Multilayer sheets, padding for clothing, and polyurethane foam.
Patent Information
- Authority / Receiving Office
- VN · VN
- Patent Type
- Applications
- Current Assignee / Owner
- INOAC CORP
- Filing Date
- 2023-09-22
- Publication Date
- 2026-07-01
Smart Images
Figure VN1202603278_0
Abstract
Description
Laminate, garment pad, and polyurethane foam
[0001] The present disclosure relates to laminates, garment pads, and polyurethane foams.
[0002] Patent Document 1 discloses a flexible polyurethane foam using toluene diisocyanate (TDI) as an aromatic isocyanate, and states that the use of a phosphorus-based antioxidant and a hindered amine-based light stabilizer can prevent discoloration of the flexible polyurethane foam due to nitrogen oxides and can also prevent discoloration due to heat when wet.
[0003] JP 2010-100717 A
[0004] In laminates in which polyurethane foam and fabric or the like are laminated, it is desirable to use polyamide for the fabric from the viewpoint of various physical properties such as feel to the skin. However, when polyamide fabric is used, there is a problem that the laminate turns yellow.
[0005] The present disclosure has been made in view of the above-described circumstances, and aims to provide a technique for suppressing yellowing of a laminate. The present disclosure can be realized in the following aspects.
[0006] [1] A laminate comprising a polyamide section and a polyurethane foam section, wherein the polyurethane foam section is a foam obtained from a composition containing a polyol and an isocyanate, and the isocyanate contains diphenylmethane diisocyanate. [2] A clothing pad comprising the laminate according to [1]. [3] A polyurethane foam for use in producing a laminate comprising a polyamide section and a polyurethane foam section, wherein the polyurethane foam is a foam obtained from a composition containing a polyol and an isocyanate, and the isocyanate contains diphenylmethane diisocyanate. [4] The polyurethane foam according to [3], wherein the composition contains one or more selected from the group consisting of a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a hindered amine-based light stabilizer. [5] The polyurethane foam according to [3] or [4], having an air permeability of 30 L / min or more as measured in accordance with ASTM D 3574.
[0007] According to the present disclosure, a technique for suppressing yellowing of a laminate can be provided.
[0008] 1A and 1B are cross-sectional views of a laminate according to an embodiment of the present invention, and are diagrams for explaining a method for manufacturing the laminate.
[0009] The present disclosure will be described in detail below. In this specification, when a numerical range is indicated using "-", it is assumed that the range includes both the lower limit and the upper limit unless otherwise specified. For example, the expression "10-20" includes both the lower limit "10" and the upper limit "20". In other words, "10-20" has the same meaning as "10 or more and 20 or less". In addition, in this specification, the upper limit and lower limit of each numerical range can be combined in any way.
[0010] 1. Laminate 10 As shown in Figures 1 and 2, the laminate 10 is a laminate formed by laminating a polyamide portion 12 and a polyurethane foam portion 11. The polyurethane foam portion 11 is made of a foam 11A obtained from a composition containing a polyol and an isocyanate. The isocyanate contains diphenylmethane diisocyanate.
[0011] (1) Polyamide Portion 12 The polyamide portion 12 includes a polyamide-based resin. The polyamide-based resin is, for example, one or more selected from the group consisting of aliphatic polyamides (nylons), para-type wholly aromatic polyamides, and meta-type wholly aromatic polyamides. Aliphatic polyamides are obtained, for example, by polycondensation or co-condensation polymerization of an aminocarboxylic acid, a lactam, or a diamine with a dicarboxylic acid. Aliphatic polyamides include, for example, nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 46, nylon 6T, nylon 6I, nylon 9T, nylon M5T, and nylon 612. Para-type wholly aromatic polyamides are obtained, for example, by polycondensation of an aromatic diamine with a dicarboxylic acid.
[0012] From the viewpoint of improving breathability, the polyamide portion 12 is preferably made of a fabric 12A of polyamide-based resin fibers. The form of the fabric 12A is not particularly limited. The form of the fabric 12A may be, for example, a woven fabric, a knitted fabric, a nonwoven fabric, or the like.
[0013] 1 and 2, a polyamide portion 12, a polyurethane foam portion 11, and a polyamide portion 13 are laminated in this order. The polyamide portion 13 is made of, for example, a fabric 13A similar to the fabric 12A of the polyamide portion 12. The polyamide portion 13 may have the same configuration as the polyamide portion 12, or may have various configurations depending on the application of the laminate 10, etc.
[0014] (2) Polyurethane Foam Section 11 The polyurethane foam section 11 is composed of a foam 11A obtained from a composition containing a polyol and an isocyanate. In addition to the polyol and the isocyanate, the composition may also contain a discoloration inhibitor, a blowing agent, a catalyst, a foam stabilizer, etc.
[0015] (2.1) Polyol The polyol is not particularly limited. The polyol includes, for example, polyether polyol, polymer polyol, polyester polyol, etc. Among these, the polyol preferably includes polyether polyol.
[0016] Examples of polyether polyols include polyhydric alcohols such as propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose, or polyether polyols obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to such polyhydric alcohols. Only one type of polyether polyol may be used, or two or more types of polyether polyols may be used in combination. The use of polyether polyols can improve the flexibility of the polyurethane foam portion 11. Among these, polyols containing polypropylene glycol are preferred.
[0017] The weight average molecular weight of the polyether polyol is preferably 1,000 or more and 10,000 or less, more preferably 1,500 or more and 6,000 or less, and even more preferably 1,800 or more and 4,500 or less. The number of functional groups of the polyether polyol is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and even more preferably 2 or 3. The content of the polyether polyol is not particularly limited. The content of the polyether polyol is preferably 40 parts by mass or more and 100 parts by mass or less, more preferably 60 parts by mass or more and 100 parts by mass or less, and even more preferably 80 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the total polyol.
[0018] The polymer polyol is not particularly limited. The polymer polyol is, for example, a liquid containing finely divided polymer particles dispersed in a polyol. Examples of finely divided polymer particles include polymers such as styrene, acrylonitrile, acrylic, and melamine, as well as polyurea. The polymer polyol is preferably a polyether polyol (base polyol) polymerized with styrene or acrylonitrile, or styrene and acrylonitrile. The polymer content of the polymer polyol (the mass ratio of the portion other than the base polyol to the entire polymer polyol) is preferably 10% by mass or more and 55% by mass or less, and more preferably 20% by mass or more and 45% by mass or less. From the perspective of improving the strength of the polyurethane foam portion 11, a higher polymer content is preferable, but if the polymer content is too high, the viscosity may increase, potentially reducing workability. The polymer polyol may contain only one type of polymer polyol, or two or more types of polymer polyols with different weight-average molecular weights, polymer contents, and functional groups may be used in combination. The use of a polymer polyol can improve the hardness of the polyurethane foam portion 11.
[0019] The weight average molecular weight of the polymer polyol is preferably 1000 or more and 10,000 or less, more preferably 1500 or more and 6,000 or less, and even more preferably 1800 or more and 4,500 or less. The number of functional groups of the polymer polyol is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and even more preferably 2.5 or more and 3.5 or less. The content of the polymer polyol is not particularly limited. From the viewpoint of ensuring the amount of general-purpose polyether polyol used, the content of the polymer polyol is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, when the total amount of polyol is 100 parts by mass. The lower limit of the content of the polymer polyol is not particularly limited, and may be 0 parts by mass.
[0020] (2.2) Isocyanate The isocyanate contains diphenylmethane diisocyanate. The isocyanate may contain at least diphenylmethane diisocyanate, and may be crude MDI or polymeric MDI, but it is preferable that the isocyanate contains diphenylmethane diisocyanate. Diphenylmethane diisocyanate is colorless to pale yellow, and therefore is suitable for products requiring initial whiteness (e.g., clothing pads) compared to crude MDI or polymeric MDI, which are brown.
[0021] Diphenylmethane diisocyanate is also called monomeric MDI or pure MDI. Examples of diphenylmethane diisocyanate include 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), and mixtures of two or more of these.
[0022] From the viewpoint of handleability, diphenylmethane diisocyanate preferably exists as a liquid at 25°C and 1 atmospheric pressure. At 25°C and 1 atmospheric pressure, 4,4'-MDI is typically a solid, and 2,4'-MDI is typically a liquid. From the viewpoint of handleability, diphenylmethane diisocyanate preferably contains 2,4'-MDI. When the total amount of diphenylmethane diisocyanate is 100 parts by mass, the content of 2,4'-MDI is preferably 30 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass or more and 70 parts by mass or less, and even more preferably 45 parts by mass or more and 65 parts by mass or less. In the case of the above-mentioned 2,4'-MDI content, the content of 4,4'-MDI is preferably 20 parts by mass or more and 70 parts by mass or less, more preferably 30 parts by mass or more and 60 parts by mass or less, and even more preferably 35 parts by mass or more and 55 parts by mass or less. From the viewpoint of handling, diphenylmethane diisocyanate may be contained in the composition in the form of a prepolymer.
[0023] Commercially available diphenylmethane diisocyanate may be used, such as "Millionate NM" manufactured by Tosoh Corporation, "G412" and "0129M" manufactured by Covestro, "Cosmonate PI" manufactured by Mitsui Chemicals, Inc., and "Lupranate MI" and "Lupranate MP102" manufactured by BASF.
[0024] The content of diphenylmethane diisocyanate is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 90 parts by mass or more, based on 100 parts by mass of the total isocyanate, from the viewpoint of suppressing yellowing of the polyamide portion 12. The upper limit of the content of diphenylmethane diisocyanate is not particularly limited, and may be 100 parts by mass.
[0025] The isocyanate index (INDEX) is preferably 80 or more and 120 or less. The isocyanate index is a value obtained by dividing the number of moles of isocyanate groups in an isocyanate by the total number of moles of active hydrogen groups such as hydroxyl groups of a polyol and water as a blowing agent, and multiplying the result by 100, and is calculated as [NCO equivalent of isocyanate / active hydrogen equivalent × 100].
[0026] (2.3) Discoloration Preventive Agent The discoloration preventive agent is not particularly limited, and antioxidants, discoloration preventive agents, light stabilizers, etc. can be used as appropriate. From the viewpoint of suppressing yellowing of the laminate 10, the composition preferably contains one or more selected from the group consisting of phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, benzotriazole-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, and hindered amine-based light stabilizers. Specifically, the phenolic antioxidant is, for example, a hindered phenolic antioxidant such as benzenepropanoic acid or 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters. The phosphorus-based antioxidant is, for example, a phosphite ester-based antioxidant such as tris(tridecyl)phosphite. The benzotriazole-based ultraviolet absorber is, for example, a benzotriazole-based ultraviolet absorber such as phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecyl-, branched and linear.
[0027] (2.4) Blowing Agent The blowing agent is not particularly limited. Examples of the blowing agent include water, pentane, cyclopentane, methylene chloride, and carbon dioxide gas. These blowing agents may be used alone or in combination of two or more. When water is used as the blowing agent, the blending amount of the blowing agent is preferably 1.0 part by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the total polyol.
[0028] (2.5) Foam Stabilizer The foam stabilizer is not particularly limited. Examples of the foam stabilizer include silicone compounds such as organopolysiloxane, organopolysiloxane-polyoxyalkylene copolymer, polyalkenylsiloxane having a polyoxyalkylene side chain, and silicone-grease copolymer; anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate; polyethersiloxane; and phenolic compounds. These foam stabilizers may be used alone or in combination of two or more. The amount of the foam stabilizer is not particularly limited. The amount of the foam stabilizer is preferably 0.03 parts by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the total polyol.
[0029] (2.6) Catalyst The composition preferably contains a catalyst. The catalyst primarily serves to promote the urethanization reaction between the polyol and the isocyanate. Examples of the catalyst that can be used include tertiary amines such as triethylenediamine, N,N-dimethylaminoethanol, 1,2-dimethylimidazole, and N,N',N'-trimethylaminoethylpiperazine; organometallic compounds such as stannous octoate and tin octoate (tin octoate); acetates; and alkali metal alcoholates. The total catalyst content in the composition is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, based on 100 parts by mass of the total polyol.
[0030] (2.7) Other Components The composition may contain other components in addition to those described above, as needed. Examples of other components include thickeners, plasticizers, antibacterial agents, and colorants.
[0031] (3) Physical Properties of Foam 11A The physical properties of the foam 11A can be set appropriately depending on the application, etc. The foam 11A is preferably a flexible polyurethane foam. The polyurethane foam preferably has the following physical properties.
[0032] (3.1) Apparent density The apparent density (JIS K7222:2005) is 8 kg / m ３ -150 kg / m ３ is preferred, and 10 kg / m ３ -100 kg / m ３More preferably, 20 kg / m ３ -60 kg / m ３ is more preferred.
[0033] (3.2) 25% Hardness The 25% hardness (JIS K6400-2 D method: 2012) is preferably 10N to 600N, more preferably 20N to 400N, and still more preferably 50N to 200N.
[0034] (3.3) Asker F Hardness The Asker F hardness is preferably 40 or more and 90 or less, more preferably 55 or more and 85 or less, and even more preferably 65 or more and 80 or less. The Asker F hardness was measured using an Asker F hardness tester. The Asker F hardness was measured by placing the Asker F hardness tester on the test piece and reading the value after 3 seconds.
[0035] (3.4) Rebound Resilience The rebound resilience (JIS K6400-3:2011) is preferably 10% to 60%, more preferably 20% to 50%, and even more preferably 25% to 45%.
[0036] (3.5) Tensile Strength and Elongation The tensile strength (JIS K6400-5:2012) is preferably 30 kPa or more, more preferably 50 kPa or more, and even more preferably 100 kPa or more. The elongation (JIS K6400-5:2012) is preferably 50% to 500%, and may be 100% or more, or 150% or more.
[0037] (3.6) Breathability The air permeability measured in accordance with ASTM D 3574 is preferably 30 L / min or more, more preferably 50 L / min or more, and even more preferably 70 L / min or more. If the air permeability is equal to or greater than the lower limit, the fabric is less likely to become stuffy and more comfortable when used in clothing. The upper limit of the air permeability is not particularly limited, and is usually 840 L / min or less, and may be 200 L / min or less.
[0038] (4) Configuration and Use of Laminate 10 The laminate 10 is formed by laminating a polyamide portion 12 and a polyurethane foam portion 11. In the laminate 10, the polyamide portion 12 and the polyurethane foam portion 11 may be bonded together with an adhesive (not shown). Alternatively, the laminate 10 may be formed by laminating the polyamide portion 12 and the polyurethane foam portion 11 and then heat-press molding the laminate. Heat-press molding will be described later.
[0039] The arrangement of the polyamide portion 12 and the polyurethane foam portion 11 is not particularly limited. The polyamide portion 12 is preferably located in the outermost layer of the laminate 10 because of its pleasant feel. Specifically, the polyamide portion 12 and the polyamide portion 13 are preferably located in both the front and back layers of the laminate 10. For example, the laminate 10 is preferably configured such that the polyurethane foam portion 11 is sandwiched between the polyamide portions 12 and 13. As in the laminate 210 of FIG. 3 , the polyamide portion 12 may be located in only one of the front and back layers of the laminate 210. Furthermore, the laminate of the present disclosure may further include other portions in addition to the polyamide portions 12, 13 and the polyurethane foam portion 11.
[0040] The use of the laminate 10 is not particularly limited. Because yellowing is suppressed, the laminate 10 is suitable as a clothing pad. Examples of clothing pads include bra pads and shoulder pads. When the laminate 10 is used as a bra pad, the laminate 10 is preferably cup-shaped. Furthermore, because yellowing is suppressed, the laminate 10 is suitable for applications other than clothing pads, such as cushioning materials, furniture, automotive interior materials, clothing, toys, and housing components. Examples of cushioning materials include protectors, bicycle saddle cushions, VR goggle pads, and shoe upper materials. Examples of furniture include cushions, mattresses, and sofas. Examples of automotive interior materials include interior materials such as seats, armrests, ceilings, and doors. Examples of clothing include hats, goggles, shoes, and masks. Examples of housing components include wallpaper.
[0041] (5) Requirements for ΔYI Value of Laminate 10 The laminate 10 is heat-pressed at 185°C for 300 seconds and then stored in a thermostatic chamber at 70°C and a relative humidity of 90% RH for 21 days. The ΔYI value, which is the change in yellow index, is preferably 0 or more and less than 20, more preferably 0 or more and less than 16, and even more preferably 0 or more and less than 10. The yellow index is measured on the surface of the polyamide portion 12 opposite to the polyurethane foam portion 11.
[0042] 2. Manufacturing Method of Laminate 10 There are no particular limitations on the manufacturing method of the laminate 10. An example of a manufacturing method of the laminate 10 will be described with reference to Fig. 2. The laminate 10 can be manufactured using, for example, a pair of openable and closable molding dies 21, 22. When the pair of molding dies 21, 22 are closed, a space corresponding to the shape of the laminate 10 is formed between the molding dies 21, 22.
[0043] In the manufacturing method of the laminate 10 shown in Fig. 2, the polyamide portion 12, the polyurethane foam portion 11, and the polyamide portion 13 are laminated in this order, followed by heat press molding. An adhesive (not shown) may be applied between the polyamide portion 12 and the polyurethane foam portion 11. An adhesive (not shown) may also be applied between the polyurethane foam portion 11 and the polyamide portion 12. In the manufacturing method of the laminate 210 shown in Fig. 3, the polyamide portion 12 and the polyurethane foam portion 11 are laminated, followed by heat press molding. An adhesive (not shown) may be applied between the polyamide portion 12 and the polyurethane foam portion 11.
[0044] The conditions for the heat press molding are not particularly limited. The heat press temperature can be, for example, 150°C or higher and 250°C or lower. The heat press time can be, for example, 60 seconds or higher and 600 seconds or lower. The compression rate of the polyurethane foam portion 11 during heat press molding can be, for example, 95% or lower. The compression rate of the polyurethane foam portion 11 can be calculated as the ratio of the thickness of the foam 11A during heat press molding to the thickness of the foam 11A before heat press molding. If the compression rate differs in each portion of the polyurethane foam portion 11, the compression rate of the polyurethane foam portion 11 during heat press molding is the compression rate of the portion of the polyurethane foam portion 11 with the highest compression rate.
[0045] 3. Function and Effect of Laminate 10 The laminate 10 can suppress yellowing of the polyamide portion 12. Yellowing of a typical laminate can be attributed to three factors: yellowing of the polyurethane foam portion, yellowing of the polyamide portion, and yellowing due to dye migration from the polyurethane foam portion to the polyamide portion. As a result of research conducted by the present inventors, it was newly discovered that when diphenylmethane diisocyanate is used as the isocyanate, yellowing due to dye migration from the polyurethane foam portion to the polyamide portion can be suppressed more effectively than when toluene diisocyanate is used, and yellowing of the polyurethane foam portion can also be suppressed. It was also discovered that when diphenylmethane diisocyanate is used as the isocyanate to form the laminate 10, yellowing of the polyamide portion 12 can be suppressed more effectively than when the polyamide portion is used alone. The laminate 10 was developed based on the above findings.
[0046] The foam 11A used in the laminate 10 can maintain the same feel and physical properties as the foam 11A containing only toluene diisocyanate as the isocyanate. Furthermore, when the isocyanate contains diphenylmethane diisocyanate, a sufficient 25% hardness can be achieved without using a polymer polyol as the polyol.
[0047] 4. Polyurethane Foam The polyurethane foam is a polyurethane foam for producing a laminate, in which a polyamide portion 12 and a polyurethane foam portion 11 are laminated. The polyurethane foam is a foam obtained from a composition containing a polyol and an isocyanate. The isocyanate contains diphenylmethane diisocyanate.
[0048] In addition to the polyol and isocyanate, the composition may contain a discoloration inhibitor, a blowing agent, a catalyst, a foam stabilizer, etc. In describing the polyurethane foam, the descriptions of the components of the composition in the sections "(2.1) Polyol," "(2.2) Isocyanate," "(2.3) Discoloration inhibitor," "(2.4) Blowing agent," "(2.5) Foam stabilizer," "(2.6) Catalyst," and "(2.7) Other components" described above in "(2) Polyurethane foam portion 11" apply as is, and descriptions thereof will be omitted.
[0049] From the viewpoint of breathability, a slab foam is preferred as the foam. Slab foams are obtained by discharging a mixed composition onto a belt conveyor and foaming it at atmospheric pressure and room temperature. Individual cells in a slab foam are surrounded by the cell skeleton and cell membranes between adjacent cells. When the cell membranes are broken by carbon dioxide gas or the like generated during foaming and curing of the slab foam, adjacent cells communicate with each other. When the slab foam is cut to form the polyurethane foam section 11, the cells remain open on the cut surface. This allows air to pass through from the front surface to the back surface of the slab foam. Thus, when a slab foam is used as a polyurethane foam for laminate production, the breathability of the laminate can be improved more favorably than when, for example, a molded foam is used.
[0050] The polyurethane foam can be used as a foam for manufacturing a laminate. In the description of the polyurethane foam, the physical properties of the polyurethane foam are the same as those described above in the sections "(3.1) Apparent Density," "(3.2) 25% Hardness," "(3.3) Asker F Hardness," "(3.4) Resilience," "(3.5) Tensile Strength, Elongation," and "(3.6) Breathability" in "(3) Physical Properties of Foam 11A," and the descriptions thereof will be omitted.
[0051] Next, the above embodiment will be described in more detail with reference to examples and comparative examples. 1. Production of polyurethane foams (foams) Each component was prepared in the blending ratio shown in Table 1 below, and polyurethane foams of the examples and comparative examples were produced by slab foaming. Details of each raw material are as follows. Polyol 1: polypropylene glycol, weight average molecular weight 3000, number of functional groups 3, hydroxyl value 56 mg KOH / g Polyol 2: polymer polyol obtained by graft polymerizing a vinyl monomer onto a polyether polyol, vinyl monomer graft amount (solid content) 42 mass%, number of functional groups 3, hydroxyl value 28 mg KOH / g Polyol 3: polyether polyol, weight average molecular weight 2000, number of functional groups 2 Isocyanate 1: toluene diisocyanate (TDI), molecular weight 174 (molar mass), number of NCO groups 2, NCO% 48.2 Isocyanate 2: diphenylmethane diisocyanate (pure MDI), molecular weight 250 (molar mass), number of NCO groups 2, NCO% 33.6, 2,2'-MDI content 0.80 mass parts or less, 2,4'-MDI content 50.00 parts by mass or more and less than 60.00 parts by mass, 4,4'-MDI content 39.20 parts by mass or more Blowing agent: Water Amine catalyst 1: 33% TEDA (triethylenediamine) in DPG (dipropylene glycol) Amine catalyst 2: N,N-dimethylaminoethanol Amine catalyst 3: DMI (1,2-dimethylimidazole) in 30% DEG (diethylene glycol) Foam stabilizer: Organic-containing silicone, manufactured by Toray Dow Co., Ltd., product number: SZ1136 Discoloration inhibitor 1: Ultraviolet absorber, manufactured by UNION CHEMICAL, product number: UHS-430LF Discoloration inhibitor 2: Benzotriazole-based ultraviolet absorber, Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecyl-, branched and linear. Anti-tarnish agent 3: phosphite ester-based UV absorber, tris(tridecyl)phosphite. Anti-tarnish agent 4: hindered phenol-based antioxidant, benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters.
[0052]
[0053] 2. Evaluation of Polyurethane Foam Next, the obtained polyurethane foams of Example 1 and Comparative Examples 1 and 2 were evaluated as follows. The evaluation results are also shown in Table 1. (1) Density (Apparent Density) The apparent density was measured in accordance with JIS K7222:2005. (2) 25% ILD Hardness (25% Hardness) The 25% hardness was measured in accordance with JIS K6400-2 D Method:2012. (3) F Hardness (Asker F Hardness) The Asker F hardness was measured by attaching an Asker hardness tester, Type F, to the test piece and reading the value after 3 seconds. (4) Rebound Resilience The rebound resilience was measured in accordance with JIS K6400-3:2011. (5) Tensile Strength and Elongation The tensile strength and elongation were measured in accordance with JIS K6400-5:2012. (6) Air Permeability The air permeability was measured in accordance with ASTM D 3574.
[0054] 3. Production of Laminates Samples measuring 100 mm x 50 mm x 5 mm were cut out from the polyurethane foams (foams) of Example 1 and Comparative Examples 1 and 2. The following fabrics were cut to 100 mm x 50 mm. Nylon 6 fabric was laminated onto the polyurethane foam samples, and the laminates were produced by hot press molding under the following hot press conditions.
[0055] <Heat Press Conditions> Mold: Equipped with a pair of heat press plates. The molding surfaces of the pair of heat press plates are parallel to each other. Compression rate of polyurethane foam: 80% compression (thickness when compressed: 4 mm). Condition 1: Heat press temperature: 185°C; Heat press time: 300 seconds (120 seconds + 180 seconds). Specifically, after 120 seconds of pressing, the yellow index (YI) of the polyamide part (fabric) was measured. Then, after 180 seconds of pressing, the yellow index (YI) of the polyamide part (fabric) was measured. Condition 2: Heat press temperature: 170°C; Heat press time: 300 seconds (120 seconds + 180 seconds). Specifically, after 120 seconds of pressing, the yellow index (YI) of the fabric was measured. Then, after 180 seconds of pressing, the yellow index (YI) of the fabric was measured. Condition 3: Heat press temperature: 185°C; Heat press time: 300 seconds (120 seconds + 180 seconds). Specifically, after pressing for 120 seconds, the fabric was peeled off from the polyurethane foam and the yellow index (YI) of the polyurethane foam was measured. Thereafter, the polyurethane foam and the fabric were laminated together, and after pressing for 180 seconds, the fabric was peeled off from the polyurethane foam and the yellow index (YI) of the polyurethane foam was measured. Condition 4: Heat press temperature: 170°C, Heat press time: 300 seconds (120 seconds + 180 seconds). Specifically, after pressing for 120 seconds, the fabric was peeled off from the polyurethane foam and the yellow index (YI) of the polyurethane foam was measured. Thereafter, the polyurethane foam and the fabric were laminated together, and after pressing for 180 seconds, the fabric was peeled off from the polyurethane foam and the yellow index (YI) of the polyurethane foam was measured.
[0056] 4. Evaluation of Laminates (1) Humid Heat Aging Test Next, a moist heat aging test was conducted on the laminates of Example 1 and Comparative Examples 1 and 2. The conditions for the moist heat aging test were as follows. At test times of 0 days, 7 days, 14 days, and 21 days, the change in yellow index (ΔYI) from the yellow index (YI) before heat pressing (blank) was determined. Note that the "test time of 0 days" is the difference (ΔYI) between the blank YI value and the YI value after the above-mentioned 180-second pressing. The measurement results are shown in Table 2.
[0057] <Conditions for moist heat aging test> Apparatus: Model QS-200-4M manufactured by Dongguan Qishi Testing Machines Co., Ltd. Conditions: Temperature 70°C, relative humidity 90% RH
[0058] Specifically, the change in yellow index (ΔYI) was determined for the polyamide portion (textile) of the laminate obtained under the above conditions 1 and 2. The yellow index of the polyamide portion (textile) was measured on the surface of the polyamide portion opposite the polyurethane foam portion, i.e., the surface of the laminate. In this example, a color difference meter (model number: CS-820) manufactured by Hangzhou CHN Spec Technology Co., Ltd. was used to measure the yellow index.
[0059] The change in yellow index (ΔYI) was also determined for the polyurethane foam portion (foam) of the laminate obtained under the above conditions 3 and 4. The yellow index of the polyurethane foam portion (foam) was measured on the surface of the polyurethane foam portion facing the polyamide portion after peeling the polyamide portion from the polyurethane foam portion.
[0060] As Comparative Example 3, the fabric for the polyamide portion cut in the same manner as above was heat-pressed under the heat-pressing conditions of Conditions 1 and 2, and the same moist heat aging test was carried out.
[0061]
[0062] (2) Combustion Gas Test Samples measuring 100 mm x 50 mm x 5 mm were cut out from the polyurethane foams (foams) of Example 1 and Comparative Examples 1 and 2, and were subjected to heat press molding. The heat press conditions were the same as those of Conditions 1 and 2. In the combustion gas test, no fabric was laminated on the polyurethane foam samples.
[0063] A sample that had not been subjected to a moist heat aging test (moist heat aging 0 days) was prepared from the hot press molded samples, and a sample that had been subjected to a moist heat aging test for 2 days (moist heat aging 2 days) was prepared from the hot press molded samples.
[0064] A combustion gas test was conducted on the sample (humid heat aging 0 days) and the sample (humid heat aging 2 days). The conditions for the combustion gas test are as follows. After the combustion gas test, the change in yellow index (ΔYI) from the yellow index (YI) before heat pressing (blank) was determined. The measurement results are shown in Table 3. <Conditions for combustion gas test> Apparatus: Smoke fastness tester, model RF1106 Conditions: Conforms to AATCC23.
[0065]
[0066] 5. Results Example 1 satisfies the following requirements (a) to (c). Comparative Examples 1 and 2 do not satisfy the following requirement (c). Comparative Example 3 does not satisfy the following requirements (a) to (c). Requirement (a): The laminate is a laminate of a polyamide portion and a polyurethane foam portion. Requirement (b): The polyurethane foam portion is made of a foam obtained from a composition containing a polyol and an isocyanate. Requirement (c): The isocyanate contains diphenylmethane diisocyanate.
[0067] The ΔYI of the polyamide portion (fabric) in Table 2 is compared between Example 1 and Comparative Example 1, which contain the same amount of discoloration inhibitor. Under condition 1, where the heat press temperature was 185°C and 21 days of moist heat aging, the ΔYI of Example 1 was 6, and the ΔYI of Comparative Example 1 was 26. Under condition 2, where the heat press temperature was 170°C and 21 days of moist heat aging, the ΔYI of Example 1 was 5, and the ΔYI of Comparative Example 1 was 16. These results demonstrate that under moist heat conditions after heat pressing, Example 1, which used monomeric MDI, suppresses yellowing of the polyamide portion (fabric) more than Comparative Example 1, which used TDI. This suppression of yellowing of the polyamide portion (fabric) is more significant than the suppression of yellowing of the polyurethane foam portion (foam) described below, suggesting that Example 1 effectively suppresses dye migration from the polyurethane foam portion to the polyamide portion.
[0068] The ΔYI of the polyurethane foam portion (foam) in Table 2 is compared between Example 1 and Comparative Example 1, which contain the same amount of anti-tarnish agent. Under condition 3, where the heat press temperature was 185°C and humid heat aging was performed for 21 days, the ΔYI of Example 1 was 25 and the ΔYI of Comparative Example 1 was 36. Under condition 4, where the heat press temperature was 170°C and humid heat aging was performed for 21 days, the ΔYI of Example 1 was 25 and the ΔYI of Comparative Example 1 was 28. These results demonstrate that under humid heat conditions after heat pressing, Example 1, which used monomeric MDI, suppressed yellowing of the polyamide portion (fabric) more than Comparative Example 1, which used TDI.
[0069] The ΔYI of the polyamide portion (fabric) in Table 2 is compared between Example 1, which is a laminate, and Comparative Example 3, which is a fabric alone. Under condition 1, where the heat press temperature was 185°C and 21 days of moist heat aging, the ΔYI of Example 1 was 6, and the ΔYI of Comparative Example 3 was 12. Under condition 2, where the heat press temperature was 170°C and 21 days of moist heat aging, the ΔYI of Example 1 was 5, and the ΔYI of Comparative Example 3 was 11. These results demonstrate that the presence of the polyurethane foam portion of Example 1 suppresses yellowing of the polyamide portion (fabric) under moist heat conditions after heat pressing, more so than when the polyurethane foam portion is not present. It was suggested that Example 1, which used monomeric MDI, effectively suppresses dye migration from the polyurethane foam portion to the polyamide portion.
[0070] The ΔYI of the polyurethane foam (humid heat aging 0 days) in Table 3 is compared between Example 1 and Comparative Example 1, which contain the same amount of anti-tarnish agent. At a heat press temperature of 185°C under Condition 1, the ΔYI was 37, and the ΔYI of Comparative Example 1 was 62. At a heat press temperature of 170°C under Condition 2, the ΔYI of Example 1 was 15, and the ΔYI of Comparative Example 1 was 36. The ΔYI of the polyurethane foam (humid heat aging 2 days) in Table 3 is also compared between Example 1 and Comparative Example 1, which contain the same amount of anti-tarnish agent. At a heat press temperature of 185°C under Condition 1, the ΔYI was 64, and the ΔYI of Comparative Example 1 was 104. At a heat press temperature of 170°C under Condition 2, the ΔYI of Example 1 was 59, and the ΔYI of Comparative Example 1 was 102. From these results, it can be seen that Example 1, which used monomeric MDI, produced a lower nitrogen oxide (NO ) than Comparative Example 1, which used TDI. ｘ ) was found to improve discoloration resistance.
[0071] 6. Effects of the Examples According to the above examples, a technique for suppressing yellowing of a laminate was provided.
[0072] The present disclosure is not limited to the above-described embodiments, and various modifications and variations are possible within the scope of the claims of the present disclosure.
[0073] 10, 210...Laminate 11...Polyurethane foam portion 11A...Foam 12, 13...Polyamide portion 12A, 13A...Fabric
Claims
1. A laminate comprising a polyamide section and a polyurethane foam section, the polyurethane foam section being made of a foam obtained from a composition containing a polyol and an isocyanate, and the isocyanate containing diphenylmethane diisocyanate.
2. A garment pad comprising the laminate according to claim 1.
3. A polyurethane foam for producing a laminate, in which a polyamide portion and a polyurethane foam portion are laminated, the polyurethane foam being a foam obtained from a composition containing a polyol and an isocyanate, the isocyanate containing diphenylmethane diisocyanate.
4. The polyurethane foam according to claim 3, wherein the composition contains one or more members selected from the group consisting of phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and hindered amine-based light stabilizers.
5. The polyurethane foam according to claim 3 or 4, having an air permeability measured in accordance with ASTM D 3574 of 30 L / min or more.