Urethane foam and laminates for frame lamination

Abstract

The present invention provides a urethane foam for frame lamination that has a high biomass content, is environmentally friendly, exhibits a good balance of compression residual strain and flame retardancy, and shows good fusion properties suitable for the frame lamination method, as well as a laminate comprising the urethane foam for frame lamination and a surface material. [Solution] The urethane foam for frame lamination contains a polyol component, an isocyanate component, and a flame retardant. In 100% by mass of the polyol component, (A) modified castor oil polyol is 20% by mass or more and 80% by mass or less, (B) urethane modified polyol is 10% by mass or more and 50% by mass or less, and (C) polyether polyol is 0% by mass or more and 40% by mass or less. The ΔW, which is the value obtained by subtracting the polyether polyol content (by mass) from the urethane modified polyol content (by mass) is -10 or more and ΔW is 50 or less.

Description

Technical Field

[0001] The present invention relates to a urethane foam for frame laminates that exhibits flame retardancy and a significant biomass degree, and a laminate in which the urethane foam and a skin material are laminated and adhered by a frame lamination method.

Background Art

[0002] As vehicle interior materials exemplified by vehicle seats, furniture exterior materials, or base materials thereof, seat materials having cushioning properties are used. Examples of the seat material having cushioning properties include a laminate in which a urethane foam and a skin material are laminated.

[0003] The laminate can be manufactured by a frame lamination method in which the skin material and the urethane foam, which is a cushioning material, are bonded together using the heat melting property and adhesiveness of the urethane foam. The frame lamination method can laminate and bond the skin material and the urethane foam without using an adhesive, so that the drying process and curing process of the adhesive are unnecessary, and the processing speed is also high. Therefore, the frame lamination method is suitable as a manufacturing method of the laminate. In other words, as the urethane foam constituting the laminate, a member suitable for the frame lamination method is required.

[0004] Patent Document 1 proposes a polyurethane foam (hereinafter also referred to as the prior art 1) in which the plant degree is increased by using a plant-derived polyol and which is applicable to the frame lamination method. Patent Document 1 states that among plant-derived polyols, hydrophobic castor oil polyol is preferable, and an example using castor oil is also disclosed in the examples.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] However, the inventors' investigations revealed that Conventional Technology 1 tended to have high compression residual strain, and that increasing the castor oil polyol content tended to result in polyurethane foam with poor foam properties. Therefore, Conventional Technology 1 had room for improvement in terms of sufficient cushioning and high biomass content.

[0007] Furthermore, although Patent Document 1 suggests that a flame retardant may be included in the prior art 1, no examples of actual use of a flame retardant are disclosed, and there is no substantial disclosure regarding the technology of using a flame retardant in combination with castor oil.

[0008] Furthermore, in order to properly laminate and bond the urethane foam and the surface material using the frame lamination method, it is necessary for the urethane foam to quickly exhibit adhesive properties when heated by a flame. This property of quickly exhibiting adhesive properties when heated by a flame will be referred to as fusion properties below. According to the inventor's research, it was found that the conventional technology 1 may have insufficient fusion properties.

[0009] The present invention has been made in view of the above problems, and aims to provide a urethane foam for frame lamination that exhibits a significant biomass content, is environmentally friendly, exhibits a good balance of compression residual strain and flame retardancy, and shows good fusion properties suitable for the frame lamination method, as well as a laminate comprising the urethane foam for frame lamination and a surface material. [Means for solving the problem]

[0010] The urethane foam for frame lamination of the present invention contains a polyol component, an isocyanate component, and a flame retardant, wherein in 100% by mass of the polyol component, (A) modified castor oil polyol is 20% by mass or more and 80% by mass or less, (B) urethane modified polyol is 10% by mass or more and 50% by mass or less, and (C) polyether polyol is 0% by mass or more and 40% by mass or less, and satisfies the following conditions. In other words, in the present invention, ΔW, which is the value obtained by subtracting the polyether polyol content (mass%) from the urethane-modified polyol content (mass%), is adjusted to fall within the range of the following formula (1). [Formula 1] -15 ≤ ΔW ≤ 50·····(1)

[0011] Furthermore, the laminate of the present invention is characterized by comprising a urethane foam for frame lamination and a surface material laminated and bonded to at least one side of the urethane foam for frame lamination by a frame lamination method. [Effects of the Invention]

[0012] The urethane foam for frame lamination of the present invention exhibits a significant biomass content, demonstrating environmental considerations while also exhibiting a well-balanced combination of compression residual strain and flame retardancy, and showing good fusion properties suitable for frame lamination methods. Furthermore, the laminate of the present invention, comprising the urethane foam for frame lamination and the surface material, exhibits excellent properties of the urethane foam, such as biomass content, flame retardancy, and compression residual strain. This suppresses the occurrence of displacement and delamination between the urethane foam and the surface material, resulting in a good laminated state. [Modes for carrying out the invention]

[0013] The urethane foam for frame lamination of the present invention comprises a polyol component, an isocyanate component, and a flame retardant, and in 100% by mass of the polyol component, it contains modified castor oil polyol, urethane-modified polyol, and polyether polyol within the following ranges (A), (B), and (C). (A) Contains modified castor oil polyol in an amount of 20% by mass or more and 80% by mass or less. (B) Contains urethane-modified polyol in an amount of 10% by mass or more and 50% by mass or less. (C) Contains polyether polyol in an amount of 0% to 40% by mass. In addition to the above, the urethane foam for frame lamination of the present invention satisfies the following conditions. In other words, in the urethane foam for frame lamination of the present invention, ΔW, which is the value obtained by subtracting the polyether polyol content (mass%) from the urethane-modified polyol content (mass%), is adjusted to fall within the range of the following formula (1). [Formula 2] -15 ≤ ΔW ≤ 50·····(1)

[0014] The inventors, after diligently investigating the above-mentioned problems, found that when unmodified castor oil is used as a polyol, the compression residual strain of the polyurethane foam tends to be large, and the fusion properties tend to be insufficient. Furthermore, it was found that when unmodified castor oil is used in combination with a flame retardant, the compatibility between the two is insufficient, and the foam properties tend to be poor. In response to this, the inventors have discovered that by using a modified castor oil polyol within a predetermined range as the polyol component, and by using a urethane-modified polyol in combination within a predetermined range, it is possible to prevent the compression residual strain of the resulting urethane foam from becoming excessive, improve its fusion properties, and provide a urethane foam with good foam properties even when used in combination with a flame retardant, thus completing the present invention. In the following, the urethane foam for frame lamination of the present invention may be simply referred to as urethane foam.

[0015] That is, the urethane foam of the present invention having the above-described configuration has a high biomass content, is environmentally considerate, and exhibits excellent balance in compression residual strain and flame retardancy. Further, the urethane foam of the present invention shows good adhesion suitable for the frame lamination method and is excellent in productivity. Therefore, the urethane foam of the present invention is suitably applied to technical fields where flame retardancy and cushioning properties are required, such as vehicle interior materials and furniture exterior materials. The details of the configuration of the present invention will be described below.

[0016] [Polyol component] The urethane foam of the present invention preferably contains a urethane-modified polyol at a predetermined ratio together with a modified castor oil polyol to satisfactorily solve the intended problems. Further, the urethane foam of the present invention can more satisfactorily solve the intended problems by further containing a polyether polyol as a polyol component. In 100% by mass of the polyol component contained in the present invention, the sum of the contents of the modified castor oil polyol, the urethane-modified polyol, and the polyether polyol can be appropriately determined within a range not impairing the object and effects of the present invention, but the sum is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.

[0017] That is, the urethane foam of the present invention includes, as a polyol component, one or a combination of two or more other arbitrary polyols other than the modified castor oil polyol, the urethane-modified polyol, and the polyether polyol.

[0018] [Modified castor oil polyol] The modified castor oil polyol in the present invention is a polyol obtained by modifying unmodified castor oil, which is a component using plant-derived oil and fat, with a dibasic acid. For example, modified castor oil can be obtained by crosslinking unmodified castor oil by a dehydration condensation reaction or the like with a dibasic acid. Examples of the above dibasic acids include aliphatic dibasic acids, aromatic dibasic acids, and alicyclic dibasic acids. Examples of aliphatic dibasic acids include sebacic acid, malonic acid, glutaric acid, suberic acid, oxalic acid, succinic acid, dodecanoic acid, tetradecanedioic acid, pentadecanedioic acid, heptadecanedioic acid, maleic acid, fumaric acid, itaconic acid, etc., but are not limited thereto. Examples of the above aromatic dibasic acids include phthalic acid, terephthalic acid, isophthalic acid, biphenylcarboxylic acid, diphenylsulfonedicarboxylic acid, tolylene dicarboxylic acid, etc., but are not limited thereto. Examples of the above alicyclic dibasic acids include cyclohexanedicarboxylic acid, tetrahydrophthalic acid, cyclopentanedicarboxylic acid, etc., but are not limited thereto. The modified castor oil polyol may be contained alone or in combination of two or more. The molecular weight of the above modified castor oil polyol is not particularly limited, but generally, those having an average molecular weight of about 1000 to 4000 are preferred.

[0019] From the viewpoint that the compatibility with other components such as flame retardants, urethane-modified polyols, and polyether polyols is good and the foam properties are easily maintained even when the biomass content is increased, as the modified castor oil contained in the urethane foam of the present invention, it is preferable to include a modified castor oil obtained by modifying unmodified castor oil with an aliphatic dibasic acid, and more preferably to include a modified castor oil obtained by modifying unmodified castor oil with sebacic acid. Among them, it is still more preferable that the modified castor oil contained in the urethane foam of the present invention is a modified castor oil obtained by modifying unmodified castor oil with sebacic acid.

[0020] <Urethane-modified polyol> The urethane-modified polyol in this invention refers to a polyol that can be used in the manufacture of urethane foam, and is a modified polyol obtained by modifying a polyether polyol. For example, as the modified polyol, a modified polyol used in the manufacture of flexible polyurethane foam as disclosed in Japanese Patent No. 2592057 can be selected. The urethane-modified polyol may be included alone or in combination of two or more types.

[0021] More specifically, for example, a urethane-modified polyol that can be contained in the urethane foam of the present invention can be obtained by reacting a polyether polyol with bisphenol A and an isocyanate (polyisocyanate). As the isocyanate, for example, tolylene diisocyanate (TDI) is preferred. The urethane-modified polyol used in the present invention preferably has a hydroxyl value in the range of 30 to 100, and more preferably has a hydroxyl value of 50 to 80. The urethane-modified polyol may be included alone or in combination of two or more types. The molecular weight of the urethane-modified polyol is not particularly limited, but generally, an average molecular weight of around 1000 to 4000 is preferred.

[0022] <Polyether polyol> The polyether polyol in the present invention can be appropriately selected from one or more known polyether polyol components that can be reacted with a polyisocyanate component to produce polyurethane foam, in combination. The urethane foam of the present invention includes embodiments that do not contain polyether polyol, but by further including polyether polyol in a predetermined range in addition to modified castor oil polyol and urethane-modified polyol, it can exhibit superior compressive residual strain. For convenience, the urethane foam of the present invention may be described as "containing modified castor oil polyol, urethane-modified polyol, and polyether polyol in predetermined ranges at 100% by mass of the polyol component," but this description includes the case where the polyether polyol is 0% by mass.

[0023] Examples of the above-mentioned polyether polyols include alcohols such as aliphatic alcohols, aromatic alcohols, and the above-mentioned polyhydric alcohols; aliphatic amines such as ethanolamine, diethanolamine, triethanolamine, and ethylenediamine; aromatic amines such as toluenediamine and methylenedianiline; and polyether polyols obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to Mannich condensates, etc. From another viewpoint, examples of the above-mentioned polyether polyols include polypropylene glycol, polytetramethylene glycol or modified versions thereof, or compounds obtained by adding alkylene oxide to glycerin, such as glycerol-propylene oxide polymer. Polyether polyols may be included individually or in combination of two or more types. The molecular weight of the above-mentioned polyether polyol is not particularly limited, but generally, an average molecular weight of around 1000 to 4000 is preferred.

[0024] <Any polyol> Other than modified castor oil polyols, urethane-modified polyols, and polyether polyols, any other polyol can be appropriately selected from known polyol components capable of producing polyurethane foam by reacting with a polyisocyanate component. Examples of the above-mentioned optional polyols include phosphorus-containing polyols, polyester polyols, polymer polyols, and the like. In the embodiment of the present invention that contains an optional polyol, the optional polyol may be contained alone or in an appropriate combination of two or more types.

[0025] Examples of the above-mentioned phosphorus-containing polyols include tris(ethylene glycol) phosphate, tris(propylene glycol) phosphate, diethyl-N,N-bis(2-hydroxyethyl)aminomethanephosphonate (FYROL(trademark)-6, manufactured by Akzo Japan), and diisopropyl-N,N-bis(2-hydroxyethyl)aminomethanephosphonate (FYROL(trademark)-7, manufactured by Akzo Japan). The molecular weight of the phosphorus-containing polyol is not particularly limited, but generally, one with an average molecular weight of around 200 to 300 is preferred. Phosphorus-containing polyols have active hydrogen and react with isocyanates, thus exhibiting excellent long-term stability of flame retardancy. In other words, the polyurethane foam of the present invention that contains a phosphorus-containing polyol is preferred in that it exhibits superior flame retardancy.

[0026] When the urethane foam of the present invention contains phosphorus-containing polyol, it is preferable to include the phosphorus-containing polyol in an amount of 0.5 parts by mass to 5 parts by mass, and more preferably in an amount of 1 part by mass to 3 parts by mass, per 100 parts by mass of the sum of the contents of modified castor oil polyol, urethane-modified polyol, and polyether polyol.

[0027] A desirable example of a phosphorus-containing polyol is the compound shown in the following structural formula (Chemical Formula 1). In the following structural formula, PO represents propylene oxide. [ka]

[0028] The above-mentioned polyester polyols include polyols obtained by condensing a polyhydric alcohol with a polycarboxylic acid, and polyols obtained by ring-opening polymerization of cyclic esters. Examples of polycarboxylic acids include succinic acid, glutanoic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, isophthalic acid, and their anhydrides. On the other hand, examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, and bisphenol A.

[0029] Examples of the polymer polyols mentioned above include polyols obtained by copolymerizing acrylonitrile or styrene in a polyether polyol, in which polymer fine particles are dispersed in the polyether polyol. The molecular weight of the above polymer polyol is not particularly limited, but generally, an average molecular weight of around 2000 to 7000 is preferred.

[0030] <Content ratio of each polyol component> The urethane foam of the present invention contains, in 100% by mass of the polyol component, modified castor oil polyol, urethane-modified polyol, and polyether polyol, each within a predetermined range. In other words, the urethane foam of the present invention contains modified castor oil polyol in an amount of 20% to 80% by mass of 100% by mass of the polyol component. From the viewpoint of providing a urethane foam with a higher biomass content, it is preferable that the modified castor oil polyol be present in an amount of 30% or more by mass, more preferably 40% or more by mass, and even more preferably 50% or more by mass, of the 100% by mass of the polyol component. In other words, the urethane foam of the present invention containing modified castor oil polyol within the above range can exhibit a high biomass content without impairing the compression residual strain. Furthermore, from the viewpoint of adjusting the compression residual strain to a more suitable range while exhibiting a high biomass content, it is preferable that the modified castor oil polyol be present in an amount of 70% or less by mass, and more preferably 60% or less by mass, of the 100% by mass of the polyol component.

[0031] Furthermore, the urethane foam of the present invention contains urethane-modified polyol in an amount of 10% to 50% by mass of 100% by mass of the polyol component. From the viewpoint of more adequately preventing problems such as increased compression set, poor fusion properties, and deterioration of foam properties, it is preferable that the urethane-modified polyol be present in an amount of 15% by mass or more, and more preferably 20% by mass or more, of the polyol component. Furthermore, from the viewpoint of more adequately preventing increased fusion properties and decreased compression set, it is preferable that the urethane-modified polyol be present in an amount of 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, of the polyol component.

[0032] Furthermore, in the urethane foam of the present invention, the content ratio of polyether polyol is in the range of 0% to 40% by mass in 100% by mass of the polyol component. From the viewpoint of more effectively preventing an increase in compression residual strain, it is preferable that the polyether polyol is contained in 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, in 100% by mass of the polyol component. Furthermore, from the viewpoint of providing a polyurethane foam that exhibits a high biomass content while showing better fusion properties, it is preferable that the polyether polyol is contained in 38% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, in 100% by mass of the polyol component.

[0033] [Isocyanate component] The polyisocyanate component in the present invention can be appropriately selected from known polyisocyanate components that can be reacted with a polyol component to produce polyurethane foam. For example, as the polyisocyanate, a polyisocyanate component selected from tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate, etc. Another example is a modified polyisocyanate obtained by modifying the polyisocyanate component exemplified above. Examples of modified polyisocyanates include products obtained by partial chemical reactions of polyisocyanates, such as polyisocyanates containing one or more groups from among esters, urea, biuret, allophanate, carbodiimide, isocyanurate, urethane, etc. The polyisocyanate components described above can be used individually or in combination of two or more as appropriate. The amount of polyisocyanate component is not particularly limited, but it can be adjusted so that the isocyanate index shown in formula (2) below is between 50 and 300. In formula (2) below, "NCO group" refers to the total number of NCO groups in the formulation containing each composition for forming the polyurethane foam, and "active hydrogen" refers to the total number of active hydrogens in the formulation containing each composition for forming the polyurethane foam. [Formula 3] Isocyanate index = NCO group / active hydrogen of polyol × 100 ... (2)

[0034] [Flame retardant] The flame retardant used in the present invention is not particularly limited, but preferred examples of flame retardants include condensed phosphate ester flame retardants. Examples of the above-mentioned condensed phosphate esters include halogen-containing condensed phosphate esters, non-halogen condensed phosphate esters, and aromatic condensed phosphate esters, with halogen-containing condensed phosphate esters being preferred.

[0035] Examples of halogen-containing condensed phosphate esters include tris(chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, tetrakis(2-chloroethyl)dichloroisopentyl diphosphate, polyoxyalkylene bis(dichloroalkyl) phosphate, and halogen-containing condensed phosphate esters which are condensates thereof. Among these, polymerized halogen-containing condensed phosphate esters are preferred as flame-retardant materials for automobiles due to their excellent flame retardancy and fogging resistance. However, conventionally, halogen-containing condensed phosphate esters have poor compatibility with unmodified castor oil polyols, and in particular, attempts to increase the biomass content by increasing the content of unmodified castor oil polyols tended to result in poor foam formation. Note that the polymerized halogen-containing condensed phosphate esters referred to here refer to halogen-containing condensed phosphate esters with a molecular weight of 400 or more. In contrast, modified castor oil polyol and halogen-containing condensed phosphate ester have good compatibility, therefore, the present invention can provide a polyurethane foam with a high biomass content while maintaining good foam properties.

[0036] In addition to the composition described above, the urethane foam of the present invention may contain one or more other compositions that are generally found in polyurethane foam. Examples of other compositions include, but are not limited to, catalysts, foam stabilizers, blowing agents, and colorants.

[0037] [Physical properties of urethane foam] The following describes the preferred physical properties of the urethane foam of the present invention. The urethane foam of the present invention is not limited to the physical property values, but may exhibit the following preferred physical properties.

[0038] <Biomass content> The urethane foam of the present invention contains 20% or more by mass of modified castor oil polyol, which is obtained by modifying unmodified castor oil polyol, a plant-derived polyol, relative to 100% by mass of the polyol component, and therefore exhibits a significant biomass content. Accordingly, the urethane foam of the present invention can be considered an environmentally friendly material. The biomass content of the urethane foam of the present invention is not particularly limited, but it is preferably 20% or more, more preferably 25% or more, even more preferably 30% or more, and particularly preferably 40% or more. If the urethane foam exhibits such a high biomass content, when it is laminated and bonded with a surface material by frame lamination to form a laminate, the overall biomass content of the laminate can be significantly improved.

[0039] The above biomass content is calculated using the following formula (3). [Formula 4] Biomass percentage (%) = (Total weight of plant-derived raw materials in polyurethane foam) / (Total weight of all raw materials constituting the polyurethane foam) × 100 ... (3)

[0040] <75% compression residual strain> The urethane foam of the present invention contains a modified castor oil polyol, rather than the conventional unmodified castor oil polyol, and also contains a urethane-modified polyol within a predetermined range. As a result, while exhibiting a significant biomass content, the increase in residual compressive strain is suppressed. Furthermore, in order to provide a polyurethane foam that exhibits even better residual compressive strain, the present invention also includes embodiments that further contain a polyether polyol within a predetermined range. The value of the compression residual strain of the urethane foam of the present invention is not particularly limited, but from the viewpoint of exhibiting good cushioning properties and being suitably used, for example, as an interior material for vehicles or as a base material therefor, the 75% residual compression strain is preferably 10% or less, preferably 8.5% or less, more preferably less than 8%, even more preferably 7.5% or less, even more preferably 7% or less, and particularly preferably 6.5% or less.

[0041] In this invention, the compressive residual strain refers to the 75% compressive residual strain, and is measured in accordance with JIS K6400-4:2004 4.5.2A method.

[0042] <Flame-retardant> The polyurethane foam of the present invention contains a flame retardant and exhibits flame retardancy. For example, halogen-containing condensed phosphate esters and the like mentioned above are suitable flame retardants used in polyurethane foam, but their compatibility with unmodified castor oil polyols is poor. Therefore, it has been difficult to provide a polyurethane foam that is both highly flame-retardant and has improved biomass content by incorporating unmodified castor oil polyols. However, according to the polyurethane foam of the present invention, which contains modified castor oil polyol as one of the polyol components, it is possible to provide a polyurethane foam that contains halogen-containing condensed phosphate esters and the like, exhibits high flame retardancy, and also has improved biomass content.

[0043] For example, according to the present invention, it is possible to provide a urethane foam having a 75% residual compressive strain of 10% or less, a biomass content of 20% or more, and excellent flame retardancy. In the context of the present invention, flame retardancy refers to flame retardancy measured by the FMVSS302 flammability test. The specific method for conducting the FMVSS302 flammability test is described in the examples below.

[0044] <Fusibility> The urethane foam of the present invention exhibits excellent fusion properties. One of the factors contributing to this is the combined use of urethane-modified polyol with modified castor oil polyol. Because the urethane foam of the present invention contains urethane-modified polyol in an appropriate range, a moderate level of stickiness is generated on the surface of the urethane foam when heated with a flame. As a result, the surface material and the urethane foam can be laminated and bonded well by the frame lamination method, providing an excellent laminate without misalignment between the surface material and the urethane foam. The method for evaluating fusion properties is described in the examples below.

[0045] <density> The density of the polyurethane foam of the present invention is not particularly limited, but from the viewpoint of exhibiting moderate flexibility and being suitably usable as a component constituting, for example, vehicle interior material or its base material, the density (kg / m³) is suitable. 3 ) is 30 kg / m 3 The following is preferable: The method for measuring the density of polyurethane foam is described in the examples below.

[0046] <40% hardness> The 40% hardness (N) of the polyurethane foam of the present invention is not particularly limited, but from the viewpoint of processability, it is preferably in the range of 70(N) to 500(N), more preferably in the range of 80(N) to 300(N), and even more preferably in the range of 85(N) to 200(N). The method for measuring the 40% hardness of polyurethane foam is described in the examples below.

[0047] [Frame lamination method] The frame lamination method involves heating the surface of a urethane foam with a flame to melt it and create adhesive properties, then laminating and bonding various surface materials together. The urethane foam of the present invention has excellent fusion properties and can be used as a urethane foam suitable for known frame lamination methods. The urethane foam for frame lamination of the present invention is generally formed in sheet form and used for frame lamination. The thickness of the sheet-shaped urethane foam of the present invention used for frame lamination is not particularly limited, but from the viewpoint of the specifications of the final product and the frame lamination process, it is preferable to have a thickness of 1 mm to 20 mm.

[0048] [Laminated structure] Next, the laminate of the present invention will be described. The laminate of the present invention comprises the urethane foam of the present invention described above, and a surface material laminated and bonded to at least one side of the urethane foam by a frame lamination method. As described above, the urethane foam of the present invention has excellent fusion properties, so when heated with a flame, the surface has sufficient adhesiveness (stickiness) and excellent lamination adhesion with the surface material. Therefore, the laminate of the present invention has a good laminated state and is difficult to peel off even after time has passed. Furthermore, as described above, the urethane foam of the present invention exhibits a significant biomass content, and therefore, the laminate of the present invention comprising such urethane foam can also be considered a component with a significant biomass content. Moreover, while exhibiting a significant biomass content, the urethane foam of the present invention has its compressive residual strain kept within an appropriate range and exhibits flame retardancy. Laminates comprising such urethane foam are suitable, for example, as interior materials for vehicles or as their base materials.

[0049] The thickness of the laminate of the present invention can be adjusted as appropriate depending on the application. For example, when used as an interior material for vehicles or as a base material for them, the thickness is preferably in the range of 3 mm to 20 mm. The ratio of the thickness of polyurethane foam to 100% of the thickness of the laminate is not particularly limited, but can be, for example, 50% to 90%.

[0050] <Skin material> The surface material constituting the laminate of the present invention may be any sheet-like member that can be laminated and bonded with polyurethane foam (particularly sheet-like polyurethane foam). The above-mentioned surface material may be a single-layer sheet or a multi-layer sheet consisting of multiple layers. Examples of a single-layer sheet-like surface material include woven or knitted fabrics made from natural or synthetic fibers. Examples of a multi-layer sheet-like surface material include synthetic leather comprising a base fabric and a resin layer. The above-mentioned synthetic leather may further have an arbitrary surface treatment layer on its surface. When laminating and bonding the above-mentioned synthetic leather and the polyurethane foam of the present invention to form a laminate, it is preferable to laminate and bond the polyurethane foam and the base fabric of the synthetic leather facing each other. Examples of the base fabric of the above-mentioned synthetic leather include woven fabrics, knitted fabrics, nonwoven fabrics, etc. The synthetic leather that constitutes the laminate of the present invention also includes so-called artificial leather.

[0051] The laminate of the present invention includes embodiments in which a surface material is laminated and bonded to only one side of a sheet-like urethane foam, and embodiments in which a surface material is laminated and bonded to both sides of a sheet-like urethane foam. In the embodiment in which a surface material is laminated and bonded to both sides of a urethane foam, the surface material laminated and bonded to one side and the surface material laminated and bonded to the other side may have the same configuration or different configurations. [Examples]

[0052] The present invention will be further described below with reference to examples, but these examples are not intended to limit the present invention in any way. Each example and comparative example was manufactured using the compositions shown in Tables 1 to 3, following a general method for manufacturing polyurethane foam. In Tables 1 to 3, the examples show the amount (in parts by mass) of each composition relative to a total of 100 parts by mass of modified castor oil polyol, urethane-modified polyol, and polyether polyol. The comparative examples show the amount (in parts by mass) of each composition relative to a total of 100 parts by mass of unmodified castor oil polyol or modified castor oil polyol, urethane-modified polyol, and polyether polyol. Details of each composition are shown below.

[0053] <Polyol 1> Modified castor oil polyol (a polyol obtained by modifying unmodified castor oil with sebacic acid, with an average number of functional groups of 3.5, a hydroxyl value of 90 mgKOH / g, and an average molecular weight of 2182). <Polyol 2> Unmodified castor oil polyol (average number of functional groups 2.7, hydroxyl value 160 mgKOH / g, average molecular weight 947, product name: H-30, manufactured by Ito Oil Co., Ltd.) <Polyol 3> Urethane-modified polyol (a prepolymer polyol with a hydroxyl value of 69 mg KOH / g, obtained by reacting polyether polyol, bisphenol A, and TDI) <Polyol 4> Polyether polyol (average number of functional groups: 3, hydroxyl value: 56.1 mg KOH / g, average molecular weight: 3000, product name: GP-3050, manufactured by Sanyo Chemical Industries, Ltd.) <Polyol 5> Phosphorus-containing polyol (compound with the structural formula (Chemical Formula 1) described above, average number of functional groups 2.8, hydroxyl value 183 mgKOH / g, average molecular weight 855, product name: Y-24, manufactured by Sanyo Chemical Industries, Ltd.) <Flame retardant> Halogen-containing condensed phosphate ester (Product name: CR-504L, manufactured by Daihachi Chemical Industry Co., Ltd.) <Foam stabilizer> Silicone foam stabilizer (Product name: VORASURF) TM 2904 (Manufactured by Dow Toray Industries, Inc.) <Tin catalyst> Stanoct (Product name: Neostan U-28, manufactured by Nitto Kasei Co., Ltd.) <Amine catalyst> Tertiary amine catalyst (Product name: TEDA(registered trademark)-L33, manufactured by Tosoh Corporation) <Foaming agent> Water (deionized water) <Isocyanate> Tolylene diisocyanate (Product name: Cosmonate T-80, manufactured by Mitsui Chemicals, Inc.)

[0054] As described above, the polyurethane foams of each example and comparative example were measured and evaluated using the following methods. The results of the measurements and evaluations are shown in Tables 1 to 3.

[0055] <Biomass content> The biomass content of the polyurethane foam was calculated using the following formula (3). [Formula 5] Biomass percentage (%) = (Total weight of plant-derived raw materials in polyurethane foam) / (Total weight of all raw materials constituting the polyurethane foam) × 100 ... (3)

[0056] The biomass content calculated as described above was evaluated according to the following criteria. ◎: The biomass content was between 20% and 60%. ○: The biomass content was between 10% and 20%. ×: The biomass content was less than 10%.

[0057] <75% compression residual strain> The 75% compression residual strain (%) of polyurethane foam was measured in accordance with JIS K6400-4:2004 4.5.2A method.

[0058] The 75% compressive residual strain values ​​measured as described above were evaluated according to the following criteria. ◎: The 75% compression residual strain was between 0% and 8%. ○: The compression residual strain was between 8% and 10% at 75%. △: The 75% compression residual strain was greater than 10% but less than or equal to 15%. ×: The 75% compression residual strain exceeded 15%.

[0059] <Flame-retardant> The flame retardancy of polyurethane foam was evaluated in accordance with the US automotive safety standard FMVSS302 flammability test. Specifically, a burner was placed under the wire mesh and adjusted to a flame height of 38 mm. Five test pieces measuring 102 mm x 356 mm and 13 mm thick were cut from the polyurethane foam used for the test. Markings were drawn at 38 mm (marking A) and 292 mm (marking B), with one end of the length being marked as 0 mm. The test pieces were horizontally fixed to a U-shaped metal frame, and the U-shaped frame was positioned so that the flame struck the end of the test piece with the markings facing upwards. After 15 seconds of indirect flame exposure, the gas was turned off. The time and distance until the flame disappeared from the test piece were measured. The same test was performed five times, and the most frequent evaluation (or the lower evaluation in case of a tie) that met the following conditions was determined to be the flame retardancy of the polyurethane foam. ○: Self-extinguishing before mark A. △: Self-extinguishing within a burning distance of 51 mm or less (and within 60 seconds), or with a burning distance of 102 mm / min or less. ×: Items that do not meet the above criteria

[0060] <Fusibility> The fusion properties of polyurethane foam were evaluated as follows. The surface of the polyurethane foam was heated by applying the tip of a gas burner flame for 3 seconds, and the surface condition immediately afterward was evaluated by touch as follows. The evaluation was conducted by 5 people, and the most frequent evaluation (or the lower evaluation in case of a tie) was adopted as the fusion property of the polyurethane foam. ○: Very sticky. △: Not very sticky. ×: It is not sticky at all.

[0061] <density> Polyurethane foam density (kg / m³) 3 The volume was calculated by dividing the mass of the polyurethane foam by the volume calculated based on its dimensions.

[0062] <40% hardness> The 40% hardness (N) of the polyurethane foam was measured according to the JIS K 6400-2A method.

[0063] [Table 1]

[0064] [Table 2]

[0065] [Table 3]

[0066] The above embodiment encompasses the following technical concepts. (1) Contains polyol components, isocyanate components, and flame retardants, In the aforementioned polyol component at 100% by mass, (A) The modified castor oil polyol is 20% by mass or more and 80% by mass or less, (B) Urethane-modified polyol is 10% by mass or more and 50% by mass or less, (C) Polyether polyol is 0% by mass or more and 40% by mass or less, The value ΔW, which is obtained by subtracting the polyether polyol content (mass%) from the urethane-modified polyol content (mass%), is within the range of the following formula (1). [Formula 6] -15 ≤ ΔW ≤ 50·····(1) A urethane foam for frame lamination characterized by the following features. (2) The urethane foam for frame lamination described in (1) above, which has a biomass content of 20% or more. (3) A urethane foam for frame lamination as described in (1) or (2) above, wherein the 75% residual compressive strain is 10% or less. (4) The urethane foam for frame lamination according to any one of the above items (1) to (3), wherein the modified castor oil polyol in (A) contains modified castor oil obtained by modifying unmodified castor oil with sebaciic acid. (5) A urethane foam for frame lamination as described in any one of items (1) to (4) above, A surface material laminated and bonded to at least one side of the aforementioned urethane foam for frame lamination using a frame lamination method, A laminate characterized by comprising the following features.

Claims

1. Contains polyol components, isocyanate components, and flame retardants. In the aforementioned polyol component at 100% by mass, (A) The modified castor oil polyol is 20% by mass or more and 80% by mass or less, (B) The urethane-modified polyol is 10% by mass or more and 50% by mass or less. (C) Polyether polyol is 0% by mass or more and 40% by mass or less, The value ΔW, which is obtained by subtracting the polyether polyol content (mass%) from the urethane-modified polyol content (mass%), is within the range of the following formula (1). [Formula 1] -15 ≤ ΔW ≤ 50 ..... (1) A urethane foam for frame lamination characterized by the following features.

2. The urethane foam for frame lamination according to claim 1, wherein the biomass content is 20% or more.

3. The urethane foam for frame lamination according to claim 1, wherein the (A) modified castor oil polyol comprises modified castor oil obtained by modifying unmodified castor oil with sebaciic acid.

4. A urethane foam for frame lamination according to any one of claims 1 to 3, A surface material laminated and bonded to at least one side of the aforementioned urethane foam for frame lamination using a frame lamination method, A laminate characterized by comprising the following features.

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