JP2016147409A - Decorative sheet and method for producing decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having a printed portion which is formed by an inkjet method and is excellent in color development; and a method for producing a decorative sheet capable of efficiently producing a decorative sheet having a printed portion excellent in color development.SOLUTION: A decorative sheet has: a fibrous base material which has been subjected to preliminary treatment; a printed layer formed on the fibrous base material which has been subjected to the preliminary treatment by an inkjet method; and a hard material layer arranged on the side of a surface of the fibrous base material in which the printed layer is provided. The hard material layer is preferably formed of a material containing a melamine-based resin. The preliminary treatment includes preferably forming a resin portion which is impregnated into a gap between fibers constituting the fibrous base material.SELECTED DRAWING: None

Description

  The present invention relates to a decorative sheet and a method for manufacturing the decorative sheet.

  A good-looking space is produced by attaching a plurality of decorative sheets (decorative panels) to the walls of buildings, hotels, condominiums, conference rooms, and office walls. Moreover, such a decorative sheet is used not only as a real estate but also as an interior material for a vehicle such as a train.

  Such a decorative sheet has a hard material layer made of melamine resin or the like on its surface, has excellent hardness, and is hardly damaged.

  And generally, each pattern, such as a grain tone and a stone tone, is provided in the decorative sheet by gravure printing.

  Gravure printing is excellent in productivity when printing the same pattern in large quantities, but it is necessary to prepare a new plate when printing different patterns. Even if the pattern is slightly changed, it is necessary to prepare a new plate. For these reasons, conventionally, it has been difficult to produce a small amount of various types of decorative sheets.

  In addition, for example, when a decorative sheet having a new pattern is produced, it is necessary to manufacture a plurality of plates by adjusting a delicate pattern or the like even in the trial production stage.

  In particular, when producing custom-made decorative sheets, a great deal of time is spent in the trial production stage.

  Therefore, it has not been possible to meet the demands of consumers who demand delivery of decorative sheets in a short period of time.

  In order to solve the above problems, for example, it is conceivable to employ an inkjet method as a printing method.

  However, when the ink jet method is used instead of gravure printing, the following problems occur.

  That is, when the ink jet method is simply used instead of gravure printing, the coloring property of the printing portion is inferior in the decorative sheet, and the aesthetics of the decorative sheet cannot be sufficiently improved.

JP 2013-202906 A

  An object of the present invention is to provide a decorative sheet formed by an ink jet method and having a printed part with excellent color developability, and to efficiently form a decorative sheet having a printed part formed by an ink jet method and excellent in color developable. It is providing the manufacturing method of the decorative sheet which can be manufactured.

Such an object is achieved by the present inventions (1) to (14) below.
(1) a fibrous base material that has been subjected to a pretreatment;
A printed layer formed by an inkjet method on the fibrous base material subjected to the pretreatment;
A decorative sheet comprising: a hard material layer disposed on a side of the fibrous base material on which the printed layer is provided.

  (2) The decorative sheet according to (1), wherein the hard material layer is made of a material containing a melamine resin.

  (3) The decorative sheet according to (1) or (2), wherein the pretreatment is formation of a resin portion in a gap between fibers constituting the fibrous base material.

  (4) The decorative sheet according to (3), wherein the resin portion is made of a material including an acrylic resin and a urethane resin.

  (5) The decorative sheet according to (3) or (4), wherein the resin portion is made of a material containing a melamine resin.

  (6) The decorative sheet according to any one of (1) to (5), wherein a core material is provided on a surface opposite to the surface on which the printed layer of the fibrous base material is provided.

  (7) The decorative sheet according to (6), wherein the core material is made of glass cloth.

  (8) The decorative sheet according to any one of (1) to (7), wherein the fibrous base material includes titanium oxide.

(9) a printing process for forming a printing layer by an inkjet method on a fibrous base material that has been subjected to a pretreatment;
A method for producing a decorative sheet, comprising: a hard material layer forming step of forming a hard material layer on a surface side of the fibrous base material on which the printed layer is provided.

  (10) The above pretreatment is performed by impregnating the fibrous base material not subjected to the pretreatment with a resin material and / or a material containing a precursor thereof. Method for manufacturing decorative sheets.

  (11) The method for producing a decorative sheet according to (9) or (10), further including a core material bonding step of bonding a core material to the fibrous base material.

  (12) The manufacturing method of the decorative sheet according to (11), wherein the core material joining step is performed after the printing step.

  (13) The printing layer is formed by applying an ink containing a curable resin by an inkjet method and then curing the curable resin, according to any one of the above (9) to (12). Method for manufacturing decorative sheets.

  (14) The printing layer may be formed by applying an ink containing a thermoplastic resin by an ink jet method and then drying the solvent component of the ink according to any one of (9) to (12). The manufacturing method of the decorative sheet of description.

  ADVANTAGE OF THE INVENTION According to this invention, the makeup | decoration sheet | seat which is formed with the inkjet method and has a printing part excellent in coloring property can be provided, and the makeup | decoration which can manufacture efficiently the decorative sheet which has a printing part excellent in coloring property. A sheet manufacturing method can be provided.

It is sectional drawing which shows suitable embodiment of the decorative sheet of this invention. It is sectional drawing which shows suitable embodiment of the manufacturing method of the decorative sheet of this invention. It is sectional drawing which shows other suitable embodiment of the decorative sheet of this invention. It is sectional drawing which shows other suitable embodiment of the decorative sheet of this invention.

  Hereinafter, a decorative sheet and a method for manufacturing the decorative sheet of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

<< Cosmetic sheet >>
First, the decorative sheet will be described.

  A decorative sheet can improve the appearance of a space by being attached to a wall of a building, a hotel, a condominium lobby, a conference room, an office, or the like. In addition, the decorative sheet may be used not only as a real estate but also as an interior material for a vehicle such as a train.

FIG. 1 is a cross-sectional view showing a preferred embodiment of the decorative sheet of the present invention.
As shown in FIG. 1, the decorative sheet 100 includes a fibrous base material 1, a printed layer (printing unit) 2, and a hard material layer disposed on the surface side where the printed layer 2 of the fibrous base material 1 is provided. 3 and a core material 4 provided on the surface of the fibrous base material 1 opposite to the surface on which the printed layer 2 is provided.

  When the decorative sheet 100 is in use, the upper side in FIG. 1 is the observer's viewpoint side.

<Fibrous substrate>
The fibrous base material 1 is comprised with the material containing fibrous substances, such as a cellulose fiber. By providing such a fibrous base material 1, the adhesiveness of each part which comprises the decorative sheet 100 can be made excellent, and the durability of the decorative sheet 100 can be made excellent.

As the fibrous base material 1, for example, various papers, non-woven fabrics, cloths, woven fabrics and the like can be used.
In particular, the fibrous base material 1 is preferably paper.

  Since paper can be obtained stably and easily, it is advantageous from the viewpoint of stable supply of the decorative sheet 100. In addition, since paper is generally excellent in concealment, it is possible to effectively prevent a member or the like disposed on the back side of the decorative sheet 100 from adversely affecting the appearance of the printing layer 2. The visibility of the layer 2 and the aesthetics of the decorative sheet 100 can be more reliably improved. Further, since paper is generally inexpensive, it is advantageous from the viewpoint of suppressing the production cost of the decorative sheet 100.

  The paper as the fibrous base material 1 may be plain paper or the like, for example, or may be special paper (for example, ink jet special paper) provided with a receiving layer.

The fibrous base material 1 may be composed of only a fibrous substance, but may include other components.
For example, the fibrous base material 1 may contain titanium oxide (not shown).

  Thereby, the concealability of the fibrous base material 1 can be made particularly excellent, and the visibility of the printed layer 2, the aesthetics of the decorative sheet 100, etc. can be made particularly excellent. In addition, since titanium oxide has excellent ultraviolet absorption characteristics, for example, a member (for example, a core) provided on the back surface of the fibrous base material 1 (the surface opposite to the surface on which the printing layer 2 is provided). Even if the material 4) is made of a material having low light resistance to ultraviolet light, it is possible to effectively prevent unintentional modification / degradation of the member due to ultraviolet light, and the light resistance of the decorative sheet 100 as a whole. Property and durability can be made particularly excellent.

  When the fibrous base material 1 contains titanium oxide, the content of titanium oxide in the fibrous base material 1 (ratio of titanium oxide to the fibrous base material 1 in a state where a resin portion 12 described later is not provided) Is preferably 3% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 20% by mass or more and 40% by mass or less.

  When the content of titanium oxide is a value within the above range, the effect of including titanium oxide as described above is more significantly exhibited while suppressing an increase in the cost of the fibrous base material 1. In addition, if the fibrous base material contains titanium oxide at such a relatively high content, an attempt is made to form a printing portion (printing layer) by an ink jet method in a state where the pretreatment described in detail later is not performed. However, according to the present invention, the fibrous group containing titanium oxide at a relatively high content rate was generated. Even when a material is used, such a problem can be reliably prevented. Therefore, when the content of titanium oxide is a value within the above range, the effect of the present invention is more remarkably exhibited.

  The average particle diameter of titanium oxide is not particularly limited, but is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 5 μm or less.

  Thereby, the effect by including a titanium oxide as mentioned above can be exhibited more notably, making the flexibility of the fibrous base material 1 excellent.

  In the present specification, the average particle diameter means a volume-based average particle diameter unless otherwise specified.

  Here, the particle diameter can be measured by dispersing the target particles in water by ultrasonic treatment for 1 minute using, for example, a laser diffraction particle size distribution analyzer SALD-7000.

The basis weight of the fibrous base material 1 is not particularly limited, but is preferably 30 g / ^{m 2} or more 150 g / ^{m 2} or less.

  When the basis weight is less than the lower limit value, the fibrous base material 1 is likely to be cut and wrinkled or the like when forming the resin portion 12 described in detail later on the fibrous base material 1.

  On the other hand, if the basis weight exceeds the upper limit, unevenness is likely to occur in the resin amount at each site when the resin portion is formed in the fibrous base material 1.

  The fibrous base material 1 is subjected to a pretreatment before the printing layer 2 described in detail later is provided.

  Thereby, at the time of formation of the printing layer 2, it can prevent that an ink penetrate | infiltrate into the inside of the fibrous base material 1 too much, and on the surface (observer side surface) of the fibrous base material 1, The printing layer 2 can be formed. As a result, the color developability of the printing layer 2 can be made excellent, and the decorative sheet 100 can have excellent aesthetics.

  In particular, in the present embodiment, the resin portion 12 is provided in the gap between the fibers 11 constituting the fibrous base material 1 by the pretreatment.

  As a result, the effect of performing the pretreatment as described above can be exhibited more remarkably, and the strength of the decorative sheet 100 can be made particularly excellent, and is included in the fibrous base material 1. It is possible to effectively prevent the minute fibers 11 from being unintentionally scattered.

  Although the constituent material of the resin part 12 is not specifically limited, For example, when it contains an acrylic resin and a urethane resin, the softness | flexibility of the decorative sheet 100 shall be suitable, and the handleability (ease of handling) of the decorative sheet 100 is suitable. Can be made particularly excellent.

  When the resin part 12 is comprised with the material containing an acrylic resin and a urethane resin, the resin part 12 may have a different phase structure of an acrylic resin and a urethane resin.

  Thereby, the adhesiveness of the resin part 12 and the fiber 11 can be made especially excellent. Further, the bonding strength between the fibrous base material 1 and the core material 4 can be particularly excellent. Furthermore, the urethane resin is particularly excellent in toughness, elasticity, and flexibility, and the acrylic resin is particularly excellent in transparency, durability, weather resistance, chemical resistance, and film-forming properties. Excellent features can be demonstrated.

  In the present specification, “heterophasic structure” means a structure in which a plurality of phases composed of different types of resins are present in one particle, and examples thereof include a core-shell structure, a localized structure, and a sea-island structure. It is done.

  Moreover, when the resin part 12 is comprised with the material containing a melamine-type resin, the adhesiveness of the fibrous base material 1 in which the resin part 12 was provided, and the hard material layer 3 shall be made especially excellent. The durability of the decorative sheet 100 can be made particularly excellent. Moreover, the flame retardance of the decorative sheet can be made particularly excellent.

  The resin part 12 should just be provided in at least one part of the clearance gap between the fibers 11 which comprise the fibrous base material 1, and does not fill up all the clearance gaps of the fiber 11 which exists in the fibrous base material 1. Also good.

<Print layer>
The fibrous base material 1 (the fibrous base material 1 provided with the resin portion 12 in the configuration shown in the drawing) is provided with a printing layer 2 formed by an ink jet method.

  By adopting the ink jet method in this manner, unlike gravure printing or the like, it is not necessary to prepare a plate, and printing portions (printing layers) of various patterns can be suitably formed in a short period of time. Therefore, various types of decorative sheets can be suitably provided.

  Moreover, since it can respond suitably also to the fine adjustment of a pattern etc., it can respond to a consumer's request | requirement exactly.

  In particular, in the present invention, a printing layer (printing layer) is not simply provided on a fibrous base material made of a fibrous material, but a printing layer is formed on a fibrous base material that has been pretreated.

  Thereby, it is possible to prevent the ink from penetrating excessively into the fibrous base material, and to form a printing portion (printing layer) on the surface of the fibrous base material (observer-side surface). be able to. As a result, the color developability of the printing part (printing layer) can be made excellent, and the decorative sheet can be made aesthetic.

  Such an excellent effect can be obtained by forming a printing part (printing layer) by an inkjet method on a fibrous base material that has been pretreated beforehand. It cannot be obtained, for example, when a printing part is provided by an ink jet method without any treatment.

  The print layer 2 may be provided in any pattern, but is usually determined according to the demand of the consumer.

  Examples of the pattern of the printing layer 2 include a wood tone, a stone tone, a metal tone with a line processing, various geometric patterns, and the like.

<Hard material layer>
A hard material layer 3 is disposed on the side of the fibrous base material 1 on which the printing layer 2 is provided.

By having such a hard material layer 3, the decorative sheet 100 has excellent surface hardness and is hardly damaged.
The hard material layer 3 also has a function of protecting the printing layer 2 and the like.

  Therefore, the pattern of the printing layer 2 can be suitably displayed stably over a long period of time. In other words, the durability of the decorative sheet 100 can be improved.

  Examples of the constituent material of the hard material layer 3 include melamine resin, vinyl chloride, phenol resin, and the like. The hard material layer 3 is preferably made of a material containing a melamine resin. .

  When the hard material layer 3 is made of a material containing a melamine resin, the decorative sheet 100 generally has appropriate elasticity and rigidity, and is excellent in handleability (easy to handle). Become. Further, the melamine-based resin has an appropriate surface hardness and is particularly excellent in scratch resistance, antifouling property (difficulty of adhesion of dirt) and the like, and therefore, the aesthetic properties and durability of the decorative sheet 100 are excellent. It is also preferable from the viewpoint.

The hard material layer 3 preferably has a Martens hardness of 300 MPa or more and 800 MPa or less, more preferably 400 MPa or more and 600 MPa or less, on the surface (surface opposite to the surface facing the fibrous base material 1).
Thereby, the decorative sheet 100 can be made particularly difficult to be damaged.

  On the other hand, when the Vickers hardness of the surface of the hard material layer 3 is less than the lower limit value, the hard material layer 3 has low scratch resistance and is easily scratched.

  Moreover, when the Vickers hardness of the surface of the hard material layer 3 exceeds the said upper limit, the workability of the decorative sheet 100 may become low.

  In the present invention, the value obtained by measurement according to JIS Z 2244: 2009 is adopted as the value of Vickers hardness.

  The arithmetic average roughness Ra of the surface of the hard material layer 3 (surface opposite to the surface facing the fibrous base material 1) is preferably 300 nm or less, and more preferably 150 nm or less.

  Thereby, the surface of the hard material layer 3 becomes smoother and the high-quality feeling of the decorative sheet 100 can be made higher.

Further, the outer surface of the hard material layer 3 (surface opposite to the surface facing the fibrous base material 1) may be subjected to surface finish such as mirror finish or emboss finish.
Thereby, the further improvement of the aesthetics of the decorative sheet 100 can be aimed at.

<Core material>
A core material (core material layer) 4 is provided on the surface of the fibrous base material 1 opposite to the surface on which the printing layer 2 is provided.

  Thereby, the rigidity and the like of the decorative sheet 100 are excellent, and the stability of the shape of the decorative sheet 100 and the ease of handling are excellent. Further, for example, the heat resistance, nonflammability and the like of the decorative sheet 100 can be made particularly excellent.

Examples of the core material 4 include those made of glass cloth, those having a layer made of a phenolic resin, and those having a metal layer.
Among these, the core material 4 is preferably made of glass cloth.

  Thereby, while making the rigidity, flexibility, etc. of the decorative sheet 100 optimal, the heat resistance, nonflammability, etc. of the decorative sheet 100 can be made particularly excellent.

  The glass cloth is not particularly limited, and examples thereof include a glass woven fabric and a glass nonwoven fabric. Among these, a glass woven fabric is preferable from the viewpoint of nonflammability and strength.

  Moreover, as glass which comprises a glass cloth, E glass, C glass, A glass, S glass, D glass, NE glass, T glass, H glass etc. are mentioned, for example. Among these, when T glass is used, the thermal expansion coefficient of the glass cloth can be reduced. Moreover, when E glass is used, the production cost of the decorative sheet 100 can be made lower while ensuring a sufficient function.

The weight of the glass cloth is not particularly limited, but if it is necessary to satisfy the “combustible cracks / penetration after combustion” requirement of Article 2-9 of the Building Standards Act The basis weight is preferably 80 g / m ² or more. Moreover, although the upper limit of a weight does not require a restriction | limiting especially, the basic weight of 250 g / m < ² > or less is preferable from the surface of material cost and workability.

  The core material 4 may be a laminate of a plurality of layers. For example, a core material 4 can be formed by joining a plurality of members obtained by impregnating a fibrous base material with a fibrous base material (for example, a base material made of paper such as kraft paper).

The thickness (average thickness) of the core material 4 is preferably 100 μm or more.
Thereby, the heat resistance and nonflammability of the decorative sheet 100 can be made particularly excellent. Further, the upper limit of the thickness is not particularly limited, but the thickness and weight of the decorative sheet 100 increase as the thickness increases, and the cost also increases. Therefore, within the allowable range in the design of the final product. It is preferably set, and specifically, for example, it is preferably 350 μm or less.

  In addition, the decorative sheet 100 preferably has an overall thickness (average thickness) of 0.1 mm to 2 mm, and more preferably 0.1 mm to 1.2 mm.

  As a result, the decorative sheet 100 has particularly high workability and handleability while having sufficient strength.

<< Method for manufacturing decorative sheet >>
Next, the manufacturing method of a decorative sheet is demonstrated.
FIG. 2 is a cross-sectional view showing a preferred embodiment of the method for producing a decorative sheet of the present invention.

  As shown in FIG. 2, the manufacturing method of the present embodiment includes a fibrous base material preparation step (1 a) for preparing the fibrous base material 1, and a pretreatment step for performing a pretreatment on the fibrous base material 1 ( 1b), a printing step (1c) for forming a printing layer 2 on the fibrous base material 1 subjected to the pretreatment by an ink jet method, and the surface side of the fibrous base material 1 on which the printing layer 2 is provided. The core material (core material layer) 4 is bonded to the surface opposite to the surface on which the printed layer 2 of the fibrous base material 1 is provided, and the hard material layer forming step (1d) for forming the hard material layer 3 And a core material joining step (1e).

<Fibrous substrate preparation process>
In the fibrous base material preparation step, a fibrous base material as described above is prepared (1a).

<Pretreatment process>
Next, the fibrous base material 1 prepared in the above step is subjected to a pretreatment (1b).

  By performing the pretreatment prior to the formation of the printing layer 2 described in detail later, it is possible to prevent the ink from excessively penetrating into the fibrous base material 1 when the printing layer 2 is formed, The printed layer 2 can be formed on the surface of the fibrous base material 1 (the surface on the observer side). As a result, the color developability of the printing layer 2 can be made excellent, and the decorative sheet 100 can have excellent aesthetics.

  The pretreatment is not particularly limited as long as it prevents or suppresses excessive penetration of the ink (particularly the colorant) used for forming the printing layer 2 into the gaps of the fibers 11 constituting the fibrous base material 1. In this embodiment, the fibrous base material 1 is impregnated with a resin material and / or a material containing a precursor thereof (composition for pretreatment), and the fibrous base material 1 is used. The resin portion 12 is formed in the gap between the fibers 11 constituting 1.

  As a result, the effect of performing the pretreatment as described above can be exhibited more remarkably, and the strength of the decorative sheet 100 can be made particularly excellent, and is included in the fibrous base material 1. It is possible to effectively prevent the minute fibers 11 from being unintentionally scattered.

  The resin part 12 may be formed by, for example, applying a liquid composition in which a resin material is dissolved, dispersed, or melted in a solvent to the fibrous base material 1, or a resin material precursor (resin part). 12 may be performed by applying to the fibrous base material 1 a liquid composition containing a prepolymer, an oligomer (including dimer, trimer, etc.), a monomer, etc.) corresponding to the resin material constituting the resin material 12.

  For example, when the resin part 12 is made of a material containing an acrylic resin and a urethane resin, particles (composite particles) having a different phase structure of an acrylic resin and a urethane resin are dispersed in a single particle. The dispersion may be used as a liquid composition (a composition for pretreatment).

  Thereby, the adhesiveness of the resin part 12 and the fiber 11 to be formed can be made particularly excellent. Further, the bonding strength between the fibrous base material 1 and the core material 4 can be particularly excellent. Furthermore, the urethane resin is particularly excellent in toughness, elasticity, and flexibility, and the acrylic resin is particularly excellent in transparency, durability, weather resistance, chemical resistance, and film-forming properties. Excellent features can be demonstrated.

  Among the foregoing, particles (composite particles) made of a material containing an acrylic resin and a urethane resin are particularly preferably an aqueous clear type having a core-shell structure with an acrylic resin as a core and a urethane resin as a shell.

  Specific methods for applying the liquid composition (preparation composition) to the fibrous base material 1 include various methods such as dipping, spraying, roll coater, knife coater, and blade coater. Examples include a coating method using a coater and various printing methods.

  After applying the liquid composition to the fibrous base material 1, a post-treatment such as removal of the solvent and polymerization reaction (curing reaction) of the components of the liquid composition may be performed as necessary.

  When the resin part 12 shall be comprised with curable resin, the resin part 12 formed at this process may not have completed the polymerization reaction. Even in such a case, the polymerization reaction of the constituent components of the resin part 12 can be advanced in a later step, and the durability, reliability, etc. of the decorative sheet 100 finally obtained are particularly excellent. It can be.

<Printing process>
Next, the printing layer 2 is formed by the inkjet method with respect to the fibrous base material 1 to which the pretreatment was performed (1c).

  By forming the printing layer 2 using the inkjet method, unlike the case of adopting gravure printing or the like, it is not necessary to prepare a plate, and the printing layer 2 having various patterns can be suitably formed in a short period of time. . Therefore, a wide variety of decorative sheets 100 can be suitably provided.

  Moreover, since it can respond suitably also to the fine adjustment of a pattern etc., it can respond to a consumer's request | requirement exactly.

  Further, since the fibrous base material 1 has been subjected to a pretreatment prior to this step, the ink is prevented from excessively penetrating into the fibrous base material 1, and the fibrous base material 1. The printing layer 2 can be suitably formed on the surface (the surface on the observer side). As a result, the color developability of the printing layer 2 can be made excellent, and the decorative sheet 100 can have excellent aesthetics.

The ink used for forming the printing layer 2 may be any type, for example, a water-based ink containing water as a solvent or dispersion medium, a solvent-based ink containing an organic solvent as a solvent or dispersion medium, or a curing containing a curable component. System inks can be used.
Among these, a curable ink containing a curable component is preferable.

  Thereby, after giving the ink (curing ink) to the fibrous base material 1 subjected to the pretreatment by the ink jet method, the curing reaction of the curable component is advanced, so that the productivity of the decorative sheet 100 is particularly excellent. In addition, the adhesion of the printed layer 2 to the fibrous base material 1 (the fibrous base material 1 subjected to the pretreatment) can be made particularly excellent, and the durability of the decorative sheet 100 is particularly excellent. Can be. In addition, when the ink is simply applied by an inkjet method without performing a pretreatment on the fibrous base material, if the fibrous base material contains titanium oxide, a curable ink is used for forming the printing layer. In the present invention, the present inventors have found that the problem of a decrease in color developability of the printed portion occurs more significantly, but in the present invention, a printing material containing titanium oxide as a fibrous base material is used. Even when a curable ink is used as the forming ink, the above problems can be reliably prevented. Therefore, it is possible to reliably prevent the occurrence of the problem of deterioration in the color development of the printed portion while exhibiting the effect of including the titanium oxide as described above and the effect of using the curable ink. The effect of the invention is more remarkably exhibited.

  Moreover, as ink used for formation of the printing layer 2, you may use the ink (latex ink) which contains a thermoplastic resin with water.

  When using a latex ink, after applying ink (curing ink) to the fibrous base material 1 subjected to the pretreatment by an ink jet method, water is removed by a drying treatment, and subsequently the thermoplastic resin is softened by heating, Then, the printed layer 2 firmly fixed on the fibrous base material 1 can be formed by cooling.

Moreover, since latex ink contains water as a liquid component to be removed, it is environmentally friendly.
In this step, a plurality of types of inks may be used.

  As a result, for example, the color reproduction range can be widened, and a delicate gradation can be expressed more suitably.

The ink used for forming the printing layer 2 will be described in detail below.
In this step, after application of the ink by the ink jet method, for example, post-treatment such as heating and light irradiation may be performed as necessary for the purpose of progress of the curing reaction, removal of the solvent, and the like.

  Moreover, when the printing layer 2 shall be comprised with curable resin, the printing layer 2 formed at this process may not have completed the polymerization reaction. Even in such a case, the polymerization reaction of the constituent components of the printing layer 2 can be advanced in a later step, and the durability and reliability of the decorative sheet 100 finally obtained are particularly excellent. It can be.

<Hard material layer formation process>
Next, the hard material layer 3 is formed on the side of the fibrous base material 1 on which the printing layer 2 is provided (1d).

  As a result, the printed layer 2 and the like are suitably protected, and the decorative sheet 100 finally obtained has excellent surface hardness and is hardly damaged. Therefore, the pattern of the printing layer 2 can be suitably displayed stably over a long period of time. In other words, the durability of the decorative sheet 100 can be improved.

  The hard material layer 3 is used for forming the hard material layer by various methods such as dipping, spraying, coating using various coaters such as roll coater, knife coater, blade coater, and various printing methods. It can form suitably by giving a composition to the surface side in which the printing layer 2 of the fibrous base material 1 was provided, and performing hardening reaction after that.

  The composition used for forming the hard material layer 3 (hard material layer forming composition) will be described in detail below.

  Further, the hard material layer 3 may be formed by bonding a member for forming a hard material layer formed into a sheet shape to the surface side of the fibrous base material 1 on which the printing layer 2 is provided.

  The joining of the hard material layer forming member and the fibrous base material 1 can be performed by, for example, pressure bonding.

  When joining the member for forming a hard material layer and the fibrous base material 1 by pressure bonding, the joining of the fibrous base material 1 and the member for forming a hard material layer may be heated at the time of pressure bonding, for example.

  Thereby, the productivity of the decorative sheet 100 can be made particularly excellent, and the bonding strength between the fibrous base material 1 and the hard material layer 3 can be made particularly excellent. Further, for example, the polymerization reaction of the components contained in the hard material layer 3 can be suitably advanced, and the hardness of the hard material layer 3, the durability of the decorative sheet 100, and the reliability can be made particularly excellent. .

  Conditions for pressure-bonding the hard material layer forming member and the fibrous base material 1 are not particularly limited. For example, temperature: 40 ° C. to 120 ° C., pressure: 0.5 MPa to 8 MPa, time: 3 minutes It can be 120 minutes or less.

  Thereby, the effects as described above can be exhibited more significantly while effectively preventing unintentional modification, deterioration, and the like of the constituent materials.

  Further, at the time of joining the hard material layer forming member and the fibrous base material 1, a mirror finish is applied to the outer surface of the hard material layer forming member (the surface opposite to the surface facing the fibrous base material 1). A mirror finish can be achieved by stacking the plates, and an emboss finish can be achieved by stacking embossed plates or embossed films.

  When the hard material layer 3 is composed of a curable resin, the hard material layer 3 formed in this step may be one in which the polymerization reaction has not ended. Even in such a case, the polymerization reaction of the constituent components of the hard material layer 3 can be advanced in a later step, and the durability and reliability of the decorative sheet 100 finally obtained are particularly excellent. Can be.

<Core material joining process>
Next, a core material (core material layer) 4 is provided on the surface of the fibrous base material 1 opposite to the surface on which the printing layer 2 is provided (1e).
Thereby, the decorative sheet 100 is obtained.

  Thus, by having the core material joining process which joins the fibrous base material 1 and the core material 4, the rigidity of the decorative sheet 100 is made excellent, the stability of the shape of the decorative sheet 100, and the handling of the decorative sheet 100 are improved. Ease is excellent. Further, for example, the heat resistance, nonflammability and the like of the decorative sheet 100 can be made particularly excellent.

  In particular, in this embodiment, the core material joining process which joins the fibrous base material 1 and the core material 4 is performed after the printing process mentioned above.

  Thereby, the process before a core material joining process can be performed more smoothly, and the productivity of the decorative sheet 100 can be made particularly excellent. For example, the transportability of the fibrous base material 1 in the printing process can be made excellent.

  The core material 4 and the fibrous base material 1 can be joined by, for example, melting and softening a part of the resin portion 12 provided in the fibrous base material 1. That is, the resin portion 12 formed in the above-described pretreatment process can be used for joining the core material 4 and the fibrous base material 1.

  As a result, the bonding strength between the fibrous base material 1 (the fibrous base material 1 provided with the resin portion 12) and the core material 4 is particularly excellent, and the durability of the decorative sheet 100 is particularly excellent. And the productivity of the decorative sheet 100 can be made particularly excellent.

  More specifically, the joining of the fibrous base material 1 and the core material 4 can be performed by, for example, pressure bonding.

  When joining the fibrous base material 1 and the core material 4 by pressure bonding, the joining of the fibrous base material 1 and the core material 4 may be heated at the time of pressure bonding, for example.

  As a result, the productivity of the decorative sheet 100 can be made particularly excellent, and the bonding strength between the fibrous base material 1 and the core material 4 can be made particularly excellent. Further, for example, the polymerization reaction of the components contained in the hard material layer 3 can be suitably advanced, and the hardness of the hard material layer 3, the durability of the decorative sheet 100, and the reliability can be made particularly excellent. .

  The conditions for crimping the fibrous base material 1 and the core material 4 are not particularly limited. For example, the temperature: 130 ° C. or more and 150 ° C. or less, the pressure: 2 MPa or more and 8 MPa or less, the time: 3 minutes or more and 60 minutes or less can do.

  Thereby, the effects as described above can be exhibited more significantly while effectively preventing unintentional modification, deterioration, and the like of the constituent materials.

  Further, when the fibrous base material 1 and the core material 4 are joined, a mirror finish plate is superimposed on the outer surface of the hard material layer 3 (the surface opposite to the surface facing the fibrous base material 1). A mirror finish can be used, and an emboss finish can be obtained by stacking embossed plates or embossed films.

<Ink>
Hereinafter, the ink used for forming the printing layer 2 will be described in detail.

  As described above, the ink used for forming the printing layer 2 is, for example, a water-based ink containing water as a solvent or a dispersion medium, a solvent-based ink containing an organic solvent as a solvent or a dispersion medium, a curable ink containing a curable component, and the like. However, the curable ink will be mainly described below.

(Coloring agent)
The ink usually contains a colorant.

As the colorant, for example, various pigments, various dyes, and the like can be used, and a fluorescent material, a phosphorescent material, and the like can also be used. However, the ink preferably contains a pigment as the colorant.
Thereby, the durability of the decorative sheet 100 can be made particularly excellent.

  In the case of using a plurality of types of inks, for example, inks corresponding to the three primary colors (cyan (cyan purple), magenta (crimson purple), and yellow (yellow)) can be used.

  Thereby, the color reproduction range can be easily widened. In particular, when the reflected light is used for the appearance of the decorative sheet 100 using the light-shielding (light concealing) fibrous base material 1 or the like, the beauty of the decorative sheet 100 can be made particularly excellent. .

  Further, for example, inks corresponding to the three primary colors of light (red (red), green (green), and blue (blue)) may be used.

  Thereby, the color reproduction range can be easily widened. In particular, when the transmitted light is used for the appearance of the decorative sheet 100 using the light-transmitting fibrous base material 1 or the like, the aesthetics of the decorative sheet 100 can be made particularly excellent.

Further, for example, black ink may be used in combination with chromatic ink.
As a result, it is possible to obtain an effect such that a dark color can be suitably expressed while tightening black can be expressed while suppressing the amount of ink used.

For example, white ink may be used.
Thereby, for example, even if the light concealability of the fibrous base material 1 or the like is relatively low, the contrast and visibility of the printing layer 2 with the chromatic ink can be made particularly excellent, The aesthetics of the decorative sheet 100 can be made particularly excellent.

  In particular, when using an indigo purple pigment ink exhibiting indigo purple (cyan), examples of the pigment constituting the ink include C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 2, and C.I. I. It is preferable to use one or more selected from the group consisting of CI Pigment Blue 60.

  When a reddish violet pigment ink exhibiting reddish purple (magenta) is used, examples of the pigment constituting the ink include C.I. I. Pigment violet 19, C.I. I. Pigment red 122, and C.I. I. It is preferable to use one or more selected from the group consisting of CI Pigment Violet 37.

  When a yellow pigment ink exhibiting yellow (yellow) is used, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 138, and C.I. I. It is preferable to use one or more selected from the group consisting of CI Pigment Yellow 139.

  When a red pigment ink exhibiting red (red) is used, C.I. I. Pigment red 177 and / or C.I. I. Pigment Red 254 is preferably used.

  When a green pigment ink exhibiting green (green) is used, C.I. I. Pigment green 36 and / or C.I. I. It is preferable to use CI Pigment Green 58.

  When a blue pigment ink exhibiting blue (blue) is used, C.I. I. Pigment Blue 15: 6 is preferably used.

  In addition, when a black pigment ink exhibiting black (black) is used, the pigment constituting the ink is selected from the group consisting of carbon black, iron black, manganese ferrite black, cobalt ferrite black, copper chrome black, and copper chrome manganese black. It is preferable to use one or more selected.

  In addition, when a white pigment ink exhibiting white (white) is used, the pigment constituting the ink includes titanium oxide, white lead, zinc white, lithopone, zinc sulfide, antimony oxide, calcium carbonate, kaolin, mica, barium sulfate. Alumina, talc, silica, calcium silicate, gloss white, white plastic pigment, and the like can be used.

(Polymerizable compound)
The curable ink contains a polymerizable compound. By including the polymerizable compound, the adhesion of the printing layer 2 to the fibrous base material 1 can be made excellent.

As the polymerizable compound, for example, those that are polymerized and cured by heating and those that are polymerized and cured by irradiation of light (for example, ultraviolet rays) can be used, but those that are polymerized and cured by irradiation of ultraviolet rays are those. preferable.
Thereby, the productivity of the decorative sheet 100 can be made particularly excellent.

The polymerizable compound is preferably a liquid.
Accordingly, it is not necessary to separately use a liquid component (volatile component) that is removed (evaporates) in the process of manufacturing the decorative sheet 100 as a solvent or a dispersion medium, and the liquid component (volatile component) is also used in manufacturing the decorative sheet 100. Therefore, the productivity of the decorative sheet 100 can be made particularly excellent. Moreover, since it is not necessary to use what is generally used as an organic solvent as a liquid component (volatile component), generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented. Moreover, the adhesiveness of the printing layer 2 with respect to various fibrous base materials 1 can be made excellent by including a polymeric compound.

  As the polymerizable compound, for example, various monomers, various oligomers (including dimers, trimers, etc.), prepolymers and the like can be used, but the ink preferably contains at least a monomer component as the polymerizable compound. Since the monomer is generally a component having a low viscosity as compared with the oligomer component or the like, it is advantageous for making the ejection stability of the ink by the ink jet method particularly excellent.

  Examples of the monomer as the polymerizable compound include isobornyl acrylate, 4-hydroxybutyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, phenoxyethyl acrylate, isooctyl acrylate, stearyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, Benzyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, t-butyl acrylate, tetrahydrofurfuryl acrylate , Ethyl carbitol acrylate, 2,2,2-trifluoroethyl acrylate, 2, , 2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, phenylglycidyl ether acrylate, phenoxy Diethylene glycol acrylate, EO-modified phenol acrylate, EO-modified cresol acrylate, methoxypolyethylene glycol acrylate, dipropylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 2-n-butyl-2-ethyl-1,3-propane Diol diacrylate, tripropylene glycol diacrylate, Traethylene glycol diacrylate, 1.9-nonanediol diacrylate, 1,4-butanediol diacrylate, bisphenol A EO modified diacrylate, 1.6-hexanediol diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 300 di Acrylate, neopentyl glycol hydroxypiparate diacrylate, 2-ethyl-2-butyl-propanediol diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polypropylene glycol diacrylate, PO-modified bisphenol A diacrylate, EO-modified Hydrogenated bisphenol A diacrylate, dipropylene glycol diacrylate, trimethylol pro Triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate And 2- (2-vinyloxyethoxy) ethyl acrylate. Among them, 4-hydroxybutyl acrylate, phenoxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propane EO-modified triacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and 2- (2-vinyloxyethoxy) ethyl acrylate are preferred.

(Other ingredients)
The ink may contain components other than those described above (other components). Examples of such components include photopolymerization initiators, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, Examples include antiseptics, antioxidants, chelating agents, thickeners, antifoaming agents, and sensitizers (sensitizing dyes).

  The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by ultraviolet irradiation and initiates the polymerization reaction of the polymerizable compound. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator can be used, but it is preferable to use a radical photopolymerization initiator. When using a photopolymerization initiator, the photopolymerization initiator preferably has an absorption peak in the ultraviolet region.

  Examples of the photo radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, Examples thereof include ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  Among these, at least one selected from an acylphosphine oxide compound and a thioxanthone compound is preferable from the viewpoint of solubility in a polymerizable compound and curability, and it is more preferable to use an acylphosphine oxide compound and a thioxanthone compound in combination.

  Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine. , Carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl Oxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. 1 type or 2 types or more selected from these can be used in combination.

  The content of the photopolymerization initiator in the ink is preferably 0.5 wt% or more and 10 wt% or less. When the content of the photopolymerization initiator is within the above range, the ultraviolet curing rate is sufficiently high, and the photopolymerization initiator is hardly dissolved or colored due to the photopolymerization initiator.

  If the ink contains a slip agent, the smoothness of the surface of the printing layer 2 is improved by the leveling action.

  Although it does not specifically limit as a slip agent, For example, silicone type surfactants, such as polyester modified silicone and polyether modified silicone, can be used, It is preferable to use polyether modified polydimethylsiloxane or polyester modified polydimethylsiloxane. .

  If the ink contains a dispersant, the dispersibility of dispersoids such as pigments can be made excellent, and the storage stability and ejection stability of the ink can be made particularly excellent. The dispersant is not particularly limited, and examples thereof include polyoxyalkylene polyalkylene polyamines, vinyl polymers and copolymers, acrylic polymers and copolymers, polyesters, polyamides, polyimides, polyurethanes, amino polymers, silicon-containing polymers, and sulfur-containing polymers. , Fluorine-containing polymers, epoxy resins and the like.

  The ink preferably does not contain an organic solvent that is removed (evaporates) in the manufacturing process of the decorative sheet 100. Thereby, generation | occurrence | production of the problem of a volatile organic compound (VOC) can be prevented effectively.

  Although the curable ink has been described above, when a water-based ink is used as the ink used for forming the printing layer 2, an ink containing water as a solvent or a dispersion medium can be used. The water-based ink may contain the aforementioned polymerizable compound, but usually does not contain the polymerizable compound.

  As other components constituting the water-based ink, those shown as the components of the curable ink described above can be used.

  In addition, when a solvent-based ink is used as the ink used for forming the printing layer 2, an ink containing an organic solvent as a solvent or a dispersion medium can be used. The solvent-based ink may contain the above-described polymerizable compound, but usually does not contain the polymerizable compound.

  The organic solvent constituting the solvent-based ink may be any organic compound that is liquid under the ink discharge conditions (for example, normal temperature (20 ° C.) and normal pressure (1 atm)). Alcohol compounds (monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, isopropyl alcohol, polyhydric alcohols such as ethylene glycol and glycerin, and fluorides thereof), ketone compounds (acetone, methyl ethyl ketone, Cyclohexanone, etc.), carboxylic acid ester compounds (methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ether compounds (diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), lactone compounds It can be used.

  As other components constituting the solvent-based ink, those shown as the constituent components of the curable ink described above can be used.

  The viscosity of the ink at room temperature (20 ° C.) is preferably 20 mPa · s or less, and more preferably 3 mPa · s or more and 15 mPa · s or less. Thereby, the droplet discharge by an inkjet method can be performed more suitably.

<Composition for forming hard material layer>
Hereinafter, the composition for forming a hard material layer used for forming the hard material layer 3 will be described in detail.

  The composition for forming a hard material layer used for forming the hard material layer 3 includes the hard material constituting the hard material layer 3 and / or a precursor thereof.

  As described above, examples of the constituent material of the hard material layer 3 include melamine resin, vinyl chloride, phenol resin, and the like. In the following description, the hard material layer 3 made of melamine resin is used. The case of forming will be mainly described.

(Hard material or its precursor)
The composition for forming a hard material layer includes a hard material and / or a precursor thereof.

  When forming the hard material layer 3 composed of a melamine resin, the hard material layer forming composition comprises a melamine resin and / or a precursor of a melamine resin (a monomer corresponding to a melamine resin, an oligomer (dimer, Trimers and the like), prepolymers and the like.

  In this specification, the melamine resin refers to a resin containing a melamine compound and an aldehyde compound as constituent components.

  The melamine compound is a compound having a 1,3,5-triazine skeleton, in which three amino groups are introduced into the triazine ring.

  As a preferable structure of a melamine compound, what is represented by following formula (3) etc. are mentioned, for example.

（式（３）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に、水素原子または置換基を有していてもよい炭素数が１以上４以下の炭化水素基である。）

(In formula (3), R ¹ , R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.)

As the melamine compound, a compound (melamine) in which R ¹ , R ² and R ³ in formula (3) are all hydrogen atoms is particularly preferable.

  Thereby, the hardness of the decorative sheet 100 can be made more excellent. Moreover, the synthesis | combination of the melamine type resin which comprises the decorative sheet 100 can be performed more efficiently.

  The aldehyde compound only needs to have an aldehyde group (—CHO) in the molecule, and examples thereof include those represented by the following formula (2).

（式（２）中、Ｒは、水素原子または置換基を有していてもよい炭素数が１以上１０以下の炭化水素基である。）

(In the formula (2), R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.)

As the aldehyde compound, formaldehyde is particularly preferable.
As a result, the hardness of the hard material layer 3 can be improved. In addition, the synthesis of the melamine resin can be performed more efficiently.

  The melamine-based resin only needs to contain a melamine compound and an aldehyde compound as constituent components, but may further contain a guanamine compound as a constituent component in addition to the melamine compound and aldehyde compound.

  Thereby, the workability of the decorative sheet 100 can be made particularly excellent while making the hardness of the hard material layer 3 sufficiently excellent.

  A guanamine compound is a compound having a 1,3,5-triazine skeleton, in which two amino groups are introduced into the triazine ring.

  A preferable structure of the guanamine compound includes, for example, a structure represented by the following formula (1).

（式（１）中、Ｒは、水素原子または置換基を有していてもよい炭素数が１以上１０以下の炭化水素基である。）

(In formula (1), R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.)

  As the guanamine compound, a compound (acetoguanamine) in which R in formula (1) is a methyl group is particularly preferable.

  Thereby, the hardness and workability of the decorative sheet 100 can be compatible at a higher level. Moreover, the synthesis | combination of the melamine type resin which comprises the decorative sheet 100 can be performed more efficiently.

  The reaction molar ratio of the aldehyde compound to the melamine compound ((molar amount of aldehyde compound) / (molar amount of melamine compound) is hereinafter simply referred to as “reaction molar ratio”). Although not particularly limited, it is preferably 1.0 or more and 4.0 or less, more preferably 1.0 or more and 2.0 or less, and further preferably 1.1 or more and 1.8 or less.

  If the reaction molar ratio is less than the lower limit value, the proportion of unreacted components remaining in the hard material layer 3 to be formed tends to increase.

  Moreover, when the said upper limit is exceeded, the softness | flexibility of the hard material layer 3 formed may become remarkably low.

  The melamine-based resin may include components other than the above-described components (melamine compound, guanamine compound, aldehyde compound) as a constituent component.

  For example, the melamine-based resin preferably contains a sulfonamide compound as a constituent component.

  Thereby, the moisture resistance, antifouling property, durability, etc. of the decorative sheet 100 can be made particularly excellent.

As the sulfonamide compound, for example, p-toluenesulfonamide (CH ₃ —C ₆ H ₅ —SO ₂ NH ₂ ) or the like can be suitably used.

  Thereby, the moisture resistance, antifouling property, durability, etc. of the decorative sheet 100 can be further improved. Moreover, the synthesis | combination of the melamine type resin which comprises the decorative sheet 100 can be performed more efficiently.

  Moreover, as a melamine-type resin, commercially available things, such as a melamine-type resin by Sumitomo Chemical Co., Ltd., can also be used, for example.

(solvent)
The composition for forming a hard material layer may contain a solvent. Thereby, for example, in the composition for forming a hard material layer, the hard material and its precursor can be dissolved and / or dispersed, and the composition for forming a hard material layer is easy to handle (handleability). And the productivity of the decorative sheet 100 can be made particularly excellent.

As the solvent contained in the composition for forming a hard material layer, a polar solvent can be preferably used. Specifically, water; alcoholic solvents such as methanol, ethanol, isopropanol; ketones such as methyl ethyl ketone and acetone Solvents; Amide solvents such as dimethylformamide (DMF); Ether solvents such as tetrahydrofuran (THF) and tetrahydropyran; Sulfoxide solvents such as dimethylsulfoxide (DMSO) and the like.
Among these, water is preferably used as the solvent.

  Thereby, generation | occurrence | production of the problem of a volatile organic compound (VOC) at the time of manufacture of the decorative sheet 100 can be prevented effectively. Further, for example, when the hard material layer forming composition includes a hard material precursor, the hard material precursor can be uniformly dissolved in the hard material layer forming composition, and the hydrogen ion index ( pH) can be easily controlled, and it is possible to effectively prevent the occurrence of unintentional variations in the hydrogen ion exponent (pH) in the composition for forming a hard material layer. From such a thing, a polymerization reaction can be advanced suitably.

  When the composition for forming a hard material layer contains a solvent, the content of the solvent in the composition for forming a hard material layer is preferably 30% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 70% by mass. The following is more preferable.

(Other ingredients)
The composition for forming a hard material layer may include components other than those described above (other components). Examples of such components include catalysts such as various acidic substances and various basic substances, mold release agents, polymerization initiators, slip agents (leveling agents), dispersants, polymerization accelerators, polymerization inhibitors, and penetration accelerators. , Wetting agents (humectants), colorants, fixing agents, antifungal agents, preservatives, antioxidants, chelating agents, thickeners, antifoaming agents, sensitizers (sensitizing dyes) and the like.

  As a basic substance as a catalyst, sodium hydroxide, potassium hydroxide, etc. are mentioned, for example.

  Examples of the acidic substance as a catalyst include latent acid catalysts such as acetic acid, hydrogen chloride, sulfuric acid, nitric acid, and diammonium imidodisulfonate.

When the composition for forming a hard material layer includes other components, the content of other components in the composition for forming a hard material layer (in the case of including multiple types of components, the sum of these contents) is: It is preferably 5.0% by mass or less, and more preferably 0.1% by mass or more and 3.0% by mass or less.
Thereby, the function of the component as described above can be exhibited more effectively.

  The preferred embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention. It is.

  For example, the decorative sheet of the present invention is not limited to the form of the decorative sheet 100 shown in FIG. 1, and has a configuration other than a fibrous base material, a printed layer, a hard material layer, and a core material subjected to a pretreatment. For example, as shown in FIG. 3, the protective layer 5 is provided on the outermost layer on the design surface side, or the support layer 6 is provided on the outermost layer on the core material 4 side as shown in FIG. You may be doing something.

The protective layer 5 is not particularly limited, for example, a paper base having a basis weight of 10 g / m ² or more and 50 g / m ² or less, a melamine resin alone, or a melamine resin, aluminum hydroxide, magnesium hydroxide, Or it can obtain by impregnating the resin composition containing the inorganic filler chosen from silica, and drying this.

  In the present invention, the decorative sheet may have an intermediate layer between the fibrous base material and the core material.

  Moreover, the decorative sheet of the present invention may be any sheet as long as it has a fibrous base material, a printed layer, and a hard material layer that have been subjected to pretreatment, and may not include a core material.

  In addition, the decorative sheet of the present invention may be manufactured by any method, and is not limited to the one manufactured by the method described above. For example, the order of each step in the embodiment of the manufacturing method described above may be changed.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example 1
[1] Production of decorative sheet First, a titanium oxide-containing paper having a basis weight of 80 g / m ² was prepared as a fibrous base material. The content of titanium oxide in the fibrous base material was 30% by mass.

  Next, a thermoplastic resin emulsion is applied to the fibrous base material by a dipping method, and then dried by heating to 110 ° C., thereby forming a resin portion in the gap between the fibers constituting the fibrous base material. . As the thermoplastic resin emulsion, aqueous emulsion type composite particles (water-insoluble, average particle size: 60 nm) having a core-shell structure with an acrylic resin as a core and a urethane resin as a shell are contained as emulsion resin particles. Used was dispersed in water as a dispersion medium.

  Next, an ink containing a polymerizable compound is applied to the fibrous base material provided with the resin portion as described above in a predetermined pattern by an inkjet method, and then irradiated with ultraviolet rays to polymerize the polymerizable compound. Then, a woodgrain print layer (printing part) was formed by curing.

  As the ink, C.I. I. Indigo purple pigment ink containing CI Pigment Blue 15: 3, C.I. I. Crimson purple pigment ink containing CI Pigment Violet 19, C.I. I. A yellow pigment ink containing CI Pigment Yellow 150 and a black pigment ink containing carbon black as a pigment were used.

  Each ink is a phenoxyethyl acrylate, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, photopolymerization initiator as a polymerizable compound. Irgacure 819 (manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, and UV-3500 (manufactured by BYK Chemie) as a leveling agent ) And p-methoxyphenol as a polymerization inhibitor. The viscosity of each ink at room temperature (20 ° C.) was included in the range of 3 mPa · s to 15 mPa · s.

  Next, the hard material layer-forming composition was applied to the side of the fibrous base material on which the printed layer was formed as described above, and the hard material layer was formed.

  The composition for forming a hard material layer includes 100 parts of a melamine resin obtained by condensation reaction of melamine (M) and formaldehyde (F) at a reaction molar ratio (F / M) = 1.7. Resin solid content: 50% by mass of melamine resin varnish, thermal latent acid catalyst (“Catanit” manufactured by MRC Unitech): 0.9 part by weight, release agent (“Separ 328” manufactured by Chukyo Yushi Co., Ltd.): 0.2 mass part was added and the resin composition (varnish) obtained by stirring for 10 minutes at 23 degreeC was used.

Next, a glass woven fabric (glass cloth) made of T-glass, having a basis weight of 150 g / m ² and a thickness (average thickness) of 250 μm is prepared. The outer surface of the hard material layer is brought into contact with the surface opposite to the surface on which the material layer is provided, with the pressing member under the conditions of heating temperature: 140 ° C., pressure: 5 MPa, heating time: 30 minutes. Pressed and heated. Thereby, the decorative sheet in which the fibrous base material and the glass woven fabric (core material) were joined was obtained.

  As the pressing member, a member made of stainless steel and having a mirror finish was used.

  Also, four different decorative sheets were produced in the same manner as described above except that the pattern of the printed layer was changed. As a result, five different types of decorative sheets were obtained.

(Example 2)
A printed layer having a pattern different from each other is formed in the same manner as in Example 1 except that the resin part formed as a pretreatment for the fibrous base material has the same composition as the melamine resin constituting the hard material layer. Five types of decorative sheets were produced.

(Examples 3 to 5)
Except having changed the conditions of the titanium oxide contained in a fibrous base material as shown in Table 1, the 5 types of decorative sheets which have a printed layer of a mutually different pattern were manufactured similarly to the said Example 1. FIG.

(Example 6)
Five decorative sheets having printed layers with different patterns were produced in the same manner as in Example 1 except that the hard material layer was made of polyester (thickness: 100 μm).

(Example 7)
Five decorative sheets having printed layers with different patterns were produced in the same manner as in Example 1 except that a laminate obtained by laminating three kraft papers impregnated with phenolic resin was used as the core material. The thickness of the core material was 600 μm.

(Example 8)
Except for using an acrylic-styrene copolymer as the resin material contained in the ink and changing the content of the solvent component to 60% by mass or more, it has printing layers with patterns different from each other in the same manner as in Example 1. Five types of decorative sheets were produced.

(Comparative Example 1)
5 types of decorative sheets having printed portions with different patterns are manufactured in the same manner as in Example 1 except that the ink used for forming the printed portion is directly applied to the fibrous base material that has not been subjected to the pretreatment. did.

(Comparative Example 2)
Except that the printing part was formed by gravure printing, five types of decorative sheets having printing parts with different patterns were produced in the same manner as in Example 1.

(Comparative Example 3)
Five types of decorative sheets having printed portions having different patterns were produced in the same manner as in Comparative Example 2 except that gravure printing was directly performed on a fibrous base material that had not been subjected to a pretreatment.
Table 1 summarizes the configurations of the decorative sheets of the examples and comparative examples.

[2] Evaluation The following evaluations were performed on the decorative sheets of Examples and Comparative Examples manufactured as described above.

[2.1] Productivity Productivity of a small amount and a wide variety when producing five types of decorative sheets was evaluated according to the following criteria.

A: The productivity of the decorative sheet is very excellent.
B: Productivity of the decorative sheet is excellent.
C: The productivity of the decorative sheet is good.
D: Productivity of the decorative sheet is slightly inferior.
E: Productivity of the decorative sheet is very inferior.

[2.2] Color developability The color developability of the printed portion when visually observed from the side of the decorative sheet provided with the hard material layer was evaluated according to the following criteria.

A: The color developability of the printed part is very excellent.
B: The color developability of the printed part is excellent.
C: The color developability of the printed part is good.
D: The color developability of the printed part is slightly inferior.
E: The color developability of the printed part is very poor.

[2.3] Hardness The Martens hardness of the surface of the decorative sheet on which the hard material layer was provided was evaluated according to the following criteria.

A: Hardness is 300 MPa or more.
B: Hardness is less than 300 MPa.

[2.4] Heat resistance (nonflammability)
The amount of heat generated when the decorative sheet was subjected to a corn calorie burning test was measured, and the heat resistance (nonflammability) of the decorative sheet was evaluated according to the following criteria.

A: The calorific value is less than 8 MJ / m ² .
B: The calorific value is 8 MJ / m ² or more.

[2.5] Flexibility The minimum R shape without cracks when visually observed from the side of the decorative sheet provided with the hard material layer when subjected to external bending deformation at room temperature, according to the following criteria: The flexibility of the decorative sheet was evaluated.

A: Less than 10R.
B: 10R or more and less than 20R.
C: 20R or more.
These results are summarized in Table 2.

As is apparent from Table 2, in the present invention, the color developability of the printed portion was excellent. In addition, since the printing part was formed using the ink jet method, even a plurality of types of decorative sheets having printing parts with different patterns could be manufactured with excellent productivity without requiring the production of a plate. .
On the other hand, in the comparative example, a satisfactory result was not obtained.

100: decorative sheet 1: fibrous base material 11: fiber 12: resin part 2: printing layer (printing part)
3: Hard material layer 4: Core material (core material layer)
5: Protective layer 6: Support layer

Claims (14)

A fibrous base material that has been pretreated,
A printed layer formed by an inkjet method on the fibrous base material subjected to the pretreatment;
A decorative sheet comprising: a hard material layer disposed on a side of the fibrous base material on which the printed layer is provided.   The decorative sheet according to claim 1, wherein the hard material layer is made of a material containing a melamine-based resin.   The decorative sheet according to claim 1 or 2, wherein the pretreatment is formation of a resin portion in a gap between fibers constituting the fibrous base material.   The decorative sheet according to claim 3, wherein the resin portion is made of a material containing an acrylic resin and a urethane resin.   The decorative sheet according to claim 3 or 4, wherein the resin portion is made of a material containing a melamine-based resin.   The decorative sheet according to any one of claims 1 to 5, wherein a core material is provided on a surface of the fibrous base material opposite to a surface on which the printed layer is provided.   The decorative sheet according to claim 6, wherein the core material is made of glass cloth.   The decorative sheet according to any one of claims 1 to 7, wherein the fibrous base material contains titanium oxide. A printing step of forming a printing layer by an inkjet method on the fibrous base material subjected to the pretreatment;
A method for producing a decorative sheet, comprising: a hard material layer forming step of forming a hard material layer on a surface side of the fibrous base material on which the printed layer is provided.   The decorative sheet according to claim 9, wherein the pretreatment is performed by impregnating the fibrous base material not subjected to the pretreatment with a resin material and / or a material containing a precursor thereof. Production method.   The method for producing a decorative sheet according to claim 9 or 10, further comprising a core material joining step of joining a core material to the fibrous base material.   The said core material joining process is a manufacturing method of the decorative sheet of Claim 11 performed after the said printing process.   The decorative sheet according to any one of claims 9 to 12, wherein the printed layer is formed by applying an ink containing a curable resin by an ink jet method and then curing the curable resin. Production method.   The decorative sheet according to any one of claims 9 to 12, wherein the printing layer is formed by applying an ink containing a thermoplastic resin by an inkjet method and then drying a solvent component of the ink. Manufacturing method.

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