Laminate structure, vehicle interior material with the same laminate structure, construction interior material, or furniture, and laminate structure manufacturing method

Abstract

To provide a technology capable of preventing from the oozing of components onto a surface.SOLUTION: The present technology provides a laminate structure 1 having a skin material 11, a base material 12 bonded to the skin material, and a hydrophilic polymer 13 existing on the base material side of the skin material. The laminate structure can be applied to a vehicle interior material, a construction interior material, furniture, and so on. The present technology is a manufacturing method of the laminate structure which has the skin material, the base material bonded to the skin material, and a hydrophilic polymer existing on the base material side of the skin material. The manufacturing method of the laminate structure comprises the process of bonding the skin material to the base material after a hydrophilic polymer aqueous solution is coated on the back side of the skin material.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present technology relates to a laminated structure, a vehicle interior material, a building interior material, or furniture including the laminated structure, and a method for manufacturing the laminated structure. [Background technology]

[0002] In the fields of construction, transportation, and other industries, laminated structures with various characteristics have been developed for the purposes of heat insulation, heat resistance, sound insulation, soundproofing, sound absorption, fire prevention, flame retardancy, impact resistance, cushioning, adhesion, etc. Here, in laminated structures, each layer is often bonded by some method, but depending on the environment in which it is used, there is a problem that the adhesive or components contained in each layer seep out to the surface due to changes in the viscosity of the adhesive used for bonding or changes in the physical properties of each layer.

[0003] In response to such problems, for example, Patent Document 1 discloses a skin material that has an object of preventing liquids such as isocyanates and printing liquids from seeping out onto the main surface of the skin material, and that comprises a fiber sheet, a surfactant, and a binder resin, and that has a portion where the binder resin is present on the surface of the constituent fibers of the fiber sheet, with a layer of the surfactant interposed therebetween.

[0004] In addition, Patent Document 2 describes a fabric made of chemical fibers with a basis weight of 130 to 200 g / m, which aims to prevent the seepage of urethane foam resin into the skin material without using a fluorine-based oil repellent. 2 , thickness 1.5~2.5mm, apparent density 0.08~0.12g / cm 3The nonwoven fabric-foamed urethane laminate disclosed herein is a laminate of a nonwoven fabric treated with a non-fluorine-based waterproofing agent, in which the nonwoven fabric is impregnated with a non-fluorine-based waterproofing agent, and foamed polyurethane, wherein the nonwoven fabric treated with the non-fluorine-based waterproofing agent is impregnated with the non-fluorine-based waterproofing agent over a range of 1 / 3 to 1 / 2 of the thickness of the nonwoven fabric from the non-polyurethane foam laminated surface at a position where the nonwoven fabric is most impregnated with the non-fluorine-based waterproofing agent, and the foamed polyurethane is impregnated into a portion of the nonwoven fabric treated with the non-fluorine-based waterproofing agent. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2022-137567 A [Patent Document 2] JP 2015-3445 A Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, technological developments are underway to prevent the components of a laminate structure from seeping out to the surface. However, depending on the molding method, manufacturing conditions, materials used, etc., there are problems such as the laminate structure being insufficient in preventing seepage, and it can be said that technology to address this problem is still in the process of being developed.

[0007] Therefore, the main object of the present technology is to provide a technology for preventing the components from seeping out onto the surface. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems, and as a result, they succeeded in preventing the exudation of constituent components by using a hydrophilic polymer, thereby completing the present technology.

[0009] That is, in the present technology, first, a laminated structure is provided that has a skin material, a substrate bonded to the skin material, and a hydrophilic polymer present on the substrate side of the skin material. The skin material may be a laminate of a skin layer and a foam layer. The skin material and the base material may be bonded with an adhesive. The substrate may be a laminate of a fiber layer and a foam layer. The substrate may be a foam. In this case, the foam may be integrally formed with the skin material. The covering material may have a stitched portion.

[0010] Next, the present technology also provides a vehicle interior material, a building interior material, or furniture comprising the laminated structure according to the present technology.

[0011] The present technology further provides a method for manufacturing a laminated structure having a substrate adhered to the skin material and a hydrophilic polymer present on the substrate side of the skin material, the method comprising the steps of applying an aqueous solution of the hydrophilic polymer to the back surface of the skin material and then adhering the skin material to the substrate. [Brief description of the drawings]

[0012] [Figure 1] 1 is a conceptual cross-sectional view that illustrates a first embodiment of a laminate structure 1 according to the present technology. [Diagram 2] 1 is a conceptual cross-sectional view that illustrates a modified example of the first embodiment of the laminate structure 1 according to the present technology. [Diagram 3] 1 is a conceptual cross-sectional view that illustrates a second embodiment of the laminate structure 1 according to the present technology. [Figure 4] FIG. 11 is a conceptual cross-sectional view that illustrates a third embodiment of the laminate structure 1 according to the present technology. [Diagram 5] 1 is a conceptual cross-sectional view that illustrates a fourth embodiment of the laminate structure 1 according to the present technology. [Figure 6] 1 is a photograph substituted for a drawing showing the results of Experimental Example 1. [Figure 7] 1A to 1C are diagrams showing an example of a sewn portion 113. FIG. [Figure 8] 1 is a photograph in place of a drawing showing the results of Experimental Example 2. [Figure 9] 13 is a graph showing the results of Experimental Example 4. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, preferred embodiments for carrying out the present technology will be described with reference to FIGS. 1 to 5. FIG. The embodiments described below are representative examples of the present technology, and any of the embodiments can be combined. In addition, the scope of the present technology is not narrowed by these embodiments.

[0014] 1.Laminated structure 1 The laminated structure 1 according to the present technology at least includes a skin 11, a substrate 12 bonded to the skin 11, and a hydrophilic polymer 13 present on the substrate 12 side of the skin 11. In addition, an adhesive 14, a backing material 15, etc. may be included as necessary. Each component will be described in detail below.

[0015] (1)Skin material 11 As described above, the laminated structure 1 according to the present technology includes the skin material 11. As the material constituting the skin material 11, one or more types of materials can be freely combined and used according to the application and purpose of the laminated structure 1, as long as the action and effect of the present technology are not impaired. Specifically, for example, woven fabrics, knitted fabrics, nonwoven fabrics, etc. using one or more types of fibers such as polyethylene terephthalate (PET) fibers, polyester fibers, polypropylene fibers, polyamide fibers, acrylic fibers, vinylon fibers, polyurethane fibers (spandex), glass fibers, carbon fibers, and natural fibers (e.g., wool, cotton, cellulose nanofibers, etc.) in combination can be used. In addition, synthetic leather (e.g., PVC, urethane, etc.), genuine leather, etc. may also be used.

[0016] In addition, since the skin material 11 is disposed on the outermost surface among the essential structures of the laminated structure 1 according to the present technology, the term "skin" is used for convenience, but in an actual product, it is not limited to being disposed on the outermost surface. For example, it is also possible to further laminate a desired material on the surface of the skin material 11, to cover the skin material 11 with a desired material, or to cover the entire laminated structure 1 with a desired material.

[0017] (2) Hydrophilic polymer 13 The hydrophilic polymer 13 is present on the back surface of the skin material 11, i.e., on the side of the substrate 12. In the layered structure 1 according to the present technology, the use of the hydrophilic polymer 13 can prevent the components from seeping out to the surface.

[0018] The hydrophilic polymer 13 may be present on the substrate 12 side of the skin 11 in any manner selected from the group consisting of a state in which the hydrophilic polymer 13 is laminated on the substrate 12 side of the skin 11, a state in which a part of the hydrophilic polymer 13 has soaked in from the substrate 12 side of the skin 11, a state in which the hydrophilic polymer 13 has blended with a part or all of the adhesive 14 described below, and a state in which the hydrophilic polymer 13 has blended with a part of the substrate 12.

[0019] The hydrophilic polymer 13 is not particularly limited as long as it has hydrophilicity, and examples thereof include synthetic polymers such as polyallylamine or a salt thereof, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine or a salt thereof, polyacrylamide or a salt thereof, polydiallyldimethylammonium, and polyvinylpyridine, and polysaccharides such as starch, locust bean gum, guar gum, tamarind seed gum, chitosan, carboxymethylcellulose, alginic acid, and karaya gum. In the present technology, among these, polyallylamine or a salt thereof is particularly preferred, and polyallylamine is more preferred.

[0020] The weight average molecular weight of the hydrophilic polymer 13 is not particularly limited and is, for example, 300 to 500,000, and preferably 5,000 to 300,000.

[0021] In addition, 1m of skin material 11 2 The lower limit of the amount of the hydrophilic polymer 13 used per unit area is, for example, 0.1 g / m 2 or more, preferably 0.5 g / m 2 More preferably, 0.6 g / m 2 The amount of hydrophilic polymer 13 used was 0.1 g / m 2 By setting the thickness to 1 m or more, the effect of the hydrophilic polymer 13 can be surely exhibited. 2 The upper limit of the amount of the hydrophilic polymer 13 used per unit area is, for example, 20 g / m 2 less than 15 g / m 2 Less than 12.5 g / m 2 The amount of hydrophilic polymer 13 used was 20 g / m 2 By setting the above conditions, discoloration and changes in physical properties of the skin material 11 can be prevented.

[0022] When manufacturing the laminated structure 1, the hydrophilic polymer 13 is preferably used in a solution state in which it is dissolved in a solvent appropriate for the type of polymer. By using the hydrophilic polymer 13 in a solution state when manufacturing the laminated structure 1, the effect of suppressing the exudation of the constituent components to the surface can be further improved. The solvent can be freely selected as appropriate depending on the type of hydrophilic polymer 13, but in the present technology, it is preferable to use water as the solvent. The hydrophilic polymer 13 uses water as a catalyst and exhibits oil repellency in the form of an aqueous solution.

[0023] The hydrophilic polymer 13 can be present on the substrate 12 side of the skin 11 by, for example, applying the hydrophilic polymer 13 in a solution state to the rear surface of the skin 11. The application method can be a conventionally known method and is not particularly limited, but the hydrophilic polymer 13 in a solution state can be applied to the rear surface of the skin 11 by foaming, impregnating, spraying, transferring, scattering, or printing.

[0024] When the solvent for the hydrophilic polymer 13 is water and an aqueous solution of the hydrophilic polymer 13 is used, the lower limit of the concentration in the aqueous solution is, for example, 2.5% by weight or more, preferably 5.0% by weight or more, and more preferably 7.5% by weight or more. By setting the concentration of the aqueous solution to 2.5% by weight or more, the oil repellency effect of the aqueous solution of the hydrophilic polymer 13 can be reliably exhibited. In addition, the upper limit of the concentration in the aqueous solution is, for example, 80% by weight or less, preferably 70% by weight or less. By setting the concentration of the aqueous solution to 80% by weight or less, discoloration and changes in physical properties of the skin material 11 can be prevented.

[0025] (3) Base material 12 As described above, the laminated structure 1 according to the present technology includes the substrate 12 bonded to the skin material 11. The substrate 12 may take various forms depending on the application or purpose of the laminated structure 1, and will be described in detail in each embodiment of the laminated structure 1 below.

[0026] (4) Example of Laminate Structure 1 Note that, although embodiments of the laminate structure 1 will be described in detail below, the present technology is not limited to these embodiments.

[0027] [First embodiment] FIG. 1 is a conceptual cross-sectional view showing a first embodiment of the laminated structure 1 according to the present technology. FIG. 2 is a conceptual cross-sectional view showing a modified example of the first embodiment of the laminated structure 1 according to the present technology. The first embodiment of the laminated structure 1 according to the present technology is a laminated structure 1 having a skin 11, a substrate 12 bonded to the skin 11, and a hydrophilic polymer 13 present on the substrate 12 side of the skin 11, and the substrate 12 is a foam. In this embodiment, the foam (= substrate 12) and the skin 11 are integrally molded, so that the skin 11 and the foam (= substrate 12) are bonded to each other. In this case, in this embodiment, as shown in FIG. 2, a part of the hydrophilic polymer 13 may migrate to the substrate 12 side and be impregnated into a part of the substrate 12.

[0028] As a method for integral molding, a conventionally known method can be used, and is not particularly limited. For example, a method can be adopted in which a foam (= base material 12) is foamed in a mold to bond the skin material 11 and the base material 12 together.

[0029] Specifically, for example, in the case of integral molding, when the temperature of the hydrophilic polymer 13 side of the skin material 11 increases over time, the aqueous solution of the hydrophilic polymer 13 exhibiting oil repellency can prevent the foam-producing composition before resinification or foaming progresses from migrating to the skin material 11 side. Thereafter, when the resinification or foaming progresses in the foam-producing composition and the temperature rises due to the generation of foaming heat or the like, the aqueous solution of the hydrophilic polymer 13 becomes in a state of hydrophilic polymer 13 as the water solvent evaporates. At this time, the resinification or foaming has already progressed and the viscosity of the foam-producing composition has increased, so the occurrence of the phenomenon of penetration into the skin material 11 decreases. As a result, it is possible to prevent the foam-producing composition and various components constituting the foam-producing composition from seeping out onto the surface of the skin material 11.

[0030] <<Foam>> As the foam used in the base material 12 of the first embodiment, one or more foams that can be used in a general laminated structure can be freely selected and used as long as the action and effect of the present technology are not impaired. Specific examples include layers using polyurethane foam, polyethylene foam, polypropylene foam, vinyl chloride foam, polystyrene foam, etc. In the present technology, polyurethane foam is particularly preferred among these.

[0031] The polyurethane foam used for the foam of the first embodiment is produced using a composition for producing polyurethane foam that contains a polyol, a blowing agent, a catalyst, a foam stabilizer, an isocyanate, and, as necessary, various additives. Each raw material of the polyurethane foam will be described below.

[0032] <Polyol> The polyol used in the polyurethane foam producing composition can be one or more polyols that can be used in the production of polyurethane foam, as long as the action and effect of the present technology are not impaired.Specific examples of the polyol include polyether polyols obtained by adding alkylene oxides such as ethylene oxide (EO) and propylene oxide (PO) to polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose; polyester polyols obtained by polycondensation of aliphatic carboxylic acids such as malonic acid, succinic acid, and adipic acid, or aromatic carboxylic acids such as phthalic acid, and aliphatic glycols such as ethylene glycol, diethylene glycol, and propylene glycol; polyether ester polyols obtained by reacting the polyether polyols with polybasic acids to form polyesters; and polyether ester polyols having both polyether and polyester segments in one molecule.

[0033] <Foaming agent> The blowing agent used in the polyurethane foam-producing composition may be one or more blowing agents that can be used in the production of polyurethane foam, as long as the action and effect of the present technology is not impaired. Specific examples include water, methylene chloride, carbon dioxide, pentane, etc. The amount of the blowing agent used is not particularly limited as long as the action and effect of the present technology is not impaired, but it is preferable to use, for example, 1 part by mass to 8 parts by mass of the blowing agent per 100 parts by mass of polyol.

[0034] <Catalyst> The catalyst used in the polyurethane foam producing composition can be one or more catalysts that can be used in the production of polyurethane foam, as long as the action and effect of the present technology is not impaired. Specific examples include amine catalysts such as triethylamine, dimethylaminohexanol, triethylenediamine, and tetramethylguanidine; tin catalysts such as stannous octoate; and metal catalysts (also called "organometallic catalysts") such as phenylmercury propionate and lead octenate. The amount of the catalyst used is not particularly limited as long as the action and effect of the present technology is not impaired. For example, it is preferable to use 0.1 to 2 parts by mass of the catalyst relative to 100 parts by mass of polyol.

[0035] <Foam stabilizer> The foam stabilizer used in the polyurethane foam-producing composition may be one or more foam stabilizers that can be used in the production of polyurethane foam, as long as the action and effect of the present technology is not impaired. Specific examples include silicone-based foam stabilizers, fluorine-containing compound-based foam stabilizers, surfactants, etc. The amount of foam stabilizer used is not particularly limited as long as the action and effect of the present technology is not impaired, but it is preferable to use, for example, 0.5 to 3 parts by mass of foam stabilizer per 100 parts by mass of polyol.

[0036] <Isocyanate> The isocyanate used in the polyurethane foam producing composition can be one or more isocyanates that can be used in the production of polyurethane foam, as long as the action and effect of the present technology are not impaired. Specific examples of the isocyanate include aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexamethane diisocyanate; aromatic isocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, xylylene diisocyanate, and polymeric polyisocyanate (crude MDI); and modified polyisocyanates obtained by modifying these.

[0037] In addition, the isocyanate index of the polyurethane foam is not particularly limited as long as it does not impair the action and effect of the present technology, but for example, a polyurethane foam having an isocyanate index of 90 to 120 can be used for the foam layer 122. In the present technology, the isocyanate index is a value calculated by [(isocyanate equivalent in the composition for producing polyurethane foam / active hydrogen equivalent in the composition for producing polyurethane foam)×100].

[0038] <Other> In the composition for producing polyurethane foam, one or more additives that can be used in the production of polyurethane foam can be freely selected and used as necessary, as long as they do not impair the action or effect of the present technology. Specific examples of additives include flame retardants, stabilizers, plasticizers, colorants, pigments, antioxidants, crosslinking agents, antibacterial agents, dispersants, and ultraviolet absorbers, but the present technology is not limited to these.

[0039] [Second embodiment] FIG. 3 is a conceptual cross-sectional view showing a second embodiment of the laminated structure 1 according to the present technology. The second embodiment of the laminated structure 1 according to the present technology is a laminated structure 1 having a skin material 11, a substrate 12 bonded to the skin material 11, and a hydrophilic polymer 13 present on the substrate 12 side of the skin material 11, the skin material 11 being a laminate of a skin layer 111 and a skin-layer-side foam layer 112, and the substrate 12 being a foam. In the second embodiment, as in the first embodiment, the foam (= substrate 12) and the skin material 11 are integrally molded, so that the skin material 11 and the foam (= substrate 12) are bonded to each other. In the second embodiment, the hydrophilic polymer 13 may be impregnated into a part of the skin-layer-side foam layer 112, although not shown.

[0040] In this embodiment, even if the skin material 11 has a sewn portion 113 (i.e., a portion where the skin materials 11 are sewn together), the hydrophilic polymer 13 exerts an oil-repellent effect, thereby repelling hydrophobic components in particular and preventing them from seeping out of the sewn portion 113 to the surface.

[0041] Here, the sewn portion 113 will be described with a specific example. Fig. 7A is a perspective view showing a molded body having a second embodiment of the laminated structure 1 according to the present technology, Fig. 7B is a cross-sectional view taken along line XX, and Fig. 7C is a partially enlarged view of the dashed portion in Fig. 7B. For example, as shown in Fig. 7, in a molded body formed by sewing a skin material 11 and injecting a foam-producing composition into the interior of the molded body and foaming it, the hydrophilic polymer 13 is present on the inner surface of the skin material 11, thereby preventing the hydrophobic components from seeping out from the sewn portion 113 to the surface.

[0042] 7B and 7C, the hydrophilic polymer 13 may be present on the entire inner surface of the skin 11, but for example, although not shown, the hydrophilic polymer 13 may be present only on the inner surface of the sewn portion 113. When the hydrophilic polymer 13 is present on the entire inner surface of the skin 11, the hydrophilic polymer 13 may be present uniformly, or the hydrophilic polymer 13 may be present in a larger amount on the inner surface of the sewn portion 113 than in other portions.

[0043] <<Epidermal layer 111>> The skin layer 111 is disposed on the outermost surface of the essential structures of the laminated structure 1, and may be constructed of one or more materials similar to those constituting the skin material 11 described above, in any combination depending on the application or purpose of the laminated structure 1, as long as the action or effect of the present technology is not impaired.

[0044] <<Skin layer side foam layer 112>> As long as the action and effect of the present technology are not impaired, the skin layer side foam layer 112 can be formed by freely combining one or more of the above-mentioned foams according to the use and purpose of the laminate structure 1. In the present technology, the skin layer side foam layer 112 using polyurethane foam is preferable.

[0045] [Third embodiment] 4 is a conceptual cross-sectional view that shows a schematic diagram of a third embodiment of the laminated structure 1 according to the present technology. The third embodiment of the laminated structure 1 according to the present technology has a skin 11, a substrate 12 bonded to the skin 11, and a hydrophilic polymer 13 present on the substrate 12 side of the skin 11, and the skin 11 and the substrate 12 are bonded together with an adhesive 14.

[0046] Although not shown in the drawings, this embodiment may further include a back surface material 15 on the surface opposite to the skin material 11. The back surface material 15 will be described in detail in the Fourth Embodiment described later.

[0047] The laminated structure 1 in this embodiment can be molded by, for example, heat pressing. The adhesive 14 temporarily loses viscosity due to heating, making it easier for it to seep out onto the surface of the skin material 11, and by the time the temperature of the hydrophilic polymer 13 rises due to heat pressing, the curing reaction of the adhesive 14 progresses, causing the viscosity of the adhesive 14 to increase. In the laminated structure 1 according to this embodiment, as shown in FIG. 4, the hydrophilic polymer 13 is provided between the skin material 11 and the adhesive 14, thereby preventing the adhesive 14, whose viscosity has temporarily decreased, from penetrating into the skin material 11. Note that, since the hydrophilic polymer 13 is used in this embodiment, there is an advantage that the temperature dependency is small compared to the case where a temperature-responsive polymer is used.

[0048] Specifically, for example, when adhesive 14 is used before curing during hot press molding, the action of hydrophilic polymer 13 can prevent adhesive 14, whose viscosity has temporarily decreased before curing, from migrating toward skin 11. Thereafter, the curing reaction of adhesive 14 progresses and the viscosity of adhesive 14 increases, decreasing the occurrence of the phenomenon of adhesive 14 penetrating into skin 11. Even at the stage where the curing reaction of adhesive 14 progresses, hydrophilic polymer 13 continues to block adhesive 14 and prevent adhesive 14 from seeping out onto the surface of skin 11.

[0049] A specific example has been given above of bonding the skin material 11 and the base material 12 by heat pressing. Even in the case of using an adhesive 14 that is in a molten state at high temperatures and hardens as the temperature drops to exhibit adhesion, it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin material 11.

[0050] <<Adhesive 14>> As for the adhesive 14, one or more types of adhesives that can be used in general laminate structures can be freely selected and used depending on the types of skin material 11 and base material 12 and the application of laminate structure 1, as long as the action and effect of the present technology are not impaired. Specifically, for example, acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, α-olefin adhesives, ether adhesives, ethylene-vinyl acetate resin adhesives, epoxy resin adhesives, vinyl chloride resin adhesives, chloroprene rubber adhesives, cyanoacrylate adhesives, isocyanate adhesives, styrene-butadiene rubber adhesives, nitrile rubber adhesives, nitrocellulose adhesives, reactive hot melt adhesives, phenol resin adhesives, modified silicone adhesives, polyamide resin adhesives, polyimide adhesives, polyurethane resin adhesives, polyolefin resin adhesives, polyvinyl acetate resin adhesives, polystyrene resin solvent adhesives, polyvinyl alcohol adhesives, polyvinylpyrrolidone resin adhesives, polyvinyl butyral resin adhesives, polybenzimidazole adhesives, polymethacrylate resin adhesives, melamine resin adhesives, urea resin adhesives, resorcinol adhesives, and the like can be used. Urethane adhesives, epoxy adhesives, modified silicone adhesives, acrylic adhesives, and the like can be used. In the present technology, among these, hydrophobic adhesives are particularly preferred, and among hydrophobic adhesives, isocyanate-based adhesives are particularly preferred.

[0051] Examples of isocyanate-based adhesives include aromatic TDI (toluene diisocyanate), polymeric MDI (4,4'-diphenylmethane diisocyanate), NDI (1,5-naphthalene diisocyanate), TODI (tolidine diisocyanate), PPDI (paraphenylene diisocyanate), XDI (xylylene diisocyanate), TMXDI (tetramethylxylene diisocyanate), or modified versions of these (for example, urethane-modified, allophanate-modified, biuret-modified, carboimide / uretonimine-modified, etc.).

[0052] [Fourth embodiment] 5 is a conceptual cross-sectional view showing a fourth embodiment of the laminated structure 1 according to the present technology. The fourth embodiment of the laminated structure 1 according to the present technology includes a skin material 11, a base material 12 bonded to the skin material 11, a hydrophilic polymer 13 present on the base material 12 side of the skin material 11, and a back material 15 laminated on the surface of the base material 12 opposite to the hydrophilic polymer 13 side, and the base material 12 is a laminate of a fiber layer 121a and a fiber layer 121b sandwiching a foam layer 122. In addition, an adhesive 14a and an adhesive 14b are mixed in the fiber layer 121a and the fiber layer 121b, and the skin material 11 and the fiber layer 121a, the fiber layer 121a and the foam layer 122, the foam layer 122 and the fiber layer 121b, and the fiber layer 121b and the back material 15 are bonded by the adhesive 14a and the adhesive 14b.

[0053] As in this embodiment, the fiber layer 121 and the foam layer 122 can be bonded to each other with the adhesive 14. In the present technology, the adhesive 14 is not essential, and for example, the fiber layer 121 and the foam layer 122 can be bonded to each other by integrally molding the fiber layer 121 and the foam layer 122.

[0054] The adhesive 14 is not limited to being interposed between the fiber layer 121 and the foam layer 122, and may be mixed into the fiber layer 121. In this case, the adhesive 14 mixed into the fiber layer 121 can also bond the skin material 11 and the base material 12 (the fiber layer 121 side).

[0055] In this embodiment, the details of the skin material 11, the hydrophilic polymer 13, and the adhesive 14 (14a, 14b) are the same as those described above, so a description thereof will be omitted here.

[0056] <<Fiber layers 121a, 121b>> As the fiber layers 121a and 121b used in the base material 12, one or more types of fibers that can be used in a general laminated structure can be freely selected and used as long as the action and effect of the present technology are not impaired. Specific examples include layers using inorganic fibers such as carbon fiber, glass fiber, rock wool, and metal fiber. In the present technology, among these, the fiber layers 121a and 121b using glass fiber are particularly preferred.

[0057] <<Foam layer 122>> The foam layer 122 used in the base material 12 can be formed by freely combining one or more of the above-mentioned foams according to the use and purpose of the laminate structure 1, as long as the action and effect of the present technology are not impaired. In the present technology, the foam layer 122 using polyurethane foam is preferable.

[0058] <<Backing material 15>> In this embodiment, a back surface material 15 can be provided on the surface of the laminated structure 1 opposite to the skin material 11. The back surface material 15 is not an essential component in the present technology, but can be provided for the purpose of protecting the back surface, improving workability of the laminated structure 1, etc.

[0059] As long as the action and effect of the present technology are not impaired, the material constituting the back surface material 15 can be one or a combination of two or more of various materials depending on the application and purpose of the laminated structure 1. For example, the same materials as those usable for the skin material 11 described above can be used, or films, sheets, various plate materials, etc. using resin, wood, metal, etc. can be used for the back surface material 15.

[0060] 2. Applications of laminated structure 1 The laminated structure 1 according to the present technology can be used for any purpose as long as it does not impair the function or effect of the present technology. For example, it can be used for interior materials for vehicles such as vehicle ceiling materials, arm rests, head rests, seats, pillar covers, rear trays, door trims, trunk trims, console boxes, airbag covers, instrument panels, meter covers, and crash pads; interior materials for buildings such as floor materials, architectural ceiling materials, wall materials, and wallpaper materials; and furniture such as carpets, sofas, cushions, futon covers, pillows, and mattresses.

[0061] As described above, even when the upholstery material 11 has a sewn portion 113 (i.e., a portion where upholstery materials 11 are sewn together), the hydrophilic polymer 13 exerts an oil repellent effect, thereby repelling hydrophobic components and preventing them from seeping out to the surface from the sewn portion 113. Therefore, the laminated structure 1 according to the present technology can be applied to those applications having the sewn portion 113 among the above uses.

[0062] In addition, the laminate structure 1 according to the present technology can be given any function depending on the application or purpose, as long as the action or effect of the present technology is not impaired. For example, functions such as heat insulation, heat resistance, sound insulation, sound insulation, sound absorption, fire prevention, flame retardancy, impact resistance, cushioning, and adhesiveness can be given. In addition, the desired function can be given to each layer constituting the laminate structure 1, or to the entire laminate structure 1.

[0063] As described above, the laminated structure 1 according to the present technology can prevent the components from seeping out, and therefore it is also possible to suppress the deterioration of the functions imparted to the components constituting the laminated structure 1. Conventionally, in order to suppress the seeping out of the components, for example, a method of providing a non-permeable layer such as a film between the skin material 11 and the base material 13 has been used, but there is a problem that the film reduces the amount of air permeability, thereby decreasing the functions such as sound absorption. On the other hand, as described above, in the present technology, it is not necessary to provide a non-permeable layer such as a film. In addition, for example, when the base material 12 is provided with a foam layer 122 and this foam layer 122 has various functions, the moldability of the foam layer 122 is improved by preventing the seeping out of the foam manufacturing composition before resinification or foaming, and the deterioration of various functions expected of the foam layer 122 can be suppressed.

[0064] 3. Manufacturing method of laminated structure 1 The manufacturing method according to the present technology is a method for manufacturing a laminated structure 1 having a skin 11, a substrate 12 bonded to the skin 11, and a hydrophilic polymer 13 present on the substrate 12 side of the skin 11, and includes a step (A) of applying an aqueous solution of the hydrophilic polymer 13 to the back surface of the skin 11, and then bonding the skin 11 and the substrate 12. Other steps may also be included as necessary.

[0065] (1) Process (A) In this step, an aqueous solution of the hydrophilic polymer 13 is applied to the rear surface of the skin 11, and then the skin 11 is bonded to the substrate 12. As described above, the method for applying the hydrophilic polymer 13 may be a conventionally known method, and is not particularly limited. The hydrophilic polymer 13 may be applied to the rear surface of the skin 11 by foaming, impregnating, spraying, transferring, scattering, or printing the hydrophilic polymer 13 in a solution state.

[0066] As a method for bonding the skin material 11 and the base material 12, when the skin material 11 or the base material 12 contains a foam, a method of forming them integrally by foaming them in a mold can be used, or a method of bonding them using an adhesive 14 can be used. When the adhesive 14 is used, a heat press may be performed as necessary.

[0067] (2) Other processes Other steps include a step of preparing an aqueous solution of the hydrophilic polymer 13, a step of preparing a foam-producing composition, a step of processing the obtained laminate structure 1 so as to be suitable for a desired use (for example, a step of sewing together the skin materials 11 to form the sewn part 113, etc.), etc. These steps are appropriately performed based on the technical common sense of a person skilled in the art.

[0068] The present technology can also be configured as follows. [1] A skin material; A substrate adhered to the skin material; a hydrophilic polymer present on the substrate side of the skin material; A laminated structure having the above structure. [2] The laminate structure according to [1], wherein the skin material is a laminate of a skin layer and a foam layer. [3] The laminated structure according to [1] or [2], wherein the skin material and the base material are bonded with an adhesive. [4] The laminate structure according to any one of [1] to [3], wherein the substrate is a laminate of a fiber layer and a foam layer. [5] The laminate structure according to any one of [1] to [3], wherein the substrate is a foam. [6] The laminate structure according to [5], wherein the foam is integrally molded with the skin material. [7] The laminated structure according to any one of [1] to [6], wherein the skin material has a sewn portion. [8] A vehicle interior material, a building interior material, or furniture, comprising the laminate structure according to any one of [1] to [7]. [9] A method for producing a laminated structure having a skin material, a substrate bonded to the skin material, and a hydrophilic polymer present on the substrate side of the skin material, comprising the steps of: A method for manufacturing a laminated structure, comprising a step of applying an aqueous solution of a hydrophilic polymer to a back surface of a skin material, and then bonding the skin material to a substrate. EXAMPLES

[0069] The present technology will be described in more detail below based on examples. Note that the examples described below are representative examples of the present technology, and the scope of the present technology is not to be interpreted narrowly by these examples.

[0070] <Experimental Example 1> In Experimental Example 1, the influence of differences in the configuration of the laminated structure on the appearance was examined.

[0071] (1) Manufacturing of laminated structures [Example 1] Using the materials shown in Table 1 below, a laminated structure (headrest) in the form shown in Fig. 7 was manufactured by integrally molding the constituent components by foaming them in a mold. As the aqueous solution of the hydrophilic polymer, a 10% aqueous solution of polyallylamine (manufactured by Nittobo Medical Co., Ltd.) was added to 1 m of the skin material. 2 The coating was applied to the back of the skin material so as to obtain the values ​​shown in Table 1 below, and the material was used as is. The skin material (artificial leather) used had a stitched section, and leakage of the components from the stitched section was also checked. [Comparative Example 1] Using the materials shown in Table 1 below, the components were foamed in a mold to form an integral mold in the same manner as in Example 1, except that the hydrophilic polymer was not included in the laminated structure shown in Figure 7. As with Example 1, a skin material having a sewn portion was used, and bleeding from the sewn portion was also confirmed.

[0072] (2) Evaluation The produced laminated structures were evaluated as follows.

[0073] [Appearance (bleed)] ○: No leakage from the stitching ×: Leaking from the stitching

[0074] (3) Results The results are shown in Table 1 and FIG.

[0075] [Table 1] *1: Because the skin material was synthetic leather, no seepage was found on the skin material, but leakage from the stitching was found in Comparative Example 1 (see "Comparative Example 1" in Figure 6).

[0076] (4) Discussion As shown in Table 1 and Figure 6, Comparative Example 1, which did not have a hydrophilic polymer, was unable to prevent leakage of the components from the sewn parts and had a poor appearance, whereas Example 1, which had a hydrophilic polymer, was able to prevent leakage of the components from the sewn parts.

[0077] <Experimental Example 2> In Experimental Example 2, the influence of differences in the composition of the laminated structure on the appearance was examined.

[0078] (1) Manufacturing of laminated structures [Examples 2 and 3] Using the materials shown in Table 2 below, a laminated structure (floor mat) in the form shown in FIG. 2 was produced by hot pressing at a molding temperature of 110° C. As the aqueous solution of the hydrophilic polymer, a 10% aqueous solution of polyallylamine (manufactured by Nittobo Medical Co., Ltd.) was applied to 1 m of the surface material. 2 The coating was applied to the back surface of a skin material (PET: polyethylene terephthalate) so as to give the values ​​shown in Table 2 below, and the material was used as is. [Comparative Example 2] Using the materials shown in Table 2 below, the components were foamed in a mold to form an integral mold in the same manner as in Examples 2 and 3, except that the laminate structure shown in FIG. 2 did not contain a hydrophilic polymer.

[0079] (2) Evaluation The produced laminated structures were evaluated as follows.

[0080] [Appearance (bleed)] ○: No bleeding from the skin ×: Oozing from the surface material

[0081] (3) Results The results are shown in Table 2 and FIG.

[0082] [Table 2]

[0083] (4) Discussion As shown in Table 2 and Figure 8, Comparative Example 2, which did not have a hydrophilic polymer, was unable to prevent the exudation of the components and had a poor appearance. On the other hand, Examples 2 and 3, which had a hydrophilic polymer, were able to prevent the exudation of the components.

[0084] <Experimental Example 3> In Experimental Example 3, the effects of differences in the configuration of the laminated structure and manufacturing conditions on the appearance were investigated.

[0085] (1) Manufacturing of laminated structures [Examples 4 to 10] Using the materials shown in Table 3 below, a laminated structure (ceiling surface material) in the form shown in FIG. 5 was produced by hot pressing at the molding temperature shown in Table 3 below. The names of the materials in Table 3 are shown below. As the aqueous solution of the hydrophilic polymer, a 10% aqueous solution of polyallylamine was applied to 1 m of the surface material. 2 The coating was applied to the back of the skin material so as to give the values ​​shown in Table 3 below, and the material was used as is.

[0086] Skin material: PET (polyethylene terephthalate (knitted skin)) Polyallylamine (manufactured by Nittobo Medical Co., Ltd.) Adhesive 1: Polymeric MDI (viscosity: approx. 0.22 Pa·s, NCO%: approx. 30%) Adhesive 2: Urethane-modified MDI (viscosity: approx. 2.40 Pa·s, NCO%: approx. 30%) Fiber layer: Fiberglass Foam layer: polyurethane foam (hereinafter, in Table 3, this is written as (i))

[0087] [Comparative Examples 3 to 5] Using the materials shown in Table 3 below, the components were foamed in a mold to form an integral mold in the same manner as in Examples 4 to 10, except that the layered structure shown in FIG. 5 did not contain a hydrophilic polymer.

[0088] (2) Evaluation The produced laminated structures were evaluated as follows.

[0089] [Appearance (bleed)] ◎: No bleeding or other defects ○: No bleeding, but some blurry darkness △: Several spots of bleeding ×: 10% or more of the material has leaked out

[0090] (3) Results The results are shown in Table 3.

[0091] [Table 3]

[0092] (4) Discussion As shown in Table 3, Comparative Examples 3 to 5, which did not have a hydrophilic polymer, were unable to prevent the exudation of the components, with more than 10% of the components exuding, resulting in poor appearance. On the other hand, Examples 4 to 10, which did have a hydrophilic polymer, were able to almost completely prevent the exudation of the components.

[0093] <Experimental Example 4> In Experimental Example 4, the effects of differences in the composition of the laminated structure and manufacturing conditions on the physical properties (normal incidence sound absorption coefficient) and appearance were investigated.

[0094] (1) Manufacturing of laminated structures [Example 11] Using the materials shown in Table 4 below, a laminated structure (ceiling surface material) in the form shown in FIG. 5 was produced by hot pressing at the molding temperature shown in Table 4 below. The names of the materials in Table 4 are shown below. As the aqueous solution of the hydrophilic polymer, a 10% aqueous solution of polyallylamine was applied to 1 m of the surface material. 2 The coating was applied to the back of the skin material so as to give the values ​​shown in Table 4 below, and the material was used as is.

[0095] Skin material: PET (polyethylene terephthalate (knitted skin)) Polyallylamine (manufactured by Nittobo Medical Co., Ltd.) Adhesive 1: Polymeric MDI (viscosity: approx. 0.22 Pa·s, NCO%: approx. 30%) Adhesive 3: Polymeric MDI (viscosity: approx. 9.80 Pa·s, NCO%: approx. 30%) Fiber layer: Fiberglass Foam layer: polyurethane foam (hereinafter, in Table 4, this is indicated as (i))

[0096] [Comparative Examples 6 and 7] Using the materials shown in Table 4 below, the components were foamed in a mold to form an integral mold in the same manner as in Example 11, except that the hydrophilic polymer was not included in the laminate structure shown in Figure 5.

[0097] (2) Evaluation The produced laminated structures were evaluated as follows.

[0098] [Appearance (bleed)] ◎: No bleeding or other defects ○: No bleeding, but some blurry darkness △: Several spots of bleeding ×: 10% or more of the material has leaked out

[0099] (3) Results The results are shown in Tables 4 and 5 and in FIG.

[0100] [Table 4]

[0101] [Table 5]

[0102] (4) Discussion As shown in Table 4, Comparative Example 6 and Comparative Example 7, which did not have a hydrophilic polymer, were unable to prevent the exudation of the components, with more than 10% exudation observed and poor appearance. On the other hand, Example 11, which had a hydrophilic polymer, was able to prevent the exudation of the components. Furthermore, as shown in Figure 9, Example 11 maintained the normal incidence sound absorption coefficient without any particular problems compared to Comparative Examples 6 and 7. [Explanation of symbols]

[0103] 1 Laminated structure 11 Skin material 12 Base material 13 Hydrophilic polymers 111 Epidermal layer 112 Skin layer side foam layer 113 Sewing department 121, 121a, 121b Fiber layer 122 Foam layer 14, 14a, 14b Adhesive 15 Backing material

Claims

1. A skin material; A substrate adhered to the skin material; a hydrophilic polymer present on the substrate side of the skin material; A laminated structure having the above structure.

2. The laminated structure according to claim 1 , wherein the skin material is a laminate of a skin layer and a foam layer.

3. The laminated structure according to claim 1 , wherein the skin material and the base material are bonded with an adhesive.

4. The laminate structure of claim 1 , wherein the substrate is a laminate of a fiber layer and a foam layer.

5. The laminate structure of claim 1 , wherein the substrate is a foam.

6. The laminate structure according to claim 5 , wherein the foam is integrally molded with the skin material.

7. The laminate structure of claim 1 , wherein the skin has stitching.

8. A vehicle interior material, a building interior material, or furniture, comprising the laminate structure according to any one of claims 1 to 7.

9. A method for producing a laminated structure having a skin material, a substrate bonded to the skin material, and a hydrophilic polymer present on the substrate side of the skin material, comprising the steps of: A method for manufacturing a laminated structure, comprising a step of applying an aqueous solution of a hydrophilic polymer to a back surface of a skin material, and then bonding the skin material to a substrate.

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