WO2021118259A1

WO2021118259A1 - Polyurethane laminate and production method thereof

Info

Publication number: WO2021118259A1
Application number: PCT/KR2020/018058
Authority: WO
Inventors: 박민기; 문갑수; 전영찬
Original assignee: 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사
Priority date: 2019-12-11
Filing date: 2020-12-10
Publication date: 2021-06-17

Abstract

The present invention relates to: a polyurethane laminate in which a first polyurethane layer and a second polyurethane layer are laminated in this order; and a production method thereof, wherein the first polyurethane layer satisfies an Asker C-type surface hardness of 15 to 35, thus having excellent buffer effects and shrinkage prevention effects. Thus, the laminate including the polyurethane layer can exhibit excellent properties when applied to the metallic outer plating of a ship, a vehicle, a storage tank, a pipe, a valve, a refrigerator, or the like.

Description

Polyurethane laminate and manufacturing method thereof

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. In particular, 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.

Accordingly, in the prior art, a nonwoven fabric capable of performing a buffer function between the outer plate and the polyurethane foam has been additionally used. However, 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.

For example, 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. Disclosed is a door structure for a refrigerator capable of preventing bending. However, since 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.

[Prior art literature]

[Patent Literature]

(Patent Document 1) Korean Patent No. 0997220

Accordingly, 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.

In the laminate according to one embodiment, 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.

In addition, 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.

In addition, 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. In addition, 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.

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'.

3 shows a laminate according to an embodiment.

[Explanation of code]

1: refrigerator door

a: door inner plate

b: door shell

2: Laminate

100: base layer

200: first polyurethane layer

210: core layer

220: surface layer

300: second polyurethane layer

Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

All numbers and expressions indicating amounts of ingredients, reaction conditions, etc. described herein are to be understood as being modified by the term "about" in all cases unless otherwise specified.

In the present specification, in the case where it is described as being formed on "on" or "under" of each layer or the like, "on" and "under" are "directly" or formed “indirectly” with other components.

The size of each component in the drawings may be exaggerated for explanation, and may be different from the size actually applied.

In the present specification, "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.

In this specification, terms such as first, second, etc. are used to describe various components, and the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.

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.

Specifically, 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.

In such a refrigerator door, 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. Accordingly, 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'. Specifically, 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.

As shown in FIG. 2, 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. can In addition, by including the second polyurethane layer 300 on one surface of the first polyurethane layer 200, heat insulation and insulation effect can be improved.

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. More specifically, 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|stacked in order is shown.

Since 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.

적층체laminate

The thickness of the laminate may be 44 mm to 110 mm. For example, 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.

base layer

The base layer may be a material having a blocking function between the external environment and the storage space. Specifically, the base layer may be a metal material such as a stainless steel plate or a color steel plate. For example, 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. For example, 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. When the thickness of the base layer satisfies the above range, it is possible to maximize the effect of preventing deformation such as bending.

first polyurethane layer

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. For example, 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. When the Asker C type surface hardness of the first polyurethane layer satisfies the above range, it is possible to improve the buffering effect and the anti-shrinkage effect.

The free rise density of the first polyurethane layer may be 15 kg/m³ to 35 kg/m³. For example, 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. When the free foaming density of the first polyurethane layer satisfies the above range, the buffering effect and the shrinkage prevention effect can be improved.

Specifically, since 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. For example, 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.

In addition, the thickness of the first polyurethane layer may be 1 mm to 10 mm. For example, 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. Specifically, 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 ).

Here, 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. In addition, 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. Specifically, 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. For example, 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. When the thickness of the core layer and the surface layer respectively satisfy the above ranges, 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. For example, 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 , and 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 .

Specifically, since 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. Specifically, 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.

In addition, the laminate according to the embodiment does not include a separate adhesive layer between the base layer and the first polyurethane layer. Specifically, since 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.

Specifically, 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.

More specifically, 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, and 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. For example, 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.

In addition, 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. may be more than 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. For example, 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

In addition, 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%. For example, 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. %, and 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.

In addition, 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. For example, 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. For example, it is preferable to use water, but is not limited thereto.

In addition, 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. For example, 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. When 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. For example, 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. For example, 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 When 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.

In addition, the first diisocyanate composition may include a first diisocyanate. Specifically, 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.

In addition, 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. For example, 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. For example, 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.

second polyurethane layer

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.

More specifically, 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

Specifically, 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 By including 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. For example, the Asker C type surface hardness of the second polyurethane layer may be 35 to 100, 50 to 90, or 55 to 85.

In addition, the free foaming density of the second polyurethane layer may be 20 kg/m³ to 30 kg/m³. For example, 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. When 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.

In addition, the thickness ratio of the first polyurethane layer and the second polyurethane layer may be 1: 5 to 20. For example, 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. When 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.

In addition, the second polyol composition may include a tetrafunctional or higher aliphatic alcohol. Specifically, 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%. For example, 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. For example, 5 wt% to 35 wt%, 8 wt% to 30 wt%, 10 wt% to 28 wt%, 12 wt% to 20 wt% or 12 wt% to 18 wt% of the trifunctional or higher aliphatic alcohol and 65 wt% to 95 wt%, 65 wt% to 90 wt%, 68 wt% to 85 wt%, 70 wt% to 80 wt% or 72 wt% to 88 wt% of the alkylene oxide can be included as

In addition, 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. The catalyst, the foaming agent, the foam stabilizer, and the crosslinking agent are the same as described above.

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.

In addition, the weight ratio of the second polyol composition and the second diisocyanate may be 1:0.7 to 1.3. For example, 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.

nonwoven layer

According to another embodiment, the laminate may further include a nonwoven fabric layer interposed between the first polyurethane layer and the second polyurethane layer.

Specifically, 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. However, 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.

When 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.

적층체의 제조 방법Method for manufacturing a laminate

First, a first polyurethane layer is formed by spraying a first liquid and a second liquid on the base layer.

Specifically, 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. According to the embodiment, 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.

Therefore, 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.

According to the embodiment, the first liquid and the second liquid may be sprayed at the same time. Alternatively, 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.

In addition, 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.

More specifically, when the first liquid and the second liquid are simultaneously sprayed on the base layer, a core layer may be formed on the base layer and a surface layer may be formed on the core layer. As the first liquid and the second liquid are simultaneously sprayed, 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.

In addition, since 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, and 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. For example, the injection ratio of the first liquid and the second liquid may be 1:0.95 to 1.05 or 1:1. Specifically, the injection ratio of the first liquid and the second liquid may be performed by adjusting each injection speed. When the injection ratio of the first liquid and the second liquid satisfies the above range, the buffer effect and the shrinkage prevention effect can be maximized.

In addition, the injection speed of the first liquid and the second liquid may be 0.5 kg/min to 3.0 kg/min, respectively. For example, 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. For example, 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. In addition, when the injection speed and the injection angle of the first liquid and the second liquid are equal to each other, 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. For example, the forming step of the first polyurethane layer is 25 ℃ to 80 ℃, 25 ℃ to 50 ℃, 30 ℃ to 60 ℃ or 40 ℃ to 80 ℃ 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.

Thereafter, a second polyurethane layer is formed on the first polyurethane layer.

Specifically, 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. For example, 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 above will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

[실시예][Example]

제 1 폴리올 조성물의 제조 Preparation of the first polyol composition

제조예 1-1Preparation 1-1

Prepare a four-necked flask equipped with a condenser, agitator and temperature controller on a heating mantle, and add 5 wt% of glycerin (GLY) and 95 wt% of propylene oxide (PO) as trifunctional or higher aliphatic alcohols to flask A. Polyol composition A was prepared. Then, 10 wt% of dipropylene glycol (DPG) and 90 wt% of propylene oxide (PO) were added to flask B to prepare a polyol composition B.

After mixing the polyol compositions A and B, 2 wt% of Niax Catalyst A-1 (manufacturer: momentive) and 6 wt% of Niax Catalyst A-33 (manufacturer: momentive) were added as catalysts, and 7 wt% of water was added did. Thereafter, the first polyol composition was prepared by slowly dissolving it at 70° C. at a stirring rate of 60 rpm to 80 rpm.

제조예 1-2Preparation 1-2

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.

제 1 디이소시아네이트 조성물의 제조Preparation of the first diisocyanate composition

제조예 2 Preparation 2

Prepare a four-necked flask equipped with a condenser, agitator and temperature controller on a heating mantle, and 80 wt% of monomeric methylenediphenyl diisocyanate (MMDI) and 20 wt% of glycerin (Gly) as the first diisocyanate in the flask was added to prepare a first diisocyanate composition.

폴리우레탄 조성물의 제조Preparation of polyurethane composition

제조예 3Preparation 3

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.

After mixing the polyol compositions C and D, 2 wt% of Polyolcat-8 (manufacturer: Evonik) and 0.3 wt% of Polyolcat-5 (manufacturer: Evonik) were added as catalysts, and a foam stabilizer (TEGOSTAB B-8462, manufacturer: Evonik) 2 wt%, water 2 wt%, and cyclopentane 15 wt% as a foaming agent were added, and then slowly stirred at 25° C. at a stirring speed of 60 rpm to 80 rpm to prepare a second polyol composition.

Then, 45 wt% of the second polyol composition and 55 wt% of polymeric methylenediphenyl diisocyanate (PMDI) (M-200, manufacturer: Kumho Mitsui) as a second diisocyanate were added at a temperature of 20°C and A polyurethane composition was prepared by mixing at a pressure of 130 bar.

적층체의 제조Preparation of laminates

실시예 1Example 1

(1) Preparation of the first polyurethane layer

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. After putting the first polyol composition prepared in Preparation Example 1-1 as a first liquid in the two-liquid separation container and putting the first diisocyanate composition prepared in Preparation Example 2 as a second liquid, 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.

(2) Preparation of the second polyurethane layer

After placing a mold on the first polyurethane layer, injecting the polyurethane composition prepared in Preparation Example 3, and curing at 45° C. for 3 minutes to form a second polyurethane layer having a thickness of 50 mm was prepared.

실시예 2Example 2

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.

[실험예][Experimental example]

실험예 1: 표면 경도Experimental Example 1: Surface hardness

For the first polyurethane layer prepared in step (1) of Examples 1 and 2, the surface hardness was measured using an Asker C type hardness meter (manufacturer: Asker).

실험예 2: 자유 발포 밀도Experimental Example 2: Free Foam Density

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.

Specifically, using the spray device used in step (1) of Examples 1 and 2, spraying at a spraying speed of 1.4 kg/min and a spraying angle of 90° with respect to the open box, 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.

실험예 3: 최대용적 도달시간(rising time)Experimental Example 3: Maximum volume reaching time (rising time)

When the first polyurethane layers of Examples 1 and 2 were formed 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 time to reach the maximum volume was measured.

Specifically, using the spray device used in 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.

구분division	표면 경도surface hardness	자유 발포 밀도 (kg/m³)free foam density (kg/m³)	최대용적 도달시간(초)maximum volume Arrival time (sec)
실시예 1Example 1	2323	25.125.1	55
실시예 2Example 2	2525	26.326.3	66

As shown in Table 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.

Specifically, 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.

Claims

The base layer, the first polyurethane layer, and the second polyurethane layer are sequentially laminated,

The Asker C type surface hardness of the first polyurethane layer is 15 to 35, the laminate.
The method of claim 1,

The first polyurethane layer is a spray foam,

wherein the second polyurethane layer is a rim (RIM) foam or a mold foam.
The method of claim 1,

A laminate that does not include a separate adhesive layer between the base layer and the first polyurethane layer.
The method of claim 1,

The Asker C type surface hardness of the second polyurethane layer is 35 to 100, the laminate.
The method of claim 1,

The first polyurethane layer comprises a core layer located on a surface opposite to the base layer and a surface layer located on a surface opposite to the second polyurethane layer,

The density of the surface layer is greater than the density of the core layer,

The thickness of the surface layer is 0.1 mm to 1 mm,

The thickness of the core layer is 1 mm to 3 mm, the laminate.
The method of claim 1,

The thickness of the first polyurethane layer is 1 mm to 10 mm,

The thickness ratio of the first polyurethane layer and the second polyurethane layer is 1: 5 to 20, the laminate.
The method of claim 1,

The free foaming density of the first polyurethane layer is 15 kg/m³ to 35 kg/m³,

wherein the free foaming density of the second polyurethane layer is 20 kg/m³ to 30 kg/m³.
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,

The thickness ratio of the first polyurethane layer and the second polyurethane layer is 1: 5 to 20, the laminate.
Forming a first polyurethane layer comprising the step of spraying the first liquid and the second liquid on the base layer;

Forming a second polyurethane layer on the first polyurethane layer,

The Asker C type surface hardness of the first polyurethane layer is 15 to 35, the method of manufacturing a laminate.
10. The method of claim 9,

The injection ratio of the first liquid and the second liquid is 1: 0.9 to 1.1,

The injection speed of the first liquid and the second liquid is 0.5 kg / min to 3.0 kg / min, respectively,

The first liquid and the second liquid are each sprayed at an angle of 10 ° to 170 ° with respect to the base layer, the manufacturing method of the laminate.
10. The method of claim 9,

The forming step of the first polyurethane layer is carried out at 25 ℃ to 80 ℃ for 2 seconds to 40 seconds,

The forming step of the second polyurethane layer is carried out at 25 °C to 85 °C for 1 minute to 5 minutes, the method for producing a laminate.
10. The method of claim 9,

Forming the first polyurethane layer comprises forming a core layer and forming a surface layer,

A method of manufacturing a laminate, wherein the forming of the core layer and the forming of the surface layer are performed simultaneously.
10. The method of claim 9,

A method for producing a laminate, which does not include the step of forming a separate adhesive layer between the base layer and the first polyurethane layer.
10. The method of claim 9,

The said 1st liquid is a polyol composition, and the said 2nd liquid is a diisocyanate composition, The manufacturing method of the laminated body.