CN117162622A - Degradable floor and preparation method thereof - Google Patents
Degradable floor and preparation method thereof Download PDFInfo
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- CN117162622A CN117162622A CN202311144184.4A CN202311144184A CN117162622A CN 117162622 A CN117162622 A CN 117162622A CN 202311144184 A CN202311144184 A CN 202311144184A CN 117162622 A CN117162622 A CN 117162622A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 claims abstract description 124
- 230000001070 adhesive effect Effects 0.000 claims abstract description 124
- 239000010410 layer Substances 0.000 claims abstract description 113
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 89
- 239000002344 surface layer Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 98
- 229960004441 tyrosine Drugs 0.000 claims description 49
- 235000019710 soybean protein Nutrition 0.000 claims description 47
- 229920005989 resin Polymers 0.000 claims description 29
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- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
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- 229910052618 mica group Inorganic materials 0.000 claims description 13
- 229920005749 polyurethane resin Polymers 0.000 claims description 13
- QMZHDWXCDDBKJY-VIFPVBQESA-N (2s)-2-(hydroxymethylamino)-3-(4-hydroxyphenyl)propanoic acid Chemical compound OCN[C@H](C(O)=O)CC1=CC=C(O)C=C1 QMZHDWXCDDBKJY-VIFPVBQESA-N 0.000 claims description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 12
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- 239000000428 dust Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 4
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 4
- -1 pentaerythritol ester Chemical class 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
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- 235000021355 Stearic acid Nutrition 0.000 claims description 2
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- 229910021538 borax Inorganic materials 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
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- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- ODHUFJLMXDXVRC-UHFFFAOYSA-N tripropyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCOC(=O)CC(O)(C(=O)OCCC)CC(=O)OCCC ODHUFJLMXDXVRC-UHFFFAOYSA-N 0.000 claims description 2
- XYRAEZLPSATLHH-UHFFFAOYSA-N trisodium methoxy(trioxido)silane Chemical compound [Na+].[Na+].[Na+].CO[Si]([O-])([O-])[O-] XYRAEZLPSATLHH-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 54
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- 238000003756 stirring Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- 238000009408 flooring Methods 0.000 description 5
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- MJEUSIKCFAYXPP-UHFFFAOYSA-N azanium pentane-2,4-dione acetate Chemical compound [NH4+].CC([O-])=O.CC(=O)CC(C)=O MJEUSIKCFAYXPP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
Abstract
The invention discloses a degradable floor and a preparation method thereof. The degradable floor prepared by the invention is prepared into a composite floor by adopting a multilayer structure, and comprises a surface layer, a middle layer and a first bottom layer, wherein the surface layer comprises a wear-resistant layer, a decorative layer and a second bottom layer. The invention adopts the structure of the composite floor and the environment-friendly degradable raw materials, and the prepared degradable floor has good stability, strong durability and high environment-friendly property by strictly controlling the preparation process conditions. Compared with the prior art, the modified soy protein adhesive is adopted, so that the stability and antibacterial property of the degradable floor are improved, the formaldehyde release amount of the floor is reduced, and the environmental pollution is reduced. The preparation method is simple, is convenient for mass production and is worthy of popularization.
Description
Technical Field
The invention relates to the technical field of layered products composed of synthetic resin, in particular to a degradable floor and a preparation method thereof.
Background
With the improvement of environmental awareness, more and more people choose to use the degradable floor. The degradable floor is a green floor with environmental protection consciousness, the performance index of the degradable floor is equivalent to that of the traditional floor, and the manufacturing materials and the production process accord with the environmental protection standard. The degradable floor not only has similar physical properties as the traditional floor, such as wear resistance, water resistance and the like, but also has better environmental protection performance, and can effectively reduce the release of harmful gases such as indoor formaldehyde and the like. In addition, the degradable floor is made of biodegradable materials, such as natural high molecular compounds of starch, cellulose and the like, which can be decomposed in natural environment and are harmless to the environment. While the traditional floor materials such as wood, plastic and the like can be used for manufacturing floors, the traditional floor materials cannot be degraded, and can pollute the environment after long-term use.
CN217379640U discloses a mineral substance degradable floor, which comprises a floor body, wherein the floor body comprises a wear-resistant layer, a decorative layer, a covering layer, a substrate layer, a buffer layer and a waterproof layer from top to bottom in sequence, and each layer is fixedly connected. According to the mineral substance degradable floor, through the arrangement of the floor body, the characteristics of each layer of material in the floor body are utilized, so that the attractive appearance and the decoration of the floor body are improved, the mineral substance degradable floor has high wear resistance, good damping effect and waterproof performance, the biodegradability of the floor body is correspondingly improved, and the pollution to the environment is avoided. Although the degradable floor provided by the invention has better environmental protection, the durability of the degradable floor is still to be explored.
CN111873592B discloses a degradable floor and a preparation method thereof. The degradable floor comprises a surface layer, a middle layer and a first bottom film layer from top to bottom, wherein the surface layer comprises a TPU wear-resistant layer, a decorative layer and a second bottom film layer from top to bottom, and the second bottom film layer is in contact with the middle layer. According to the invention, the degradable material TPU is used as a raw material for preparing the wear-resistant layer and the negative film layer, and the wood fiber is used as a main component for preparing the middle layer, so that the degradable part of the integral floor accounts for 95-100%, and the environmental protection property of the integral floor is improved. According to the invention, the preparation raw materials of the degradable floor are reasonably proportioned, and the floor preparation process conditions are strictly controlled, so that the prepared degradable floor has better fireproof performance and stability, but has weaker mildew resistance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a degradable floor and a method for manufacturing the same. The preparation raw materials are environment-friendly, the proportion is reasonable, the preparation process conditions are strict, and the prepared degradable floor has good stability, durability, antibacterial property and environment friendliness.
The invention aims at providing a preparation method of a degradable floor, which comprises the following steps:
(1) Preparation of the wear-resistant layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor and acrylic copolymer in a mixer; plasticizing by using an internal mixer; press-forming by a press; cutting after cooling to obtain a wear-resistant layer;
(2) Preparation of the second backsheet layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor, acrylic copolymer, mica powder and lubricant in a mixer; plasticizing by using an internal mixer; press-forming by a press; cooling and cutting to obtain a second negative film layer;
(3) Preparation of the surface layer: laminating the wear layer, the decorative layer and the second backsheet; pushing the stacked materials into a press after the stacking, and discharging after hot pressing treatment and cold pressing treatment to obtain a surface layer.
(4) Preparation of an intermediate layer: mixing cork wood dust, a fireproof agent, a waterproof agent and a preservative in a mixer to obtain a mixture; transferring the adhesive and the mixture into a high-speed mixer for uniform mixing; extruding and molding through an extruder to obtain an intermediate layer;
(5) Preparation of the first backsheet layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor, acrylic copolymer, mica powder and lubricant in a mixer; plasticizing by using an internal mixer; press-forming by a press; cooling and cutting to obtain a first negative film layer;
(6) Carrying out UV heat treatment on the surface layer obtained in the step (3);
(7) Attaching the surface layer subjected to UV heat treatment to the intermediate layer obtained in the step (4) through an adhesive, wherein the intermediate layer is in contact with a second bottom layer in the surface layer; adhering the first bottom sheet layer obtained in the step (5) to the middle layer through an adhesive to obtain a composite board, wherein the adhesive is a soybean protein series adhesive;
(8) And (3) carrying out hot pressing treatment on the composite board obtained in the step (7) through a constant-temperature hot press to obtain the degradable floor.
Preferably, the weight parts of the raw material components are as follows:
wear-resistant layer: 100 parts of polylactic acid resin, 2-5 parts of plasticizer, 0.1-1 part of hydrolysis resistance agent and 0.5-1 part of acrylic copolymer;
a second backsheet layer: 100 parts of polylactic acid resin, 15-25 parts of plasticizer, 2-10 parts of hydrolysis resistance agent, 1-10 parts of acrylic copolymer, 300-500 parts of mica powder and 3-8 parts of lubricant;
a first backsheet layer: 100 parts of polylactic acid resin, 15-25 parts of plasticizer, 2-10 parts of hydrolysis resistance agent, 1-10 parts of acrylic copolymer, 300-500 parts of mica powder and 3-8 parts of lubricant;
an intermediate layer: 50-80 parts of cork wood dust, 10-15 parts of adhesive, 2-5 parts of fireproof agent, 2-5 parts of waterproof agent and 0.1-1 part of preservative.
Further preferably, the plasticizer is selected from one of tricresyl phosphate, dibutyl phthalate and tripropyl citrate; the hydrolysis resistance agent is selected from one of polyurethane resin, polyester polyol and polyacrylate resin; the lubricant is selected from one of stearic acid, calcium stearate and magnesium stearate; the cork wood chips are selected from one of pine wood chips, eucalyptus wood chips and willow wood chips; the adhesive is polyurethane resin; the fire retardant is one of melamine, pentaerythritol ester and ammonium polyphosphate; the waterproof agent is selected from one of methyltrichlorosilane, polyurethane waterproof paint and sodium methyl silicate; the preservative is selected from one of ACQ wood preservative, sodium fluoride and borax.
Preferably, in the step (7), the adhesive coating amount is 180-250g/m 2 The adhesive is one of a soybean protein adhesive, a polyamide epichlorohydrin resin modified soybean protein adhesive, a glutaraldehyde modified soybean protein adhesive, a hydroxymethyl L-tyrosine modified soybean protein adhesive and a tetraepoxy L-tyrosine modified soybean protein adhesive.
Preferably, the tetraepoxy L-tyrosine modified soybean protein adhesive consists of 1-10wt% of tetraepoxy L-tyrosine and 90-99wt% of soybean protein adhesive.
Preferably, in the step (1), the plasticizing temperature is controlled to be 110-120 ℃, the press molding temperature is controlled to be 100-110 ℃, the wear-resistant layer is cut after cooling to 35-25 ℃, and the thickness of the wear-resistant layer is 0.5-1mm.
Preferably, in the step (2), the plasticizing temperature is controlled to be 130-140 ℃, the press molding temperature is controlled to be 120-135 ℃, the second negative film layer is cut after being cooled to 35-25 ℃, and the thickness of the second negative film layer is 0.5-1mm.
Preferably, in the step (3), the decorative layer is a floor decorative color film; the hot press forming temperature is controlled to be 120-130 ℃, the hot press time is controlled to be 20-30min, the cold press forming temperature is controlled to be 35-25 ℃, the cold press time is controlled to be 20-30min, and the thickness of the surface layer is 1-2mm.
Preferably, in the step (4), the extrusion temperature is 110-130 ℃, and the thickness of the intermediate layer is 5-8mm.
Preferably, in the step (5), the plasticizing temperature is controlled to be 130-140 ℃, the press molding temperature is controlled to be 120-135 ℃, the first negative film layer is cut after being cooled to 35-25 ℃, and the thickness of the first negative film layer is 1-2mm.
Preferably, in the step (6), the illumination intensity of the UV heat treatment is 400-600mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The speed is 14-18m/min.
Preferably, in the step (8), the hot press forming temperature is controlled to be 120-130 ℃, the hot press time is controlled to be 20-30min, and the thickness of the degradable floor is 7-12mm.
The second object of the invention is to provide a degradable floor, which is prepared by the method.
The invention has the beneficial effects that:
1. compared with the prior art, the invention uses the soybean protein series adhesive as the adhesive of the degradable floor, the soybean protein adhesive is derived from natural biological material soybean, can be biodegraded, does not contain formaldehyde and other harmful substances, and improves the degradability and environmental protection of the floor. According to the invention, the soy protein adhesive is modified by using the tetraepoxy L-tyrosine, so that not only is the bonding strength of the degradable wood board improved, but also the mold resistance of the degradable wood board is improved, and the service life of the degradable wood board prepared by the invention is prolonged. The soy protein molecules in the soy protein adhesive are mainly connected by hydrogen bonds, ionic bonds and intermolecular forces, which are easily destroyed by water, and the crosslinked structure of the cured adhesive is not tight and stable enough. With the addition of tetraepoxy L-tyrosine, the tetraepoxy L-tyrosine and the soy protein construct more stable covalent bond acting force among soy protein molecules through a crosslinking reaction, so that the formation of a tighter adhesive molecular network structure is promoted, and the shearing strength of the adhesive is gradually increased. The soy protein adhesive is modified by the tetraepoxy L-tyrosine, so that the complex structure of soy protein molecules is improved, a firm plate gluing bond is formed between the modified soy protein adhesive and the degradable floor, and the mechanical interlocking between the modified soy protein adhesive and the degradable floor is enhanced, thereby being beneficial to providing better performance and better floor adhesion, and obviously improving the gluing strength of the degradable floor. Meanwhile, with the addition of the tetraepoxy L-tyrosine, the epoxy group of the tetraepoxy L-tyrosine interacts with active groups (such as carboxyl, amino, sulfhydryl and the like) of the mould protein to prevent the normal metabolism of the mould protein, so that a certain antibacterial effect is achieved, and the degradable floor prepared by the invention has better mould proof performance.
2. Compared with the prior art, the degradable floor prepared by the invention adopts a multi-layer structure to prepare the composite floor, and comprises a surface layer, a middle layer and a first bottom layer, wherein the surface layer comprises a wear-resistant layer, a decorative layer and a second bottom layer. This construction provides a significant improvement in both stability and durability of the floor. Particularly, the surface is covered with a wear-resistant layer, so that the wear resistance of the floor is improved. The invention uses polylactic acid resin as a raw material for preparing the degradable floor, wherein the polylactic acid resin is a biodegradable material, is obtained by chemical modification of plant starch, can be naturally degraded, and does not cause long-term pollution to the environment. The polylactic acid resin can be formed by melting at high temperature, has good processing performance, and simultaneously has good mechanical properties, and can meet the mechanical property requirements of the degradable floor in the use process. The raw materials and the manufacturing process adopted by the invention for preparing the degradable floor are beneficial to improving the degradability and stability of the floor.
3. The preparation method has the advantages that the raw materials are prepared in reasonable proportion, and the preparation process conditions are strictly controlled, so that the prepared degradable floor has good stability, durability, antibacterial property and environmental protection. The invention has simple manufacturing steps, is convenient for batch processing and production, and is worth popularizing.
Drawings
FIG. 1 is a schematic diagram of the dimensional area and the direction of the tensile force applied during the test of the sample of the degradable floor glue strength test example 1.
Detailed Description
The parameters and sources of some of the substances in the examples are as follows:
polylactic acid resin: white powder, 100 mesh, manufacturer, name: 7001D.
Polyurethane resin: white milky suspension, purity: AR, manufacturer is Guangdong Weng Jiang chemical agent Co., ltd., product number: WB11060.
Acrylic copolymer: the purity of the white emulsion is 98%, and the manufacturer is Hubei Lishengchang new material science and technology Co., ltd., product number: 25035-69-2.
Mica powder: white powder, 800 mesh, relative density: 2.77g/cm 3 The manufacturer is Hubei real biosciences limited company.
Pine wood chips: purchased from general pine wood processing plants, without particular limitation.
ACQ wood preservative: the total solid content of the Bao-blue liquid is more than or equal to 15%, and the manufacturer is Hangzhou Qian-located biotechnology Co.
Polyamide epichlorohydrin resin: pale yellow transparent liquid, solid content: 12.5+ -0.5%, viscosity: 50cp, pH:4.5, the manufacturer is the Taan City Dow Co., ltd., model: ts1022.
Floor decoration color film: purchased from Jiangsu Bo New Material technologies Co., ltd., product number: 010.
example 1
A degradable floor is prepared by the following steps:
(1) Preparation of the wear-resistant layer: mixing 100kg of polylactic acid resin, 3kg of tricresyl phosphate, 0.3kg of polyurethane resin and 0.5kg of acrylic copolymer in a mixer; plasticizing at 110 deg.c with an internal mixer; pressing and forming at 110 ℃ through a press; cooling to 30deg.C, cutting to obtain wear-resistant layer with thickness of 0.5mm;
(2) Preparation of the second backsheet layer: mixing 100kg of polylactic acid resin, 20kg of tricresyl phosphate, 5kg of polyurethane resin, 5kg of acrylic copolymer, 450kg of mica powder and 5kg of magnesium stearate in a mixer; plasticizing at 135 deg.c with an internal mixer; pressing and forming at 130 ℃ through a press; cooling to 30deg.C, cutting to obtain second negative film layer with thickness of 0.5mm;
(3) Preparation of the surface layer: laminating the wear layer, the decorative layer and the second backsheet; pushing the stacked materials into a press after the stacking is completed, and carrying out hot pressing treatment for 30min at the temperature of 120 ℃; then cold-pressing for 30min at 30 ℃; unloading to obtain a surface layer with the thickness of 1mm;
(4) Preparation of an intermediate layer: mixing 60kg of pine wood chips, 2kg of melamine, 2kg of methyltrichlorosilane and 0.2kg of ACQ wood preservative in a mixer to obtain a mixture; transferring 15kg of polyurethane resin and the mixture into a high-speed mixer for uniform mixing; extruding and molding the intermediate layer with the thickness of 6mm by an extruder at 130 ℃;
(5) Preparation of the first backsheet layer: mixing 100kg of polylactic acid resin, 20kg of tricresyl phosphate, 5kg of polyurethane resin, 5kg of acrylic copolymer, 450kg of mica powder and 5kg of magnesium stearate in a mixer; plasticizing at 135 deg.c with an internal mixer; pressing and forming at 130 ℃ through a press; cooling to 30deg.C, cutting to obtain a first film layer with thickness of 2mm;
(6) The surface layer obtained in the step (3) is irradiated with 500mJ/cm 2 Carrying out UV heat treatment at the speed of 16 m/min;
(7) According to 200g/m 2 The surface layer after UV heat treatment is stuck to the middle layer obtained in the step (4) through an adhesive, wherein the middle layer is contacted with the second bottom layer in the surface layer; according to 200g/m 2 The first negative film layer obtained in the step (5) is adhered to the middle layer through an adhesive to obtain a composite board;
(8) And (3) carrying out hot pressing treatment on the composite board obtained in the step (7) for 30min at 120 ℃ by a constant-temperature hot press to obtain the degradable floor with the thickness of 9mm.
The decorative layer is a floor decorative color film.
The adhesive is a soybean protein adhesive, and the preparation method thereof comprises the following steps: 12kg of soy protein isolate and 88kg of deionized water were stirred in a vessel at room temperature for 10min to form a homogeneous system to obtain a soy protein adhesive based on soy protein isolate.
Example 2
A degradable floor is prepared by the following steps:
(1) Preparation of the wear-resistant layer: mixing 100kg of polylactic acid resin, 3kg of tricresyl phosphate, 0.3kg of polyurethane resin and 0.5kg of acrylic copolymer in a mixer; plasticizing at 110 deg.c with an internal mixer; pressing and forming at 110 ℃ through a press; cooling to 30deg.C, cutting to obtain wear-resistant layer with thickness of 0.5mm;
(2) Preparation of the second backsheet layer: mixing 100kg of polylactic acid resin, 20kg of tricresyl phosphate, 5kg of polyurethane resin, 5kg of acrylic copolymer, 450kg of mica powder and 5kg of magnesium stearate in a mixer; plasticizing at 135 deg.c with an internal mixer; pressing and forming at 130 ℃ through a press; cooling to 30deg.C, cutting to obtain second negative film layer with thickness of 0.5mm;
(3) Preparation of the surface layer: laminating the wear layer, the decorative layer and the second backsheet; pushing the stacked materials into a press after the stacking is completed, and carrying out hot pressing treatment for 30min at the temperature of 120 ℃; then cold-pressing for 30min at 30 ℃; unloading to obtain a surface layer with the thickness of 1mm;
(4) Preparation of an intermediate layer: mixing 60kg of pine wood chips, 2kg of melamine, 2kg of methyltrichlorosilane and 0.2kg of ACQ wood preservative in a mixer to obtain a mixture; transferring 15kg of polyurethane resin and the mixture into a high-speed mixer for uniform mixing; extruding and molding the intermediate layer with the thickness of 6mm by an extruder at 130 ℃;
(5) Preparation of the first backsheet layer: mixing 100kg of polylactic acid resin, 20kg of tricresyl phosphate, 5kg of polyurethane resin, 5kg of acrylic copolymer, 450kg of mica powder and 5kg of magnesium stearate in a mixer; plasticizing at 135 deg.c with an internal mixer; pressing and forming at 130 ℃ through a press; cooling to 30deg.C, cutting to obtain a first film layer with thickness of 2mm;
(6) The surface layer obtained in the step (3) is irradiated with 500mJ/cm 2 Carrying out UV heat treatment at the speed of 16 m/min;
(7) According to 200g/m 2 The surface layer after UV heat treatment is adhered to the middle layer obtained in the step (4) through an adhesive, wherein the middle layer is adhered to the middle layerThe interlayer is in contact with the second underlayer in the surface layer; according to 200g/m 2 The first negative film layer obtained in the step (5) is adhered to the middle layer through an adhesive to obtain a composite board;
(8) And (3) carrying out hot pressing treatment on the composite board obtained in the step (7) for 30min at 120 ℃ by a constant-temperature hot press to obtain the degradable floor with the thickness of 9mm.
The decorative layer is a floor decorative color film.
The adhesive is a polyamide epichlorohydrin resin modified soybean protein adhesive, and the preparation method comprises the following steps:
after 12kg of isolated soy protein and 64kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 24kg of polyamide epichlorohydrin resin with the soybean protein adhesive, and stirring for 1h at 25 ℃ to obtain the polyamide epichlorohydrin resin modified soybean protein adhesive.
Example 3
The degradable floor is different from the example 2 in that the adhesive is glutaraldehyde modified soybean protein adhesive, and the preparation method is as follows:
after 12kg of isolated soy protein and 76kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. 12kg glutaraldehyde and the soybean protein adhesive are mixed and stirred for 1h at 25 ℃ to obtain the glutaraldehyde modified soybean protein adhesive.
Example 4
The degradable floor is different from the example 2 in that the adhesive is hydroxymethyl L-tyrosine modified soybean protein adhesive, and the preparation method comprises the following steps:
uniformly mixing 25kg of L-tyrosine, 100kg of deionized water and 34kg of formaldehyde (40 wt%) aqueous solution, heating to 30 ℃, then adding 10kg of NaOH (40 wt%) aqueous solution, stirring for 48h under heat preservation, and finally freeze-drying for 12h to obtain the hydroxymethyl L-tyrosine.
After 9.6kg of isolated soy protein and 86.4kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 4kg of the obtained hydroxymethyl L-tyrosine with the soybean protein adhesive, and stirring at 25 ℃ for 20min to obtain the hydroxymethyl L-tyrosine modified soybean protein adhesive.
Example 5
The degradable floor is different from the example 2 in that the adhesive is a tetraepoxy L-tyrosine modified soy protein adhesive, the tetraepoxy L-tyrosine modified soy protein adhesive consists of 4wt% of tetraepoxy L-tyrosine and 96wt% of soy protein adhesive, and the preparation method comprises the following steps:
105kg of epichlorohydrin, 20kg of L-tyrosine and 2.5kg of tetrabutylammonium bromide were introduced into a device equipped with a stirrer and a condenser and stirred at 110℃for 3 hours. Subsequently, the excess epichlorohydrin was separated by vacuum distillation, 10kg of methylene chloride was added to the apparatus to dilute and dissolve the residue, and 36kg of 50wt% aqueous sodium hydroxide solution was slowly added to the apparatus, and stirring was continued at 25 ℃ for 5 hours. Finally, the sodium chloride is separated by adding deionized water for multiple extractions, and residual methylene dichloride and water are removed by vacuum distillation, so that the tetraepoxy L-tyrosine is obtained.
After 9.6kg of isolated soy protein and 86.4kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 4kg of the obtained tetraepoxy L-tyrosine with the soybean protein adhesive, and stirring for 30min at 25 ℃ to prepare the tetraepoxy L-tyrosine modified soybean protein adhesive.
In the embodiment, the epoxy groups on the epoxy chloropropane are successfully grafted to the amino, carboxyl and phenolic hydroxyl groups of the L-tyrosine by epoxidation by taking the L-tyrosine and the epoxy chloropropane as raw materials, so that the L-tyrosine is endowed with crosslinking performance and antibacterial performance, and the tetraepoxy L-tyrosine with a plurality of epoxy groups is obtained. The tetraepoxy L-tyrosine is mixed with the soybean protein adhesive, and the tetraepoxy L-tyrosine modified soybean protein adhesive is obtained through multiple chemical reactions between epoxy groups of the tetraepoxy L-tyrosine and active groups of soybean protein isolate, so that the crosslinking density and stability of the adhesive are improved.
Example 6
The difference between the degradable floor and the example 5 is that the added tetraepoxy L-tyrosine modified soybean protein adhesive consists of 1wt% of tetraepoxy L-tyrosine and 99wt% of soybean protein adhesive, and the preparation method is as follows:
after 9.9kg of isolated soy protein and 89.1kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 1kg of tetraepoxy L-tyrosine with the soy protein adhesive, and stirring for 30min at 25 ℃ to prepare the tetraepoxy L-tyrosine modified soy protein adhesive.
The preparation method of the tetraepoxy L-tyrosine is the same as that of the example 5.
Example 7
The difference between the degradable floor and the example 5 is that the added tetraepoxy L-tyrosine modified soybean protein adhesive consists of 6 weight percent of tetraepoxy L-tyrosine and 94 weight percent of soybean protein adhesive, and the preparation method comprises the following steps:
after 9.4kg of isolated soy protein and 84.6kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 6kg of tetraepoxy L-tyrosine with the soy protein adhesive, and stirring for 30min at 25 ℃ to prepare the tetraepoxy L-tyrosine modified soy protein adhesive.
The preparation method of the tetraepoxy L-tyrosine is the same as that of the example 5.
Example 8
The difference between the degradable floor and the example 5 is that the added tetraepoxy L-tyrosine modified soybean protein adhesive consists of 10 weight percent of tetraepoxy L-tyrosine and 90 weight percent of soybean protein adhesive, and the preparation method comprises the following steps:
after 9kg of isolated soy protein and 81kg of deionized water were stirred and mixed in a vessel, the pH was adjusted to 9 with an aqueous solution of sodium hydroxide (40 wt%) and then stirred at 50℃for 30 minutes to prepare a soy protein adhesive. Mixing 10kg of tetraepoxy L-tyrosine with the soy protein adhesive, and stirring for 30min at 25 ℃ to prepare the tetraepoxy L-tyrosine modified soy protein adhesive.
The preparation method of the tetraepoxy L-tyrosine is the same as that of the example 5.
Test example 1
Testing of glue strength of degradable floor
The degradable floors prepared in examples 1 to 5 were subjected to shear tests according to the procedure described in the national standard of China (GB/T17657-2022). The degradable floor was sawn off (25 mm. Times.100 mm) from the 400 mm. Times.400 mm samples of floors prepared in examples 1-5, 15 samples per example. The dimensional area of the sample of the example and the direction of the tensile force applied during the test are shown in figure 1.
The dry bond strength was tested using a universal mechanical tester at an operating speed of 20.0 mm/min. For the water-resistant bonding strength measurement, the plywood sample was immersed in water at 63±2 ℃ for 3 hours, taken out of the water, cooled to room temperature and then subjected to tensile test. The dry and water-resistant bond strength was calculated using the following formula:
plywood bond strength (MPa) =maximum load (N)/bond area (mm) 2 )
The test results were averaged and the specific values are shown in table 1.
Table 1 dry and water-resistant bond strength of the examples
| Dry shear strength (MPa) | Wet shear Strength (MPa) | |
| Example 1 | 1.42 | 0.68 |
| Example 2 | 1.85 | 0.88 |
| Example 3 | 1.89 | 1.21 |
| Example 4 | 2.12 | 1.45 |
| Example 5 | 2.25 | 1.86 |
As can be seen from the test results in Table 1, the dry and wet shear strengths of example 1 were the lowest, and the dry and wet shear strengths of examples 2-5 were all improved as compared with example 1, indicating that the modified soy protein adhesive improved the bonding strength of the degradable floor. The comparative examples 2-5, example 5, which had the highest dry and wet shear strengths, demonstrate the more significant efficacy of using the tetraepoxy L-tyrosine modified soy protein adhesive to enhance the glue strength of the degradable flooring because the modification of the soy protein adhesive by the tetraepoxy L-tyrosine improves the complex structure of soy protein molecules, promotes the formation of strong board glue bonds, enhances the mechanical interlocking between the adhesive and the flooring boards, and facilitates the provision of better performance and better flooring adhesion, resulting in a significant increase in the glue strength of the degradable flooring. The better the bonding strength, the better the stability of the board, and the adoption of the tetraepoxy L-tyrosine modified soybean protein adhesive is beneficial to improving the durability of the floor.
Test example 2
Anti-mould property of adhesive
Mold is one of the fungi, the structure and composition of the different fungi are similar, candida albicans [ CMCC (F) 98001] is one of the most common species for antifungal testing, which was selected as the test species. Candida albicans was co-cultured with the adhesives prepared in examples 1-5, and then the bacteriostatic activity of each example was determined by coating plate counting.
30mg of the adhesive prepared in each of examples 1 to 5 was sterilized and then added to a solution containing 3mL of Candida albicans (10 6 CFU/mL), the control group was not added with any material. The culture tubes were placed in a thermostatic shaker at 28℃and shaken at 150rpm for 18h. After the completion of the culture, the co-culture solution was diluted 10 4 Multiple times. 100. Mu.L of the dilutions were measured separately and spread evenly on potato dextrose agar solid medium. And finally, placing the culture medium in a constant temperature incubator at 28 ℃ for culturing for 72 hours, and then photographing to record the colony count. The fungus concentration was calculated as follows:
fungal concentration (CFU/mL) =m×n×10
Where m is the colony count and n is the dilution factor.
The bacteriostasis rate is calculated according to the following formula:
antibacterial ratio (%) = (1-m) 1 /n 1 )×100％
M is in 1 Is the concentration of fungi in the sample group, n 1 Is the fungus concentration of the control group.
The test results were averaged and the specific values are shown in table 2.
Table 2 antibacterial ratio of each example
As shown in the test results of Table 2, the antibacterial rate of example 1 is the lowest, and compared with example 1, the antibacterial rates of examples 2-5 are all improved, but the antibacterial rates of example 2 and example 3 are not obviously increased, and the antibacterial rates of example 4 and example 5 are obviously improved, which indicates that the antibacterial effect of the adhesive is not very good by using polyamide epichlorohydrin resin or glutaraldehyde modified soybean protein adhesive, but the antibacterial effect of the adhesive is obviously improved by using hydroxymethyl L-tyrosine or tetraepoxy L-tyrosine modified soybean protein adhesive, and the antibacterial rate of the hydroxymethyl L-tyrosine modified soybean protein adhesive is as high as 98.5%. Therefore, the degradable floor adopting the hydroxymethyl L-tyrosine modified soybean protein adhesive has stronger mould resistance.
Test example 3
Degradable floor formaldehyde emission test
The formaldehyde emission of the degradable floor is measured by a dryer method in China national Standard (GB/T17657-2022). The degradable floors (150 mm. Times.50 mm) prepared in example 1, example 4 and example 5 were placed in a 10L desiccator at 25℃for 24 hours, and the released formaldehyde was absorbed by 300mL distilled water in a crystallization dish at the bottom of the desiccator. Subsequently, 25mL of the formaldehyde absorbing solution and 25mL of the acetylacetone-ammonium acetate solution were mixed in a 100mL flask, reacted at 65.+ -. 2 ℃ for 10min, and then cooled in a dark place for 60.+ -. 5min. Finally, the absorbance of the reacted solution at 412nm was measured by an ultraviolet spectrophotometer. The formaldehyde mass concentration is calculated according to the following formula:
C＝f×(A-A 0 )/S×1800
wherein: c is formaldehyde mass concentration in units of mg/L; f is the slope of the standard curve in units of mg/L; s is the surface area of the test piece in units of (mm 2 ) The method comprises the steps of carrying out a first treatment on the surface of the A is absorbance of formaldehyde absorption liquid solution; a is that 0 Is the absorbance of distilled water solution.
The test results are shown in Table 3.
TABLE 3 formaldehyde emissions for the examples
| Formaldehyde emission (mg/L) | |
| Example 1 | 0.002 |
| Example 4 | 0.45 |
| Example 5 | 0.001 |
As can be seen from the test results of Table 3, the comparative examples 1, 4 and 5, examples 1 and 5, have very low formaldehyde emission, whereas example 4 has formaldehyde emission up to 0.45mg/L, indicating that the degradable floor using the soy protein adhesive or the tetraepoxy L-tyrosine modified soy protein adhesive hardly emits formaldehyde, and the degradable floor using the hydroxymethyl L-tyrosine modified soy protein adhesive generates formaldehyde because the hydroxymethyl group of the hydroxymethyl L-tyrosine, which is not reacted with soy protein, is decomposed to generate free formaldehyde, thereby causing formaldehyde emission.
In summary, although the degradable floor of the hydroxymethyl L-tyrosine modified soybean protein adhesive has strong mold resistance, the formaldehyde release amount is large, so that the degradable floor is not optimally selected. Comparing example 4 with example 5, the degradable floor using tetra-epoxy L-tyrosine modified soybean protein adhesive is preferable, and has higher bonding strength, good antibacterial performance and good environmental protection.
Test example 4
The adhesive and the degradable floor prepared in example 5, example 6, example 7 and example 8 were taken respectively, the viscosity and fluidity of the adhesive were measured, and the bonding strength of the degradable floor was measured.
Adhesive viscosity test
The method of NDJ-1 rotary viscometer is adopted, and the rest refers to GB/T2794-2022.
Adhesive flowability test
And (3) inserting a glass rod with the thickness of 6mm into the adhesive emulsion at the depth of 10cm, then picking up the adhesive solution, and calculating that the fluidity is qualified when the broken line of the adhesive solution is larger than 3 cm.
Testing of glue strength of degradable floor
The test method is the same as that of test example 1, and overall evaluation is made according to the test result of the bonding strength of the degradable floor.
The measured data are averaged and the specific results are shown in table 4.
Table 4 test cases for various examples
| Adhesive viscosity (Pa, s) | Adhesive flowability | Floor bonding strength | |
| Example 5 | 8.68 | Good (good) | Good (good) |
| Example 6 | 6.34 | Good (good) | Poor quality |
| Example 7 | 30.26 | Difference of difference | Difference of difference |
| Example 8 | 50.38 | Difference of difference | Difference of difference |
As can be seen from table 4, the viscosities of comparative examples 5, 6, 7 and 8 were found to have good fluidity, but the adhesion strength of example 5 was better than that of example 6, and the viscosities of examples 7 to 8 were higher than those of examples 5 and 6, and the fluidity was poor, and the adhesion strength was poor, indicating that the increase in the amount of tetra-epoxy L-tyrosine used affected the viscosity and fluidity of the adhesive, and thus the adhesion strength of the degradable floor. The viscosity of the adhesive can influence the fluidity, and the insufficient fluidity caused by the excessive viscosity can lead the adhesive to be incapable of fully filling the defects on the surface of the floor board, so that the bonding strength of the adhesive is reduced; too low a viscosity results in too high a flowability, and the adhesive may excessively penetrate to the surface of the flooring board, resulting in lack of a sufficient adhesive layer on the surface, resulting in a decrease in the bonding strength thereof, and a decrease in the stability of the degradable floor.
Claims (10)
1. A method for preparing a degradable floor, comprising the steps of:
(1) Preparation of the wear-resistant layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor and acrylic copolymer in a mixer; plasticizing by using an internal mixer; press-forming by a press; cutting after cooling to obtain a wear-resistant layer;
(2) Preparation of the second backsheet layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor, acrylic copolymer, mica powder and lubricant in a mixer; plasticizing by using an internal mixer; press-forming by a press; cooling and cutting to obtain a second negative film layer;
(3) Preparation of the surface layer: stacking the wear-resistant layer, the decorative layer and the second bottom sheet layer from top to bottom; pushing the stacked materials into a press after the stacking is completed, and unloading the stacked materials after hot pressing treatment and cold pressing treatment to obtain a surface layer;
(4) Preparation of an intermediate layer: mixing cork wood dust, a fireproof agent, a waterproof agent and a preservative in a mixer to obtain a mixture; transferring the adhesive and the mixture into a high-speed mixer for uniform mixing; extruding and molding through an extruder to obtain an intermediate layer;
(5) Preparation of the first backsheet layer: mixing polylactic acid resin, plasticizer, hydrolysis inhibitor, acrylic copolymer, mica powder and lubricant in a mixer; plasticizing by using an internal mixer; press-forming by a press; cooling and cutting to obtain a first negative film layer;
(6) Carrying out UV heat treatment on the surface layer obtained in the step (3);
(7) Attaching the surface layer subjected to UV heat treatment to the intermediate layer obtained in the step (4) through an adhesive, wherein the intermediate layer is in contact with a second bottom layer in the surface layer; adhering the first bottom sheet layer obtained in the step (5) to the middle layer through an adhesive to obtain a composite board, wherein the adhesive is a soybean protein series adhesive;
(8) And (3) carrying out hot pressing treatment on the composite board obtained in the step (7) through a constant-temperature hot press to obtain the degradable floor.
2. A method of manufacturing a degradable floor according to claim 1, characterized in that: the weight portion ratio of each raw material component is as follows:
wear-resistant layer: 100 parts of polylactic acid resin, 2-5 parts of plasticizer, 0.1-1 part of hydrolysis resistance agent and 0.5-1 part of acrylic copolymer;
a second backsheet layer: 100 parts of polylactic acid resin, 15-25 parts of plasticizer, 2-10 parts of hydrolysis resistance agent, 1-10 parts of acrylic copolymer, 300-500 parts of mica powder and 3-8 parts of lubricant;
a first backsheet layer: 100 parts of polylactic acid resin, 15-25 parts of plasticizer, 2-10 parts of hydrolysis resistance agent, 1-10 parts of acrylic copolymer, 300-500 parts of mica powder and 3-8 parts of lubricant;
an intermediate layer: 50-80 parts of cork wood dust, 10-15 parts of adhesive, 2-5 parts of fireproof agent, 2-5 parts of waterproof agent and 0.1-1 part of preservative.
3. A method of manufacturing a degradable floor according to claim 2, characterized in that: the plasticizer is selected from one of tricresyl phosphate, dibutyl phthalate and tripropyl citrate; the hydrolysis resistance agent is selected from one of polyurethane resin, polyester polyol and polyacrylate resin; the lubricant is selected from one of stearic acid, calcium stearate and magnesium stearate; the cork wood chips are selected from one of pine wood chips, eucalyptus wood chips and willow wood chips; the adhesive is polyurethane resin; the fire retardant is one of melamine, pentaerythritol ester and ammonium polyphosphate; the waterproof agent is selected from one of methyltrichlorosilane, polyurethane waterproof paint and sodium methyl silicate; the preservative is selected from one of ACQ wood preservative, sodium fluoride and borax.
4. A method of manufacturing a degradable floor according to claim 1, characterized in that: the adhesive coating amount in the step (7) is 180-250g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The soybean protein series adhesive is one of a soybean protein adhesive, a polyamide epoxy chloropropane resin modified soybean protein adhesive, a glutaraldehyde modified soybean protein adhesive, a hydroxymethyl L-tyrosine modified soybean protein adhesive and a tetraepoxy L-tyrosine modified soybean protein adhesive; the tetraepoxy L-tyrosine modified soybean protein adhesive consists of 1-10wt% of tetraepoxy L-tyrosine and 90-99wt% of soybean protein adhesive.
5. A method of manufacturing a degradable floor according to claim 1, characterized in that: in the step (1), the plasticizing temperature is controlled to be 110-120 ℃; the press molding temperature is controlled to be 100-110 ℃; cooling to 35-25 deg.c and cutting; the thickness of the wear-resistant layer is 0.5-1mm.
6. A method of manufacturing a degradable floor according to claim 1, characterized in that: in the step (2), the plasticizing temperature is controlled to be 130-140 ℃; the press molding temperature is controlled to be 120-135 ℃; cooling to 35-25deg.C, and cutting; the second backsheet layer has a thickness of 0.5-1mm.
7. A method of manufacturing a degradable floor according to claim 1, characterized in that: in the step (3), the decorative layer is a floor decorative color film; the molding temperature of the hot press is controlled to be 120-130 ℃, and the hot pressing time is controlled to be 20-30min; the cold press molding temperature is controlled to be 35-25 ℃, and the cold press time is controlled to be 20-30min; the thickness of the surface layer is 1-2mm.
8. A method of manufacturing a degradable floor according to claim 1, characterized in that: in the step (4), the extrusion temperature is 110-130 ℃; the thickness of the middle layer is 5-8mm; in the step (5), the plasticizing temperature is controlled to be 130-140 ℃; the press molding temperature is controlled to be 120-135 ℃; cooling to 35-25deg.C, and cutting; the thickness of the first bottom sheet layer is 1-2mm; in the step (6), the illumination intensity of the UV heat treatment is 400-600mJ/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The speed is 14-18m/min.
9. A method of manufacturing a degradable floor according to claim 1, characterized in that: in the step (8), the press forming temperature of the hot press is controlled to be 120-130 ℃, and the hot press time is controlled to be 20-30min; the thickness of the degradable floor is 7-12mm.
10. A degradable floor, characterized in that: prepared by the process of any one of claims 1-9.
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