Resin-impregnated decorative sheet and method of producing resin-impregnated decorative sheet

Abstract

To provide a resin-impregnated decorative sheet that has excellent wear resistance and can develop gross-matte ornamental design.SOLUTION: Provided is a resin-impregnated decorative sheet 10, wherein the resin-impregnated decorative sheet includes a porous substrate 1, a decorative layer 2, and a release layer 3 which has a pattern shape and contains a cured product of a curable resin X, arranged in this order in a thickness direction. Viewed from the thickness direction, the resin-impregnated decorative sheet has a first region overlapping with the release layer and a second region not overlapping with the release layer. In the second region, on the surface of the decorative layer opposite to the porous substrate, there is arranged, in this order from the decorative layer side, a cured resin layer 4 containing the cured product of a curable resin Y and a surface protective layer 5. Both the cured resin layer and the surface protective layer have a pattern shape, and the porous substrate contains the cured product of the curable resin Y.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to resin-impregnated decorative boards and methods for making resin-impregnated decorative boards. [Background technology]

[0002] Conventionally, resin-impregnated decorative boards have been known, which are obtained by impregnating a porous substrate with a precursor (uncured resin) such as melamine resin, and then curing the resin precursor by hot pressing. Resin-impregnated decorative boards are used for walls, furniture, floors, etc. in homes, stores, public facilities, etc.

[0003] Melamine decorative boards that express a glossy matte design are known. For example, Patent Document 1 discloses a decorative board having a release layer in a part of the surface of a porous substrate, and a thermosetting resin layer in the remaining part of the surface of the porous substrate that does not have the release layer, and the thermosetting resin is impregnated and cured in the porous substrate. In the manufacture of such melamine decorative boards, for example, a decorative sheet having a release layer in harmony with a pattern arranged on a part of the surface of titanium paper is used, and a process of impregnating a precursor (uncured resin) such as a melamine resin into the decorative sheet, a process of thermally curing the uncured resin after arranging a release film on the uncured resin layer to obtain a melamine layer, and a peeling process of peeling off the melamine layer in the area covering the release layer by peeling off the release film are performed. In addition, Patent Document 2 and Patent Document 3 disclose a method of using a transfer sheet including a substrate layer, a transfer layer, and an adhesion layer arranged on the surface of the transfer layer opposite to the substrate layer in the manufacture of a melamine decorative board. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6716877 [Patent Document 2] Patent Publication No. 2021-062580 [Patent Document 3] Patent Publication No. 2022-172800 Summary of the Invention [Problem to be solved by the invention]

[0005] As described above, in the manufacturing process of a melamine decorative board that expresses a glossy matte design, a peeling process of the melamine layer is required. Therefore, it is difficult to use the method of laminating an overlay paper or the like on the surface to improve abrasion resistance, which is performed in the conventional manufacturing of melamine decorative boards. Therefore, there is room for improvement in achieving both a glossy matte design and abrasion resistance.

[0006] The present disclosure has been made in consideration of the above circumstances, and has as its main object to provide a resin-impregnated decorative board that has excellent abrasion resistance and is capable of expressing a gloss matte design. [Means for solving the problem]

[0007] The present disclosure provides a resin-impregnated decorative board having, in that order in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of curable resin X, and when viewed in the thickness direction, the resin-impregnated decorative board has a first region that overlaps with the release layer and a second region that does not overlap with the release layer, and in the second region, a cured resin layer containing a cured product of curable resin Y and a surface protective layer are arranged in this order from the design layer side on the side of the design layer opposite the porous substrate, the cured resin layer and the surface protective layer each having a pattern shape, and the porous substrate contains the cured product of curable resin Y.

[0008] The present disclosure also provides a method for producing a resin-impregnated decorative board, comprising: a decorative sheet preparation step of preparing a decorative sheet having, in this order in a thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of curable resin X; an impregnation step of impregnating the porous substrate of the decorative sheet with curable resin Y via the design layer to form a curable resin layer that contains the curable resin Y and covers the design layer and the release layer; a transfer sheet preparation step of preparing a transfer sheet having a release film and a transfer layer disposed on one side of the release film, the transfer layer having a surface protective layer; and (i) a transfer sheet preparation step of transferring the decorative sheet, the curable resin layer, and the transfer sheet to a thickness of 1000 mm. and (ii) a laminate formation step of forming a laminate in which the surface of the transfer sheet facing the transfer layer faces the curable resin layer, a heating and pressurizing step of heating and pressurizing the laminate to form a cured resin layer from the curable resin layer while curing the curable resin Y, thereby obtaining a cured laminate, and a peeling step of peeling the release film of the transfer sheet from the cured laminate, thereby removing the cured resin layer and the transfer layer arranged in a first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer and the transfer layer arranged in a second region not overlapping with the release layer in the thickness direction. Effect of the Invention

[0009] The present disclosure has an effect of providing a resin-impregnated decorative board that has excellent abrasion resistance and is capable of expressing a gloss matte design. [Brief description of the drawings]

[0010] [Figure 1] 1 is a schematic cross-sectional view illustrating a resin-impregnated decorative board according to the present disclosure. [Diagram 2] 1 is a schematic cross-sectional view illustrating a resin-impregnated decorative board according to the present disclosure. [Diagram 3] 1 is a schematic cross-sectional view illustrating a method for producing a resin-impregnated decorative board according to the present disclosure. [Figure 4] 1 is a schematic cross-sectional view illustrating a method for producing a resin-impregnated decorative board according to the present disclosure. [Diagram 5] 1 is a schematic cross-sectional view illustrating a method for producing a resin-impregnated decorative board in Comparative Example 1. FIG. [Figure 6] FIG. 2 is a schematic diagram illustrating a method for measuring the peel strength between a release film and a surface protective layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following describes the embodiments with reference to the drawings. However, the present disclosure can be implemented in many different forms and is not limited to the description of the embodiments exemplified below. In addition, in order to clarify the description, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form, but this is merely an example and should not be interpreted as being limiting.

[0012] In this specification, when describing a mode in which another component is disposed on a certain component, the term "above" or "below" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified. In addition, in this specification, when describing a mode in which another component is disposed on the surface of a certain component, the term "on the surface" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified.

[0013] A. Resin-impregnated decorative board The resin-impregnated decorative board of the present disclosure will be described in detail below. Figures 1 and 2 are schematic cross-sectional views illustrating an example of a resin-impregnated decorative board of the present disclosure. As shown in Figure 1, the resin-impregnated decorative board 10 of the present disclosure is a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape and containing a cured product of a curable resin X, which are arranged in a thickness direction D. T In the thickness direction DT When viewed from the side, the laminate has a first region R1 overlapping with the release layer 3 and a second region R2 not overlapping with the release layer 3. In the present disclosure, in the second region R2, a cured resin layer 4 containing a cured product of the curable resin Y and a surface protective layer 5 are arranged on the surface of the design layer 2 opposite the porous substrate 1 from the design layer 2 side, and the porous substrate 1 contains a cured product of the curable resin Y. Also, as shown in FIG. 2(a), the resin-impregnated decorative board 10 in the present disclosure preferably has an adhesion layer 6 between the cured resin layer 4 and the surface protective layer 5 in the second region R2. As shown in FIG. 2(b), the porous substrate 1 may have a porous core substrate 40 on the surface opposite the design layer 2.

[0014] Patent Documents 2 and 3 disclose a method for producing a melamine decorative board using a transfer sheet including a base layer, a transfer layer, and an adhesion layer provided on the surface of the transfer layer opposite to the base layer. This method produces a melamine decorative board having a structure in which the adhesion layer and the transfer layer are directly arranged on the impregnated base paper. This type of melamine decorative board has poor abrasion resistance because it does not have a hard cured resin layer (melamine layer) between the impregnated base paper and the transfer layer. In addition, since the ionizing radiation curable resin of the transfer layer is photocured after transfer, the melamine resin is easily deteriorated, such as discolored and embrittled, by the irradiated ionizing radiation curable resin.

[0015] According to the present disclosure, the release layer 3 containing the cured product of the curable resin X arranged in the first region R1 and the cured resin layer 4 and surface protective layer 5 containing the cured product of the curable resin Y arranged in the second region show different design senses. For example, in the resin-impregnated decorative board 10 shown in FIG. 1, the second region R2 gives a glossy design sense, and the first region R1 gives a matte design sense, thereby expressing a gloss-matte design sense. Furthermore, by having both the cured resin layer 4 and the surface protective layer 5 in the second region R2, it has abrasion resistance.

[0016] I. First and second areas The resin-impregnated decorative board of the present disclosure has a first region R1 that overlaps with the release layer 3, and a second region R2 that does not overlap with the release layer 33. The first region does not usually have a surface protective layer. For example, it is possible that the first region has a small amount of surface protective layer at the boundary with the second region (when viewed in the thickness direction, a portion of the surface protective layer slightly protrudes from the second region into the first region), and in such a case, the first region has at least a release layer exposed from the surface protective layer when viewed in the thickness direction. Also, in the first region, the release layer 3 may be the outermost layer.

[0017] In the second region R2, a cured resin layer 4 containing a cured product of the curable resin Y and a surface protective layer 5 are arranged in this order from the side of the design layer 2 on the side opposite the porous substrate 1 of the design layer 2. The cured resin layer 4 and the surface protective layer 5 each have a pattern shape. The cured resin layer 4 and the surface protective layer 5 correspond to, for example, a pattern shape that is an inversion of the pattern shape of the release layer 3. The second region R2 is, for example, a porous substrate 1, a design layer 2, a cured resin layer 4, and a surface protective layer 5 arranged in a thickness direction D T 2(a), the second region preferably has an adhesive layer 6 between the cured resin layer 4 and the surface protective layer 5. In this case, the second region R2 has, for example, the porous substrate 1, the design layer 2, the cured resin layer 4, the adhesive layer 6, and the surface protective layer 5 arranged in the thickness direction D. T In this order:

[0018] In the present disclosure, in the second region, the total thickness of the layers disposed on the surface opposite to the porous substrate of the design layer is preferably 7 μm or more, more preferably 14 μm or more. If the total thickness is within the above range, the abrasion resistance is improved. On the other hand, the total thickness is preferably 60 μm or less, more preferably 40 μm or less, and particularly preferably 30 μm or less. If the total thickness is within the above range, the cured resin layer and the transfer layer in the first region can be easily peeled off and removed in the manufacturing process of the resin-impregnated decorative board, and the gloss matte design can be stably expressed.

[0019] In the second region, the total thickness of the layers disposed on the surface opposite to the porous substrate of the design layer is the thickness direction D T In this case, it refers to the length from the surface of the design layer 2 opposite the porous substrate 1 (reference surface p) to the surface of the resin-impregnated decorative board 10 in the second region R2 facing the surface protective layer 5 (outermost surface q). "The surface of the resin-impregnated decorative board facing the surface protective layer in the second region" refers to the surface of the resin-impregnated decorative board 10 in the second region R2 that is located on the surface protective layer 5 side, with the porous substrate 1 as the reference. For example, when the layers arranged on the surface of the design layer opposite the porous substrate are a cured resin layer, an adhesion layer, and a surface protective layer, it means the total thickness of these layers.

[0020] In the present disclosure, the surface height difference between the first region and the second region is, for example, preferably 5 μm or more and 50 μm or less, more preferably 5 μm or more and 28 μm or less, and particularly preferably 8 μm or more and 20 μm or less. T In this case, it refers to the length from the surface (outermost surface r) of the resin-impregnated decorative board 10 on the release layer 3 side in the first region R1 to the surface (outermost surface q) of the resin-impregnated decorative board 10 on the surface protective layer 5 side in the second region R2. The outermost surface r is preferably lower than the outermost surface q.

[0021] II. About each layer 1.Surface protection layer The resin-impregnated decorative board of the present disclosure has a surface protective layer on the side of the cured resin layer opposite to the design layer in the second region. The surface protective layer has a pattern shape, for example, a pattern shape that corresponds to an inverted pattern shape of the release layer. The surface protective layer contributes to improving the abrasion resistance of the resin-impregnated decorative board. The surface protective layer and the cured resin layer may be arranged to be in direct contact with each other, or may not be in direct contact with each other.

[0022] The surface protective layer contains a cured product (crosslinked structure) of a curable resin. In the present disclosure, the curable resin in the surface protective layer may be referred to as a curable resin Z. The proportion of the cured product of the curable resin Z is, for example, 70% by mass or more, may be 90% by mass or more, may be 95% by mass or more, or may be 100% by mass, based on the total resin components constituting the surface protective layer.

[0023] Examples of the curable resin Z include ionizing radiation curable resins and thermosetting resins. The ionizing radiation curable resin is a compound having an ionizing radiation curable functional group (hereinafter, also referred to as "ionizing radiation curable compound"). Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet ray curable resins. Among these, electron beam curable resins are preferred because they do not require a polymerization initiator, have less odor, and are less likely to be colored. In addition, electron beam curable resins have the advantage that they are less likely to cause poor curing due to weathering agents.

[0024] The ionizing radiation curable functional group is a group that crosslinks and cures when irradiated with ionizing radiation. Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV). Other examples of ionizing radiation include electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.

[0025] As the ionizing radiation curable resin, for example, a compound having a (meth)acryloyl group is preferable. The (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In addition, as the ionizing radiation curable resin, in addition to a compound having a (meth)acryloyl group, a compound having a functional group having an ethylenic double bond such as a vinyl group or an allyl group can be mentioned. In the present disclosure, only one type of ionizing radiation curable resin may be used, or two or more types may be used.

[0026] The number of functional groups of the ionizing radiation curable compound is preferably from 2 to 20, more preferably from 2 to 18, and even more preferably from 2 to 15. This is because the abrasion resistance of the surface protective layer is improved.

[0027] An example of the ionizing radiation curable resin (ionizing radiation curable compound) is urethane (meth)acrylate. (Meth)acrylate refers to acrylate or methacrylate. In this case, the cured product of the curable resin Z contains a (meth)acrylic component and a urethane component. A (meth)acrylic component refers to an acrylic component or a methacrylic component. A urethane component refers to a urethane bond. In addition to urethane (meth)acrylate, examples of the ionizing radiation curable resin include epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate.

[0028] The urethane (meth)acrylate is preferably a caprolactone-based urethane (meth)acrylate, since this makes it easier to improve the weather resistance and scratch resistance of the surface protective layer. In addition, as the ionizing radiation curable resin, a caprolactone-based urethane (meth)acrylate and a urethane (meth)acrylate that is not modified with caprolactone may be used. In this case, the content of the caprolactone-based urethane (meth)acrylate contained in the surface protective layer is set to M CLUA The content of urethane (meth)acrylate not modified with caprolactone is M UA Let us assume that UA and M. CLUA M for the sum of CLUA Mass ratio (M CLUA / (M UA +M CLUA )) is, for example, 10% by mass or more and 90% by mass or less, alternatively 20% by mass or more and 80% by mass or less, or alternatively 30% by mass or more and 70% by mass or less.

[0029] When a caprolactone-based urethane (meth)acrylate is used as the ionizing radiation curable compound, the number of functional groups of the caprolactone-based urethane (meth)acrylate is preferably from 2 to 9, more preferably from 2 to 5. By setting the number of functional groups of the caprolactone-based urethane (meth)acrylate within the above range, abrasion resistance tends to be improved.

[0030] Caprolactone-based urethane (meth)acrylate can usually be obtained by reacting caprolactone-based polyol, organic isocyanate, and hydroxy (meth)acrylate. For example, the synthesis method includes reacting polycaprolactone-based polyol with organic polyisocyanate to generate a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then reacting it with hydroxy (meth)acrylate.

[0031] As the caprolactone-based polyol, commercially available products can be used, preferably those having two hydroxyl groups and a number average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. In addition, polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can be used by mixing one or more polyols at any ratio. As the organic polyisocyanate, diisocyanates having two isocyanate groups are preferred, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferred. As the hydroxy(meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferred.

[0032] When using a caprolactone-based polyol, the caprolactone-based urethane (meth)acrylate is preferably a caprolactone diol-based urethane (meth)acrylate. The caprolactone diol-based urethane (meth)acrylate refers to a urethane (meth)acrylate having a diethylene glycol terminal among caprolactone-based urethane (meth)acrylates. By using the caprolactone diol-based urethane (meth)acrylate, it is possible to suppress the occurrence of cracks and whitening in the surface protective layer.

[0033] The number average molecular weight of the ionizing radiation curable resin (ionizing radiation curable compound) is, for example, from 1,000 to 10,000, and may be from 2,000 to 10,000. The number average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0034] For example, when the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable resin composition preferably contains at least one of a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, and thioxanthones. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0035] The curable resin Z may be a thermosetting resin. Details of the thermosetting resin are the same as those described later for the adhesion layer.

[0036] The surface protective layer preferably contains a weathering agent. The cured resin layer in the present disclosure is prone to deterioration such as discoloration and embrittlement due to ultraviolet rays. Therefore, by the surface protective layer containing a weathering agent, the deterioration of the cured resin layer can be suppressed. Examples of the weathering agent include an ultraviolet absorber and a light stabilizer. The surface protective layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The surface protective layer may contain one or more ultraviolet absorbers. Similarly, the surface protective layer may contain one or more light stabilizers.

[0037] Examples of the ultraviolet absorbing agent contained in the surface protective layer include organic ultraviolet absorbing agents such as triazine-based ultraviolet absorbing agents, benzotriazole-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, oxybenzophenone-based ultraviolet absorbing agents, salicylic acid ester-based ultraviolet absorbing agents, and cyano(meth)acrylate-based ultraviolet absorbing agents, and inorganic ultraviolet absorbing agents such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based ultraviolet absorbing agents are more preferred.

[0038] Examples of triazine-based ultraviolet absorbers include hydroxyphenyl triazine-based ultraviolet absorbers. Examples of hydroxyphenyl triazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, azine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0039] The content of the ultraviolet absorber in the surface protective layer is, for example, 0.5 parts by mass or more and 10 parts by mass or less, or may be 0.8 parts by mass or more and 8 parts by mass or less, or may be 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the ultraviolet absorber is high, bleeding out of the ultraviolet absorber may occur, and if the content of the ultraviolet absorber is low, sufficient ultraviolet absorbing performance may not be obtained.

[0040] The light stabilizer contained in the surface protective layer may be, for example, a hindered amine light stabilizer. Examples of the hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0041] The content of the light stabilizer in the surface protective layer is, for example, 1 part by mass to 10 parts by mass, or may be 1.5 parts by mass to 8 parts by mass, or may be 2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the light stabilizer is high, bleeding out of the light stabilizer may occur, and if the content of the light stabilizer is low, sufficient light stability may not be obtained.

[0042] The surface protective layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, an anti-wear agent, an antibacterial agent, an antiviral agent, and an antifungal agent.

[0043] The surface protective layer may have a single layer structure or a multilayer structure in which a plurality of layers are laminated. The surface protective layer can be formed, for example, by transfer using a transfer sheet described later.

[0044] The thickness of the surface protective layer is, for example, preferably 2 μm or more, more preferably 3 μm or more, and particularly preferably 4 μm or more. When the thickness of the surface protective layer is in the above range, sufficient abrasion resistance is obtained. On the other hand, the thickness of the surface protective layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. When the thickness of the surface protective layer is in the above range, the cured resin layer and the transfer layer in the first region can be easily peeled off and removed in the manufacturing process of the resin-impregnated decorative board. The thickness of each layer is determined, for example, by observing the cross section of each layer using a laser microscope and calculating the arithmetic mean value of thicknesses measured at any three points.

[0045] The surface of the surface protective layer on the side of the cured resin layer may be subjected to a surface treatment for the purpose of improving adhesion to other layers (e.g., an adhesive layer). Examples of the surface treatment include a corona discharge treatment and a plasma treatment.

[0046] 2. Cured resin layer The resin-impregnated decorative board of the present disclosure has a cured resin layer containing a cured product of curable resin Y in the second region. The cured resin layer has a pattern shape, for example, corresponding to a pattern shape obtained by inverting the pattern shape of the release layer. The cured resin layer is disposed between the surface protective layer and the design layer.

[0047] A wide variety of thermosetting resins can be used as the curable resin Y. Examples of the curable resin Y include melamine-based resins (melamine-based resin precursors), melamine-urea co-condensation resins, unsaturated polyester-based resins, polyurethane-based resins (including two-component curing polyurethanes), epoxy-based resins, aminoalkyd-based resins, phenol-based resins, urea-based resins, diallyl phthalate-based resins, guanamine-based resins, silicon-based resins, and polysiloxane-based resins.

[0048] The thickness of the cured resin layer is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more. When the thickness of the cured resin layer is in the above range, sufficient abrasion resistance is obtained. On the other hand, the thickness of the cured resin layer is, for example, preferably 50 μm or less, more preferably 30 μm or less, even more preferably 27 μm or less, and particularly preferably 20 μm or less. When the thickness of the cured resin layer is in the above range, the cured resin layer and the transfer layer in the first region can be easily peeled off and removed in the manufacturing process of the resin-impregnated decorative board. The thickness of the cured resin layer is preferably larger than the thickness of the release layer. That is, it is preferable that the cured resin layer protrudes from the release layer in the thickness direction.

[0049] 3.Release layer The release layer in the present disclosure is disposed on the surface of the design layer opposite the porous substrate, has a pattern shape, and contains a cured product of curable resin X. When the design layer has a design layer, it is preferable that at least a part of the release layer is disposed on the surface of the design layer opposite the porous substrate.

[0050] In addition, the release layer is preferably arranged so as to be in harmony with the pattern of the design layer. "In harmony" means that the shapes and positions of the two target patterns are roughly the same. Specifically, it means that the shapes and positions of the pattern of the release layer and at least a part of the pattern constituting the design of the design layer are in harmony to an extent that does not impair the sense of realism and luxury. By arranging the pattern of the release layer so as to be in harmony with the pattern of the design layer, a high quality texture can be obtained.

[0051] The release layer contains a resin component. The resin component is typically a cured product (crosslinked structure) of a curable resin. In the present disclosure, the curable resin in the release layer may be referred to as a curable resin X. The release layer contains a cured product of the curable resin, so that a release layer having good abrasion resistance can be obtained. In addition, the release layer contains a cured product of the curable resin, so that the release layer has good releasability with respect to the cured resin layer.

[0052] Examples of the curable resin include ionizing radiation curable resins and thermosetting resins. Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet ray curable resins.

[0053] The ionizing radiation curable resin (ionizing radiation curable compound) is not limited as long as it undergoes a crosslinking polymerization reaction by irradiation with ionizing radiation and changes into a three-dimensional polymer structure. Examples of the ionizing radiation curable resin include prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule that can be crosslinked by irradiation with ionizing radiation. In the present disclosure, only one type of ionizing radiation curable resin may be used, or two or more types may be used. Among these, it is preferable to use at least one of a multifunctional monomer and an oligomer as the ionizing radiation curable resin. In the present disclosure, only one type of ionizing radiation curable resin may be used, or two or more types may be used. Among these, it is preferable to use at least one of a multifunctional monomer and an oligomer as the ionizing radiation curable resin.

[0054] Examples of the ionizing radiation curable compound include (meth)acrylate-based resins such as urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate; silicon-based resins such as siloxane; ester-based resins; and epoxy-based resins. (Meth)acrylate-based resins refer to acrylate-based resins or methacrylate-based resins.

[0055] The weight average molecular weight of the ionizing radiation curable compound is, for example, from 500 to 80,000, and may be from 1,000 to 50,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0056] The ionizing radiation curable compound preferably contains at least a polyfunctional monomer or oligomer having a weight average molecular weight of at least 500. Examples of such polyfunctional monomers or oligomers include (meth)acrylate resins such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate.

[0057] On the other hand, examples of thermosetting resins include unsaturated ester resins, urethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine urea co-condensation resins, silicon resins, and siloxane resins.

[0058] The release layer may contain a matting agent. Examples of the matting agent include inorganic particles and synthetic resin particles. Examples of the inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of the synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin wax (e.g., polypropylene wax, polyethylene wax).

[0059] The average particle size of the matting agent is, for example, 0.3 μm or more and 10 μm or less, and may be 0.5 μm or more and 7 μm or less, or 1 μm or more and 5 μm or less. The average particle size is D50 according to the volume-based particle size distribution measured by a laser diffraction scattering method. The content of the matting agent may be, for example, 5 parts by mass or more and 40 parts by mass or less, and may be 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component of the release layer.

[0060] The release layer may contain a release agent. The addition of the release agent improves the releasability. Examples of the release agent include silicone-based release agents such as silicone oil, wax-based release agents such as polyolefin wax, and fluorine-based release agents. The silicone oil may be reactive silicone oil or non-reactive silicone oil.

[0061] Reactive silicone oil refers to modified silicone oils that have an organic group introduced into the side chain or end, and have reactivity due to the nature of the organic group introduced.Specific examples of reactive silicone oils include modified silicone oil side chain type, modified silicone oil both ends type, modified silicone oil one end type, modified silicone oil side chain both ends type, etc., in which the organic group introduced is amino-modified, epoxy-modified, mercapto-modified, carboxyl-modified, carbinol-modified, phenol-modified, methacryl-modified, heterogeneous functional group-modified, etc.These reactive silicone oils can be used alone or in combination of two or more.

[0062] The non-reactive silicone oil is not particularly limited as long as it is a silicone oil that does not have a reactive functional group such as an amino group, an epoxy group, a mercapto group, a carboxy group, a hydroxy group, a (meth)acryloyl group, or an allyl group. Examples of the non-reactive silicone oil include silicone oils made of polysiloxane, polyether-modified silicone oils, aralkyl-modified silicone oils, fluoroalkyl-modified silicone oils, long-chain alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, higher fatty acid amide-modified silicone oils, and phenyl-modified silicone oils. These non-reactive silicone oils can be used alone or in combination of two or more kinds.

[0063] The content of the release agent is, for example, 0.1 parts by mass or more and 50 parts by mass or less, 0.5 parts by mass or more and 20 parts by mass or less, 3 parts by mass or more and 20 parts by mass or less, or 3 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the resin component of the release layer. The release layer may be colorless or colored. In the latter case, it is preferable that the release layer contains a colorant. The colorant may be the same as the colorant used in the pattern layer described later.

[0064] The pure water contact angle of the surface of the release layer is, for example, 90° or more, and preferably 100° or more. The release layer having the above pure water contact angle has good releasability of the cured resin layer, and is therefore likely to become a resin-impregnated decorative plate with improved gloss matte design. The pure water contact angle of the release layer is, for example, 130° or less, and preferably 125° or less.

[0065] In the present disclosure, the pure water contact angle of the surface of the release layer is a value obtained by measuring by the following method. The surface of the release layer refers to the surface of the release layer opposite to the design layer. That is, the decorative sheet is placed on a horizontal surface so that the release layer is the upper surface. Next, a water droplet (pure water, 2.0 μL) is dropped on the release layer (first region) from a direction perpendicular to the horizontal surface. At this time, the water droplet is not dropped on the boundary between the first region and the second region, but is dropped so that the entire water droplet is in contact with the release layer. After dropping the water droplet, wait for 1 second, and use a contact angle meter to measure the contact angle between the release layer and pure water. The above measurement is performed at any 10 points, and the average value is taken as the pure water contact angle.

[0066] The pure water contact angle can be adjusted by adjusting the content of the release agent and the thickness of the release layer. For example, the pure water contact angle can be increased by increasing the content of the release agent. For example, the pure water contact angle can be increased by increasing the thickness of the release layer.

[0067] The release layer may contain additives such as ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, coupling agents, plasticizers, antifoaming agents, fillers, thermal radical generators, aluminum chelating agents, etc. The thickness of the release layer is not particularly limited, but is, for example, 0.1 μm or more and 20 μm or less.

[0068] Also, when the decorative sheet is viewed from the thickness direction, if the area of ​​the release layer is S1 and the area of ​​the design layer is S2, the ratio of S1 to S2 (S1 / S2) is, for example, 5% or more, and may be 10% or more. On the other hand, S1 / S2 is, for example, 80% or less, 70% or less, or 60% or less. Also, when the decorative sheet is viewed from the thickness direction, if the area of ​​the release layer is S1 and the area of ​​the porous substrate is S3, the ratio of S1 to S3 (S1 / S3) is, for example, 5% or more, and may be 10% or more. On the other hand, S1 / S3 is, for example, 80% or less, 70% or less, or 60% or less.

[0069] The release layer can be obtained, for example, by applying a release layer-forming ink containing a curable resin to the surface of the design layer opposite the porous substrate, and then curing the ink.

[0070] When the ink for forming the release layer contains an electron beam curable resin, the cured product of the electron beam curable resin is usually obtained by irradiating it with an electron beam. Examples of the electron beam source include various electron beam accelerators such as Cockcroft-Walt type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type. The energy of the electron beam is, for example, 100 kV or more and 1000 kV or less, or may be 100 kV or more and 300 kV or less. The irradiation dose of the electron beam is, for example, 2 Mrad or more and 15 Mrad or less.

[0071] When the ink for forming the release layer contains an ultraviolet-curable resin, the ultraviolet-curable resin is usually cured by irradiating it with ultraviolet light. Examples of ultraviolet light sources include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps. The wavelength of the ultraviolet light is, for example, 190 nm or more and 380 nm or less.

[0072] When the ink for forming the release layer contains a thermosetting resin, it is usually heated to obtain a cured product of the thermosetting resin. The heating temperature is appropriately set according to the type of the thermosetting resin. The ink for forming the release layer may contain a crosslinking agent, a curing agent such as a polymerization initiator, and a polymerization accelerator together with the thermosetting resin. Examples of the curing agent include isocyanate, organic sulfonate, organic amine, peroxide (e.g., methyl ethyl ketone peroxide), and radical initiator (azoisobutylnitrile).

[0073] The ink for forming the release layer may contain a solvent as necessary. Examples of the solvent include water; hydrocarbon compounds such as toluene and xylene; alcohol compounds such as methanol, ethanol and methyl glycol; ketone compounds such as acetone and methyl ethyl ketone; ester compounds such as methyl formate and ethyl acetate; nitrogen-containing compounds such as N-methylpyrrolidone and N,N-dimethylformamide; ether compounds such as tetrahydrofuran and dioxane; halogenated hydrocarbon compounds such as methylene chloride and chloroform; and dimethyl sulfoxide. The ink for forming the release layer is preferably less hydrophilic than uncured resins such as hydrophilic melamine resins.

[0074] 4. Design layer The design layer in the present disclosure is disposed on one surface of the porous substrate. The design layer preferably has a pattern.

[0075] Examples of patterns of the design layer include organic patterns, inorganic patterns, and abstract patterns. Organic patterns are patterns derived from the life activities of living organisms such as animals and plants. Inorganic patterns are patterns that do not fall under the category of organic patterns. Abstract patterns are patterns that interpret objects (e.g., images that exist in nature) abstractly and do not express a clear shape. Examples of organic patterns include wood grain patterns, leather patterns, floral patterns, and botanical patterns. Examples of inorganic patterns include stone patterns, concrete patterns, sand patterns, cloth patterns, metal patterns, tile patterns, and brick masonry patterns. Examples of abstract patterns include flickering patterns (e.g., ink flickering patterns), smoke patterns, and marble patterns.

[0076] The design layer has, for example, a pattern layer. The design layer may have a solid layer on the porous substrate side of the pattern layer. In the present disclosure, the pattern layer means a layer formed partially (particularly in a pattern) on one side of the porous substrate. The solid layer means a layer formed on the entire surface of one side of the porous substrate.

[0077] The design layer contains, for example, a colorant and a resin component. Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc oxide, red iron oxide, Prussian blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; and luminous pigments. Dyes may also be used as the colorant.

[0078] Examples of the resin component include (meth)acrylic resins, ester urethane resins, acrylamide resins, ethylene oxide resins, N-vinylpyrrolidone resins, ester resins, amide resins, vinyl acetate resins, vinyl chloride resins, urethane (meth)acrylic resins, natural rubber, and synthetic rubber. Among these, (meth)acrylic resins and urethane (meth)acrylic resins are preferred.

[0079] It is preferable that the resin component contains a resin having at least one polar group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group. By containing the resin having the polar group, the impregnation of the curable resin Y into the porous substrate is improved.

[0080] A resin having a polar group contains at least one of the following polar groups: a hydroxy group (-OH), an amino group (-NH2), and a carboxy group (-COOH). The polar group may be ionized and stabilized, for example, by the influence of a solvent or other functional groups. Therefore, the "hydroxy group (-OH)" is in the ionized state, "-O - " and the above "amino group (-NH2)" is in the ionized state "-NH3 + " is a concept that includes "carboxyl group (-COOH)" in its ionized state, "-COO - " is a concept that includes

[0081] Examples of resins having one or more polar groups, such as a hydroxy group (-OH), an amino group (-NH2), or a carboxy group (-COOH), include aqueous proteins such as casein, cellulose derivatives such as cellulose, acetyl cellulose, cellulose nitrate, hydroxypropyl cellulose, and carboxymethyl cellulose, polyvinyl alcohol derivatives such as polyvinyl butyral resin, amino resins such as melamine resin, (meth)acrylic acid resins, phenolic resins, acrylic polyols, and natural polymers (for example, polynucleotides, polypeptides, and polysaccharides).

[0082] The design layer in the present disclosure preferably contains one or more of casein, melamine-based resin, polyvinyl alcohol, polyvinyl alcohol derivative, cellulose, and cellulose derivative as a resin having a polar group, and more preferably contains casein. As casein, α-casein, β-casein, γ-casein, or a mixture thereof can be used. As casein, derivatives such as sodium caseinate and ammonium caseinate can be used alone or in combination.

[0083] The ratio of the resin having the polar group to the resin components contained in the design layer is, for example, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more. On the other hand, the ratio of the resin having the polar group is, for example, 100% by mass or less, or 90% by mass or less. If the content of the resin having the polar group is within the above range, the penetration of the ink of the release layer into the porous substrate can be further suppressed without inhibiting the penetration of the curable resin Y into the porous substrate.

[0084] The design layer may contain additives such as fillers (e.g., silica), extender pigments (e.g., organic beads), neutralizers, surfactants, etc., as necessary. The thickness of the design layer is not particularly limited, but is, for example, 0.1 μm or more and 20 μm or less.

[0085] The method for forming the design layer includes, for example, a coating method using an ink for forming the design layer containing a colorant, a binder resin, and a solvent (or a dispersion medium). For example, the ink for forming the design layer is applied to one side of the porous substrate and dried to obtain the design layer.

[0086] Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water.

[0087] Examples of the coating method include printing. Examples of the printing method include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Examples of the coating method for forming a solid layer include various coating methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating.

[0088] 5. Porous base material The porous substrate in the present disclosure contains a cured product of an uncured resin (curable resin Y). Examples of the porous substrate include permeable fibrous substrates. Examples of the permeable fibrous substrate include paper, synthetic paper, nonwoven fabric, and woven fabric. Examples of the paper include titanium paper, tissue paper, craft paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, parchment paper, and Japanese paper. In addition, vinyl wallpaper rolls (paper dry-laminated with polyvinyl chloride resin) can also be used as the fibrous substrate. Other examples of the fibrous substrate include nonwoven fabrics or woven fabrics containing inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber. Other examples of the fibrous substrate include nonwoven fabrics or woven fabrics containing synthetic resin fibers such as polyester, vinylon, polyethylene, and polypropylene. Among these porous substrates, titanium paper, thin paper, kraft paper, coated paper, art paper, parchment paper, paraffin paper and Japanese paper are preferred in terms of impregnation with uncured resin. Titanium paper is particularly preferred as a porous substrate because it has excellent impregnation with uncured resin and excellent hiding power.

[0089] The porous substrate may be colored. For example, a colorant is added at the manufacturing stage of the porous substrate to obtain a colored porous substrate. For example, when the porous substrate is paper, a colorant is added at the papermaking stage to obtain colored paper. Examples of colorants include inorganic pigments such as titanium dioxide, carbon black, and iron oxide, organic pigments such as phthalocyanine blue, and various dyes. In addition, the porous substrate may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers, as necessary.

[0090] The basis weight of the porous substrate is not particularly limited, but is, for example, 40 g / m 2 More than 150g / m 2The thickness of the porous substrate is not particularly limited, but is, for example, 50 μm or more and 170 μm or less. For example, in order to improve the adhesion of the ink that forms the design layer, the surface of the porous substrate on the design layer side may be subjected to a corona discharge treatment.

[0091] The cured product of the curable resin Y filled in the porous substrate and the cured product of the curable resin Y contained in the cured resin layer are formed from the same curable resin Y, as described below.

[0092] 6.Other The resin-impregnated decorative board of the present disclosure essentially includes the porous substrate, design layer, release layer, cured resin layer, and surface protective layer described above, but may also include other layers.

[0093] (1) Adhesion layer The resin-impregnated decorative board of the present disclosure preferably has an adhesive layer 6 between the cured resin layer 4 and the surface protective layer 5 in the second region R2, as shown in FIG. 2(a), for example. The adhesive layer preferably has a pattern shape. The adhesive layer corresponds to, for example, a pattern shape obtained by inverting the pattern shape of the release layer. By disposing the adhesive layer, the adhesiveness between the cured resin layer and the transfer layer (including at least the surface protective layer) is improved. As a result, in the manufacturing process of the resin-impregnated decorative board, the transfer layer disposed in the second region is left on the decorative sheet side, and the cured resin layer and the transfer layer disposed in the first region are easily peeled off and removed, so that a good gloss matte design can be stably expressed. The adhesive layer and the surface protective layer may be disposed so as to be in direct contact with each other, or may be disposed through another layer. The adhesive layer and the cured resin layer may be disposed so as to be in direct contact with each other, or may be disposed through another layer.

[0094] The adhesive layer contains a cured product (crosslinked structure) of the curable resin α. The cured product of the curable resin α preferably contains a (meth)acrylic component and a urethane component. The proportion of the cured product of the curable resin α is, for example, 70% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass, based on the total resin components constituting the adhesive layer.

[0095] Examples of the curable resin α include thermosetting resins. Examples of the thermosetting resin include urethane (meth)acrylic resins. Examples of the thermosetting resin include urethane (meth)acrylic resins, (meth)acrylic resins, urethane resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins, in addition to urethane (meth)acrylic resins. In the present disclosure, only one type of thermosetting resin may be used, or two or more types may be used. In addition, the thermosetting resin composition containing the thermosetting resin may further contain a curing agent such as an isocyanate curing agent or an epoxy curing agent.

[0096] The urethane (meth)acrylic resin is preferably a urethane (meth)acrylic copolymer, and more preferably a polycarbonate-based urethane (meth)acrylic copolymer. The polycarbonate-based urethane (meth)acrylic copolymer is a resin obtained by radically polymerizing a (meth)acrylic monomer with a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol with a (di)isocyanate.

[0097] Examples of the (di)isocyanate include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, o-isocyanate phenylsulfonyl isocyanate, and p-isocyanate phenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; and alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0098] Examples of the (meth)acrylic monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0099] In the polycarbonate-based urethane (meth)acrylic copolymer, the mass ratio of the urethane component to the total of the (meth)acrylic component and the urethane component ([urethane component] / ([(meth)acrylic component]+[urethane component]) is, for example, 65% by mass or more and 95% by mass or less, and may be 70% by mass or more and 90% by mass or less. If the mass ratio of the urethane component is too high, the adhesion (particularly initial adhesion) to the surface protective layer may be reduced.

[0100] The adhesive layer preferably contains a weathering agent. Examples of weathering agents include an ultraviolet absorber and a light stabilizer. The adhesive layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The preferred types and modes of the weathering agent are the same as those described for the surface protective layer, and therefore will not be described here. In particular, the adhesive layer preferably contains a triazine-based ultraviolet absorber. The adhesive layer preferably contains a hindered amine-based light stabilizer.

[0101] The content of the ultraviolet absorber in the adhesion layer is, for example, 0.1 parts by mass or more and 50 parts by mass or less, or may be 3 parts by mass or more and 40 parts by mass or less, or may be 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component. The content of the ultraviolet absorber in the adhesion layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the ultraviolet absorber in the surface protective layer (content relative to 100 parts by mass of the resin component).

[0102] The content of the light stabilizer in the adhesion layer is, for example, 0.1 to 15 parts by mass, or 1 to 15 parts by mass, or 3 to 10 parts by mass, relative to 100 parts by mass of the resin component. The content of the light stabilizer in the adhesion layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the light stabilizer in the surface protective layer (content relative to 100 parts by mass of the resin component).

[0103] The adhesion layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, and an antiblocking agent.

[0104] The thickness of the adhesion layer is, for example, 1 μm or more, preferably 2 μm or more. When the adhesion layer is in the above range, the adhesion between the transfer layer and the cured resin layer in the second region is improved, and peeling of the transfer layer can be suppressed. On the other hand, the thickness of the adhesion layer may be, for example, 5 μm or less, or 4 μm or less. When the thickness of the adhesion layer is in the above range, the cured resin layer and the transfer layer in the first region can be easily peeled off and removed in the manufacturing process of the resin-impregnated decorative board.

[0105] (2) Core substrate The resin-impregnated decorative board of the present disclosure may have a porous core substrate 40 on the surface of the porous substrate 1 opposite to the design layer 2, as shown in Fig. 2(b). An example of the core substrate is phenolic resin-impregnated paper. The phenolic resin-impregnated paper is paper obtained by impregnating kraft paper, which is a core paper, with phenolic resin and drying it.

[0106] 7.Applications The resin-impregnated decorative board in the present disclosure is used, for example, by being disposed on the surface of a substrate. Examples of substrates include wood members, resin members, metal members, and ceramic members. Examples of wood members include wood veneer, wood plywood, particle board, and wood fiberboard. Examples of wood used for wood members include cedar, cypress, pine, and lauan. Examples of resins used for resin members include vinyl chloride resins, (meth)acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenolic resins, cellulose resins, carbonate resins, melamine resins, and rubber. Examples of metals used for metal members include iron and aluminum. The material of the ceramic members may be ceramics such as glass and porcelain, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (lightweight aerated concrete).

[0107] The resin-impregnated decorative board of the present disclosure can be used, for example, as a building material or furniture. The building material can be an interior material or an exterior material. The building material can be, for example, a wall, a floor, a ceiling, a door, or a shelf. The furniture can be, for example, a table, a desk, or a cabinet.

[0108] B. Manufacturing method of resin-impregnated decorative panels Hereinafter, the manufacturing method of the resin-impregnated decorative board in the present disclosure will be described in detail. Figures 3 and 4 are schematic cross-sectional views illustrating the manufacturing method of the resin-impregnated decorative board in the present disclosure. First, as shown in Figure 3(a), a decorative sheet 15 having a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape and containing a cured product of a curable resin X in this order in the thickness direction is prepared (decorative sheet preparation step). Next, as shown in Figure 3(b), the porous substrate 1 of the decorative sheet 15 is impregnated with the curable resin Y through the design layer 2, and a curable resin layer 30 containing the curable resin Y and covering the design layer and the release layer is formed (impregnation step). Next, as shown in Figure 3(c), a transfer sheet 20 is prepared having a release film 21 and a transfer layer 22 arranged on one side of the release film 21, and the transfer layer 22 has a surface protective layer 5 (transfer sheet preparation step). The transfer layer 22 of the transfer sheet 20 shown in Fig. 3(c) has an adhesive layer 6 on the surface of the surface protective layer 5 opposite to the release film 21. Next, as shown in Fig. 3(d), (i) the decorative sheet 15, the curable resin layer 30, and the transfer sheet 20 are laminated in the thickness direction D T (ii) forming a laminate 11 arranged such that the surface of the transfer sheet 20 on the transfer layer 22 side faces the curable resin layer 30 (laminate formation step). Next, as shown in FIG. 4(a), the laminate 11 is heated and pressurized to form the curable resin layer 4 from the curable resin layer 30 while curing the curable resin Y, thereby obtaining a cured laminate 12 (heating and pressing step). Next, as shown in FIG. 4(b), a peeling step is performed in which the release film 21 of the transfer sheet 22 is peeled off from the cured laminate 12 to remove the cured resin layer 4 and the transfer layer 22 arranged in the first region R1 overlapping with the release layer 3 in the thickness direction, while leaving the cured resin layer 4 and the transfer layer 22 arranged in the second region R2 not overlapping with the release layer 3 in the thickness direction.

[0109] According to the present disclosure, it is possible to easily manufacture a resin-impregnated decorative board that has excellent abrasion resistance and can express a gloss matte design. Furthermore, since a decorative sheet containing a cured product of curable resin X, i.e., a pre-cured release layer, is used, deterioration of the cured resin layer due to ultraviolet irradiation, etc. can be suppressed.

[0110] 1.Decorative sheet preparation process As shown in FIG. 3(a), the decorative sheet 15 prepared in this step has a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape and containing a cured product of a curable resin X, in this order in the thickness direction. The porous substrate, the design layer, and the release layer are as described above. In this step, a release layer that has been cured in advance is used, so there is no need to perform a curing process for the release layer in a later step. Therefore, deterioration of the cured resin layer (e.g., a melamine layer) due to ultraviolet irradiation or the like can be suppressed.

[0111] 2. Impregnation process This process is a process in which a curable resin Y is impregnated into the porous substrate 1 of the decorative sheet 15 through the design layer 2, as shown in Figure 3(b), to form a curable resin layer 30 that contains the curable resin Y and covers the design layer 2 and the release layer 3.

[0112] In this step, for example, the decorative sheet is immersed in a curable resin composition containing the curable resin Y. After immersion, it is preferable to dry the sheet. At this time, a part of the curable resin may be cured to a semi-cured state. Examples of methods for impregnating the decorative sheet with the curable resin Y include a method of immersing the decorative sheet in a bath containing the curable resin Y; a method of applying the curable resin Y to the decorative sheet using a coater such as a kiss coater or a comma coater; and a method of spraying the curable resin Y onto the decorative sheet using a spray device or a shower device.

[0113] The ratio of the curable resin Y in the curable resin composition is, for example, 50 mass % or more, or may be 70 mass % or more, or may be 90 mass % or more. The curable resin composition may contain, for example, water, alcohol, or an organic solvent as a solvent.

[0114] 3. Transfer sheet preparation process As shown in FIG. 3(c), the transfer sheet 20 prepared in this step has a release film 21 and a transfer layer 22 arranged on one side of the release film 21, and the transfer layer 22 has a surface protective layer 5. The transfer layer 22 may have an adhesive layer 6 on the surface of the surface protective layer 5 opposite the release film 21. In this case, the transfer sheet 20 is formed by arranging the surface protective layer 5 and the adhesive layer 6 from the release film 1 side in the thickness direction D. T In this order, the surface protective layer and the adhesive layer are the same as those described in "A. Resin-impregnated decorative board". The total thickness of the transfer layer in the transfer sheet and the cured resin layer arranged in the second region described later is preferably 7 μm or more, more preferably 14 μm or more. If the total thickness is within the above range, a resin-impregnated decorative board with improved abrasion resistance can be obtained. On the other hand, the total thickness is preferably 30 μm or less, more preferably 25 μm or less. If the total thickness is within the above range, the cured resin layer and the transfer layer in the first region can be easily peeled and removed in the peeling process, and a gloss matte design can be stably expressed.

[0115] The transfer sheet has a release film. The release film and the surface protective layer may be disposed so as to be in direct contact with each other, or may be disposed via another layer.

[0116] The release film preferably contains a resin film, for example, an ester resin, an olefin resin, a styrene resin, a vinyl resin, a (meth)acrylic resin, an amide resin, an imide resin, or a carbonate resin.

[0117] The resin film preferably contains an ester-based resin or an olefin-based resin. Examples of ester-based resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Among these, PET or PBT is preferred, and PET is more preferred, from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0118] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0119] The resin film may be a stretched film or an unstretched film. The stretch ratio in the machine direction (MD) of the stretched film is, for example, 5 times or more and 30 times or less. The stretch ratio in the width direction (TD) of the stretched film is, for example, 5 times or more and 30 times or less. The thickness of the release film is, for example, 10 μm or more and 200 μm or less, may be 15 μm or more and 150 μm or less, or may be 20 μm or more and 100 μm or less.

[0120] The transfer sheet is preferably a transfer sheet capable of transferring the transfer layer arranged in the second region to the decorative sheet side while peeling off the transfer layer and the cured resin layer arranged in the first region together with the release film when peeling off the release film from the cured laminate in the peeling step described later. In such a transfer sheet, the peel strength between the release film and the surface protective layer is preferably 50 mN / 25 mm or more, more preferably 100 mN / 25 mm or more. By having the peel strength in the above range, it becomes easy to peel off the cured resin layer arranged in the first region in the peeling step described later. On the other hand, the peel strength between the release film and the surface protective layer is preferably 1000 mN / 25 mm or less, more preferably 800 mN / 25 mm or less. By having the peel strength in the above range, it becomes easy to transfer the transfer layer arranged in the second region to the decorative sheet side in the peeling step described later.

[0121] The peel strength between the release film and the surface protective layer in the transfer sheet is a value measured according to the following procedure in accordance with JIS Z0237:2022 10.4 Measurement of peel adhesion. 1) Cut the transfer sheet to a size 25mm wide x 120mm long. 2) Prepare a metal plate (100 mm x 150 mm) and attach the transfer sheet from 1) to the metal plate with double-sided tape so that the surface protective layer side (transfer layer side) faces the metal plate. At this time, be careful not to attach the edge of the transfer sheet to 20 to 30 mm. 3) Attach one end of a 25 mm wide piece of Nichiban Cellotape (registered trademark) to the end of the transfer sheet in 2) (the length of the tape should be approximately 300 mm), and then fold the cellotape so that the sticky sides touch each other to form a tab. 4) As shown in Fig. 6, a metal plate 61 is placed, and while the lower part of the metal plate 61 is fixed with a chuck 62, the tab of the cellophane tape 63 is pulled in the 180 degree direction (upward) at 100 mm / min. In Fig. 6, 64 denotes a double-sided tape. 5) Ignore the first 25 mm of the pulling distance and take the average force after pulling 50 mm as the peel strength.

[0122] The peel strength can be increased, for example, by a method of decreasing the crosslink density or hardness of the surface protective layer (for example, by using a resin having few functional groups involved in curing or a resin having a large molecular weight), a method of providing an easy-adhesion layer on the surface of the release film, a method of previously performing a surface treatment on the surface of the release film by corona treatment, plasma treatment, etc. On the other hand, the peel strength can be decreased by a method of increasing the crosslink density or hardness of the surface protective layer (for example, by using a resin having many functional groups involved in curing or a resin having a small molecular weight), a method of adding a release agent such as silicone to the release film, etc.

[0123] The transfer sheet in the present disclosure preferably has an adhesive layer on the surface opposite to the release film of the surface protective layer. By using a transfer sheet having an adhesive layer, the adhesion between the cured resin layer and the transfer layer is improved in the manufacturing process of the resin-impregnated decorative board. This makes it possible to easily leave the transfer layer arranged in the second region on the decorative sheet side, and to easily peel and remove the cured resin layer and the transfer layer arranged in the first region, thereby stably expressing a good gloss matte design. In addition, the transfer sheet may have a primer layer arranged between the adhesive layer and the surface protective layer to assist the interlayer strength between the adhesive layer and the surface protective layer.

[0124] The method for producing the transfer sheet includes, for example, a surface protective layer forming treatment for forming a surface protective layer by applying a first composition containing the above-mentioned curable resin Z to the surface of the release film and curing the composition. The first composition is a composition for forming a surface protective layer, and contains, for example, the above-mentioned curable resin Z and a weathering agent.

[0125] Examples of the method for applying the first composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. The first coating layer is obtained by applying the first composition. Examples of the method for curing the first coating layer include a method of irradiating with ionizing radiation such as electron beams and ultraviolet rays, and a method of applying heat.

[0126] The method for producing the transfer sheet may also include a process for forming an adhesive layer by applying a second composition containing the curable resin α to the surface of the surface protective layer opposite to the release film, and curing the composition to form an adhesive layer. The second composition is a composition for forming an adhesive layer, and contains, for example, the curable resin α and a weathering agent.

[0127] Examples of the method for applying the second composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. By applying the second composition, a second coating layer is obtained. Examples of the method for curing the second coating layer include a method of applying heat.

[0128] 4.Laminate formation process In this step, as shown in FIG. 3(d), (i) the decorative sheet 15, the curable resin layer 30, and the transfer sheet 20 are laminated in the thickness direction D T and (ii) forming a laminate 11 having the above-mentioned components in this order, and arranged such that the surface of the transfer sheet 20 on the transfer layer 22 side faces the curable resin layer 30.

[0129] The method for forming such a laminate is not particularly limited. For example, as shown in FIG. 3(d), the transfer sheet 20 described above is placed on the decorative sheet 15 and the curable resin layer 30 obtained in the impregnation step so as to face the curable resin layer 30. This allows the laminate 11 to be obtained. At this time, the core substrate 40 may be placed so as to face the porous substrate 1.

[0130] 5. Heat and pressure process In this step, as shown in FIG. 4(a), the laminate 11 is heated and pressurized to form the cured resin layer 4 from the curable resin layer 30 while curing the curable resin Y, thereby obtaining the cured laminate 12. The cured laminate 12 preferably has a high adhesion strength between the cured resin layer 4 and the transfer layer 22. This is because, in the subsequent peeling step, the transfer layer in the second region can be easily left on the decorative sheet side, and the cured resin layer and the transfer layer arranged in the first region can be easily peeled off and removed, and a good gloss matte design can be stably expressed. In order to improve the adhesion strength between the cured resin layer and the transfer layer, it is preferable to use the transfer sheet 20 having the above-mentioned adhesion layer 6 as shown in FIG. 4(a). Furthermore, from the viewpoint of increasing the adhesion strength between the cured resin layer and the transfer layer, it is preferable that the heating temperature and the applied pressure in this step are low enough not to cause the effect of the curable resin Y to be poor. By lowering the heating temperature and applied pressure, the curable resin Y can be prevented from being cured too quickly, and can penetrate into the adhesive layer or the surface protective layer, improving the adhesive strength between the cured resin layer and the transfer layer. The heating temperature is, for example, 160°C or lower, preferably 150°C or lower, and more preferably 140°C or lower. On the other hand, the heating temperature is, for example, 100°C or higher. The applied pressure is, for example, 150 kg / cm 2 Less than 100kg / cm 2 On the other hand, the applied pressure is preferably 50 kg / cm or less. 2 The heating and pressing time is, for example, from 30 seconds to 30 minutes. The release layer has releasability with respect to the cured resin layer located between the release layer and the transfer sheet.

[0131] 6. Peeling process In this step, as shown in FIG. 4(b), the release film 21 of the transfer sheet 20 is peeled off from the cured laminate 12. TIn this manner, the cured resin layer 4 and the transfer layer 22 arranged in the first region R1 that overlaps with the release layer 3 are removed together with the release film 21. Meanwhile, the cured resin layer 4 and the transfer layer 22 arranged in the second region R2 that does not overlap with the release layer 3 in the thickness direction remain on the decorative sheet 15 side. In this manner, the resin-impregnated decorative board 10 is obtained.

[0132] 7. Resin-impregnated decorative panels The resin-impregnated decorative board obtained by each of the above-mentioned steps is the same as that described above in "A. Resin-impregnated decorative board."

[0133] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0134] [Example 1] (Manufacture of decorative sheet 1) As a porous substrate, the basis weight is 80g / m 2 Titanium base paper for building materials (PM-77P, manufactured by KJ Specialty Paper Co., Ltd.) was prepared. A design layer (picture layer) having a thickness of 2 μm was partially laminated on the porous substrate so as to have a stone pattern design by gravure printing using a printing ink having the following composition. Furthermore, the ink for forming a release layer described below was laminated on the picture layer in synchronization with the picture layer, and then an electron beam of 3 Mrad was irradiated at an acceleration voltage of 165 kV to form a release layer having a thickness of 5 μm. The ratio of the area of ​​the design layer (picture layer) and the release layer to the area of ​​the porous substrate in the thickness direction was adjusted to 40% or more and 50% or less in all cases, including the examples and comparative examples described later. As a result, a decorative sheet was produced in which the porous substrate, the design layer, and the release layer were laminated in this order.

[0135] <Printing ink> Pigments (azo, quinacridone, carbon black, etc.) 10 parts by weight Casein / acrylic resin (mass ratio 45:55) 10 parts by mass ·Water 70 parts by mass Dipropyl glycol 5 parts by weight Isopropyl alcohol 5 parts by weight

[0136] <Ink for forming release layer> Ionizing radiation curable monomer (Aronix M-400, manufactured by Toagosei Co., Ltd.) 48 parts by weight Reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by weight (8.3 parts by weight per 100 parts by weight of resin component) Silane coupling treated silica (particle size 2 μm) 8 parts by weight (16.6 parts by weight per 100 parts by weight of resin component) Methyl ethyl ketone 40 parts by weight

[0137] (Manufacture of peel-off transfer sheet 1) The following ink 1 for forming a surface protective layer was applied to the adhesive side of a 50 μm-thick PET film (Cosmoshine (registered trademark) A4160 manufactured by Toyobo Co., Ltd.) in an amount of 5 g / m2 after drying. 2 After coating, the substrate was dried at 70°C for 1 minute, and then irradiated with an electron beam (voltage: 175 kV, 5 Mrad (50 kGy)) to form a 5 μm thick surface protective layer. Furthermore, the surface side of the formed surface protective layer was subjected to corona treatment at 90 kW.

[0138] <Ink for forming surface protective layer 1> Urethane acrylate: 100 parts by weight (bifunctional caprolactone-modified urethane acrylate / multifunctional urethane acrylate = 50 / 50 (weight ratio)) -UV absorber: 1.5 parts by weight (product name: Tinuvin 479, manufactured by BASF) Light stabilizer: 3 parts by weight (product name: LS-3410, manufactured by Nippon Nyukazai Co., Ltd.) Nanosilica (average particle size: less than 1 μm): 2 parts by weight Non-reactive silicone: 0.2 parts by weight Solvent: appropriate amount (methyl ethyl ketone)

[0139] Next, the following ink 1 for forming an adhesive layer was applied to the formed surface protective layer in a coating amount of 3 g / m2 after drying. 2 and dried at 70° C. for 1 minute to form an adhesive layer having a thickness of 2 μm. This resulted in a peel-off transfer sheet 1. The surface protective layer and the adhesive layer became the transfer layer.

[0140] <Ink for forming adhesive layer 1> Polycarbonate-based urethane acrylic copolymer: 100 parts by weight (urethane component / acrylic component = 90 / 10 (weight ratio)) Ultraviolet absorber: 30 parts by weight (16 parts by weight of "Tinuvin 479" (BASF) and 14 parts by weight of "Tinuvin 400" (BASF)) Light stabilizer: 3 parts by weight ("Tinuvin 123" (BASF)) ·Silica (average particle size: 3~5μm): 3 parts by mass Hexamethylene diisocyanate hardener: 10 parts by weight Solvent: appropriate amount (methyl ethyl ketone)

[0141] (Production of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2 The melamine resin was then scraped off once each from the front and back of the base paper with a rubber spatula, and then the base paper was dried to produce an impregnated decorative sheet.

[0142] The impregnated decorative sheet is made by impregnating craft paper with phenolic resin liquid, with a basis weight of 245g / m 2The laminate was then laminated on top of a core substrate consisting of three sheets of phenolic resin-impregnated core paper (obtained by impregnating a core craft paper with a liquid uncured resin composition made of phenolic resin), and the peelable transfer sheet 1 was then laminated on top of the impregnated decorative sheet such that the adhesive layer of the transfer sheet 1 was in contact with the curable resin layer of the impregnated decorative sheet, thereby obtaining a laminate.

[0143] The laminate was sandwiched between two mirror-finished plates and heated at a pressure of 100 kg / cm using a heat press. 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150° C. for 10 minutes to form a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0144] Next, the transfer sheet 1 was peeled off from the cured resin layer containing the cured product of the melamine resin, removing the cured resin layer, adhesion layer, and surface protective layer arranged in the first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer, adhesion layer, and surface protective layer arranged in the second region not overlapping with the release layer. This resulted in a resin-impregnated decorative board. The configuration of the first region and the configuration of the second region (the layer arranged on the side opposite the porous substrate of the design layer) and the thickness of each layer are shown in Table 1. The thicknesses of the surface protective layer and adhesion layer were obtained by observing the cross section of each layer in the peel-off transfer sheet using a laser microscope and taking the arithmetic average value of the thicknesses measured at any three points. The thicknesses of the other layers were obtained by observing the cross section of the resin-impregnated decorative board and taking the arithmetic average value of the thicknesses measured at any three points.

[0145] [Example 2] (Production of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2The melamine resin was impregnated so as to obtain a ratio of 1:1 (when dry). The melamine resin on the front and back of the base paper was not scraped off with a rubber spatula, but was allowed to dry, thereby producing an impregnated decorative sheet.

[0146] The impregnated decorative sheet was laminated on the above-mentioned core substrate, and the above-mentioned peeling transfer sheet 1 was further laminated on the impregnated decorative sheet so that the adhesive layer of the peeling transfer sheet 1 was in contact with the curable resin layer of the impregnated decorative sheet, thereby obtaining a laminate.

[0147] The formed laminate was sandwiched between two mirror-finished plates and heat-molded using a heat press under conditions of a pressure of 100 kg / cm2 and a molding temperature of 150°C for 10 minutes to thermally cure the uncured melamine resin composition, thereby forming a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0148] Next, the peeling transfer sheet 1 was peeled off from the cured resin layer containing the cured product of the melamine resin, thereby removing the cured resin layer, the adhesion layer and the surface protective layer arranged in the first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer, the adhesion layer and the surface protective layer arranged in the second region not overlapping with the release layer. In this way, a resin-impregnated decorative board was obtained.

[0149] [Example 3] (Manufacture of peel-off transfer sheet 2) The above-mentioned ink 1 for forming a surface protective layer was applied to the adhesive surface of a 50 μm-thick PET film (Cosmoshine (registered trademark) A4160 manufactured by Toyobo Co., Ltd.) in an amount of 3 g / m2 after drying. 2 After drying at 70°C for 1 minute, the coating was irradiated with an electron beam (voltage: 175 kV, 5 Mrad (50 kGy)) to form a 3 μm thick surface protective layer. Furthermore, the surface side of the formed surface protective layer was subjected to corona treatment at 90 kW.

[0150] Next, the above-mentioned ink 1 for forming an adhesive layer was applied onto the formed surface protective layer in such a manner that the coating amount after drying was 1.5 g / m 2 The mixture was dried at 70° C. for 1 minute to form an adhesive layer having a thickness of 1 μm. This resulted in a peel-off transfer sheet 2.

[0151] (Manufacture of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2 The melamine resin was then scraped off from the front and back of the base paper three times with a rubber spatula, and the paper was then dried to produce an impregnated decorative sheet.

[0152] The impregnated decorative sheet was laminated on the above-mentioned core substrate, and a peelable transfer sheet 2 was further laminated on the impregnated decorative sheet so that the adhesive layer of the transfer sheet 2 was in contact with the curable resin layer of the impregnated decorative sheet, to obtain a laminate.

[0153] The formed laminate was sandwiched between two mirror-finished plates and heat-molded using a heat press under conditions of a pressure of 100 kg / cm2 and a molding temperature of 150°C for 10 minutes to thermally cure the uncured melamine resin composition, thereby forming a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0154] Next, the transfer sheet 2 was peeled off from the cured resin layer containing the cured product of the melamine resin, removing the cured resin layer, adhesion layer, and surface protective layer arranged in the first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer, adhesion layer, and surface protective layer arranged in the second region not overlapping with the release layer. This resulted in a resin-impregnated decorative board.

[0155] [Example 4] (Manufacture of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2 The melamine resin was scraped off once from the front and back of the base paper with a rubber spatula and then dried to produce an impregnated decorative sheet. The uncured melamine resin was applied to the impregnated decorative sheet at a ratio of 10 g / m 2 (when dry) was applied.

[0156] The impregnated decorative sheet after being coated with the uncured melamine resin was laminated on the above-mentioned core substrate, and further, transfer sheet 1 was laminated on the impregnated decorative sheet so that the adhesive layer of transfer sheet 1 was in contact with the curable resin layer of the impregnated decorative sheet, thereby obtaining a laminate.

[0157] The formed laminate was sandwiched between two mirror-finished plates and heat-molded using a heat press under conditions of a pressure of 100 kg / cm2 and a molding temperature of 150°C for 10 minutes to thermally cure the uncured melamine resin composition, thereby forming a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0158] Next, the transfer sheet 1 was peeled off from the cured resin layer containing the cured product of the melamine resin, removing the cured resin layer, adhesion layer, and surface protective layer arranged in the first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer, adhesion layer, and surface protective layer arranged in the second region not overlapping with the release layer. This resulted in a resin-impregnated decorative board.

[0159] [Example 5] (Manufacture of peel-off transfer sheet 3) The above-mentioned ink 1 for forming a surface protective layer was applied to the adhesive surface of a 50 μm-thick PET film (Cosmoshine (registered trademark) A4160 manufactured by Toyobo Co., Ltd.) in an amount of 5 g / m2 after drying. 2After drying at 70°C for 1 minute, the coating was irradiated with an electron beam (applied voltage: 175 kV, 5 Mrad (50 kGy)) to form a surface protective layer with a thickness of 5 μm. Furthermore, the surface side of the formed surface protective layer was subjected to corona treatment at 90 kW. This resulted in a peel-off transfer sheet 3.

[0160] (Production of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2 The melamine resin was scraped off once each from the front and back of the base paper with a rubber spatula, and then the paper was dried to produce an impregnated decorative sheet.

[0161] The impregnated decorative sheet was laminated on the above-mentioned core substrate, and then a peelable transfer sheet 3 was laminated on the impregnated decorative sheet so that the surface protective layer of the transfer sheet 3 was in contact with the curable resin layer of the impregnated decorative sheet, thereby obtaining a laminate.

[0162] The laminate was sandwiched between two mirror-finished plates and heated at a pressure of 100 kg / cm using a heat press. 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150° C. for 10 minutes to form a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0163] Next, the transfer sheet 3 was peeled off from the cured resin layer containing the cured product of the melamine resin, removing the cured resin layer and the surface protective layer arranged in the first region overlapping with the release layer in the thickness direction, while leaving the cured resin layer and the surface protective layer arranged in the second region not overlapping with the release layer. This resulted in a resin-impregnated decorative board.

[0164] [Comparative Example 1] (Preparation of release film) A coating solution containing 100 parts by mass of ionizing radiation curable monomer, 2 parts by mass of reactive silicone, 8 parts by mass of silica, and 50 parts by mass of ethyl acetate was applied at 5 g / m to the adhesive side of a 50 μm-thick PET film (Cosmoshine (registered trademark) A4160 manufactured by Toyobo Co., Ltd.). 2 The coating was applied in an amount of (when dry) and cured by irradiation with an electron beam of 5 Mrad at an acceleration voltage of 165 kV to produce a release film having a peelable layer.

[0165] (Manufacture of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device. 2 The melamine resin was scraped off once from the front and back of the base paper with a rubber spatula, and then dried to produce an impregnated decorative sheet.

[0166] As shown in FIG. 5(a), the impregnated decorative sheet was laminated on the above-mentioned core substrate 40, and a release film 50 was further laminated on the impregnated decorative sheet so that the peel layer of the release film 50 was in contact with the curable resin layer 30 of the impregnated decorative sheet, thereby obtaining a laminate 51.

[0167] Next, as shown in FIG. 5(b), the formed laminate was sandwiched between two mirror-finished plates and pressed with a heat press at a pressure of 100 kg / cm. 2 The uncured melamine resin composition was heat-molded at a molding temperature of 150° C. for 10 minutes to thermally cure the uncured melamine resin composition, thereby forming a cured resin layer 4 (melamine layer) containing a cured product of the melamine resin. Thus, a cured laminate 52 was obtained.

[0168] 5(c), the release film 50 was peeled off from the cured resin layer 4 containing the cured product of the melamine resin, thereby removing the cured resin layer 4 arranged in the first region that overlaps with the release layer in the thickness direction of the cured resin layer, while leaving the cured resin layer 4 arranged in the second region that does not overlap with the release layer. In this way, a resin-impregnated decorative board 60 was obtained.

[0169] [Comparative Example 2] (Manufacture of peel-off transfer sheet 4) The following ink 2 for forming a surface protective layer was applied to the adhesive side of a 50 μm-thick PET film (Cosmoshine (registered trademark) A4160 manufactured by Toyobo Co., Ltd.) in an amount of 5 g / m2 after drying. 2 Next, the ink 1 for forming the adhesive layer was applied onto the coating layer that had not been irradiated with the electron beam (hereinafter, referred to as the surface protective layer (before curing)) so that the coating amount after drying was 3 g / m 2 The mixture was dried at 70° C. for 1 minute to form an adhesive layer having a thickness of 2 μm. This resulted in a peel-off transfer sheet 4.

[0170] <Ink for forming surface protective layer 2> Photocurable acrylate oligomer: 100 parts by weight (including 70 parts by weight of tack-free oligomer) -UV absorber: 1 part by weight (product name: Tinuvin 479, manufactured by BASF) Light stabilizer: 0.3 parts by weight (product name: LS-3410, manufactured by Nippon Nyukazai Co., Ltd.) Silica (average particle size: less than 6 μm): 40 parts by weight Non-reactive silicone: 0.2 parts by weight Solvent: appropriate amount (methyl ethyl ketone)

[0171] (Production of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 1 produced above at a concentration of 80 g / m using an impregnation device.2 The melamine resin was scraped off from the front and back of the base paper 10 times each with a rubber spatula, and then the base paper was dried to produce an impregnated decorative sheet.

[0172] The impregnated decorative sheet was laminated on the above-mentioned core substrate, and then a peelable transfer sheet 4 was laminated on the impregnated decorative sheet so that the adhesive layer of the transfer sheet 4 was in contact with the curable resin layer of the impregnated decorative sheet, to obtain a laminate.

[0173] The laminate was sandwiched between two mirror-finished plates and heated at a pressure of 100 kg / cm using a heat press. 2 The uncured melamine resin composition was heat-cured by heat molding at a molding temperature of 150° C. for 10 minutes, thereby obtaining a cured laminate.

[0174] Next, the transfer sheet 4 was peeled off to remove the adhesion layer and the surface protection layer (before curing) arranged in the first region overlapping with the release layer in the thickness direction, while leaving the adhesion layer and the surface protection layer (before curing) arranged in the second region not overlapping with the release layer. This resulted in a resin-impregnated decorative board. The resin-impregnated decorative board was irradiated with an electron beam (applied voltage: 175 kV, 5 Mrad (50 kGy)) to cure the surface protection layer.

[0175] [Comparative Example 3] (Manufacture of decorative sheet 2) As a porous substrate, the basis weight is 80g / m 2 Titanium base paper for building materials (PM-77P, manufactured by KJ Specialty Paper Co., Ltd.) was prepared. A design layer (picture layer) having a thickness of 2 μm was partially laminated on the porous substrate by gravure printing using the above printing ink so as to form a stone grain pattern design. In this way, a decorative sheet 2 having a porous substrate and a design layer was produced.

[0176] (Production of resin-impregnated decorative panels) A liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, NikaResin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was applied to the decorative sheet 2 produced above using an impregnation device so that the uncured melamine resin composition was 80 g / m 2 The melamine resin was then scraped off once each from the front and back of the base paper with a rubber spatula, and then the base paper was dried to produce an impregnated decorative sheet.

[0177] The impregnated decorative sheet was laminated on the above-mentioned core substrate, and the above-mentioned peelable transfer sheet 1 was further laminated on the impregnated decorative sheet so that the adhesive layer of the transfer sheet 1 was in contact with the curable resin layer of the impregnated decorative sheet, thereby obtaining a laminate.

[0178] The laminate was sandwiched between two mirror-finished plates and heated at a pressure of 100 kg / cm using a heat press. 2 The uncured melamine resin composition was heat-cured at a molding temperature of 150° C. for 10 minutes to form a cured resin layer (melamine layer) containing a cured product of the melamine resin, thereby obtaining a cured laminate.

[0179] Next, the release film of the transfer sheet 1 was peeled off from the cured resin layer containing the cured product of the melamine resin, thereby obtaining a resin-impregnated decorative board with the adhesive layer and the surface protective layer transferred over the entire surface.

[0180] [evaluation] (Gloss matte design evaluation) The gloss matte design of the obtained melamine decorative board was visually evaluated. Specifically, the obtained decorative board was visually observed from a distance of 50 cm under a light source of natural color fluorescent lamp color rendering AA (manufactured by Panasonic Corporation, model number: FLR40S·D-SDL / M), and the gloss matte design and the state of the matte part (release layer) were confirmed.

[0181] The observers scored the gloss matte design on a scale of 1 to 5 (1 being the worst and 5 being the best). The scale was set up so that 1 point was given when most of the melamine was peeled off or significant whitening was observed in the matte area or nearby areas, and sufficient gloss matte design could not be confirmed, and 5 points was given when no peeled melamine was found in the matte area and sufficient gloss matte design could be confirmed. Ten observers each conducted the test, and the average score was calculated to evaluate the gloss matte design according to the following criteria. Evaluation criteria A: The average score for the evaluation of gloss matte design is 3 points or more. B: The average score when evaluating the gloss matte design is 2 points or more but less than 3 points. C: The average score for the evaluation of gloss matte design is less than 2 points.

[0182] (Wear resistance evaluation) The obtained melamine decorative board was subjected to an abrasion test based on the JAS Flooring Abrasion Test A to evaluate its scratch resistance. A Taber abrasion tester was used, and the test was performed 50 times with abrasive paper: S-42 and a load of 1000g. When the melamine decorative board was viewed from above in a plane, the ratio of the area where the pattern of the decorative board had been removed to the total area of ​​the test part was calculated. This test was performed three times at different positions on the melamine decorative board, and the arithmetic average value of the above ratio was calculated and evaluated according to the following criteria. A: Pattern remaining 70% or more B: Pattern remaining 50% or more C: Less than 50% of the pattern remains

[0183] [Table 1]

[0184] As shown in Table 1, the resin-impregnated decorative boards of Examples 1 to 5 were good in both gloss mat design and abrasion resistance. On the other hand, the resin-impregnated decorative board of Comparative Example 1 had low abrasion resistance because it did not have a surface protective layer in the second region. The resin-impregnated decorative board of Comparative Example 2 had low abrasion resistance because it did not have a melamine layer in the second region. Comparative Example 3 did not have a first region, so it did not exhibit gloss mat design. In Examples 1 and 2, the thickness of the second region (the total thickness of the melamine layer, the adhesion layer, and the surface protective layer) was 7 μm or more and 30 μm or less, so the gloss mat design and abrasion resistance were better than those of Examples 3 and 4. In addition, compared to Example 5, which used the peeling transfer sheet 3 without an adhesion layer, Example 1, which used the peeling transfer sheet 1 with an adhesion layer, had good releasability of the melamine layer arranged in the first region and had a better gloss mat design.

[0185] Thus, in the present disclosure, for example, the following inventions are provided:

[0186] [1] A resin-impregnated decorative board, The resin-impregnated decorative board has a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of a curable resin X, in this order in the thickness direction; When viewed in the thickness direction, the resin-impregnated decorative board has a first region that overlaps with the release layer and a second region that does not overlap with the release layer, In the second region, a cured resin layer containing a cured product of the curable resin Y and a surface protective layer are arranged in this order from the design layer side on the surface of the design layer opposite to the porous substrate; the cured resin layer and the surface protective layer each have a pattern shape, The porous substrate contains a cured product of the curable resin Y, forming a resin-impregnated decorative board.

[0187] [2] The resin-impregnated decorative board described in [1], wherein in the second region, the total thickness of the layers disposed on the side of the decorative layer opposite the porous substrate is 7 μm or more and 30 μm or less.

[0188] [3] The resin-impregnated decorative board according to [1] or [2], wherein the surface protective layer contains a cured product of a curable resin Z.

[0189] [4] The resin-impregnated decorative board according to [3], wherein the cured product of the curable resin Z contains a (meth)acrylic component and a urethane component.

[0190] [5] The resin-impregnated decorative board according to any one of [1] to [4], further comprising an adhesive layer between the cured resin layer and the surface protective layer in the second region.

[0191] [6] The resin-impregnated decorative board according to any one of [1] to [5], wherein the surface of the release layer has a pure water contact angle of 100° or more.

[0192] [7] The resin-impregnated decorative board according to any one of [1] to [6], wherein the surface protective layer contains a weathering agent.

[0193] [8] The resin-impregnated decorative board according to [5], wherein the adhesion layer contains a weather resistance agent.

[0194] [9] A method for producing a resin-impregnated decorative board, comprising: A decorative sheet preparation step of preparing a decorative sheet having, in this order in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of a curable resin X; An impregnation step of impregnating the porous substrate of the decorative sheet with a curable resin Y through the design layer to form a curable resin layer containing the curable resin Y and covering the design layer and the release layer; A transfer sheet preparation step of preparing a transfer sheet having a release film and a transfer layer disposed on one surface of the release film, the transfer layer having a surface protective layer; (i) a laminate formation step of forming a laminate having the decorative sheet, the curable resin layer, and the transfer sheet in this order in the thickness direction, and (ii) a laminate arranged such that the surface of the transfer sheet facing the transfer layer faces the curable resin layer; a heating and pressurizing step of heating and pressurizing the laminate to cure the curable resin Y and form a cured resin layer from the curable resin layer to obtain a cured laminate; a peeling process for peeling the release film of the transfer sheet from the cured laminate, thereby removing the cured resin layer and the transfer layer arranged in a first region that overlaps with the release layer in the thickness direction, while leaving the cured resin layer and the transfer layer arranged in a second region that does not overlap with the release layer in the thickness direction.

[0195]

[10] The method for producing a resin-impregnated decorative board according to [9], wherein in the peeling step, the total thickness of the cured resin layer and the transfer layer disposed in the second region is 7 μm or more and 30 μm or less.

[0196]

[11] The method for producing a resin-impregnated decorative board described in [9] or

[10] , wherein the transfer layer in the transfer sheet has an adhesion layer on the side of the surface protection layer opposite the release film. [Explanation of symbols]

[0197] 1...Porous base material 2…Design layer 3…Release layer 4...cured resin layer 5…Surface protective layer 10...Resin-impregnated decorative board 20...Transfer sheet 40…Core substrate 30…Curable resin layer

Claims

1. A resin-impregnated decorative board, The resin-impregnated decorative board has a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of a curable resin X, in this order in the thickness direction; When viewed in the thickness direction, the resin-impregnated decorative board has a first region that overlaps with the release layer and a second region that does not overlap with the release layer, In the second region, a cured resin layer containing a cured product of the curable resin Y and a surface protective layer are arranged in this order from the design layer side on the surface of the design layer opposite to the porous substrate; the cured resin layer and the surface protective layer each have a pattern shape, The porous substrate contains a cured product of the curable resin Y, and the resin-impregnated decorative board.

2. The resin-impregnated decorative board according to claim 1, wherein in the second region, the total thickness of the layers disposed on the surface of the decorative layer opposite the porous substrate is 7 μm or more and 30 μm or less.

3. The resin-impregnated decorative board according to claim 1 , wherein the surface protective layer comprises a cured product of a curable resin Z.

4. The resin-impregnated decorative board according to claim 3 , wherein the cured product of the curable resin Z contains a (meth)acrylic component and a urethane component.

5. The resin-impregnated decorative board according to claim 1 , further comprising an adhesive layer between the cured resin layer and the surface protective layer in the second region.

6. 2. The resin-impregnated decorative board according to claim 1, wherein the surface of said release layer has a contact angle with pure water of 100[deg.] or more.

7. The resin-impregnated decorative board according to claim 1 , wherein the surface protective layer contains a weathering agent.

8. The resin-impregnated decorative board according to claim 5 , wherein the adhesion layer contains a weathering agent.

9. A method for producing a resin-impregnated decorative board, comprising: A decorative sheet preparation step of preparing a decorative sheet having, in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape and containing a cured product of a curable resin X, in this order; An impregnation step of impregnating the porous substrate of the decorative sheet with a curable resin Y through the design layer to form a curable resin layer containing the curable resin Y and covering the design layer and the release layer; A transfer sheet preparation step of preparing a transfer sheet having a release film and a transfer layer disposed on one surface of the release film, the transfer layer having a surface protective layer; (i) forming a laminate having the decorative sheet, the curable resin layer, and the transfer sheet in this order in the thickness direction, and (ii) forming a laminate in which the transfer layer side of the transfer sheet is disposed so as to face the curable resin layer; a heating and pressurizing step of heating and pressurizing the laminate to cure the curable resin Y while forming a cured resin layer from the curable resin layer, thereby obtaining a cured laminate; a peeling process for peeling the release film of the transfer sheet from the cured laminate, thereby removing the cured resin layer and the transfer layer arranged in a first region that overlaps with the release layer in the thickness direction, while leaving the cured resin layer and the transfer layer arranged in a second region that does not overlap with the release layer in the thickness direction.

10. The method for producing a resin-impregnated decorative board according to claim 9 , wherein in the peeling step, a total thickness of the cured resin layer and the transfer layer disposed in the second region is 7 μm or more and 30 μm or less.

11. The method for producing a resin-impregnated decorative board according to claim 9 , wherein the transfer layer in the transfer sheet has an adhesion layer on the surface of the surface protective layer opposite to the release film.

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