Non-yellowing polyurethane insole composition and product thereof
Through the polymerization reaction and foaming treatment of the main agent component, catalyst component and non-yellowing hardener component in a specific ratio, the problems of yellowing and insufficient hardness of the polyurethane midsole composition are solved, and a low-density, high-hardness non-yellowing shoe midsole is prepared.
Patent Information
- Application Number
- CN202410303314.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-18
- Publication Date
- 2025-09-19
AI Technical Summary
Existing polyurethane midsole compositions are prone to yellowing during use, and it is difficult to prepare low-density shoe midsoles that meet hardness standards, resulting in insufficient hardness of the shoe midsole or the inability to form a shape.
A main agent component, a catalyst component and a non-yellowing hardener component in a specific ratio are used, including a first high molecular weight polyol, a chain extender, water, a foam stabilizer, an aliphatic diisocyanate monomer, an aliphatic diisocyanate polymer and a polyurethane prepolymer, to form a non-yellowing shoe midsole through polymerization reaction and foaming treatment.
A non-yellowing shoe midsole with low density (0.2g/cm3 to 0.4g/cm3) and a hardness of 20Shore C to 70Shore C was produced, which has excellent non-yellowing properties and meets industry standards.
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Abstract
Description
Technical Field
[0001] The present invention relates to a polymer composition and a shoe component, in particular to a non-yellowing polyurethane midsole composition and a non-yellowing shoe midsole. Background Art
[0002] Currently, the industry generally uses a polyurethane midsole composition containing a main agent, a catalyst, and a non-yellowing hardener to prepare shoe midsoles. The main agent includes a polymer polyol, water, and a foam stabilizer, and the non-yellowing hardener is an aliphatic diisocyanate monomer. However, the shoe midsoles made using the above polyurethane midsole composition will still gradually turn yellow with the increase of usage time. Therefore, the existing polyurethane midsole composition cannot solve the problem of yellowing of shoe midsoles. In addition, the above polyurethane midsole composition cannot meet the current downstream manufacturers' requirements for a 0.4g / cm 3 However, if the amount of each component in the above polyurethane midsole composition is adjusted to prepare a low-density shoe midsole with a density of 0.4 g / cm 3 The following shoe midsoles will actually reduce the hardness of the shoe midsole, causing the hardness of the produced shoe midsole to be less than 20 Shore C, failing to meet the current industry hardness standards for shoe midsoles. They may even cause the foamed structure formed by the polyurethane midsole composition to become coarse, making it impossible to form a shoe midsole.
[0003] Based on the above, how to make the manufactured shoe midsole have the properties of non-yellowing, low density and hardness that meets industry standards is a problem that needs to be solved at present. Summary of the Invention
[0004] An object of the present invention is to provide a non-yellowing polyurethane midsole composition capable of preparing a shoe midsole having non-yellowing properties, low density and suitable hardness.
[0005] The non-yellowing polyurethane midsole composition of the present invention comprises a main agent component, a catalyst component and a non-yellowing hardener component.
[0006] The main agent components include a first high molecular weight polyol, a first chain extender, a second chain extender, water, and a foam stabilizer. The average molecular weight of the first high molecular weight polyol ranges from 100 g / mol to 10,000 g / mol. The first chain extender is selected from one of ethylene glycol, diethylene glycol, and triethylene glycol. The second chain extender is selected from a polyol other than the first chain extender. Based on 100 parts by weight of the total amount of the first high molecular weight polyol, the amount of the first chain extender ranges from 0.25 parts by weight to 30 parts by weight, the amount of the second chain extender ranges from 0.25 parts by weight to 30 parts by weight, the amount of water ranges from 0.1 parts by weight to 20 parts by weight, and the amount of the foam stabilizer ranges from 0.1 parts by weight to 15 parts by weight.
[0007] The catalyst components are selected from at least two of tin-based catalysts, potassium-based catalysts, silver-based catalysts, titanium-based catalysts, zinc-based catalysts, and tertiary amine-based catalysts.
[0008] The non-yellowing hardener component includes a first aliphatic diisocyanate monomer, an aliphatic diisocyanate polymer, and a polyurethane prepolymer. The first aliphatic diisocyanate monomer is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. The aliphatic diisocyanate polymer has an average molecular weight ranging from 100 g / mol to 10,000 g / mol and is selected from at least one of polyhexamethylene diisocyanate and polyisocyanate. The polyurethane prepolymer is prepared by polymerization of reactants comprising a second aliphatic diisocyanate monomer and a second high molecular weight polyol. The second aliphatic diisocyanate monomer is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. The second high molecular weight polyol has an average molecular weight ranging from 100 g / mol to 10,000 g / mol.
[0009] Based on the total amount of the main agent component as 100 parts by weight, the amount of the catalyst component used ranges from 0.5 parts by weight to 30 parts by weight, and based on the total amount of the main agent component and the catalyst component as 100 parts by weight, the amount of the non-yellowing hardener component used ranges from 20 parts by weight to 300 parts by weight.
[0010] In the non-yellowing polyurethane midsole composition of the present invention, the first high molecular weight polyol is selected from one of polytetramethylene sulfone, polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol.
[0011] In the non-yellowing polyurethane midsole composition of the present invention, the second chain extender is selected from one of 2-methyl-1,3-propanediol, pentaerythritol, and dipentaerythritol.
[0012] In the non-yellowing polyurethane midsole composition of the present invention, the second high molecular weight polyol is selected from one of polytetramethylene sulfone, polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol.
[0013] In the non-yellowing polyurethane midsole composition of the present invention, based on 100 parts by weight of the total amount of the non-yellowing hardener component, the amount of the aliphatic diisocyanate polymer ranges from 25 parts by weight to 50 parts by weight.
[0014] In the non-yellowing polyurethane midsole composition of the present invention, the main agent component further includes an additive component, and the additive component is selected from at least one of a UV absorber, a light stabilizer, an antioxidant, a heat reducer, and a colorant.
[0015] In the non-yellowing polyurethane midsole composition of the present invention, the non-yellowing hardener component further includes an aromatic diisocyanate polymer, and the aromatic diisocyanate polymer is selected from one of polyxylylene diisocyanate and polyhydrogenated xylylene diisocyanate.
[0016] Another object of the present invention is to provide a non-yellowing shoe midsole.
[0017] The non-yellowing shoe midsole of the present invention is formed by reacting the non-yellowing polyurethane midsole composition described above.
[0018] In the non-yellowing shoe midsole of the present invention, the density range of the non-yellowing shoe midsole is 0.2g / cm 3 to 0.4g / cm 3 .
[0019] In the non-yellowing shoe midsole of the present invention, the hardness range of the non-yellowing shoe midsole is 20 Shore C to 70 Shore C.
[0020] The beneficial effect of the present invention is that: by matching the first chain extender and the second chain extender in the main agent component, the aliphatic diisocyanate polymer in the non-yellowing hardener component, the amount of each component in the main agent component, and the amount of the main agent component, the catalyst component and the non-yellowing hardener component, the non-yellowing shoe midsole prepared with the non-yellowing polyurethane midsole composition has a non-yellowing strength of 0.2 g / cm 3 to 0.4g / cm 3 Low density, hardness from 20Shore C to 70Shore C and excellent non-yellowing properties. DETAILED DESCRIPTION
[0021] The non-yellowing polyurethane midsole composition of the present invention comprises a main component, a catalyst component, and a non-yellowing hardener component. The main component, catalyst component, and non-yellowing hardener component are not in contact with each other. When using the non-yellowing polyurethane midsole composition to prepare a non-yellowing shoe midsole, the main component, catalyst component, and non-yellowing hardener component are mixed, subjected to a polymerization reaction, foamed, and then molded to obtain the non-yellowing shoe midsole.
[0022] The main agent components include a first high molecular weight polyol, a first chain extender, a second chain extender, water and a foam stabilizer.
[0023] The first high molecular weight polyol is the main component of the non-yellowing shoe midsole formed by polymerization reaction with the non-yellowing hardener component. In the present invention, the average molecular weight of the first high molecular weight polyol ranges from 100 g / mol to 10,000 g / mol. By controlling the average molecular weight of the first high molecular weight polyol to be above 100 g / mol, it is possible to avoid the foaming structure produced by the foaming treatment of the non-yellowing polyurethane midsole composition from becoming coarse, so that the non-yellowing polyurethane midsole composition can be formed after the foaming treatment to obtain the non-yellowing shoe midsole, and the non-yellowing shoe midsole has a thickness of 0.4 g / cm 3 The first polymer polyol has a density below 10,000 g / mol and a hardness above 20 Shore C. By controlling the average molecular weight of the first polymer polyol to below 10,000 g / mol, the main component can have good fluidity, thereby enabling the non-yellowing polyurethane midsole composition to be used in the mass production of the non-yellowing shoe midsole. The type of the first polymer polyol is not particularly limited; any agent capable of polymerizing with the non-yellowing hardener component to form the non-yellowing shoe midsole is suitable for use in the present invention. In some embodiments of the present invention, the first polymer polyol is selected from polytetrahydrofuran, polyether polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol. In some embodiments of the present invention, the first polymer polyol can be a polymer polyol obtained through artificial synthesis or a polymer polyol derived from biomass. Examples of biomass-derived polymer polyols include, but are not limited to, soybean oil, corn oil, and palm oil.
[0024] The first chain extender is mainly used to match with the second chain extender, so as to give the non-yellowing shoe midsole a 0.2g / cm 3 to 0.4g / cm 3 The low density of the non-yellowing shoe midsole makes the non-yellowing shoe midsole lightweight and has a hardness of 20 Shore C to 70 Shore C. The first chain extender is selected from one of ethylene glycol, diethylene glycol, and triethylene glycol.
[0025] The second chain extender is mainly used to match the first chain extender, so as to give the non-yellowing shoe midsole a viscosity of 0.2 g / cm2 without changing the volume of the required shoe midsole. 3 to 0.4g / cm 3The low density of the non-yellowing midsole imparts lightweight properties and a hardness of 20 to 70 Shore C. The second chain extender is selected from a polyol other than the first chain extender. In some embodiments of the present invention, the second chain extender is selected from 2-methyl-1,3-propanediol, pentaerythritol, and dipentaerythritol.
[0026] The foaming agent is primarily used to allow the non-yellowing polyurethane midsole composition to form a non-yellowing shoe midsole having uniform foaming pores and a dense foam structure after foaming. The type of foaming agent is not particularly limited; any chemical agent capable of imparting uniform foaming and a dense foam structure to the non-yellowing shoe midsole formed by foaming the non-yellowing polyurethane midsole composition is suitable for use in the present invention.
[0027] In the main component, based on 100 parts by weight of the total amount of the first high molecular weight polyol, the amount of the first chain extender is in a range of 0.25 to 30 parts by weight, the amount of the second chain extender is in a range of 0.25 to 30 parts by weight, the amount of water is in a range of 0.1 to 20 parts by weight, and the amount of the foam stabilizer is in a range of 0.1 to 15 parts by weight. In the present invention, the amount of the first chain extender is 0.25 parts by weight or more, so that the non-yellowing shoe midsole has uniform foaming pores and dense foaming structure, and the amount of the first chain extender is 30 parts by weight or less, so as to avoid the problem of the non-yellowing shoe midsole collapsing after molding; the amount of the second chain extender is 0.25 parts by weight or more, so that the non-yellowing shoe midsole has a hardness of 20 Shore C or more, and after the non-yellowing shoe midsole is continuously irradiated with ultraviolet light for 96 hours, the non-yellowing shoe midsole will not have aging phenomena such as powdering, and the amount of the second chain extender is 30 parts by weight or less, so as to avoid the problem of the non-yellowing shoe midsole collapsing after molding; the amount of water is 0.1 parts by weight or more, so that the non-yellowing shoe midsole has a hardness of 0.4 g / cm 3 The density of the non-yellowing midsole is 0.2 g / cm2, and the amount of water is 20 parts by weight or less. 3 The density is above; the amount of the foaming agent is 0.1 parts by weight or more, so that the non-yellowing shoe midsole has uniform foaming pores and dense foaming structure, and the amount of the foaming agent is 15 parts by weight or less, in order to avoid the problem of the non-yellowing shoe midsole collapsing after molding.
[0028] In some embodiments of the present invention, to further adjust the reactivity of the polymerization reaction between the main agent component and the non-yellowing hardener component, or to further adjust the properties of the non-yellowing shoe midsole, the main agent component further includes an additive component, and the additive component is at least one selected from the group consisting of a UV absorber, a light stabilizer, an antioxidant, a heat reducer, and a colorant. In some embodiments of the present invention, when the main agent component further includes the additive component, and the additive component is a UV absorber, a light stabilizer, an antioxidant, or a heat reducer, the amount of each of the UV absorber, the light stabilizer, the antioxidant, and the heat reducer is each in the range of 0.1 to 15 parts by weight, based on 100 parts by weight of the total amount of the first high molecular weight polyol. An amount of 0.1 parts by weight or greater for each of the UV absorber, the light stabilizer, the antioxidant, and the heat reducer to fully exert their respective effects. The amount of the ultraviolet absorber, the light stabilizer, the antioxidant and the heat reducer is each less than 15 parts by weight, so that the non-yellowing polyurethane midsole composition can be smoothly formed after the foaming treatment to obtain the non-yellowing shoe midsole. In some embodiments of the present invention, when the main component also includes the additive ingredient, and the additive ingredient is a colorant, the amount of the colorant ranges from 0.001 parts by weight to 10 parts by weight based on the total amount of the first polymer polyol as 100 parts by weight. The colorant can only play its role when it is used in an amount of 0.001 parts by weight or more, and the amount of the colorant is less than 10 parts by weight so that the color of the non-yellowing shoe midsole is white.
[0029] The catalyst component is used to promote a polymerization reaction between the main component and the non-yellowing hardener component, thereby forming the non-yellowing polyurethane midsole composition into the non-yellowing shoe midsole. The catalyst component is selected from at least two of a tin-based catalyst, a potassium-based catalyst, a silver-based catalyst, a titanium-based catalyst, a zinc-based catalyst, and a tertiary amine-based catalyst. In some embodiments of the present invention, the catalyst component includes a titanium-based catalyst and a potassium-based catalyst.
[0030] The non-yellowing hardener component undergoes a polymerization reaction with the main agent component to form the non-yellowing polyurethane midsole composition into the non-yellowing shoe midsole. The non-yellowing hardener component includes a first aliphatic diisocyanate monomer, an aliphatic diisocyanate polymer, and a polyurethane prepolymer.
[0031] Herein, “aliphatic diisocyanate monomer” refers to a compound having two isocyanate groups; and “aliphatic diisocyanate polymer” refers to a compound having three or more isocyanate groups.
[0032] The first aliphatic diisocyanate monomer is used to impart the non-yellowing property to the non-yellowing shoe midsole made from the non-yellowing polyurethane midsole composition. The first aliphatic diisocyanate monomer is selected from hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (4,4'-diisocyanato dicyclohexylmethane, HDI), and the like. 12 At least one of MDI and isophorone diisocyanate (IPDI). In some embodiments of the present invention, the first aliphatic diisocyanate monomer includes hexamethylene diisocyanate and isophorone diisocyanate. In some embodiments of the present invention, the amount of the first aliphatic diisocyanate monomer ranges from 1 part by weight to 75 parts by weight based on 100 parts by weight of the total amount of the non-yellowing hardener component. In some embodiments of the present invention, the amount of the first aliphatic diisocyanate monomer ranges from 37.5 parts by weight to 50 parts by weight based on 100 parts by weight of the total amount of the non-yellowing hardener component.
[0033] The function of the aliphatic diisocyanate polymer is to cooperate with the first aliphatic diisocyanate monomer, thereby facilitating the foaming and molding of the non-yellowing polyurethane midsole composition to obtain the non-yellowing shoe midsole, and the non-yellowing shoe midsole will not have the problem of collapse after molding. At the same time, the aliphatic diisocyanate polymer can also give the non-yellowing shoe midsole the property of non-yellowing. In addition, the aliphatic diisocyanate polymer can also give the non-yellowing shoe midsole a 0.2g / cm 3 to 0.4g / cm 3The low density of the aliphatic diisocyanate polymer provides lightweight properties while maintaining the required volume of the midsole, and the non-yellowing midsole has a hardness of 20 Shore C to 70 Shore C. The aliphatic diisocyanate polymer has an average molecular weight ranging from 100 g / mol to 10,000 g / mol and is selected from at least one of polyhexamethylene diisocyanate and polyisophorone diisocyanate. In some embodiments of the present invention, the polyhexamethylene diisocyanate is a hexamethylene diisocyanate dimer. In some embodiments of the present invention, the polyisophorone diisocyanate is an isophorone diisocyanate dimer. In the present invention, controlling the average molecular weight of the aliphatic diisocyanate polymer to be above 100 g / mol is intended to enhance the reactivity of the non-yellowing hardener component, thereby enabling the polymerization reaction and foaming of the non-yellowing polyurethane midsole composition. Controlling the average molecular weight of the aliphatic diisocyanate polymer to be below 10,000 g / mol improves the fluidity of the non-yellowing hardener component, thereby facilitating the mass production of the non-yellowing polyurethane midsole composition. In some embodiments of the present invention, to enhance the reactivity of the non-yellowing hardener component and facilitate polymerization and foaming of the non-yellowing polyurethane midsole composition, the average molecular weight of the aliphatic diisocyanate polymer ranges from 100 g / mol to 3,000 g / mol.
[0034] In some embodiments of the present invention, the amount of the aliphatic diisocyanate polymer is in the range of 1 to 75 parts by weight, based on 100 parts by weight of the total amount of the non-yellowing hardener component. In some embodiments of the present invention, in order to further improve the reactivity between the non-yellowing hardener component and the first chain extender and the second chain extender in the main agent component, thereby being more conducive to imparting the non-yellowing shoe midsole with a hardness of 20 to 70 Shore C and 0.2 g / cm 3 to 0.4g / cm 3 The density of the non-yellowing hardener component is 100 parts by weight, and the amount of the aliphatic diisocyanate polymer is in the range of 25 parts by weight to 50 parts by weight.
[0035] The polyurethane prepolymer facilitates the polymerization reaction between the main component and the non-yellowing hardener component, thereby enabling the non-yellowing polyurethane midsole composition to form the non-yellowing shoe midsole. The polyurethane prepolymer is produced by polymerization of reactants comprising a second aliphatic diisocyanate monomer and a second polymeric polyol. The second aliphatic diisocyanate monomer is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. The average molecular weight of the second polymeric polyol ranges from 100 g / mol to 10,000 g / mol. The type of the second polymeric polyol is not particularly limited; any agent capable of polymerizing with the second aliphatic diisocyanate monomer to form the polyurethane prepolymer is suitable for use in the present invention. In some embodiments of the present invention, the second polymeric polyol is selected from polytetrahydrofuran, polyether polyol, polyester polyol, polycaprolactone polyol, and polycarbonate polyol. In some embodiments of the present invention, the amount of the polyurethane prepolymer used ranges from 1 to 75 parts by weight, based on 100 parts by weight of the total amount of the non-yellowing hardener component. In some embodiments of the present invention, the amount of the polyurethane prepolymer used ranges from 12.5 to 30 parts by weight, based on 100 parts by weight of the total amount of the non-yellowing hardener component.
[0036] In some embodiments of the present invention, to further accelerate the polymerization reaction between the main component and the non-yellowing hardener component, the non-yellowing hardener component further comprises an aromatic diisocyanate polymer. The aromatic diisocyanate polymer is selected from poly(m-xylylenediisocyanate) and poly(hydrogenated m-xylylenediisocyanate). Furthermore, in addition to accelerating the polymerization reaction between the main component and the non-yellowing hardener component, the aromatic diisocyanate polymer also imparts a non-yellowing property to the non-yellowing shoe midsole. In some embodiments of the present invention, the amount of the aromatic diisocyanate polymer ranges from 1 to 75 parts by weight, based on 100 parts by weight of the non-yellowing hardener component. The aromatic diisocyanate polymer is used in an amount of 1 part by weight or more to ensure its reactivity. The aromatic diisocyanate polymer is used in an amount of 75 parts by weight or less to avoid the problem of the non-yellowing midsole collapsing after molding. In some embodiments of the present invention, to further impart suitable toughness and tear strength to the non-yellowing midsole, the aromatic diisocyanate polymer is used in an amount ranging from 1 part by weight to 15 parts by weight, based on 100 parts by weight of the total amount of the non-yellowing hardener component. In some embodiments of the present invention, to further adjust the toughness and tear strength of the non-yellowing midsole, the aromatic diisocyanate polymer is used in an amount ranging from 5 parts by weight to 15 parts by weight, based on 100 parts by weight of the total amount of the non-yellowing hardener component.
[0037] In the non-yellowing polyurethane midsole composition, the amount of the catalyst component ranges from 0.5 to 30 parts by weight, based on 100 parts by weight of the total amount of the main agent component. Furthermore, the amount of the non-yellowing hardener component ranges from 20 to 300 parts by weight, based on 100 parts by weight of the total amount of the main agent component and the catalyst component. In the present invention, the amount of the catalyst component is 0.5 parts by weight or more to enable the non-yellowing polyurethane midsole composition to undergo a polymerization reaction and be molded after foaming to obtain the non-yellowing shoe midsole. The amount of the catalyst component is 30 parts by weight or less to prevent the non-yellowing shoe midsole from collapsing after molding. The amount of the non-yellowing hardener component is 20 parts by weight or more to enable the non-yellowing polyurethane midsole composition to undergo a polymerization reaction, and the amount of the non-yellowing hardener component is 300 parts by weight or less to prevent the non-yellowing shoe midsole from collapsing after molding.
[0038] The present invention also provides a non-yellowing shoe midsole, which is formed by reacting the non-yellowing polyurethane midsole composition described above.
[0039] In some embodiments of the present invention, the density of the non-yellowing midsole is in the range of 0.2 g / cm 3 to 0.4g / cm 3 .
[0040] In some embodiments of the present invention, the hardness of the non-yellowing shoe midsole ranges from 20 Shore C to 70 Shore C.
[0041] The present invention will be further described with reference to the following examples. However, it should be understood that the examples are for illustration only and should not be construed as limiting the present invention.
[0042] [Example 1]
[0043] 100 parts by weight of a first polymer polyol (polyether polyol, brand: Shell Chemicals, model: CARADOL MC28-02, average molecular weight 6000 g / mol), 6 parts by weight of a first chain extender (diethylene glycol), 10 parts by weight of a second chain extender (2-methyl-1,3-propanediol), 2 parts by weight of water, 2 parts by weight of an ultraviolet absorber (manufactured by BASF, trade name: 213), 1 part by weight of a light stabilizer (manufactured by BASF, trade name: 765), 1 part by weight of an antioxidant (manufactured by BASF, trade name: 1135), 2 parts by weight of a heat reducer (type: dihydrate gypsum), 2 parts by weight of a foam stabilizer (brand: Momentive, model: L-580) and 0.1 parts by weight of a colorant (brand: Milliken, model: REACTINT Blue X3LV) were mixed to obtain a total of 126.1 parts by weight of the main agent component. 5 parts by weight of a titanium catalyst (manufactured by DuPont, trade name: TE, compound English name: (2-propanolato)-[(2,2',2"-nitrilotris[ethanolato])-(3)-N,O,O',O"]titanium, CAS number: 14483-21-7) and 8 parts by weight of a potassium-based catalyst (type: potassium 2-ethylhexanoate) were mixed to obtain a total of 13 parts by weight of a catalyst component. 100 parts by weight of a non-yellowing hardener component was prepared by mixing 30 parts by weight of hexamethylene diisocyanate (HDI, as the first aliphatic diisocyanate monomer), 15 parts by weight of isophorone diisocyanate (IPDI, as the first aliphatic diisocyanate monomer), 15 parts by weight of hexamethylene diisocyanate dimer (HDI dimer, as the aliphatic diisocyanate polymer), 10 parts by weight of uretidione dimer of isophorone diisocyanate (IPDI dimer, as the aliphatic diisocyanate polymer), and 30 parts by weight of a polyurethane prepolymer. The polyurethane prepolymer was prepared by mixing 50 parts by weight of a polyether polyol (brand: Shell Chemicals, model: CARADOL MC28-02, average molecular weight 6000 g / mol) and 50 parts by weight of dicyclohexylmethane diisocyanate (HDI). 12 The catalyst component is prepared by polymerization reaction of reactants composed of MDI. The amount of the catalyst component is calculated based on 100 parts by weight of the total amount of the main agent component. The amount of the non-yellowing hardener component is calculated based on 100 parts by weight of the total amount of the main agent component and the catalyst component.
[0044] The main component and the catalyst component are mixed and stirred until uniformly mixed, then added to the Polyol raw material barrel of a two-liquid quantitative mixing and foaming machine (brand: Huasheng Technology, model: G-380). The non-yellowing hardener component is also added to the ISO raw material barrel of the two-liquid quantitative mixing and foaming machine. The main component, the catalyst component, and the non-yellowing hardener component are then mixed using the mixing head of the two-liquid quantitative mixing and foaming machine to produce a reactant. This reactant is then injected into an aluminum mold for a shoe midsole, where it undergoes a polymerization reaction and foaming treatment. After the foaming treatment, the reactant is molded to produce a non-yellowing shoe midsole. The temperature of the aluminum mold for the shoe midsole is controlled between 25°C and 50°C.
[0045] [Examples 2 to 9]
[0046] Examples 2 to 9 were prepared using a similar method to Example 1 to obtain non-yellowing polyurethane midsole compositions, and the non-yellowing polyurethane midsole compositions were used to form non-yellowing shoe midsoles in the same manner as Example 1. The non-yellowing polyurethane midsole compositions of Examples 2 to 9 differ from the non-yellowing polyurethane midsole composition of Example 1 in that: Examples 2 to 3 varied the amounts of the first and second chain extenders, Examples 4 to 5 varied the amounts of the titanium and potassium catalysts, and Examples 6 to 9 varied the amounts or types of the components in the non-yellowing hardener component. In Examples 8 and 9, aromatic diisocyanate polymers such as polyxylylene diisocyanate (abbreviated as poly-XDI) and polyhydrogenated xylylene diisocyanate (abbreviated as poly-H6XDI) were added to the non-yellowing hardener components, respectively, as shown in Table 1.
[0047] [Comparative Example 1]
[0048] Comparative Example 1 uses a similar method to Example 1 to obtain a non-yellowing polyurethane midsole composition, and the non-yellowing polyurethane midsole composition is formed into a non-yellowing shoe midsole in the same manner as Example 1. The difference between the non-yellowing polyurethane midsole composition of Comparative Example 1 and the non-yellowing polyurethane midsole composition of Example 1 is that the main component of Comparative Example 1 does not contain the first chain extender and the second chain extender.
[0049] [Comparative Example 2]
[0050] In Comparative Example 2, a non-yellowing polyurethane midsole composition was obtained in a manner similar to that of Example 1, and the non-yellowing polyurethane midsole composition was then formed into a non-yellowing shoe midsole in the same manner as in Example 1. The difference between the non-yellowing polyurethane midsole composition of Comparative Example 2 and that of Example 1 is that the non-yellowing hardener component of Comparative Example 2 does not contain an aliphatic diisocyanate polymer.
[0051] [Evaluation items]
[0052] The following description is made using the non-yellowing shoe midsole of Example 1 as an example. The non-yellowing shoe midsoles of the remaining Examples 2 to 9 and the non-yellowing shoe midsoles of Comparative Examples 1 and 2 are tested in the same manner.
[0053] Hardness: The hardness of the non-yellowing shoe midsole of Example 1 was measured using an ASKER C-type (ball-type) hardness tester. The results are shown in Table 1. The hardness of the non-yellowing shoe midsoles of Examples 2 to 9 and Comparative Examples 1 and 2 is shown in Tables 1 and 2.
[0054] Density: The density of the non-yellowing shoe midsole of Example 1 was measured using a multi-functional solid / liquid density tester (MatsuHaku, Model: MH-120S) according to ASTM D792-20, Plastics - Displacement Density and Specific Gravity (Relative Density). The results are shown in Table 1. The densities of the non-yellowing shoe midsoles of Examples 2 to 9 and Comparative Examples 1 and 2 are shown in Tables 1 and 2.
[0055] Non-yellowing properties: The non-yellowing shoe midsole of Example 1 was exposed to continuous UV light according to ASTM G154-16 [Standard Practice for Operating Fluorescent Ultraviolet (UV) Lamp Apparatus for Exposure of Materials] or ASTM D1148 [Standard Test Method for Rubber Deterioration-Discoloration from Ultraviolet (UV) and Heat Exposure of Light-Colored Surfaces]. The QUV rating of the non-yellowing shoe midsole of Example 1 was measured using a QUV tester (Q-Lab, USA, Model: Lu-0801). The results are shown in Table 3.
[0056] Table 1
[0057]
[0058]
[0059] Table 2
[0060]
[0061]
[0062]
[0063] Table 3
[0064]
[0065] Referring to Tables 1 and 2, the non-yellowing polyurethane midsole compositions of Examples 1 to 9 are prepared by adjusting the amounts of the first chain extender and the second chain extender in the main agent component, the aliphatic diisocyanate polymer in the non-yellowing hardener component, and the components in the main agent component, as well as the amounts of the main agent component, the catalyst component, and the non-yellowing hardener component. Thus, the non-yellowing shoe midsoles of Examples 1 to 9 have a strength of 0.2 g / cm 3 to 0.4g / cm 3 The density is such that the shoe midsole has the advantage of being light in weight while the required volume of the shoe midsole remains unchanged. In addition, the non-yellowing shoe midsoles of Examples 1 to 9 have a hardness of 20 Shore C to 70 Shore C, which meets the industry's hardness standards for shoe midsoles.
[0066] In contrast, in Comparative Examples 1 and 2, the main component of the non-yellowing polyurethane midsole composition of Comparative Example 1 does not contain the first chain extender and the second chain extender. Therefore, the density of the non-yellowing midsole of Comparative Example 1 is as high as 0.45 g / cm 3 However, the density is too high, resulting in a heavy weight of the non-yellowing midsole while maintaining the required volume. Furthermore, the hardness of the non-yellowing midsole of Comparative Example 1 is only 15 Shore C, which fails to meet the industry's hardness standards for midsoles. The non-yellowing hardener component of the non-yellowing polyurethane midsole composition of Comparative Example 2 does not contain an aliphatic diisocyanate polymer, so the density of the non-yellowing polyurethane midsole of Comparative Example 2 is as high as 0.45 g / cm 3 However, there is a problem that the density is too high, so that the weight of the non-yellowing shoe midsole is too heavy when the required volume of the shoe midsole remains unchanged, and the hardness of the non-yellowing shoe midsole of Comparative Example 2 is only 15 Shore C, which cannot meet the industry's hardness standards for shoe midsoles.
[0067] On the other hand, according to the current industry standard for determining the non-yellowing properties of shoe midsoles, if a shoe midsole has a QUV rating of 3.5 or higher after continuous UV irradiation for 24 hours, it indicates that the shoe midsole has good non-yellowing properties. Referring to the non-yellowing test results in Table 3, it can be seen that the non-yellowing shoe midsoles of Examples 1 to 9 still have QUV ratings of 4 to 4.5 after 96 hours of continuous UV irradiation, indicating that the non-yellowing shoe midsoles of Examples 1 to 9 have very excellent non-yellowing properties. In contrast, the non-yellowing shoe midsoles of Comparative Examples 1 to 2 only have QUV ratings of 2.5 to 3.5 after 24 hours of continuous UV irradiation, indicating that the non-yellowing shoe midsoles of Comparative Examples 1 to 2 have poor non-yellowing properties.
[0068] In summary, the non-yellowing polyurethane midsole composition of the present invention is obtained by combining the main agent component, the catalyst component, and the non-yellowing hardener component, especially the first chain extender and the second chain extender in the main agent component, the aliphatic diisocyanate polymer in the non-yellowing hardener component, and the amounts of the components in the main agent component, as well as the amounts of the main agent component, the catalyst component, and the non-yellowing hardener component. Therefore, the non-yellowing shoe midsole prepared with the non-yellowing polyurethane midsole composition has a non-yellowing strength of 0.2 g / cm 3 to 0.4g / cm 3 The low density and light weight of the midsole are achieved while maintaining the required volume of the midsole, making it comparable to midsoles made of ethylene-vinyl acetate copolymer (i.e., EVA midsoles). Furthermore, the non-yellowing polyurethane midsole composition not only imparts a low density to the prepared midsole, but also maintains the hardness of the midsole, thereby allowing the midsole to have a hardness of 0.2 g / cm 3 to 0.4g / cm 3 The non-yellowing polyurethane midsole composition has the advantage of low density and a hardness of 20 to 70 Shore C, which meets industry standards. In addition, the non-yellowing shoe midsole prepared by the non-yellowing polyurethane midsole composition also has excellent non-yellowing properties, thereby effectively achieving the purpose of the present invention.
[0069] However, the above is only an embodiment of the present invention and should not be used to limit the scope of implementation of the present invention. All simple equivalent changes and modifications made according to the claims and description of the present invention are still within the scope of the patent of the present invention.
Claims
1. A non-yellowing polyurethane midsole composition comprising: a main agent component, a catalyst component, and a non-yellowing hardener component; characterized in that: The main agent components include The first high molecular weight polyol has an average molecular weight ranging from 100 g / mol to 10,000 g / mol, The first chain extender is selected from one of ethylene glycol, diethylene glycol and triethylene glycol. The second chain extender is a polyol selected from the group consisting of the first chain extender and the like. Water, and Foam stabilizer, Based on 100 parts by weight of the total amount of the first polymer polyol, the amount of the first chain extender ranges from 0.25 parts by weight to 30 parts by weight, the amount of the second chain extender ranges from 0.25 parts by weight to 30 parts by weight, the amount of water ranges from 0.1 parts by weight to 20 parts by weight, and the amount of the foam stabilizer ranges from 0.1 parts by weight to 15 parts by weight; The catalyst component is selected from at least two of tin-based catalysts, potassium-based catalysts, silver-based catalysts, titanium-based catalysts, zinc-based catalysts, and tertiary amine-based catalysts; The non-yellowing hardener component includes The first aliphatic diisocyanate monomer is at least one selected from hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate. an aliphatic diisocyanate polymer having an average molecular weight ranging from 100 g / mol to 10,000 g / mol and selected from at least one of polyhexamethylene diisocyanate and polyisophorone diisocyanate, and The polyurethane prepolymer is prepared by polymerization of reactants comprising a second aliphatic diisocyanate monomer and a second high molecular weight polyol, wherein the second aliphatic diisocyanate monomer is selected from at least one of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate, and the second high molecular weight polyol has an average molecular weight ranging from 100 g / mol to 10,000 g / mol. Based on the total amount of the main agent component as 100 parts by weight, the amount of the catalyst component used ranges from 0.5 parts by weight to 30 parts by weight, and based on the total amount of the main agent component and the catalyst component as 100 parts by weight, the amount of the non-yellowing hardener component used ranges from 20 parts by weight to 300 parts by weight.
2. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: The first high molecular weight polyol is selected from one of polytetrahydrofuran, polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol.
3. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: The second chain extender is selected from one of 2-methyl-1,3-propanediol, pentaerythritol and dipentaerythritol.
4. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: The second high molecular weight polyol is selected from one of polytetrahydrofuran, polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol.
5. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: Based on 100 parts by weight of the total amount of the non-yellowing hardener component, the amount of the aliphatic diisocyanate polymer is in a range of 25 parts by weight to 50 parts by weight.
6. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: The main agent component further includes an additive component, and the additive component is selected from at least one of an ultraviolet absorber, a light stabilizer, an antioxidant, a heat reducer, and a colorant.
7. The non-yellowing polyurethane midsole composition according to claim 1, characterized in that: The non-yellowing hardener component further includes an aromatic diisocyanate polymer, and the aromatic diisocyanate polymer is selected from one of polyxylylene diisocyanate and polyhydrogenated xylylene diisocyanate.
8. A non-yellowing shoe midsole, characterized by: The non-yellowing shoe midsole is formed by reacting the non-yellowing polyurethane midsole composition according to any one of claims 1 to 7.
9. The non-yellowing shoe midsole according to claim 8, characterized in that: The density range of the non-yellowing shoe midsole is 0.2g / cm 3 to 0.4g / cm 3 .
10. The non-yellowing shoe midsole according to claim 8, characterized in that: The hardness range of the non-yellowing shoe midsole is 20 Shore C to 70 Shore C.