Laminate, mat for clothing, and polyurethane foam

Abstract

Provided is a technique for suppressing yellowing of a laminate. The laminate (10) is obtained by laminating a polyamide part (12) and a polyurethane foam part (11). The polyurethane foam part (11) is configured from a foam body (11A), and the foam body (11A) is obtained from a composition containing a polyol and an isocyanate. And the isocyanate contains diphenylmethane diisocyanate.

Description

Technical Field

[0001] This disclosure relates to a laminate, a pad for clothing, and a polyurethane foam. Background Technology

[0002] Patent Document 1 discloses a flexible polyurethane foam using toluene diisocyanate (TDI) as an aromatic isocyanate. Patent Document 1 describes how, by using phosphorus-based antioxidants and hindered amine light stabilizers, the flexible polyurethane foam can be prevented from discoloring due to nitrogen oxides, and also from discoloration due to heat, etc., during humid conditions.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2010-100717 Summary of the Invention The problem the invention aims to solve In laminates composed of polyurethane foam and fabric, polyamide is preferred for the fabric from the viewpoint of various physical properties such as skin feel. However, when polyamide fabrics are used, there is a problem of the laminate turning yellow.

[0004] This disclosure was made in view of the above-mentioned circumstances, and its purpose is to provide a technique for suppressing yellowing of laminates. This disclosure can be implemented in the following ways.

[0005] means for solving problems [1] A laminate composed of a polyamide portion and a polyurethane foam portion, The polyurethane foam portion is composed of a foam body obtained from a composition containing polyols and isocyanates. The isocyanate contains diphenylmethane diisocyanate.

[0006] [2] A pad for clothing, having the laminated body described in [1].

[0007] [3] A polyurethane foam for manufacturing a laminate, said laminate being composed of a polyamide portion and a polyurethane foam portion laminated together. The polyurethane foam is a foam obtained from a composition containing polyols and isocyanates. The isocyanate contains diphenylmethane diisocyanate.

[0008] [4] The polyurethane foam according to [3], wherein the composition contains one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers and hindered amine light stabilizers.

[0009] [5] The polyurethane foam according to [3] or [4] has an air permeability of 30 L / min or more as determined according to ASTM D 3574.

[0010] The effects of the invention According to this disclosure, a technique for suppressing yellowing of laminates can be provided. Attached Figure Description

[0011] Figure 1 This is a cross-sectional view of a laminated body according to one embodiment.

[0012] Figure 2 This is a diagram used to illustrate the manufacturing method of laminates.

[0013] Figure 3 This is a diagram used to illustrate the manufacturing method of laminates. Detailed Implementation

[0014] The present disclosure will now be described in detail. Furthermore, in this specification, regarding numerical ranges, the use of the hyphen "-" includes both the lower and upper limits unless otherwise specified. For example, the description "10-20" includes both the lower limit "10" and the upper limit "20". That is, "10-20" means the same as "more than 10 and less than 20". Additionally, in this specification, the upper and lower limits of each numerical range can be arbitrarily combined.

[0015] 1. Laminated body 10 like Figure 1 as well as Figure 2 As shown, the laminate 10 is a laminate composed of a polyamide portion 12 and a polyurethane foam portion 11. The polyurethane foam portion 11 is composed of a foam 11A, which is obtained from a composition containing a polyol and an isocyanate. The isocyanate contains diphenylmethane diisocyanate.

[0016] (1) Polyamide part 12 The polyamide portion 12 comprises a polyamide resin. The polyamide resin is, for example, one or more selected from the group consisting of aliphatic polyamides (nylon), para-aromatic polyamides, and meta-aromatic polyamides. The aliphatic polyamide is, for example, obtained by polycondensation or co-condensation of an aminocarboxylic acid, lactam, or diamine with a dicarboxylic acid. Examples of aliphatic polyamides include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 46, nylon 6T, nylon 6I, nylon 9T, nylon M5T, and nylon 612. The para-aromatic polyamide is, for example, obtained by polycondensation of an aromatic diamine with a dicarboxylic acid.

[0017] From the viewpoint of improving breathability, the polyamide portion 12 is preferably composed of a fabric 12A made of polyamide resin fibers. The type of fabric 12A is not particularly limited. For example, the fabric 12A can be woven, knitted, or nonwoven.

[0018] In addition, Figure 1 as well as Figure 2 In the laminate 10, the polyamide portion 12, the polyurethane foam portion 11, and the polyamide portion 13 are laminated in this order. The polyamide portion 13 is, for example, made of the same fabric 13A as the fabric 12A of the polyamide portion 12. In addition, the polyamide portion 13 can have the same structure as the polyamide portion 12, and can have various structures depending on the application of the laminate 10, etc.

[0019] (2) Polyurethane foam part 11 The polyurethane foam component 11 is composed of a foaming body 11A, which is obtained from a composition containing a polyol and an isocyanate. In addition to polyol and isocyanate, the composition may also contain an anti-discoloration agent, a foaming agent, a catalyst, a foam stabilizer, etc.

[0020] (2.1) Polyols The polyol is not particularly limited. Examples of polyols include polyether polyols, polymer polyols, and polyester polyols. Among these, polyether polyols are preferred.

[0021] Polyether polyols include, for example, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, butanediol, neopentyl glycol, glycerol, pentaerythritol, trimethylolpropane, sorbitol, sucrose, and other polyols, or polyether polyols obtained by addition reactions of such polyols with ethylene oxide, propylene oxide, or other epoxides. Furthermore, a single polyether polyol may be used, or two or more polyether polyols may be used in combination. By using polyether polyols, the flexibility of the polyurethane foam portion 11 can be improved. Preferably, the polyol contains polypropylene glycol.

[0022] 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.

[0023] The number of functional groups in 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.

[0024] The content of polyether polyol is not particularly limited. When the total polyol is set to 100 parts by weight, the content of polyether polyol is preferably 40 parts by weight or more and 100 parts by weight or less, more preferably 60 parts by weight or more and 100 parts by weight or less, and even more preferably 80 parts by weight or more and 100 parts by weight or less.

[0025] The polymeric polyol is not particularly limited. For example, a polymeric polyol is a liquid containing dispersed microparticle polymers. Microparticle polymers include, for example, polymers such as styrene, acrylonitrile, acrylic acid, melamine, and polyurea. The polymeric polyol is preferably a substance formed by polymerizing styrene or acrylonitrile in a polyether polyol (base polyol), or by polymerizing styrene and acrylonitrile. The polymer content (the mass ratio of the portion other than the base polyol to the total polymeric polyol) of the polymeric polyol is preferably 10% by mass or more and 55% by mass or less, more preferably 20% by mass or more and 45% by mass or less. From the viewpoint of improving the strength of the polyurethane foam portion 11, a high polymer content is preferred; however, if the polymer content is too high, the viscosity increases, and productivity may decrease. Furthermore, the polymeric polyol may contain only one type of polymeric polyol, or it may use two or more polymeric polyols with different weight average molecular weights, polymer contents, or number of functional groups. By using polymeric polyols, the hardness of the polyurethane foam portion 11 can be improved.

[0026] The weight average molecular weight of the polymer 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.

[0027] The number of functional groups in 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.

[0028] The content of the polymeric polyol is not particularly limited. From the viewpoint of ensuring the use of a generally suitable amount of polyether polyol, when the total polyol content is set to 100 parts by weight, the content of the polymeric polyol is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less. The lower limit of the polymeric polyol content is not particularly limited and may also be 0 parts by weight.

[0029] (2.2) Isocyanates The isocyanate contains diphenylmethane diisocyanate (MDI). The isocyanate need to contain at least diphenylmethane diisocyanate; it can be crude MDI or polymeric MDI, but isocyanate containing diphenylmethane diisocyanate is preferred. Diphenylmethane diisocyanate is colorless to pale yellow; therefore, compared to brown crude MDI or polymeric MDI, diphenylmethane diisocyanate is suitable for products requiring initial whiteness (e.g., pads for clothing).

[0030] Diphenylmethane diisocyanate is also known as monomeric MDI or pure MDI. Examples of diphenylmethane diisocyanates 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 the above substances.

[0031] From an operational point of view, diphenylmethane diisocyanate is preferably present as a liquid at 25°C and one atmosphere. At 25°C and one atmosphere, 4,4'-MDI is generally a solid, while 2,4'-MDI is generally a liquid. From an operational point of view, diphenylmethane diisocyanate preferably contains 2,4'-MDI. When the total amount of diphenylmethane diisocyanate is set to 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. With 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 an operational point of view, diphenylmethane diisocyanate can also be included in the composition as a prepolymer.

[0032] Diphenylmethane diisocyanate can be commercially available. Examples of commercially available products include "Millionate NM" manufactured by Tosoh Corporation, "G412" and "0129M" manufactured by Covestro, "Cosmonate PI" manufactured by Mitsui Chemicals, and "Lupranate MI" and "Lupranate MP102" manufactured by BASF.

[0033] When the total isocyanate content is set to 100 parts by weight, from the viewpoint of suppressing yellowing of the polyamide portion 12, the content of diphenylmethane diisocyanate is preferably 60 parts by weight or more, more preferably 80 parts by weight or more, and even more preferably 90 parts by weight or more. The upper limit of the above-mentioned diphenylmethane diisocyanate content is not particularly limited and can be 100 parts by weight.

[0034] The isocyanate index (INDEX) is preferably 80 or higher and 120 or lower. The isocyanate index is the value obtained by dividing the number of moles of isocyanate groups in the isocyanate by the total number of moles of hydroxyl groups in the polyol or the total number of moles of active hydrogen groups such as water used as a blowing agent, and then multiplying the result by 100. It is calculated by "NCO equivalent of isocyanate / active hydrogen equivalent × 100".

[0035] (2.3) Anti-discoloration agent The anti-coloring agent is not particularly limited, and antioxidants, anti-coloring agents, light stabilizers, etc., can be used appropriately. From the viewpoint of inhibiting the yellowing of the laminate 10, the composition preferably contains one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, and hindered amine light stabilizers. Specifically, phenolic antioxidants include, for example, hindered phenolic antioxidants such as benzoenepropanoic acid and 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9 branched alkyl esters. Phosphorus antioxidants include, for example, phosphite antioxidants such as tridecyl phosphite. Benzotriazole UV absorbers include, for example, branched and linear benzotriazole UV absorbers such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecyl-).

[0036] (2.4) Foaming agent The foaming agent is not particularly limited. Examples of foaming agents include water, pentane, cyclopentane, dichloromethane, and carbon dioxide. These foaming agents can be used alone or in combination of two or more. When using water as the foaming agent, and assuming the total amount of polyol is 100 parts by weight, the preferred amount of foaming agent is 1.0 parts by weight or more and 5.0 parts by weight or less.

[0037] (2.5) Foam stabilizer Foam stabilizers are not particularly limited. Preferred foam stabilizers include, for example, organopolysiloxanes, organopolysiloxane-polyoxyalkylene copolymers, polyolefin siloxanes with polyoxyalkylene side chains, silicone-oil copolymers, and other silicone compounds; anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate; polyether siloxanes; and phenolic compounds. These foam stabilizers can be used alone or in combination of two or more. The amount of foam stabilizer is not particularly limited. When the total amount of polyol is 100 parts by weight, the amount of foam stabilizer is preferably 0.03 parts by weight or more and 5.0 parts by weight or less.

[0038] (2.6) Catalyst The composition preferably contains a catalyst. The catalyst is primarily a substance used to promote the carbamate reaction between the polyol and the isocyanate. Examples of catalysts 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 stannous 2-ethylhexanoate (stannous octoate); acetates; and alkali metal alkoxides. When the total polyol content is 100 parts by mass, the total amount of catalyst in the composition is preferably 0.1 parts by mass or more and 5.0 parts by mass or less.

[0039] (2.7) Other components The composition may contain other ingredients besides those mentioned above, as needed. Other ingredients include, for example, thickeners, plasticizers, antibacterial agents, and colorants.

[0040] (3) Physical properties of foam 11A The physical properties of the foam 11A can be appropriately set according to the application, etc. The foam 11A is preferably a flexible polyurethane foam.

[0041] Polyurethane foam preferably has the following physical properties.

[0042] (3.1) Apparent density The apparent density (JIS K7222:2005) is preferably 8 kg / m³. 3 -150kg / m 3 More preferably 10 kg / m 3 -100kg / m 3 Further preferred is 20kg / m 3 -60kg / m 3 .

[0043] (3.2) 25% hardness The 25% hardness (JIS K6400-2D method: 2012) is preferably 10N-600N, more preferably 20N-400N, and even more preferably 50N-200N.

[0044] (3.3) Asker F type hardness The Asker F-type hardness is preferably 40 or higher and 90 or lower, more preferably 55 or higher and 85 or lower, and even more preferably 65 or higher and 80 or lower. Furthermore, the Asker F-type hardness is measured using an Asker F-type hardness tester. In the Asker F-type hardness measurement, the Asker F-type hardness tester is placed on the test piece, and the value is read after 3 seconds.

[0045] (3.4) Rebound elasticity The resilience (JIS K6400-3:2011) is preferably 10%-60%, more preferably 20%-50%, and even more preferably 25%-45%.

[0046] (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.

[0047] The elongation (JIS K6400-5:2012) is preferably 50%-500%, but can also be 100% or more, or 150% or more.

[0048] (3.6) Breathability The air permeability, as measured according to 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 above the lower limit, it will not be stuffy and will be comfortable to wear when used in clothing. In addition, the upper limit of the above air permeability is not particularly limited, and is usually 840 L / min or less, and may also be 200 L / min or less.

[0049] (4) Structure and uses of laminate 10 In the laminate 10, a polyamide portion 12 and a polyurethane foam portion 11 are laminated. The polyamide portion 12 and the polyurethane foam portion 11 can be bonded together in the laminate 10 using an adhesive (not shown). Alternatively, the laminate 10 can be formed by laminating the polyamide portion 12 and the polyurethane foam portion 11 and then hot-pressing them. Hot-pressing will be described later.

[0050] The configuration of the polyamide portion 12 and the polyurethane foam portion 11 is not particularly limited. From the perspective of good skin feel, it is preferable that the polyamide portion 12 is located in the outermost layer of the laminate 10. Specifically, the polyamide portion 12 and the polyamide portion 13 can be located in both the surface layer and the back layer of the laminate 10. For example, the laminate 10 is preferably constructed by sandwiching the polyurethane foam portion 11 between the polyamide portion 12 and the polyamide portion 13. Alternatively, it can be like... Figure 3 As with the laminate 210, the polyamide portion 12 is located only on either the surface layer or the back layer of the laminate 210. Furthermore, the laminate of this disclosure may have other portions in addition to the polyamide portions 12 and 13 and the polyurethane foam portion 11.

[0051] The application of the laminate 10 is not particularly limited. Because it inhibits yellowing, the laminate 10 is suitable as a pad for clothing. Examples of clothing pads include bra pads and shoulder pads. When the laminate 10 is used as a bra pad, it can be formed into a cup shape. Furthermore, because it inhibits yellowing, the laminate 10 is suitable not only for clothing pads but also for cushioning components, furniture, automotive interior materials, clothing, toys, and residential components. Examples of cushioning components include protective gear, bicycle saddle pads, VR (Virtual Reality) mask pads, and shoe upper materials. Examples of furniture include seat cushions, mattresses, and sofas. Examples of automotive interior materials include seat, armrest, roof, and door interior materials. Examples of clothing include hats, goggles, shoes, and masks. Examples of residential components include wallpaper.

[0052] (5) Requirements regarding the ΔYI value of the laminate 10 After the laminate 10 is hot-pressed at 185°C for 300 seconds, the change in yellowness index, i.e., ΔYI value, after being placed in a constant temperature bath at 70°C and 90% RH for 21 days 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.

[0053] Furthermore, the aforementioned yellowness index was measured on the side of the polyamide portion 12 opposite to the polyurethane foam portion 11.

[0054] 2. Method for manufacturing the laminate 10 The manufacturing method of the laminate 10 is not particularly limited. (See reference...) Figure 2 This illustrates an example of a method for manufacturing the laminate 10. The laminate 10 can be manufactured, for example, using a pair of molds 21, 22 that can be opened and closed. With the pair of molds 21, 22 closed, a space corresponding to the shape of the laminate 10 is formed between the molds 21, 22.

[0055] exist Figure 2 In the manufacturing method of the laminate 10 shown, the polyamide portion 12, the polyurethane foam portion 11, and the polyamide portion 13 are laminated in this order and then hot-pressed. An adhesive (not shown) can be applied between the polyamide portion 12 and the polyurethane foam portion 11. An adhesive (not shown) can also be applied between the polyurethane foam portion 11 and the polyamide portion 12.

[0056] exist Figure 3 In the manufacturing method of the laminate 210 shown, the polyamide portion 12 and the polyurethane foam portion 11 are laminated and then hot-pressed. An adhesive (not shown) can be applied between the polyamide portion 12 and the polyurethane foam portion 11.

[0057] The conditions for hot pressing are not particularly limited. The hot pressing temperature can be, for example, 150°C or higher and 250°C or lower. The hot pressing time can be, for example, 60 seconds or higher and 600 seconds or lower. The compression ratio of the polyurethane foam portion 11 during hot pressing can be, for example, 95% or lower. Furthermore, the compression ratio of the polyurethane foam portion 11 can be calculated by comparing the thickness of the foam body 11A during hot pressing with the thickness of the foam body 11A before hot pressing. If the compression ratio differs at different parts of the polyurethane foam portion 11, the compression ratio of the part with the highest compression ratio in the polyurethane foam portion 11 is taken as the compression ratio of the polyurethane foam portion 11 during hot pressing.

[0058] 3. The function and effect of the laminate 10 The laminate 10 can suppress the yellowing of the polyamide portion 12. Generally, yellowing of laminates is mainly caused by three factors: yellowing of the polyurethane foam portion, yellowing of the polyamide portion, and yellowing due to migration from the polyurethane foam portion to the polyamide portion. The inventors of this application have newly discovered, through research, that when using diphenylmethane diisocyanate as the isocyanate, compared to using toluene diisocyanate, yellowing due to migration from the polyurethane foam portion to the polyamide portion can be suppressed, thus suppressing the yellowing of the polyurethane foam portion. Furthermore, it has been found that when using the laminate 10 as the isocyanate, yellowing of the polyamide portion 12 is suppressed more effectively than when using the polyamide portion alone. The laminate 10 was developed based on the above insights.

[0059] Furthermore, the foam 11A used in the laminate 10 can maintain the same tactile feel and physical properties as the foam 11A containing only toluene diisocyanate as the isocyanate. Moreover, when the isocyanate contains diphenylmethane diisocyanate, a sufficient hardness of 25% can be achieved even without using a polymer polyol as the polyol.

[0060] 4. Polyurethane foam The polyurethane foam is a polyurethane foam used to manufacture a laminate of polyamide portion 12 and polyurethane foam portion 11. The polyurethane foam is a foam obtained from a composition containing a polyol and an isocyanate. The isocyanate contains diphenylmethane diisocyanate.

[0061] In addition to polyols and isocyanates, the composition may also contain anti-discoloration agents, foaming agents, catalysts, foam stabilizers, etc. In the description of polyurethane foam, the descriptions of each component of the composition can be directly applied to the descriptions in the columns "(2) Polyurethane Foam Part 11" above, namely "(2.1) Polyol", "(2.2) Isocyanate", "(2.3) Anti-discoloration agent", "(2.4) Foaming agent", "(2.5) Foam stabilizer", "(2.6) Catalyst" and "(2.7) Other components", without omitting their descriptions.

[0062] From the viewpoint of air permeability, slab foam is preferred. Slab foam is obtained by spraying a mixed composition onto a conveyor belt and foaming it at atmospheric pressure and room temperature. Each bubble in the slab foam is surrounded by a cell skeleton and a bubble film located between adjacent bubbles. If the bubble film ruptures due to carbon dioxide gas or other gases generated during the foaming and hardening of the slab foam, adjacent bubbles become interconnected. When the slab foam is cut to form polyurethane foam portions 11, the bubbles are open at the cut surfaces. Therefore, air channels can be formed from the surface to the back of the slab foam. Thus, when using slab foam as polyurethane foam for laminate manufacturing, for example, compared to using molded foam, the air permeability of the laminate can be significantly improved.

[0063] Polyurethane foam can be used as a foaming material for manufacturing laminates. In the description of polyurethane foam, the physical properties of polyurethane foam are directly used from the descriptions in the columns "(3) Physical properties of foam 11A" above, namely "(3.1) Apparent density", "(3.2) 25% hardness", "(3.3) Asker F type hardness", "(3.4) Resilience", "(3.5) Tensile strength and elongation", and "(3.6) Air permeability", without omitting their descriptions.

[0064] Example Next, examples and comparative examples will be given to illustrate the above implementation methods in more detail.

[0065] 1. Manufacturing of polyurethane foam (expanded body) The components were prepared according to the mixing ratios shown in Table 1 below, and the polyurethane foams of the examples and comparative examples were manufactured by block foaming.

[0066] Details of each raw material are as follows.

[0067] Polyol 1: Polypropylene glycol, with a weight average molecular weight of 3000, 3 functional groups, and a hydroxyl value of 56 mg KOH / g.

[0068] Polyol 2: Polymer polyols grafted with vinyl monomers in polyether polyols, with a vinyl monomer grafting amount (solid content) of 42% by mass, 3 functional groups, and a hydroxyl value of 28 mg KOH / g.

[0069] Polyol 3: Polyether polyol with a weight average molecular weight of 2000 and 2 functional groups.

[0070] Isocyanate 1: Toluene diisocyanate (TDI), with a molecular weight of 174 (molar mass), an NCO base of 2, and an NCO% of 48.2%.

[0071] Isocyanate 2: Diphenylmethane diisocyanate (pure MDI), with a molecular weight of 250 (molar mass), an NCO base of 2, an NCO% of 33.6%, a 2,2'-MDI content of less than 0.80 parts by mass, a 2,4'-MDI content of more than 50.00 parts by mass and less than 60.00 parts by mass, and a 4,4'-MDI content of more than 39.20 parts by mass.

[0072] Foaming agent: water.

[0073] Amine catalyst 1: 33% TEDA (triethylenediamine) dissolved in DPG (dipropylene glycol).

[0074] Amine catalyst 2: N,N-dimethylethanolamine.

[0075] Amine catalyst 3: DMI (1,2-dimethylimidazole) is soluble in 30% DEG (diethylene glycol).

[0076] Foam stabilizer: Contains organic silicone, manufactured by Dow Toray Co., Ltd., product number: SZ1136.

[0077] Anti-discoloration agent 1: Ultraviolet absorber, manufactured by UNION CHEMICAL, product number UHS-430LF.

[0078] Anti-coloring agent 2: Benzotriazol-based ultraviolet absorber, branched and linear 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (Phenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-dodecyl-, branched and linear).

[0079] Anti-discoloration agent 3: Phosphite-based ultraviolet absorber, tridecyl phosphite.

[0080] Anti-discoloration agent 4: Hindered phenolic antioxidant, Benzenepropanoic acid, 3,5-di-tert-butyl-4-hydroxyphenylpropanoic acid branched C7-C9 carbon alkyl esters.

[0081] [Table 1]

[0082] 2. Evaluation of polyurethane foam Next, the polyurethane foams obtained in Example 1, Comparative Example 1, and 2 were evaluated as follows. The evaluation results are recorded in Table 1.

[0083] (1) Density (apparent density) Apparent density was determined according to JIS K7222:2005.

[0084] (2) 25% ILD hardness (25% hardness) The 25% hardness was determined using JIS K6400-2 D method: 2012.

[0085] (3) F hardness (Asker F type hardness) The Asker F type hardness is determined by placing the Asker F type hardness tester on the test piece and reading the value after 3 seconds.

[0086] (4) Rebound elasticity The resilience was measured according to JIS K6400-3:2011.

[0087] (5) Tensile strength and elongation Tensile strength and elongation were determined according to JIS K6400-5:2012.

[0088] (6) Air permeability Air permeability was measured according to ASTM D 3574.

[0089] 3. Fabrication of laminated bodies Samples measuring 100mm × 50mm × 5mm were cut from the polyurethane foam (foam body) of Examples 1, 1, and 2. The following fabric was cut to 100mm × 50mm. Nylon 6 fabric was laminated onto the polyurethane foam sample, and the laminate was manufactured by hot pressing under the following conditions.

[0090] <Hot pressing conditions> Forming mold: It has a pair of hot press plates. The forming surfaces of the pair of hot press plates are parallel to each other.

[0091] The compression ratio of polyurethane foam is 80% (thickness 4mm when compressed).

[0092] Condition 1: The hot pressing temperature is 185℃.

[0093] The hot pressing time was 300 seconds (120 seconds + 180 seconds). Specifically, after pressing for 120 seconds, the yellowness index (YI) of the polyamide part (fabric) was measured. Subsequently, after pressing for 180 seconds, the yellowness index (YI) of the polyamide part (fabric) was measured again.

[0094] Condition 2: The hot pressing temperature is 170℃.

[0095] The hot pressing time was 300 seconds (120 seconds + 180 seconds). Specifically, the yellowness index (YI) of the fabric was measured after 120 seconds of pressing. Subsequently, the yellowness index (YI) of the fabric was measured after 180 seconds of pressing.

[0096] Condition 3: The hot pressing temperature is 185℃.

[0097] The hot-pressing time was 300 seconds (120 seconds + 180 seconds). Specifically, after pressing for 120 seconds, the fabric was peeled off from the polyurethane foam and the yellowness index (YI) of the polyurethane foam was measured. Subsequently, the polyurethane foam and fabric were layered, and after pressing for 180 seconds, the fabric was peeled off from the polyurethane foam and the yellowness index (YI) of the polyurethane foam was measured.

[0098] Condition 4: The hot pressing temperature is 170℃.

[0099] The hot-pressing time was 300 seconds (120 seconds + 180 seconds). Specifically, after pressing for 120 seconds, the fabric was peeled off from the polyurethane foam and the yellowness index (YI) of the polyurethane foam was measured. Subsequently, the polyurethane foam and fabric were layered, and after pressing for 180 seconds, the fabric was peeled off from the polyurethane foam and the yellowness index (YI) of the polyurethane foam was measured.

[0100] 4. Evaluation of laminated structures (1) Damp heat aging test Next, the laminates of Example 1, Comparative Examples 1 and 2 were subjected to a damp heat aging test. The conditions for the damp heat aging test are as follows. The change (ΔYI) of the yellowness index relative to the yellowness index (YI) before hot pressing (blank control) was calculated at test times of 0 days, 7 days, 14 days, and 21 days. Furthermore, "test time 0 days" refers to the difference (ΔYI) between the YI value of the blank control and the YI value after 180 seconds of pressing. The results of each measurement are recorded in Table 2.

[0101] <Conditions for Damp Heat Aging Test> Device: Manufactured by Dongguan Qishi Testing Machines Co., Ltd. (Dongguan Xingye Metal Materials Co., Ltd.), model QS-200-4M.

[0102] Conditions: Temperature 70℃, relative humidity 90%RH.

[0103] Specifically, the change in yellowness index (ΔYI) is calculated for the polyamide portion (fabric) of the laminate obtained under conditions 1 and 2 above. The yellowness index of the polyamide portion (fabric) is measured on the surface of the laminate, on the side opposite to the polyurethane foam portion within the polyamide portion. In this embodiment, the yellowness index is measured using a colorimeter (model: CS-820) manufactured by Hangzhou CHNSpec Technology Co., Ltd.

[0104] Furthermore, the change in yellowness index (ΔYI) is calculated for the polyurethane foam portion (foam body) of the laminate obtained from conditions 3 and 4 above. Regarding the yellowness index of the polyurethane foam portion (foam body), the polyamide portion is peeled off from the polyurethane foam portion, and the measurement is performed on the polyamide portion side of the polyurethane foam portion.

[0105] As a comparative example 3, the fabric monomers for the polyamide part, which were cut in the same manner as described above, were hot-pressed under the hot-pressing conditions of conditions 1 and 2, and the same damp heat aging test was conducted.

[0106] [Table 2]

[0107] (2) Combustion gas test Samples measuring 100mm × 50mm × 5mm were cut from the polyurethane foams (foam bodies) of Examples 1, 1, and 2, and then hot-pressed. The hot-pressing conditions were the same as those for conditions 1 and 2 above. Furthermore, in the combustion gas test, no fabric was layered on top of the polyurethane foam samples.

[0108] For samples that have already been hot-pressed, prepare samples that have not undergone a damp heat aging test (damp heat aging is 0 days). In addition, for samples that have already been hot-pressed, prepare samples that have undergone a damp heat aging test for 2 days (damp heat aging is 2 days).

[0109] Combustion gas tests were conducted on samples (with 0 days of damp heat aging) and samples (with 2 days of damp heat aging). The conditions for the combustion gas tests are as follows. After the combustion gas tests, the change in yellowness index (ΔYI) relative to the yellowness index before hot pressing (blank control) was calculated. The results are recorded in Table 3.

[0110] <Conditions for Combustion Gas Testing> Apparatus: Gas fume color fastness tester, model RF1106.

[0111] Condition: According to AATCC23.

[0112] [Table 3]

[0113] 5. Results Example 1 satisfies requirements (a)-(c) below. Comparative Example 1 and Comparative Example 2 do not satisfy requirement (c) below. Comparative Example 3 does not satisfy requirements (a)-(c) below.

[0114] Requirement (a): A laminate consisting of a polyamide portion and a polyurethane foam portion.

[0115] Requirement (b): The polyurethane foam is composed of a foam body, which is obtained from a composition containing a polyol and an isocyanate.

[0116] Requirement (c): The isocyanate contains diphenylmethane diisocyanate.

[0117] Regarding the ΔYI of the polyamide portion (fabric) in Table 2, Example 1 and Comparative Example 1, which contain the same amount of anti-fading agent, are compared. Under the conditions of hot pressing temperature of 185°C and 21 days of damp heat aging in Condition 1, the ΔYI of Example 1 is 6, and the ΔYI of Comparative Example 1 is 26. Under the conditions of hot pressing temperature of 170°C and 21 days of damp heat aging in Condition 2, the ΔYI of Example 1 is 5, and the ΔYI of Comparative Example 1 is 16.

[0118] Based on these results, it can be seen that under the humid heat conditions after hot pressing, Example 1, which used monomer MDI, suppressed yellowing of the polyamide portion (fabric) compared to Comparative Example 1, which used TDI. The suppression of yellowing in the polyamide portion (fabric) was significantly greater than that in the polyurethane foam portion (foam body), which will be described later. Example 1 provides an insight that dye migration from the polyurethane foam portion to the polyamide portion can be effectively suppressed.

[0119] Regarding the ΔYI of the polyurethane foam (foam body) in Table 2, Example 1 and Comparative Example 1, which contain the same amount of anti-color change agent, were compared. Under the conditions of hot pressing temperature of 185°C and hygrothermal aging for 21 days in Condition 3, the ΔYI of Example 1 was 25, and the ΔYI of Comparative Example 1 was 36. Under the conditions of hot pressing temperature of 170°C and hygrothermal aging for 21 days in Condition 4, the ΔYI of Example 1 was 25, and the ΔYI of Comparative Example 1 was 28.

[0120] According to the results, under the humid heat conditions after hot pressing, Example 1, which used monomer MDI, suppressed the yellowing of the polyamide portion (fabric) compared to Comparative Example 1, which used TDI.

[0121] For the ΔYI of the polyamide portion (fabric) in Table 2, Example 1 as a laminate and Comparative Example 3 as a fabric monomer are compared. Under the conditions of hot pressing temperature of 185°C and 21 days of damp heat aging in Condition 1, the ΔYI of Example 1 is 6, and the ΔYI of Comparative Example 3 is 12. Under the conditions of hot pressing temperature of 170°C and 21 days of damp heat aging in Condition 2, the ΔYI of Example 1 is 5, and the ΔYI of Comparative Example 3 is 11.

[0122] The results indicate that, under the humid and hot conditions following hot pressing, the polyurethane foam portion of Example 1 is present; therefore, compared to the case without the polyurethane foam portion, yellowing of the polyamide portion (fabric) is suppressed. Example 1, which uses the monomer MDI, provides insight into how dye migration from the polyurethane foam portion to the polyamide portion can be effectively suppressed.

[0123] For the ΔYI of the polyurethane foam (0 days of damp heat aging) in Table 3, Example 1 and Comparative Example 1, which contain the same amount of anti-color change agent, are compared. Under condition 1 (hot pressing temperature 185°C), ΔYI is 37, and for Comparative Example 1, ΔYI is 62. Under condition 2 (hot pressing temperature 170°C), ΔYI of Example 1 is 15, and for Comparative Example 1, ΔYI is 36.

[0124] Furthermore, for the ΔYI of the polyurethane foam (wet heat aging for 2 days) in Table 3, Example 1 and Comparative Example 1, which contain the same amount of anti-color change agent, were compared. At a hot-pressing temperature of 185°C under condition 1, ΔYI was 64, while the ΔYI of Comparative Example 1 was 104. At a hot-pressing temperature of 170°C under condition 2, the ΔYI of Example 1 was 59, while the ΔYI of Comparative Example 1 was 102.

[0125] Based on these results, Example 1, which used monomeric MDI, showed improved protection against nitrogen oxides (NOx) compared to Comparative Example 1, which used TDI. x ( ) colorfastness.

[0126] 6. Effects of the Implementation Examples Based on the above embodiments, a technique for inhibiting yellowing of laminates can be provided.

[0127] This disclosure is not limited to the embodiments described in the detailed description above, and various modifications or alterations can be made within the scope of the claims of this disclosure.

[0128] Explanation of reference numerals in the attached figures 10, 210: Layered bodies 11: Polyurethane foam section 11A: Foamed body, 12, 13: Polyamide section 12A, 13A: Fabric.

Claims

1. A laminated body comprising a polyamide portion and a polyurethane foam portion, wherein, The polyurethane foam portion is composed of a foam body obtained from a composition containing polyols and isocyanates. The isocyanate contains diphenylmethane diisocyanate.

2. A pad for clothing, wherein, It has the laminate as described in claim 1.

3. A polyurethane foam for manufacturing a laminate, said laminate being composed of a polyamide portion and a polyurethane foam portion, wherein, The polyurethane foam is a foam obtained from a composition containing polyols and isocyanates. The isocyanate contains diphenylmethane diisocyanate.

4. The polyurethane foam according to claim 3, wherein, The composition contains one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, and hindered amine light stabilizers.

5. The polyurethane foam according to claim 3 or 4, wherein, The air permeability, as measured according to ASTM D 3574, is above 30 L / min.

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