JP2021169208A - Manufacturing method for decorative article of unburnable wood and decorative article, as well as manufacturing method for surface-treated article of unburnable wood and surface-treated article - Google Patents

Abstract

To provide a manufacturing method for a decorative article of an unburnable wood and a decorative article as well as a manufacturing method for a surface-treated article of an unburnable wood and a surface-treated article, which can improve drying performance and improve productivity.SOLUTION: A manufacturing method for a surface-treated article of an unburnable wood includes: a surface-treatment liquid application step of applying surface-treatment liquid including at least water, a color material fixing agent and a surface tension adjuster to an unburnable wood W made of a wood subjected to fireproofing; and a printing step of performing inkjet printing to the unburnable wood W applied with the surface-treatment liquid. In the surface treatment liquid application step, a density of the surface treatment liquid to be applied to a surface of a core material portion W1 of the unburnable wood W is set to be lower than a density of a surface treatment liquid to be applied to a surface of a sapwood part W2 around the core material portion.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a decorative article of non-combustible wood, which is decorated by inkjet printing on non-combustible wood that has been subjected to non-combustible treatment, a decorative article that is decorated on non-combustible wood, and a surface-treated article of non-combustible wood. It relates to a manufacturing method and a surface-treated article.

Conventionally, non-combustible wood produced by injecting a non-combustible agent such as boron-based (borax and boric acid) or phosphoric acid-based (ammonium phosphate or the like) into wood has been proposed (see, for example, Patent Document 1). .. Such non-combustible wood can be used as a building member, for example, to prevent a fire.

JP-A-2018-103452 JP-A-2018-70758

Here, when non-combustible wood is used as a building member, for example, as described above, it is preferable that the non-combustible wood can be decorated with ink or the like for a wide range of uses. However, Patent Document 1 does not mention anything about decorating non-combustible wood.

However, wood, which is the raw material of non-combustible wood, has pipes (conduit) that have the role of passing water. This tube also exists in non-combustible wood. For example, when inkjet printing is performed directly using water-based ink, the inside of the conduit is exposed on the surface of the wood processed into a plate shape, so that bleeding occurs along the conduit. , Fine line reproducibility is reduced.

On the other hand, for example, in Patent Document 2, although it is not non-combustible wood, in order to suppress the above-mentioned bleeding when direct inkjet printing is applied to ordinary wood, a surface treatment liquid is applied to the surface of the wood for surface treatment. A method of forming a layer and performing inkjet printing on the surface-treated layer has been proposed.

Therefore, even when inkjet printing is performed on non-combustible wood, it is conceivable to apply a surface treatment liquid to the non-combustible wood to form a surface treatment layer before inkjet printing.

Here, the wood, which is the raw material of non-combustible wood, has characteristic parts called heartwood and knots. Specifically, when a tree is sliced into round slices, concentric annual rings appear, but the central side is a dark brown "heartwood" (red meat), and the outside near the bark is a light-colored "sapwood" (white meat). Called. Growth occurs in the white part, and at that time, new conduits for passing sap are born one after another on the outside, while by the time more than 10 years have passed, the conduit on the central side has finished its role, and the cells are pigmented and rotted. A number of "heartwood substances" that are resistant to the accumulation of materials accumulate, causing a reddish or blackish brown color.

In addition, the node is born from the branch branching from the trunk, and that part is caught inside the trunk as the trunk continues to grow. The heartwood and knots are preferred as they are natural wood, but they are dark brown, dense and hard. In addition, there is a large amount of resin in the nodes and their surrounding areas.

Therefore, when the above-mentioned surface treatment liquid is applied to the heartwood portion and the sapwood portion in the same manner, the surface treatment liquid is less likely to permeate into the inside of the heartwood portion than the sapwood portion, and the surface of the heartwood portion is covered. Excessive surface treatment liquid is unevenly distributed. Since the surface treatment liquid is excessively unevenly distributed on the surface in this way, the ink tends to stay in the vicinity of the surface more than necessary, so that there is a problem that the drying property of the ink is lowered and the productivity is lowered.

The present invention provides a method for producing a decorative article of non-combustible wood and a decorative article capable of improving dryness and productivity, and a method for producing a surface-treated article of non-combustible wood and a surface-treated article. The purpose is to do.

The method for producing a decorative article of non-combustible wood of the present invention is a surface treatment liquid for applying a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent to the non-combustible wood obtained by subjecting the wood to a non-combustible treatment. In the surface treatment liquid application step, the concentration of the surface treatment liquid to be applied to the surface of the core material portion of the non-combustible wood is determined by including the coating step and the printing step of performing inkjet printing on the non-combustible wood coated with the surface treatment liquid. The concentration should be lower than the concentration of the surface treatment liquid applied to the surface of the sapwood part around the part.

According to the method for producing a decorative article of non-combustible wood of the present invention, a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent is applied to the non-combustible wood obtained by subjecting the wood to a non-combustible treatment. In the treatment liquid application step, the concentration of the surface treatment liquid applied to the surface of the core material portion of non-combustible wood was made lower than the concentration of the surface treatment liquid applied to the surface of the sapwood portion around the core material portion, so that the drying property was reduced. Can be improved and productivity can be improved.

Schematic diagram showing an example of the core and sapwood parts of non-combustible wood The figure for demonstrating the structure which uses different coating members for the core material part and the two sapwood parts on both sides thereof. The figure for demonstrating the method of measuring the pressure of a coating member with respect to a non-combustible member.

Hereinafter, a method for producing a decorative article of non-combustible wood of the present invention and an embodiment of the decorative article will be described in detail with reference to the drawings.

In the method for producing a decorative article of a non-combustible member of the present embodiment, a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent is applied to the non-combustible wood obtained by subjecting the wood to a non-combustible treatment. In the surface treatment liquid application step, the concentration of the surface treatment liquid to be applied to the surface of the core material portion of the noncombustible wood is determined, including a liquid application step and a printing step of performing inkjet printing on the noncombustible wood coated with the surface treatment liquid. The concentration should be lower than the concentration of the surface treatment liquid applied to the surface of the sapwood portion around the core material portion.

FIG. 1 is a diagram showing an example of a core material portion W1 and a sapwood portion W2 in a non-combustible wood W. The non-combustible wood W shown in FIG. 1 is a plate-shaped wood formed by cutting the trunk in the length direction and subjected to non-combustible treatment. Sapwood portions W2 are formed on both sides of W1 including the outer surface. The core material portion W1 includes the above-mentioned knot portion S. In the present embodiment, as described above, the concentration of the surface treatment liquid applied to the surface of the core material portion W1 is lower than the concentration of the surface treatment liquid applied to the surface of the sapwood portion W2. That is, different concentrations of surface treatment liquids are applied on the surface of one piece of non-combustible wood.

As a result, the drying property of the surface treatment liquid can be improved, and the productivity can be improved. The lower the concentration of the surface treatment liquid, the smaller the solid component contained in the surface treatment liquid, so that the evaporation rate is faster and the drying property can be improved.

The concentration of the surface treatment liquid of the core material portion can be, for example, 1/2 or less of the concentration of the surface treatment liquid of the sapwood portion.

However, if the concentration of the surface treatment liquid is too low, it becomes difficult to fully exert the function of the surface treatment liquid itself. Therefore, the concentration of the surface treatment liquid of the core material portion is, for example, the concentration of the surface treatment liquid of the sapwood portion. It is desirable to make it larger than 1/4. As a result, the image quality of the decorative article can be ensured while improving the drying property of the surface treatment liquid.

Further, as a means for applying the surface treatment liquid to the non-combustible wood W as shown in FIG. 1, for example, as shown in FIG. 2, the core material portion W1 and the two sapwood portions W2 on both sides thereof are different from each other. It is preferable to use the coating members P1 to P3. As the coating members P1 to P3, for example, sponge cloth or urethane sponge can be used.

By using the three coating members P1 to P3 in this way, for example, if a mechanism for simultaneously moving the three coating members P1 to P3 with respect to the non-combustible wood W in the direction of the arrow shown in FIG. By moving the coating members P1 to P3, the surface treatment liquid can be applied to the non-combustible wood W, and the productivity can be improved.

In the above description, the coating members P1 to P3 are moved, but the present invention is not limited to this, and a mechanism for fixing the coating members P1 to P3 and moving the non-combustible wood W in the direction in which the core material portion W1 extends is provided. You may do so.

The decorative article of the present embodiment is obtained by implementing the method for manufacturing the decorative article of the non-combustible member of the above embodiment, and specifically, the non-combustible wood obtained by subjecting the wood to a non-combustible treatment. A surface treatment layer formed on the surface of non-combustible wood using a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent, and an inkjet printing layer formed on the surface treatment layer are provided.

In the decorative article of the present embodiment, the amount of the solid component of the surface treatment liquid in the surface treatment layer formed on the surface of the core material portion of the non-combustible wood is the surface of the surface treatment layer formed on the surface of the sapwood portion. It is less than the amount of solid components in the treatment liquid. In the present specification, the amount of the solid component of the surface treatment liquid is the amount obtained by subtracting the amount of water from the amount of the surface treatment liquid before drying.

The non-combustible wood used in the present embodiment is a member produced by injecting a non-combustible agent such as boron-based (for example, borax and boric acid) or phosphoric acid-based (for example, ammonium phosphate) into the wood. Non-combustible wood is used, for example, as a building material, but its use is not limited to this.

The mechanism of non-combustible wood will be described below. When exposed to heat, non-combustible wood first undergoes an endothermic decomposition reaction to lower the ambient temperature. When heated to a higher temperature, the injected non-combustible agent foams to form a layer of glass. The foamed glass layer wraps the wood, blocking oxygen and heat, making it harder to burn.

As the non-combustible wood, it is preferable to use wood that has passed the certification test set by the government. In the non-combustible wood certification test, two tests, "heat generation test" and "gas toxicity test", are generally performed.

The exothermic test is performed using a cone calorimeter. The corn calorie meter has a mechanism to know how much it has burned by the amount of oxygen reduction in the test piece. The criteria for certification of non-combustible wood by the Ministry of Land, Infrastructure, Transport and Tourism are the following three points.
1. The total calorific value for 20 minutes after the start of heating is 8 MJ / m ² or less.
2. The heat generation rate for 20 minutes after the start of heating should not exceed ^{200 Kw / m 2 continuously for 10 seconds or more.}
3. There should be no cracks reaching the back surface or harmful deformation for fire protection within 20 minutes after the start of heating.

Furthermore, gas toxicity tests are being conducted on those that have passed the exothermic test. It is required not to generate harmful smoke or gas for evacuation.

The gas toxicity test is evaluated by the action stop time when the test body (220 mm square) is heated and the generated combustion gas is exposed to the mouse.

Here, wood, which is a raw material for non-combustible wood, has a pipe (conduit) that has a role of passing water. Depending on how the conduits are distributed, a grain pattern appears on the surface of the wood.

On the other hand, on the surface of wood processed into a plate shape as described above, the inside of the conduit is exposed. Therefore, when printing is performed on the surface with water-based ink, bleeding occurs along the conduit and fine line reproducibility is improved. It will decrease. On the other hand, by performing the surface treatment with the surface treatment liquid of the present embodiment, the color material fixing component (for example, a cationic water-dispersible resin) in the surface treatment liquid controls the wetting and spreading of the ink inside the conduit. As a result, it is possible to form a printed image that is less likely to bleed, has good fine line reproducibility, and has good color development. Specifically, the anionic component contained in the ink reacts with the cationic component contained in the surface treatment liquid, and the penetration of the ink component such as the coloring material into the wood can be controlled, and the coloring material can be used on the wood surface. Can be fastened to. The surface treatment liquid will be described in detail later.

Next, a method of applying the surface treatment liquid to non-combustible wood will be described.

Non-combustible wood is formed by infiltrating non-combustible chemicals into wood as described above, but the permeation of this non-combustible chemical narrows the conduits of the wood, so it is less wet than wood without non-combustible treatment. descend.

When the wettability is lowered in this way, the contact angle of the surface treatment liquid described above becomes high, and it becomes difficult to uniformly apply the surface treatment liquid to the non-combustible wood. If the surface treatment liquid is not applied uniformly, the printed image formed on the surface is deteriorated. The contact angle of the surface treatment liquid with respect to non-combustible wood is an index of wettability, and can be measured by measuring the change over time of the dynamic contact angle by the sessile drop method (measuring device, contact angle meter DM-500, manufactured by Kyowa Interface Science Co., Ltd.). The larger the dynamic contact angle 1 second after the surface treatment liquid (1.0 μL of droplets) lands on the non-combustible wood, the lower the wettability, and the more difficult it is to apply the surface treatment liquid uniformly. Specifically, when the dynamic contact angle of the surface treatment liquid with respect to the non-combustible wood is 10 ° or more, it is difficult to uniformly apply the surface treatment liquid.

Therefore, in the present embodiment, the surface treatment liquid is applied to the surface of the non-combustible wood by a contact-type coating method. As a result, the surface treatment liquid can enter the inside of the pipe of the non-combustible wood, the surface treatment liquid can be uniformly applied to the surface of the non-combustible wood, and uneven coating can be suppressed. As a result, the quality of the printed image of the decorative article can be improved. In particular, as described above, a remarkable effect can be obtained when the dynamic contact angle of the surface treatment liquid with respect to the non-combustible wood is 10 ° or more.

When the surface treatment liquid is applied by the contact type coating method, the surface treatment liquid is absorbed on the surface of the non-combustible wood by absorbing the surface treatment liquid such as a sponge and then pressing it against the non-combustible wood at a predetermined pressure. A coating member is used that allows the liquid to flow out and adhere. However, as described above, in order to uniformly apply the surface treatment liquid to the surface of non-combustible wood having low wettability, it is necessary to have some absorbency.

Specifically, in the surface treatment liquid coating step of applying the surface treatment liquid to non-combustible wood, it is preferable to use a coating member having ^{a water absorption of 0.44 g / cm 3 or more.} As a result, the surface treatment liquid can be sufficiently contained in the coating member, and the surface treatment liquid can be uniformly applied to the non-combustible wood. The method for measuring water absorption will be described in detail later.

Further, the coated member adheres to the non-combustible wood by being deformed, but if the amount of deformation when pressed is too large, it may be difficult to uniformly apply the surface treatment liquid. Therefore, in the surface treatment liquid coating step, it is preferable to use a coating member having a deformation amount of 25 mm or less when pressed with a pressure of 30 kPa. As a result, the adhesion between the coating member and the non-combustible wood can be ensured, and the surface treatment liquid can be uniformly applied to the non-combustible wood. The method of measuring the amount of deformation will be described in detail later.

Further, if the pressure when the coating member is pressed against the non-combustible wood and the coating is applied is low, the surface treatment liquid does not sufficiently flow out from the coating member, or the adhesion between the coating member and the non-combustible wood is lowered, resulting in non-combustibility. It may be difficult to evenly apply the surface treatment liquid to wood. Therefore, in the surface treatment liquid coating step, it is preferable to press the coating member against the non-combustible wood at a pressure of 5 kPa or more. As a result, the surface treatment liquid can be sufficiently discharged from the coating member, the adhesion between the coating member and the non-combustible wood can be ensured, and the surface treatment liquid can be uniformly applied to the non-combustible wood. .. The pressure measuring method will be described in detail later.

That is, as a condition for uniformly applying the surface treatment liquid to the surface of non-combustible wood, ^{a coating member having a water absorption of 0.44 g / cm 3} or more and a deformation amount of 25 mm or less when pressed at a pressure of 30 kPa is used. It is more preferable to press the coated member against the non-combustible wood at a pressure of 5 kPa or more. At this time, the coating amount of the surface treatment liquid is preferably ^{50 g / m 2 or less as described above.} The amount of the surface treatment liquid to be applied to the non-combustible wood ^{is preferably 9.5 g / m 2} or more. More preferably, it is 14.3 g / m ² or more. As a result, the surface treatment liquid can be uniformly applied to the non-combustible wood.

Further, as a means for applying the surface treatment liquid to the non-combustible wood using the above-mentioned coating member, the coating member may be pressed against the non-combustible wood by a human hand to apply the surface treatment liquid, or a predetermined mechanical mechanism may be used. The coating member may be pressed against the non-combustible wood for coating. At this time, the speed at which the coating member is moved on the surface of the non-combustible wood (coating speed) is preferably, for example, 300 mm / s.

Then, it is preferable to apply the surface treatment liquid to the non-combustible wood, dry it, and then perform inkjet printing. At that time, it is preferable to dry at room temperature without performing heat drying. This makes it possible to prevent the non-combustible wood from being deformed by heating. On the other hand, it is also possible to perform inkjet printing immediately after applying the surface treatment liquid to the non-combustible wood, that is, without drying the surface treatment liquid. When the surface treatment liquid is dried, it is preferably left at 22 ° C. and a humidity of 50% overnight.

Next, a printing process for performing inkjet printing on non-combustible wood coated with a surface treatment liquid will be described.

The ink used for inkjet printing is not particularly limited, but is preferably a non-UV curable ink, and more preferably a water-based ink. That is, it is preferable that the ink contains water, a binder resin, and a coloring material. The ink will be described in detail later.

Inkjet printing can be performed using a general recording head, and there are no particular restrictions on the printing method, the device used, or the like. After printing, it is dried to obtain a decorative article in which water and other volatile components are volatilized from the printed ink and a printed image is formed on the surface of non-combustible wood. As the drying conditions, it is preferable to heat the printed surface at 80 ° C. for 10 minutes to dry the printed surface.

According to the method of applying the surface treatment liquid of the present embodiment, the surface treatment can be uniformly applied to the non-combustible wood as described above. As a result, it is possible to control the wetting and spreading of the ink, to form a printed image that is less likely to bleed, has good fine line reproducibility, and has good color development. Therefore, for example, when a wood grain pattern is printed on surface-treated non-combustible wood, the wood grain pattern can be reproduced as good as real wood.

Further, when a full-color gradation image is printed on the surface-treated non-combustible wood, the gradation can be reproduced well.

Further, when a solid image of CMYK is printed on the surface-treated non-combustible wood, the same color development property as that of the inkjet paper can be obtained.

Further, when a fine line of 0.3 mm is printed on the surface-treated non-combustible wood, bleeding, fading, and cutting can be prevented.

Hereinafter, the above-mentioned surface treatment liquid will be described in detail.

The surface treatment liquid preferably contains at least water, a coloring material fixing component, and a surface tension adjusting agent. The color material fixing component is preferably a cationic water-dispersible resin, and preferably contains large particles having a median diameter of 1 μm or more and 10 μm or less as measured by a dynamic light scattering method. Further, it is more preferable to include small particles having a median diameter of less than 1 μm measured by a dynamic light scattering method.

The surface treatment liquid of the present embodiment is particularly preferably used as a surface treatment liquid before forming a printed image using a non-UV curable ink (for example, a water-based ink). By using the surface treatment liquid of the present embodiment in advance before printing and then forming a printed image with inkjet ink, the wetting spread of the ink is controlled as described above, thereby preventing bleeding and good fine line reproducibility. Moreover, it is possible to form a printed image having good color development.

Cationic water-dispersible resin particles are positively charged resin particles in which the surface of the resin particles is positively charged, and are dispersed in particles without being dissolved in water, and are oil in water (O / W). It is capable of forming mold emulsions. Like the self-emulsifying resin, the cationic functional group of the resin may be present on the particle surface, or the surface of the resin particle may be surface-treated such as by adhering a cationic dispersant.

Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, benzopyrazole groups and the like. The cationic dispersant is a primary, secondary, tertiary or quaternary amino group-containing acrylic polymer, polyethyleneimine, a cationic polyvinyl alcohol resin, a cationic water-soluble polybranched polyesteramide resin, and the like.

The amount of surface charge of the resin particles can be evaluated with a particle charge meter. The amount of surface charge can be calculated by measuring the amount of anions or cations required to neutralize the sample. Specifically, the amount of surface charge is preferably +300 μeq / g or more. As the particle charge meter, a colloid particle charge meter Model CAS manufactured by Nihon Rufuto Co., Ltd. can be used.

As the water-dispersible resin, it is preferable to use a resin that forms a transparent coating film. Further, in the production of the treatment liquid, it can be blended as an oil-in-water type resin emulsion.

Typically, ethylene-vinyl chloride copolymer resin, (meth) acrylic resin, styrene-maleic anhydride copolymer resin, urethane resin, vinyl acetate- (meth) acrylic copolymer resin, vinyl acetate-ethylene copolymer weight. Examples thereof include coalesced resins and resin emulsions thereof. Here, "(meth) acrylic resin" indicates both an acrylic resin and a methacrylic resin. These resins may be used alone or in combination of two or more. As will be described later, a resin emulsion in which these resins are combined may be used. As described above, a cationic functional group can be introduced into these resins, or the surface can be surface-treated with a cationic dispersant or the like to give a positive surface charge.

The particle size of the resin particles is not particularly limited, and a plurality of types of particles having different particle sizes can be used in any combination. However, from the viewpoint of easily staying on the surface of non-combustible wood, it is preferable to include particles having a size of 1 μm or more in median diameter (average particle size) measured by a dynamic light scattering method. Further, the average particle size of the resin particles is preferably 10 μm or less, which allows the resin particles to penetrate into the recesses and voids on the surface of the non-combustible wood while making the best use of the characteristics of the non-combustible wood as wood.

That is, in non-combustible wood, by setting the median diameter (average particle size) of the resin particles to 1 μm or more and 10 μm or less, the surface treatment layer can be efficiently formed according to the size of the above-mentioned pipe of non-combustible wood. can. In particular, for wood, the size of the pipe (average diameter) differs depending on the classification of softwood and hardwood. For example, the average diameter of the tamo lumber, which is a hardwood ring pore material, is about 260 μm, and the average diameter of the maple lumber, which is a perforated lumber, is about 60 μm. On the other hand, the average diameter of hinoki cypress, which is a coniferous tree, is about 10 μm. As described above, the size of the voids of wood differs depending on the tree species, and since it is a natural product, there is no wood in which the distribution of voids of the base material is exactly the same. By doing so, the surface treatment layer can be formed even on a base material having irregular voids such as wood without deteriorating the original function of the base material (hygroscopicity in wood).

Further, it is preferable that the surface treatment liquid also contains small particles having a median diameter (average particle size) of less than 1 μm measured by a dynamic light scattering method. Thereby, in addition to the above-mentioned image quality, the water resistance of the ink layer can be further improved.

When using large particles and small particles, if the number of small particles is too small with respect to the large particles, the fixability is insufficient, and if the number of small particles is too large, the treated layer may be filmed and hinder the hygroscopicity of wood. Therefore, it is preferable that the number of small particles is about 0.1 to 1.5 with respect to 1 large particle in terms of weight ratio. In addition, in this specification, "weight" and "mass" are used interchangeably.

The average particle size of the resin particles is a volume-based particle size value (median diameter) in the particle size distribution measured by the dynamic light scattering method. As a dynamic light scattering type particle size distribution measuring device, a nanoparticle analyzer nano Partica SZ-100 (Horiba Seisakusho Co., Ltd.) or the like is used, and water is used so that the concentration of the water-dispersible resin becomes 0.5% by mass. It can be diluted and measured at 25 ° C.

In the surface treatment liquid or the ink described later, the resin particles may be present in the state of independent fine particles or in the state of aggregates in which independent fine particles are aggregated. Dynamic light scattering The median diameter measured by the method is defined as the "average particle size".

The average particle size of the resin particles is preferably measured in the state of the raw material emulsion before preparing the surface treatment liquid or the ink, because in the case of the ink, the influence of the coloring material (pigment particles) can be eliminated. The measured value can be used as the average particle size of the present embodiment.

The average particle size of the large particles is more preferably 7 μm or less, and even more preferably 5 μm or less. The average particle size of the small particles is more preferably 500 nm or less. The lower limit of the average particle size is not particularly limited, but from the viewpoint of storage stability of the surface treatment liquid, it is preferably about 5 nm or more, and more preferably 10 nm or more.

Further, it is preferable that the large particles and the small particles have two peaks in the particle size distribution when the average particle size is measured by mixing them, that is, each of them has a different peak value.

Further, the large particles and the small particles may have other differences in addition to the difference in the average particle size value. For example, large particles preferably have a minimum film forming temperature (MFT) of 70 ° C. or higher, while small particles preferably have an MFT of less than 70 ° C. This MFT is the temperature required for the emulsion to form a film (film formation), and can be measured according to JIS K6828-2. Here, the water-dispersible resin that does not form a film even at 70 ° C. is included in the water-dispersible resin having an MFT of 70 ° C. or higher.

More preferably, the MFT of the large particles is 100 ° C. or higher, the MFT of the small particles is 50 ° C. or lower, and in particular, the small particles are preferably formed at room temperature, so that the MFT is 40 ° C. or lower. ..

The difference between the MFT of large particles and the MFT of small particles is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, and even more preferably 100 ° C. or higher.

The molecular structures of the large-particle and small-particle resins may be the same, but different ones may be used.

As the large particles, for example, a polymer having an anionic functional group represented by a carboxy group, a sulfo group or the like and a polymer having a cationic functional group represented by an amino group or an amide group are compounded and obtained. It is also preferable to use composite organic particles having a core-shell structure in which the core portion is an anionic polymer and the shell portion is a cationic polymer.

Examples of the anionic polymer of the composite organic particles include a polymer containing (meth) acrylic acid as a repeating unit, and more specifically, a styrene- (meth) acrylic acid copolymer. Other than styrene and (meth) acrylic acid, vinyl compounds copolymerizable with these may be contained.

The cationic polymer (basic polymer) of the composite organic particles is, for example, a polymer containing a nitrogen-containing monomer, and is a nitrogen heterocycle such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazolidone, and N-vinylimidazole. Examples include homopolymers or copolymers containing the compound as a repeating unit. As the comonomer forming the copolymer, for example, one or more general vinyl compounds such as styrene, (meth) acrylic acid ester, vinyl acetate, and acrylamide can be selected and used.

In this case, the ratio of the anionic polymer to the cationic polymer used is preferably 3 to 10 in terms of weight ratio of the cationic polymer to 1 in order to make the charge on the particle surface cationic. ..

As commercially available products of such composite organic particles, "PP-15" and "PP-17" (both from Meisei Chemical Works, Ltd.) can be preferably used.

The amount of the water-dispersible resin in the surface treatment liquid (the total solid content of both large particles and small particles when used) is 2% by weight or more from the viewpoint of ink fixability on the surface of the base material during treatment. Is more preferable, and it is more preferably 3% by weight or more, and further preferably 5% by weight or more. On the other hand, if the viscosity of the treatment liquid is too high, uniform treatment becomes difficult, so the amount of resin is preferably 50% by weight or less, and more preferably 30% by weight or less.

The water contained in the surface treatment liquid functions as a solvent for the surface treatment liquid, that is, a vehicle, and tap water, ion-exchanged water, deionized water, and the like can be used. Water is a highly volatile solvent and easily evaporates after being discharged to the base material. Therefore, it is possible to prevent the voids of the base material after the surface treatment from being closed, and after the surface treatment such as moisture absorption of wood. It acts to prevent deterioration of the original characteristics of the base material. In addition, water is harmless, highly safe, and does not have problems such as VOC, so that the surface-treated base material can be made environmentally friendly.

The higher the content of water in the surface treatment liquid, the lower the viscosity of the surface treatment liquid and the easier it is to handle. Therefore, the water content is preferably 60% by weight or more, preferably 65% by weight or more, based on the total amount of the treatment liquid. Is more preferable.

The upper limit of the water content is not particularly limited, but in one embodiment containing large particles and small particles of the water-dispersible resin in the treatment liquid, the water content is preferably 95% by weight or less. , 90% by weight or less is more preferable. In another embodiment, the water content is preferably 85% to 95% by weight.

The solvent of the surface treatment liquid is preferably composed mostly of water, but if necessary, a water-soluble organic solvent may be contained in addition to water. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and is soluble in water can be used, and it is preferable to use a water-soluble organic solvent that is uniformly mixed with the same volume of water at 1 atm and 20 ° C. ..

For example, lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene. Glycols such as glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; glycerins such as glycerin, diglycerin, triglycerin, polyglycerin; acetylines such as monoacetin, diacetin, triacetin; ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene Glycol ethers such as glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2- Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, β-thiodiglycol, sulfolane and the like can be used. The boiling point of the water-soluble organic solvent is preferably 100 ° C. or higher, more preferably 150 ° C. or higher.

These water-soluble organic solvents may be used alone, or may be used in combination of two or more as long as they form a single phase with water. The content of the water-soluble organic solvent is preferably 30% by weight or less (or 50% by weight or less in the solvent) in the treatment liquid from the viewpoint of viscosity adjustment and moisturizing effect.

Further, the surface treatment liquid is used to reduce the surface tension so that it can be uniformly applied to the surface of non-combustible wood, and when it contains water-dispersible resin particles (small particles) having a small particle size. It is preferable to further contain a surface tension adjusting agent (surfactant) in order to suppress aggregation and enhance the storage stability of the liquid.

Surfactants are roughly classified into those having an ionic (cationic / anionic / dual) hydrophilic portion and those having a nonionic (nonionic) hydrophilic portion. In the present embodiment, the surface treatment liquid foams. From this point of view, it is preferable to use a nonionic surfactant that does not easily foam. Further, either a small molecule system or a polymer system (generally, a substance having a molecular weight of about 2000 or more) may be used, but it is preferable to use a polymer system surfactant. The HLB value is preferably about 5 to 20 surfactants.

Examples of the nonionic surfactant include ester-type surfactants such as glycerin fatty acid ester and fatty acid sorbitan ester, and ether-type surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxypropylene alkyl ether. , Ether ester type such as polyoxyethylene sorbitan fatty acid ester and the like.

In this embodiment, an acetylene glycol-based surfactant and a silicone-based surfactant can be preferably used.

Commercially available products of acetylene glycol-based surfactants include acetylene glycols, surfinol 104E and 104H, acetylene glycol with ethylene oxide added, surfinol 420, 440, 465, 485, etc. (Air Products & Chemicals), acetylene. Glycol Orphine E-1004, E-1010, E-1020, PD-002W, PD-004, EXP. 4001, EXP-4200, EXP-4123, EXP-4300, etc. (Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P of acetylene glycol, acetylenol E40, E100, etc. with a structure to which ethylene oxide of acetylene glycol is added (Kawaken Fine Chemicals) Co., Ltd.).

Since the silicone-based surfactant has a very high surface tension lowering ability and contact angle lowering ability, the surface treatment liquid can be rapidly diffused on the surface of the non-combustible wood even if the surface is not hydrophilic. As a result, the functional expression component of the surface treatment liquid can be uniformly fixed on the surface of the non-combustible wood, so that the ink is uniformly fixed on the treated portion at the time of printing, and a high-colored and high-quality printed image can be obtained. Can be done.

Among the silicone-based surfactants, a polyether-modified silicone-based surfactant, an alkyl-aralkyl co-modified silicone-based surfactant, and an acrylic silicone-based surfactant are preferable. As a commercially available product, "Silface SAG series" (Nisshin Kagaku Kogyo Co., Ltd.) can be preferably used.

As the surfactant, the above-mentioned silicone-based surfactant or the like may be used alone, or a plurality of surfactants having good compatibility with each other may be used in combination.

When a surfactant is used, the content in the surface treatment liquid is preferably about 0.1% by weight or more, more preferably 0.3% by weight or more, and more preferably 0.5% by weight or more. On the other hand, the amount of the surfactant is preferably about 5% by weight or less, more preferably 4% by weight or less, and further preferably 3% by weight or less.

In addition to the above components, known additives such as moisturizers, antifoaming agents, pH adjusters, antioxidants, and preservatives are optionally added to the surface treatment liquid as long as the functions of the treatment liquid are not impaired. can. A plurality of types of these additives may be used in combination.

As the surface treatment liquid, water, a cationic water-dispersible resin, a surface tension adjuster, and an additive to be added arbitrarily, if any, are put together in a known disperser such as a bead mill. Alternatively, it can be prepared by dividing the mixture, adding the mixture, dispersing the mixture, and, if desired, passing through a known filter such as a membrane filter.

Further, when the surface treatment liquid contains large particles and small particles as the cationic water-dispersible resin, the application of the surface treatment liquid can be performed in two steps. That is, for example, a surface treatment liquid containing either large particles or small particles and a surface treatment liquid containing the other one can be prepared and both can be applied to non-combustible wood. When applying the large particles and the small particles separately, if the small particles are applied first, the non-combustible wood may permeate into the voids and the effect as a binder for the ink may be diminished. Therefore, the large particles are applied first. It is preferable to apply to. When two types of surface treatment liquids are applied as described above, the amount of the surface treatment liquid is the total value of the amounts of the two types of surface treatment liquids.

Next, the ink used in inkjet printing will be described in detail.

The ink used for inkjet printing is not particularly limited as described above, but is preferably a non-UV curable ink, and more preferably a water-based ink. That is, it is preferable that the ink contains water, a binder resin, and a coloring material.

The water is not particularly limited as long as it functions as an ink solvent, that is, a vehicle, and tap water, ion-exchanged water, deionized water, and the like can be used. As described above for the surface treatment liquid, since water is safe and highly volatile, it is possible to prevent deterioration of the original performance of the decorated non-combustible wood.

The content of water in the ink is preferably 30% by weight or more, more preferably 60% by weight or more, and further preferably 65% by weight or more of the total amount of ink. The water content is preferably 95% by weight or less, more preferably 90% by weight or less.

The solvent of the ink is preferably composed mostly of water, but may contain a water-soluble organic solvent in addition to water, if necessary. As the water-soluble organic solvent, one or two or more kinds of solvents similar to those that can be used for the surface treatment liquid can be selected and used.

When two or more kinds of water-soluble organic solvents are used, the total content thereof is preferably 5 to 50% by mass, more preferably 10 to 35% by mass.

As the binder resin, a water-soluble resin or a hydrophilic resin can be used, and is not particularly limited. In order to improve the water resistance of the obtained image, it is preferable to contain a water-dispersible resin, and the water-dispersible resin may be used in combination with the water-soluble resin.

Examples of the water-soluble resin include polyvinyl alcohol, polyacrylic acid, neutralized polyacrylic acid, acrylic acid / maleic acid copolymer, acrylic acid / sulfonic acid copolymer, styrene / maleic acid copolymer and the like. These can be used alone or in combination of two or more.

In the case of a water-dispersible resin, it is preferable to use anionic resin particles having a negatively charged particle surface and a negative charge. This is capable of forming an oil-in-water (O / W) type emulsion by dispersing in particles without being dissolved in water. Like the self-emulsifying resin, the anionic functional group of the resin may be present on the particle surface, or the surface of the resin particle may be surface-treated such as attaching an anionic dispersant. The anionic functional group is typically a carboxy group, a sulfo group or the like, and the anionic dispersant is an anionic surfactant or the like. When the surface is anionic, a chemical interaction with the cationic water-dispersible resin in the surface treatment liquid is obtained, and as a result, the fixing of the coloring material is further strengthened and the durability of the image is further improved. Can be enhanced.

The surface charge of the resin particles can be evaluated by measuring the zeta potential. Specifically, the absolute value of the zeta potential is preferably 30 mV or more.

As the type of resin, it is preferable to use a resin that forms a transparent coating film. In addition, it can be blended as a resin emulsion in the production of ink.

Typically, ethylene-vinyl chloride copolymer resin, (meth) acrylic resin, styrene-maleic anhydride copolymer resin, urethane resin, vinyl acetate- (meth) acrylic copolymer resin, vinyl acetate-ethylene copolymer resin. Examples thereof include coalesced resins and resin emulsions thereof, which can be used alone or in combination of two or more. Here, "(meth) acrylic resin" indicates both an acrylic resin and a methacrylic resin.

As described above, an anionic functional group can be introduced into these resins, or the surface can be surface-treated with an anionic dispersant or the like to give a negative surface charge.

Among these water-dispersible resins (or emulsions thereof), urethane resins having a glass transition temperature (Tg) of 35 to 40 ° C. from the viewpoint of stable ejection performance from an inkjet head and adhesion to a substrate (Tg). Emulsion) is preferably used. Specific examples of such resin emulsions include Superflex 460, 420, 470, 460S (carbonate-based urethane resin emulsions, all of which are trade names) and 150HS (ester / ether-based urethane resin emulsions / products) of Daiichi Kogyo Seiyaku Co., Ltd. Name), 740, 840 (aromatic isocyanate-based ester-based urethane resin emulsion, all trade names), DSM NeoRez R-9660, R-2170 (aliphatic polyester-based urethane resin emulsion, all trade names), NeoRez Examples thereof include R-966, R-967, R-650 (polyurethane polyether urethane resin emulsion, all trade names), R-986, R-9603 (polyurethane polycarbonate, all trade names) and the like.

Further, from the viewpoint of stability in ink, it is also preferable to use a (meth) acrylic resin or a (meth) acrylic resin copolymer. Specifically, Japan Coating Resin Co., Ltd.'s Movinyl 966A, 6963, 6960 (acrylic resin emulsion, all trade names), 6696D, RA-033A4 (styrene / acrylic resin emulsion, all trade names) and BASF John Krill 7100, PDX-7370, PDX-7341 (styrene / acrylic resin emulsion, all trade names), Boncoat EC-905EF, 5400EF, CG-8400 (acrylic / styrene emulsion) of DIC Co., Ltd. Be done.

The water-dispersible resin may be composed of a single resin (or an emulsion thereof) such as a urethane resin or an acrylic resin, or may be composed of a combination of a plurality of resins (or emulsions thereof). good.

The water-dispersible resin particles forming the emulsion may have a particle size suitable for inkjet printing, and generally have an average particle size (medium diameter measured by a dynamic light scattering method on a volume basis) of 300 nm or less. It is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less. The lower limit of the average particle size is not particularly limited, but from the viewpoint of storage stability of the ink, it is preferably about 5 nm or more, and more preferably 10 nm or more.

The amount (solid content) of the water-dispersible resin and / or the water-soluble resin in the ink is preferably 1: 0.5 to 1: 7 (weight ratio) in terms of the ratio of the coloring material to the resin (coloring material: resin). By setting the resin content within this range, it is possible to sufficiently ensure the water scratch resistance and high image quality of the image printed on the surface of the base material. If the ratio of the resin to the color material 1 is less than 0.5, the fixability of the pigment may be deteriorated, and if it is larger than 7, the viscosity may be high and the ink may not be ejected from the head that ejects the ink. There is.

As the color material of the ink, either a pigment or a dye can be used, and both may be used alone or in combination. From the viewpoint of weather resistance and print density of the decorative image, it is preferable to use a pigment as a coloring material.

The content of the coloring material is preferably in the range of 0.01 to 20% by weight with respect to the total amount of ink. Further, the content of the coloring material is more preferably 0.1% by weight or more, further preferably 0.5% by weight or more, further preferably 1% by weight or more, and 15% by weight. % Or less, more preferably 10% by weight or less, and even more preferably 8% by weight or less.

As the dye, a dye generally used in the technical field of printing can be used, and the dye is not particularly limited. Specific examples thereof include basic dyes, acidic dyes, direct dyes, soluble bat dyes, acidic medium dyes, medium dyes, reactive dyes, bat dyes, sulfide dyes, etc. Among these, water-soluble dyes, reduction dyes, etc. Those that become more water-soluble can be used. More specifically, azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, methylene blue and the like can be mentioned. These dyes may be used alone or in combination of two or more.

As the pigment, organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments and dyed lake pigments, and inorganic pigments can be used. Examples of the azo pigment include soluble azo lake pigments, insoluble azo pigments and condensed azo pigments. Examples of the phthalocyanine pigment include metal phthalocyanine pigments and non-metal phthalocyanine pigments. Polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindolin pigments, isoindolinone pigments, dioxysazine pigments, thioindigo pigments, anthracinone pigments, quinophthalone pigments, and metal complex pigments. And diketopyrrolopyrrole (DPP) and the like. Typical examples of the inorganic pigment include carbon black and titanium oxide. These pigments may be used alone or in combination of two or more.

A pigment dispersant can be added to the ink, if necessary, in order to improve the dispersion of the pigment in the ink. The pigment dispersant that can be used is not particularly limited as long as it stably disperses the pigment in the solvent, and is, for example, a known pigment represented by a polymer dispersant or a surfactant having a pigment-dispersing ability. It is preferable to use a dispersant. Specific examples of the polymer dispersant include Solspers (trade name) series manufactured by Nippon Lubrizol Co., Ltd., John Krill (trade name) series manufactured by Johnson Polymer Co., Ltd., DISPERBYK series manufactured by BYK, and BYK series. .. Specific examples of surfactants include nonionic polys such as anionic fatty acid salts, alkyl sulfates, alkyl ether sulfates, and alkylbenzene sulfonates, such as the Demol (trade name) series manufactured by Kao Co., Ltd. Examples thereof include oxyalkylene alkyl ether.

The content of the pigment dispersant is sufficient as long as the pigment can be sufficiently dispersed in the solvent, and can be appropriately set, for example, in the range of 0.01 to 2 by weight with respect to the pigment 1.

In addition, a surface tension lowering agent (surfactant) is used to reduce the surface tension of the ink in the ink, ensure ejection stability when introduced into the inkjet head, and allow the ink to quickly penetrate into the substrate to be printed. Agent) can be added. As the surface tension lowering agent, a surfactant having an effect of further suppressing the aggregation of water-dispersible resin particles, for example, a surfactant similar to that blended in the surface treatment liquid can also be used. A surfactant having both a pigment dispersion function and a surface tension lowering function may be used.

The amount of the surface tension lowering agent in the ink is preferably about 0.1% by weight or more, more preferably 0.3% by weight or more, and even more preferably 0.5% by weight or more. On the other hand, the amount of the surface tension lowering agent is preferably about 5% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less.

In addition to the above components, other components such as a moisturizer, an antifoaming agent, a pH adjuster, an antioxidant, and a preservative can be added to the ink as long as the properties of the ink are not adversely affected.

The method for producing the ink is not particularly limited, and the ink can be appropriately produced by a known method. For example, all the components can be collectively or divided and dispersed in a known disperser such as a bead mill, and if desired, can be prepared by passing through a known filter such as a membrane filter. For example, a mixed solution in which the entire amount of water and the coloring material is uniformly mixed is prepared in advance, dispersed by a disperser, and then the remaining components are added to the dispersant and passed through a filter to prepare the mixture. Can be done.

Next, the efflorescence phenomenon of non-combustible wood will be described. According to the applicant's experiment, it is known that the efflorescence phenomenon occurs when the surface treatment liquid is applied to non-combustible wood.

Specifically, as described above, an auxiliary agent is added when non-combustible treatment is performed with a boron-based or phosphoric acid-based non-combustible agent to produce non-combustible wood, and the agent added as the auxiliary agent has high hygroscopicity. Therefore, as a result of applying the surface treatment liquid, it was found that the precipitated crystals cause an efflorescence phenomenon in which the surface becomes white. The auxiliary agent is an agent used to increase the solubility of boron or phosphoric acid in water and promote the penetration of the non-combustible agent into non-combustible wood, and for example, an ammonium salt such as diammonium phosphate is used. Such an auxiliary agent has a high affinity for water molecules and reacts with water contained in the surface treatment liquid, so that the above-mentioned efflorescence phenomenon occurs.

If inkjet printing is performed while the efflorescence phenomenon occurs, the quality of the printed image deteriorates due to the precipitated crystals. In addition, the crystals precipitated by the efflorescence phenomenon cannot be easily removed from the non-combustible wood, and if they are forcibly removed, marks will remain on the surface and the quality of the decorative article will be deteriorated.

Therefore, in the surface treatment liquid application step of the present embodiment, the amount of the surface treatment liquid applied to the non-combustible wood ^{is preferably 50 g / m 2} or less. In the present specification, the amount of the surface treatment liquid is the amount measured immediately after the surface treatment liquid is applied to the non-combustible wood.

The surface treatment layer of the decorative article of the present embodiment is preferably formed so that the amount of the surface treatment liquid applied to the non-combustible wood is 50 g / m ^{2 or less.}

As a result, the efflorescence phenomenon caused by the reaction of the water contained in the surface treatment liquid with the auxiliary agent contained in the non-combustible wood can be suppressed, and the deterioration of the printed image due to the efflorescence phenomenon can be suppressed. ..

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

As shown in Tables 1 and 2, surface treatment liquids 1 to surface treatment liquids 3 having different concentrations are applied to non-combustible wood by contact coating, and the surface treatment liquids 1 to surface treatment liquid 3 are dried and dried. I confirmed the sex. Further, after the surface treatment liquids 1 to 3 were dried, inkjet printing was performed to evaluate the image quality.

The surface treatment liquid 1 is a surface treatment liquid having a standard concentration (a surface treatment liquid consisting of each component shown in Table 3 below), and the surface treatment liquid 2 is a surface having a concentration 1/2 that of the surface treatment liquid 1. It is a treatment liquid, and the surface treatment liquid 3 is a surface treatment liquid having a concentration of 1/4 that of the surface treatment liquid 1.

The surface treatment liquid 1 was obtained by premixing each component listed in Table 3 below at the ratio shown in Table 3 below, and then dispersing the surface treatment liquid 1 with a homogenizer for 1 minute. Then, the surface treatment liquid 1 was diluted with water to obtain the surface treatment liquid 2 and the surface treatment liquid 3. That is, the weight% of the components other than water in the surface treatment liquid 2 is 1/2 that of the surface treatment liquid 1, and the weight of water is 83.6% by weight. Further, the weight% of the components other than water in the surface treatment liquid 2 is reduced to 1/4, and the weight of water is 91.8% by weight.

In Example 1, the surface treatment liquid 1 was applied to the surface of the sapwood portion of the non-combustible wood, and the surface treatment liquid 2 (concentration 1/2) was applied to the surface of the heartwood portion. In Comparative Example 1, the surface treatment liquid 2 (concentration 1/2) was applied to the surface of the sapwood portion of the non-combustible wood, and the surface treatment liquid 1 (standard concentration) was applied to the surface of the core wood portion. In Comparative Example 3, the surface treatment liquid 3 (concentration 1/4) was applied to the surface of the sapwood portion of the non-combustible wood, and the surface treatment liquid 3 (concentration 1/4) was applied to the surface of the heartwood portion.

The details of the raw materials shown in Table 3 above are as follows.
"PP-15": Cationic water-dispersible composite organic particles manufactured by Meisei Chemical Industry Co., Ltd. (average particle size of about 1.8 μm, no film formation at 100 ° C.)
"Polysol AE-803" is a cationic water-based acrylic resin emulsion manufactured by Showa Denko KK (average particle size 419 nm, MFT 0 ° C.).
"Silface SAG503A": Nisshin Kagaku Kogyo Co., Ltd., silicone-based surfactant "Orfin E1010": Nisshin Kagaku Kogyo Co., Ltd., acetylene glycol-based surfactant

The average particle size of the resin is determined by using a dynamic light scattering type particle size distribution measuring device "nano particle analyzer nano Prtica SZ-100" (manufactured by Horiba Seisakusho Co., Ltd.) to obtain a particle concentration of 0.5 mass for each resin dispersion. It was diluted with purified water so as to be%, and the dispersion medium refractive index was set to 1.333, the sample refractive index was set to 1.600, the dispersion form was set to "multidisperse" and "narrow", and the measurement was performed at a temperature of 25 ° C. Volume-based median diameter.

As a method of applying the surface treatment liquid 1 to the surface treatment liquid 3, first, the coating member was immersed in water for 30 seconds and taken out, and then the water drips disappeared. A sponge cloth (material: cellulose) was used as the coating member. The size of the coating member was 70 mm in length × 70 mm in width × 30 mm in thickness.

Next, the coating member was squeezed by placing a 2 kg weight on the coating member for 10 seconds with no water dripping.

After that, as shown in FIG. 3, the non-combustible wood is erected so that the coating surface S of the non-combustible wood W is in the vertical direction, and the coating member is 70 mm long × 70 mm wide on one side of the non-combustible wood in that state. The surface was pressed by hand, and the coating was performed at a coating speed of 300 mm / s.

Then, the pressure was measured by installing a pressure gauge P (using the "product name digital force gauge CPU GAUGE 9500 series" manufactured by Aiko Engineering) on the other side surface of the non-combustible wood. Since the non-combustible wood is made of a hard material that does not deform, the pressure at which the coating member is pressed against the coating surface of the non-combustible wood is indirectly measured by measuring the pressure as described above.

As the non-combustible wood, non-combustible wood manufactured by ARS Co., Ltd. (length 300 mm × width 600 mm × thickness 50 mm) was used, and the pressure of the coating member was 10 kPa. After applying the surface treatment liquid, it was dried overnight, and inkjet printing was performed to evaluate the image quality and dryness. The amount of the surface treatment liquid applied to the non-combustible wood was 10 g / m ² .

For the inks used in the evaluations in Tables 1 and 2, each component shown in Table 4 was premixed at the ratio shown in Table 4 (in terms of solid content), and the obtained dispersion was passed through a membrane filter having a pore size of 3 μm. A water-based ink set consisting of four colors (cyan, magenta, yellow and black) was obtained.

Details of the raw materials shown in Table 4 are as follows.
"CAB-O-JET 250C": Cabot, water-based self-dispersing cyanide pigment dispersion "CAB-O-JET 260M": Cabot, water-based self-dispersing magenta pigment dispersion "CAB-O-JET 270": Cabot Water-based self-dispersion yellow pigment dispersion "CAB-O-JET 200" manufactured by Cabot Corporation, water-based self-dispersion black pigment dispersion "Takelac W-5661" manufactured by Cabot Corporation: Urethane resin emulsion "Surfinol 465" manufactured by Mitsui Chemicals Co., Ltd. ”: Acetylene glycol-based surfactant manufactured by Nissin Chemical Industry Co., Ltd.

As for the image quality, the reproducibility of the wood grain image, the reproducibility of the gradation image, the color development, and the bleeding were evaluated.

Regarding the reproducibility of the wood grain image, the wood grain image was printed on the non-combustible wood, and the reproducibility of the wood grain image was visually confirmed. The evaluation when the wood grain pattern can be reproduced as good as the real wood is given as "A", and the evaluation when the wood grain pattern can be reproduced although it is inferior to "A" is given as "B", and the wood grain pattern can be reproduced. The evaluation when it was not done was set to "C".

Regarding the reproducibility of the gradation image, a full-color gradation image was printed on non-combustible wood, and the reproducibility was visually confirmed. The evaluation when the gradation could be reproduced well was given as "A", and the evaluation when the gradation could not be reproduced was given as "C".

Regarding the color development property, solid images of C (cyan), M (magenta), Y (yellow) and K (black) were printed on the non-combustible wood, and the color development property was visually confirmed. It was confirmed whether or not the color development was equivalent to that of the inkjet paper. The evaluation when the color development is equivalent to that of the inkjet paper is "A", and the evaluation when the color is inferior to "A" but the color development is close to that of the inkjet paper and the color is sufficient for actual use is "A". It was set to "B", and the evaluation when it was dull and did not reach the color development property of the inkjet paper was set to "C".

Regarding bleeding, a fine line of 0.3 mm was printed on non-combustible wood, and the degree of bleeding of the thin line was visually confirmed. The evaluation when there is no bleeding, blurring or cutting is "A", and the evaluation when there is bleeding, blurring or cutting, but the level is not noticeable is "B", and the thin line is greatly blurred. The evaluation when it could not be reproduced was set to "C".

Regarding the dryness, in order to evaluate the reproducibility of the above-mentioned gradation image, after printing a full-color gradation image on non-combustible wood and leaving it in an environment of room temperature 23 ° C. and humidity 50% for 15 minutes, the printed part is printed. It was confirmed by rubbing 5 times with a cotton rod under a load of 100 g. The 100 g load was measured by placing the printed non-combustible wood on a balance and balancing it with a 100 g weight.

The evaluation when there is no distortion of the printed image is "A", and the evaluation when there is some distortion of the printed image but is not noticeable is "B". The evaluation of the case was set to "C".

As shown in Tables 1 and 2, in Example 1, all the evaluations of image quality and dryness were "A".

Further, in Comparative Example 2, since the concentration of the surface treatment liquid was the standard concentration in the core material portion, the evaluation of the image quality was all "A", but the evaluation of the dryness was "C". Further, in the sapwood portion, the concentration of the surface treatment liquid was 1/2, so the evaluation of the dryness was "A", but the evaluation of the reproducibility of the wood grain image was "C", and the evaluation of the reproducibility of the wood grain image was "C". The evaluation of reproducibility and color development was "B".

Further, in Comparative Example 3, since the concentration of the surface treatment liquid was 1/4 in the sapwood portion, the evaluation of the dryness was "A", but all the items of the image quality were "C". rice field. Further, in the heartwood portion, the concentration of the surface treatment liquid was 1/4, so the evaluation of dryness was "A", but regarding the image quality, although the reproducibility of the gradation image was "A", The evaluation of the reproducibility of the wood grain image was "C", and the evaluation of the color development and the bleeding was "B".

Further, in Example 1, Comparative Example 1 and Comparative Example 2 shown in Table 1 and Table 2, the above-mentioned efflorescence phenomenon did not occur.

Next, Table 5 shows an example in which the amount of the surface treatment liquid applied and the presence or absence of the efflorescence phenomenon were confirmed.

As shown in Table 5, in Examples 2 to 7, water was applied to the non-combustible wood by contact type application using the application members 1 to 6, and the amount of water applied immediately after the application was measured. , The presence or absence of the white flower phenomenon was confirmed. The water applied to the non-combustible wood is used as a substitute for the above-mentioned surface treatment liquid, and the presence or absence of a whitening phenomenon depending on the amount of water applied and the above-mentioned surface treatment liquid (for example, water, cation) are used. The cationic water-dispersible resin, which contains a water-dispersible resin and a surface tension modifier, is composed of large particles having a median diameter of 1 μm or more and 10 μm or less and small particles of less than 1 μm as measured by a dynamic light scattering method. It was confirmed that the presence or absence of the whitening phenomenon was the same depending on the coating amount when a certain surface treatment liquid) was used. This is because the efflorescence phenomenon is greatly affected by the water contained in the surface treatment liquid. Therefore, in Examples 2 to 7 shown in Table 4, the concentration of the surface treatment liquid was not changed between the heartwood portion and the sapwood portion, but for the whitening phenomenon, the amount of the surface treatment liquid (g / m). ^Since it depends on 2), the result is the same regardless of whether or not the concentration of the surface treatment liquid is changed.

As a coating method, first, each coating member 1 to 6 was immersed in water for 30 seconds and taken out, and then the water drip was eliminated. Next, each coating member 1 to 6 was squeezed by placing a 2 kg weight on each coating member for 10 seconds in a state where no water drips.

After that, as shown in FIG. 3, the non-combustible wood is erected so that the coated surface S of the non-combustible wood W is in the vertical direction, and the coated members 1 to 6 are manually pressed against one side surface of the non-combustible wood in that state. The application was applied at a coating speed of 300 mm / s. Then, the pressure was measured by installing a pressure gauge P (using the "product name digital force gauge CPU GAUGE 9500 series" manufactured by Aiko Engineering) on the other side surface of the non-combustible wood. Since the non-combustible wood is made of a hard material that does not deform, the pressure of each coating member 1 to 6 pressed against the coated surface of the non-combustible wood was indirectly measured by measuring the pressure as described above.

Then, the coating amount was controlled by setting the above-mentioned pressures to 5 kPa, 10 kPa, 20 kPa and 40 kPa. The amount of coating and the presence or absence of the efflorescence phenomenon are shown in Table 5.

As the non-combustible wood, non-combustible wood manufactured by ARS Co., Ltd. was used, and the size thereof was 300 mm in length × 600 mm in width × 50 mm in thickness.

The following materials were used as the coating member, and the size thereof was 70 mm in length × 70 mm in width × 30 mm in thickness. A surface of 70 mm in length × 70 mm in width was pressed against the coated surface of non-combustible wood for coating.
Coating member 1: Sponge cloth (material: cellulose)
Coating member 2: Urethane sponge A
Coating member 3: Urethane sponge B
Coating member 4: Urethane sponge C
Coating member 5: Melamine sponge Coating member 6: PVA (polyvinyl alcohol) sponge

The coating amount was calculated by subtracting the weight of the non-combustible wood before coating from the weight of the non-combustible wood immediately after applying water and dividing the subtracted value by the area of the coated surface. The coating amount of 0.0 g / m ² does not mean that the coating amount is not applied at all, and the coating amount is less than ^{0.1 g / m 2.}

The presence or absence of the efflorescence phenomenon was visually checked. As can be seen from Examples 2 to 7, the efflorescence phenomenon occurred when ^{the coating amount exceeded 50 g / m 2.} Although not shown as an example, it was confirmed that the efflorescence phenomenon did not occur up to a coating amount of 50 g / m ^2.

Next, the relationship between the water absorption, water retention and deformation amount of the coated member, the pressing pressure on the non-combustible wood, and the coating uniformity of the surface treatment liquid on the non-combustible wood was evaluated. As the coating member, a coating member 7 (urethane sponge D) was used in addition to the coating members 1 to 6 used in Examples 2 to 7 described above. Table 6 shows the physical characteristics (water absorption, water retention amount and deformation amount) of the coating members 1 to 7.

The water absorption is an index indicating the amount of the surface treatment liquid that can be absorbed by the coating member and retained inside per unit volume. The water absorption was calculated by immersing each coated member in water for 30 seconds, taking it out, measuring the weight at the time when the water drips disappeared, and dividing the measured weight by the volume of each coated member.

The amount of water retained is determined by squeezing each of the coated members 1 to 7 by placing a 2 kg weight on each coated member for 10 seconds in a state where no water drips in the above-mentioned evaluation of water absorption, and measuring the weight immediately after the squeezing. Then, the measured weight was calculated by dividing by the volume of each of the coated members 1 to 7.

The amount of deformation is determined by pressing a pressure gauge (the pressure gauge uses the "Product Name Digital Force Gauge CPU GAUGE 9500 Series" manufactured by Aiko Engineering) against the surface of each coating member 1 to 7, and when the pressure reaches 30 kPa. The depth from the surface of the most deformed part before deformation was measured.

The coating method is the same as the coating method described in the above-mentioned evaluation of the coating amount. As for the uniform coating property, it was confirmed that the uniform coating property when water was used and the uniform coating property when the above-mentioned surface treatment liquid was used were the same as in the evaluation of the coating amount.

Further, the amount of the surface treatment liquid (water) was set to 35 g / m ^2, and it was confirmed that the efflorescence phenomenon did not occur in all the examples shown below.

Table 7 shows the evaluation results of the coating uniformity of the surface treatment liquid when the pressing pressure against the non-combustible wood was changed by using the coating members 1 to 6. The pressures when the coated members 1 to 6 were pressed against the non-combustible wood were 3 kPa, 5 kPa, 10 kPa, 20 kPa and 40 kPa. The uniform coating property is evaluated visually, and the evaluation when the coating is uniform is given as "A", the evaluation when the coating unevenness occurs is given as "B", and the evaluation when the coating unevenness is conspicuous is evaluated. It was designated as "C". Table 7 shows the evaluation results of the uniform coatability for each of the coated members 1 to 6.

From the evaluation results of Examples 8 to 20 shown in Table 7, it was found that the pressure for pressing the coated member against the non-combustible wood is preferably 5 kPa or more.

Next, Table 8 shows the relationship between the water absorption of the coating members 1 to 7 and the coating uniformity of the surface treatment liquid. The pressure for pressing the coating members 1 to 7 against the non-combustible wood was the pressure shown in Table 8.

From the evaluation results of Examples 21 to 35 shown in Table 8, it was found that ^{the water absorption of the coated member is preferably 0.44 g / cm 3 or more.}

Next, Table 9 shows the relationship between the amount of deformation of the coating members 1 to 7 and the coating uniformity of the surface treatment liquid. The pressure for pressing the coating members 1 to 7 against the non-combustible wood was the pressure shown in Table 9.

From the evaluation results of Examples 36 to 48 shown in Table 9, it was found that the amount of deformation of the coated member is preferably 25 mm or less.

The following additional notes are further disclosed with respect to the method for producing a decorative article of non-combustible wood and the decorative article of the present invention, and the method for producing a surface-treated article of non-combustible wood and the surface-treated article.
(Additional note)

In the method for producing a decorative article of non-combustible wood of the present invention, the amount of the surface treatment liquid applied to the non-combustible wood ^{is preferably 50 g / m 2} or less.

The decorative article of the present invention is a surface treatment layer formed on the surface of a non-combustible wood using a non-combustible wood obtained by subjecting the wood to a non-combustible treatment and a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent. And an inkjet printing layer formed on the surface treatment layer, and the amount of the solid component of the surface treatment liquid in the surface treatment layer formed on the surface of the core material portion of non-combustible wood is the amount of the sapwood portion around the core material portion. It is less than the amount of solid components of the surface treatment liquid in the surface treatment layer formed on the surface.

In the method for producing a surface-treated article of non-combustible wood of the present invention, a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent is applied to the non-combustible wood obtained by subjecting the wood to a non-combustible treatment. In the surface treatment liquid application step including the liquid coating step, the concentration of the surface treatment liquid applied to the surface of the core material portion of the non-combustible wood is applied to the surface of the sapwood portion around the core material portion. Lower than.

The non-combustible wood surface-treated article of the present invention is formed on the surface of non-combustible wood using a non-combustible wood obtained by subjecting the wood to a non-combustible treatment and a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent. The amount of the solid component of the surface treatment liquid in the surface treatment layer formed on the surface of the core material portion of the non-combustible wood is the surface treatment layer formed on the surface of the sapwood portion around the core material portion. Less than the amount of solid components in the surface treatment solution.

W Non-combustible wood W1 Core material part W2 Sapwood part S Coating surface P Pressure gauge P1 to P3 Coating member

Claims (5)

A surface treatment liquid application step of applying a surface treatment liquid containing at least water, a color material fixing component and a surface tension adjusting agent to the non-combustible wood obtained by applying the non-combustible treatment to the wood, and the non-combustible wood to which the surface treatment liquid is applied. Including the printing process of performing inkjet printing on the surface
In the surface treatment liquid application step, the concentration of the surface treatment liquid applied to the surface of the core material portion of the non-combustible wood is made lower than the concentration of the surface treatment liquid applied to the surface of the sapwood portion around the core material portion. A method of manufacturing decorative timber. The method for producing a decorative article of non-combustible wood according to claim 1, wherein the amount of the surface treatment liquid applied to the non-combustible wood is 50 g / m ^{2 or less.} Non-combustible wood with non-combustible treatment and
A surface treatment layer formed on the surface of the non-combustible wood using a surface treatment liquid containing at least water, a coloring material fixing component, and a surface tension adjusting agent.
An inkjet printing layer formed on the surface treatment layer is provided.
The amount of the solid component of the surface treatment liquid in the surface treatment layer formed on the surface of the core material portion of the non-combustible wood is the surface treatment in the surface treatment layer formed on the surface of the sapwood portion around the core material portion. Decorative items that are less than the amount of solid components in the liquid. A surface treatment liquid application step of applying a surface treatment liquid containing at least water, a color material fixing component and a surface tension adjusting agent to the non-combustible wood obtained by subjecting the wood to a non-combustible treatment is included.
In the surface treatment liquid application step, the concentration of the surface treatment liquid applied to the surface of the core material portion of the non-combustible wood is made lower than the concentration of the surface treatment liquid applied to the surface of the sapwood portion around the core material portion. A method for manufacturing surface-treated wood articles. Non-combustible wood with non-combustible treatment and
A surface treatment layer formed on the surface of the non-combustible wood using a surface treatment liquid containing at least water, a coloring material fixing component and a surface tension adjusting agent is provided.
The amount of the solid component of the surface treatment liquid in the surface treatment layer formed on the surface of the core material portion of the non-combustible wood is the surface treatment in the surface treatment layer formed on the surface of the sapwood portion around the core material portion. A surface-treated article of non-combustible wood that is less than the amount of solid components in the liquid.

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