Laminated structure, and interior material for vehicle, interior material for construction, and furniture equipped with the laminated structure

Abstract

To provide a technique of preventing exudation of constituents onto a surface without affecting an inherent function in a laminated structure and adhesiveness of each layer.SOLUTION: A laminated structure 1 has a skin material 11, a base material 13 adhered to the skin material, and temperature-responsive polymer 12 present on a side closer to the base material of the skin material. In the laminated structure, the skin material and the base material can be adhered by an adhesive agent. The laminated structure can be used for an interior material for vehicle, an interior material for construction, and furniture or the like.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present technology relates to a laminated structure, and to a vehicle interior material, a building interior material, and furniture including 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. For example, Patent Document 1 discloses a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is formed on a substrate, the pressure-sensitive adhesive layer being made of a pressure-sensitive adhesive composition, in which a base polymer is a copolymer containing a structure derived from (a) a water-insoluble hydrophilic monomer and (b) a nitrogen-containing hydrophilic monomer, and the content of the structure derived from (a) the water-insoluble hydrophilic monomer in the base polymer is 40 mass% or more.

[0003] In a laminated structure, each layer is often bonded by some method. However, depending on the environment in which it is used, there is a problem that the viscosity of the adhesive used for bonding or the physical properties of each layer may change, causing the adhesive or components contained in each layer to seep out to the surface.

[0004] In recent years, techniques for reducing the seepage of components in a laminated structure have been developed. For example, Patent Document 2 describes a composite skin material in which a foam layer is laminated on the back surface of a fiber-based skin material, and the foam layer is laminated with a basis weight of about 30 to 100 g / m. 2 Ventilation volume: approx. 5-40cm 3 / cm 2 By adjusting the relative humidity to 100%, a composite skin material with a foam layer has been proposed that does not impair the sound absorption performance of the vehicle ceiling material and prevents the isocyanate components from seeping out to the skin side during the molding of the ceiling material. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2021-120449 A [Patent Document 2] JP 2003-11257 A Summary of the Invention [Problem to be solved by the invention]

[0006] As mentioned above, technological developments are underway to prevent the components in a laminated structure from seeping out onto the surface, but using a film or other material to prevent the components from seeping out can reduce the functions that are originally expected of the laminated structure, such as sound absorption performance. In addition, some materials used to prevent the components from seeping out can reduce the adhesion of each layer.

[0007] Therefore, the main object of the present technology is to provide a technology that prevents the components from seeping out to the surface without affecting the original functions of the laminated structure or the adhesiveness of each layer. [Means for solving the problem]

[0008] The inventors conducted intensive research to solve the above problems and succeeded in preventing the bleeding of components by using a temperature-responsive polymer without affecting the original functions of the laminated structure or the adhesion of each layer, thereby completing the present technology.

[0009] That is, in the present technology, first, a skin material and A substrate adhered to the skin material; a temperature responsive polymer present on the substrate side of the skin material; The present invention provides a laminate structure having the following structure: In the laminated structure according to the present technology, the skin material and the base material can be bonded to each other with an adhesive. In the laminated structure according to the present technology, the substrate may be a laminate of a fiber layer and a foam layer. The substrate may be a foam.

[0010] Next, the present technology provides a vehicle interior material, a building interior material, and furniture that include the laminated structure according to the present technology. [Brief description of the drawings]

[0011] [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] 1 is a conceptual cross-sectional view that illustrates a modified example of the second embodiment of the laminate structure 1 according to the present technology. [Diagram 5] 1 is a conceptual cross-sectional view that illustrates a third embodiment of the laminate structure 1 according to the present technology. [Figure 6] 1 is a conceptual cross-sectional view that illustrates a fourth embodiment of the layered structure 1 according to the present technology. [Figure 7] 13 is a graph showing the measurement results of normal incidence sound absorption coefficient in Experimental Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] A preferred embodiment for carrying out the present technology will be described below. The embodiments described below are examples of typical embodiments of the present technology, and any of the embodiments can be combined. In addition, the scope of the present technology is not narrowly interpreted by these.

[0013] 1.Laminated structure 1 The laminated structure 1 according to the present technology includes at least a skin material 11, a temperature-responsive polymer 12, and a substrate 13. In addition, it may include an adhesive 14, a backing material 15, etc., as necessary. Each component will be described in detail below. The substrate 13, the adhesive 14, and the backing material 15 will be described later with reference to specific embodiments.

[0014] (1)Skin material 11 The laminated structure 1 according to the present technology includes a skin material 11. As long as the action and effect of the present technology are not impaired, the material constituting the skin material 11 can be any material, or two or more materials can be freely combined according to the application and purpose of the laminated structure 1. Examples of such materials include woven fabrics, knitted fabrics, nonwoven fabrics, etc., which use one or two 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.).

[0015] Woven fabrics and knitted fabrics are coarser than nonwoven fabrics, and therefore are more susceptible to exudation of the components into the skin material 11 in the laminate structure 1. However, in the present technology, by providing a temperature-responsive polymer 12 described below, it is possible to prevent exudation of the components even in the skin material 11 made of woven fabric or knitted fabric.

[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, a desired material may be further laminated on the surface of the skin material 11, the skin material 11 may be covered with a desired material, or the entire laminated structure 1 may be covered with a desired material.

[0017] (2) Temperature-responsive polymer 12 The temperature-responsive polymer 12 is present on the back surface of the skin material 11, i.e., on the substrate 13 side. The manner in which the temperature-responsive polymer 12 is present is not limited as long as it is present on the substrate 13 side of the skin material 11. For example, the temperature-responsive polymer 12 may be present on the substrate 13 side of the skin material 11 in one or more states selected from a state in which a part of the temperature-responsive polymer 12 has soaked in from the substrate 13 side of the skin material 11, a state in which the temperature-responsive polymer 12 has blended with a part or all of the adhesive 14, and a state in which the temperature-responsive polymer 12 has blended with a part of the substrate 13 (not shown).

[0018] The temperature-responsive polymer used in the temperature-responsive polymer 12 is a polymer whose physicochemical properties change depending on the temperature. There are two types of temperature-responsive polymer: a lower critical solution temperature (LCST) type that dissolves in water at low temperatures and becomes insoluble at high temperatures, and an upper critical solution temperature (UCST) type that is insoluble at low temperatures and soluble at high temperatures.

[0019] As the temperature-responsive polymer 12, for example, a copolymer of a hydrophilic monomer and a hydrophobic monomer can be used. In the present technology, as the copolymer of a hydrophilic monomer and a hydrophobic monomer, it is preferable to use a copolymer of allylamine and a vinylamine having an arbitrary alkyl group. In addition, as long as the action and effect of the present technology are not impaired, one or more general lower critical solution temperature (LCST) type polymers or upper critical solution temperature (UCST) type polymers can be freely selected and used as the temperature-responsive polymer 12.

[0020] Examples of the lower critical solution temperature (LCST) type polymer include poly(N-alkylacrylamide) polymers such as poly(N-isopropylacrylamide), poly(N-ethylacrylamide), poly(N-propylacrylamide), poly(N-ethyl,N-methylacrylamide), poly(N,N-diethylacrylamide), poly(N-isopropyl,N-methylacrylamide), poly(N-cyclopropylacrylamide), poly(N-acryloylpyrrolidine), and poly(N-acryloylpiperidine); Poly(N-alkyl methacrylamide) polymers such as poly(N-isopropyl methacrylamide), poly(N-ethyl methacrylamide), poly(N-propyl methacrylamide), poly(N-ethyl,N-methyl methacrylamide), poly(N,N-diethyl methacrylamide), poly(N-isopropyl,N-methyl methacrylamide), poly(N-cyclopropyl methacrylamide), poly(N-methacryloylpyrrolidine), and poly(N-methacryloylpiperidine); poly(N-alkyl methacrylamide) polymers such as poly(methyl vinyl ether), poly(ethyl vinyl ether), ... polyvinyl alkyl ethers such as poly(propyl vinyl ether), poly(butyl vinyl ether), poly(pentenyl ether), poly(hexyl vinyl ether), poly(heptyl vinyl ether), and poly(octyl ether); poly-N-vinyl alkyl amides such as poly(isopropyl vinyl acrylamide), poly(n-propyl vinyl acrylamide), poly(n-butyl vinyl acrylamide), poly(tert-butyl vinyl acrylamide), poly(sec-butyl vinyl acrylamide), poly(methyl vinyl acrylamide), poly(ethyl vinyl acrylamide), poly(n-pentyl vinyl acrylamide), and poly(isopentyl vinyl acrylamide); alkyl-substituted celluloses such as methyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose; poly(2-alkyl-2-oxazolines such as poly(2-isopropyl-2-oxazoline); poly(N-vinyl caprolactam); and polyethylene glycol / polypropylene glycol block copolymers.

[0021] Examples of upper critical solution temperature (UCST) polymers include polymers of N,N'-dimethyl(acrylamidopropyl)ammonium propanesulfonic acid, polyethylene oxide, poly(vinyl alcohol), poly(hydroxyethyl methacrylate), poly(uracil acrylate), poly(methylacrylamide) / poly(N-acetylacrylamide) copolymers, poly(N-acryloylasparagine amide), poly(N-acryloylglutamine amide), poly(N-acryloylglycine amide), poly(N-methylacryloylasparagine amide), and poly(riboadenylic acid).

[0022] When manufacturing the laminate structure 1, the temperature-responsive polymer 12 is preferably used in a solution state in which it is dissolved in a solvent appropriate for the type of polymer. By using the temperature-responsive polymer 12 in a solution state when manufacturing the laminate structure 1, the effect of suppressing the exudation of the constituent components to the surface can be further improved. The solvent can be appropriately selected depending on the type of the temperature-responsive polymer 12, and for example, water can be used as the solvent.

[0023] The laminated structure 1 according to the present technology can prevent exudation of components by using the temperature-responsive polymer 12 without affecting the inherent functions of the laminated structure 1 or the adhesiveness of each layer. The reason for this will be described with reference to specific embodiments.

[0024] [First embodiment] Fig. 1 is a conceptual cross-sectional view that shows a first embodiment of a laminated structure 1 according to the present technology. Fig. 2 is a conceptual cross-sectional view that shows 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 has a skin material 11, a substrate 13 bonded to the skin material 11, and a temperature-responsive polymer 12 present on the substrate 13 side of the skin material 11, and the skin material 11 and the substrate 13 are bonded with an adhesive 14.

[0025] The laminated structure 1 can be formed, for example, by heat pressing. The adhesive 14 exhibits such behavior that the viscosity is temporarily reduced by heating, and by the time the temperature of the temperature-responsive polymer 12 is increased by heat pressing, the curing reaction of the adhesive 14 progresses, and the viscosity of the adhesive 14 increases. In the laminated structure 1 according to the first embodiment, as shown in FIG. 1, the temperature-responsive polymer 12 is provided between the skin material 11 and the adhesive 14, so that the adhesive 14 with reduced viscosity is blocked from penetrating into the skin material 11, and the adhesive 14 is not hindered from bonding the skin material 11 and the base material 13 when the curing reaction of the adhesive 14 progresses. Therefore, the adhesive 14 can be prevented from seeping out onto the surface of the skin material 11 without affecting the adhesion between the skin material 11 and the base material 13.

[0026] More specifically, for example, in the case of performing heat press molding, a case where an adhesive 14 that exhibits oiliness before hardening is used will be described. When using an adhesive 14 that exhibits oiliness before hardening, it is preferable to use a lower critical solution temperature (LCST) type polymer. A lower critical solution temperature (LCST) type polymer exhibits hydrophilicity at temperatures below the lower critical solution temperature (LCST), and can block the adhesive 14 that exhibits oiliness before hardening from migrating toward the skin material 11. Thereafter, when the temperature of the temperature-responsive polymer 12 increases by heat press and exceeds the lower critical solution temperature (LCST), the temperature-responsive polymer 12 becomes hydrophobic. The hydrophobic temperature-responsive polymer 12 cannot block the oily adhesive 14 from migrating toward the skin material 11, but by this time, the hardening reaction of the adhesive 14 has already progressed and the viscosity of the adhesive 14 has increased, so the occurrence of the phenomenon of the adhesive penetrating into the skin material 11 decreases. Furthermore, at the stage where the curing reaction of the adhesive 14 progresses, the temperature-responsive polymer 12 has become hydrophobic, and therefore becomes compatible with the oil-based adhesive 14 and does not block the oil-based adhesive 14 from migrating toward the skin 11. Therefore, there is no effect on the adhesion between the skin 11 and the substrate 13. As a result, it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin 11 without affecting the adhesion between the skin 11 and the substrate 13.

[0027] Next, for example, in the case of performing heat press molding, a case where an adhesive 14 that is water-based before curing is used will be described. When using an adhesive 14 that is water-based before curing, it is preferable to use an upper critical solution temperature (UCST) type polymer. Since an upper critical solution temperature (UCST) type polymer is hydrophobic at a temperature below the upper critical solution temperature (UCST), it can block the migration of the water-based adhesive 14 that is water-based before curing toward the skin material 11. After that, when the temperature of the temperature-responsive polymer 12 is increased by heat press and exceeds the upper critical solution temperature (UCST), the temperature-responsive polymer 12 becomes hydrophilic. The hydrophilic temperature-responsive polymer 12 cannot block the migration of the water-based adhesive 14 toward the skin material 11, but since the curing reaction of the adhesive 14 has already progressed and the viscosity of the adhesive 14 has increased by this time, the occurrence of the phenomenon of the adhesive penetrating into the skin material 11 decreases. Furthermore, at the stage where the curing reaction of the adhesive 14 progresses, the temperature-responsive polymer 12 has become hydrophilic, and therefore becomes compatible with the water-based adhesive 14 and does not block the migration of the hydrophilic adhesive 14 toward the skin 11. Therefore, there is no effect on the adhesion between the skin 11 and the base material 13. As a result, it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin 11 without affecting the adhesion between the skin 11 and the base material 13.

[0028] The above describes a specific example of bonding the skin material 11 and the base material 13 by heat pressing. However, even when using an adhesive 14 that is in a molten state at high temperatures and hardens to exhibit adhesion as the temperature decreases, by appropriately selecting the lower critical solution temperature (LCST) and upper critical solution temperature (UCST), it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin material 11 without affecting the adhesion between the skin material 11 and the base material 13.

[0029] For example, a case where an adhesive 14 that exhibits oiliness in a molten state at high temperature is used will be described. When an adhesive 14 that exhibits oiliness before hardening at high temperature is used, it is preferable to use an upper critical solution temperature (UCST) type polymer. The upper critical solution temperature (UCST) type polymer exhibits hydrophilicity at temperatures above the upper critical solution temperature (UCST), and can block the adhesive 14 that exhibits oiliness before hardening from migrating toward the skin material 11. Thereafter, as the temperature decreases, the temperature of the temperature-responsive polymer 12 also decreases, and when it becomes less than the upper critical solution temperature (UCST), the temperature-responsive polymer 12 becomes hydrophobic. The hydrophobic temperature-responsive polymer 12 cannot block the adhesive 14 that exhibits oiliness from migrating toward the skin material 11, but by this time, the hardening reaction of the adhesive 14 has already progressed and the viscosity of the adhesive 14 has increased, so the occurrence of the phenomenon of the adhesive penetrating into the skin material 11 decreases. Furthermore, at the stage where the curing reaction of the adhesive 14 progresses, the temperature-responsive polymer 12 has become hydrophobic, and therefore becomes compatible with the oil-based adhesive 14 and does not block the oil-based adhesive 14 from migrating toward the skin 11. Therefore, there is no effect on the adhesion between the skin 11 and the substrate 13. As a result, it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin 11 without affecting the adhesion between the skin 11 and the substrate 13.

[0030] Also, for example, a case where an adhesive 14 that is water-based in a molten state at high temperature is used will be described. When an adhesive 14 that is oil-based before hardening at high temperature is used, it is preferable to use a lower critical solution temperature (LCST) type polymer. The lower critical solution temperature (LCST) type polymer is hydrophobic at a temperature above the lower critical solution temperature (LCST), and can block the adhesive 14 that is water-based before hardening from migrating toward the skin material 11. Thereafter, as the temperature decreases, the temperature of the temperature-responsive polymer 12 also decreases, and when it becomes less than the lower critical solution temperature (LCST), the temperature-responsive polymer 12 becomes hydrophilic. The hydrophilic temperature-responsive polymer 12 cannot block the adhesive 14 that is water-based from migrating toward the skin material 11, but by this time, the hardening reaction of the adhesive 14 has already progressed and the viscosity of the adhesive 14 has increased, so the occurrence of the phenomenon of the adhesive penetrating into the skin material 11 decreases. Furthermore, at the stage where the curing reaction of the adhesive 14 progresses, the temperature-responsive polymer 12 has become hydrophilic, and therefore becomes compatible with the water-soluble adhesive 14 and does not block the migration of the water-soluble adhesive 14 toward the skin 11. Therefore, there is no effect on the adhesion between the skin 11 and the base material 13. As a result, it is possible to prevent the adhesive 14 from seeping out onto the surface of the skin 11 without affecting the adhesion between the skin 11 and the base material 13.

[0031] The adhesive 14 that can be used in the present technology can be one or more adhesives that can be used in general laminate structures, freely selected depending on the types of skin material 11 and base material 13 and the application of laminate structure 1, as long as the action and effect of the present technology is not impaired. Examples of the adhesive include 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, phenolic 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, and resorcinol adhesives. Urethane adhesives, epoxy adhesives, modified silicone adhesives, and acrylic adhesives can be used. Among these, in the present technology, it is preferable to use an isocyanate adhesive.

[0032] 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), and modified versions of these (for example, urethane-modified, allophanate-modified, biuret-modified, carboimide / uretonimine-modified, etc.).

[0033] The base material 13 will be described in the second and third embodiments described later.

[0034] [Second embodiment] 3 is a conceptual cross-sectional view that shows a schematic diagram of 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 has a skin material 11, a substrate 13 bonded to the skin material 11, and a temperature-responsive polymer 12 present on the substrate 13 side of the skin material 11, and the skin material 11 and the substrate 13 are bonded with an adhesive 14. The substrate 13 is a laminate of a fiber layer 131 and a foam layer 132, and the fiber layer 131 and the foam layer 132 are bonded with an adhesive 133.

[0035] The details of the skin material 11, the temperature responsive polymer 12, and the adhesive 14 in the second embodiment are the same as those of the skin material 11, the temperature responsive polymer 12, and the adhesive 14 in the first embodiment described above, so a description thereof will be omitted here.

[0036] (1) Fiber layer 131 As the fiber layer 131 used in the base material 13 of the second embodiment, 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. For example, layers using inorganic fibers such as carbon fiber, glass fiber (glass fiber), rock wool, and metal fiber can be used, and in the present technology, the fiber layer 131 using glass fiber is preferable.

[0037] (2) Foam layer 132 As the foam layer 132 used in the base material 13 of the second embodiment, one or more types of foams that can be used in a general laminate structure can be freely selected and used as long as the action and effect of the present technology are not impaired. For example, layers using polyurethane foam, polyethylene foam, polypropylene foam, vinyl chloride foam, polystyrene foam, etc. can be mentioned, and in the present technology, a foam layer 132 using polyurethane foam is preferable.

[0038] The polyurethane foam that can be used for the foam layer 132 of the second embodiment is produced using a composition for producing polyurethane foam that contains polyol, a blowing agent, a catalyst, a foam stabilizer, isocyanate, and other additives as necessary. The raw materials of the polyurethane foam will be described below.

[0039] <Polyol> The polyol used in the polyurethane foam production 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. 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.

[0040] <Foaming agent> The blowing agent used in the polyurethane foam-producing composition can 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. Examples of the blowing agent include water, methylene chloride, carbon dioxide gas, and hydrocarbons such as pentane. 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 to 8 parts by mass of the blowing agent per 100 parts by mass of polyol.

[0041] <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. Examples of the catalyst include amine-based catalysts such as triethylamine, dimethylaminohexanol, triethylenediamine, and tetramethylguanidine; tin-based 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 per 100 parts by mass of polyol.

[0042] <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. Examples of the foam stabilizer include silicone-based foam stabilizers, fluorine-containing compound-based foam stabilizers, and surfactants. The amount of the 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 the foam stabilizer per 100 parts by mass of polyol.

[0043] <Isocyanate> The isocyanate used in the polyurethane foam production 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. 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.

[0044] 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 132. 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].

[0045] <Other> In the composition for producing polyurethane foam, one or more of various other components that can be used in the production of polyurethane foam can be freely selected according to the purpose, as long as the action and effect of the present technology are not impaired. Examples of such components include flame retardants, stabilizers, plasticizers, colorants, pigments, antioxidants, crosslinking agents, antibacterial agents, dispersants, and ultraviolet absorbers.

[0046] The physical properties of the laminate structure can be controlled by adjusting the composition of the foam used in the above-described foam layer 132. For example, when a polyurethane foam is used as the foam layer 132, the physical properties of the polyurethane foam can be controlled by controlling the isocyanate index of the polyurethane foam, and therefore the physical properties of the laminate structure 1 can also be controlled.

[0047] More specifically, for example, by increasing the isocyanate index of the polyurethane foam, the bending load and gradient of the polyurethane foam can be increased, and the bending load and gradient of the laminated structure 1 can also be increased accordingly. On the other hand, by decreasing the isocyanate index of the polyurethane foam, the polyurethane foam becomes soft, and the occurrence of cracks during molding can be prevented. Conventionally, when a soft polyurethane foam is used in a laminated structure, it was necessary to take measures such as increasing the amount of adhesive, etc., described later, in order to improve the strength of the laminated structure. However, by increasing the amount of adhesive, etc., there was a problem that the problem of exudation to the surface occurred. In contrast, in the present technology, the exudation of the adhesive 133, etc. can be prevented by using the temperature-responsive polymer 12, so that it is also possible to increase the amount of the adhesive 133, etc., in order to improve the strength of the laminated structure 1. In addition, by suppressing the exudation of the components of the adhesive 133, etc. to the surface, the components of the adhesive 133, etc. remain in their original positions, and therefore the original functions of the components of the adhesive 133, etc. can be fully exerted without impairing the original functions of the components of the adhesive 133, etc. Therefore, for example, when a soft foam is used in the laminated structure 1, the strength of the laminated structure 1 can be maintained without increasing the amount of adhesive 133.

[0048] (3) Adhesive 133 The fiber layer 131 and the foam layer 132 can be bonded to each other with an adhesive 133. In the present technology, the adhesive 133 is not essential, and it is also possible to bond the fiber layer 131 and the foam layer 132 to each other by, for example, integrally molding the foam layer 132 with the fiber layer 131.

[0049] The adhesive 133 is not limited to being interposed between the fiber layer 131 and the foam layer 132, and may be mixed into the fiber layer 131, for example, as in a modified example of the laminated structure 1 according to the second embodiment shown in Fig. 4. In this case, the adhesive 133 mixed into the fiber layer 131 can also bond the skin material 11 and the base material 13 (fiber layer 131).

[0050] The adhesive 133 that can be used for the substrate 13 may be the same as or a different type from the adhesive 14 used for bonding the skin material 11 and the substrate 13. Note that specific examples of the adhesive 133 that can be used for the substrate 13 are the same as the adhesive 14 used for bonding the skin material 11 and the substrate 13, and therefore will not be described here.

[0051] [Third embodiment] 5 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 13 bonded to the skin 11, and a temperature-responsive polymer 12 present on the substrate 13 side of the skin 11, and the substrate 13 is a foam. In the third embodiment, the foam (substrate 13) is integrally molded with the skin 11, thereby bonding the skin 11 and the foam (substrate 13).

[0052] The lower critical solution temperature (LCST) and upper critical solution temperature (UCST) of the temperature-responsive polymer 12 used in the third embodiment can be appropriately selected depending on the temperature of the mold used for integral molding, the temperature of the raw material, the heat of foaming, etc.

[0053] For example, in the case of integral molding, when the temperature of the skin material 11 on the side of the temperature-responsive polymer 12 increases over time, it is preferable to use a lower critical solution temperature (LCST) type polymer. The lower critical solution temperature (LCST) type polymer is hydrophilic at temperatures below the lower critical solution temperature (LCST), and can block the foam-producing composition from migrating toward the skin material 11 before resinification or foaming progresses. Thereafter, as the foam-producing composition progresses in resinification or foaming and the temperature rises due to the generation of foaming heat or the like, when the temperature exceeds the lower critical solution temperature (LCST), the temperature-responsive polymer 12 becomes hydrophobic. The hydrophobic temperature-responsive polymer 12 cannot block the foam-producing composition from migrating toward the skin material 11, but by this time, 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. Furthermore, at the stage where resinification and foaming progress, the temperature-responsive polymer 12 becomes hydrophobic and therefore blends with the foam-producing composition, and does not block the foam-producing composition from migrating toward the skin 11. This does not affect the integral molding (adhesion) between the skin 11 and the base material 13 made of a foam. 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 11 without affecting the integral molding (adhesion) between the skin 11 and the base material 13.

[0054] Furthermore, for example, in the case of integral molding, when the temperature of the skin material 11 on the side of the temperature-responsive polymer 12 decreases over time, it is preferable to use an upper critical solution temperature (UCST) type polymer. The upper critical solution temperature (UCST) type polymer exhibits hydrophilicity at temperatures above the upper critical solution temperature (UCST), and can block the foam-producing composition from migrating toward the skin material 11 before resinification or foaming progresses. Thereafter, when the foam-producing composition progresses in resinification or foaming and the temperature decreases and becomes lower than the upper critical solution temperature (UCST), the temperature-responsive polymer 12 becomes hydrophobic. The hydrophobic temperature-responsive polymer 12 cannot block the foam-producing composition from migrating toward the skin material 11, but by this time, resinification and foaming have 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. Furthermore, at the stage where resinification and foaming progress, the temperature-responsive polymer 12 becomes hydrophobic and therefore blends with the foam-producing composition, and does not block the foam-producing composition from migrating toward the skin 11. This does not affect the integral molding (adhesion) between the skin 11 and the base material 13 made of a foam. 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 11 without affecting the integral molding (adhesion) between the skin 11 and the base material 13.

[0055] The details of the foam that can be used in the third embodiment are the same as those of the foam that can be used for the foam layer 132 in the second embodiment described above, and therefore a description thereof will be omitted here.

[0056] [Fourth embodiment] 6 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 13 bonded to the skin material 11, a temperature-responsive polymer 12 present on the base material 13 side of the skin material 11, and a back material 15 laminated on the surface of the base material 13 opposite to the temperature-responsive polymer 12, and the base material 13 is a laminate of a fiber layer 131a and a fiber layer 131b sandwiching a foam layer 132. In addition, an adhesive 133a and an adhesive 133b are mixed in the fiber layer 131a and the fiber layer 131b, and the skin material 11 and the fiber layer 131a, the fiber layer 131a and the foam layer 132, the foam layer 132 and the fiber layer 131b, and the fiber layer 131b and the back material 15 are bonded by the adhesive 133a and the adhesive 133b.

[0057] The details of the skin material 11, the temperature responsive polymer 12, the fiber layer 131a, the fiber layer 131b, the adhesive 133a, and the adhesive 133b in the fourth embodiment are the same as those of the skin material 11, the temperature responsive polymer 12, the fiber layer 131, and the adhesive 133 in the second embodiment described above, so a description thereof will be omitted here.

[0058] (1) Backing material 15 The laminated structure 1 according to the present technology may be provided on the surface opposite to the skin material 11 with a back surface material 15. The back surface material 15 is not essential in the present technology, but may 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 any material, or two or more materials can be freely combined according to the use and purpose of the laminated structure 1. For example, the same material as that which can be used for the skin material 11 described above can be used, or a film, sheet, plate material, etc. using resin, wood, metal, etc. can be used as 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, floor mats, seat sheets, 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; furniture such as carpets, sofas, cushions, futon covers, pillows, and mattresses; and the like.

[0061] Furthermore, the laminate structure 1 according to the present technology can be given any function depending on the application or purpose, so 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 resistance, flame retardancy, impact resistance, cushioning, and adhesiveness can be given. Specifically, for example, the desired function can be given to each layer constituting the laminate structure 1, or the desired function can be given to the entire laminate structure 1.

[0062] As described above, in the laminated structure 1 according to the present technology, since the exudation of the constituent components can be prevented, it is also possible to suppress the deterioration of the functions imparted to the constituent components constituting the laminated structure 1. Conventionally, in order to suppress the exudation of the constituent 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 the film or the like reduces the amount of air permeability, and functions such as sound absorption may be reduced. On the other hand, in the present technology, as described above, it is not necessary to provide a non-permeable layer such as a film. In addition, for example, as in the second to fourth embodiments, when the base material 13 is provided with a foam layer 132 and this foam layer 132 has various functions, the moldability of the foam layer 132 is improved by preventing the exudation of the foam manufacturing composition before resinification or foaming, and the deterioration of various functions expected of the foam layer 132 can be suppressed.

[0063] This technology can also be configured as follows: [1] A skin material; A substrate adhered to the skin material; a temperature responsive polymer present on the substrate side of the skin material; A laminated structure having the above structure. [2] The laminated structure according to [1], wherein the skin material and the base material are bonded with an adhesive. [3] The laminate structure according to [1] or [2], wherein the substrate is a laminate of a fiber layer and a foam layer. [4] The laminate structure described in [3], wherein an adhesive is mixed into the fiber layer. [5] The laminate structure according to [1] or [2], 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 laminate structure according to any one of [1] to [6], wherein a backing material is laminated on a surface of the laminate structure opposite to the skin material. [8] A vehicle interior material, a building interior material, or furniture, comprising the laminate structure according to any one of [1] to [7]. EXAMPLES

[0064] 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.

[0065] <Experimental Example 1> In Experimental Example 1, the influence of differences in the configuration of the laminate structure 1 on the physical properties and appearance was investigated.

[0066] (1) Manufacturing of laminated structure 1 Using the materials shown in Table 1 below, the laminate structure 1 shown in Fig. 4 was manufactured by hot pressing at the molding temperature shown in Table 1. The adhesive and catalyst were impregnated into the fiber layer, and each material was laminated. The temperature-responsive polymer aqueous solution was applied to the back side of the skin material and used as it was.

[0067] (2) Evaluation The physical properties of bending load and peel strength of the produced laminate structure 1 were measured by the following methods. In addition, the appearance (bleed-out) as viewed from the skin material 11 side was evaluated based on the following criteria.

[0068] Bending Load The measurements were performed using a method conforming to JIS K7017. Detailed conditions were: test speed: 50 mm / min, compression elements: up and down, R3.2, pressing direction: from the skin side, distance between supports: 100 mm.

[0069] [Peel strength] A test piece measuring 150 mm x 25 mm was taken from the manufactured laminated structure 1. The skin material and glass fiber laminate were peeled off about 80 mm parallel to the short piece from the urethane foam. The peeled skin and mat were attached to an Instron type tensile tester and peeled off at a speed of 200 mm / min. The peeling condition was confirmed, and the peel strength (N / 25 mm) was calculated from the obtained chart.

[0070] [Appearance (bleed)] ◎: No appearance defects ○: No bleeding △: Several spots of bleeding ×: 10% or more of the total area has been exuded

[0071] (3) Results The results are shown in Table 1.

[0072] [Table 1]

[0073] (4) Discussion As shown in Table 1, Comparative Examples 1 to 4, which did not have a temperature-responsive polymer, were unable to prevent the adhesive from seeping out and had poor appearances. On the other hand, Examples 1 to 11, which had a temperature-responsive polymer, were able to prevent the adhesive from seeping out.

[0074] Comparing Examples 1 to 3 with Comparative Examples 1 to 3, the bending load was improved in Examples 1 to 3 having a temperature-responsive polymer compared to Comparative Examples 1 to 3 not having a temperature-responsive polymer. The peel strength was lower in Examples 2 and 3 having a temperature-responsive polymer compared to Comparative Examples 2 and 3 not having a temperature-responsive polymer, but the results of the peel strength in Examples 1 to 8 show that the peel strength can be improved, i.e., the adhesiveness can be improved, by selecting a temperature-responsive polymer having an optimal phase transition temperature according to the adhesive and molding temperature.

[0075] Furthermore, when Examples 9 to 11 are compared with Comparative Example 4, it is found that the use of a temperature-responsive polymer can prevent bleeding, even though the amount of adhesive used in Examples 9 to 11 is greater than that in Comparative Example 4. Furthermore, the results of Examples 6 to 8 and Examples 9 to 11 show that when the amount of adhesive is increased, bleeding can be prevented by also increasing the amount of temperature-responsive polymer. These results show that a high bleeding prevention effect can be achieved by adjusting the amount of temperature-responsive polymer according to the type and amount of adhesive used.

[0076] Furthermore, it was found that the physical properties of the laminated structure differ depending on the composition of the foam layer. Specifically, when comparing Examples 1 to 3, it was found that when the compounding ratio of isocyanate and polyol is different, the bending load increases as the isocyanate index increases. The bending loads of the laminated structures of Examples 2 and 3 are reversed because there is no significant difference in the bending load of the polyurethane foam constituting the foamed material layer, and the variation due to other components of the laminated structure affects the bending load.

[0077] <Experimental Example 2> In Experimental Example 2, the effect on sound absorption properties when the laminated structure 1 is used as a sound absorbing material was investigated.

[0078] (1) Manufacturing of laminated structure 1 Using the materials shown in Table 2 below, the laminate structure 1 shown in Fig. 4 was produced by hot pressing at the molding temperature shown in Table 2. The names of the materials in Table 2 are the same as those in Table 1.

[0079] (2) Evaluation The appearance (bleed-through) of the manufactured laminated structure 1 as viewed from the skin material 11 side was evaluated based on the same criteria as in the aforementioned Experimental Example 1. The normal incidence sound absorption coefficient of the manufactured laminated structure 1 was measured by the following method. In this experimental example, five test pieces were taken from each of the laminated structures 1 of the example and the comparative example and evaluated.

[0080] [Vertical incidence sound absorption coefficient] The measurement was performed using a method conforming to JIS A 1405-2 (ISO 10534-2). Test equipment: Bruel & Kjaer Type 4206 Impedance Tube, tube diameter: φ28.4 mm.

[0081] (3) Results The evaluation results of appearance (bleeding) are shown in Table 2, and the measurement results of normal incidence sound absorption coefficient are shown in Figure 7.

[0082] [Table 2]

[0083] (4) Discussion As shown in Fig. 7, the normal incidence sound absorption coefficient of the example having the temperature-responsive polymer was equivalent to that of the comparative example not having the temperature-responsive polymer. This result shows that the temperature-responsive polymer has no effect on sound absorption. [Explanation of symbols]

[0084] 1 Laminated structure 11 Skin material 12 Temperature-responsive polymers 13 Base material 131, 131a, 131b Fiber layer 132, 132a, 132b Foam layer 14,133 Adhesives 15 Backing material

Claims

1. A skin material; A substrate adhered to the skin material; a temperature responsive 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 and the base material are bonded with an adhesive.

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

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

5. 5. A vehicle interior material, a building interior material, or furniture, comprising the laminate structure according to claim 1.

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