JP2016147410A - 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 aesthetic property; and a method for producing a decorative sheet capable of efficiently producing a decorative sheet having a printed portion which is formed by an inkjet method and is excellent in color development and aesthetic property.SOLUTION: A decorative sheet has: a base material formed of a material containing a resin material; a printed layer formed on the base material by imparting ink containing a solvent which dissolves or swells the resin material to the base material by an inkjet method; and a hard material layer arranged on the side of a surface of the base material in which the printed layer is provided. The hard material layer is preferably formed of a material containing a melamine-based resin.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 the decorative sheet generally has a paper base material on which various patterns such as wood grain tone and stone tone are provided 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 having a printed part formed by an ink jet method and having excellent color developability and aesthetics, and a printed part formed by an ink jet method and having excellent color developability and aesthetics. It is providing the manufacturing method of the decorative sheet which can manufacture the decorative sheet which has it efficiently.

Such an object is achieved by the present inventions (1) to (11) below.
(1) a base material composed of a material including a resin material;
A printing layer formed by applying an ink containing a solvent that dissolves or swells the resin material to the substrate by an inkjet method;
A decorative sheet comprising: a hard material layer disposed on a surface side of the substrate on which the printed layer is provided.

  (2) The decorative sheet according to (1), wherein the base material has a thickness of 20 μm or more and 250 μm or less.

  (3) The decorative sheet according to (1) or (2), wherein the base material is made of polyethylene terephthalate.

  (4) The decorative sheet according to any one of (1) to (3), wherein the ink contains at least one compound selected from an alkylene glycol compound and a lactone compound as the solvent.

  (5) The decorative sheet according to any one of (1) to (4), wherein the hard material layer 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 substrate is provided.

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

(8) an ink application step of applying an ink containing a solvent that dissolves or swells the resin material to a base material made of a material containing the resin material by an inkjet method;
Removing the solvent and forming a printed layer;
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 substrate on which the printed layer is provided.

  (9) The manufacturing method of the decorative sheet according to (8), further including a core material bonding step of bonding a core material to the base material.

  (10) The said core material joining process is a manufacturing method of the decorative sheet as described in said (9) performed after the said solvent removal process.

  (11) The method for producing a decorative sheet according to (9) or (10), wherein the ink contains at least one compound selected from an alkylene glycol compound and a lactone compound as the solvent.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has the printing part which was formed with the inkjet method and was excellent in color development property and aesthetics is provided, and the decorative sheet which has the printing part excellent in color development property and aesthetics is efficiently obtained. The manufacturing method of the decorative sheet which can be manufactured can be provided.

It is sectional drawing which shows 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. 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 sectional view showing a preferred embodiment of the decorative sheet of the present invention, and FIG. 2 is a sectional view showing another preferred embodiment of the decorative sheet of the present invention.

  A decorative sheet 100 shown in FIG. 1 includes a base material 1, a printing layer (printing unit) 2, a hard material layer 3 disposed on the surface side of the base material 1 on which the printing layer 2 is provided, and the base material 1. It has a core material 4 provided on the side opposite to the surface on which the printing layer 2 is provided. Moreover, the decorative sheet 100 shown in FIG. 2 has the base material 1, the printing layer (printing part) 2, and the hard material layer 3 distribute | arranged to the surface side in which the printing layer 2 of the base material 1 was provided. ing.

  In use, the decorative sheet 100 is such that the upper side in FIGS. 1 and 2 is the observer's viewpoint side.

<Base material>
The base material 1 is made of a material containing a resin material. By providing such a base material 1, the color developability of a printing layer 2 (a printing layer 2 formed by ejecting an ink containing a solvent that dissolves or swells a resin material by an ink jet method) as will be described in detail later. Can be made excellent, and the aesthetics of the decorative sheet 100 can be made excellent. Further, the adhesiveness to the printing layer 2 (printing layer 2 formed by ejecting an ink containing a solvent that dissolves or swells the resin material by an ink jet method) as described in detail later may be excellent. The durability of the decorative sheet 100 can be made excellent. Moreover, since it is not necessary to provide the base material comprised by the paper which was used conventionally by providing the base material 1 comprised with the material containing a resin material, the decorative sheet 100 can be reduced in weight. Moreover, the bending property of the decorative sheet 100 can be excellent.

  On the other hand, for example, when a paper base is used, the ink applied by the ink jet method excessively penetrates into the base (paper base) during the production of the decorative sheet, and the color of the printed layer is increased. And the aesthetics of the decorative sheet cannot be made sufficiently excellent.

  In addition, when a paper base material is used, even if a printing layer and a hard material layer are provided, the flexural modulus of the decorative sheet as a whole is small, and the stiffness (stretch) cannot be sufficient. Further, since the ease of handling of the decorative sheet (e.g., the ease of work of attaching to a wall or the like) is low, it was necessary to further provide a core material or the like. As shown, even if it does not have a core material, if it has a base material, a printed layer, and a hard material layer, sufficient stiffness can be obtained, and the decorative sheet should be easy to handle Can do. Moreover, since it is not necessary to provide a core material etc., a decorative sheet can be reduced in weight suitably and bending workability etc. can be made especially excellent.

  Further, the paper base material is easily affected by humidity and easily causes problems such as dimensional change due to moisture absorption. However, by using the base material 1 made of a resin material, the occurrence of such a problem is effective. Can be prevented.

  As a resin material which comprises the base material 1, various thermoplastic resins, the hardened | cured material of curable resin material, etc. can be used, for example. Specific examples of the resin material constituting the substrate 1 include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin (COP), modified polyolefin, polychlorinated Vinyl, polyvinylidene chloride, polystyrene, polyamide (eg, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin) Butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. Polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aroma Polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin , Polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluororubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, melamine resins , Unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, poly-dichloro-xylylene para-xylylene), poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene and other polyparaxylylene resins, etc. Copolymer, blend, polymer alloy, etc., one or more of these Combination (e.g., blend resin, polymer alloy, as a laminate or the like) can be used.

  In particular, when the base material 1 is composed of polyethylene terephthalate, the color development of the printing layer (printing portion) 2 is particularly excellent, and the aesthetics of the decorative sheet 100 are particularly excellent. it can. In addition, the bendability and durability of the decorative sheet 100 can be made particularly excellent. Moreover, in order to show moderate solubility and swellability to various solvents, the adhesion between the substrate 1 and the printing unit 2 is more effectively prevented while preventing the unintentional disturbance of the pattern of the printing unit 2 more effectively. The durability of the decorative sheet 100 can be made particularly excellent. Further, when the hard material layer 3 is formed by using a hard material layer forming composition that will be described in detail later, the adhesion between the base material 1 and the hard material layer 3 is particularly excellent. can do. As a result, the durability of the decorative sheet 100 can be further improved.

  The substrate 1 may be one having pores (for example, including a fibrous substrate such as a nonwoven fabric, a cloth, a woven fabric, etc.), but preferably has a dense sheet shape. . Thereby, it can prevent more reliably that the ink used for formation of the printing part 2 permeate | transmits the inside of the base material 1 more reliably, and the coloring property and the aesthetics of the printing part 2 are especially excellent. It can be.

  The base material 1 should just contain a resin material, and may contain another component. Examples of such components include colorants, slip agents (leveling agents), fillers, antifungal agents, antiseptics, antioxidants, chelating agents, thickeners, antifoaming agents, and sensitizers (sensitizing dyes). ) And the like.

Although the content rate of the resin material in the base material 1 is not specifically limited, It is preferable that it is 50 mass% or more, It is more preferable that it is 80 mass% or more, It is further more preferable that it is 90 mass% or more.
Thereby, the effects as described above are more remarkably exhibited.

  Although the thickness of the base material 1 is not specifically limited, It is preferable that they are 20 micrometers or more and 250 micrometers or less, and it is more preferable that they are 50 micrometers or more and 130 micrometers or less.

  As a result, the decorative sheet 100 can be made thin, and the decorative sheet can be made particularly excellent in bending workability, durability, reliability, and the like.

<Print layer>
The substrate 1 is provided with a printing layer 2 formed by an ink jet method.

  By adopting the ink jet method in this way, unlike gravure printing or the like, it is not necessary to prepare a plate, and it is possible to suitably form printing portions (printing layers) 2 having various patterns 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.

  The printed layer 2 is formed using an ink containing a solvent that can dissolve or swell the resin material constituting the substrate 1.

  Thereby, at the time of formation of the printing layer 2 (at the time of ink application), a part of the substrate 1 (region near the surface to which the ink has been applied) can be dissolved or swollen, and then the solvent is removed. Thus, the printed layer 2 that is firmly bonded to the substrate 1 can be obtained. As a result, the durability and reliability of the decorative sheet 100 can be improved.

  Further, since the printing layer 2 is formed by applying an ink containing a solvent capable of dissolving or swelling the resin material constituting the substrate 1 by an ink jet method, when the printing layer 2 is formed, The amount of ink applied can be accurately controlled, it is not necessary to apply more solvent than necessary to the substrate 1, and the solvent can be removed relatively quickly after ink landing. For this reason, it can prevent reliably that the base material 1 receives a damage and the pattern of the printing layer 2 is disturb | confused, acquiring the above effects. Therefore, it is possible to easily and reliably form the printing layer 2 having a desired shape and pattern while reliably preventing deformation or the like of the substrate 1, and to make sure that the decorative sheet 100 has excellent aesthetics and the like. be able to.

  The printing layer 2 is usually made of a material containing a colorant, but may contain other components. Examples of such components include resin materials, slip agents (leveling agents), dispersants, penetration enhancers, wetting agents (humectants), fixing agents, antifungal agents, antiseptics, antioxidants, chelating agents, A thickener, an antifoamer, a sensitizer (sensitizing dye), etc. are mentioned.

  In particular, when the printing layer 2 is made of a material containing a resin material, the adhesion between the printing layer 2 and the substrate 1 is particularly excellent, and the durability of the decorative sheet 100 is particularly excellent. can do.

  As a resin material which comprises the printing layer 2, various thermoplastic resins, the hardened | cured material of curable resin material, etc. can be used, for example. Specific examples of the resin material constituting the printing layer 2 include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin (COP), modified polyolefin, polychlorinated Vinyl, polyvinylidene chloride, polystyrene, polyamide (eg, nylon 6, nylon 46, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, nylon 6-12, nylon 6-66), polyimide, polyamideimide, polycarbonate (PC), poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS tree) ), Butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. Polyester, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, Aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin , Polyvinyl chloride, polyurethane, polyester, polyamide, polybutadiene, trans polyisoprene, fluoro rubber, chlorinated polyethylene, and other thermoplastic elastomers, epoxy resins, phenol resins, urea resins, melamines Resin, unsaturated polyester, silicone resin, urethane resin, poly-para-xylylene, poly-monochloro-para-xylylene, poly-dichloroparaxylylene -para-xylylene), poly-monofluoro-para-xylylene, poly-monoethyl-para-xylylene and other polyparaxylylene resins, etc. And copolymers, blends, polymer alloys, etc., and one or more of these Can be used in combination (e.g., blend resin, polymer alloy, as a laminate, etc.).

  Especially, as a resin material which comprises the printing layer 2, acrylic resin (especially the polymer which contains the polymeric compound explained in full detail later as a structural component) is preferable. Thereby, the adhesiveness of the printing layer 2 and the base material 1 can be made more excellent, and the durability of the decorative sheet 100 can be made more excellent.

  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.

  In the configuration shown in the figure, there is a clear interface between the base material 1 and the printed layer 2. For example, in the process of manufacturing the decorative sheet 100, the base material 1 is partially dissolved to The interface between the material 1 and the printing layer 2 may be unclear (unclear).

<Hard material layer>
A hard material layer 3 is disposed on the side of the substrate 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 (the surface opposite to the surface facing the substrate 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 substrate 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.

The hard material layer 3 may have a surface finish such as a mirror finish or an emboss finish on the outer surface (the surface opposite to the surface facing the substrate 1).
Thereby, the further improvement of the aesthetics of the decorative sheet 100 can be aimed at.

<Core material>
In the configuration shown in FIG. 1, a core material (core material layer) 4 is provided on the side of the substrate 1 opposite to the surface on which the printed layer 2 is provided.

  Thereby, the rigidity of the decorative sheet 100 is particularly excellent. For example, even when the rigidity of the substrate 1 is low, the stability of the shape of the decorative sheet 100 and the ease of handling are particularly excellent. Can be. 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. 3 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. 3, the manufacturing method of this embodiment includes a base material preparation step (1a) for preparing the base material 1, and an ink application step (1b) for applying ink 2 'to the base material 1 by an ink jet method. ), A solvent removal step (1c) for removing the solvent contained in the ink 2 'applied on the substrate 1 to form the printing layer 2, and the surface of the substrate 1 on which the printing layer 2 is provided. The core which joins the core material (core material layer) 4 to the surface side opposite to the surface on which the printed layer 2 of the base material 1 is provided and the hard material layer forming step (1d) for forming the hard material layer 3 And a material joining step (1e).

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

  As the substrate 1, a film-like material can be suitably used. Further, in this step, for example, a long base material wound up in a roll shape can be used, and the base material is cut into a predetermined length during this step or after this step. Also good.

  In addition, the base material 1 prepared in this step has been subjected to various surface treatments (surface activation treatment) such as plasma treatment, ultraviolet irradiation treatment, primer treatment, etc. prior to the subsequent ink application step. May be. Thereby, the adhesiveness of the base material 1 and the printing layer 2 can be made especially excellent.

<Ink application process>
Next, an ink 2 ′ containing a solvent that dissolves or swells the resin material constituting the substrate 1 is applied to the substrate 1 prepared in the above step by an ink jet method (1b).

  By applying the ink 2 ′ using the ink jet 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.

  In this step, the solvent contained in the ink 2 ′ applied to the substrate 1 dissolves or swells a part of the substrate 1 (region near the surface to which the ink 2 ′ is applied). As a result, the applied ink 2 ′ can be suitably attached to the target portion of the substrate 1, and the repelling of the ink 2 ′ on the substrate 1 and excessive wetting and spreading are effectively prevented. be able to. As a result, the print layer 2 having a desired pattern can be easily and reliably formed. Further, when the ink 2 ′ dissolves or swells a part of the substrate 1, the printing portion 2 formed by removing the solvent from the ink 2 ′ is firmly bonded to the substrate 1. Thus, the adhesion of the printing layer 2 to the surface can be made excellent, and the durability and reliability of the decorative sheet 100 finally obtained can be made excellent.

In this step, a plurality of types of inks 2 ′ 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 2 ′ used for forming the print layer 2 will be described in detail later.

<Solvent removal step>
Next, the solvent contained in the ink 2 ′ applied to the substrate 1 is removed to form a solid print layer 2 (1c).

As described above, the ink 2 ′ contains a solvent that dissolves or swells the resin material, so that at the end of the ink application process (before the solvent removal process), a part of the substrate 1 (ink 2 ′ is applied). The region near the surface is dissolved or swollen by the solvent. From this state, by removing the solvent from the ink 2 ′ in this step (solvent removal step), the formed printing portion 2 is firmly bonded to the base material 1, and the printed layer on the base material 1 2 can be made excellent, and the durability and reliability of the decorative sheet 100 finally obtained can be made excellent.
The removal of the solvent can be performed, for example, by performing a heat treatment or a reduced pressure treatment.

  When this step is performed by heat treatment, the heating temperature varies depending on the type of the solvent contained in the ink 2 ′, but when the boiling point of the solvent is Tbp [° C.], (Tbp-60) ° C. or more (Tbp− 5) It is preferable that it is below degrees C, and it is more preferable that it is (Tbp-50) degree C or more and (Tbp-10) degrees C or less.

  Thereby, since the solvent can be efficiently removed while preventing bumping of the solvent, the productivity and yield of the decorative sheet 100 can be made particularly excellent.

  In the illustrated configuration, in order to facilitate understanding, the solvent removal step (1c) is performed after the ink application step (1b) is completed. However, the ink application step and the solvent removal step are performed simultaneously. It may be performed sequentially and progressively. For example, the ink may be applied to other portions of the pattern while performing the solvent removal process on the ink 2 ′ applied to the portion corresponding to a part of the target pattern. For example, such a configuration can be suitably obtained by applying the ink 2 ′ by an ink jet method while heating the substrate 1 to which the ink 2 ′ is applied. Thereby, the productivity of the decorative sheet 100 can be made particularly excellent.

  In addition, when the ink 2 ′ includes a curable resin as a constituent component, the curing reaction (polymerization reaction) of the curable resin can be suitably advanced by performing the heat treatment in this step, and the decorative sheet 100. In particular, the adhesion between the substrate 1 and the printed layer 2 can be made particularly excellent.

  In addition, when the ink 2 ′ includes a curable resin as a constituent component, the printing layer 2 formed in this step may not have completed the polymerization reaction of the curable resin. 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, reliability, etc. of the decorative sheet 100 finally obtained are sufficiently excellent. Can be.

  In the present invention, when the polymerizable compound (for example, a monomer or the like) is liquid by itself and has a function of dissolving or swelling the resin material constituting the base material, The compound is handled as the solvent. In this case, the polymerizable compound (liquid polymerizable compound) is treated as a product from which the solvent has been removed when it becomes solid by the polymerization reaction.

<Hard material layer formation process>
Next, the hard material layer 3 is formed on the side of the substrate 1 on which the printed 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 base material 1 was provided, and performing a hardening reaction after that.

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

  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 substrate 1 on which the printing layer 2 is provided.

The joining of the member for forming a hard material layer and the substrate 1 can be performed, for example, by pressure bonding.
When joining the member for forming a hard material layer and the substrate 1 by pressure bonding, the joining between the substrate 1 and the member for forming a hard material layer may be heated at the time of pressing, for example.

  As a result, the productivity of the decorative sheet 100 can be made particularly excellent, and the bonding strength between the substrate 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 member for forming a hard material layer and the 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 to 120 Can be less than or equal to minutes.

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

  In addition, when the member for forming a hard material layer and the substrate 1 are joined, a mirror finish plate is stacked on the outer surface (the surface opposite to the surface facing the substrate 1) of the member for forming a hard material layer. Thus, a mirror finish can be obtained, and an emboss finish can be obtained by stacking an emboss plate or an emboss film.

  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, the core material (core material layer) 4 is provided on the surface opposite to the surface on which the printed layer 2 of the substrate 1 is provided (1e).
Thereby, the decorative sheet 100 is obtained.

  Thus, by having the core material joining process which joins the 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 ease of handling. Will be 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 for joining the base material 1 and the core material 4 is performed after the solvent removing process (printing layer forming process) described 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 substrate 1 in the ink application process can be made excellent.

For example, when the core material 4 includes a resin material, the core material 4 and the base material 1 can be joined by melting and softening a part of the core material 4.
Moreover, you may perform joining of the core material 4 and the base material 1 by adhesion | attachment, for example.

  In addition, when manufacturing as a decorative sheet 100 as what does not have the core material 4, the decorative sheet 100 can be manufactured by skipping the core material joining process mentioned above.

<Ink>
Hereinafter, the ink 2 ′ used for forming the printing layer 2 will be described in detail.
As described above, the ink 2 ′ used for forming the printing layer 2 includes at least a solvent as described above.

Hereinafter, components of the ink 2 ′ will be described.
(solvent)
The ink 2 ′ contains at least a solvent having a function of dissolving or swelling the resin material constituting the substrate 1.

  By including such a solvent, when the ink 2 ′ is applied to the base material 1, it is absorbed by a part of the base material 1 (region near the surface to which the ink 2 ′ is applied), and the base material 1 is partially Can be dissolved or swollen. As a result, the printed portion 2 to be formed is firmly bonded to the base material 1, and the adhesion of the printed layer 2 to the base material 1 can be made excellent. Durability and reliability can be made excellent. Further, since the ink 2 ′ can be selectively absorbed by a desired portion of the substrate 1, it is possible to prevent the repelling and excessive wetting and spreading on the substrate 1, and the pattern of the printing layer 2 is disturbed. Can be surely prevented. Therefore, it is possible to easily and reliably form the printing layer 2 having a desired shape and pattern while reliably preventing deformation or the like of the substrate 1, and to make sure that the decorative sheet 100 has excellent aesthetics and the like. be able to.

  The ink 2 ′ may be any ink as long as it has a function of dissolving or swelling the resin material constituting the substrate 1, for example, an alcohol compound (methyl alcohol, ethyl alcohol, propyl alcohol, butyl). Monohydric alcohols such as alcohol and 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, etc.) Propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ether compounds (diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), lactone compounds, and the like.

  When the ink 2 ′ contains at least one compound selected from an alkylene glycol compound and a lactone compound as a solvent, the storage stability of the ink 2 ′ and the ejection stability by the ink jet method are particularly excellent. Can do. Further, since the solvent can be quickly removed from the ink 2 ′ after ejection by the ink jet method, the productivity of the decorative sheet 100 can be made particularly excellent.

  Examples of the alkylene glycol compound that can be used as the solvent include alkylene glycols such as ethylene glycol and propylene glycol, and compounds in which at least one hydroxyl group of the alkylene glycol is etherified or esterified.

  Examples of the alkylene glycol moiety of the alkylene glycol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.

  Specific examples of the alkylene glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, pro Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and the like.

  Specific examples of the alkylene glycol diether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol diether. Butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether Le, and the like.

  Examples of the lactone compound that can be used as the solvent include γ-butyrolactone, δ-valerolactone, ε-caprolactone, and the like.

  Among these, the solvent may include one or more selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dibutyl ether, and γ-butyrolactone. Thereby, the storage stability of the ink 2 'and the ejection stability by the ink jet method can be further improved.

  Further, the ink 2 ′ only needs to include a solvent having a function of dissolving or swelling the resin material constituting the substrate 1. For example, a liquid polymerizable compound (for example, a monomer) is used as the solvent. It may be included.

  Thereby, the adhesiveness with respect to the base material 1 of the printing part 2 formed using ink 2 'can be made especially excellent. In addition, for example, it is not necessary to use a volatile component (a component removed by volatilization in the production of the decorative sheet 100) as a solvent, and even when a volatile component is used, the amount of use can be suppressed. Therefore, the productivity of the decorative sheet 100 can be made particularly excellent.

  As the liquid polymerizable compound, for example, various curable resins such as a thermosetting resin and a photocurable resin can be used, and a photocurable resin is preferable, and an ultraviolet curable resin is more preferable.

  By including a photo-curable resin (particularly, an ultraviolet curable resin) as a liquid polymerizable compound, the above-described solvent removal step (printing portion forming step) can be more easily and reliably applied to the ink 2 ′ at an appropriate timing. Since the contained curable resin (photo-curable resin) can be reliably cured (the liquid polymerizable compound can be removed), the printed layer 2 having a desired shape and pattern can be formed more easily and reliably. Can do.

  The liquid polymerizable compound (for example, monomer) as the solvent will be described in detail in the item “(resin material)” later.

  The content of the solvent in the ink 2 'is not particularly limited, but is preferably 50% by mass or more and 99% by mass or less, and more preferably 75% by mass or more and 95% by mass or less.

  Thereby, while being able to exhibit the effect by including the above-mentioned solvent (solvent which has the function to dissolve or swell the resin material which comprises the base material 1) more remarkably, a solvent can be rapidly used as needed. Since it can remove, the productivity of the decorative sheet 100 can be made particularly excellent.

(Coloring agent)
The ink 2 'usually contains a colorant as a solid content.

As the colorant, for example, various pigments, various dyes, and the like can be used, and fluorescent materials, phosphorescent materials, and the like can also be used. However, the ink 2 ′ preferably includes a pigment as a colorant. .
Thereby, the durability of the decorative sheet 100 can be made particularly excellent.

  When a plurality of types of inks 2 ′ are used, for example, inks 2 ′ corresponding to the three primary colors (cyan (blue 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) base material 1 or the like, the aesthetics of the decorative sheet 100 can be made particularly excellent.

  Further, for example, ink 2 ′ 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 substrate 1 or the like, the cosmetic sheet 100 can be made particularly excellent in aesthetics.

  Further, for example, the black ink 2 'may be used in combination with the chromatic ink 2'.

Thereby, while suppressing the usage amount of the ink 2 ′, it is possible to obtain an effect such that a dark color can be suitably expressed or a tightened black can be expressed.
For example, white ink 2 ′ may be used.

  Thereby, for example, even if the light concealability of the substrate 1 or the like is relatively low, the contrast and visibility of the printed layer 2 by the chromatic ink 2 ′ 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.

(Resin material)
The ink 2 ′ may include a resin material.

Thereby, the adhesiveness with respect to the base material 1 of the printing part 2 formed using ink 2 'can be made especially excellent.
As the resin material, various thermoplastic resins, curable resin materials, and the like can be used.

  In addition, when the ink 2 ′ includes a curable resin material, the adhesion of the printing unit 2 formed using the ink 2 ′ to the substrate 1 can be particularly excellent.

  Further, since the ink 2 ′ contains a photocurable resin (particularly, an ultraviolet curable resin), the fluidity of the ink 2 ′ can be more easily and reliably adjusted at an appropriate timing by adjusting the light irradiation timing. The printed layer 2 having a desired shape and pattern can be more easily and reliably formed.

  The photocurable resin may be any resin that undergoes a curing reaction (polymerization reaction) upon irradiation with light. For example, a resin that undergoes a curing reaction (polymerization reaction) upon irradiation with visible light or a curing reaction upon irradiation with ultraviolet light. Although what (polymerization reaction) advances (ultraviolet curable resin) etc. can be used, it is preferable that hardening reaction (polymerization reaction) advances by irradiation of an ultraviolet-ray.

  Thereby, the reaction rate of the curing reaction of the photocurable resin can be made particularly excellent, and the productivity of the decorative sheet 100 can be made particularly excellent. Moreover, since a widely distributed ultraviolet lamp or the like can be used as a light source for ultraviolet irradiation, a special light source is not required, and the configuration of the manufacturing apparatus for the decorative sheet 100 can be simplified. It is possible to reduce the manufacturing cost of the decorative sheet 100. Moreover, since the cured product of the ultraviolet curable resin is generally highly transparent, it is possible to more effectively prevent the color tone of the printing unit 2 from being adversely affected.

  The photocurable resin (polymerizable compound) is a liquid in itself, and has a function of dissolving or swelling the resin material constituting the base material, that is, a function of the solvent. preferable.

  Accordingly, the viscosity of the ink 2 ′ can be made sufficiently low without using a volatile component that evaporates in the manufacturing process of the decorative sheet 100 as the solvent, and droplet discharge by the inkjet method can be suitably performed. it can. Therefore, it is possible to prevent deformation of the pattern accompanying the removal of the liquid component (volatile component), and it is possible to easily and reliably form the print layer 2 having a desired shape and pattern.

  As the photocurable resin (polymerizable compound), for example, various monomers, various oligomers (including dimers, trimers, and the like), prepolymers, and the like can be used, but the ink 2 ′ is a photocurable resin (polymerizable). The compound) preferably includes at least a monomer component. Since the monomer is generally a low-viscosity component compared to the oligomer component or the like, it can function as the solvent. Further, it is advantageous for making the ejection stability of the ink 2 'by the ink jet method particularly excellent.

  As a monomer as a photocurable resin (polymerizable compound), for example, 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 acetate Relate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, methoxytriethylene glycol acrylate, PO-modified nonylphenol acrylate, EO-modified nonylphenol acrylate, EO-modified 2-ethylhexyl acrylate, phenyl Glycidyl ether acrylate, phenoxydiethylene 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-propanediol diacrylate, tripropylene glycol Acrylate, tetraethylene 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 diacrylate, 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, Methylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane EO-modified triacrylate, glycerin PO-added triacrylate, trisacryloyloxyethyl phosphate, pentaerythritol tetraacrylate, PO-modified trimethylolpropane triacrylate, tris (acryloxyethyl) Examples include isocyanurate and 2- (2-vinyloxyethoxy) ethyl acrylate. Among them, 4-hydroxybutyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane EO modified triacrylate, pentaerythritol tetraacrylate 2- (2-vinyloxyethoxy) ethyl acrylate is preferred. Although these monomers depend on the constituent materials of the substrate 1, they can function suitably as the solvent.

(Other ingredients)
The ink 2 ′ may include 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, Preservatives, antioxidants, chelating agents, thickeners, antifoaming agents, sensitizers (sensitizing dyes), solvents that do not have a function of dissolving or swelling the resin material constituting the substrate 1 (other solvents) ) And the like.

  The photopolymerization initiator is not particularly limited as long as it generates active species such as radicals and cations by light irradiation and initiates the polymerization reaction of the photocurable resin (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 photocurable resin (polymerizable compound) and curability, and an acylphosphine oxide compound and a thioxanthone compound are used in combination. More preferably.

  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.

  If the ink 2 '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. .

  When the ink 2 ′ contains a dispersant, the dispersibility of the dispersoid such as a pigment can be made excellent, and the storage stability and ejection stability of the ink 2 ′ 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.

  When the ink 2 ′ contains a solvent (other solvent) that does not have a function of dissolving or swelling the resin material constituting the substrate 1 together with a solvent having a function of dissolving or swelling the resin material constituting the substrate 1 In addition, the solubility of the resin material as a whole of the ink 2 ′ can be controlled more suitably, and unintentional deformation of the substrate 1, unintentional disturbance of the printing layer 2, etc. can be more effectively prevented. .

  The viscosity of the ink 2 '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. Further, the adhesion between the substrate 1 and the hard material layer 3 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, 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 It is easy to control (pH), and it is possible to effectively prevent the occurrence of unintentional variations in hydrogen ion index (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 FIGS. 1 and 2, and may have a configuration other than the base material, the printed layer, the hard material layer, and the core material. For example, as shown in FIG. 4, the outermost layer on the design surface side (the surface side on which the hard material layer 3 of the substrate 1 is provided) has a protective layer 5, or as shown in FIG. The support surface 6 may be provided on the outermost layer on the side opposite to the design surface side (the surface side of the base material 1 on which the hard material layer 3 is provided).

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 base material and the 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 base material (resin film) made of polyethylene terephthalate having a thickness of 125 μm was prepared.

  Next, by applying an ink containing diethylene glycol diethyl ether as a solvent in a predetermined pattern to the above substrate by an ink jet method, and then performing a heat treatment under the condition of 40 ° C. × 360 seconds, By removing the solvent, a woodgrain printing layer (printing portion) was formed.

  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 used was one containing a thermoplastic resin (polyester). Further, the content of the solvent in each ink was 80% by mass or more and 95% by mass or less. 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 composition for forming a hard material layer is applied to the surface side of the substrate on which the printing layer is formed as described above, and the hard material layer is formed, and the substrate and the printing layer are formed. A decorative sheet provided with a hard material layer was obtained.

  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.

  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)
Phenoxyethyl acrylate which is a liquid polymerizable compound as a solvent, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, Irgacure 819 as a photopolymerization initiator (Manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 (manufactured by BYK Chemy) as a leveling agent, and Using an ink containing p-methoxyphenol as a polymerization inhibitor and not containing a thermoplastic resin, the solvent is removed (polymerization and curing of the polymerizable compound), and ultraviolet rays having a peak wavelength of 350 to 400 nm are irradiated. Except that went by was prepared Five decorative sheet having a printed layer of different patterns in the same manner as in Example 1.

(Example 3)
Five decorative sheets having printed layers with different patterns were produced in the same manner as in Example 2 except that the hard material layer was made of polyester (thickness: 100 μm).

Example 4
Except that the core material composed of glass woven fabric (glass cloth) was joined to the surface opposite to the surface on which the printed layer and hard material layer of the substrate were provided, the same as in Example 1 above Five types of decorative sheets having printed layers with different patterns were produced.

As the glass woven fabric (glass cloth), a glass cloth having a basis weight of 150 g / m ² and a thickness (average thickness) of 250 μm was used.

  The base material and the glass woven fabric (core material) are joined with the hard material layer in a state where the glass woven fabric is in contact with the surface opposite to the surface on which the printed layer and the hard material layer are provided. The outer surface was pressed and heated with a pressing member under the conditions of heating temperature: 140 ° C., pressure: 5 MPa, heating time: 30 minutes. As the pressing member, a member made of stainless steel and having a mirror finish was used.

(Example 5)
Five decorative sheets having printed layers with different patterns were produced in the same manner as in Example 4 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 6)
Phenoxyethyl acrylate which is a liquid polymerizable compound as a solvent, 2- (2-hydroxyethoxy) ethyl acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 4-hydroxybutyl acrylate, Irgacure 819 as a photopolymerization initiator (Manufactured by Ciba Japan), Speedcure TPO (manufactured by ACETO) as a photopolymerization initiator, Speedcure DETX (manufactured by Lambson) as a photopolymerization initiator, UV-3500 (manufactured by BYK Chemy) as a leveling agent, and Using an ink containing p-methoxyphenol as a polymerization inhibitor and not containing a thermoplastic resin, the solvent is removed (polymerization and curing of the polymerizable compound) and irradiated with ultraviolet rays having a peak wavelength of 350 to 400 nm. Except that went by and were prepared five kinds of decorative sheet having a printed layer to different patterns from each other in the same manner as in Example 4.

  Each ink used in each of the above examples included a solvent that dissolves or swells the resin material constituting the substrate. In addition, the solvent content in each ink used in each of the examples was 80% by mass or more and 95% by mass or less. The viscosity of each ink at room temperature (20 ° C.) was included in the range of 3 mPa · s to 15 mPa · s.

(Example 7)
Five decorative sheets having printed layers having different patterns were produced in the same manner as in Example 6 except that a substrate having a thickness of 50 μm was used as the substrate.

(Comparative Example 1)
Except for using plain paper with a basis weight of 80 g / m ² as the base material, five types of decorative sheets having printed portions with different patterns were produced in the same manner as in Example 4.

(Comparative Example 2)
As the ink, except that the pigment used in Example 1 above, Surfinol 465 (manufactured by Nissin Chemical Industry Co., Ltd.), Polyflow 401 (manufactured by Nissin Chemical Industry Co., Ltd.), and ion-exchanged water were used. In the same manner as in Example 4, five types of decorative sheets having printed portions having different patterns were produced. That is, in this comparative example, a water-based ink that does not contain a solvent for dissolving or swelling the resin material was used.

(Comparative Example 3)
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 4.

(Comparative Example 4)
Except for using plain paper with a basis weight of 80 g / m ² as the base material, five types of decorative sheets having printed portions with different patterns were produced in the same manner as in Comparative Example 3.

  The content of the resin material in the base materials used in each of the examples and comparative examples was 95% by mass or more.

  Table 1 summarizes the conditions of the inks used in the production of the decorative sheets of the examples and comparative examples, and the configurations of the decorative sheets of the examples and comparative examples. In Table 1, diethylene glycol diethyl ether as a solvent is represented by DEGDEE, phenoxyethyl acrylate as a solvent (polymerizable compound) is represented by FEA, and acrylic acid 2- (2-hydroxyethoxy) as a solvent (polymerizable compound) ) Ethyl is indicated by HEEA, tripropylene glycol diacrylate as solvent (polymerizable compound) is indicated by TPGDA, dipropylene glycol diacrylate as solvent (polymerizable compound) is indicated by DPGDA, and solvent (polymerizable compound) is indicated. 4-Hydroxybutyl acrylate is represented by 4HBA, polyester as a resin material (thermoplastic resin) is represented by PEs, Surfynol 465 as a resin material (thermoplastic resin) is represented by S465, resin material (thermosetting resin) Polyflo as 401 are shown in P401, it showed polyethylene terephthalate as the resin material PET.

[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] Pattern shape The pattern shape of the printing part of the decorative sheet when visually observed from the side of the decorative sheet on which the hard material layer was provided was evaluated according to the following criteria.

A: The printing part is provided in a desired shape, and no pattern disturbance is observed.
B: Almost no pattern disturbance is observed in the printed part.
C: Although the pattern disorder in a printing part is recognized slightly, it is in the tolerance | permissible_range.
D: Disturbance of the pattern in the printing part is clearly recognized.
E: Pattern disturbance in the printed portion is noticeable.

[2.4] 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.

[2.5] Adhesiveness Check the peeled state between the printed part and the base material layer when visually observed from the side of the decorative sheet on which the hard material layer is provided. The adhesion with the printed layer was evaluated.

A: No peeling occurs for any external stimulus.
B: Peeling occurred in heat shock and wet heat repeated tests.
C: Peeling occurred during tape peeling.
D: Peeling occurs when lightly rubbed with a finger.
E: Not closely attached.

[2.6] 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.

[2.7] Bending workability A minimum R shape with no 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 bendability 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. Moreover, the unintentional disorder of the pattern of the printing layer (printing part) was prevented effectively, the desired pattern could be obtained, and the aesthetics of the decorative sheet were 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. . Moreover, in the decorative sheet of Examples 1-3 which does not have a core material, weight reduction and thickness reduction of the decorative sheet were able to be achieved, maintaining sufficient stiffness (tension).
On the other hand, in the comparative example, a satisfactory result was not obtained.

100: decorative sheet 1: base material 2: printing layer (printing section)
2 ': Ink 3: Hard material layer 4: Core material (core material layer)
5: Protective layer 6: Support layer

Claims (11)

A base material composed of a material including a resin material;
A printing layer formed by applying an ink containing a solvent that dissolves or swells the resin material to the substrate by an inkjet method;
A decorative sheet comprising: a hard material layer disposed on a surface side of the substrate on which the printed layer is provided.   The decorative sheet according to claim 1, wherein a thickness of the base material is 20 μm or more and 250 μm or less.   The decorative sheet according to claim 1 or 2, wherein the substrate is composed of polyethylene terephthalate.   The decorative sheet according to any one of claims 1 to 3, wherein the ink contains at least one compound selected from an alkylene glycol compound and a lactone compound as the solvent.   The decorative sheet according to any one of claims 1 to 4, wherein the hard material layer is made of a material containing a melamine resin.   The decorative sheet according to any one of claims 1 to 5, wherein a core material is provided on a surface of the substrate 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. An ink application step of applying an ink containing a solvent that dissolves or swells the resin material to a base material made of a material containing the resin material by an inkjet method;
Removing the solvent and forming a printed layer;
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 substrate on which the printed layer is provided.   The method for manufacturing a decorative sheet according to claim 8, further comprising a core material bonding step of bonding a core material to the base material.   The method for producing a decorative sheet according to claim 9, wherein the core material joining step is performed after the solvent removing step.   The method for producing a decorative sheet according to claim 9 or 10, wherein the ink contains at least one compound selected from an alkylene glycol compound and a lactone compound as the solvent.

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