WO2021118259A1 - Stratifié en polyuréthane et son procédé de production - Google Patents

Stratifié en polyuréthane et son procédé de production Download PDF

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Publication number
WO2021118259A1
WO2021118259A1 PCT/KR2020/018058 KR2020018058W WO2021118259A1 WO 2021118259 A1 WO2021118259 A1 WO 2021118259A1 KR 2020018058 W KR2020018058 W KR 2020018058W WO 2021118259 A1 WO2021118259 A1 WO 2021118259A1
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WIPO (PCT)
Prior art keywords
layer
polyurethane layer
polyurethane
liquid
laminate
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PCT/KR2020/018058
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English (en)
Korean (ko)
Inventor
박민기
문갑수
전영찬
Original Assignee
미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사
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Priority claimed from KR1020200171734A external-priority patent/KR102497290B1/ko
Application filed by 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사 filed Critical 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사
Publication of WO2021118259A1 publication Critical patent/WO2021118259A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates

Definitions

  • the present invention relates to a polyurethane laminate and a method for producing the same.
  • Polyurethane foam is light and has excellent insulation, soundproofing and molding processability, so it is widely used as insulation for refrigerators and buildings, sound absorbing materials, and insulating materials.
  • polyurethane foam is also used in metal exterior plates such as ships, vehicles, storage tanks, piping, valves, and refrigerators. There is a problem of causing deformation, such as bending of the outer plate due to one shrinkage.
  • a nonwoven fabric capable of performing a buffer function between the outer plate and the polyurethane foam has been additionally used.
  • the nonwoven fabric is expensive, and an adhesion process for adhering the nonwoven fabric or an additional process of cutting to fit the size is required. Accordingly, there is a problem that not only increases the process cost due to this, but also other defects may occur in additional processes such as adhesion and cutting.
  • Korean Patent Registration No. 0997220 discloses that by providing a nonwoven fabric layer having a predetermined elasticity on the inner surface of the door outer plate, the door outer plate is partially covered by the difference in the amount of shrinkage of the urethane foam foamed and filled between the door outer plate and the door inner plate.
  • a door structure for a refrigerator capable of preventing bending.
  • the nonwoven fabric layer is attached to the inner surface of the door outer plate using an acrylic adhesive, cost and defects may still occur in this additional process.
  • Patent Document 1 Korean Patent No. 0997220
  • an object of the present invention is to provide a polyurethane laminate and a method for manufacturing the same, which can effectively prevent deformation of a bonded metal substrate due to excellent buffering effect and anti-shrinkage effect.
  • a base layer, a first polyurethane layer, and a second polyurethane layer are sequentially stacked, and the Asker C type surface hardness of the first polyurethane layer is 15 to 35.
  • the laminate according to another embodiment includes a first polyurethane layer having a thickness of 1 mm to 10 mm; and a second polyurethane layer having a thickness of 35 mm to 100 mm, wherein a thickness ratio of the first polyurethane layer and the second polyurethane layer is 1: 5 to 20.
  • a method of manufacturing a laminate according to another embodiment includes: forming a first polyurethane layer comprising spraying a first liquid and a second liquid on a base layer; and forming a second polyurethane layer on the first polyurethane layer, wherein the Asker C type surface hardness of the first polyurethane layer is 15 to 35.
  • the laminate according to the embodiment includes the first polyurethane layer having an Asker C type surface hardness of 15 to 35, and thus has excellent cushioning effect and anti-shrinkage effect. Therefore, when the laminate is applied to an outer plate made of a metal material such as a ship, vehicle, storage tank, pipe, valve, or refrigerator, the deformation prevention effect of the bonded metal substrate is excellent, and deformation such as bending occurs in the metal substrate The quality is excellent.
  • the laminate according to the embodiment includes a second polyurethane layer having a higher Asker C type surface hardness than the first polyurethane layer on one surface of the first polyurethane layer, so that the insulation and insulation effect are excellent. Accordingly, the laminate may be applied to an outer plate made of a metal material such as a ship, a vehicle, a storage tank, a pipe, a valve, and a refrigerator to exhibit excellent properties.
  • the manufacturing method of the laminate according to the embodiment includes the step of forming the first polyurethane layer by spraying the first liquid and the second liquid on the base layer, so that it can be produced quickly without the conventional adhesion and cutting process, It is possible to minimize defects that may occur in the manufacturing process.
  • the substrate layer is not deformed in the manufacturing process, so the quality is excellent, and the laminate can be manufactured simply and quickly regardless of the size of the substrate layer.
  • FIG. 1 schematically shows a refrigerator door manufactured using a laminate according to an embodiment.
  • FIG. 2 is a cross-sectional view showing the refrigerator door of FIG. 1 taken along line X-X'.
  • FIG. 3 shows a laminate according to an embodiment.
  • a mixture thereof means that two or more kinds of substances are included.
  • the “mixture” may include, but is not limited to, a uniformly and/or non-uniformly mixed state, a dissolved state, a uniformly and/or non-uniformly dispersed state, and the like.
  • FIG. 1 schematically shows a refrigerator door manufactured using a laminate according to an embodiment.
  • the use of the laminate is not limited to the refrigerator door, and FIG. 1 illustrates a refrigerator door to which the laminate is applied.
  • FIG. 1 exemplifies the exterior of a refrigerator door provided in a typical refrigerator, wherein the refrigerator door 1 includes a door inner plate (a) in contact with a storage space in which food is stored, and an exterior other than the storage space. It may include a door outer plate (b) in contact with the environment.
  • a function of blocking and insulating between an external environment and a storage space is essential for refrigeration or freezing at an appropriate temperature so that food, etc. can be stored at a low temperature.
  • a substrate such as a metal may be used for a blocking function between the external environment and the storage space, and an insulating material may be used for an insulating function with the storage space.
  • FIG. 2 is a cross-sectional view showing the refrigerator door of FIG. 1 taken along line X-X'.
  • FIG. 2 shows a base layer 100 positioned on the surface of the door outer plate b that does not come into contact with a storage space in which food is stored, a first polyurethane layer 200 positioned on one surface of the base layer, and the first The second polyurethane layer 300 positioned on one surface of the first polyurethane layer is illustrated. More specifically, a structure in which the base layer 100 , the first polyurethane layer 200 , and the second polyurethane layer 300 are sequentially stacked is illustrated.
  • the laminate includes a first polyurethane layer 200 having excellent cushioning effect and shrinkage prevention effect on one surface of the base layer 100, thereby effectively preventing deformation such as bending in the base layer.
  • a first polyurethane layer 200 having excellent cushioning effect and shrinkage prevention effect on one surface of the base layer 100, thereby effectively preventing deformation such as bending in the base layer.
  • the second polyurethane layer 300 on one surface of the first polyurethane layer 200, heat insulation and insulation effect can be improved.
  • FIG. 3 shows a laminate according to an embodiment. Specifically, FIG. 3 is a laminate including a base layer 100, a first polyurethane layer 200 positioned on the base layer, and a second polyurethane layer 300 positioned on the first polyurethane layer ( The structure of 2) is exemplified.
  • the first polyurethane layer 200 includes a core layer 210 and a surface layer 220, and the core layer 210 is located on a surface opposite to the base layer 100, and the surface layer ( 220) is located on the surface opposite to the second polyurethane layer 300, the base layer 100, the core layer 210 of the first polyurethane layer, the surface layer 220 of the first polyurethane layer, and the second The structure of the laminated body 2 in which 2 polyurethane layers 300 were laminated
  • the laminate according to the embodiment has a structure such as that of FIG. 2 or FIG. 3, barrier properties and thermal insulation properties, as well as deformation such as bending, can be effectively prevented, so various products storing contents, especially low temperature, must be maintained. It can be applied to products that do this and exhibit excellent properties.
  • a base layer, a first polyurethane layer, and a second polyurethane layer are sequentially stacked, and the Asker C type surface hardness of the first polyurethane layer is 15 to 35.
  • the laminate according to another embodiment includes a first polyurethane layer having a thickness of 1 mm to 10 mm; and a second polyurethane layer having a thickness of 35 mm to 100 mm, wherein a thickness ratio of the first polyurethane layer and the second polyurethane layer is 1: 5 to 20.
  • the thickness of the laminate may be 44 mm to 110 mm.
  • the thickness of the laminate may be 44 mm to 110 mm, 44 mm to 105 mm, 44 mm to 103 mm, 44.2 mm to 100 mm, 44.2 mm to 90 mm, 45 mm to 85 mm, 43 mm to 80 mm. mm, 43 mm to 75 mm or 43 mm to 70 mm.
  • the base layer may be a material having a blocking function between the external environment and the storage space.
  • the base layer may be a metal material such as a stainless steel plate or a color steel plate.
  • the base layer may be a metal material that can be used for an outside plate such as a ship, a vehicle, a storage tank, a pipe, a valve, and a refrigerator, but is not limited thereto.
  • the thickness of the base layer may be 3 mm to 20 mm.
  • the thickness of the base layer may be 3 mm to 20 mm, 3 mm to 15 mm, 3 mm to 10 mm, 4 mm to 8 mm, 5 mm to 10 mm or 10 mm to 15 mm, It is not limited.
  • the thickness of the base layer satisfies the above range, it is possible to maximize the effect of preventing deformation such as bending.
  • the laminate according to the embodiment includes a first polyurethane layer on one surface of the base layer.
  • the Asker C type surface hardness of the first polyurethane layer may be 15 to 35.
  • the Asker C type surface hardness of the first polyurethane layer may be 15 to 35, 17 to 35, 20 to 30, or 22 to 27.
  • the free rise density of the first polyurethane layer may be 15 kg/m3 to 35 kg/m3.
  • the free foaming density of the first polyurethane layer is 15 kg/m3 to 35 kg/m3, 20 kg/m3 to 35 kg/m3, 20 kg/m3 to 33 kg/m3, 20 kg/m3 to It can be 30 kg/m3 or 22 kg/m3 to 28 kg/m3.
  • the first polyurethane layer satisfies the Asker C type surface hardness and free foaming density as described above, the shrinkage phenomenon hardly occurs and the buffering effect is also excellent.
  • the free foaming density is a measure of the density when manufactured in a state with minimal interference from the outside.
  • the density of the first polyurethane layer manufactured by foaming in an open box without a lid may be measured, but is not limited thereto.
  • the thickness of the first polyurethane layer may be 1 mm to 10 mm.
  • the thickness of the first polyurethane layer is 1 mm to 10 mm, 1 mm to 9 mm, 2 mm to 9 mm, 2 mm to 8 mm, 3 mm to 8 mm, 3 mm to 7 mm, 4 mm to 9 mm, 1 mm to 3.5 mm, 1 mm to 3 mm, 1.2 mm to 3 mm, 3.5 mm to 8 mm or 4.5 mm to 5.5 mm.
  • the first polyurethane layer according to the embodiment may include a core layer and a surface layer.
  • the first polyurethane layer may include a core layer positioned on a surface opposite to the base layer and a surface layer positioned on a surface opposite to the second polyurethane layer (see FIG. 3 ).
  • the core layer refers to an area from the surface in contact with the base layer to the portion ranging from 1 mm to 3 mm in the thickness direction, based on the first polyurethane layer formed on the base layer.
  • the surface layer refers to a region from the opposite surface in contact with the base layer to a portion of 0.1 mm to 1 mm in the thickness direction, based on the first polyurethane layer formed on the base layer.
  • the thickness of the surface layer may be thinner than the thickness of the core layer.
  • the thickness of the core layer may be 1 mm to 3 mm, and the thickness of the surface layer may be 0.1 mm to 1 mm.
  • the thickness of the core layer may be 1 mm to 3 mm, 1 mm to 2.7 mm, 1.3 mm to 2.5 mm, 1.5 mm to 2.5 mm, or 2 mm to 3 mm, and the thickness of the surface layer is 0.1 mm to 1 mm, 0.3 mm to 1 mm, 0.3 mm to 0.7 mm, 0.1 mm to 0.5 mm, 0.4 mm to 0.8 mm or 0.7 mm to 1 mm.
  • the buffer effect and the absorption prevention effect of other materials can be maximized.
  • the density of the surface layer may be greater than the density of the core layer.
  • the density of the surface layer may be greater than 25 g/cm 3 to 35 g/cm 3 or less, 28 g/cm 3 to 35 g/cm 3 or 28 g/cm 3 to 33 g/cm 3
  • the density of the core layer is 15 g/cm 3 or more and less than 25 g/cm 3 may be 15 g/cm 3 to 23 g/cm 3 or 18 g/cm 3 to 20 g/cm 3 .
  • the density of the surface layer is greater than the density of the core layer, it is possible to prevent the surface layer from being mixed or absorbed with a material in contact with one surface of the surface layer. More specifically, when the second polyurethane layer is formed on the surface layer, it is possible to prevent the second polyurethane layer from being absorbed into the first polyurethane layer.
  • the first polyurethane layer according to the embodiment may be a spray foam.
  • the first polyurethane layer may be a spray foam formed using a spray device. Since the first polyurethane layer is a spray foam, it is easy to form a thin layer. In addition, the first polyurethane layer has an excellent cushioning effect while being thin.
  • the laminate according to the embodiment does not include a separate adhesive layer between the base layer and the first polyurethane layer.
  • the first polyurethane layer is formed by spraying on the base layer using a spray device, a separate adhesive layer is not included. Accordingly, as compared to a conventional laminate including an adhesive layer, deformation such as bending hardly occurs.
  • the first polyurethane layer according to the embodiment may be formed using the first polyol composition and the first diisocyanate composition.
  • the first polyol composition may include a trifunctional or higher aliphatic alcohol, an alkylene oxide including ethylene oxide or propylene oxide, and a glycol having a weight average molecular weight of 50 g/mol to 3,000 g/mol.
  • the first polyol composition may be a mixture of polyol composition A and polyol composition B.
  • the polyol composition A may include a trifunctional or higher aliphatic alcohol, and an alkylene oxide including ethylene oxide or propylene oxide
  • the polyol composition B is a glycol having a weight average molecular weight of 50 g/mol to 3,000 g/mol; And it may include an alkylene oxide containing ethylene oxide or propylene oxide.
  • the trifunctional or higher aliphatic alcohol may be at least one selected from the group consisting of glycerin, trimethylolpropane, erythritol, pentaerythritol and sorbitol.
  • the glycerin may be preferable in terms of improving the degree of crosslinking, but is not limited thereto.
  • the glycol may have a weight average molecular weight of 50 g/mol to 3,000 g/mol.
  • the weight average molecular weight of the glycol is 50 g/mol to 3,000 g/mol, 50 g/mol to 2,500 g/mol, 70 g/mol to 2,500 g/mol, 80 g/mol to 2,200, 100 g /mol to 1800, 100 g/mol to 1,300 g/mol, 100 g/mol to 1,000 g/mol, 100 g/mol to 800 g/mol or 50 g/mol to 600 g/mol.
  • the glycol is one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetramethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol and neopentyl glycol.
  • ethylene glycol diethylene glycol, triethylene glycol, tetramethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol and neopentyl glycol.
  • Dipropylene glycol may be preferable in terms of forming a stable structure, but is not limited thereto.
  • the polyol composition A may include 1 wt% to 15 wt% of the trifunctional or higher aliphatic alcohol, and 85 wt% to 99 wt% of the alkylene oxide.
  • the polyol composition A contains 1 wt% to 15 wt%, 1 wt% to 13 wt%, 2 wt% to 10 wt%, 3 wt% to 10 wt% or 3 wt% of the trifunctional or higher aliphatic alcohol % to 8% by weight, 85% to 99% by weight, 88% to 98% by weight, 90% to 98% by weight or 92% to 97% by weight of the alkylene oxide can
  • the polyol composition B may include the glycol in an amount of 1 wt% to 25 wt%, and the alkylene oxide in an amount of 75 wt% to 99 wt%.
  • the polyol composition B may contain 1 wt% to 25 wt%, 3 wt% to 20 wt%, 3 wt% to 18 wt%, 5 wt% to 15 wt%, or 8 wt% to 13 wt% of the glycol.
  • % may include the alkylene oxide in an amount of 75 wt% to 99 wt%, 80 wt% to 95 wt%, 83 wt% to 92 wt%, or 87 wt% to 92 wt%.
  • the first polyol composition may further include at least one catalyst selected from the group consisting of an alkali metal compound, an alkaline earth metal compound, triethylamine, dimethyloctylamine, a phosphazene compound, and a phosphazenium compound.
  • the first polyol composition may further include 0.0001 wt% to 15 wt% of a catalyst based on the total weight of the first polyol composition.
  • the content of the catalyst may be 0.0001 wt% to 15 wt%, 0.0005 wt% to 13 wt%, 0.001 wt% to 13 wt%, 0.01 wt% to 10 wt% based on the total weight of the first polyol composition % or 0.1% to 8% by weight.
  • the first polyol composition may further include at least one selected from the group consisting of a foaming agent, a foam stabilizer, and a crosslinking agent.
  • the blowing agent may be at least one selected from the group consisting of water, methylene chloride, liquid carbon dioxide, n-pentane, cyclopentane, and hydrochlorofluorocarbons.
  • water methylene chloride
  • liquid carbon dioxide n-pentane
  • cyclopentane cyclopentane
  • hydrochlorofluorocarbons it is preferable to use water, but is not limited thereto.
  • the first polyol composition may further include 1 wt% to 20 wt% of a blowing agent based on the total weight of the first polyol composition.
  • the content of the blowing agent may be 1 wt% to 20 wt%, 3 wt% to 18 wt%, 5 wt% to 18 wt%, 8 wt% to 16 wt%, based on the total weight of the first polyol composition , 10% to 16% by weight or 13% to 16% by weight.
  • the content of the foaming agent satisfies the above range, stability during the foaming process may be improved.
  • the foam stabilizer facilitates mixing of the composition, and may improve stability, fluidity and uniformity during a foaming process using the composition, for example, a silicone foam stabilizer may be used, but is not limited thereto.
  • the first polyol composition may further include 1 wt% to 10 wt% of a foam stabilizer based on the total weight of the first polyol composition.
  • the content of the foam stabilizer may be 1 wt% to 10 wt%, 1 wt% to 8 wt%, or 1.5 wt% to 6.5 wt% based on the total weight of the first polyol composition.
  • the crosslinking agent may be ethylene glycol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, diethanolamine, triethanolamine, butanediol, or a mixture thereof, but is not limited thereto. it is not
  • the first polyol composition may further include 1 wt% to 20 wt% of a crosslinking agent based on the total weight of the first polyol composition.
  • the content of the crosslinking agent may be 1 wt% to 20 wt%, 3 wt% to 18 wt%, 5 wt% to 18 wt%, or 7 wt% to 16 wt%, based on the total weight of the first polyol composition can be
  • the content of the crosslinking agent satisfies the above range, the durability of the first polyurethane layer may be improved, and uniformity and stability may be improved by increasing the crosslinking density.
  • the first diisocyanate composition may include a first diisocyanate.
  • the first diisocyanate is monomeric methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, dimethylbiphenyl diisocyanate, xylene diisocyanate, methylene diisocyanate.
  • isocyanate hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, norborene diisocyanate or a combination thereof.
  • the first diisocyanate composition may include a trifunctional or more aliphatic alcohol.
  • the trifunctional or higher aliphatic alcohol may be at least one selected from the group consisting of glycerin, trimethylolpropane, erythritol, pentaerythritol and sorbitol.
  • the first diisocyanate composition may include 1 wt% to 30 wt% of a trifunctional or higher aliphatic alcohol based on the total weight of the first diisocyanate composition.
  • the content of the first diisocyanate may be 1 wt% to 30 wt%, 5 wt% to 30 wt%, 10 wt% to 28 wt%, 15 wt% to 25 wt%, or 18 wt% to 23 wt% It can be %.
  • the weight ratio of the first polyol composition and the first diisocyanate composition may be 1: 0.8 to less than 1.4.
  • the weight ratio of the first polyol composition and the first diisocyanate composition may be 1: 0.8 to less than 1.3, 1: 0.85 to 1.25 or 1: 0.9 to 1.2.
  • the laminate according to the embodiment includes a second polyurethane layer on one surface of the first polyurethane layer. Specifically, the second polyurethane layer is different from the first polyurethane layer.
  • the second polyurethane layer according to the embodiment may be a rim (RIM) foam or a mold (mold) foam.
  • the laminate according to the embodiment includes a second polyurethane layer, which is a rim foam or a mold foam, on one surface of the first polyurethane layer, which is a spray foam, and improves the cushioning effect and shrinkage prevention effect, as well as the heat insulation and insulation effect can do it
  • the laminate includes a first polyurethane layer having an Asker C type surface hardness of 15 to 35 on one surface of the base layer having barrier properties from the external environment, and the first polyurethane layer on one surface of the first polyurethane layer
  • a second polyurethane layer having a higher Asker C type surface hardness than the first polyurethane layer on the first polyurethane layer heat insulation and insulation effects are also excellent.
  • the Asker C type surface hardness of the second polyurethane layer may be 35 to 100.
  • the Asker C type surface hardness of the second polyurethane layer may be 35 to 100, 50 to 90, or 55 to 85.
  • the free foaming density of the second polyurethane layer may be 20 kg/m3 to 30 kg/m3.
  • the free foaming density of the second polyurethane layer may be from 22 kg/m3 to 28 kg/m3, from 20 kg/m3 to 24 kg/m3, from 23 kg/m3 to 27 kg/m3 or from 25 kg/m3 to It can be 30 kg/m3.
  • the thickness of the second polyurethane layer may be thicker than the thickness of the first polyurethane layer. Specifically, the thickness of the second polyurethane layer may be 35 mm to 100 mm. For example, the thickness of the second polyurethane layer may be 35 mm to 100 mm, 35 mm to 70 mm, 40 mm to 80 mm, 45 mm to 55 mm, or 70 mm to 100 mm.
  • the thickness of the second polyurethane layer satisfies the above range, the heat insulation and insulation effect can be improved without reducing the buffer effect and the shrinkage prevention effect.
  • the thickness ratio of the first polyurethane layer and the second polyurethane layer may be 1: 5 to 20.
  • the thickness ratio of the first polyurethane layer and the second polyurethane layer is 1: 5 to 20, 1: 5 to 18, 1: 5 to 15, 1: 6 to 15, 1: 7 to 13, It may be 1: 8 to 12 or 1: 9 to 10.
  • the thickness ratio of the first polyurethane layer and the second polyurethane layer satisfies the above range, it is possible to have an excellent effect of preventing deformation such as a cushioning effect and bending, and at the same time having an excellent heat insulation and insulation effect.
  • the second polyurethane layer according to the embodiment may be formed using the second polyol composition and the second diisocyanate.
  • the second polyol composition may include a trifunctional or higher aliphatic alcohol, and an alkylene oxide including ethylene oxide or propylene oxide.
  • the trifunctional or higher aliphatic alcohol may be at least one selected from the group consisting of glycerin, trimethylolpropane, erythritol, pentaerythritol and sorbitol.
  • the glycerin may be preferable in terms of improving the degree of crosslinking, but is not limited thereto.
  • the second polyol composition may include a tetrafunctional or higher aliphatic alcohol.
  • the second polyol composition may be a mixture of the trifunctional aliphatic alcohol and the tetrafunctional or higher aliphatic alcohol. More specifically, the trifunctional aliphatic alcohol may be glycerin, and the tetrafunctional or higher aliphatic alcohol may be sucrose. When a mixture of trifunctional and tetrafunctional or more aliphatic alcohols is included, surface hardness can be further improved.
  • the second polyol composition may be a mixture of polyol composition C and polyol composition D.
  • the polyol composition C may include the tetrafunctional or higher aliphatic alcohol in an amount of 25 wt% to 75 wt%, and the alkylene oxide in an amount of 25 wt% to 75 wt%.
  • the polyol composition C may contain 25 wt% to 75 wt%, 30 wt% to 70 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of the tetrafunctional or higher aliphatic alcohol. and may include 25 wt% to 75 wt%, 30 wt% to 70 wt%, 40 wt% to 60 wt%, or 45 wt% to 55 wt% of the alkylene oxide.
  • the polyol composition D may include 5 wt% to 35 wt% of the tetrafunctional or higher aliphatic alcohol, and 65 wt% to 95 wt% of the alkylene oxide.
  • the second polyol composition may further include at least one selected from the group consisting of a catalyst, a foaming agent, a foam stabilizer, and a crosslinking agent.
  • a catalyst e.g., platinum, palladium, platinum, nickel, nickel, nickel, nickel, nickel, nickel, nickel, nickel, zinc, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • the second diisocyanate is monomeric methylene diphenyl diisocyanate, polymeric methylene diphenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, dimethylbiphenyl diisocyanate, xylene diisocyanate, methylene diisocyanate, hexadecimal. It may be at least one selected from the group consisting of methylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and norborene diisocyanate.
  • the weight ratio of the second polyol composition and the second diisocyanate may be 1:0.7 to 1.3.
  • the weight ratio of the second polyol composition and the second diisocyanate composition may be 1: 0.7 to 1.3, 1: 0.75 to 1.3, or 1: 0.8 to 1.25.
  • the laminate may further include a nonwoven fabric layer interposed between the first polyurethane layer and the second polyurethane layer.
  • the nonwoven fabric which has been conventionally used as a buffer, is easily attached to the base layer of a metal material by using an adhesive, so that deformation such as bending in the bonding process is easy to occur, so the quality is highly likely to be deteriorated.
  • the laminate according to the embodiment includes a nonwoven fabric layer on one surface of the first polyurethane layer having an Asker C type surface hardness of 15 to 35, thereby remarkably reducing the defect rate that may occur during the formation of the nonwoven fabric layer. More specifically, since the first polyurethane layer has an Asker C type surface hardness of 15 to 35, viscoelasticity is very good. Therefore, when the nonwoven fabric layer is formed on one surface of the first polyurethane layer, deformation such as bending hardly occurs.
  • the laminate according to the embodiment further includes a nonwoven fabric layer, mixing or absorption between each other that may occur between the first polyurethane layer and the second polyurethane layer can be more effectively prevented.
  • a method of manufacturing a laminate according to another embodiment includes: forming a first polyurethane layer comprising spraying a first liquid and a second liquid on a base layer; and forming a second polyurethane layer on the first polyurethane layer, wherein the Asker C type surface hardness of the first polyurethane layer is 15 to 35.
  • a first polyurethane layer is formed by spraying a first liquid and a second liquid on the base layer.
  • the step of forming the first polyurethane layer may be performed using a spray device equipped with a two-liquid separation type container capable of spraying a first liquid and a second liquid different from the first liquid, respectively.
  • the first polyurethane layer may be formed by spraying the first liquid and the second liquid on the base layer using a spray device.
  • the description of the base layer is the same as described above.
  • the manufacturing method of the laminate according to the embodiment includes the step of forming the first polyurethane layer using the spray device, thereby eliminating the need for conventional adhesion and cutting processes, and manufacturing without being limited to the size of the base layer Since it can be quickly formed by a simple process, it is possible to not only have high utilization but also reduce process costs.
  • the first liquid and the second liquid may be sprayed at the same time.
  • the first liquid and the second liquid may be sequentially sprayed. Specifically, after the first liquid is sprayed, the second liquid may be sprayed, and after the second liquid is sprayed, the first liquid may be sprayed.
  • the step of forming the first polyurethane layer according to the embodiment may include forming a core layer and forming a surface layer. Specifically, the step of forming the core layer and the step of forming the surface layer may be performed simultaneously.
  • a core layer may be formed on the base layer and a surface layer may be formed on the core layer.
  • the density of the surface layer in contact with the outside may be greater than the density of the core layer in contact with the base layer.
  • a core layer may be formed on the base layer and a surface layer may be formed on the core layer.
  • the density of the surface layer in contact with the outside may be greater than the density of the core layer in contact with the base layer.
  • the first polyurethane layer is formed by a spray process, it is easy to form the first polyurethane layer with a thin thickness, and the process time is short, so the deformation of the base layer hardly occurs when the first polyurethane layer is formed. does not
  • the first liquid may be a first polyol composition
  • the second liquid may be a first diisocyanate composition.
  • the description of the first polyol composition and the first diisocyanate composition is the same as described above.
  • the injection ratio of the first liquid and the second liquid may be 1:0.9 to 1.1.
  • the injection ratio of the first liquid and the second liquid may be 1:0.95 to 1.05 or 1:1.
  • the injection ratio of the first liquid and the second liquid may be performed by adjusting each injection speed.
  • the injection speed of the first liquid and the second liquid may be 0.5 kg/min to 3.0 kg/min, respectively.
  • the injection speed of the first liquid and the second liquid is 0.5 kg/min to 3.0 kg/min, 0.7 kg/min to 2.8 kg/min, 0.9 kg/min to 2.4 kg/min, 1.0 kg, respectively.
  • /min to 2.2 kg/min 1.0 kg/min to 2.0 kg/min
  • 1.2 kg/min to 1.8 kg/min 1.2 kg/min to 1.6 kg/min or 1.3 kg/min to 1.5 kg/min .
  • the first liquid and the second liquid may be sprayed at an angle of 10° to 170°, respectively, with respect to the base layer.
  • the injection angles of the first liquid and the second liquid are each 10° to 170°, 15° to 165°, 20° to 160°, 30° to 120°, 50° to 110°, 65°, respectively. to 105°, 80° to 100° or 85° to 100°.
  • the injection speed and the injection angle of the first liquid and the second liquid may be the same or different from each other, respectively, and the injection speed and the injection angle of the first liquid and the second liquid satisfy the above ranges, respectively, so that the first polyurethane layer of the foaming uniformity can be further improved.
  • the uniformity of foaming of the first polyurethane layer may be maximized, but the present invention is not limited thereto.
  • the forming step of the first polyurethane layer may be performed at 25° C. to 80° C. for 2 seconds to 40 seconds.
  • the forming step of the first polyurethane layer is 25 °C to 80 °C, 25 °C to 50 °C, 30 °C to 60 °C or 40 °C to 80 °C 2 seconds to 30 seconds, 2 seconds to 10 seconds, It may be performed for 5 seconds to 30 seconds, 5 seconds to 20 seconds, 10 seconds to 35 seconds, or 10 seconds to 30 seconds.
  • a second polyurethane layer is formed on the first polyurethane layer.
  • a second polyurethane layer may be formed by coating a polyurethane composition on one surface of the first polyurethane layer. More specifically, it may be formed by disposing a mold having a certain shape on one surface of the first polyurethane layer, injecting the polyurethane composition, and then curing. Description of the polyurethane composition is as described above.
  • the forming step of the second polyurethane layer may be performed at 25° C. to 85° C. for 1 minute to 5 minutes.
  • the forming step of the second polyurethane layer is 25 °C to 85 °C, 25 °C to 50 °C, 30 °C to 60 °C or 40 °C to 80 °C for 1 minute to 5 minutes or 2 minutes to 4 minutes. can be performed.
  • the first polyol composition was prepared by slowly dissolving it at 70° C. at a stirring rate of 60 rpm to 80 rpm.
  • a first polyol composition was prepared in the same manner as in Preparation Example 1-1, except that ethylene oxide was used instead of propylene oxide.
  • a polyol composition C was prepared by mixing 50% by weight of a mixture of sucrose and glycerin (Gly) and 50% by weight of propylene oxide (PO) as a tetrafunctional or higher aliphatic alcohol, and 15% by weight of glycerin (Gly) and propylene oxide (PO) 85% by weight was mixed to prepare polyol composition D.
  • a stainless steel plate as a base layer was prepared, and a spray device equipped with a two-liquid separation type container capable of spraying a first liquid and a second liquid different from the first liquid, respectively, was prepared.
  • a spray device equipped with a two-liquid separation type container capable of spraying a first liquid and a second liquid different from the first liquid, respectively was prepared.
  • 1.4 kg/min A first polyurethane layer having a thickness of 5 mm was formed by simultaneously spraying at a spraying speed and a spraying angle of 90° with respect to the base layer. At this time, the injection ratio of the first liquid and the second liquid was equalized to be the same and the injection ratio was 1:1.
  • a laminate was prepared in the same manner as in Example 1, except that the first polyol composition prepared in Preparation Example 1-2 was used.
  • the surface hardness was measured using an Asker C type hardness meter (manufacturer: Asker).
  • the free foaming density was measured by forming the first polyurethane layers of Examples 1 and 2 in an open box made of plywood having a width of 20 cm, a length of 20 cm, and a height of 20 cm.
  • the first polyurethane layer After forming, it was cut into a width of 100 mm, a length of 100 mm, and a height of 100 mm to measure the density.
  • step (1) of Examples 1 and 2 spray at a spraying speed of 1.4 kg/min and a spraying angle of 90° with respect to the open box to reach the highest volume. time was measured. At this time, the injection rate of the first liquid and the second liquid was made the same, and the injection ratio was 1:1.
  • the first polyurethane layer of the laminates of Examples 1 and 2 had surface hardness, free foam density, and maximum volume reaching time all within preferred ranges.
  • the laminates of Examples 1 and 2 include the first polyurethane layer having excellent surface hardness, free foam density, and maximum volume reach time, so it is applied to various products storing contents, especially products that need to maintain a low temperature. It has excellent cushioning and deformation prevention effects.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne : un stratifié en polyuréthane dans lequel une première couche en polyuréthane et une seconde couche en polyuréthane sont stratifiées dans cet ordre ; et son procédé de production, la première couche de polyuréthane satisfaisant une dureté de surface de type Asker C de 15 à 35, ayant ainsi d'excellents effets de tampon et d'excellents effets de prévention de retrait. Ainsi, le stratifié comprenant la couche en polyuréthane peut présenter d'excellentes propriétés lorsqu'il est appliqué au placage externe métallique d'un navire, d'un véhicule, d'un réservoir de stockage, d'un tuyau, d'une vanne, d'un réfrigérateur ou similaire.
PCT/KR2020/018058 2019-12-11 2020-12-10 Stratifié en polyuréthane et son procédé de production WO2021118259A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2019-0164686 2019-12-11
KR20190164686 2019-12-11
KR1020200171734A KR102497290B1 (ko) 2019-12-11 2020-12-09 폴리우레탄 적층체 및 이의 제조 방법
KR1020200171735A KR102576400B1 (ko) 2019-12-11 2020-12-09 폴리우레탄 적층체의 제조 방법 및 이로부터 제조된 적층체
KR10-2020-0171734 2020-12-09
KR10-2020-0171735 2020-12-09

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WO2021118259A1 true WO2021118259A1 (fr) 2021-06-17

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009024060A (ja) * 2007-07-18 2009-02-05 Nippon Polyurethane Ind Co Ltd ポリウレタン積層体、及びその製造方法、並びにそれを用いたシール材料、制振緩衝材料
KR20130120567A (ko) * 2012-04-26 2013-11-05 한일이화주식회사 폴리우레탄 폼을 갖는 자동차 내장재용 적층체 및 제조방법
JP2015024028A (ja) * 2013-07-26 2015-02-05 旭硝子株式会社 車輌用シートクッション
JP2017165024A (ja) * 2016-03-17 2017-09-21 新日鐵住金株式会社 多層ポリウレタン被覆鋼材
KR20180007135A (ko) * 2016-07-12 2018-01-22 김정수 하이브리드 폴리우레탄 발포체의 제조방법
JP2019001015A (ja) * 2017-06-13 2019-01-10 三菱瓦斯化学株式会社 ポリウレタン多層フィルム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009024060A (ja) * 2007-07-18 2009-02-05 Nippon Polyurethane Ind Co Ltd ポリウレタン積層体、及びその製造方法、並びにそれを用いたシール材料、制振緩衝材料
KR20130120567A (ko) * 2012-04-26 2013-11-05 한일이화주식회사 폴리우레탄 폼을 갖는 자동차 내장재용 적층체 및 제조방법
JP2015024028A (ja) * 2013-07-26 2015-02-05 旭硝子株式会社 車輌用シートクッション
JP2017165024A (ja) * 2016-03-17 2017-09-21 新日鐵住金株式会社 多層ポリウレタン被覆鋼材
KR20180007135A (ko) * 2016-07-12 2018-01-22 김정수 하이브리드 폴리우레탄 발포체의 제조방법
JP2019001015A (ja) * 2017-06-13 2019-01-10 三菱瓦斯化学株式会社 ポリウレタン多層フィルム

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