Laminate and manufacturing method thereof, as well as wallpaper and decorative sheet

Abstract

To provide a laminate that efficiently exhibits water repellency. [Solution] A laminate comprising a base material layer, a foamed resin layer, and a water-repellent layer laminated in this order, the surface of the foamed resin layer having a contact angle of 20° or more, and the surface of the foamed resin layer being partially covered by the water-repellent layer.

Description

[Technical Field]

[0001] The present invention relates to a laminate, a method for producing the same, and to wallpaper and decorative sheets. [Background technology]

[0002] The properties required for a laminate vary widely depending on its application and the location where it is used. For example, when a laminate is used as wallpaper or a decorative sheet for use in a house or office, strength and water repellency are required in addition to design. To satisfy such properties, techniques such as embossing the surface of the wallpaper or decorative sheet or providing a coating layer are used.

[0003] For example, Patent Document 1 discloses wallpaper having a surface protective layer on the surface side of a polyvinyl chloride resin layer, and Patent Document 2 discloses wallpaper having a surface functional layer made of a matting agent on the surface of which exposed portions of a foamed resin layer are dispersed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-109087 [Patent Document 2] Japanese Patent Publication No. 2020-190041 Summary of the Invention [Problem to be solved by the invention]

[0005] However, laminates having a water-repellent layer covering the entire surface have the problem that when the laminate is further heated (hereinafter also referred to as "reheating") after formation and embossed, punctures occur, resulting in a decrease in design. Also, when the water-repellent layer is formed on only a part of the surface of the laminate, there is the problem that the water-repellent performance is not efficiently exhibited.

[0006] In view of the above circumstances, an object of the present invention is to provide a laminate that efficiently exhibits water repellency. [Means for solving the problem]

[0007] As a result of extensive research, the inventors have discovered that the above problem can be solved by setting the contact angle of the surface of a foamed resin layer within a predetermined range in a laminate having a specific layer structure, and have thus completed the present invention.

[0008] That is, the present invention relates to the following.

[0009] Aspect 1 of the present invention is a base layer, a foamed resin layer, and a water-repellent layer laminated in this order; the surface of the foamed resin layer has a contact angle of 20° or more; The present invention relates to a laminate in which the surface of the foamed resin layer is partially covered with the water-repellent layer.

[0010] A second aspect of the present invention is the laminate of the first aspect, The laminate has an area covered by the water-repellent layer that is 50 to 90% of the surface area of ​​the foamed resin layer.

[0011] A third aspect of the present invention is the laminate of the first or second aspect, The present invention relates to a laminate in which the water repellent agent contained in the water repellent layer is a non-fluorine-based water repellent agent.

[0012] A fourth aspect of the present invention is a laminate according to any one of the first to third aspects, The present invention relates to a laminate, wherein the foamed resin layer contains a polyvinyl chloride resin.

[0013] A fifth aspect of the present invention is the laminate of the fourth aspect, The laminate has a polyvinyl chloride resin content of 30 to 65% by mass based on the total mass of the foamed resin layer.

[0014] A sixth aspect of the present invention relates to the laminate of the fourth or fifth aspect, the foamed resin layer further contains a filler; The laminate has a filler content of more than 0 parts by mass and 30 parts by mass or less, relative to 100 parts by mass of the polyvinyl chloride resin in the foamed resin layer.

[0015] A seventh aspect of the present invention is a laminate according to any one of the first to sixth aspects, wherein: The present invention relates to a laminate for use in wallpaper.

[0016] Aspect 8 of the present invention is a laminate of any one of aspects 1 to 7, The present invention relates to a laminate for use in a decorative sheet.

[0017] A ninth aspect of the present invention is a step of forming a foamed resin precursor layer from a foamed resin layer-forming composition; applying a water-repellent layer-forming composition to the surface of the foamed resin precursor layer with a bias mesh roll; and The present invention relates to a method for producing a laminate according to any one of Aspects 1 to 8, comprising the steps of: foaming the foam resin precursor layer to form a foam resin layer, in this order.

[0018] A tenth aspect of the present invention is The present invention relates to wallpaper comprising the laminate of any one of aspects 1 to 7, wherein the surface of the laminate facing the water-repellent layer is embossed.

[0019] An eleventh aspect of the present invention is The present invention relates to a decorative sheet comprising the laminate of any one of aspects 1 to 6 and 8, wherein the surface of the laminate facing the water-repellent layer is embossed. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a laminate that efficiently exhibits water repellency. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a diagram showing one embodiment of a layer structure in a laminate according to an embodiment of the present invention. [Figure 2] FIG. 2 is a diagram showing an embodiment in which the surface of a foamed resin layer is partially covered with a water-repellent layer. [Figure 3] FIG. 3 is a diagram showing an embodiment in which the surface of a foamed resin layer is partially covered with a water-repellent layer. DETAILED DESCRIPTION OF THE INVENTION

[0022] The laminate of the present invention, its manufacturing method, and wallpaper or decorative sheet will be described below, but the present invention is not limited thereto. In addition, in this specification, the term "A to B" indicating a range of numerical values ​​means a range including A and B, and indicates "not less than A and not more than B."

[0023] <Laminate> The laminate according to an embodiment of the present invention comprises a base layer, a foamed resin layer, and a water-repellent layer laminated in this order, the surface of the foamed resin layer having a contact angle of 20° or more, and the surface of the foamed resin layer being partially covered by the water-repellent layer. One embodiment is a laminate 10 having a layer structure in which a foamed resin layer 2 is laminated on a base material layer 1, and the surface of the foamed resin layer 2 is partially laminated with a water-repellent layer 3, as shown in Figure 1.

[0024] [Base material layer] In the present embodiment, the substrate layer is not particularly limited, and examples thereof include those used as substrates for wallpaper or decorative sheets. More specific examples include paper, fabric, nonwoven fabric, synthetic resin sheet, or composite materials thereof.

[0025] Examples of paper that can be used for the base layer include coated paper, kenaf paper, plain paper, recycled paper, Japanese paper, fine paper, etc. Furthermore, these papers may contain inorganic fillers (such as aluminum hydroxide) and flame retardants. Examples of fabrics that can be used for the substrate layer include knitted fabrics and woven fabrics made of natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, and the like. Examples of synthetic resin sheets that can be used for the substrate layer include polyolefin, vinyl chloride resin, olefin thermoplastic elastomer, and ABS (acrylonitrile-butadiene-styrene) resin.

[0026] The substrate layer can be selected depending on the application and desired properties of the laminate. For example, using paper for the base layer is preferable because it allows for inexpensive application using starch paste, and using nonwoven fabric for the base layer is preferable because it allows for easy peeling from the substrate and the subsequent application of new wallpaper or decorative sheeting.

[0027] The thickness of the substrate layer is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.11 mm or more, and even more preferably 0.13 mm or more, and is preferably 0.2 mm or less, more preferably 0.16 mm or less, and even more preferably 0.15 mm or less. In particular, a thickness of the substrate layer of 0.11 mm or more is preferred because it improves unevenness concealment, and a thickness of 0.15 mm or less is preferred because it improves fire resistance.

[0028] [Foam resin layer] (surface contact angle) In this embodiment, the surface of the foamed resin layer has a contact angle of 20° or more, preferably 25° or more, more preferably 30° or more, and even more preferably 35° or more. There is no particular upper limit to the contact angle of the surface of the foamed resin layer, but it can be, for example, 60° or less. The contact angle in this specification can be measured by a method in accordance with JIS R 3257:1999.

[0029] If the contact angle on the surface of the foamed resin layer is less than 20°, the water repellency of the laminate may not be exhibited, and the water repellency after reheating may be poor. Here, reheating the laminate corresponds to the heating performed when embossing wallpaper or decorative sheets. That is, when a laminate in which the contact angle of the surface of the foamed resin layer is less than 20° is used for wallpaper or decorative sheets, the wallpaper or decorative sheet obtained after embossing or the like may have poor water repellency.

[0030] The reason why such an effect is obtained when the surface of the foamed resin layer has a contact angle of 20° or more is not clear, but it is thought that there are some areas of the foamed resin layer that are not covered by the water-repellent layer and are exposed, and the properties of this exposed foamed resin layer affect the water-repellent performance of the laminate.

[0031] The contact angle on the surface of the foamed resin layer can be adjusted appropriately by changing the composition of the foamed resin layer. For example, when the foamed resin layer contains an emulsifier, the contact angle on the surface of the foamed resin layer can be adjusted to be high by reducing the content of the emulsifier based on the total mass of the foamed resin layer. The preferred content of the emulsifier in the foamed resin layer can be appropriately set depending on the type of emulsifier. Furthermore, for example, if the content of the filler, etc. based on the total mass of the foamed resin layer is increased and the content of the polyvinyl chloride resin is reduced, the emulsifier content is reduced, and the contact angle on the surface of the foamed resin layer can be adjusted to be high. In addition, for example, by lowering the content of the hydrophilic additive based on the total mass of the foamed resin layer, the contact angle on the surface of the foamed resin layer can be adjusted to be high.

[0032] (Polyvinyl chloride resin) The foamed resin layer preferably contains a polyvinyl chloride resin. The resin component contained in the foamed resin layer is preferably made of a polyvinyl chloride resin. The reasons why it is preferable to use a polyvinyl chloride resin for the foamed resin layer are as follows. First, polyvinyl chloride resins are preferable because the viscosity of the resin can be appropriately adjusted using a plasticizer, allowing for a high degree of freedom in the design of the foamed resin layer. Furthermore, polyvinyl chloride resins are preferable because they have chlorine atoms, which makes them flame-retardant and eliminates the need to add a flame retardant to the foamed resin layer. Furthermore, polyvinyl chloride resins are preferable because they have a molecular structure in which chlorine atoms are bonded to every other carbon chain, making them resistant to ultraviolet light and increasing the resistance of the foamed resin layer to oxidation and deterioration over time.

[0033] The content of the polyvinyl chloride resin based on the total mass of the foamed resin layer is not particularly limited, but is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more. Also, it is preferably 65% ​​by mass or less, more preferably 60% by mass or less. In one embodiment, the content of the polyvinyl chloride resin based on the total mass of the foamed resin layer can be 30 to 65% by mass. A content of 30% by mass or more is preferred because it increases the strength of the laminate, and is therefore preferred because, when the laminate is used as wallpaper or a decorative sheet, the strength of the wallpaper or decorative sheet after embossing can be maintained at a good level. Furthermore, if the content is 65% by mass or less, air bubbles are less likely to remain in the foamed resin layer, which is preferable. For example, when the laminate is used as wallpaper or a decorative sheet, this is preferable because it can prevent punctures during embossing due to air bubbles in the foamed resin layer.

[0034] The average polymerization degree of the polyvinyl chloride resin contained in the foamed resin layer is not particularly limited, but is preferably 750 or more, more preferably 950 or more, and even more preferably 1,000 or more. Also, it is preferably 1,600 or less, more preferably 1,400 or less, and even more preferably 1,200 or less. An average degree of polymerization of 750 or more is preferred because it improves the surface strength of the laminate and the durability of the entire laminate. For example, when the laminate is used as wallpaper or a decorative sheet, it is preferred because it improves the surface strength of the wallpaper or decorative sheet and the durability of the entire wallpaper or decorative sheet while maintaining the reproducibility of the embossing. Furthermore, an average degree of polymerization of 1,600 or less is preferable because it improves the processability of the laminate, and is therefore preferable because it improves the reproducibility of embossing when the laminate is used as wallpaper or a decorative sheet, for example.

[0035] (filler) The foamed resin layer preferably contains a filler. The reasons why it is preferable to use a filler in the foamed resin layer are as follows. First, if the composition for forming the foamed resin layer (hereinafter also referred to as "foamed resin layer-forming composition") contains a filler, it is preferable because the composition can be easily applied to a substrate. Also, if the composition for forming a foamed resin layer contains a filler, it is preferable because the production cost of the laminate is reduced. Furthermore, it is preferable because the reproducibility of embossing is improved when the laminate is used for wallpaper or decorative sheet, for example.

[0036] The filler that can be contained in the foamed resin layer is not particularly limited, but examples thereof include calcium carbonate, magnesium carbonate, magnesium silicate, aluminum hydroxide, talc, silica, and diatomaceous earth. These fillers may be used alone or in combination of two or more. Among these fillers, calcium carbonate and aluminum hydroxide are preferred. When the foamed resin layer-forming composition contains these preferred fillers, the composition has excellent sol stability and is easily applied to a substrate. Furthermore, when the laminate is used as wallpaper or a decorative sheet, the reproducibility of embossing is improved. Furthermore, calcium carbonate is advantageous in terms of cost and flame retardancy, and aluminum hydroxide is particularly advantageous in terms of flame retardancy.

[0037] The content of the filler in the foamed resin layer is not particularly limited, but for example, when the content of the polyvinyl chloride resin is taken as 100 parts by mass, the content of the filler is preferably more than 0 parts by mass, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. When the content is more than 0 parts by mass, the surface strength of the foamed resin layer is improved, which is preferable. Furthermore, when the laminate is used as wallpaper or a decorative sheet, it is preferable in that it has excellent conformability to the base material (such as gypsum board). In addition, when the content is 30 parts by mass or less, the production cost is low and the foamed resin layer-forming composition is easily applied to the substrate, which is preferable. Furthermore, when the laminate is used as wallpaper or a decorative sheet, for example, the reproducibility of embossing is improved, which is preferable.

[0038] When the foamed resin layer contains a polyvinyl chloride resin, the laminate according to an embodiment of the present invention can be, for example, a laminate in which the foamed resin layer further contains a filler, and the content of the filler is more than 0 parts by mass and not more than 30 parts by mass when the content of the polyvinyl chloride resin in the foamed resin layer is taken as 100 parts by mass.

[0039] (Other agents) The foamed resin layer may contain other agents in addition to the polyvinyl chloride resin and filler. The other agents that the foamed resin layer may contain are not particularly limited, but examples thereof include anionic emulsifiers such as alkylbenzene sulfonates, nonionic emulsifiers such as fatty acid esters, stabilizers such as metal halides, barium compounds, calcium compounds, tin compounds, zinc compounds, and potassium compounds, foaming agents such as azo compounds, colorants, processing aids, antibacterial agents, antifungal agents, flame retardants, defoamers, and viscosity reducers.

[0040] (Characteristics of foamed resin layer) The thickness of the foamed resin layer is not particularly limited, but is preferably 0.2 mm or more, more preferably 0.3 mm or more, and even more preferably 0.4 mm or more, and is preferably 0.9 mm or less, more preferably 0.8 mm or less, and even more preferably 0.7 mm or less.

[0041] [Water-repellent layer] In this embodiment, the surface of the foamed resin layer is partially covered with a water-repellent layer.

[0042] (Composition of water-repellent layer) The water-repellent layer usually contains a water-repellent agent. The water-repellent agents used in the water-repellent layer can be broadly divided into, for example, fluorine-based water-repellent agents and non-fluorine-based water-repellent agents. Examples of non-fluorine-based water-repellent agents include silicone-based water-repellent agents, polyurethane-based water-repellent agents, and polyacrylic-based water-repellent agents. From the viewpoint of reducing the environmental impact, in this embodiment, the water repellent agent contained in the water repellent layer is preferably a non-fluorine-based water repellent agent, since fluorine-based water repellents take time to decompose and there is concern that they may cause air pollution, soil pollution, and water contamination.

[0043] The water-repellent layer is usually formed by coating or printing an emulsion containing a water-repellent agent. There are no particular restrictions on the content of the water-repellent agent based on the total mass of the emulsion used to form the water-repellent layer, but it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more. It is also preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less.

[0044] The water-repellent layer may contain other agents in addition to the water-repellent agent. There are no particular limitations on the other agents that the water-repellent layer may contain, but examples thereof include antibacterial agents.

[0045] (area ratio) The ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more. Also, it is preferably 90% or less, and more preferably 80% or less. In one embodiment, the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer can be 50 to 90%. A ratio of 50% or more is preferred because water repellency is easily achieved, while a ratio of 90% or less is preferred because gas generated by decomposition of the foaming agent can be released more easily, preventing punctures during embossing and providing a foamed resin layer with excellent design.

[0046] In this specification, the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer can be determined from the shape of a plate used to print the water-repellent layer-forming composition, which is the material for the water-repellent layer. More specifically, it can be determined from the specifications of the plate used to print the water-repellent layer-forming composition, i.e., the volume value, which is the printing volume per unit area, and the depth and shape of the recesses in the plate.

[0047] For example, when printing the water-repellent layer-forming composition using a bias mesh roll (described later), the water-repellent layer-forming composition is printed in accordance with the shape of the recesses in the plate, and the shape of the recesses in the plate differs depending on the engraving method of the bias mesh roll (for example, a conical shape or a cylindrical shape). Therefore, the ratio (unit: %) of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer is expressed as a volume value (unit: cm 3 / m 2 ) and depth (unit: μm) in the following order: (1) 1m 2 Printing area per unit (m 2 ) Derivation of Equation (A) If the recessed portion of the plate is conical, 1m 2 The following relationship holds between the print area per hit, the volume value, and the depth: [Volume (cm 3 / m 2 )] / 1,000,000×3 =[1m 2 Printing area per unit (m 2)]×[depth (μm)] / 1,000,000 From this equation, the following equation (A) is derived. [1m 2 Printing area per unit (m 2 )] = [Volume value (cm 3 / m 2 )]×3÷[depth (μm)] ··· (A) (2) Calculation of the ratio (area ratio) (%) of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer From the above formula (A), "1m 2 Printing area per unit (m 2 )" and substitute this value into the following formula (B) to calculate the "area ratio (%)". [Area ratio (%)] =[1m 2 Printing area per unit (m 2 )]÷1(m 2 )×100 (B)

[0048] The shape and area of ​​the portion where the water-repellent layer is formed depend on the type of printing plate used. For example, when the water-repellent layer is formed by gravure printing, the recesses of the printing plate correspond to the portions where the water-repellent layer is formed, and the shape and area of ​​these recesses determine the area and shape of the water-repellent layer. In other words, even when the composition for forming a water-repellent layer is printed using a method other than the bias mesh roll, 2 The relationship between the print area per unit area, volume value, and depth can be determined obviously from the shape of the recesses on the plate. Therefore, the area ratio can be calculated using a method similar to the calculation method described above depending on the specifications of the plate.

[0049] As long as the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer is within the above-mentioned range, there are no particular limitations on the shape of the water-repellent layer to be formed or the shape of the part where the water-repellent layer is not formed. Examples of such shapes include stripes, lattice patterns, spots, islands-in-the-sea patterns such as circles, ellipses, and rectangles, and random shapes. Of these shapes, stripe, lattice, and sea-island shapes are preferred, and circular, elliptical, and rectangular shapes are more preferred, as they allow the water-repellent layer to be uniformly applied to the surface of the foamed resin layer. The shapes may be arranged in an aligned, staggered, or random pattern.

[0050] 2 and 3 are schematic diagrams showing the state in which a water-repellent layer is formed on the surface of a foamed resin layer. In these figures, rectangular or circular portions correspond to portions where the water-repellent layer is not formed. Furthermore, these figures are intended to show the shape of the portions where the water-repellent layer is not formed, and do not accurately show the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer.

[0051] (Characteristics of water-repellent layer) There is no particular limitation on the thickness of the water-repellent layer, but it is preferably 2.0 μm or more, more preferably 3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less.

[0052] [Other layers] The laminate according to the embodiment of the present invention may include, in addition to the substrate layer, the foamed resin layer, and the water-repellent layer, other layers, such as a pattern layer and an anchor coat layer. Other layers may be provided between the foamed resin layer and the water-repellent layer as long as they do not impede the effects of the present invention.

[0053] [Applications of laminates] The uses of the laminate according to the embodiment of the present invention are not particularly limited, and examples thereof include wallpaper, decorative sheets, baseboards, etc. In one aspect, the laminate according to the embodiment of the present invention is a laminate for use as wallpaper. In another aspect, the laminate according to the embodiment of the present invention is a laminate for use as a decorative sheet. The laminate according to the embodiment of the present invention will be described below using a laminate for use as wallpaper or a decorative sheet as an example, but there is no particular limitation on the use.

[0054] When the laminate according to the embodiment of the present invention is used as wallpaper, one embodiment thereof is wallpaper that includes the above-described laminate and has an embossed surface on the water-repellent layer side of the laminate. Furthermore, when the laminate according to the embodiment of the present invention is used as a decorative sheet, one embodiment thereof is a decorative sheet comprising the above-mentioned laminate, the surface of the laminate facing the water-repellent layer of which is embossed. The laminate according to the embodiment of the present invention has a water-repellent layer formed on the surface in a manner that prevents punctures during embossing, and therefore can be suitably used as a laminate for obtaining wallpaper or decorative sheets with excellent design, particularly when producing embossed wallpaper or decorative sheets.

[0055] <Method of manufacturing laminate> There are no particular limitations on the method for producing the laminate, as long as the laminate according to the embodiment of the present invention can be obtained. One embodiment of the method for producing the laminate will be described below.

[0056] [Method for forming foamed resin layer] The foamed resin layer can be formed, for example, by appropriately selecting a known method. Examples of such methods include laminating a foamed resin layer-forming composition on a substrate by a paste coating method, a calendar molding method, or the like to form a pre-foamed resin layer (hereinafter also referred to as a "foamed resin precursor layer"). The foamed resin precursor layer is then heated or otherwise foamed to obtain a foamed resin layer.

[0057] In this embodiment, the following method can be used to form a foamed resin layer whose surface is partially covered with a water-repellent layer. That is, a foamed resin precursor layer is formed by the above-mentioned method, and a water-repellent layer is further formed on the obtained foamed resin precursor layer by the method described below. Thereafter, the foamed resin precursor layer with the water-repellent layer formed thereon is foamed by heating or the like, thereby forming the desired foamed resin layer.

[0058] [Method for forming water-repellent layer] The water-repellent layer can be formed by, for example, appropriately selecting a known method. An example of such a method is a method of applying a composition for forming a water-repellent layer using gravure printing. Alternatively, gravure printing using a bias mesh roll can be used to form the composition for forming a water-repellent layer. Here, the bias mesh roll is a roll having a plurality of convex portions formed on its surface corresponding to the exposed portions of the foamed resin layer. Formation of the layer using the bias mesh roll can be carried out, for example, according to the method described in JP-A-2020-190041.

[0059] From the viewpoint of preventing punctures in wallpaper or decorative sheets, a method of applying a water-repellent layer-forming composition using a bias mesh roll is preferred as a method of forming a water-repellent layer. In the production of wallpaper or decorative sheets having a water-repellent layer, punctures can occur during embossing due to bubbles generated by gas generated during the formation of a foamed resin layer, but when a bias mesh roll is used, areas where gas escapes (areas where the water-repellent layer-forming composition is not applied by the bias mesh roll) are created on the surface of the foamed resin layer, preventing punctures. That is, the method for producing a laminate according to an embodiment of the present invention preferably includes a step of applying a water-repellent layer-forming composition to the surface of a foamed resin precursor layer using a bias mesh roll.

[0060] [Other layer formation methods] In addition to the above-described methods for forming each layer, a laminate including other layers can be obtained by appropriately adding a method for forming other layers, if necessary. The method for forming other layers can be appropriately selected from known methods.

[0061] [Method of manufacturing laminate] The laminate according to the embodiment of the present invention can be produced by combining the above-described methods for forming each layer. In one aspect, the laminate can be produced by a method including, in this order, a step of forming a foamed resin precursor layer from a foamed resin layer-forming composition, a step of applying a water-repellent layer-forming composition to the surface of the foamed resin precursor layer with a bias mesh roll, and a step of foaming the foamed resin precursor layer to form a foamed resin layer. [Example]

[0062] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0063] Example 1 [Formation of foam resin precursor layer with substrate] Composition A for forming a foamed resin layer was obtained by kneading 100 parts by mass of polyvinyl chloride resin resin A, 47 parts by mass of DOP (bis(2-ethylhexyl) phthalate, plasticizer), 15 parts by mass of calcium carbonate, 2.5 parts by mass of a Ba-Zn compound (custom-made product, stabilizer), 3.0 parts by mass of ADCA (azodicarbonamide, foaming agent), and 9.0 parts by mass of titanium oxide using a dissolver-type kneader (manufactured by Primix Corporation). The foamed resin layer-forming composition A was applied onto the backing paper of the substrate using a coater, and after a drying step, a foamed resin precursor layer A with the substrate was obtained.

[0064] [Formation of water-repellent layer] Using a gravure printing method using a bias mesh roll with a circular convex surface formed on the roll surface, a water-repellent agent (vinyl chloride emulsion, product name "Viniblan (custom-made product)", manufactured by Nissin Chemical Industry Co., Ltd.) was printed on the main surface of the foamed resin precursor layer A with substrate obtained above, facing the foamed resin precursor layer, and a drying process was performed to form a water-repellent layer A.

[0065] [Laminate formation] The foamed resin precursor layer A with the substrate on which the water-repellent layer A was formed was heated at 255°C for 25 seconds (product name "Gear Oven", manufactured by Toyo Seiki Seisakusho, Ltd.) to foam the foamed resin precursor layer into a foamed resin layer, thereby obtaining a laminate A. Measurements using a dial gauge revealed that the thickness of the foamed resin layer in laminate A was 0.745 mm, and the thickness of water-repellent layer A was 3 μm. Furthermore, water-repellent layer A was formed so that the shape of the portion where it was not formed was circular.

[0066] [Laminate evaluation] The laminate and the foamed resin layer were evaluated as follows.

[0067] (Contact angle before reheating) The contact angle of each surface described below was measured by a method in accordance with JIS R 3257:1999, and the contact angle before reheating was recorded. The results are shown in Table 1. Contact angle of the laminate surface: Refers to the contact angle of the laminate surface obtained by heating and foaming the foam resin precursor layer on which the water-repellent layer is formed. Contact angle on the surface of the foamed resin layer: Refers to the contact angle on the surface of the foamed resin layer obtained by heating and foaming the foamed resin precursor layer A without forming a water-repellent layer.

[0068] (Contact angle of laminate after reheating) Using a heating tester (trade name "Gear Oven," manufactured by Toyo Seiki Seisakusho, Ltd.), the laminate was reheated at 190°C for 60 seconds, 200°C for 30 seconds, or 210°C for 30 seconds. After returning to room temperature, the contact angle of the laminate surface was measured according to JIS R 3257:1999, and this was taken as the contact angle of the laminate after reheating. The results are shown in Table 1.

[0069] (The ratio of the surface area covered by the water-repellent layer to the surface area of ​​the foamed resin layer) The ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer is determined by the following volumetric value (unit: cm ) specified for the bias mesh roll (the shape of the recessed portion of the plate: conical). 3 / m 2) and depth (unit: μm). Specifically, the area ratio (unit: %) was calculated from the above-mentioned formula (A) and formula (B) below, and this was defined as the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer. [1m 2 Printing area per unit (m 2 )] = [Volume value (cm 3 / m 2 )]×3÷[depth (μm)] ··· (A) [Area ratio (%)] =[1m 2 Printing area per unit (m 2 )]÷1(m 2 )×100 (B)

[0070] Here, the volume values ​​and depths obtained from the specifications of the bias mesh roll used in Example 1 were as follows. Volume: 9.0cm 2 / m 3 Depth: 35μm When these values ​​were substituted into the above formulas (A) and (B), the area ratio was calculated to be 77%, i.e., the ratio of the area covered by the water-repellent layer to the surface area of ​​the foamed resin layer in the laminate A was 77%.

[0071] <Example 2> A foamed resin precursor layer B with a substrate and a laminate B were obtained in the same manner as in Example 1, except that polyvinyl chloride resin B was used instead of polyvinyl chloride resin A. The obtained laminate and foamed resin layer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0072] Example 3 A foamed resin precursor layer C with a substrate and a laminate C were obtained in the same manner as in Example 1, except that polyvinyl chloride resin C was used instead of polyvinyl chloride resin A. The obtained laminate and foamed resin layer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0073] Example 4 A foamed resin precursor layer D with a substrate and a laminate D were obtained in the same manner as in Example 1, except that polyvinyl chloride resin D was used instead of polyvinyl chloride resin A. The obtained laminate and foamed resin layer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0074] <Comparative Example 1> A foamed resin precursor layer E with a substrate and a laminate E were obtained in the same manner as in Example 1, except that polyvinyl chloride resin E was used instead of polyvinyl chloride resin A. The obtained laminate and foamed resin layer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0075] <Comparative Example 2> A foamed resin precursor layer F with a substrate and a laminate F were obtained in the same manner as in Example 1, except that polyvinyl chloride resin F was used instead of polyvinyl chloride resin A. The obtained laminate and foamed resin layer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0076] Details of the materials used in the above examples and comparative examples are as follows. Polyvinyl chloride resin A: Custom-made product (contains polyvinyl chloride resin (average degree of polymerization: 820) and emulsifier) Polyvinyl chloride resin B: Custom-made product (contains polyvinyl chloride resin (average degree of polymerization: 950) and emulsifier) Polyvinyl chloride resin C: Custom-made product (contains polyvinyl chloride resin (average degree of polymerization: 950) and emulsifier) Polyvinyl chloride resin D: Custom-made product (contains polyvinyl chloride resin (average degree of polymerization: 900) and emulsifier) Polyvinyl chloride resin E: Product name "LB-133", manufactured by Tosoh Corporation (contains polyvinyl chloride resin (average degree of polymerization: 900) and emulsifier) Polyvinyl chloride resin F: Product name "PR-W", manufactured by Formosa (contains polyvinyl chloride resin (average degree of polymerization: 869) and emulsifier)

[0077] [Table 1]

[0078] From the above results, it was found that in Examples 1 to 4, the contact angle on the surface of the foamed resin layer was large (high water repellency), and further, the contact angle on the surface on the water-repellent layer side of the laminate formed using these was also large (high water repellency). Furthermore, the laminates of Examples 1 to 4 were prevented from decreasing in the contact angle on the surface on the water-repellent layer side even after reheating, which showed that the water repellency of the laminate was maintained even by heat. In contrast, in Comparative Examples 1 and 2, the contact angle on the surface of the foamed resin layer side of the intermediate laminate was small (low water repellency), and furthermore, the contact angle on the surface of the water-repellent layer side of the laminate formed using this was also small (low water repellency). [Industrial Applicability]

[0079] The laminate of the present invention can be used, for example, as wallpaper, decorative sheets, baseboards, and the like. [Explanation of symbols]

[0080] 1 Base material layer 2. Foamed resin layer 3 Water-repellent layer 10 Laminate

Claims

1. a base layer, a foamed resin layer, and a water-repellent layer laminated in this order; the surface of the foamed resin layer has a contact angle of 20° or more; the surface of the foamed resin layer is partially covered with the water-repellent layer, a ratio of an area covered by the water-repellent layer to an area of ​​the surface of the foamed resin layer is more than 70% and 90% or less; the shape of the portion where the water-repellent layer is formed or the shape of the portion where the water-repellent layer is not formed is a stripe shape, a lattice shape, or a sea-island shape, But not embossed, laminate.

2. The laminate according to claim 1 , wherein the water repellent agent contained in the water repellent layer is a non-fluorine-based water repellent agent.

3. The laminate according to claim 1 , wherein the foamed resin layer comprises a polyvinyl chloride resin.

4. 4. The laminate according to claim 3, wherein the content of the polyvinyl chloride resin is 30 to 65% by mass based on the total mass of the foamed resin layer.

5. the foamed resin layer further contains a filler; 5. The laminate according to claim 4, wherein the content of the filler in the foamed resin layer is more than 0 parts by mass and not more than 30 parts by mass when the content of the polyvinyl chloride resin in the foamed resin layer is 100 parts by mass.

6. 10. The laminate of claim 1 for use in wallpaper.

7. The laminate according to claim 1 for use as a decorative sheet.

8. a step of forming a foamed resin precursor layer from a foamed resin layer-forming composition; applying a water-repellent layer-forming composition to the surface of the foamed resin precursor layer with a bias mesh roll; and The method for producing a laminate according to any one of claims 1 to 7, comprising the steps of: foaming the foam resin precursor layer to form a foam resin layer, in this order.

9. A method for manufacturing wallpaper, comprising a step of embossing the surface of the water-repellent layer side of the laminate described in any one of claims 1 to 6.

10. A method for manufacturing a decorative sheet, comprising a step of embossing the surface of the laminate described in any one of claims 1 to 5 and 7 on the side of the water-repellent layer.

Images