CN109468876A - Abrasion-proof paper and its manufacturing method - Google Patents

Abrasion-proof paper and its manufacturing method Download PDF

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Publication number
CN109468876A
CN109468876A CN201811228320.7A CN201811228320A CN109468876A CN 109468876 A CN109468876 A CN 109468876A CN 201811228320 A CN201811228320 A CN 201811228320A CN 109468876 A CN109468876 A CN 109468876A
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weight
modified
parts
abrasion
powder
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CN109468876B (en
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朱雪男
卢健
张发
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Tianjin Shengshi New Mstar Technology Ltd
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Tianjin Shengshi New Mstar Technology Ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds

Abstract

The present invention relates to abrasion-proof paper and its manufacturing method, the abrasion-proof paper includes that body paper, dipping are coated in body paper and the modification impregnating resin of outer layer and the complex abrasion-proof reinforced phase being compatible in the modified resin-impregnated layer in body paper side；Wherein, the modified impregnating resin raw material includes: modified matrix resin adhesive liquid, acetaldehyde solution, sodium hydroxide solution, modified enzymolysis lignin；Wherein, the raw material of the modified matrix resin adhesive liquid includes: formalin, acetaldehyde solution, sodium hydroxide solution, melamine and deionized water；The raw material of the modified enzymolysis lignin includes: enzymolysis xylogen, ionized water, sodium hydroxide solution, formalin；Wherein, the complex abrasion-proof reinforced phase deposits nano-TiO by surface2Nanometer γ-Al2O3Powder, β-Si3N4Powder composition.Compared with prior art, the present invention abrasion-proof paper according to an embodiment of the present invention, can significantly reduce process costs while significantly improving the performances such as wear-resisting property, transparency, intensity.

Description

Abrasion-proof paper and its manufacturing method
Technical field
The invention belongs to impregnated paper production technical field more particularly to a kind of abrasion-proof paper and its manufacturing methods.
Background technique
With economic development, living standards of the people are improved, and building trade also continues to develop, and in recent years, impregnated paper strengthens wood Floor has developed into China's Flooring share most because the advantages that its is beautiful and stylish, product category is abundant is liked by market deeply Big main force's product, the ground for being widely used in family room and public place are laid with.
Impregnated paper laminated flooring be by Jing Guo Jin Zi surface layer abrasion-proof layer, facing paper and balance paper and substrate by hot pressing It merges.Impregnated paper laminated flooring had not only eliminated cement, stone material, " hard " of ceramic pavement, " cold " sense, but also had overcome Solid wooden floor board is afraid of abrasion, is afraid of to scald the deficiency for pollution of burning, be afraid of, and it is more cheap than solid wooden floor board, and construction and installation are more convenient, spell It is almost seamless after dress, it is smooth bright and clean.
In practical applications, the performance that impregnated paper strengthens wood floors is heavily dependent on surface abrasion resistance protective layer Performance, the i.e. performance of wear-resistant immersion paper.The corrosion resistance of abrasion-proof paper, etch resistance can especially wear-resisting property, directly determine The service life of impregnated paper laminated flooring.It also requires abrasion-proof paper while assigning floor surface good wear resistance, has There is good transparency, will not influence the beauty and use of composite floor board decorative pattern.In addition, with the increasing of people's environmental consciousness By force, the environmental protection characteristic of abrasion-proof paper is required also higher and higher.
Currently, existing wear-resistant immersion paper is primarily present following deficiency: 1) existing wear-resistant immersion paper uses Al2O3As enhancing Phase is enhanced by way of decorative paper after making an addition in body paper or mixing with impregnating resin；Al2O3Dispersibility and The compatibility of itself and impregnating resin is the main reason for hindering abrasion-proof paper performance to further increase；2) existing resistance to reduce cost Mill paper largely uses low-poison urea-formaldehyde resin part substitution melamine to carry out multi-pass dipping, thus the abrasion-proof paper of manufacture and reinforcing There is release formaldehyde with not can avoid in wood based panel；3) prior art is at high cost, requires equipment and raw material high: to mention High Al2O3Dispersibility in resin needs constantly to recycle hybrid resin, it is desirable that increases impregnating prodn. line Special installation, while also having very high requirement to resin used.
Therefore, the high-performance abrasion-proof paper with environmental protection characteristic how is prepared, while reducing production cost, there is important meaning Justice.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of abrasion-proof paper and preparation method thereof, and present subject matter is such as Under:
According to an aspect of the present invention, a kind of abrasion-proof paper is coated in body paper including body paper, dipping and the modified of outer layer is soaked Stain resin and the complex abrasion-proof reinforced phase being compatible in the modified resin-impregnated layer in body paper side；Wherein, the modified dipping tree Fat raw material includes: modified matrix resin adhesive liquid, acetaldehyde solution, sodium hydroxide solution, modified enzymolysis lignin；Wherein, described to change The raw material of property matrix resin glue includes: formalin, acetaldehyde solution, sodium hydroxide solution, melamine and deionized water；Institute The raw material for stating modified enzymolysis lignin includes: enzymolysis xylogen, ionized water, sodium hydroxide solution, formalin；Wherein, described Complex abrasion-proof reinforced phase deposits nano-TiO by surface2Nanometer γ-Al2O3Powder, β-Si3N4Powder composition；The nanometer γ- Al2O3Powder and β-Si3N4The mixed proportion of powder is 100:(0.5-5 by weight), average grain diameter is respectively 50nm-65nm And 30nm-50nm, the average thickness that surface deposits nano TiO 2 is 5nm-10nm.
An exemplary embodiment of the present invention, modified impregnating resin raw material includes: 400 part by weight modified matrix resin glue 28% hydroxide of liquid, 120 parts by weight, 40% acetaldehyde solution, the part by weight modified enzymolysis xylogen of 1-10 and 160-220 parts by weight Sodium.
An exemplary embodiment of the present invention, the raw material of the modified matrix resin adhesive liquid include: 100 parts by weight 38% Formalin, 35 parts by weight, 40% acetaldehyde solution, 350 parts by weight melamines and 260 parts by weight of deionized water and 130-190 weight Measure 33% sodium hydroxide solution of part.
An exemplary embodiment of the present invention, the raw material of the modified enzymolysis lignin include: 100 parts by weight enzymatic hydrolysis wood 33% hydrogen-oxygen of quality, 310-350 parts by weight of deionized water, the formalin of 15-50 parts by weight 28% and 80-135 parts by weight Change sodium solution.
An exemplary embodiment of the present invention, the volatile content of the abrasion-proof paper are 6.3%-8.2%, procuring degree For 42%-53%；The quantification of 29g/m2-45g/m2 of the abrasion-proof paper, tightness are not more than 0.33g/cm3, transparency 49%- 72%, machine direction tensile strength is not less than 5.38kN/m, and longitudinal wet strength is not less than 3.93kN/m, and wear-resisting revolution is not less than 6809 Turn.
According to another aspect of the present invention, a kind of manufacturing method of abrasion-proof paper, which comprises
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: nanometer γ-Al2O3Powder, β-Si3N4Powder 100:(0.5-5 by weight) it is sufficiently mixed It is even；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
Mixed powder and the dehydrated alcohol ratio of 8:100 by weight, are dissolved in dehydrated alcohol for mixed powder, obtain uniformly Solution；Gained homogeneous solution is added in sol solutions for homogeneous solution and the sol solutions ratio of 100:535 by weight, and 35 Electromagnetic agitation 25min-40min is carried out at a temperature of DEG C ± 2 DEG C, is sufficiently cleaned using dehydrated alcohol, and in 60 DEG C ± 1 DEG C of temperature Degree is lower to carry out isothermal holding, and soaking time 15min-25min obtains surface deposition nano-TiO2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 310-350 parts by weight of deionized water are abundant It is uniformly mixed, uses 33% sodium hydroxide solution of 80-135 parts by weight to adjust pH value as 8.2-8.5,15-50 parts by weight are added 28% formalin is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis Lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 130-190 parts by weight；It is added 350 parts by weight melamines and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 160-220 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；It is added 100 Part by weight modified matrix resin glue, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrixes are added The part by weight modified enzymolysis xylogen of resin adhesive liquid, 1-10, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, Obtain modified impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2It carries out molten Agent displacement, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtains modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper is impregnated into gluing in modified impregnating resin；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper；
3) it is dried and obtains abrasion-proof paper.
An exemplary embodiment of the present invention, the body paper use 100% GREAT LACK for raw material, Beating degree is 36 ° of SR-38 ° of SR, quantification of 18g/m2-25g/m2。
An exemplary embodiment of the present invention, the dipping gluing total amount are 250%-550%.
An exemplary embodiment of the present invention, the additive amount of the composite strengthening powder are 10g/m2-20g/m2。
An exemplary embodiment of the present invention, described be dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature is 125 DEG C -130 DEG C, and third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120℃-125℃。
Compared with prior art, abrasion-proof paper according to an embodiment of the present invention, 1) use nanoscale Al2O3、Si3N4As Reinforced phase by the optimum choice to its crystal form, partial size and mixing ratio, and uses nano-TiO2Surface is carried out to mixing reinforced phase Deposition, is activated, and while increasing the compatibility of reinforced phase and impregnating resin, significantly improves the wearability of abrasion-proof paper Energy；2) enzymolysis xylogen is used, and activation modification is carried out to it；Using the indexs modified resin glue such as formaldehyde, acetaldehyde, melamine Liquid；It is modified impregnating resin using preparations such as activation modification enzymolysis xylogen, modified resin glue, acetaldehyde solution and sodium hydroxides, Significantly improve the impregnation performance and environmental-protecting performance of impregnating resin；3) abrasion-proof paper wear-resisting property, transparency, intensity etc. are being significantly improved While performance, process costs are significantly reduced.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, the present invention is made into one by following specific embodiment Step detailed description.Obviously, described embodiments are some of the embodiments of the present invention, instead of all the embodiments.Based on this Embodiment in invention, those of ordinary skill in the art are obtained every other without making creative work Embodiment shall fall within the protection scope of the present invention.
Embodiment 1: the preparation of abrasion-proof paper
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: by the nanometer γ-Al of partial size 50nm2O3Powder, the β-Si that partial size is 50nm3N4Powder is by weight Amount part 100:0.5 is sufficiently mixed uniformly；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2, deposition thickness 10nm；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
8:100 by weight (mixed powder: dehydrated alcohol), is dissolved in dehydrated alcohol for mixed powder, obtains uniformly molten Liquid；100:535 by weight, by gained homogeneous solution be added sol solutions in, and 35 DEG C ± 2 DEG C at a temperature of carry out electromagnetism Stir 25min-40min, sufficiently cleaned using dehydrated alcohol, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, when heat preservation Between 15min-25min, obtain surface deposition nano-TiO2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 310 parts by weight of deionized water are sufficiently mixed Uniformly, 33% sodium hydroxide solution of 80 parts by weight is used to adjust pH value as 8.2-8.5, the formaldehyde that 15 parts by weight 28% are added is molten Liquid is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 130 parts by weight；It is added 290 Parts by weight melamine and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 160 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added Glue, 1 part by weight modified enzymolysis xylogen, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, are changed Property impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper uses 100% GREAT LACK for raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 18g/m2；Body paper is impregnated into gluing in modified impregnating resin, dipping gluing total amount is 250%；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper, the additive amount of composite strengthening powder is 10g/ m2；
3) it is dried, being dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature It is 125 DEG C -130 DEG C, third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120 DEG C -125 DEG C, is obtained resistance to Grind paper.
Embodiment 2: the preparation of abrasion-proof paper
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: the nanometer γ-Al for being 55nm by partial size2O3Powder, the β-Si that partial size is 45nm3N4Powder is pressed Parts by weight 100:1.5 is sufficiently mixed uniformly；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2, deposition thickness 8nm；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
Mixed powder is dissolved in dehydrated alcohol, obtains homogeneous solution by 8:100 by weight；By weight 100: 535, by gained homogeneous solution be added sol solutions in, and 35 DEG C ± 2 DEG C at a temperature of carry out electromagnetic agitation 25min-40min, Sufficiently cleaned using dehydrated alcohol, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, soaking time 15min-25min is obtained Nano-TiO is deposited to surface2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 322 parts by weight of deionized water are sufficiently mixed Uniformly, 33% sodium hydroxide solution of 90 parts by weight is used to adjust pH value as 8.2-8.5, the formaldehyde that 28 parts by weight 28% are added is molten Liquid is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 135 parts by weight；It is added 301 Parts by weight melamine and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 168 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added Glue, 2 part by weight modified enzymolysis xylogens, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, are changed Property impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper uses 100% GREAT LACK for raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 20g/m2；Body paper is impregnated into gluing in modified impregnating resin, dipping gluing total amount is 300%；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper, the additive amount of composite strengthening powder is 12g/ m2；
3) it is dried, being dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature It is 125 DEG C -130 DEG C, third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120 DEG C -125 DEG C, is obtained resistance to Grind paper.
Embodiment 3: the preparation of abrasion-proof paper
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: the nanometer γ-Al for being 55nm by partial size2O3Powder, the β-Si that partial size is 45nm3N4Powder is pressed Parts by weight 100:2 is sufficiently mixed uniformly；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2, deposition thickness 7nm；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
Mixed powder is dissolved in dehydrated alcohol, obtains homogeneous solution by 8:100 by weight；By weight 100: 535, by gained homogeneous solution be added sol solutions in, and 35 DEG C ± 2 DEG C at a temperature of carry out electromagnetic agitation 25min-40min, Sufficiently cleaned using dehydrated alcohol, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, soaking time 15min-25min is obtained Nano-TiO is deposited to surface2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 334 parts by weight of deionized water are sufficiently mixed Uniformly, it uses 33% sodium hydroxide solution of 105 parts by weight to adjust pH value as 8.2-8.5, the formaldehyde of 37 parts by weight 28% is added Solution is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 143 parts by weight；It is added 321 Parts by weight melamine and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 176 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added Glue, 5 part by weight modified enzymolysis xylogens, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, are changed Property impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper uses 100% GREAT LACK for raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 22g/m2；Body paper is impregnated into gluing in modified impregnating resin, dipping gluing total amount is 350%；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper, the additive amount of composite strengthening powder is 15g/ m2；
3) it is dried, being dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature It is 125 DEG C -130 DEG C, third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120 DEG C -125 DEG C, is obtained resistance to Grind paper.
Embodiment 4: the preparation of abrasion-proof paper
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: the nanometer γ-Al for being 60nm by partial size2O3Powder, the β-Si that partial size is 38nm3N4Powder is pressed Parts by weight 100:3.8 is sufficiently mixed uniformly；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2, deposition thickness 6nm；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
Mixed powder is dissolved in dehydrated alcohol, obtains homogeneous solution by 8:100 by weight；By weight 100: 535, by gained homogeneous solution be added sol solutions in, and 35 DEG C ± 2 DEG C at a temperature of carry out electromagnetic agitation 25min-40min, Sufficiently cleaned using dehydrated alcohol, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, soaking time 15min-25min is obtained Nano-TiO is deposited to surface2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 343 parts by weight of deionized water are sufficiently mixed Uniformly, it uses 33% sodium hydroxide solution of 118 parts by weight to adjust pH value as 8.2-8.5, the formaldehyde of 48 parts by weight 28% is added Solution is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 169 parts by weight；It is added 332 Parts by weight melamine and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 182 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added Glue, 8 part by weight modified enzymolysis xylogens, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, are changed Property impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper uses 100% GREAT LACK for raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 23g/m2；Body paper is impregnated into gluing in modified impregnating resin, dipping gluing total amount is 480%；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper, the additive amount of composite strengthening powder is 18g/ m2；
3) it is dried, being dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature It is 125 DEG C -130 DEG C, third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120 DEG C -125 DEG C, is obtained resistance to Grind paper.
Embodiment 5: the preparation of abrasion-proof paper
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: the nanometer γ-Al for being 65nm by partial size2O3Powder, partial size are 30nm β-Si3N4Powder is by weight Amount part 100:5 is sufficiently mixed uniformly；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2, deposition thickness 5nm；
Specifically, by volume 25:1:2:4:1 prepare dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are successively added to absolute ethanol progress by butyl titanate and titanium tetrachloride Uniformly mixing, 2-5s sequentially add diethanol amine and titanium tetrachloride, obtain sol solutions；
Mixed powder is dissolved in dehydrated alcohol, obtains homogeneous solution by 8:100 by weight；By weight 100: 535, by gained homogeneous solution be added sol solutions in, and 35 DEG C ± 2 DEG C at a temperature of carry out electromagnetic agitation 25min-40min, Sufficiently cleaned using dehydrated alcohol, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, soaking time 15min-25min is obtained Nano-TiO is deposited to surface2Composite strengthening powder.
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 350 parts by weight of deionized water are sufficiently mixed Uniformly, it uses 33% sodium hydroxide solution of 135 parts by weight to adjust pH value as 8.2-8.5, the formaldehyde of 50 parts by weight 28% is added Solution is warming up to 65 DEG C -80 DEG C, keeps the temperature 30min-55min, is condensed back, and rotary evaporation obtains modified enzymolysis lignin；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are filled Divide mixing, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 190 parts by weight；It is added 350 Parts by weight melamine and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment Reaction kettle uses the 28% sodium hydroxide adjusting pH value of 220 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added Glue, 10 part by weight modified enzymolysis xylogens, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, are changed Property impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper uses 100% GREAT LACK for raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 25g/m2；Body paper is impregnated into gluing in modified impregnating resin, dipping gluing total amount is 550%；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper, the additive amount of composite strengthening powder is 20g/ m2；
3) it is dried, being dried is four sections, and first segment drying temperature is 115 DEG C -120 DEG C, second segment drying temperature It is 125 DEG C -130 DEG C, third section drying temperature is 135 DEG C -140 DEG C, and the 4th section of drying temperature is 120 DEG C -125 DEG C, is obtained resistance to Grind paper.
Embodiment 6:
According to abrasion-proof paper prepared by embodiment 1-5, performance parameter is shown in Table 1.
Table 1
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include Within protection scope of the present invention.

Claims (10)

1. a kind of abrasion-proof paper, which is characterized in that the abrasion-proof paper includes body paper, dipping is coated in body paper and the modified leaching of outer layer Stain resin and the complex abrasion-proof reinforced phase being compatible in the modified resin-impregnated layer in body paper side；Wherein, the modified dipping tree Fat raw material includes: modified matrix resin adhesive liquid, acetaldehyde solution, sodium hydroxide solution, modified enzymolysis lignin；Wherein, described to change The raw material of property matrix resin glue includes: formalin, acetaldehyde solution, sodium hydroxide solution, melamine and deionized water；Institute The raw material for stating modified enzymolysis lignin includes: enzymolysis xylogen, ionized water, sodium hydroxide solution, formalin；Wherein, described Complex abrasion-proof reinforced phase deposits nano-TiO by surface2Nanometer γ-Al2O3Powder, β-Si3N4Powder composition；The nanometer γ- Al2O3Powder and β-Si3N4The mixed proportion of powder is 100:(0.5-5 by weight), average grain diameter is respectively 50nm-65nm And 30nm-50nm, surface deposit nano-TiO2Average thickness be 5nm-10nm.
2. abrasion-proof paper according to claim 1, which is characterized in that the modified impregnating resin raw material includes: 400 parts by weight Modified matrix resin adhesive liquid, 120 parts by weight, 40% acetaldehyde solution, the part by weight modified enzymolysis xylogen of 1-10 and 160-220 weight 28% sodium hydroxide of part.
3. abrasion-proof paper according to claim 1, which is characterized in that the raw material of the modified matrix resin adhesive liquid includes: 100 38% formalin of parts by weight, 35 parts by weight, 40% acetaldehyde solution, 290-350 parts by weight melamine and 260 parts by weight go from 33% sodium hydroxide solution of sub- water and 130-190 parts by weight.
4. abrasion-proof paper according to claim 1, which is characterized in that the raw material of the modified enzymolysis lignin includes: 100 weights Measure part enzymolysis xylogen, 310-350 parts by weight of deionized water, the formalin of 15-50 parts by weight 28% and 80-135 parts by weight 33% sodium hydroxide solution.
5. abrasion-proof paper according to claim 1 to 4, which is characterized in that the volatile content of the abrasion-proof paper is 6.3%-8.2%, procuring degree 42%-53%；The quantification of 29g/m of the abrasion-proof paper2-45g/m2, tightness is not more than 0.33g/cm3, transparency 49%-72%, machine direction tensile strength is not less than 5.38kN/m, and longitudinal wet strength is not less than 3.93kN/m, wear-resisting revolution are not less than 6809 turns.
6. a kind of manufacturing method of abrasion-proof paper, which is characterized in that the described method includes:
One, prepared by complex abrasion-proof reinforced phase
1) reinforced phase is compound: nanometer γ-Al2O3Powder, β-Si3N4Powder 100:(0.5-5 by weight) it is sufficiently mixed uniformly, it obtains To mixed powder；
2) reinforced phase is surface-treated: depositing nano-TiO on the surface of mixed powder2；
25:1:2:4:1 prepares dehydrated alcohol, 4- hydroxy 3-methoxybenzene ethyl ketone, diethanol amine, butyl titanate by volume With titanium tetrachloride, successively 4- hydroxy 3-methoxybenzene ethyl ketone, butyl titanate are added to absolute ethanol and are uniformly mixed, Diethanol amine and titanium tetrachloride are sequentially added after 2-5s, obtain sol solutions；
Mixed powder is dissolved in dehydrated alcohol, obtains homogeneous solution by 8:100 by weight；100:535 by weight, will Homogeneous solution is added in sol solutions, and in 35 DEG C ± 2 DEG C of at a temperature of progress electromagnetic agitation 25min-40min, using anhydrous second Alcohol sufficiently cleans, and 60 DEG C ± 1 DEG C at a temperature of carry out isothermal holding, soaking time 15min-25min obtains surface deposition Nano-TiO2Composite strengthening powder；
Two, modified impregnating resin preparation
1) enzymolysis xylogen activation modification: 100 parts by weight enzymolysis xylogens and 310-350 parts by weight of deionized water are sufficiently mixed Uniformly, it uses 33% sodium hydroxide solution of 80-135 parts by weight to adjust pH value as 8.2-8.5,15-50 parts by weight 28% is added Formalin, be warming up to 65 DEG C -80 DEG C, keep the temperature 30min-55min, be condensed back, it is wooden to obtain modified enzymolysis for rotary evaporation Element；
2) prepared by modified matrix resin adhesive liquid: by 38% formalin, 100 parts by weight, 40% acetaldehyde solution, 35 parts by weight are sufficiently mixed It closes, pH value is adjusted to 9.0,30 DEG C of heat preservation 30-50min using 33% sodium hydroxide solution of 130-190 parts by weight；290- is added 350 parts by weight melamines and 260 parts by weight of deionized water, 65 DEG C of ± 2 DEG C of heat preservation 30min, obtain matrix resin glue；
3) modified impregnating resin preparation: by 100 part by weight modified matrix resin glues, 120 part of 40% acetaldehyde solution investment reaction Kettle uses the 28% sodium hydroxide adjusting pH value of 160-220 parts by weight for 8.5-8.8,75 DEG C of reaction 25min；100 weight are added Part modified matrix resin adhesive liquid, adjusting pH value are 6.2-6.8,80 DEG C of reaction 30min；200 part by weight modified matrix resins are added The part by weight modified enzymolysis xylogen of glue, 1-10, adjusting pH value are 7.8-8.2, and 95 DEG C of reaction 30min are cooled to 50 DEG C, obtain Modified impregnating resin glue；Glue is immersed to the supercritical drying device for storing dehydrated alcohol, is passed through liquid CO2Solvent is carried out to set It changes, removes formaldehyde, acetaldehyde and the ethyl alcohol in removing glue liquid, obtain modified impregnating resin；
Three, prepared by abrasion-proof paper
1) body paper is impregnated into gluing in modified impregnating resin；
2) composite strengthening powder is equably sprayed on to the wear-resistant surface of impregnated paper；
3) it is dried and obtains abrasion-proof paper.
7. manufacturing method according to claim 6, which is characterized in that the body paper uses 100% bleached sulfite needle Leaf wood pulp is raw material, and beating degree is 36 ° of SR-38 ° of SR, quantification of 18g/m2-25g/m2。
8. manufacturing method according to claim 6, which is characterized in that the dipping gluing total amount is 250%-550%.
9. manufacturing method according to claim 6, which is characterized in that the additive amount of the composite strengthening powder is 10g/m2- 20g/m2。
10. manufacturing method according to claim 7, which is characterized in that described be dried is four sections, the dry temperature of first segment Degree be 115 DEG C -120 DEG C, second segment drying temperature be 125 DEG C -130 DEG C, third section drying temperature be 135 DEG C -140 DEG C, the 4th Section drying temperature is 120 DEG C -125 DEG C.
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CN110616591A (en) * 2019-08-30 2019-12-27 江苏星光新材料科技有限公司 Composite wear-resistant paper and preparation method thereof
CN110629588A (en) * 2019-08-30 2019-12-31 江苏星光新材料科技有限公司 Colored decorative paper and preparation method thereof
CN110670405A (en) * 2019-08-30 2020-01-10 江苏星光新材料科技有限公司 Preparation method of composite decorative paper
CN114164712A (en) * 2021-12-21 2022-03-11 湖北鸿连实业有限公司 Preparation method of spray paper

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CN102304337A (en) * 2011-05-27 2012-01-04 天津市鑫源森达新材料科技有限公司 Novel environmental-friendly modified glue for impregnated paper and preparation method thereof
CN108560313A (en) * 2018-03-27 2018-09-21 江苏建丰装饰纸有限公司 The preparation method of wet-heat resisting wear-resistant decorative paper

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CN101698604A (en) * 2009-11-03 2010-04-28 东北林业大学 Method for manufacturing enzymatic hydrolysis lignin ceramics
CN102086616A (en) * 2010-10-28 2011-06-08 天津市鑫源森达木业有限公司 Method for manufacturing surface wear-resisting impregnated paper of laminate floor by dry-spraying Al2O3
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CN114164712B (en) * 2021-12-21 2023-02-10 湖北鸿连实业有限公司 Preparation method of spray paper

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