WO2021189502A1 - 一种 pu 板材及其制备方法 - Google Patents

一种 pu 板材及其制备方法 Download PDF

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Publication number
WO2021189502A1
WO2021189502A1 PCT/CN2020/081950 CN2020081950W WO2021189502A1 WO 2021189502 A1 WO2021189502 A1 WO 2021189502A1 CN 2020081950 W CN2020081950 W CN 2020081950W WO 2021189502 A1 WO2021189502 A1 WO 2021189502A1
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WIPO (PCT)
Prior art keywords
layer
surface layer
board
core layer
core
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PCT/CN2020/081950
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English (en)
French (fr)
Inventor
唐道远
李磊
吴光荣
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安徽森泰木塑集团股份有限公司
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Publication of WO2021189502A1 publication Critical patent/WO2021189502A1/zh

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention relates to the technical field of wood-plastic material production, in particular to a PU board and a preparation method.
  • PU board In the flooring industry, PU board is an emerging material. It is light in weight and its strength is comparable to that of wood. Compared with PVC foamed board, PU board has better soft touch and better environmental safety. Therefore, PU board has become an important direction in the current imitation wood board field.
  • the PCT patent with publication number WO2018154287A1 discloses a low endothermic flame-retardant polyurethane wood-like material.
  • the polyurethane wood-like board includes a rigid plastic foam core and a plastic layer covering it.
  • the plastic layer contains light-reflecting Microspheres.
  • the plastic foam core can provide the required structural support while keeping the floor light.
  • the microspheres can reflect light and reduce the amount of radiation absorbed by the floor when exposed to direct sunlight. Therefore, the microspheres can effectively prevent the floor from becoming hot when exposed to direct sunlight.
  • the present invention aims to solve the above-mentioned problems, thereby providing a PU board.
  • the foam core and the plastic layer of the board have the advantage of not being easy to crack.
  • a PU board comprising a flexible unfoamed PU surface layer and a rigid foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer And part of the PU core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the continuous phase means that the boundary is unclear, the boundary presents a certain transition shape, and has continuity; for example, there is no obvious interface between the PU surface layer and the PU core layer, but still It can be roughly distinguished at the boundary between the two; the boundary refers to the PU fusion layer; the PU fusion layer is integrally connected with the PU surface layer, and is also integrally connected with the PU core layer.
  • the thickness of the PU fusion layer is 100-3000 ⁇ m.
  • the thickness of the PU fusion layer is 200-2000 ⁇ m.
  • the thickness of the PU fusion layer is 500-1000 ⁇ m.
  • the PU surface layer contains inorganic nanoparticles, and the inorganic nanoparticles are selected from one of silica, titanium dioxide, zirconium dioxide, ceramic powder, porcelain clay or composite nano-powdered materials or Many kinds.
  • the PU surface layer has wood texture or other patterns produced by casting.
  • the PU fusion layer is covered by the raw material of the PU core layer on the incompletely cured PU surface layer, and during the foaming and molding of the core layer, the partially incompletely cured PU skin layer is combined with the newly formed PU skin layer. Part of the PU core layer is fused.
  • the formation of the PU fusion layer is formed by a casting process, during this process, the heat transfer has a significant heat dissipation effect, so the PU surface layer is cured from the part that is in close contact with the intaglio mold , That is, curing from the inside out.
  • the patterned part has the highest degree of curing, while the surface curing state is incomplete, and even has weak fluidity; at this time, the raw material of the PU core layer is covered on it, and the The PU core layer is foamed to obtain a board with a foam core and a PU skin layer; and a fusion layer is formed between the foam core and the PU skin layer of the board, so that the board has better integrity, that is, the foam core and the PU skin layer It is not easy to crack between.
  • Another object of the present invention is to provide a method for preparing the above PU board.
  • a preparation method of PU board includes the following steps:
  • Preparation of PU surface layer mix the raw materials containing at least polyether polyol/polyester polyol, isocyanate and curing agent into a rigid mold; obtain an incompletely cured PU surface layer;
  • PU core layer preparation mix the raw materials containing at least water, polyether polyol/polyester polyol, and isocyanate, and then input them into the rigid mold where the incompletely cured PU surface layer of step a is not taken out; control the raw materials of the core layer The temperature of the mixture is 20 ⁇ 40°C to make the raw materials of the PU core layer self-foam; at the same time, a PU fusion layer is formed between the newly formed part of the PU core layer and the part of the incompletely cured PU surface layer.
  • Product PU sheet mix the raw materials containing at least water, polyether polyol/polyester polyol, and isocyanate, and then input them into the rigid mold where the incompletely cured PU surface layer of step a is not taken out; control the raw materials of the core layer The temperature of the mixture is 20 ⁇ 40°C to make the raw materials of the PU core layer self-foam; at the same time, a PU fusion layer is formed between the newly formed part of
  • step b the pressure in the foaming cavity is controlled to be 4-10 MPa during foaming; preferably 4-6 MPa.
  • the pressure in the foaming cavity is controlled to be 4-10 MPa, while the prior art is generally controlled to be 1 to 3 MPa. This is because the greater the pressure, the more dense the cells of the foamed core layer. The strength is also higher; and more importantly, the increase in the pressure in the foaming cavity can better promote the fusion between the incompletely cured PU surface layer and the PU core layer that has not yet been fully foamed, which is to further promote Formation of PU fusion layer. However, a higher pressure, such as above 10 MPa, may affect the progress of foaming.
  • the raw material of the PU core layer is input into the mold cavity of the molding method, the raw material of the PU core layer is stirred for 5-10 seconds to make it flow relative to the incompletely cured PU surface layer. After the raw material of the PU core layer is stationary, adjust the mold pressure to 4 ⁇ 6MPa.
  • stirring the raw materials of the PU core layer can not only make it more uniform, but more importantly, make the raw materials of the PU core layer relative to the incompletely cured PU surface layer produce relative movement, promote their fusion, that is, further Promotes the formation of PU fusion layer.
  • the raw material in step a contains inorganic nanoparticles, and the inorganic nanoparticles are selected from nano-powdered materials of silica, titania, zirconia, ceramic powder, porcelain clay or their composites. One or more.
  • the subsequent processing in step c includes the processing of cutting the initial PU board.
  • the subsequent treatment in step c includes surface texture treatment on the preliminary PU board.
  • the raw materials used to prepare the PU surface layer in step a include 100 ⁇ 130 parts of polyether polyol, 0.05 ⁇ 0.1 part of catalyst, 20 ⁇ 45 parts of isocyanate, 1.5 ⁇ 4 parts of light stabilizer;
  • the temperature of the PU surface layer raw material mixture is controlled at 30-40°C;
  • the catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate, and triethylene diamine; in step b
  • the raw materials used to prepare the Pu core layer include 100 ⁇ 140 parts of polyether polyol, 5.5 ⁇ 8.5 parts of deionized water, 20 ⁇ 50 parts of heavy calcium, 5 ⁇ 10 parts of wood fiber, 2 ⁇ 5 parts of glass fiber, and 140 ⁇ of isocyanate.
  • the temperature of the PU core layer raw material mixture is controlled at 20-40°C.
  • the PU board of the present invention has a rigid PU foam core and a flexible PU surface layer, and a PU fusion layer is formed between the PU surface layer and the PU foam core, which makes the PU surface layer and the PU foam core form a continuous phase, thereby greatly improving The bonding strength between the PU foam core and the flexible PU surface layer is improved, so that the PU board is not easy to crack.
  • the present invention also adds inorganic nanoparticles to the raw materials forming the PU surface layer.
  • the addition of inorganic nanoparticles not only improves the surface strength and wear resistance of the PU board, but also improves the burning resistance of the PU board.
  • the PU foam core of the present invention adopts full water-based foaming.
  • the foaming agent does not use 141B, but deionized water; the foaming mechanism is to generate CO2 through the reaction of R-NCO and H2O, thereby giving the product a better environment safety.
  • the PU surface layer material of the present invention adopts polyether polyol/polyester polyol and isocyanate.
  • the mixture formed by uniformly mixing polyether polyol/polyester polyol and isocyanate has good fluidity, which can make the surface layer of the PU board in the casting process
  • the medium can better flow to all parts of the intaglio mold, so that the final pattern on the surface of the PU sheet has a better definition and a more three-dimensional effect.
  • the freeze-thaw cycle test shows that the board of the present invention has good stability and is not easy to crack between layers.
  • Fig. 1 is a result test table of the product of Example 1 and the product of Comparative Example 1 of the present invention.
  • a PU board comprising a flexible unfoamed PU surface layer and a rigid foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer And part of the PU core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the PU surface layer contains inorganic nanoparticles, the inorganic nanoparticles are ceramic powder, and the addition amount is 20 wt% of the mass of the PU surface layer.
  • the thickness of the PU surface layer is 0.5 cm
  • the thickness of the PU core layer is 2 cm
  • the thickness of the PU fusion layer is about 300 ⁇ m.
  • a preparation method of PU board the specific steps are as follows:
  • Core layer casting 148kg polyether polyol YNW-6001A, 7kg deionized water, 40kg heavy calcium, 10kg wood fiber, 2kg glass fiber, 200kg isocyanate Wanhua MDI-8214, 0.6kg stannous octoate/triethylene Amine (7/10) composite catalyst and 0.2kg of silicone oil foam stabilizer are uniformly stirred and mixed in the second storage tank. Keep the temperature of the mixture at 20°C, and pour the mixture from the storage tank into the mold tank for semi-solidification On the skin layer of the shape, stir the mixture for 10 seconds. After it is still, control the temperature of the mold at 35°C and adjust the mold pressure to 4MPa to foam the mixed raw materials of the core layer;
  • a PU board comprising a non-foamed PU surface layer and a foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer and part of the PU The core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the PU surface layer contains inorganic nanoparticles, the inorganic nanoparticles are ceramic powder, and the addition amount is 15 wt% of the mass of the PU surface layer.
  • the thickness of the PU surface layer is 0.5 cm
  • the thickness of the PU core layer is 2 cm
  • the thickness of the PU fusion layer is about 300 ⁇ m.
  • a preparation method of PU board the specific steps are as follows:
  • Core layer casting 148kg polytetrahydrofuran ether glycol, 7.5kg deionized water, 50kg heavy calcium, 5kg wood fiber, 5kg glass fiber, 200kg isocyanate Japan MI 100, 0.6kg stannous octoate/triethylene diamine (7 /10)
  • the composite catalyst and 0.2kg of silicone oil foam stabilizer are uniformly stirred and mixed in the second storage tank, and the temperature of the mixture is maintained at 25°C.
  • the mixture is poured from the storage tank into the semi-solidified skin layer in the mold tank Above, control the temperature of the mold at 30°C, while adjusting the mold pressure to 5MPa to foam the mixed raw materials of the core layer;
  • a PU board comprising a non-foamed PU surface layer and a foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer and part of the PU The core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the PU surface layer contains inorganic nanoparticles, the inorganic nanoparticles are ceramic powder, and the addition amount is 15 wt% of the mass of the PU surface layer.
  • the thickness of the PU surface layer is 0.3 cm
  • the thickness of the PU core layer is 1.8 cm
  • the thickness of the PU fusion layer is about 200 ⁇ m.
  • a preparation method of PU board the specific steps are as follows:
  • Core layer casting 148kg polyether polyol 4110, 6.8kg deionized water, 45kg heavy calcium, 8kg wood fiber, 3kg glass fiber, 200kg isocyanate Wanhua MDI 8214, 0.6kg stannous octoate/triethylenediamine ( 7/10)
  • the composite catalyst and 0.2kg of silicone oil foam stabilizer are uniformly stirred and mixed in the second storage tank, and the temperature of the mixture is maintained at 30°C.
  • the mixture is poured from the storage tank into the mold tank in a semi-solidified form. On the skin layer, control the temperature of the mold at 40°C while adjusting the mold pressure to 6MPa to foam the mixed raw materials of the core layer;
  • a PU board comprising a non-foamed PU surface layer and a foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer and part of the PU The core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the PU surface layer contains inorganic nanoparticles, the inorganic nanoparticles are ceramic powder, and the addition amount is 15 wt% of the mass of the PU surface layer.
  • the thickness of the PU surface layer is 0.25 cm
  • the thickness of the PU core layer is 1.8 cm
  • the thickness of the PU fusion layer is about 180 ⁇ m.
  • a preparation method of PU board the specific steps are as follows:
  • Core layer casting 120kg polyether polyol 4110, 6.5kg deionized water, 20kg heavy calcium, 6kg wood fiber, 5kg glass fiber, 175kg isocyanate Wanhua MDI 8214, 0.5kg stannous octoate/triethylenediamine ( 7/10)
  • the composite catalyst and 0.1kg of silicone oil foam stabilizer are uniformly stirred and mixed in the second storage tank, and the temperature of the mixture is maintained at 35°C.
  • the mixture is poured from the storage tank into the mold tank in a semi-solidified form On the skin layer, control the temperature of the mold at 35°C while adjusting the mold pressure to 7MPa to foam the mixed raw materials of the core layer;
  • a PU board comprising a non-foamed PU surface layer and a foamed PU core layer, and a PU fusion layer located between the PU surface layer and the PU core layer; the PU fusion layer includes part of the PU surface layer and part of the PU The core layer, and part of the PU surface layer penetrates into the part of the PU core layer, so that the PU surface layer and the PU core layer become a continuous phase.
  • the PU surface layer contains inorganic nanoparticles, the inorganic nanoparticles are ceramic powder, and the addition amount is 15 wt% of the mass of the PU surface layer.
  • the thickness of the PU surface layer is 0.25 cm
  • the thickness of the PU core layer is 1.8 cm
  • the thickness of the PU fusion layer is about 180 ⁇ m.
  • a preparation method of PU board the specific steps are as follows:
  • Core layer casting 100kg polyether polyol YNW-6001A, 6.0kg deionized water, 30kg heavy calcium, 5kg wood fiber, 4kg glass fiber, 155kg isocyanate Wanhua MDI 8214, 0.4kg stannous octoate/triethylene
  • the amine (7/10) composite catalyst and 0.1kg of silicone oil foam stabilizer are uniformly stirred and mixed in the second storage tank. Keep the temperature of the mixture at 40°C, and pour the mixture from the storage tank into the mold tank for semi-solidification On the skin layer of the shape, control the temperature of the mold at 25°C, while adjusting the mold pressure to 8MPa to foam the mixed raw materials of the core layer;
  • a low endothermic flame-retardant polyurethane wood-like material a PU board is prepared.

Abstract

本发明涉及木塑材料生产技术领域，尤其涉及一种PU板材及制备方法。一种PU板材，包括不发泡的PU表层和发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。本发明的PU板材，具有刚性的PU泡沫芯和柔性的PU表层，并且PU表层与PU泡沫芯之间形成有PU融合层，这使得PU表层与PU泡沫芯形成连续相，从而大大提高了PU泡沫芯和柔性的PU表层之间的结合强度，使得PU板材不易开裂。

Description

一种PU板材及其制备方法 技术领域
本发明涉及木塑材料生产技术领域，尤其涉及一种PU板材及制备方法。
 背景技术
在地板行业中，PU板材是一种新兴的材料。它质量轻，强度与木材相当。相较于PVC发泡板材，PU板材具有更好的软触感和更好的环境安全性。因此，PU板材成为当前仿木板材领域的重要方向。
公开号为WO2018154287A1的PCT专利公开了一种低吸热阻燃型聚氨酯仿木材料，该聚氨酯仿木板材包括刚性的塑料泡沫芯和覆盖在其上的塑料层，该塑料层包含可反射光的微球。塑料泡沫芯在保持地板质轻的同时还能产生所需的结构支撑。微球可反射光，减少地板在阳光直射时吸收的辐射量，因此微球可有效防止地板在被阳光直射时变热。
 技术问题
但是，该板材的塑料泡沫芯和覆盖在其上的塑料层之间由于材质的原因，容易开裂，致使产品质量下降。
 技术解决方案
本发明要解决上述问题，从而提供了一种PU板材。该板材的泡沫芯和塑料层之间具有不易开裂的优点。
本发明解决上述问题的技术方案如下：
一种PU板材，包括柔性的不发泡的PU表层和刚性的发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。
本发明上述技术方案中，所述的连续相是指边界不清，边界处呈现出一定的过渡形态，并且具有连续性；如PU表层和PU芯层之间不存在明显的分界面，但仍能在两者的边界处大致区分；所述的边界处即指所述的PU融合层；所述的PU融合层与所述的PU表层一体连接，与所述的PU芯层也一体连接。
作为上述技术方案的优选，所述PU融合层的厚度为100~3000μm。
作为上述技术方案的进一步优选，所述PU融合层的厚度为200~2000μm。
作为上述技术方案更进一步的优选，所述PU融合层的厚度为500~1000μm。
作为上述技术方案的优选，所述PU表层含有无机纳米粒子，所述无机纳米粒子选自二氧化硅、二氧化钛、二氧化锆、陶瓷粉、瓷土或其复合物的纳米粉状材料其中一种或多种。
作为上述技术方案的优选，所述PU表层具有浇注产生的木材纹理或其他图案。
作为上述技术方案的优选，所述PU融合层由PU芯层的原料覆盖在不完全固化的PU表层上，并在芯层发泡成型的过程中，使部分不完全固化的PU皮层与新生成的部分PU芯层融合而成。
在本发明的上述技术方案中，由于PU融合层的形成是通过浇注工艺形成的，在这个过程中，热传递具有明显的散热效果，因此PU表层是从与凹版模具密切接触的部位开始固化的，也即由内而外的固化。因此当PU表层还在半固化状态时，图刻部分固化程度最高，而表面固化状态不完全，甚至还具有弱的流动性；此时，再将PU芯层的原料覆盖在其上，并使PU芯层进行发泡，可以得到具有泡沫芯和PU皮层的板材；并且该板材的泡沫芯和PU皮层之间形成有融合层，使得该板材具有更好的整体性，即泡沫芯和PU皮层之间不易开裂。
本发明的另一个目的是提供上述PU板材的一种制备方法。
一种PU板材的制备方法，包括以下步骤：
a、PU表层制备：将至少包含聚醚多元醇/聚酯多元醇、异氰酸酯及固化剂的原料混匀后输入刻板模具中；得到不完全固化的PU表层；
b、PU芯层制备：将至少包含水、聚醚多元醇/聚酯多元醇、异氰酸酯的原料混匀后输入步骤a的不完全固化的PU表层未取出的刻板模具中；控制芯层原料的混合物温度在20~40℃，使PU芯层的原料自发泡；同时在新生成的部分PU芯层与部分的不完全固化的PU表层之间生成PU融合层，发泡完全后脱模得到初品PU板材；
c、对初品PU板材进行后续处理得到PU板材。
作为上述技术方案的优选，步骤b中，发泡时控制发泡腔内的压强为4~10MPa；优选为4~6MPa。
本发明上述技术方案中，发泡腔内压强控制为4~10MPa，而现有技术一般控制为1~3MPa，这是因为压强越大，发泡芯层的泡孔更趋向于致密，芯层的强度也更高；而更加重要的是，发泡腔内压强的增大可以更好地促进不完全固化的PU表层与尚未发泡完全的PU芯层之间的融合，也就是进一步促进了PU融合层的形成。而更大的压强，如10MPa以上，恐影响发泡的进行。
作为上述技术方案的进一步优选，在将PU芯层的原料输入模压法的模具腔内时，搅拌PU芯层的原料5~10s，使其相对于不完全固化的PU表层产生相对的流动，待PU芯层的原料静止不动后，调整模压到4~6MPa。
本发明上述技术方案中，搅拌PU芯层的原料除了可使之更加均匀外，更重要的是使PU芯层的原料相对不完全固化的PU表层产生相对的运动，促进他们的融合，即进一步促进了PU融合层的形成。
作为上述技术方案的优选，步骤a所述的原料中含有无机纳米粒子，所述无机纳米粒子选自二氧化硅、二氧化钛、二氧化锆、陶瓷粉、瓷土或其复合物的纳米粉状材料其中一种或多种。
作为上述技术方案的优选，步骤c所述的后续处理包括对所述初品PU板材进行切割的处理。
作为上述技术方案的优选，步骤c所述的后续处理包括对所述初品PU板材进行的表面纹饰处理。
作为上述技术方案的优选，步骤a中用于制备PU表层的原料包括聚醚多元醇100~130份、催化剂0.05~0.1份、异氰酸酯20~45份、光稳定剂1.5~4份；在PU表层制备过程中，控制PU表层原料混合物的温度在30~40℃；所述的催化剂选自二丁基二月桂酸锡、辛酸亚锡、三乙烯二胺中的一种或多种；步骤b中用于制备Pu芯层的原料包括聚醚多元醇100~140份、去离子水5.5~8.5份、重钙20~50份、木纤维5~10份、玻纤2~5份、异氰酸酯140~210份、辛酸亚锡/三乙烯二胺复合催化剂0.3~0.7份、有机硅油匀泡剂0.1~0.4份，在PU芯层制备过程中，控制PU芯层原料混合物的温度在20~40℃。
 有益效果
1、本发明的PU板材，具有刚性的PU泡沫芯和柔性的PU表层，并且PU表层与PU泡沫芯之间形成有PU融合层，这使得PU表层与PU泡沫芯形成连续相，从而大大提高了PU泡沫芯和柔性的PU表层之间的结合强度，使得PU板材不易开裂。
2、本发明还在形成PU表层的原料中添加有无机纳米粒子，无机纳米粒子的添加不仅提高了PU板材的表面强度和耐磨性，还提高了PU板材的耐灼烧性能。
3、本发明的PU泡沫芯采用全水基发泡，发泡剂不采用141B，而是去离子水；发泡的机理是通过R-NCO与H2O反应生成CO2，从而赋予产品更好的环境安全性。
4、本发明的PU表层原料采用聚醚多元醇/聚酯多元醇和异氰酸酯，聚醚多元醇/聚酯多元醇和异氰酸酯均匀混合形成的混合物具有良好的流动性，可使得PU板材的表层在浇注过程中能够更好地流动到凹版模具各个部位，使得最终形成的PU板材表面的图案具有更好的清晰度和更加立体的效果。
5、经冻融循环试验表明，本发明的板材具有良好的稳定性，层间不易开裂。
 附图说明
图1是本发明实施例一的产品和对比例1的产品的结果测试表。
 本发明的最佳实施方式
实施例一
一种PU板材，包括柔性的不发泡的PU表层和刚性的发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。所述PU表层含有无机纳米粒子，所述无机纳米粒子为陶瓷粉，添加量为PU表层质量的20wt%。本实施例中，PU表层厚度0.5cm，PU芯层厚度2cm，PU融合层厚度约300μm。
一种PU板材的制备方法，具体步骤如下：
   1、表层浇注：将1kg色粉、100kg聚醚多元醇4110、50g二丁基二月桂酸锡、20kg异氰酸酯PM 200、1kgUV-1、2.5kgUV-196在第一储料罐中进行均匀搅拌混合呈液态，将搅拌混合均匀的混合物加热至30℃，浇注到模具中，控制模具温度为60℃，控制冷却速度生成半固化形态的PU表层；所述模具为凹版浮雕模具；
2、芯层浇注：将148kg聚醚多元醇YNW-6001A、7kg去离子水、40kg重钙、10kg木纤维、2kg玻纤、200kg异氰酸酯万华MDI-8214、0.6kg辛酸亚锡/三乙烯二胺（7/10）复合催化剂、0.2kg有机硅油匀泡剂在第二储料罐中进行均匀搅拌混合均匀，保持混合物温度在20℃，将混合物从储料罐里浇注到模具槽中半固化形态的皮层上，搅拌混合物10s，待其静止不动后，控制模具的温度在35℃，调整模压到4MPa，使芯层的混合原料发泡；
3、表面纹饰处理：完全固化后，将成型的复合板整板脱离模具，然后将板材的皮层的表面纹理进行纹饰处理，具体为上黑色底漆，涂仿木颜色的聚氨酯耐磨涂料，形成老船木风格；
4、后处理：根据实际需要将整板按规格切割成多个小板。
 本发明的实施方式
实施例二
一种PU板材，包括不发泡的PU表层和发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。所述PU表层含有无机纳米粒子，所述无机纳米粒子为陶瓷粉，添加量为PU表层质量的15wt%。本实施例中，PU表层厚度0.5cm，PU芯层厚度2cm，PU融合层厚度约300μm。
一种PU板材的制备方法，具体步骤如下：
   1、表层浇注：将2kg色粉、100kg聚醚多元醇YNW-6001A、80g二丁基二月桂酸锡、41kg异氰酸酯MDI-5005、1kgUV-196、3.0kgUV2-315在第一储料罐中进行均匀搅拌混合呈液态，将搅拌混合均匀的混合物加热至35℃，浇注到模具中，控制模具温度为50℃，控制冷却速度生成半固化形态的PU表层；所述模具为凹版浮雕模具；
2、芯层浇注：将148kg聚四氢呋喃醚二醇、7.5kg去离子水、50kg重钙、5kg木纤维、5kg玻纤、200kg异氰酸酯日本MI 100、0.6kg辛酸亚锡/三乙烯二胺（7/10）复合催化剂、0.2kg有机硅油匀泡剂在第二储料罐中进行均匀搅拌混合均匀，保持混合物温度在25℃，将混合物从储料罐里浇注到模具槽中半固化形态的皮层上，控制模具的温度在30℃，同时调整模压到5MPa，使芯层的混合原料发泡；
3、表面纹饰处理：完全固化后，将成型的复合板整板脱离模具，然后将板材的皮层的表面纹理进行纹饰处理，具体为上黑色底漆，涂仿木颜色的聚氨酯耐磨涂料，形成老船木风格；
4、后处理：根据实际需要将整板按规格切割成多个小板。
实施例三
一种PU板材，包括不发泡的PU表层和发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。所述PU表层含有无机纳米粒子，所述无机纳米粒子为陶瓷粉，添加量为PU表层质量的15wt%。本实施例中，PU表层厚度0.3cm，PU芯层厚度1.8cm，PU融合层厚度约200μm。
一种PU板材的制备方法，具体步骤如下：
   1、表层浇注：将3kg色粉、100kg聚四氢呋喃醚二醇、100g胺类催化剂三乙烯二胺、34kg异氰酸酯IPDI、1kgUV2-315、3.0kgUV-292在第一储料罐中进行均匀搅拌混合呈液态，将搅拌混合均匀的混合物加热至40℃，浇注到模具中，控制模具温度为45℃，控制冷却速度生成半固化形态的PU表层； 所述模具为凹版浮雕模具；
2、芯层浇注：将148kg聚醚多元醇4110、6.8kg去离子水、45kg重钙、8kg木纤维、3kg玻纤、200kg异氰酸酯万华MDI 8214、0.6kg辛酸亚锡/三乙烯二胺（7/10）复合催化剂、0.2kg有机硅油匀泡剂在第二储料罐中进行均匀搅拌混合均匀，保持混合物温度在30℃，将混合物从储料罐里浇注到模具槽中半固化形态的皮层上，控制模具的温度在40℃，同时调整模压到6MPa，使芯层的混合原料发泡；
3、表面纹饰处理：完全固化后，将成型的复合板整板脱离模具，然后将板材的皮层的表面纹理进行纹饰处理，具体步骤为上黑色底漆，涂仿木颜色的聚氨酯耐磨涂料，形成老船木风格；
4、后处理：根据实际需要将整板按规格切割成多个小板。
实施例四
一种PU板材，包括不发泡的PU表层和发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。所述PU表层含有无机纳米粒子，所述无机纳米粒子为陶瓷粉，添加量为PU表层质量的15wt%。本实施例中，PU表层厚度0.25cm，PU芯层厚度1.8cm，PU融合层厚度约180μm。
一种PU板材的制备方法，具体步骤如下：
   1、表层浇注：将4kg色粉、100kg聚醚多元醇4110、50g二丁基二月桂酸锡、38kg异氰酸酯MDI-5005、1kgUV-292、2.5kgUV-581在第一储料罐中进行均匀搅拌混合呈液态，将搅拌混合均匀的混合物加热至32℃，浇注到模具中，控制模具温度为35℃，控制冷却速度生成半固化形态的PU表层； 所述模具为凹版浮雕模具；
2、芯层浇注：将120kg聚醚多元醇4110、6.5kg去离子水、20kg重钙、6kg木纤维、5kg玻纤、175kg异氰酸酯万华MDI 8214、0.5kg辛酸亚锡/三乙烯二胺（7/10）复合催化剂、0.1kg有机硅油匀泡剂在第二储料罐中进行均匀搅拌混合均匀，保持混合物温度在35℃，将混合物从储料罐里浇注到模具槽中半固化形态的皮层上，控制模具的温度在35℃，同时调整模压到7MPa，使芯层的混合原料发泡；
3、表面纹饰处理：完全固化后，将成型的复合板整板脱离模具，然后将板材的皮层的表面纹理进行表面纹饰处理，具体步骤为上黑色底漆，涂仿木颜色的聚氨酯耐磨涂料，形成老船木风格；
4、后处理：根据实际需要将整板按规格切割成多个小板。
实施例五
一种PU板材，包括不发泡的PU表层和发泡的PU芯层，还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。所述PU表层含有无机纳米粒子，所述无机纳米粒子为陶瓷粉，添加量为PU表层质量的15wt%。本实施例中，PU表层厚度0.25cm，PU芯层厚度1.8cm，PU融合层厚度约180μm。
一种PU板材的制备方法，具体步骤如下：
   1、表层浇注：将1.25kg色粉、100kg聚四氢呋喃醚二醇、80g催化剂辛酸亚锡、28kg异氰酸酯IPDI、1kgUV-581、2.5kgUV-4411在第一储料罐中进行均匀搅拌混合呈液态，将搅拌混合均匀的混合物加热至35℃，浇注到模具中，控制模具温度为45℃，控制冷却速度生成半固化形态的PU表层； 所述模具为凹版浮雕模具；
2、芯层浇注：将100kg聚醚多元醇YNW-6001A、6.0kg去离子水、30kg重钙、5kg木纤维、4kg玻纤、155kg异氰酸酯万华MDI 8214、0.4kg辛酸亚锡/三乙烯二胺（7/10）复合催化剂、0.1kg有机硅油匀泡剂在第二储料罐中进行均匀搅拌混合均匀，保持混合物温度在40℃，将混合物从储料罐里浇注到模具槽中半固化形态的皮层上，控制模具的温度在25℃，同时调整模压到8MPa，使芯层的混合原料发泡；
3、表面纹饰处理：完全固化后，将成型的复合板整板脱离模具，然后将板材的皮层的表面纹理进行表面纹饰处理，具体步骤为上黑色底漆，涂仿木颜色的聚氨酯耐磨涂料，形成老船木风格；
4、后处理：根据实际需要将整板按规格切割成多个小板。
对比例1
依据WO2018154287A1，一种低吸热阻燃型聚氨酯仿木材料所公开的方法，制备得到的一种PU板材。
依照GB/T17657-2013 《人造板及饰面人造板理化性能试验方法》的相关内容对实施例一的产品和对比例1的产品进行两次试验测试其胶合强度和浸渍剥离度，得到结果如图1所示。

Claims (10)

  1. 一种PU板材，包括柔性的不发泡的PU表层和刚性的发泡的PU芯层，其特征在于：还包括位于PU表层和PU芯层之间的PU融合层；所述PU融合层包含部分的PU表层和部分的PU芯层，并且部分的PU表层渗透入部分的PU芯层内，使得所述的PU表层和PU芯层成为连续相。
  2. 根据权利要求1所述的一种PU板材，其特征在于：所述PU融合层的厚度为100~3000μm。
  3. 根据权利要求1所述的一种PU板材，其特征在于：所述PU表层含有无机纳米粒子，所述无机纳米粒子选自二氧化硅、二氧化钛、二氧化锆、陶瓷粉、瓷土或其复合物的纳米粉状材料其中一种或多种。
  4. 根据权利要求1所述的一种PU板材，其特征在于：所述PU表层具有浇注产生的木材纹理或其他图案。
  5. 根据权利要求1所述的一种PU板材，其特征在于：所述PU融合层由PU芯层的原料覆盖在不完全固化的PU皮层上，并在芯层发泡成型的过程中，使部分不完全固化的PU皮层与新生成的部分PU芯层融合而成。
  6. 一种PU板材的制备方法，包括以下步骤：
    a、PU表层制备：将至少包含聚醚多元醇/聚酯多元醇、异氰酸酯及固化剂的原料混匀后输入刻板模具中；得到不完全固化的PU表层；
    b、PU芯层制备：将至少包含水、聚醚多元醇/聚酯多元醇、异氰酸酯的原料混匀后输入步骤a的不完全固化的PU表层未取出的刻板模具中；控制芯层原料的混合物温度在20~40℃，使PU芯层的原料自发泡；同时在新生成的部分PU芯层与部分的不完全固化的PU表层之间生成PU融合层，发泡完全后脱模得到初品PU板材；
    对初品PU板材进行后续处理得到PU板材。
  7. 根据权利要求6所述的一种PU板材的制备方法，其特征在于：步骤a所述的原料中含有无机纳米粒子，所述无机纳米粒子选自二氧化硅、二氧化钛、二氧化锆、陶瓷粉、瓷土或其复合物的纳米粉状材料其中一种或多种。
  8. 根据权利要求6所述的一种PU板材的制备方法，其特征在于：步骤c所述的后续处理包括对所述初品PU板材进行切割的处理。
  9. 根据权利要求6所述的一种PU板材的制备方法，其特征在于：步骤c所述的后续处理包括对所述初品PU板材进行的表面纹饰处理。
  10. 根据权利要求6所述的一种PU板材的制备方法，其特征在于：步骤a中用于制备PU表层的原料包括聚醚多元醇100~130份、催化剂0.05~0.1份、异氰酸酯20~45份、光稳定剂1.5~4份；在PU表层制备过程中，控制PU表层原料混合物的温度在30~40℃；所述的催化剂选自二丁基二月桂酸锡、辛酸亚锡、三乙烯二胺中的一种或多种；步骤b中用于制备Pu芯层的原料包括聚醚多元醇100~140份、去离子水5.5~8.5份、重钙20~50份、木纤维5~10份、玻纤2~5份、异氰酸酯140~210份、辛酸亚锡/三乙烯二胺复合催化剂0.3~0.7份、有机硅油匀泡剂0.1~0.4份，在PU芯层制备过程中，控制PU芯层原料混合物的温度在20~40℃。
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