CN111890743A - Thermoplastic polyurethane floor and production process thereof - Google Patents

Abstract

The invention provides a thermoplastic polyurethane floor which comprises a wear-resistant layer, a printing layer and a base material layer. The wear-resistant layer and the printing layer are made of thermoplastic polyurethane, the printing layer is connected below the wear-resistant layer, and one surface of the printing layer is printed with a pattern texture. The bottom material layer is made of thermoplastic polyurethane base material and is connected below the printing layer, wherein the thermoplastic polyurethane base material comprises 1-50 parts of polyurethane polymer, 50-100 parts of calcium carbonate, 1-20 parts of polyurethane reclaimed material, 1-30 parts of polyacetal or polyamide or acrylonitrile-butadiene-styrene polymer or polypropylene and 1-10 parts of lubricant according to parts by weight. Therefore, the thermoplastic polyurethane floor of the present invention can control the hardness of the floor by the formula of the primer layer.

Description

Thermoplastic polyurethane floor and production process thereof

Technical Field

The invention belongs to the field of floors, particularly relates to a plastic floor and a production process thereof, and particularly relates to a thermoplastic polyurethane floor and a production process thereof.

Background

With the progress of composite materials and the improvement of processing technology, various plastic floors are available on the market, which replace part of ceramic tiles and marble floors with the properties of light weight, easy laying, wear-resistant surface, thin thickness, sound absorption and buffering effect, and the like, and are widely used for household, office and sports floors.

Most of the current plastic floors are made of polyvinyl chloride (PVC) materials, which are one of common engineering plastics, but the PVC materials have poor toughness, impact resistance and easy brittle fracture, so the PVC materials cannot be used as structural materials. Further, the brittleness of polyvinyl chloride is easily affected by temperature, and its use lower limit is-15 ℃ and that of soft polyvinyl chloride is-30 ℃ and hydrogen chloride starts to decompose at 100 ℃, so that polyvinyl chloride has poor thermal stability.

Polyvinyl chloride is thermoplastic linear resin, and due to the structural characteristics of the polyvinyl chloride, a plasticizer is required to be added in the processing process, harmful substance phenol exists in the plasticizer, the plasticizer can have harmful effects on the nervous system and the urinary system of a human body after long-term contact, the polyvinyl chloride product has pungent smell in the processing process, has direct effects on the respiratory tract of the human body, is easy to pollute the environment, does not meet the requirements of international environmental RoHS, and cannot be naturally decomposed in the natural environment although the polyvinyl chloride can be recycled, so that the environmental pollution can never be caused, and the plastic floor processed by the polyvinyl chloride is not suitable for the sustainable development of the human body health and the environment.

In view of the above, how to prepare an environmentally friendly plastic floor without causing harm to human body is an object of the related industry.

Disclosure of Invention

One object of the present invention is to provide a thermoplastic polyurethane floor, which has a wide application range by adjusting the hardness of the floor according to different primer layer formulations, and does not need glue for the lamination of the layers of the floor, thereby saving raw materials and manufacturing cost and meeting the requirement of environmental protection.

Another objective of the present invention is to provide a manufacturing process of a thermoplastic polyurethane floor, which comprises sequentially hot pressing and attaching a wear layer, a printing layer, and a primer layer from top to bottom to form the thermoplastic polyurethane floor.

One embodiment of the present invention provides a thermoplastic polyurethane flooring comprising a wear layer, a print layer and a primer layer. The wear-resistant layer is made of thermoplastic polyurethane, the printing layer is made of thermoplastic polyurethane and is connected below the wear-resistant layer, a pattern texture is printed on one surface of the printing layer, the primer layer is made of thermoplastic polyurethane primer and is connected below the printing layer, wherein the thermoplastic polyurethane primer comprises, by weight, 1-50 parts of polyurethane polymer, 50-100 parts of calcium carbonate, 1-20 parts of polyurethane reclaimed material, 1-30 parts of Polyacetal (POM) or Polyamide (PA) or acrylonitrile-butadiene-styrene polymer (ABS) or polypropylene (PP) and 1-10 parts of lubricant.

The thermoplastic polyurethane flooring according to the foregoing embodiment, wherein the polyurethane polymer may be formed by polymerization of isocyanate, polyol and chain extender.

The thermoplastic polyurethane flooring according to the foregoing embodiment, wherein the molecular weight of the polyol may be 500 to 8000.

The thermoplastic polyurethane flooring according to the foregoing embodiment, wherein the thickness of the wear layer may be 0.05mm to 3.0mm, the thickness of the print layer may be 0.05mm to 1.5mm, and the thickness of the primer layer may be 0.5mm to 8.0 mm.

Another embodiment of the present invention is to provide a process for producing a thermoplastic polyurethane flooring, which comprises a mixing step, a pulling step and a bonding step. The mixing step comprises the steps of metering the thermoplastic polyurethane base material according to a ratio, premixing the thermoplastic polyurethane base material by using a mixer, and then uniformly mixing the thermoplastic polyurethane base material in a double-screw extruder, wherein the sheet pulling step comprises the steps of pulling the mixed thermoplastic polyurethane base material through a sheet die head to form a base material, then using a four-roller calender to perform sheet thickness setting on the base material to prepare a base material layer, and the attaching step comprises the steps of sequentially arranging the wear-resistant layer, the printing layer and the base material layer from top to bottom, and performing hot-press attachment to prepare the thermoplastic polyurethane floor.

The process for producing a thermoplastic polyurethane flooring according to the foregoing embodiment, wherein the temperature of the twin-screw extruder at the sheet pulling step may be 120 ℃ to 220 ℃.

The process for manufacturing a thermoplastic polyurethane flooring according to the foregoing embodiment, wherein the temperature of the applying step may be 120 ℃ to 220 ℃ and the pressure of the applying step is 3kg/cm²To 50kg/cm²。

Advantageous effects

The thermoplastic polyurethane floor controls the hardness of the floor through the formula of the primer layer, so that the application range of the thermoplastic polyurethane floor is wide, glue is not needed for the lamination of all layers of the floor, the raw materials and the manufacturing cost are saved, and the requirement of environmental protection is met.

The thermoplastic polyurethane does not contain plasticizer and formaldehyde, has the advantages of high surface hardness, wear resistance, cold resistance, water resistance, recoverability, light weight and the like, and can overcome the defects of the traditional polyvinyl chloride plastic floor. In addition, the formula of the primer layer can be adjusted according to the requirements of different hardness, and a proper polyurethane reclaimed material is added to reduce the cost, and in the production process, glue is not needed for the bonding among the wear-resistant layer, the printing layer and the primer layer, and a roller calender or a flat plate hot press can be directly used for hot-press bonding, so that the manufacturing cost is saved, and the environment-friendly thermoplastic polyurethane floor is developed.

Drawings

FIG. 1 is an exploded view of a thermoplastic polyurethane flooring according to one embodiment of the present invention;

FIG. 2 is a flow chart illustrating the steps of a process for manufacturing a thermoplastic polyurethane flooring according to another embodiment of the present invention;

100: a thermoplastic polyurethane floor; 110: a wear layer; 120: printing layer; 130: a primer layer; 200: a production process of the thermoplastic polyurethane floor; 210: a mixing step; 220: pulling a piece; 230: and (5) attaching.

Detailed Description

The embodiments of the present invention will be described in further detail with reference to the drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Embodiments of the invention are discussed in more detail below. However, this embodiment may be an application of various inventive concepts, which may be embodied within various specific ranges. The specific embodiments are for purposes of illustration only and are not to be construed as limiting the scope of the disclosure.

< thermoplastic polyurethane flooring >

Referring to fig. 1, an exploded view of athermoplastic polyurethane floor 100 according to an embodiment of the present invention is shown. In fig. 1, athermoplastic polyurethane flooring 100 comprises awear layer 110, aprint layer 120, and aprimer layer 130.

In detail, the wear-resistant layer 110 is made of thermoplastic polyurethane, which can increase the wear-resistant, waterproof, anti-slip and anti-corrosion properties of thethermoplastic polyurethane floor 100. Theprinting layer 120 is connected to the lower portion of thewear layer 110 and made of thermoplastic polyurethane, and asurface 121 of theprinting layer 120 is printed with a pattern texture, which may be but is not limited to marble, solid wood, and other patterns and colors, and may be printed on thesurface 121 of theprinting layer 120 by offset printing, silk screen printing, or gravure printing, which increases the aesthetic property of thethermoplastic polyurethane floor 100. Theprimer layer 130 is connected below theprinting layer 120 and is made of a thermoplastic polyurethane primer, wherein the thermoplastic polyurethane primer comprises, by weight, 1-50 parts of polyurethane polymer, 50-100 parts of calcium carbonate, 1-20 parts of polyurethane recycled material, 1-30 parts of Polyacetal (POM) or Polyamide (PA) or acrylonitrile-butadiene-styrene polymer (ABS) or polypropylene (PP), and 1-10 parts of lubricant.

Accordingly, thethermoplastic polyurethane flooring 100 of the present invention is composed of thewear layer 110, theprinting layer 120 and theprimer layer 130 in sequence from top to bottom, wherein the thickness of thewear layer 110 may be, but not limited to, 0.05mm to 3.0mm, the thickness of theprinting layer 120 may be, but not limited to, 0.05mm to 1.5mm, and the thickness of theprimer layer 130 may be, but not limited to, 0.5mm to 8.0 mm.

The polyurethane polymer in theprimer layer 130 of the present invention can be any polyurethane polymer known in the art or in the literature, and only needs to have a proper molecular weight, wherein the polyurethane polymer is formed by polymerizing isocyanate, polyol and a chain extender.

The isocyanate can be one kind of isocyanate, or can be formed by mixing more than two kinds of isocyanates in any proportion. The average functionality of the isocyanate is greater than or equal to 2, for example, the isocyanate can be an isocyanate containing two isocyanate groups, an isocyanate containing three isocyanate groups, an isocyanate containing more isocyanate groups, or a combination thereof, but the use of isocyanates having a functionality of 3 or more in large amounts should be avoided so as not to cause crosslinking of the polyurethane polymer.

The isocyanate may be selected from aromatic diisocyanates, aliphatic diisocyanates, cycloaliphatic diisocyanates, or combinations thereof. For example, the aromatic diisocyanate may be, but is not limited to, 4 '-diphenylmethane diisocyanate (MDI), 4' -diphenylmethane diisocyanate (MDI), 2 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, naphthalene-1, 5-diisocyanate (NDI), Toluene Diisocyanate (TDI), tetramethylxylene diisocyanate, toluene diisocyanate, dimethylbiphenyl diisocyanate (TODI), or a combination thereof. The aliphatic diisocyanate may be, but is not limited to, dodecane diisocyanate, dimer fatty acid diisocyanate, 4,4' -dibenzyl diisocyanate, 1, 6-diisocyanato-2, 4, 4-trimethylhexane, 1, 4-diisocyanatobutyl, 1, 6-diisocyanatohexyl (HDI), 1, 4-diisocyanatetetramhoxybutyl, dicyclohexylmethane diisocyanate, 1, 10-diisocyanatododecane, 1, 12-diisocyanatododecane, or combinations thereof. The cycloaliphatic diisocyanate may be, but is not limited to, 4-dicyclohexylmethane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4-diisocyanatocyclohexane, 1-isocyanomethyl-3-isocyano-1, 5, 5-trimethylcyclohexane (also known as isophorone diisocyanate, IPDI), hydrogenated MDI ([ H ]12MDI), partially hydrogenated MDI ([ H ]6MDI), Xylene Diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), dialkylene diphenylmethane diisocyanate, tetraalkylene diphenylmethane diisocyanate, or combinations thereof.

The polyol may be selected from polyester polyols, polyether polyols having a molecular weight of 500 to 8000, or combinations thereof. The polyester polyols may be prepared by transesterification or esterification of one or more diols with one or more dicarboxylic acids, wherein the molar ratio of dicarboxylic acid to diol may generally be selected from 0.950 to 1.000, in order to obtain linear chains with predominantly terminal hydroxyl groups, and the polyester polyols may further comprise various lactones, for example polycaprolactone made from caprolactone and a bifunctional initiator such as diethylene glycol.

The dicarboxylic acids of the polyester polyol may be used alone or in combination of two or more, and may be selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or combinations thereof. The dicarboxylic acid has a total of 4 to 15 carbon atoms, which may be, but is not limited to, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, etc., anhydrides of the above dicarboxylic acids may also be used, which may be, but is not limited to, phthalic anhydride, tetrahydrophthalic anhydride, etc., and adipic acid is preferred in the present invention.

The dihydric alcohol of the polyester polyol may be singly or in combination of two or more, and may be selected from aliphatic dihydric alcohol, alicyclic dihydric alcohol, aromatic dihydric alcohol or a combination thereof. The diol has a total of 2 to 12 carbon atoms, which may be, but is not limited to, ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 10-decanediol, 1, 12-dodecanediol, etc., while 1, 4-butanediol is preferred in the present invention.

The polyether polyols may be reacted by means of a diol or polyol, preferably an alkyl diol (diol) or glycol, having 2 to 15 carbon atoms with an ether comprising an alkylene oxide having 2 to 6 carbon atoms, preferably ethylene oxide or propylene oxide or mixtures thereof. For example, by first reacting propylene glycol with propylene oxide and then with ethylene oxide to produce a polyether polyol, the primary hydroxyl groups generated from ethylene oxide are more reactive than the secondary hydroxyl groups, and thus ethylene oxide is the preferred choice.

The polyether polyol may be, but is not limited to, polyethylene glycol obtained by reacting ethylene glycol with ethylene oxide, polypropylene glycol obtained by reacting propylene glycol with propylene oxide, polytetramethylene ether glycol obtained by reacting tetrahydrofuran with water, polytetramethylene ether glycol (PTMEG), or a combination thereof, and the present invention is preferably polytetramethylene ether glycol. The polyether polyol may be, but not limited to, an ethylenediamine adduct obtained by reacting ethylenediamine with propylene oxide, a diethylenetriamine adduct obtained by reacting diethylenetriamine with propylene oxide, and the like. In addition, copolyethers comprising the reaction product of tetrahydrofuran and ethylene oxide or tetrahydrofuran and propylene oxide may also be used in the present invention.

The chain extender may include a glycol and may be selected from aliphatic alcohol chain extenders, aromatic alcohol chain extenders, alicyclic alcohol chain extenders, or mixtures thereof. The aliphatic alcohol-based chain extender has 2 to 12 carbon atoms, and may be, but is not limited to, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-methyl-2, 4-pentanediol, triethylene glycol, neopentyl glycol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, trimethylolpropane, glycerol, diethylene glycol, and the like. The aromatic alcohol-based chain extender may be, but is not limited to, benzene glycol, xylene glycol, and the like. The alicyclic alcohol chain extender may be, but is not limited to, 1, 4-cyclohexanediol, hydrogenated bisphenol a, and the like.

The lubricant in theprimer layer 130 of the present invention is used to improve the adhesion of the equipment (such as roller) during the manufacturing process. For example, the slip agent may be, but is not limited to, silicones, amines, nonionic surfactants, hydrocarbon waxes, chlorinated hydrocarbons, fluorocarbons, fatty acids, esters, alcohols, polyglycols, metal soaps, metal salts, inorganic species, and the like, wherein the silicones may comprise dimethylpolysiloxanes and modifications thereof, the amines may comprise oleamides, erucamides, stearamides, bis-fatty amides, bisamides, fatty acids may comprise hydroxy fatty acids, esters may comprise lower alcohol esters, alcohols may comprise polyols, metal salts may comprise lauric oils, stearic acids, and stearic acids are preferred herein.

< production Process of thermoplastic polyurethane flooring >

Referring to fig. 2, a flow chart of steps of aprocess 200 for manufacturing a thermoplastic polyurethane floor according to another embodiment of the invention is shown. Theprocess 200 for producing a thermoplastic polyurethane flooring comprisessteps 210, 220 and 230.

Step 210 is a mixing step, in which the thermoplastic polyurethane base material is proportioned according to a mixture ratio, premixed by a mixer, and then uniformly mixed in a twin-screw extruder, wherein the mixer can also be an internal mixer, and the temperature of the twin-screw extruder can be 120 ℃ to 220 ℃. For the thermoplastic polyurethane primer, reference is made to the above description, which is not repeated herein.

Step 220 is a pulling-on step, which is to pull the mixed thermoplastic polyurethane base material through a sheet die head to form a base material, and then to perform sheet thickness setting on the base material through a four-roll calender to form a base material layer, wherein the temperature of the pulling-on step can be 120 ℃ to 220 ℃.

Step 230 is a bonding step, in which the wear layer, the printing layer and the primer layer are sequentially arranged from top to bottom, and hot-pressed to form a thermoplastic polyurethane floor, wherein the temperature in the bonding step can be 120 ℃ to 220 ℃, and the pressure in the bonding step is 3kg/cm²To 50kg/cm². In detail, the wear-resistant layer, the printing layer and the primer layer are cut to a suitable size in advance and then arranged from top to bottom in sequence, wherein the surface of the printing layer containing the pattern texture faces the wear-resistant layerAnd (3) placing in the direction of (1), and performing hot-pressing and laminating by using a flat hot press to prepare the thermoplastic polyurethane floor. Or after the sheet pulling step, the wear-resistant layer, the printing layer and the primer layer are sequentially laminated on line by hot pressing through rollers to prepare the thermoplastic polyurethane floor.

< examples/comparative examples >

The primer layer of comparative examples 1 and 2 of the present invention is prepared according to the components and weight parts of Table I.

Firstly, mixing and uniformly stirring the polyurethane polymer, the calcium carbonate, the polyurethane reclaimed material and the lubricant according to the weight part of the first formula, then putting the mixture into a double-screw extruder, carrying out sheet pulling at 180 ℃, and then carrying out hot pressing on the mixture by using rollers to prepare a primer layer plate and measuring the hardness of the primer layer plate. The hardness of comparative example 1 was 43D and that of comparative example 2 was 52D, and it was found that the polyol molecular weight in the polyurethane polymer was increased, the hardness of the primer layer was increased, and the slip agent was able to improve the tack of the primer layer on the roller.

The primer layer of examples 1 to 4 of the present invention is prepared according to the components and weight parts of table two, wherein the polyol molecular weight of the polyurethane polymer is 4000.

Firstly, mixing and uniformly stirring polyurethane polymer, calcium carbonate, polyurethane reclaimed materials, POM (polyoxymethylene), ABS (acrylonitrile butadiene styrene) or PA (polyamide) or PP (polypropylene) and a lubricant according to the weight part of the second formula, then putting the mixture into a double-screw extruder, carrying out sheet pulling at 180 ℃, and then carrying out hot pressing on the mixture by using rollers to prepare a primer layer plate, and measuring the hardness of the primer layer plate. It is understood that the hardness of example 1 is 74D, the hardness of example 2 is 67D, the hardness of example 3 is 72D, the hardness of example 4 is 66D, and the hardness of comparative examples 1 to 4 and comparative example 2 is increased by adding POM, ABS, PA, or PP.

In conclusion, the thermoplastic polyurethane material used in the invention has the advantages that the thermoplastic polyurethane does not contain plasticizer and formaldehyde, has the advantages of high surface hardness, wear resistance, cold resistance, water resistance, recoverability, light weight and the like, and can overcome the defects of the traditional polyvinyl chloride plastic floor. In addition, the formula of the primer layer can be adjusted according to the requirements of different hardness, and a proper polyurethane reclaimed material is added to reduce the cost, and in the production process, glue is not needed for the bonding among the wear-resistant layer, the printing layer and the primer layer, and a roller calender or a flat plate hot press can be directly used for hot-press bonding, so that the manufacturing cost is saved, and the environment-friendly thermoplastic polyurethane floor is developed.

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (10)

1. A thermoplastic polyurethane flooring, comprising:

the wear-resistant layer is made of a thermoplastic polyurethane material;

the printing layer is made of thermoplastic polyurethane and is connected below the wear-resistant layer, and one surface of the printing layer is printed with a pattern texture; and

the base material layer is made of a thermoplastic polyurethane base material and is connected below the printing layer, and the thermoplastic polyurethane base material comprises, by weight, 1-50 parts of polyurethane polymer, 50-100 parts of calcium carbonate, 1-20 parts of polyurethane reclaimed material, 1-30 parts of Polyacetal (POM), Polyamide (PA), acrylonitrile-butadiene-styrene polymer (ABS) or polypropylene (PP) and 1-10 parts of lubricant.

2. The thermoplastic polyurethane flooring according to claim 1, wherein the polyurethane polymer is formed by polymerizing an isocyanate, a polyol, and a chain extender.

3. The thermoplastic polyurethane floor of claim 2, wherein the molecular weight of the polyol is 500 to 8000.

4. The thermoplastic polyurethane flooring of claim 1, wherein said wear layer has a thickness of 0.05mm to 3.0 mm.

5. The thermoplastic polyurethane floor of claim 1, wherein the thickness of the print layer is 0.05mm to 1.5 mm.

6. The thermoplastic polyurethane flooring according to claim 1, wherein the primer layer has a thickness of 0.5mm to 8.0 mm.

7. A process for producing the thermoplastic polyurethane flooring according to claim 1, comprising:

a mixing step, namely metering the thermoplastic polyurethane base material according to a ratio, premixing by using a mixer, and then feeding into a double-screw extruder for uniformly mixing;

a sheet pulling step, in which the mixed thermoplastic polyurethane base material is subjected to sheet pulling through a sheet die head to form a base material, and then the base material is subjected to sheet thickness setting through a four-roller calender to form the base material layer; and

and a laminating step, namely arranging the wear-resistant layer, the printing layer and the primer layer from top to bottom in sequence, and performing hot-press lamination to prepare the thermoplastic polyurethane floor.

8. The process for producing a thermoplastic polyurethane flooring according to claim 7, wherein the temperature of the twin-screw extruder in the pulling-on step is 120 ℃ to 220 ℃.

9. The process for producing a thermoplastic polyurethane floor according to claim 7, wherein the temperature in the applying step is 120 ℃ to 220 ℃.

10. The process for producing a thermoplastic polyurethane floor as claimed in claim 7, wherein the pressure in the applying step is 3kg/cm²To 50kg/cm²。

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