unevenness | corrugation derived from an inorganic filler sometimes appeared. Further, the adhesion between the adhesive layer and the foil may be hindered by the inorganic filler.

  In contrast, in the present embodiment, the adhesive layer is formed by latex ink containing core-shell type latex resin particles. The core-shell type latex resin particles have a shell layer containing a molten resin and a core containing an elastic resin. And since the core has a relatively high storage elastic modulus even at the temperature at the time of foil transfer, the adhesive layer is hardly deformed at the time of foil transfer. Furthermore, even when latex ink is applied to a substrate having irregularities, the fluidity of the entire resin at the time of melting is not excessively increased by the effect of the core, and the adhesive layer is suppressed from being pushed into the recesses. That is, according to the latex ink of this embodiment, the foil can be transferred to a desired shape, and even a thin line pattern can be reproduced. On the other hand, since the core has a certain degree of elasticity, even if the core and the foil are pressure-bonded, the foil is not easily torn and unevenness is not easily generated on the surface of the foil after transfer.

  Furthermore, since the core-shell type latex resin particles include a shell layer made of a molten resin, the foil and the adhesive layer, as well as the adhesive layer and the base material are sufficiently bonded by the molten resin. That is, according to the latex ink of this embodiment, the substrate and the foil can be firmly bonded. In addition, since the volatile organic compound (VOC) can be suppressed to a small amount, the latex ink can be applied to indoor products such as wallpaper.

  Here, the latex ink of the present embodiment contains at least core-shell type latex resin particles and a solvent, but may contain a surfactant, various additives, and the like as necessary.

(1.1) Core-shell type latex resin particles The core-shell type latex resin particles contained in the latex ink of this embodiment include a core made of an elastic resin and a shell layer made of a molten resin.

  The latex ink preferably contains 1 to 25% by mass of core-shell type latex resin particles with respect to the total mass of the latex ink, more preferably 3 to 20% by mass, and even more preferably 5 to 18% by mass. is there. When the amount of the core-shell type latex resin particles is in the above range, the balance between the drying speed of the latex ink and the increase in viscosity tends to be in a desired range, and the printability of the latex ink tends to be good. Furthermore, it is easy to obtain an adhesive layer having a desired thickness. The viscosity of the latex ink is appropriately selected according to the method of applying the latex ink, but is preferably 1 to 30 cps, and more preferably 2 to 20 cps.

  The core-shell type latex resin particles preferably have a volume-based median diameter in the range of 50 to 500 nm, more preferably 70 to 300 nm, and still more preferably 80 to 250 nm. When the median diameter of the core-shell type latex resin particles is in the above range, nozzle clogging or the like hardly occurs when the latex ink containing the core-shell type latex resin particles is discharged from the coating apparatus. The volume-based median diameter of the core-shell type latex resin particles is measured using “UPA-150” (manufactured by Microtrack).

(core)
The shape of the core of the core-shell type latex resin particle is not particularly limited, but is preferably substantially spherical. The particle size of the core is measured before coating the shell layer. The volume-based median diameter of the core is preferably 30 to 480 nm, more preferably 50 to 280 nm, and still more preferably 60 to 230 nm. The volume-based median diameter of the core is measured using “UPA-150” (manufactured by Microtrack).

  In addition, it is preferable that the quantity of elastic resin with respect to the mass of the whole core-shell type latex resin particle is 2-10 mass%, More preferably, it is 3-8 mass%, More preferably, it is 4-7 mass%. When the amount of the elastic resin is 2% by mass or more, it is easy to maintain the shape of the adhesive layer even if heat is applied during foil transfer. On the other hand, when the amount of the elastic resin is 10% by mass or less, the amount of the molten resin or the like is relatively increased, the adhesiveness of the adhesive layer is improved, and the surface smoothness of the adhesive layer is easily increased.

Here, the elastic resin is a thermoplastic resin that has a property of being softened by heating to exhibit plasticity and solidifying by cooling, and has a storage elastic modulus G ′ (120) at 120 ° C. of 1 × 10 ⁴ to It refers to a resin that is 1 × 10 ⁶ dyn / cm ² . The storage elastic modulus G ′ (120) is more preferably 1 × 10 ^{4 to} 0.5 × 10 ⁵ dyn / cm ² . When the storage elastic modulus G ′ (120) is 1 × 10 ⁴ dyn / cm ² or more, the adhesive layer obtained from the latex ink coating film is hardly deformed by heat during foil transfer. As a result, it becomes easy to transfer the foil into a high-definition pattern. On the other hand, if the storage elastic modulus G ′ (120) of the core is excessively high, the foil cannot be deformed even by the pressure at the time of transferring the foil, the adhesiveness of the foil is lowered, and the smoothness of the transfer surface is inferior. There are problems such as. On the other hand, as in this embodiment, when the elastic modulus of the core is 1 × 10 ⁶ dyn / cm ² or less, the core is deformed to some extent by the pressure during the transfer of the foil. The balance of the suppression of sex becomes suitable. The storage elastic modulus G ′ (120) of the elastic resin is appropriately adjusted depending on the weight average molecular weight (degree of polymerization) of the elastic resin.

The storage elastic modulus G ′ (120) is measured by the following methods (1) to (4). The measurement is performed by a dynamic viscoelasticity measuring device.
(1) A dispersion of elastic resin (core) particles is placed in a measurement sample petri dish at 20 ± 1 ° C. and leveled. The petri dish is allowed to stand for 24 hours or more in an environment with a relative humidity of 50 ± 5% Rh. A 0.6 g sample is taken from the petri dish and loaded into a compression molding machine. Then, a 3 cm load is applied for 30 seconds to produce a 1 cm diameter pellet.
(2) The pellet is loaded on a parallel plate having a diameter of 0.977 cm.
(3) The measuring section temperature of the dynamic viscoelasticity measuring device is set to a temperature 20 ° C. lower than the softening point of the elastic resin measured by the method described later (softening point−20 ° C.), and the parallel plate gap is set to 3 mm. That is, compress the pellet.
(4) Thereafter, the measurement part temperature is set to 35 ° C., and the pellet is allowed to cool to 35 ° C. Then, while applying a sinusoidal vibration having a frequency of 1.0 Hz, the temperature of the measurement unit is increased at 5 ° C./min to 200 ° C. At this time, the complex elastic modulus G ^* at 120 to 150 ° C. is measured, and the storage elastic modulus G ′ (120) is obtained therefrom. The strain angle is controlled by automatic strain control of the measuring device.

Here, the softening point of the elastic resin is measured by the following method using a flow tester method. The above-mentioned dispersion of elastic resin particles is placed in a measurement sample petri dish at a temperature of 20 ± 1 ° C. and leveled. The petri dish is allowed to stand for 12 hours or more in an environment with a relative humidity of 50 ± 5% Rh. 1.1 g of a sample is taken from the petri dish and loaded into a compression molding machine. Then, a 3 cm load is applied for 30 seconds to produce a 1 cm diameter pellet.
The sample is then placed in an environment of 24 ± 5 ° C. and a relative humidity of 50 ± 20% RH. Then, using a flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)), a cylindrical die with a load of 196 N (20 kg weight), a starting temperature of 80 ° C., a preheating time of 300 seconds, and a heating rate of 6 ° C./min. A piston with a diameter of 1 cm is extruded from (1 mm × 1 mm), and the temperature at which the offset value is 5 mm is defined as the softening point.

  The elastic resin may be a crystalline resin having a melting point, or may be any amorphous resin having a glass transition point without having a melting point. In the present embodiment, the crystalline resin refers to a resin having a clear endothermic peak rather than a stepwise endothermic change in differential scanning calorimetry (DSC). A clear endothermic peak is a peak whose half-value width of the endothermic peak is 15 ° C. or less when measured at a rate of temperature increase of 10 ° C./min by differential scanning calorimetry (DSC). Further, the amorphous resin refers to a resin other than the crystalline resin that does not have a clear peak in the DSC described above.

  Examples of elastic resins contained in the core include styrene resins, (meth) acrylic resins, styrene- (meth) acrylic copolymer resins, vinyl resins such as olefin resins, polyester resins, and polyamide resins. , Known thermoplastic resins such as polycarbonate resin, polyether resin, polyvinyl acetate resin, polysulfone resin, polyurethane resin and the like are included. The core may contain only one kind of these resins or two or more kinds.

  The elastic resin contained in the core is a styrenic resin from the viewpoint of easy adjustment of the degree of polymerization for adjusting the storage elastic modulus G ′ (120) and good dispersibility after particle formation, A (meth) acrylic resin, a polyester resin, or a styrene- (meth) acrylic copolymer resin is preferable, and a styrene- (meth) acrylic copolymer resin is particularly preferable.

(Shell layer)
The shell layer of the core-shell type latex resin particle is a layer formed around the core, and may be a layer that completely covers the core or a layer that covers only a part of the core. The shell layer includes a molten resin.

  In addition, it is preferable that the quantity of molten resin is 90-98 mass% with respect to the mass of the whole core-shell type latex resin, More preferably, it is 92-97 mass%, More preferably, it is 93-96 mass%. When the amount of the molten resin is 90% by mass or more, the adhesiveness of the foil or the like tends to increase. On the other hand, when the amount of the molten resin is 98% by mass or less, the amount of the elastic resin is relatively sufficient, and the shape of the adhesive layer is easily maintained during the transfer of the foil.

  In the present embodiment, the molten resin is a thermoplastic resin having a melting point or glass transition temperature of 65 ° C. or less. The melting point or glass transition temperature of the molten resin is preferably 25 to 60 ° C, more preferably 30 to 50 ° C. When the melting point or glass transition temperature of the molten resin is 65 ° C. or lower, the shell layer is softened when the foil is transferred, and the adhesion to the foil or the substrate is increased. The melting point or glass transition temperature of the molten resin is adjusted by the weight average molecular weight (polymerization degree) of the molten resin, the type of the molten resin, and the like. The melting point or glass transition temperature of the shell layer is measured by differential scanning calorimetry (DSC).

  It is impossible to measure the glass transition temperature by separating only the shell layer after forming the core-shell particles. Therefore, without adding the core particles, resin particles made only of the molten resin are produced under the same reaction conditions as the shell layer forming conditions, and the glass transition temperature of the particles is measured.

  Here, the molten resin is, for example, a styrene resin, (meth) acrylic resin, styrene- (meth) acrylic copolymer resin, vinyl resin such as olefin resin, polyester resin, polyamide resin, polycarbonate resin, It may be a known thermoplastic resin such as polyether, polyvinyl acetate resin, polysulfone resin, polyurethane resin. The core may contain only one kind of these resins or two or more kinds.

  Among these, a styrene resin, a (meth) acrylic resin, a polyester resin, or a styrene- (meth) acrylic copolymer resin has a low viscosity when melted and has a high sharp melt property. In particular, a styrene- (meth) acrylic copolymer resin is preferable.

(Method for preparing core-shell type latex resin particles)
The core-shell type latex resin particles can be produced in the same manner as a known method for producing core-shell type particles, but is preferably produced by an emulsion polymerization method from the viewpoints of particle controllability and dispersibility after particle formation. Specifically, (i) a core is formed by a known emulsion polymerization method; (ii) a shell layer is further formed around the core, and the like.

(I) Formation of Core As described above, the core is preferably formed by an emulsion polymerization method from the viewpoint that the composition adjustment of the particles is easy and the polymerization of the monomer is easily controlled. . In the core formation step, the elastic resin raw material (polymerizable monomer) serving as a core and, if necessary, an additive component are contained in an aqueous medium containing a surfactant having a critical micelle concentration (CMC) or less. Add the dissolved or dispersed monomer solution. Then, mechanical energy is applied to the aqueous solution to form droplets. Then, a water-soluble radical polymerization initiator is added to advance the polymerization reaction in the droplets.

  The droplet may contain an oil-soluble polymerization initiator. In such a core formation process, means for mechanically emulsifying (forming droplets) (mechanical energy applying means) are a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, and the like. It is possible. The storage elastic modulus G ′ (120) of the polymerized core (elastic resin) is adjusted by the amount of the chain transfer agent and the temperature during the polymerization reaction. During the stirring, the aqueous solution may be heated as necessary.

The polymerizable monomer used for the preparation of the core is not particularly limited as long as it can prepare the elastic resin described above. Examples of polymerizable monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p Styrene monomers such as tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene;
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid t- Butyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( A monomer comprising (meth) acrylic acid or an acrylate ester such as dimethylaminoethyl (meth) acrylate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Vinyl ester monomers such as vinyl propionate, vinyl acetate and vinyl benzoate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether;
Vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl compound monomers such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone;
Vinyl compound monomers such as vinyl naphthalene and vinyl pyridine;
(Meth) acrylic acid derivatives such as (meth) acrylonitrile and acrylamide;
Polyfunctional divinyl-based single quantities such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate Body; etc. are included.

  In addition, the solvent for forming the core by the emulsion polymerization aggregation method is usually water, but a water-soluble organic solvent may be included as necessary. The water-soluble organic solvent can be the same as the water-like organic solvent contained in the later-described latex ink.

  As a polymerization initiator for polymerizing the monomer, a known oil-soluble or water-soluble polymerization initiator can be used. Examples of oil-soluble polymerization initiators include, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1 -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo- or diazo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4 4-t-butylperoxycyclohexyl) propane, tri - it includes (t-butyl peroxy) peroxide polymerization initiators such as triazines.

  Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, hydrogen peroxide and the like.

  Examples of the chain transfer agent include octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, terpinolene, carbon tetrabromide, α-methylstyrene dimer and the like. The molecular weight of the resin (elastic resin) contained in the obtained core is adjusted by the amount of the chain transfer agent. That is, the chain transfer agent is added to such an extent that the storage elastic modulus G ′ (120) of the elastic resin at 120 ° C. falls within a desired range.

  Moreover, it is also preferable to add a dispersion stabilizer for uniformly dispersing the aforementioned monomer in the aqueous solution to the reaction system. A known surfactant can be applied as the dispersion stabilizer. For example, as a dispersion stabilizer, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. Further, surfactants such as polyvinyl alcohol, gelatin, methylcellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used.

  Examples of the dispersion stabilizer include a sulfonate, a sulfate ester salt, and a fatty acid salt. Examples of the sulfonate include sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfone diphenylurea. Sodium 4,4,4-diazo-bis-amino-8-naphthol-6-sulfonate, o-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4- Ionic surfactants such as sodium diazo-bis-β-naphthol-6-sulfonate can also be used. Examples of the sulfate ester salts include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, and sodium octyl sulfate. Fatty acid salts include sodium oleate, sodium laurate, sodium caprate, sodium caprylate, and capron. Sodium acid, potassium stearate, calcium oleate and the like are included.

  Furthermore, as a dispersion stabilizer, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, Nonionic surfactants such as sorbitan esters can also be used.

(Ii) Formation of Shell Layer The core-shell type latex resin particles are made of resins having different compositions in the core and the shell layer. From the viewpoint of easy composition adjustment of the shell layer and easy control of monomer polymerization, the shell layer is preferably formed by an emulsion polymerization method. As described above, the shell layer is formed by adding a polymerization initiator and a polymerizable monomer to the core dispersion prepared by the emulsion polymerization method (first stage polymerization), and further performing a polymerization treatment (second process). It may be a method of stacking a shell layer on the core by step polymerization).

  Specifically, a method in which a monomer that is insoluble or poorly soluble in water is further dropped into an aqueous solution containing the above-described dispersion containing the core and a polymerization initiator to cause a polymerization reaction is preferable. At this time, the glass transition temperature and melting point of the molten resin to be polymerized are adjusted by the type of monomer and the amount of chain transfer agent. Stirring of the aqueous solution can be performed, for example, with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. At this time, the aqueous solution may be heated as necessary.

  The monomer, polymerization initiator, chain transfer agent, dispersant and the like used for forming the shell layer may be the same as those used for preparing the core.

(1.2) Solvent The latex ink of this embodiment contains a solvent. The solvent is mainly water, and it is preferable that 30 to 95% by mass of water is contained with respect to the total mass of the latex ink, more preferably 40 to 90% by mass, and still more preferably 50 to 70% by mass. It is. On the other hand, an organic solvent may be contained together with water from the viewpoints of adjusting the viscosity of the latex ink, promoting drying of the ink, and promoting the wetting of the core-shell type latex resin particles. From the viewpoint of compatibility with water, the organic solvent is preferably a water-soluble solvent.

  Here, when an organic solvent having a vapor pressure lower than that of water is contained, drying of the latex ink is suppressed, and for example, ink clogging in a device for applying the latex ink is suppressed. Specific examples of the water-soluble organic solvent used as a wetting agent or a drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, and 2-methyl-1,3-propanediol. Polyhydric alcohols such as 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, trimethylolpropane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monobutyl ether; 2-pyrrolidone, N-methyl-2-pyro Heterocycles such as Don, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine, urea Derivatives and the like. The latex ink may contain only one kind or two or more kinds.

  On the other hand, examples of water-soluble organic solvents used when adjusting the viscosity of latex ink include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, Monohydric alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc. Polyhydric alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Chill ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Glycol derivatives such as triethylene glycol monoethyl ether and ethylene glycol monophenyl ether; ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylene Amines such as reamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine; formamide; N, N-dimethylformamide; N, N-dimethylacetamide; dimethyl sulfoxide; sulfolane; 2-pyrrolidone; N-methyl-2-pyrrolidone; N-vinyl-2-pyrrolidone; 2-oxazolidone; 1,3-dimethyl-2-imidazolidinone; acetonitrile; acetone and the like. These may be used alone or in combination of two or more.

  The solvent contained in the latex ink is preferably a polyhydric alcohol such as glycerin or diethylene glycol, from the viewpoint of good compatibility with water and prevention of drying and viscosity adjustment at the same time. Moreover, it is preferable that 10-50 mass% of organic solvents are contained with respect to the latex ink whole quantity, More preferably, it is 10-30 mass%, More preferably, it is 10-20 mass%.

(1.3) Others The latex ink of this embodiment may contain a surfactant and other additives as long as the effects of this embodiment are not impaired. When the surfactant is contained in the latex ink, the surface tension is adjusted and bubbles are hardly generated in the ink.

  Examples of the surfactant include an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Specific examples of surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensation in hydrocarbons. Products, anionic surfactants such as polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Nonionic surfactants such as alkylamines, glycerin fatty acid esters and oxyethyleneoxypropylene block copolymers; acetylene-based polyoxyethylene oxide surfactants; N, - amine oxide type amphoteric surfactants such as dimethyl -N- alkylamine oxides; include and the like.

  Furthermore, the latex ink may contain an additive as necessary. Examples of the additive include an anti-drying agent (wetting agent), an anti-fading agent, an emulsion stabilizer, a penetration accelerator, and an ultraviolet absorber. , Antiseptics, antifungal agents, pH adjusting agents, surface tension adjusting agents, antifoaming agents, viscosity adjusting agents, dispersing agents, dispersion stabilizers, rust preventing agents, chelating agents and the like.

(1.4) Method for Preparing Latex Ink The latex ink of the present embodiment is prepared by dispersing or mixing the above-described core-shell type latex resin particles, a solvent, and other components. A method for dispersing these is not particularly limited, and examples thereof include a dispersion method using a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. The method for stirring and mixing these is not particularly limited, and examples thereof include a stirring method using a normal stirring blade, a magnetic stirrer, a high-speed disperser, and the like.

A-2. Foil Image Forming Method A foil image forming method using the latex ink described above will be described in detail. The foil image forming method of the present embodiment includes at least the following two steps.
(1) Step of applying latex ink in a pattern on a substrate to form an adhesive layer (2) Contacting the transfer surface of the transfer foil on the adhesive layer and thermocompression bonding, and a foil layer on the adhesive layer The foil image forming method of this embodiment may include other steps as necessary.

(2.1) Adhesive layer forming step In the adhesive layer forming step, the aforementioned latex ink is applied in a pattern on a substrate to form an adhesive layer. Here, the pattern to which the latex ink is applied is a pattern of a region where the foil is to be transferred.

  Here, the base material to which the latex ink is applied is not particularly limited as long as it is a material to which the adhesive layer can be bonded, and is appropriately selected depending on the application. Examples of base materials include various plastic base materials, metal base materials, glass base materials, stone base materials, cloth base materials, natural pulp base materials, fleece base materials mixed with natural pulp and synthetic fibers, Japanese paper base materials, etc. It is. For example, when wallpaper is produced by the foil image forming method of the present embodiment, the base material may be a natural pulp base material, a fleece base material obtained by mixing natural pulp and synthetic fibers, a Japanese paper base material, or the like. As described above, the adhesive layer obtained from the latex ink of the present embodiment is difficult to be pushed in at the time of transferring the foil even if the substrate has irregularities. Therefore, the foil image forming method of the present embodiment is applicable even to a substrate having irregularities.

  The method for applying the latex ink is not particularly limited as long as it is a method capable of applying the latex ink in a desired pattern, and is appropriately selected according to the area where the adhesive layer is applied, the shape of the pattern, and the like. The latex ink coating method may be a known method such as inkjet coating, dispenser coating, spray coating, or the like, but the inkjet method is preferred from the viewpoint of forming a high-definition pattern.

  After applying the latex ink on the substrate, the solvent is usually removed from the coating film to form an adhesive layer. The method for removing the solvent is not particularly limited, and may be heating with various heaters, air drying, natural drying, or the like. From the viewpoint of efficiency, it is preferable to remove the solvent by heating with various heaters. Examples of various heaters include an electric heater, an infrared heater, an electromagnetic induction (IH) heater, and the like. Moreover, when heating with a heater, a heater may be arrange | positioned at the coating-film side and may be arrange | positioned at the base-material side. It is preferable that the surface temperature of the coating film at the time of heating is 70-100 degreeC, More preferably, it is 75-90 degreeC. At this time, not only the solvent is removed from the coating film, but the shell layer of the core-shell type latex resin particles may be melted to smooth the surface of the coating film (adhesive layer).

  The thickness of the adhesive layer formed in this step is preferably 1 to 30 μm, more preferably 1 to 20 μm, and still more preferably 1 to 10 μm. When the thickness of the adhesive layer is 1 μm or more, sufficient adhesiveness of the adhesive layer is obtained, and it becomes easy to form a foil layer in the pattern of the adhesive layer. On the other hand, when the thickness of the adhesive layer is 30 μm or less, the adhesiveness between the substrate and the transfer layer is likely to increase.

(2.2) Foil layer forming step The transfer surface of the transfer foil is brought into contact with the adhesive layer of the base material on which the above-mentioned adhesive layer is formed in a pattern, and the foil layer is formed on the adhesive layer. To do.

  For example, as shown in FIG. 1C, the transfer foil brought into contact with the adhesive layer includes at least a support material 11 and a foil 12. For example, a release layer (not shown) is provided between the support material 11 and the foil 12. May be formed. Further, an adhesive layer or the like may be formed on the transfer surface of the transfer foil.

  The support material included in the transfer foil is composed of a resin film having flexibility, for example, a resin film such as a polyethylene film, a polyester film, an olefin film, a polypropylene film, and a polycarbonate film, paper, and the like. sell.

  The foil contains a colorant, a metal material, and the like, and expresses an aesthetic appearance after being transferred onto the product. When transferring onto a product, the ability to peel off more smoothly than the support material is required, and after transfer, the outermost surface of the product is formed, so durability is also required. The transfer foil is obtained by applying a known resin (foil material) satisfying the above performance on a support material using a coater such as a gravure coater, a micro gravure coater, or a roll coater. Known resins that can be the material of the foil include, for example, acrylic resins, styrene resins, melamine resins, and the like, and coloring can be performed by adding known dyes, pigments, and the like to the resin. The thickness of the foil is usually about 1 to 2 μm.

  In addition, a transfer foil including a finished foil having a metallic gloss can be obtained by laminating a layer (reflective layer) made of metal or the like on the above-described resin. Examples of the metal material forming the reflective layer include aluminum, tin, silver, chromium, nickel, gold, and alloys such as nickel-chromium-iron alloy, bronze, and aluminum bronze. The method for forming the reflective layer using the metal material is not particularly limited, and examples thereof include known methods such as vapor deposition, sputtering, and ion plating. According to these methods, a reflective layer having a thickness of about 10 nm to about 100 nm is formed. In addition, the reflective layer can be subjected to a patterning process for imparting a regular pattern by using a known processing method such as, for example, water-washed celite processing, etching processing, or laser processing.

  An adhesive layer may be formed on the transfer surface of the transfer foil. When an adhesive layer is formed on the transfer surface of the transfer foil, the adhesive layer obtained by applying the latex ink described above and the adhesive layer derived from the foil are compatible and more firmly bonded. The adhesive layer provided on the transfer foil side may contain a heat-sensitive adhesive called a so-called hot melt type that develops tackiness by heating. Examples of the heat-sensitive adhesive include known thermoplastic resins that can be used for hot-melt type adhesives such as acrylic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, and ethylene-vinyl alcohol copolymer. Can be mentioned. The said adhesive layer is obtained by apply | coating the said adhesive agent on the foil (resin layer and / or metal layer) mentioned above using coaters, such as a gravure coater, a micro gravure coater, and a roll coater, for example. The thickness of the adhesive layer on the transfer foil side is preferably 2 μm to 3 μm.

  In this step, thermocompression bonding is performed with the adhesive layer obtained by applying the latex ink and the transfer surface of the transfer foil in contact with each other. At this time, the heating temperature, pressure bonding force, and heating time are appropriately selected according to the type of the transfer foil and the like. The method of heat-pressing these is not particularly limited, and may be, for example, a method of pressure-bonding with a heating roller, a method of pressing with a heated plate-like member, or the like.

  The temperature at the time of thermocompression bonding is generally 90 to 120 ° C, preferably 100 to 110 ° C. Moreover, generally crimping | compression-bonding force is 100-700 kPa, Preferably it is 150-400 kPa. Moreover, it is preferable that thermocompression bonding time is about 0.05 to 20 seconds, More preferably, it is 0.1 to 10 seconds.

  After the transfer foil and the adhesive layer are heat-pressed, the transfer foil is removed from the substrate. At this time, the adhesive layer and the heat-pressed foil remain on the adhesive layer and become a foil layer. On the other hand, the foil in the region not in contact with the adhesive layer is removed from the substrate together with the support material. That is, the foil layer is formed in the same pattern as the adhesive layer, and a desired foil image is formed on the substrate.

(2.3) Use of laminate The use of the laminate obtained by the foil image forming method of the present embodiment is not particularly limited, and can be applied to various uses. Examples of uses of the laminate include various types of wallpaper, packaging materials, book binding, stationery, machines, equipment, electrical appliances, clothing, and the like.

  Among these, decorative wallpaper with foil transfer is suitable for wallpaper base materials, especially natural pulp, non-woven (fleece) base materials in which synthetic fibers are blended with natural pulp, and wallpaper base materials made of woven base materials such as Japanese paper. is there. Fibers are often exposed on the surface of such a wallpaper substrate, and there are minute uneven steps on the surface. Therefore, when a general adhesive is applied on the wallpaper substrate, the resin component melted by heat and pressure for foil transfer is pushed into the recess, and the transfer surface of the foil is difficult to form. The adhesive strength of the is easy to decrease.

  In contrast, according to the foil image forming method of the present embodiment, the core layer makes it difficult for the entire molten resin to flow, and thus the latex ink coating film does not flow easily inside the fibers on the wallpaper substrate surface. That is, the adhesive layer tends to stay on the wallpaper substrate surface. Therefore, the reproducibility of the foil transfer to these wallpaper base materials is ensured, and such a decorative wallpaper has good appearance and durability of the foil.

B. Second Embodiment Next, a second embodiment of the present invention will be described.
As described above, the conventional adhesive used in the foil image forming method usually exhibits adhesiveness by thermally fusing resin particles (binder resin). On the other hand, the present inventors have found that high adhesion and scratch resistance can be obtained not only by thermally fusing resin particles (binder resin) but also by crosslinking the resin.

  That is, in latex ink which is an adhesive used in a foil image forming method, resin particles contain 1) a curing agent, and 2) a crosslinkable group that reacts with the curing agent is introduced into the resin constituting the resin particle. By doing, the high adhesiveness of a base material and a foil layer can be obtained. Accordingly, the base material and the foil layer can be firmly adhered to a base material such as a fleece material, and a foil image having good adhesive strength and scratch resistance can be formed. The second embodiment of the present invention has been made based on such knowledge.

B-1. Latex ink The latex ink of the present embodiment is used as an adhesive at the time of forming a foil image; it contains resin particles and an aqueous solvent for dispersing the resin particles.

1-1. Resin Particles The resin particles include a resin having a crosslinkable group and a curing agent.

1-1-1. Resin having a crosslinkable group The resin having a crosslinkable group contained in the resin particles may be a thermoplastic resin functioning as a binder. The resin having a crosslinkable group has a crosslinkable group that reacts with the curing agent by heat at the time of thermocompression bonding in the foil transfer step. Examples of the crosslinkable group include a hydroxyl group, a carboxyl group, an amino group, an imidazole group, a thiol group, an acid anhydride group, and a glycidyl group.

  Such a resin may be a homopolymer of a polymerizable monomer (A) having a crosslinkable group, or another polymerizable monomer (B) copolymerizable with the polymerizable monomer (A). And a copolymer.

The polymerizable monomer (A) having a crosslinkable group may be a monomer having a crosslinkable group and an ethylenically unsaturated bond. The ethylenically unsaturated bond is a radically polymerizable carbon-carbon double bond, and examples of the group having such a carbon-carbon double bond include a vinyl group (CH ₂ ═CH—), (meth) acrylic group _{(CH 2 = CH-CH 2} -, CH 2 = C (CH 3) -CH 2 -), ( meth) acryloyl group _{(CH 2 = CH-CO-,} CH 2 = C (CH 3) -CO -), (meth) acryloyloxy groups _{(CH 2 = CH-COO-,} CH 2 = C (CH 3) -COO-) , and the like.

Examples of the polymerizable monomer (A) having a crosslinkable group include
(Meth) acrylic acids having 2 to 30 carbon atoms such as acrylic acid and methacrylic acid;
Hydroxyethyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxymethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyphenyl methacrylate, carboxyethyl acrylate, carboxymethyl acrylate, carboxyphenyl acrylate, 2- Acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2hydroxyethyl-phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-acryloyloxyethyl succinic acid, 2-hydroxy-3-faxipropyl acrylate, dimethyl Aminoethyl acrylate, glycidyl acrylate, glycidyl methacrylate, imidazole-4-acrylic acid, 3- (1H-imidazol-4-yl) (meth) acrylic acid esters having 2 to 30 carbon atoms such as ethyl acrylate;
Examples include olefins having 2 to 30 carbon atoms such as ethene thiol and propylene thiol. Of these, (meth) acrylic acid such as acrylic acid and methacrylic acid is preferable. The polymerizable monomer (A) may be used alone or in combination of two or more.

  The other polymerizable monomer (B) can be a monomer having an ethylenically unsaturated bond. Examples of such monomers having an ethylenically unsaturated bond include styrene or styrene derivatives, methacrylic acid ester derivatives, acrylic acid ester derivatives, olefins, vinyl esters, vinyl ethers, vinyl ketones, N-vinyl compounds. Etc. are included.

  Examples of styrene or styrene derivatives include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- Examples thereof include tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, and pn-dodecyl styrene.

  The methacrylic acid ester derivative may be an alkyl ester having 1 to 30 carbon atoms in the alkyl moiety. Examples of alkyl methacrylate esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and the like.

  The acrylic ester derivative may be an alkyl alkyl ester having 1 to 30 carbon atoms in the alkyl moiety. Examples of alkyl acrylate esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, acrylic Examples include stearyl acid, lauryl acrylate, and phenyl acrylate.

  The olefins are olefins having 2 to 30 carbon atoms, and examples thereof include ethylene, propylene, isobutylene and the like. Vinyl esters are vinyl esters having 2 to 30 carbon atoms, and examples thereof include vinyl propionate, vinyl acetate, and vinyl benzoate. Vinyl ethers are vinyl ethers having 2 to 30 carbon atoms, and examples thereof include vinyl methyl ether and vinyl ethyl ether. Vinyl ketones are vinyl ketones having 2 to 30 carbon atoms, and examples thereof include vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone. Examples of N-vinyl compounds include N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone and the like.

  Examples of other polymerizable monomers (B) include vinyl compounds such as vinyl naphthalene and vinyl pyridine, and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Other polymerizable monomers (B) may be used alone or in combination of two or more.

  Although the content rate of the structural unit derived from the polymerizable monomer (A) having a crosslinkable group in the resin is not particularly limited, it is based on the entire polymerizable monomer from the viewpoint of sufficiently performing a crosslinking reaction with the curing agent. It is preferable that it is 1-95 mass%, and it is more preferable that it is 1.5-50 mass%.

  The glass transition temperature (Tg) of the resin is preferably 25 to 70 ° C., more preferably 30 to 60 ° C., from the viewpoints of adhesiveness and ink storage stability.

The glass transition temperature of the resin can be measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) in accordance with ASTM D3418. Specifically, it can be measured by the following procedure.
1) Prepare an aluminum pan enclosing the measurement sample. Meanwhile, an empty aluminum pan is prepared for control.
2) Set these in the above apparatus, raise the temperature at a rate of temperature increase of 10 ° C./min, hold at 200 ° C. for 5 minutes, decrease the temperature from 200 ° C. to 0 ° C. using liquid nitrogen at −10 ° C./min, Hold at 0 ° C. for 5 minutes and again raise the temperature from 0 ° C. to 200 ° C. at 10 ° C./min.
3) Analyze the endothermic curve during the second temperature increase of the temperature profile, and set the onset temperature to Tg. The melting point of indium and zinc is used to correct the temperature of the detection unit of the measuring apparatus (DSC-60A); the heat of fusion of indium is used to correct the amount of heat.

  The weight average molecular weight of the resin is preferably 10,000 to 300,000, and more preferably 15,000 to 200,000, from the viewpoints of adhesiveness and ink storage stability.

The weight average molecular weight of the resin can be measured using gel permeation chromatography (GPC). The measurement conditions can be as follows.
(Measurement condition)
Solvent: Tetrahydrofuran Column: Tosoh TSKgel G4000 + 2500 + 2000HXL
Column temperature: 40 ° C
Injection volume: 100 μl
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500-sample calibration curves are used. Thirteen samples are used at approximately equal intervals.

  From the viewpoint of obtaining sufficient adhesiveness between the foil layer and the substrate, the resin content is preferably 5 to 95% by mass with respect to the entire resin particles.

1-1-2. Curing Agent The curing agent contained in the resin particles is a latent thermosetting agent that does not cure the aforementioned resin at room temperature, but cures the resin when heated to a certain temperature or higher. Specifically, the curing agent may be a latent thermosetting agent that cures the aforementioned resin when heated to 80 ° C. or higher, preferably 100 ° C. or higher.

  Such curing agents include compounds containing epoxy groups such as TGIC, HAA (β-hydroxyalkylamide), blocked isocyanate compounds, aziridine compounds, compounds containing carbodiimide groups, compounds containing oxazoline groups, hydrazide compounds, etc. It can be. Of these, a blocked isocyanate compound is preferred because both good curability and storage stability are easily achieved.

  The blocked isocyanate compound is obtained by blocking the isocyanate group of the isocyanate compound with a blocking agent. When the blocked isocyanate compound is heated to a certain temperature or more, the blocking agent is dissociated and the isocyanate group is exposed to exhibit curability.

  The isocyanate compound is a compound having one or more, preferably two, isocyanate groups in the molecule, and may be an aliphatic isocyanate compound, an alicyclic isocyanate compound, or an aromatic isocyanate compound. Examples of the aliphatic isocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate methyl ester and hydrogenated xylylene diisocyanate. Examples of the alicyclic isocyanate compound include isophorone diisocyanate, methylenebis (4,1-cyclohexylene) diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane and the like. Examples of the aromatic isocyanate compound include xylylene diisocyanate, triene diisocyanate, polymeric MDI (polymethylene polyphenyl polyisocyanate), naphthalene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, and the like.

  Examples of the blocking agent include phenols such as phenol, cresol, ethylphenol, and butylphenol; lactams such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam; methanol, ethanol, 2-propanol, 1,3-butane C2-C8 alcohols such as diols; C2-C8 esters such as dimethyl malonate and diethyl malonate are included.

  The blocked isocyanate compound can be obtained by reacting an isocyanate compound and a blocking agent under heating as necessary.

  It is preferable that the content rate of a hardening | curing agent is 5-80 mass% with respect to the whole resin particle, and it is more preferable that it is 20-50 mass%. By setting the content of the curing agent to a certain level or more, the crosslinking reaction between the resin and the curing agent can be sufficiently performed at the thermocompression bonding temperature at the time of foil transfer, and the adhesive strength and scratch resistance of the obtained foil image can be improved. Easy to increase. By setting the content of the curing agent to a certain value or less, it is easy to suppress an unintended reaction between the resin and the curing agent during ink storage.

1-1-3. Resin Particle Structure The resin particles may be composed of a single layer or multiple layers. The resin particles are preferably composed of multiple layers because it is easy to achieve a plurality of functions. The resin particle comprised by a multilayer has a core layer and the shell layer which covers the circumference | surroundings. The shell layer is preferably a layer that covers the entire surface of the core layer, but may be a layer that covers only a part of the surface of the core layer.

  The composition of the core layer and the composition of the shell layer can be different from each other. For example, the content of the hardener in the core layer is preferably greater than the content of the hardener in the shell layer; more preferably, the core layer contains the hardener and the shell layer does not substantially contain the hardener. preferable. That the shell layer does not substantially contain the curing agent specifically means that the content of the curing agent in the shell layer is 5% by mass or less, preferably 0% by mass. Accordingly, since the curing agent is difficult to be exposed on the surface of the resin particles, an unintended reaction of the curing agent during storage of the ink is suppressed, and ink storage stability is easily obtained.

  Further, the tensile elastic modulus of the shell layer can be lower than the tensile elastic modulus of the core layer. For example, the resin constituting the shell layer can be a resin having a glass transition temperature lower than that of the resin constituting the core layer. Thereby, when the base material and the transfer foil are heat-pressed through the adhesive layer containing the resin particles, the shell layer of the resin particles can be easily softened, and the adhesion between the base material and the transfer foil can be improved.

  It can be confirmed by the following method that the resin particles have a core layer and a shell layer, and that the curing agent is unevenly distributed in the core layer. That is, after applying the latex ink of this embodiment on a base film, it is dried at a temperature at which the resin and the curing agent do not react and the resin particles do not fuse to form a coating film containing the resin particles. By observing the cross section obtained by cutting the coating film with an SEM, it can be confirmed that the resin particles have a core layer and a shell layer.

  The average thickness of the shell layer is about 1 to 50%, preferably about 2 to 10% of the diameter of the core layer. The thickness of the shell layer can be measured by the aforementioned SEM observation.

  The volume average particle diameter of the resin particles is preferably 1 to 500 nm, and more preferably 80 to 300 nm, for example, in order to obtain injection stability by an ink jet method. The volume average particle diameter of the resin particles can be measured by “UPA-150” (manufactured by Microtrack).

1-1-4. Method for Producing Resin Particles Resin particles can be produced by any method such as a kneading and pulverizing method, a suspension polymerization method, an emulsion polymerization method, a dissolution suspension method, or a dispersion polymerization method. Especially, since it is easy to obtain the resin particle with a uniform average particle diameter, manufacturing by an emulsion polymerization method is preferable.

  The emulsion polymerization method is a method of polymerizing a monomer composition in an aqueous solvent. Specifically, after mixing an aqueous solvent, a monomer composition hardly soluble in an aqueous solvent, and a surfactant (emulsifier) to obtain an emulsion; soluble in the aqueous solvent in the emulsion It is possible to add a polymerization initiator to polymerize the monomer composition.

  A monomer composition contains the monomer component containing the above-mentioned polymerizable monomer (A), and the above-mentioned hardening | curing agent, and may further contain a chain transfer agent etc. as needed.

  Examples of the chain transfer agent include octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, mercaptopropionic acid derivative, thioglycolic acid derivative and the like. The addition amount of the chain transfer agent may be 0.01 to 1% by mass, preferably 0.05 to 0.5% by mass, based on the entire polymerizable monomer. By setting the addition amount of the chain transfer agent in the above range, the weight average molecular weight of the resin constituting the resin particles can be adjusted to an appropriate range.

  A surfactant can be added to uniformly disperse the above-described monomer composition in an aqueous medium. Examples of the surfactant include sulfonate, sulfate ester salt, fatty acid salt and the like. Examples of sulfonates include sodium dodecylbenzene sulfonate, sodium arylalkyl polyether sulfonate, sodium 3,3-disulfone diphenylurea-4,4-diazo-bis-amino-8-naphthol-6-sulfonate, Ionic surfactants such as o-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonic acid sodium, etc. Can be mentioned. Examples of the sulfate ester salt include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate and the like. Examples of fatty acid salts include sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate and the like.

  The polymerization initiator can be an oil-soluble or water-soluble polymerization initiator. Examples of oil-soluble polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy Carbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4 -T-butylperoxycyclohexyl) propane, tris- ( - it includes peroxides such as butyl peroxy) triazine. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, hydrogen peroxide and the like.

  The aqueous solvent is usually water, and may further contain a water-soluble organic solvent as necessary. The water-soluble organic solvent can be the same as the water-soluble organic solvent described later contained in the latex ink of this embodiment.

  The polymerization reaction is carried out while stirring the aqueous solvent until the average particle size of the resin particles is in a desired range. Stirring of the aqueous solvent can be performed, for example, with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. The temperature during the polymerization reaction can be adjusted to a temperature at which the curing agent does not react with the crosslinkable group of the resin; for example, about 70 to 90 ° C.

  Resin particles having a core layer and a shell layer are obtained by polymerizing the monomer composition constituting the core layer in an aqueous solvent to obtain core particles; the shell layer is formed in the aqueous solvent containing the core particles. It can be obtained by further adding a constituent monomer composition and polymerizing it.

  The content of the resin particles is preferably 5 to 80% by mass and more preferably 5 to 40% by mass with respect to the entire latex ink. By setting the content of the resin particles to a certain level or more, sufficient adhesiveness is easily obtained. By setting the content of the resin particles to a certain value or less, it is easy to adjust the ink viscosity to a range suitable for injection by, for example, an inkjet method.

1-2. Aqueous solvent The aqueous solvent contained in the latex ink of this embodiment contains water as a main component. The aqueous solvent may further contain a water-soluble organic solvent as necessary from the viewpoint of adjusting the viscosity of the ink or preventing the ink from drying.

The water-soluble organic solvent preferably contains an organic solvent having a vapor pressure lower than that of water from the viewpoint of suppressing drying of the ink. Examples of such water-soluble organic solvents include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol 1,2,6-hexanetriol, Polyhydric alcohols such as acetylene glycol derivatives, glycerin, trimethylolpropane;
Lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether;
Heterocycles such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethylmorpholine;
Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene;
Examples thereof include polyfunctional compounds such as diacetone alcohol and diethanolamine.

On the other hand, from the viewpoint of easily adjusting the viscosity of the ink,
Monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol;
Polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol Glycol derivatives such as diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether;
Ethamines such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine; formamide; N, N -Dimethylformamide;
N, N-dimethylacetamide; dimethyl sulfoxide; sulfolane; 2-pyrrolidone; N-methyl-2-pyrrolidone; N-vinyl-2-pyrrolidone; 2-oxazolidone; 1,3-dimethyl-2-imidazolidinone; Acetone and the like are included. A water-soluble organic solvent may be used by 1 type, and may use 2 or more types together.

  Of these, polyhydric alcohols such as glycerin and diethylene glycol and glycol derivatives are preferred from the viewpoints of good compatibility with water and easy prevention of ink drying and viscosity adjustment at the same time.

  The content ratio of the water-soluble organic solvent in the aqueous solvent may be 0 to 50% by mass, preferably 30 to 45% by mass with respect to the entire aqueous solvent.

1-3. Other Components The latex ink of the present embodiment may further contain other components as long as the effects of the present embodiment are not impaired. Examples of other components include surfactants, anti-drying agents (wetting agents), emulsion stabilizers, penetration enhancers, UV absorbers, preservatives, antifungal agents, pH adjusters, surface tension adjusters, antifoaming agents Agents, viscosity modifiers, dispersants, dispersion stabilizers, rust inhibitors, chelating agents, and the like, preferably surfactants.

  The surfactant can be an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, Anionic surfactants such as oxyethylene alkyl sulfate salts; polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Nonionic surfactants such as glycerin fatty acid esters and oxyethyleneoxypropylene block copolymers; acetylene-based polyoxyethylene oxide surfactants; N, N-dimethyl Etc. amine oxide type amphoteric surfactants such as Le -N- alkylamine oxides.

1-4. Ink Physical Properties The viscosity of the latex ink at 25 ° C. is, for example, about 1 to 40 mPa · s, preferably 5 to 40 mPa · s, from the viewpoint of improving the ejection stability of the ink in the ink jet system. The viscosity of the ink can be measured with an E-type viscometer at 25 ° C. and 1 rpm.

B-2. Forming Method of Foil Image The forming method of the foil image of the present embodiment is as follows. 1) The latex ink of the present embodiment is applied in a pattern on the substrate or the foil layer of the transfer foil (preferably on the substrate). A step of forming an adhesive layer, and 2) a step of heat-pressing the base material and the transfer foil through the adhesive layer to transfer the foil layer of the transfer foil onto the base material to form a foil image.

  FIG. 2 is a schematic diagram illustrating an example of a foil image forming method. As shown in FIG. 2, the method for forming a foil image is as follows: 1) A step of forming the adhesive layer 130 by applying the latex ink of this embodiment in a pattern on a substrate 110 that is a transfer material (FIG. 2). 2 (a) and FIG. 2 (b)), and 2) the substrate 110 and the transfer foil 150 are overlapped and thermocompression bonded via the adhesive layer 130, and the transfer foil 150 is placed on the substrate 110. A step of transferring the foil layer 190 to form a foil image 230 (see FIG. 2C and FIG. 2D).

2-1. Step 1) The latex ink of the present embodiment is applied in a pattern on the substrate 110 (see FIG. 2A).

  The base material 110 is selected according to the application, and examples thereof include various plastic base materials, metal base materials, glass base materials, stone base materials, cloth base materials, natural fiber base materials, and natural fibers and synthetic fibers. A fleece base material, a Japanese paper base material, etc. are contained. For example, the base material used for wallpaper is a natural fiber base material, a fleece base material mixed with natural fiber and synthetic fiber, a Japanese paper base material, etc., preferably a fleece base material mixed with natural fiber and synthetic fiber. It is possible.

  The pattern to which the latex ink is applied is matched with the pattern to which the foil is to be transferred (pattern of the foil image). The method for applying the latex ink is not particularly limited, and may be, for example, an inkjet method, a dispenser method, a spray method, or the like. Among these, an inkjet method is preferable because a high-definition pattern can be formed.

  Next, the solvent component is removed from the latex ink coating film applied in a pattern to obtain the adhesive layer 130 containing the resin particles 130A or a fused product thereof (see FIG. 2B). Removal of the solvent component is performed by heating, air drying, natural drying, or the like, and since the solvent component can be removed quickly, it is preferably performed by heating. The heating can be performed by various heaters such as an electric heater, an infrared heater, and an electromagnetic induction (IH) heater.

  The heating temperature is a temperature at which the solvent component evaporates, and is set to a temperature at which the resin constituting the resin particles does not react with the curing agent (does not crosslink), and may be, for example, 80 to 180 ° C. FIG. 2B shows an example in which the adhesive layer 130 is formed at a temperature at which the resin particles 130A are not fused. However, the curing agent in the resin particles 130A does not react with the resin, and the resin particles 130A melt. The adhesive layer 130 may be formed by heating at a deposition temperature.

  The thickness of the adhesive layer 130 is preferably 1 to 30 μm, and more preferably 1 to 10 μm. When the thickness of the adhesive layer 130 is equal to or greater than a certain level, the adhesive strength between the foil image and the substrate 110 can be sufficiently obtained. On the other hand, when the thickness of the adhesive layer 130 is not more than a certain value, the unevenness of the obtained laminate can be reduced.

2-2. Step 2) The adhesive layer 130 of the substrate 110 and the foil layer 190 of the transfer foil 150 are overlapped and heat-pressed with the heating roller 210 or the like (see FIG. 2C). Thereby, the adhesive layer 130 is heated and melted.

  The transfer foil 150 includes at least a support 170 and a foil layer 190.

  Examples of the support 170 include a flexible resin film such as a polyethylene film, a polyester film, an olefin film, a polypropylene film, and a polycarbonate film, and paper.

  The foil layer 190 may be a metal foil, a metal vapor deposition film, a hologram film, a pearl tone film, a iridescent film, a white / black film, a color film, a clear film, or the like. The foil layer 190 may be a layer made of a composite material of a plastic film and a metal for the purpose of improving the strength. The thickness of the foil layer 190 can be normally about 0.1 to 2 μm. In order to color the foil layer 190, a colored layer may be further laminated on the foil layer 190.

  The transfer foil 150 may further include other layers such as a release layer (not shown) between the support 170 and the foil layer 190 as necessary. The release layer may be a layer made of a resin having releasability such as fully saponified polyvinyl alcohol, fluorine resin, or silicon resin.

  The thermocompression bonding can be performed by, for example, a method of pressure bonding with a heating roller or a method of pressing with a heated plate-like member. The heating temperature, pressure, and heating time at the time of thermocompression bonding can be set according to the types of the substrate 110 and the transfer foil 150. The heating temperature is preferably equal to or higher than the temperature at which the resin particles 130 are fused, and may be, for example, 70 to 200 ° C, preferably 90 to 150 ° C. The pressure can be 100 to 700 kPa, preferably 150 to 400 kPa. The heating time can be about 0.05 to 20 seconds.

  The adhesive layer 130 includes resin particles 130A (or a fused product thereof) derived from the latex ink of the present embodiment and containing a curing agent. Therefore, the resin particles 130 </ b> A included in the adhesive layer 130 can be fused together by the heat at the time of thermocompression bonding, and the resin constituting the resin particles 130 </ b> A can be crosslinked. For example, when the curing agent contained in the adhesive layer 130 is a blocked isocyanate compound, the blocking agent is dissociated from the blocked isocyanate compound by heat during thermocompression bonding. Thereby, the isocyanate group of the exposed isocyanate compound and the crosslinkable group of the resin having a crosslinkable group react to crosslink the resin. Thereby, the foil layer 190 and the base material 110 are firmly bonded via a cured resin (crosslinked product).

  After the substrate 110 and the transfer foil 150 are heat-pressed, the support 170 of the transfer foil 150 is peeled off (see FIG. 2D). Thereby, the foil layer 190 in a region in contact with the adhesive layer 130 formed in a pattern is transferred onto the adhesive layer 130 to become a foil image 230. On the other hand, the foil layer 190 in a region not in contact with the adhesive layer 130 is removed together with the support 170. Thereby, the foil layer 190 can be transferred in the same pattern as the adhesive layer 130, and the foil image 230 can be formed.

B-3. Laminated body The laminated body of this embodiment is the base material 110, the foil layer 190 (foil image 230) formed in pattern shape, and the hardened | cured material layer 250 arrange | positioned between the base material 110 and the foil layer 190. including. The laminate of this embodiment can be obtained by the above-described foil image forming method.

  The cured product layer 250 is composed of a cured product of the latex ink of this embodiment. Thereby, the foil layer 190 and the base material 110 can be firmly bonded, and the adhesive strength and scratch resistance of the foil image 230 to the base material 110 can be improved.

  The laminated body of this embodiment is used for various applications, for example, various wallpaper, packaging materials, book bindings, stationery, machines, equipment, electrical appliances, clothing, etc., and preferably used for wallpaper.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by this.

A. Example of First Embodiment [Measurement Method of Storage Elastic Modulus]
The storage elastic modulus G ′ (120) at 120 ° C. of the elastic resin contained in the resin particles obtained in each Example and Comparative Example was measured as follows. The measurement device was an MR-500 type solid meter (manufactured by Rheology), and the measurement was performed based on the following procedures (1) to (4).

(1) A dispersion of core particles (elastic resin particles) was placed in a measurement sample petri dish at 20 ± 1 ° C. and leveled. The petri dish was left to dry for 24 hours or more in an environment with a relative humidity of 50 ± 5% Rh. Then, 0.6 g of a sample was taken from the petri dish and loaded into a compression molding machine. Thereafter, a 3 t load was applied for 30 seconds to produce a 1 cm diameter pellet.
(2) The pellets were loaded on a parallel plate having a diameter of 0.977 cm.
(3) The measurement part temperature of the measuring device was set to a temperature 20 ° C. lower than the “softening point of the elastic resin” measured by the method described later. On the other hand, the pellet was compressed by setting the parallel plate gap to 3 mm.
(4) Then, the measurement part temperature of the measuring apparatus was set to 35 degreeC, and the pellet was left to cool to 35 degreeC. Then, while applying a sinusoidal vibration with a frequency of 1.0 Hz, the temperature of the measurement part was increased to 5 ° C./min to 200 ° C. The complex elastic modulus G ^* at 120 to 150 ° C. at this time was measured, and the storage elastic modulus G ′ (120) was calculated therefrom.

(Measurement method of softening point of elastic resin)
The softening point of the elastic resin was measured by a flow tester method.
Specifically, the above-mentioned dispersion of elastic resin particles was placed in a measurement sample petri dish at a temperature of 20 ± 1 ° C. and leveled. The petri dish was allowed to stand for 12 hours or more in an environment with a relative humidity of 50 ± 5% Rh. Then, 1.1 g of a sample was taken from the petri dish and loaded into a compression molding machine. Thereafter, a 3 t load was applied for 30 seconds to produce a 1 cm diameter pellet.
The sample was then placed in an environment of 24 ± 5 ° C. and relative humidity 50 ± 20% RH. Then, using a flow tester (CFT-500D (manufactured by Shimadzu Corporation)), a cylindrical die (1 mm) under the conditions of a load of 196 N (20 kg weight), a starting temperature of 80 ° C., a preheating time of 300 seconds, and a heating rate of 6 ° C./min. A piston having a diameter of 1 cm was extruded from (× 1 mm), and the temperature at which the offset value was 5 mm was defined as the softening point.

[Example A-1]
Preparation of “Monomer Mixture 1” 567 parts by mass of styrene, 165 parts by mass of n-butyl acrylate, 68 parts by mass of methacrylic acid, and 4 parts by mass of n-octyl mercaptan were mixed together. 1 ”.

-Preparation of "Monomer Mixture 2" 390 parts by mass of styrene, 40 parts by mass of methacrylic acid, and 13 parts by mass of n-octyl mercaptan were mixed to obtain "Monomer Mixture 2".

-Core formation In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction device, 4 parts by mass of polyoxyethylene = sodium dodecyl ether sulfate and 3000 parts by mass of ion-exchanged water were added. The temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm.
After the temperature increase, an initiator solution in which 8 parts by mass of potassium persulfate (KPS) is dissolved in 200 parts by mass of ion-exchanged water is added, the temperature of the liquid is set to 75 ° C., and the above “monomer mixture 1” is added. The solution was added dropwise over 1 hour. After the dropping, a dispersion of “core A1” was prepared by performing a polymerization reaction by heating and stirring at 75 ° C. for 2 hours.

-Formation of shell layer In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device, 40 parts by mass (in terms of solid content) of the dispersion of "core A1" and polyoxyethylene = sodium dodecyl ether sulfate 2 parts by mass and 1270 parts by mass of ion-exchanged water were added, and the temperature was heated to 80 ° C.
After the heating, an initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added to the dispersion. Thereafter, the liquid temperature was set to 80 ° C., and the “monomer mixed liquid 2” was added dropwise over 1 hour. Furthermore, the polymerization reaction was carried out by heating and stirring at 80 ° C. for 2 hours, followed by cooling to 28 ° C. to obtain a dispersion of core-shell type latex resin particles (A2).

-Preparation of latex ink 58 parts by mass of the above-described core-shell type latex resin particle (A2) dispersion, 10 parts by mass of glycerin, 10 parts by mass of diethylene glycol, and 22 parts by mass of ion-exchanged water were prepared to prepare latex ink. did.

[Example A-2]
“Core A1” was prepared in the same manner as in Example A-1, except that the amount of potassium persulfate (KPS) was 10 parts by mass and the amount of n-octyl mercaptan was 8 parts by mass. Was obtained. A core-shell type latex resin particle (B2) was prepared in the same manner as in Example A-1, except that a dispersion containing “core B2” was used instead of the dispersion containing “core A1”. A latex ink containing latex resin particles (B2) was prepared.

[Example A-3]
Prepared in the same manner as in Example A-1 except that the amount of potassium persulfate (KPS) at the time of preparation of “core A1” was 10 parts by mass and no n-octyl mercaptan was added, and “core C2” was included. A dispersion was obtained. Then, core-shell type latex resin particles (C2) were prepared in the same manner as in Example A-1, except that the dispersion containing “core C2” was used instead of the dispersion containing “core A1”. A latex ink containing latex resin particles (C2) was prepared.

[Example A-4]
Latex ink containing core-shell type latex resin particles (D2) prepared in the same manner as in Example A-1, except that the amount of “core A1” at the time of shell production was 11.6 parts by mass in terms of solid content Was prepared.

[Example A-5]
A latex ink containing core-shell type latex resin particles (E2) was prepared in the same manner as in Example A-1, except that the amount of “core A1” at the time of shell preparation was 63 parts by mass in terms of solid content. did.

[Comparative Example A-1]
A core-shell type latex was prepared in the same manner as in Example A-1, except that the amount of potassium persulfate (KPS) at the time of preparation of “Core A1” was 10 parts by mass and the amount of n-octyl mercaptan was 10 parts by mass. A latex ink containing resin particles (F2) was prepared.

[Comparative Example A-2]
Prepared in the same manner as in Example A-1 except that the amount of potassium persulfate (KPS) at the time of preparation of “core A1” was 6 parts by mass and no n-octyl mercaptan was added, and core-shell type latex resin particles ( A latex ink containing G2) was prepared.

[Comparative Example A-3]
A latex ink was obtained by mixing 80 parts by mass of the dispersion of “core A1” prepared in Example A-1, 10 parts by mass of glycerin, and 10 parts by mass of diethylene glycol.

[Comparative Example A-4]
A latex ink was obtained by mixing 80 parts by mass of the dispersion of “core B1” prepared in Example A-2, 10 parts by mass of glycerin, and 10 parts by mass of diethylene glycol.

[Comparative Example A-5]
80 parts by mass of the core C1 dispersion prepared in Example A-3, 10 parts by mass of glycerin, and 10 parts by mass of diethylene glycol were mixed to obtain a latex ink.

[Comparative Example A-6]
-Preparation of monomer mixture 3 390 parts by mass of styrene, 140 parts by mass of n-butyl acrylate, 40 parts by mass of methacrylic acid, and 13 parts by mass of n-octyl mercaptan were mixed together. "

・ Preparation of particles 2 parts by mass of polyoxyethylene = sodium dodecyl ether sulfate and 1270 parts by mass of ion-exchanged water are charged into a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device, and the temperature is set to 80 ° C. Heated to.
After heating, an initiator solution in which 10 parts by mass of potassium persulfate (KPS) is dissolved in 200 parts by mass of ion-exchanged water is added to the emulsified particle dispersion, and then the liquid temperature is set to 80 ° C. Body mixture 3 ”was added dropwise over 1 hour. Furthermore, the polymerization reaction was carried out by heating and stirring at 80 ° C. for 2 hours, followed by cooling to 28 ° C. to prepare a dispersion of “resin fine particles K1”.
A latex ink was prepared by mixing 58 parts by mass of the dispersion of the resin fine particles K1, 10 parts by mass of glycerin, 10 parts by mass of diethylene glycol, and 22 parts by mass of ion-exchanged water.

[Comparative Example A-7]
Latex ink was obtained by adding 10 parts by mass of titanium oxide particles having a maximum particle size of 1 μm or less to the latex ink of Comparative Example A-6.

[Comparative Example A-8]
9 parts by mass (in terms of solid content) of the dispersion of “core A1” in Example A-1 and 91 parts by mass (in terms of solid content) of the dispersion of “resin fine particles K1” were mixed to obtain 6 elastic resins. A latex resin dispersion containing 6% was obtained.
80 parts by mass of the latex dispersion, 10 parts by mass of glycerin, and 10 parts by mass of diethylene glycol were mixed to obtain a latex ink.

[Evaluation]
An adhesive layer was formed using the latex ink prepared in the above Examples and Comparative Examples, and the transfer foil was transferred. About the obtained laminate and latex ink, adhesion between adhesive layer and foil, pattern reproducibility, surface condition after foil transfer, adhesion between fleece substrate and adhesive layer, and printability of latex ink (ink (Clogging) was evaluated as follows. The results are shown in Table 1. In addition, the formation method of the contact bonding layer and the transfer method of foil were performed as follows.

Formation of Adhesive Layer and Transfer Method The latex ink prepared above was filled into an ink tank of an on-demand type ink jet apparatus equipped with four rows of piezo heads. The piezo head had a nozzle diameter of 28 μm, a drive frequency of 18 kHz, a nozzle count of 512, a minimum droplet volume of 12 pl, and a nozzle density of 180 dpi. Then, on a commercially available image support “DEEP UV Van Nouveau Snow White (basis weight 162.5 g / m 2) (manufactured by Takeo Co., Ltd.)”, the latex ink is full droplet amount 14 pl, drive frequency 18 kHz, print resolution 720 dpi × 720 dpi. An image was formed under the following conditions. The formed image was heated at 80 ° C. for 1 minute and dried to obtain an adhesive layer having a thickness of 2.0 μm.

  After forming an adhesive layer of each latex ink on the image support with the above-described coating apparatus, the adhesive layer on the image support and the foil transfer surface (adhesive layer) of the transfer foil are overlaid, and a heating and pressing roll The foil was transferred onto the foil adhesive layer by passing between them. In addition, "BL2 gold | metal | money 2.8" made from a commercially available transfer foil Co., Ltd. Murata gold foil was used for the transfer foil.

The foil transfer was performed under the following conditions.
・ Heating roll: A silicone rubber layer with a thickness of 3 mm is disposed on an aluminum base with an outer diameter of 100 mm and a thickness of 10 mm, and the surface temperature is set to 110 ° C. ・ Pressure roll: outer diameter of 80 mm, thickness A silicone rubber layer with a thickness of 3 mm is placed on a 10 mm aluminum substrate, and the surface temperature is set to 100 ° C. ・ Heat source: Halogen lamps are placed inside the heating roll and pressure roll, respectively (the temperature is measured by a thermistor). control)
・ Nip width between heating roll and pressure roll: 7mm
-Surface pressure of heating roll and pressure roll: 300 kPa
・ Image support conveyance speed: 42 mm / min ・ Transfer foil material conveyance direction: A3 size transfer foil is conveyed in the vertical direction ・ Evaluation environment: normal temperature and normal humidity environment (temperature 20 ° C., relative humidity 50% RH)

-Evaluation of adhesion between foil and adhesive layer 5 cm x by the above-mentioned adhesive layer forming method on a base material consisting of "DEEP UV Van Nouveau Snow White (basis weight 162.5 g / m ² ) (manufactured by Takeo Co., Ltd.)" A 10 cm adhesive layer was formed. Thereafter, the foil was transferred by the above-described foil transfer method to form a 5 cm × 10 cm foil image (solid image).
And the tape was stuck on the said foil image, and it peeled off by hand. The state of the foil image at this time was confirmed with the naked eye and a 10 × magnifier, and evaluated according to the following criteria. The tape used was Scotch Mending Tape MP-18 (manufactured by Sumitomo 3M).
◎: Fine peeling that can be confirmed by magnifying glass observation was not occurred. ○: Fine peeling that could be confirmed by magnifying glass was observed, but it was within the level of the naked eye. △: Fine that could be confirmed by visual observation. Although some peeling occurred, it was within the allowable range for practical use. ×: Peeling that could be confirmed by visual observation occurred and was outside the practically acceptable range.

・ Pattern reproducibility evaluation (Pattern 1)
By using the above-mentioned adhesive layer forming method, a line drawing having a width of 2 mm is longitudinally (1.0 mm interval) with respect to the paper passing direction on a base material made of “DEEP UV van nouveau snow white (basis weight 162.5 g / m ² )”. Vertically and horizontally (parallel). Thereafter, the transfer foil was transferred by the above-described foil transfer method to form a fine line pattern.

(Pattern 2)
By using the above-mentioned adhesive layer forming method, a line drawing having a width of 1 mm is vertically applied to a substrate made of “DEEP UV van nouveau snow white (basis weight: 162.5 g / m ² ) at intervals of 0.5 mm with respect to the sheet passing direction ( Vertically and horizontally (parallel). Thereafter, the foil was transferred by the above-described foil transfer method to form a fine line pattern.

And the state of the said fine line pattern was confirmed with the naked eye and a 10 times magnifier. And it evaluated on the following references | standards.
◎: In both thin line images of the two patterns, there was no excess foil between the thin lines, and it was confirmed with a loupe that there was no chipping of the foil on the thin line. O: Minute chipping on the thin line image with a width of 1 mm. Although it was seen, it was a level that was not a problem in the naked eye observation, and there was no excess foil between the thin lines in the two patterns of thin line images. However, although it was recognized by naked-eye observation, it was within an acceptable range for practical use. X: Some thin lines were not completely reproducible, and the defect was confirmed with the naked eye and was outside the practically acceptable range.

-Evaluation of surface condition after roller pressing test A 5 cm x 10 cm adhesive layer was formed in the same manner as in the evaluation of the adhesion between the foil and the adhesive layer. Thereafter, the transfer foil was transferred to form a 5 cm × 10 cm foil image (solid image).
Then, using a commercially available pressing roller for pasting wallpaper, the foil transfer surface was pressed by the roller and reciprocated 10 times. The state of the foil image was confirmed with the naked eye and a 10 × magnifier. And it evaluated on the following references | standards.
◎: Fine scratches and peeling that could be confirmed by loupe observation did not occur. 〇: Fine scratches and peeling that could be confirmed by loupe observation occurred, but they were within the problem level with the naked eye. Although there were some fine scratches and peeling that could be confirmed, they were within the acceptable range for practical use. ×: Scratches and peeling that could be confirmed by visual observation occurred and were outside the practically acceptable range.

・ Evaluation of adhesion between adhesive layer and fleece substrate Foil transfer in the same way as the foil transfer method described above, except that a non-woven fabric for digital print wallpaper (fleece substrate) “MA8941D (manufactured by Ahlstrom)” was used as the substrate. Then, the adhesiveness, reproducibility, and surface state were evaluated in the same manner as in the above-mentioned “Method for evaluating the adhesiveness between a foil and an adhesive layer”.

・ Latex ink printability evaluation (ink clogging)
Using each latex ink, 100 sheets were continuously output in the same pattern as the adhesive layer formed in the adhesive evaluation and pattern reproducibility evaluation. Then, the state of the nozzle was confirmed.

As shown in Table 1, the resin particles contained in the latex ink have a core-shell structure, and the storage elastic modulus G ′ (120) of the resin contained in the core is 1 × 10 ⁴ to 1 × 10 ^6. When it was dyn / cm ² , the adhesiveness between the foil and the adhesive layer, the adhesiveness between the adhesive layer and the fleece base material was good, and the pattern reproducibility and the surface condition after the roller pressing test were also good. Furthermore, the ejection stability of the ink from the ink jet apparatus was also good (Examples A-1 to A-5).

  On the other hand, even if the resin particles have a core-shell structure, when the storage elastic modulus of the elastic resin contained in the core is too low, the evaluation results of the pattern reproducibility and the adhesion between the adhesive layer and the fleece substrate were poor (comparison) Example A-1). Since the core is too soft, it is surmised that the pattern reproducibility and the like are reduced by changing the shape of the adhesive layer during the transfer of the foil or by being pressed into the irregularities of the fleece base material.

  Moreover, even if the resin particles have a core-shell structure, when the storage elastic modulus of the elastic resin contained in the core is too high, the adhesion between the foil and the adhesive layer was low (Comparative Example A-2). It is inferred that the adhesion between the adhesive layer and the foil was hindered because the core was too hard.

Further, when the resin particles are composed only of an elastic resin (a resin having a storage elastic modulus G ′ (120) of 1 × 10 ⁴ to 1 × 10 ⁶ dyn / cm ² ), the adhesive layer and the foil, and the adhesive layer and the base The adhesiveness of the material was poor (Comparative Examples A-3 to A-5). It is inferred that the resin particles were hard and did not sufficiently adhere to the foil or the substrate.

On the other hand, when the resin particles are made of a resin other than an elastic resin (a resin having a storage elastic modulus G ′ (120) of 1 × 10 ³ dyn / cm ² ), the pattern reproducibility was low (Comparative Example A-6). . The adhesive layer is easily deformed, and it is presumed that the pattern reproducibility and the like are reduced due to the adhesive layer being pushed into the unevenness of the base material during the transfer of the foil. Then, when an inorganic filler was added to the ink, the pattern reproducibility was increased, but irregularities derived from the inorganic filler appeared on the foil surface, and the surface state of the foil was lowered (Comparative Example A-7). Further, it was confirmed that the latex ink of Comparative Example A-7 was clogged with nozzles considered to be caused by the added hard filler.

  In addition, when the elastic resin and the molten resin were not mixed in the core-shell structure but mixed, it was difficult to improve the pattern reproducibility (Comparative Example A-8).

B. Example of the second embodiment Resin Particle Material <Polymerizable Monomer>
1) Polymerizable monomer (A) having a crosslinkable group
Methacrylic acid Glycidyl methacrylate 2) Other polymerizable monomers (B)
styrene
n-butyl acrylate

<Curing agent>
Amine: 1,3-phenylenediamine Block isocyanate: Block isocyanate synthesized in Synthesis Example 1 below (Synthesis Example 1)
444 parts of isophorone diisocyanate was dissolved in 816 parts of toluene. To this, 90 parts of 1,3-butanediol was added dropwise at 60 ° C. over 1 hour, and then reacted for 6 hours. Subsequently, 640 parts of diethyl malonate were further added, and the reaction was performed for 6 hours. 25 parts of polyoxyethylene alkylphenyl ether was added to 500 parts of the obtained blocked isocyanate composition solution, and 391 parts of water was gradually added while stirring, followed by emulsification with a homomixer. Then, the obtained solution was decompressed and toluene was distilled off. The obtained aqueous dispersion was filtered, washed repeatedly with ion exchange water at 35 ° C., and then dried with hot air at 40 ° C. to obtain blocked isocyanate.

<Chain transfer agent>
n-octyl-3-mercaptopropionic acid ester

<Surfactant>
Sodium dodecyl sulfate

<Polymerization initiator>
Potassium persulfate (KPS)

2. Preparation of latex ink <Preparation of latex ink 1>
In a flask equipped with a stirrer, 326 parts by mass of styrene as a polymerizable monomer, 133.1 parts by mass of n-butyl acrylate and 10.8 parts by mass of methacrylic acid, and n-octyl-3-mercapto as a chain transfer agent 11.0 parts by mass of propionate and 120.2 parts by mass of blocked isocyanate as a curing agent were added and heated to 90 ° C. to obtain a mixed solution [a1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. . The surfactant solution was heated to 98 ° C., and the mixed solution [a1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 12.5 parts by mass of potassium persulfate (KPS) is dissolved in 440 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is stirred at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [1H] in which resin particles 1H containing a curing agent are dispersed was obtained. The volume average particle diameter of the resin particles contained in the resin particle dispersion [1H] was 200 nm. The volume average particle diameter was measured by “UPA-150” (manufactured by Microtrack). Latex ink 1 was prepared by further adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [1H] to adjust the solid content to 10% by mass.

<Preparation of latex ink 2>
In a flask equipped with a stirrer, 163.8 parts by mass of styrene as a polymerizable monomer, 122.3 parts by mass of n-butyl acrylate, 10.8 parts by mass of methacrylic acid, and 173 parts by mass of glycidyl methacrylate, chain transfer 11.0 parts by mass of n-octyl-3-mercaptopropionic acid ester as an agent and 120.2 parts by mass of 1,3-phenylenediamine as a curing agent were added, heated to 90 ° C., and mixed solution [b1] Got.

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. . The surfactant solution was heated to 98 ° C., and the mixed solution [b1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 12.5 parts by mass of potassium persulfate (KPS) is dissolved in 440 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is stirred at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [2H] in which resin particles 2H containing a curing agent are dispersed was obtained. The volume average particle size of the resin particles contained in the resin particle dispersion [2H] was 200 nm. Latex ink 2 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [2H] to adjust the solid content to 10% by mass.

<Preparation of latex ink 3>
1) Production of resin particles 3H In a flask equipped with a stirrer, 135.9 parts by mass of styrene as a polymerizable monomer, 55.4 parts by mass of n-butyl acrylate, and 4.5 parts by mass of methacrylic acid were cured. 120.2 parts by mass of blocked isocyanate was added as an agent and heated to 90 ° C. to obtain a mixed solution [c1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. The surfactant solution was heated to 98 ° C., and the mixed solution [c1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 5.1 parts by mass of potassium persulfate (KPS) is dissolved in 240 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is heated at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [3H] in which resin particles 3H containing a curing agent are dispersed was obtained. The volume average particle diameter of the resin particles contained in the resin particle dispersion [3H] was 160 nm.

2) Preparation of resin particle 3HM To the resin particle dispersion [3H] prepared above, an initiator solution in which 7.4 parts by mass of potassium peroxide (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added, and the temperature was increased. Was adjusted to 80 ° C. A mixed solution [c2] containing 190.1 parts by mass of styrene, 77.7 parts by mass of n-butyl acrylate, 6.3 parts by mass of methacrylic acid, and 11.0 parts by mass of n-octyl-3-mercaptopropionic acid ester. Was added dropwise over 1 hour. After completion of the dropwise addition, the resulting solution was heated and stirred for 2 hours while maintaining the temperature at 80 ° C. to conduct a polymerization reaction. The resulting solution was cooled to 28 ° C. to obtain a resin particle dispersion [3HM] in which resin particles 3HM were dispersed. The resin particle 3H has a composite structure in which the surface is coated with a resin, and the volume average particle diameter is 200 nm. Latex ink 3 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [3HM] to adjust the solid content to 10% by mass.

<Preparation of latex ink 4>
1) Production of resin particles 4H In a flask equipped with a stirrer, 17.0 parts by mass of styrene, 6.9 parts by mass of n-butyl acrylate and 0.56 parts by mass of methacrylic acid as a polymerizable monomer, and a curing agent As above, 15.0 parts by mass of blocked isocyanate was added and heated to 90 ° C. to obtain a mixed solution [d1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. This was heated to 98 ° C., and the mixed solution [d1] was further added. The obtained solution was mixed and dispersed for 2 hours with a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 5.1 parts by mass of potassium persulfate (KPS) is dissolved in 240 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is heated at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [4H] in which resin particles 4H containing a curing agent are dispersed was obtained. The volume average particle size of the resin particles contained in the resin particle dispersion [4H] was 80 nm.

2) Production of Resin Particles 4HM An initiator solution in which 7.4 parts by mass of potassium peroxide (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added to the resin particle dispersion [4H] produced above, and the temperature Was adjusted to 80 ° C. To this, 23.8 parts by mass of styrene, 9.7 parts by mass of n-butyl acrylate, 0.79 parts by mass of methacrylic acid, and 1.4 parts by mass of n-octyl-3-mercaptopropionic ester [d2] Was added dropwise over 1 hour. After completion of the dropping, the resulting solution was heated and stirred for 2 hours while maintaining at 80 ° C., and then subjected to a polymerization reaction, cooled to 28 ° C., and a resin particle dispersion in which resin particles 4HM were dispersed [ 4HM] was prepared. The resin particles 4H had a composite structure with a resin coated on the surface, and the volume average particle diameter was 100 nm. Latex ink 4 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [4HM] to adjust the solid content to 10% by mass.

<Preparation of latex ink 5>
1) Production of resin particles 5H In a flask equipped with a stirrer, 265 parts by mass of styrene, 108 parts by mass of n-butyl acrylate and 8.8 parts by mass of methacrylic acid as a polymerizable monomer, and blocked isocyanate as a curing agent 235 parts by mass were added and heated to 90 ° C. to obtain a mixed solution [e1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. The surfactant solution was heated to 98 ° C., and the mixed solution [e1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 5.1 parts by mass of potassium persulfate (KPS) is dissolved in 240 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is heated at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [5H] in which resin particles 5H containing a curing agent are dispersed was obtained. The volume average particle diameter of the resin particles contained in the resin particle dispersion [5H] was 200 nm.

2) Preparation of resin particle 5HM To the resin particle dispersion [5H], an initiator solution in which 7.4 parts by mass of potassium peroxide (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added, and the temperature was set to 80. Adjusted to ° C. To this, a mixed solution [e2] of 371 parts by mass of styrene, 152 parts by mass of n-butyl acrylate, 12.3 parts by mass of methacrylic acid, and 21.4 parts by mass of n-octyl-3-mercaptopropionic acid ester was taken for 1 hour. And dripped. After completion of dropping, the obtained solution was heated and stirred for 2 hours while maintaining at 80 ° C., followed by polymerization reaction, then cooled to 28 ° C., and resin particle dispersion in which resin particles 5HM were dispersed. [5HM] was obtained. The resin particle 5H has a composite structure in which the surface is coated with a resin, and the volume average particle diameter is 250 nm. Latex ink 5 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to this resin particle dispersion [5HM] to adjust the solid content to 10% by mass.

<Preparation of latex ink 6>
1) Production of resin particles 6H In a flask equipped with a stirrer, 1087 parts by mass of styrene as a polymerizable monomer, 443 parts by mass of n-butyl acrylate, 36 parts by mass of methacrylic acid, and 962 parts by mass of blocked isocyanate as a curing agent. And heated to 90 ° C. to obtain a mixed solution [f1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction apparatus. . The surfactant solution was heated to 98 ° C., and the mixed solution [f1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 5.1 parts by mass of potassium persulfate (KPS) is dissolved in 240 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is heated at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [6H] in which resin particles 6H containing a curing agent are dispersed was obtained. The volume average particle diameter of the resin particles contained in the resin particle dispersion [6H] was 200 nm.

2) Production of Resin Particle 6HM An initiator solution in which 7.4 parts by mass of potassium peroxide (KPS) was dissolved in 200 parts by mass of ion-exchanged water was added to the resin particle dispersion [6H] produced above, and the temperature Was adjusted to 80 ° C. A mixed solution [f2] of 1520 parts by mass of styrene, 622 parts by mass of n-butyl acrylate, 50.4 parts by mass of methacrylic acid, and 87.7 parts by mass of n-octyl-3-mercaptopropionic acid ester was added to this over 1 hour. It was dripped. After completion of the dropping, the obtained solution was heated and stirred for 2 hours while maintaining at 80 ° C. to conduct a polymerization reaction, then cooled to 28 ° C., and a resin particle dispersion in which resin particles 6HM were dispersed [ 6HM]. The resin particle 6H has a composite structure in which the surface is coated with a resin, and the volume average particle diameter is 400 nm. Latex ink 6 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [6HM] to adjust the solid content to 10% by mass.

<Preparation of latex ink 7>
In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, 326 parts by mass of styrene, 133.1 parts by mass of n-butyl acrylate and 10.8 parts by mass of methacrylic acid as a polymerizable monomer , 11.0 parts by mass of n-octyl-3-mercaptopropionic acid ester as a chain transfer agent, 120.2 parts by mass of blocked isocyanate, 100 parts by mass of toluene, and 100 parts by mass of methyl ethyl ketone as the curing agent were heated to 60 ° C. Then, 4 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to obtain a mixed solution [g1].

  On the other hand, in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, 2,700 parts by mass of ion-exchanged water was heated to 70 ° C., and the mixed solution [g1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion. Resin fine particle dispersion [7H] was obtained by removing the solvent while reducing the pressure with an evaporator to produce resin fine particles, and further adding ion-exchanged water to adjust the solid content to 20% by mass. The volume average particle diameter of the resin particles contained in the resin particle dispersion [7H] was 210 nm. Latex ink 7 was obtained by further adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [7H] to adjust the solid content to 10% by mass.

<Preparation of latex ink 8>
In a flask equipped with a stirrer, 407.5 parts by mass of styrene as a polymerizable monomer, 166.4 parts by mass of n-butyl acrylate, and 13.5 parts by mass of methacrylic acid, and n-octyl-as a chain transfer agent 13.7 mass parts of 3-mercaptopropionic acid ester was added, and it heated and mixed at 90 degreeC, and obtained liquid mixture [h1].

  On the other hand, a surfactant solution was prepared by dissolving 1.6 parts by mass of sodium dodecyl sulfate in 2,700 parts by mass of ion-exchanged water in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing apparatus. The surfactant solution was heated to 98 ° C., and the mixed solution [h1] was further added. The obtained solution was mixed and dispersed for 2 hours by a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path to obtain a dispersion (emulsion).

  Next, an initiator solution in which 12.5 parts by mass of potassium persulfate (KPS) is dissolved in 440 parts by mass of ion-exchanged water and 750 parts by mass of ion-exchanged water are added to this emulsion, and the mixture is stirred at 98 ° C. for 2 hours. The polymerization reaction was carried out with stirring. Thereby, a resin particle dispersion [8H] in which the resin particles 8H are dispersed was obtained. The volume average particle diameter of the resin particles contained in the resin particle dispersion [8H] was 200 nm. Latex ink 8 was prepared by adding 20% by mass of ethylene glycol monobutyl ether and 20% by mass of hexanediol to the resin particle dispersion [8H] to adjust the solid content to 10% by mass.

3. Formation of Foil Image <Example B-1>
A foil image was formed by the following method using the prepared latex ink.

1) Formation of Adhesive Layer The latex ink 1 produced above was filled in an ink tank of an on-demand type ink jet device (manufactured by Konica Minolta) equipped with four rows of piezo heads. The piezo head had a nozzle diameter of 28 μm, a drive frequency of 18 kHz, a nozzle count of 512, a minimum droplet volume of 12 pl, and a nozzle density of 180 dpi. Then, on a fleece wallpaper base material BR5380D (made by Ahlstrom Co., Ltd.), which is a base material, the latex ink 1 has a full droplet amount of 14 pl, a driving frequency of 18 kHz, a printing resolution of 720 dpi × 720 dpi, and a printing rate of 10 cm × 10 cm. % Solid image was formed. The formed solid image was dried by heating at 80 ° C. for 5 minutes to obtain an adhesive layer having a thickness of 1.0 μm. During image formation, the fleece wallpaper substrate was heated to 120 ° C.

2) Transfer of Foil Layer “BL No. 2 Gold 2.8” manufactured by Murata Gold Leaf Co., Ltd. was prepared as a transfer foil. Then, between the support drum of the foil transfer device and the pinch roller, the transfer foil and the fleece wallpaper base material on which the adhesive layer is formed are in close contact with the foil layer of the transfer foil and the adhesive image surface of the fleece wallpaper base material. Then, it was heat-pressed at 150 ° C. while applying a linear speed of 42 mm / min and a pressure of 300 kPa. Thereby, the foil layer of the transfer foil was transferred onto the fleece wallpaper substrate. Thereafter, the support of the transfer foil was peeled off to obtain a foil image.

<Examples B-2 to B-7 and Comparative Example B-1>
A foil image was formed in the same manner as in Example B-1, except that the latex ink 1 was changed to the latex ink shown in Table 2.

<Example B-8>
A foil image was formed in the same manner as in Example B-3 except that the fleece wallpaper base material, which is the transfer material (base material), was changed to paper.

  The adhesive strength and scratch resistance of the foil images obtained in Examples B-1 to B-8 and Comparative Example B-1 were evaluated by the following methods.

<Adhesive strength>
The following steps 1) to 3) were performed on the foil image formed on the substrate.
1) The knife blade of the cutter was folded to prepare a new blade. Next, using a cutter guide, a 3 × 3 mm square grid was cut using a cutter knife at an angle of 60 degrees to form a grid of 9 squares in total.
2) A cellophane tape (registered trademark) was lightly rubbed and crimped several times with the belly of the finger on the grid area, and then the end of the tape was peeled off at an angle of 60 degrees for 0.5 to 1.0 seconds.
3) The number of remaining squares was counted among 9 squares, and the adhesive strength was evaluated. It was judged that the number of remaining cells was 8 or more, which was good.

<Abrasion resistance>
About the foil image formed on the base material, the pencil scratch test was done based on the method described in JISK 5600-5-4. And scratch resistance was evaluated based on the following criteria.
: 3H
○: 2H
Δ: H
X: F

Table 2 shows the evaluation results of Examples B-1 to B-8 and Comparative Example B-1.

  As shown in Table 2, the foil images of Examples B-1 to B-8 formed using latex inks 1 to 6 containing resin particles containing a curing agent showed adhesion strength and scratch resistance with the substrate. The properties were all good. On the other hand, the foil image of Comparative Example B-1 formed using latex ink 7 containing resin particles not containing a curing agent had low adhesion strength to the substrate and scratch resistance.

  From the comparison between Examples B-1 and B-3, the resin particles have a core-shell structure and the core layer contains a curing agent, so that the obtained foil can be obtained rather than the resin particles having a single-layer structure. It was found that the adhesive strength and scratch resistance of the image can be further improved.

  From the comparison between Example B-1 and B-2, when the curing agent contained in the resin particles is a block isocyanate, the adhesive strength and scratch resistance of the obtained foil image are further improved than when the curing agent is an amine. I found that it could be increased.

  From the comparison between Example B-1 and B-6, by setting the volume average particle size of the resin particles to 300 nm or less, the adhesive strength and the scratch resistance of the obtained foil image can be obtained rather than the volume average particle size exceeding 300 nm. It was found that sex could be further enhanced. This is presumably because the dispersion stability of the latex ink was increased and the uniform adhesive strength was obtained by setting the volume average particle size of the resin particles to 300 nm or less.

  From the comparison between Example B-1 and B-7, the ink containing the resin particles prepared by the emulsion polymerization method can easily obtain higher adhesive strength than the ink containing the resin particles prepared by the suspension polymerization method. I understand.

  From the comparison between Example B-3 and B-8, it can be seen that even if the base material is a fleece wallpaper base material, good adhesive strength and scratch resistance equivalent to or better than those of paper can be obtained.

  This application claims priority based on Japanese Patent Application No. 2014-160377 filed on August 6, 2014 and Japanese Patent Application No. 2014-160469 filed on August 6, 2014. The contents described in these application specifications and drawings are all incorporated herein.

  The latex ink of the first embodiment of the present invention has good adhesion between the coating film (adhesive layer) and the foil, and transfers the foil to a desired pattern using the adhesion of the coating film. Can do. Further, the latex ink has a small amount of volatile organic compounds (VOC) generated from the coating film. Therefore, it is applicable not only to products used outdoors but also to products used indoors. Further, the latex ink of the second embodiment of the present invention can provide a foil image having good adhesive strength and scratch resistance even to a substrate composed of a fleece material or the like.

DESCRIPTION OF SYMBOLS 1 Base material 2 Latex ink 2 'Adhesive layer 10 Transfer foil 11 Support material 12 Foil 12' Foil layer 20 Heating roller 110 Base material 130 Adhesive layer 130A Resin particle 150 Transfer foil 170 Support body 190 Foil layer 210 Heating roller 230 Foil image 250 Hardened material layer

Claims (17)

A latex ink for forming an adhesive layer, which is used in a method for forming a foil image by heat-pressing a transfer foil on an adhesive layer formed in a pattern on a substrate and forming the foil transfer layer on the adhesive layer. Yes,
Including a solvent and core-shell type latex resin particles,
The core-shell type latex resin particles have a core made of an elastic resin and a shell layer made of a molten resin,
A latex ink, wherein the elastic resin has a storage elastic modulus G ′ (120) at 120 ° C. of 1 × 10 ⁴ to 1 × 10 ⁶ dyn / cm ² .   The latex ink according to claim 1, wherein the amount of the elastic resin is 2 to 10% by mass with respect to the total mass of the core-shell type latex resin particles. A step of applying the latex ink according to claim 1 or 2 in a pattern on a substrate to form an adhesive layer;
A step of bringing the transfer surface of the transfer foil into contact with the adhesive layer and thermocompression bonding, and forming a foil layer on the adhesive layer;
A foil image forming method.   The foil image forming method according to claim 3, wherein in the adhesive layer forming step, the latex ink is applied by an inkjet method.   The foil image forming method according to claim 3 or 4, wherein the base material is a base material selected from the group consisting of a natural pulp base material, a fleece base material obtained by mixing natural pulp and synthetic fibers, and a Japanese paper base material. . A base material, an adhesive layer formed in a pattern on the base material, and a foil layer formed in the same pattern as the adhesive layer on the adhesive layer,
A laminate in which the adhesive layer is a cured film of the latex ink according to claim 1.   The wallpaper which consists of a laminated body of Claim 6. For the adhesive layer for forming a foil image by transferring the foil layer onto the base material layer by thermocompression bonding the base material and the foil layer of the transfer foil through the adhesive layer formed in a pattern. Latex ink,
Resin particles and an aqueous solvent for dispersing the resin particles,
The resin particles are latex ink containing a resin having a crosslinkable group and a curing agent. The resin particles have a core layer and a shell layer covering the periphery of the core layer,
The latex ink according to claim 8, wherein the core layer contains the curing agent.   The latex ink according to claim 8 or 9, wherein the curing agent is a blocked isocyanate compound.   The latex ink according to any one of claims 8 to 10, wherein the resin particles have a volume average particle diameter of 80 to 300 nm.   The latex ink according to any one of claims 8 to 11, wherein the resin particles are produced by an emulsion polymerization method. A step of forming an adhesive layer by applying the latex ink according to any one of claims 8 to 12 in a pattern on a substrate or a foil layer of a transfer foil;
A step of heat-pressing the base material and the foil layer of the transfer foil through the adhesive layer formed in a pattern to transfer the foil layer of the transfer foil onto the base material to obtain a foil image; A foil image forming method.   The foil image forming method according to claim 13, wherein the adhesive layer is formed by applying the latex ink by an inkjet method.   The foil image forming method according to claim 13 or 14, wherein the substrate is a fleece substrate obtained by mixing natural fibers and synthetic fibers.   The latex ink according to any one of claims 8 to 12, which is disposed between the substrate, the foil layer disposed in a pattern on the substrate, and the substrate and the foil layer. A laminate including a material layer.   A wallpaper comprising the laminate according to claim 16.

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