CN111622018B - Production method of large ink level printing biblical paper - Google Patents
Production method of large ink level printing biblical paper Download PDFInfo
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- CN111622018B CN111622018B CN202010407659.4A CN202010407659A CN111622018B CN 111622018 B CN111622018 B CN 111622018B CN 202010407659 A CN202010407659 A CN 202010407659A CN 111622018 B CN111622018 B CN 111622018B
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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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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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
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
- D21H17/26—Ethers thereof
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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
- 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
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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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
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
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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
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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- Inorganic Chemistry (AREA)
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Abstract
The invention relates to the field of paper manufacturing, in particular to a production method of large ink level printing biblical paper, which comprises the following steps: (1) mixing and pulping the fiber raw material and titanium dioxide, and adding the imino branched polymer; (2) adding sodium carboxymethylcellulose and water, mixing and stirring to obtain a fiber stock solution; (3) forming on a net, dehydrating and drying to obtain paper sheets; (4) coating the paper sheet with a filler comprising a polymerization sizing agent, a retention aid and a lubricant on both sides, and standing until the filler is completely fixed on the paper sheet; (5) and dewatering, drying and calendaring to obtain the big ink level printing bible paper. According to the invention, the imino branched polymer is added during pulping, so that the number of hydrogen bonds among cellulose is increased, and the strength of paper is improved; the hydroxyl on the side close to the paper surface is silylated by sizing with a polymerization sizing agent on the paper surface, and a waterproof protective film formed by closely arranging ester groups is formed on the side far away from the paper surface, so that the hydrophobicity and the permeability resistance of the paper are improved.
Description
Technical Field
The invention relates to the field of paper manufacturing, in particular to a production method of large ink level printing biblical paper.
Background
The bible paper is a high-grade thin printing paper and is mainly used for printing bible books and is supplied to foreign professions; the paper is thin, tough, folding-resistant, slightly transparent, white and fine in paper surface, compact and smooth in texture and certain in water resistance, is mainly used for printing books which have more pages, higher use frequency and convenience in carrying, such as biblical bibliography, high-end dictionaries, classical books and the like, and is also applied to printing information data of aviation express; since bible papers are mostly published by professors for donations, are used in large quantities and are relatively inexpensive, low-basis weight leaflet bible readings are derived.
For example, publication No. CN110565442A, "a method for producing an ultra-low basis weight bible paper", comprises the steps of: uniformly mixing the fiber raw material and titanium dioxide, then carrying out pulping operation, and then adding a filler; diluting the mixed slurry to a mass concentration of 0.5-1.0%, sequentially adding polyamide epoxy chloropropane resin, cationic starch, polyethyleneimine, black dye and alkyl ketene dimer, and performing net-feeding forming treatment; then, carrying out press dehydration and pre-drying treatment, gluing the two sides of the paper by using a glue applicator, carrying out post-drying, and finally carrying out calendaring treatment by using a calendar. The invention has the advantages of high long fiber proportion ratio, high beating and knocking degree, sufficient fibrillation of the fibers, high paper strength and difficult occurrence of paper breaking in the process of processing; the addition amount of the titanium dioxide in the filler is increased, and the addition mode is improved, so that the product has high opacity, is not easy to have printing strike-through phenomenon, still has higher strength under the condition of extremely thin paper, and meets the requirement of continuous paper printing; better evenness and opacity, and the requirement of double-sided printing.
However, with the development of society, the progress of civilization, the rapid development of science and education culture career, the demand of people on the bible paper tends to be diversified and develops in depth. The original common white paper black characters are developed into colored base paper, the printing process is from two colors, four colors to multicolor and large ink level printing, wherein the bible paper for large ink level printing can vividly present the image-text colors due to the good printing reproduction effect, and the printed product is bright and has prominent stereoscopic impression and is deeply favored by customers. Most of bible papers for large ink level printing need full-page finishing and multicolor overprinting, and have extremely high requirements on paper strength, flatness, permeability, water absorbability and ink drying rate. The ultralow-weight biblical paper prepared by the method is still not high enough in paper strength, and is relatively high in opening air permeability and water absorption value, so that quality problems such as paper breaking, show through, plate pasting and the like are easily caused during large ink position printing.
Disclosure of Invention
The invention provides a production method of large ink level printing bible paper, aiming at overcoming the defects that the existing bible paper has low strength, high water absorption value and good permeability, and further the quality problems of paper breaking, strike-through, plate pasting and the like easily occur in large ink level printing.
In order to achieve the purpose, the invention adopts the following technical scheme:
a production method of large ink level printing biblical paper comprises the following steps:
(1) mixing the fiber raw material and titanium dioxide, pulping, adding the imino branched polymer, and uniformly mixing to obtain mixed slurry;
(2) adding sodium carboxymethylcellulose and water into the mixed slurry, and mixing and stirring to obtain a fiber stock solution;
(3) forming the fiber stock solution on a net, dehydrating and drying to obtain paper sheets;
(4) coating the paper sheet with a filler comprising 100-200 parts of a polymerization sizing agent, 20-40 parts of a retention aid and 1-2 parts of a lubricant on both sides, and standing at normal temperature until the filler is completely fixed on the paper sheet, wherein the polymerization sizing agent is formed by polymerizing saponified polyvinyl acetate and dimethoxy chlorosilyl propyl isocyanate;
(5) and dewatering, drying and calendaring to obtain the big ink level printing bible paper.
In order to satisfy the requirements of printing books with more pages, higher use frequency and convenient carrying such as the bible, the high-end dictionary, the classical book and the like, the quantitative amount of the existing bible paper is generally reduced as much as possible, even lower than 30g/m2However, at this basis weight, the strength of the paper will be greatly reduced, and the paper will be easily torn or broken; simultaneously in order to satisfy quantitative demand, the thickness of ordinary paper also can't be accomplished to the sizing agent coating on the bible paper, and the waterproof performance of paper also will greatly reduced, and then leads to the hydroscopicity and the permeability of paper to promote, when printing, especially carry out big ink level printing, appear penetrating seal, paste version scheduling problem very easily. Therefore, in order to achieve both the strength and the water resistance of the paper at a low basis weight, the invention is realized by adding the imino-branched polymer after the beating of the fibers and by using the polymeric sizing agent containing silane groups and ester groups during sizing.
Contain very many amino end groups and imino in imino branched polymer's the structure, both can form the hydrogen bond with the hydroxyl on fiber raw materials surface to this increases the hydrogen bond connection quantity between the different celluloses, or will not originally have between the cellulose of relation of connection through with imino branched polymer hydrogen bond connection and then indirectly link together, greatly increased the combination effort between the cellulose, and filled the space between the cellulose, greatly increased fibrous intensity, and then improve the intensity of paper.
During sizing, a polymerized sizing agent which is prepared from saponified polyvinyl acetate and dimethoxy chlorosilyl propyl isocyanate and contains chlorosilyl and ester groups simultaneously is adopted, so that silyl groups in the sizing agent can react with hydroxyl groups on cellulose on the surface of paper, the hydroxyl groups on the surface of the cellulose are silylated, and a layer of dense polymer hydrophobic film is formed on the surface of the cellulose through the tight connection of a plurality of polymerized monomers on the same polymer chain, and the side, close to the cellulose, of the hydrophobic film is silylated with the hydroxyl groups on the surface of the cellulose through the silylation reaction, so that most of hydrophilic hydroxyl groups on the surface of the cellulose are covered and modified; in order to enable the sizing agent to completely cover the surface of paper in the prior sizing technology, a thicker coating thickness is often needed for realization, but in the invention, because the molecular chain of the polymer is longer, a small part of hydroxyl which is not modified by silylation can also be covered by the polymeric sizing agent with longer molecular chain, the polymers of different molecular chains are mutually parallel or arranged in a staggered way and stacked on the surface of the cellulose to form a compact polymer film layer, the polymer is also connected with an ester group with better hydrophobicity, and the ester group does not react with the hydroxyl, so that the ester group at one side far away from the cellulose is also closely arranged to form an ester hydrophobic layer, the hydrophobic property of the sizing agent is further increased, the hydrophobic property of the paper can be greatly improved without the thicker coating thickness, and the paper also has better waterproofness and lower permeability under low basis weight, the requirement of large ink level printing is met.
Preferably, the fiber raw material in the step (1) comprises bleached softwood pulp and bleached hardwood pulp in a weight ratio of 3-4:1-2, the addition amount of titanium dioxide is 1.5-3 wt%, the pulp refining degree is 75-85 DEG SR, the centrifugal dryness is 20-30g, the wet weight is 2-5g, and the pH is 7.5-8.5.
The fiber raw material of the invention is prepared by matching softwood pulp with a majority of long fibers with hardwood pulp with a minority of short fibers, so that the wood pulp of the long fibers in the finally obtained pulp accounts for more than two thirds of the total fiber amount, a structure taking the long fibers as a basic skeleton is formed, the short fibers are filled in the long fiber skeleton, the long fibers and the short fibers are staggered and crossed to form more hydrogen bond connection relations among hydroxyl groups on cellulose in the wood pulp, and the connection among different long fibers is tighter, so that the finally prepared paper has higher basic strength through the coordination and cooperation of the long fibers and the short fibers.
Preferably, the imino-branched polymer is prepared by the following method:
(a) slowly dropwise adding diethylenetriamine and/or dimethylenetriamine into a methanol solution of methyl acrylate under the protection of nitrogen, and reacting for 2-5h at normal temperature to obtain a di-substituted or tri-substituted polymer monomer, wherein the molar ratio of the diethylenetriamine and/or the dimethylenetriamine to the methyl acrylate is 1:3-5, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.3-0.5: 1;
(b) distilling under reduced pressure to remove the methanol, heating to 130-170 ℃, continuing to react for 2-5h under reduced pressure until the reaction is complete, and obtaining the imino branched polymer.
The nucleophilic addition reaction between the carbon-carbon double bond of the methacrylate and the amino group of the diethylenetriamine and/or the dimethylenetriamine occurs, and the diethylenetriamine and/or the dimethylenetriamine have two terminal amino groups and an imino group, both of which can perform nucleophilic addition with the carbon-carbon double bond, so that one diethylenetriamine or dimethylenetriamine can perform two nucleophilic addition reactions with the methacrylate, and the terminal amino group can generate an imino group after participating in the addition reaction, and can further perform an addition reaction, amine compounds formed by different mono-addition or di-addition can be connected together through ester exchange reaction, and different products formed can be connected through the same reaction, so that an imino polymer with a very multi-branched structure is further formed, and the imino branched polymer is connected between different celluloses, different celluloses are closely connected through the action of hydrogen bonds, the hydrogen bond quantity among the celluloses is increased, and the strength of the finally prepared paper is greatly improved.
Because one diethylenetriamine or dimethylenetriamine can perform two nucleophilic addition reactions with methacrylate, and the terminal amino group generates an imino group after participating in the addition reaction, the addition reaction can further occur, theoretically, one diethylenetriamine or dimethylenetriamine can perform nucleophilic addition with five methacrylate at most, but actually, due to the steric hindrance, the imino group which is connected with one methacrylate group is not easy to perform nucleophilic reaction again, so the molar ratio of the methacrylate to the diethylenetriamine and/or dimethylenetriamine is set to be 1:3-5, and the two reactions have higher raw material utilization rate under the mixture ratio.
Preferably, the imino-branched polymer is added in the step (1) in an amount of 4wt% to 8 wt%. The imino branched polymer with the addition amount can effectively increase the strength of paper, does not have great influence on the quantitative determination of the paper, and can meet the requirements of high strength and low quantitative determination at the same time.
Preferably, the preparation method of the polymerization sizing agent is as follows:
(i) adding the mixture of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into ethanol in a molar ratio of 1:8-12 under the protection of inert gas, and stirring and mixing to form a mixed solution, wherein the amount of the mixture of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate added per milliliter of ethanol is 0.05-0.2 g;
(ii) and (3) reacting the mixed solution at 80-90 ℃ for 20-25 hours, and distilling under reduced pressure to remove ethanol to obtain the polymerization sizing agent.
The obtained polymerization sizing agent has a three-section main body structure and respectively contains dimethoxy chlorosilyl propyl isocyanate, ethyl acetate and hydroxyl, wherein the dimethoxy chlorosilyl propyl isocyanate can silylate the hydroxyl on the surface of cellulose to form a hydrophobic film with better hydrophobicity on the surface of the cellulose, and a small part of hydroxyl on the surface of the cellulose, which is not silylated, can be mixed with the hydroxyl on a polymer to form hydrogen bonds between the hydroxyl and the polymer, so that the bonding firmness between the polymerization sizing agent and paper is further increased, and the polymerization sizing agent is prevented from falling off the surface of the paper; the ethyl acetate forms a more compact ester-based waterproof film on the side far away from the surface of the paper, so that the waterproof performance of the paper is improved. The saponified polyvinyl acetate in the raw materials for preparing the polymerization sizing agent is a polymer, and the relative molecular mass of the polymer is high, so that the molar ratio of the polyvinyl acetate to the dimethoxy chlorosilyl propyl isocyanate is set to be 1:8-12, and under the molar ratio, the polyvinyl acetate and the dimethoxy chlorosilyl propyl isocyanate can better react and combine to form the polymerization sizing agent, the yield of the polymerization sizing agent is improved, and the raw material utilization rate of the polymerization sizing agent is increased.
Preferably, the weight average molecular weight of the saponified polyvinyl acetate is 3000-5000, and the saponification degree of the saponified polyvinyl acetate is 30-60%. The saponified polyvinyl acetate under the weight-average molecular weight has a proper chain length, so that polymer molecular chains of the polymerization sizing agent can be arranged in a staggered manner or stacked on the surface of paper to form a compact hydrophobic layer after the polymerization sizing agent is formed by reaction; the saponified polyvinyl acetate with 30-60% saponification degree has the number ratio of dimethoxy chlorosilyl propyl isocyanate group, ethyl acetate group and hydroxyl group in the polymerization sizing agent formed by polymerizing with dimethoxy chlorosilyl propyl isocyanate of 20-25:30-50:25-50, and the polymerization sizing agent with the number ratio has good performance in hydrophobicity and paper bonding strength.
Preferably, in the step (4): the amount of the polymeric sizing agent is 2.5-5wt% and/or the standing time is 3-5 h. The sizing agent has very good waterproof performance, so that the quantitative rate of paper can be further reduced while the waterproof effect is ensured by selecting a small amount of the sizing agent, so as to meet the low quantitative rate requirement of the bible paper; the standing is to further fix the polymerization sizing agent, the retention aid and the lubricant on the surface of the paper, and particularly to give sufficient time for the polymerization sizing agent to be completely reacted and combined with the cellulose on the surface of the paper so as to ensure that the finally prepared paper can achieve the preset waterproof effect.
Preferably, in the step (4): the retention aid is one or two of polyvinyl acetate latex and styrene-butadiene latex, and/or the lubricant is calcium stearate. The polyvinyl acetate latex and the styrene-butadiene latex are retention aids with good hydrophobicity, and the retention aids can better play the hydrophobic role of the polymerization sizing agent and improve the fixation of the polymerization sizing agent on the surface of paper during the sizing process.
Preferably, the slurry, the sodium carboxymethyl cellulose and the water are mixed in the step (2) according to the weight ratio of 1:2-5: 50-100.
Preferably, the water content after pre-dehydration drying in step (3) is 10-15wt%, and/or the water content after post-dehydration drying in step (5) is 1-3 wt%.
In conclusion, the invention has the following beneficial effects: (1) the imino branched polymer is added during pulping, and is connected with the hydroxyl on the surface of the cellulose through hydrogen bonds, so that the number of the hydrogen bonds among the cellulose is increased, and part of the cellulose which is originally not in a connection relation is also connected together through the imino branched polymer, so that the strength of the paper is greatly improved; (2) the surface of the paper is sized by adopting a polymerization sizing agent, the hydroxyl group close to the surface of the paper is silylated, and a waterproof protective film formed by closely arranging ester groups is formed on the side far away from the surface of the paper, so that the hydrophobicity and the permeability resistance of the paper are greatly improved.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1
A production method of large ink position biblical paper comprises the following steps:
(1) under the protection of nitrogen, slowly dropwise adding diethylenetriamine into a methanol solution of methyl acrylate, wherein the molar ratio of the diethylenetriamine to the methyl acrylate is 1:3, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.3: 1; reacting for 2 hours at normal temperature, then distilling under reduced pressure to remove methanol, heating to 130 ℃, continuing to react for 5 hours under reduced pressure until the reaction is complete, and obtaining the imino branched polymer;
(2) adding a mixture of 0.2g of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into each milliliter of ethanol solution under the protection of nitrogen, adding the mixture into ethanol, and stirring and mixing to form a mixed solution, wherein the saponified polyvinyl acetate and the dimethoxy chlorosilylpropyl isocyanate are mixed according to a ratio of 1:8 in the mixture, the saponification degree of the saponified polyvinyl acetate is 40%, and the weight-average molecular weight is 5000; then reacting the mixed solution at 80 ℃ for 25 hours, and removing ethanol by reduced pressure distillation to obtain a polymerization sizing agent;
(3) mixing bleached softwood pulp and bleached hardwood pulp according to a weight ratio of 3:1, adding 2% titanium dioxide for pulping until the pulp grinding degree is 75 DEG SR, the centrifugal dryness is 20g, the wet weight is 2g, the pH is 8, adding the imino branched polymer after pulping, and uniformly mixing to obtain mixed pulp;
(4) mixing and stirring the mixed slurry, sodium carboxymethylcellulose and water according to the weight ratio of 1:5:100 to obtain a fiber stock solution, then carrying out net-feeding forming, and dehydrating and drying until the water content is 13% to obtain a paper sheet;
(5) carrying out double-sided coating on a paper sheet by using a filler comprising 100 parts of a polymerization sizing agent, 20 parts of polyvinyl acetate latex and 2 parts of sodium stearate, and standing for 3 hours at normal temperature until the filler is completely fixed on the paper sheet, wherein the addition amount of the polymerization sizing agent is 5 wt%;
(6) and then dehydrating and drying until the water content is 3%, and calendering to obtain the large ink level printing bible paper.
Example 2
A production method of large ink position biblical paper comprises the following steps:
(1) under the protection of nitrogen, slowly dropwise adding diethylenetriamine into a methanol solution of methyl acrylate, wherein the molar ratio of the diethylenetriamine to the methyl acrylate is 1:5, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.4: 1; reacting for 5 hours at normal temperature, then distilling under reduced pressure to remove methanol, heating to 170 ℃, continuing to react for 2 hours under reduced pressure until the reaction is complete, and obtaining the imino branched polymer;
(2) adding a mixture of 0.1g of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into each milliliter of ethanol solution under the protection of nitrogen, adding the mixture into ethanol, and stirring and mixing to form a mixed solution, wherein the saponified polyvinyl acetate and the dimethoxy chlorosilylpropyl isocyanate are mixed according to a ratio of 1:10, the saponification degree of the saponified polyvinyl acetate is 60%, and the weight-average molecular weight is 4000; then reacting the mixed solution at 85 ℃ for 20 hours, and removing ethanol by reduced pressure distillation to obtain a polymerization sizing agent;
(3) mixing bleached softwood pulp and bleached hardwood pulp according to the weight ratio of 3:2, adding 1.5% titanium dioxide, pulping until the pulp grinding degree is 80SR, the centrifugal dryness is 30g, the wet weight is 5g, and the pH is 7.5, adding the imino branched polymer after pulping, and uniformly mixing to obtain mixed pulp;
(4) mixing and stirring the mixed pulp, sodium carboxymethylcellulose and water according to the weight ratio of 1:2:75 to obtain a fiber stock solution, then carrying out net-feeding forming, and dehydrating and drying until the water content is 10% to obtain a paper sheet;
(5) carrying out double-sided coating on a paper sheet by using a filler comprising 150 parts of a polymerization sizing agent, 40 parts of polyvinyl acetate latex and 2 parts of sodium stearate, and standing for 4 hours at normal temperature until the filler is completely fixed on the paper sheet, wherein the addition amount of the polymerization sizing agent is 2.5 wt%;
(6) and then dehydrating and drying until the water content is 1%, and calendering to obtain the large ink level printing bible paper.
Example 3
A production method of large ink position biblical paper comprises the following steps:
(1) under the protection of nitrogen, slowly dropwise adding diethylenetriamine into a methanol solution of methyl acrylate, wherein the molar ratio of the diethylenetriamine to the methyl acrylate is 1:4, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.5: 1; reacting for 3h at normal temperature, then distilling under reduced pressure to remove methanol, heating to 150 ℃, continuing to react for 3.5h under reduced pressure until the reaction is complete, and obtaining the imino branched polymer;
(2) adding a mixture of 0.05g of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into each milliliter of ethanol solution under the protection of nitrogen, adding the mixture into ethanol, and stirring and mixing to form a mixed solution, wherein the saponified polyvinyl acetate and the dimethoxy chlorosilylpropyl isocyanate are mixed according to a ratio of 1:10, the saponification degree of the saponified polyvinyl acetate is 30%, and the weight-average molecular weight is 3000; then reacting the mixed solution at 90 ℃ for 23 hours, and removing ethanol by reduced pressure distillation to obtain a polymerization sizing agent;
(3) mixing bleached softwood pulp and bleached hardwood pulp according to a weight ratio of 4:1, adding 3% titanium dioxide for pulping until the pulp grinding degree is 85 DEG SR, the centrifugal dryness is 30g, the wet weight is 3.5g, the pH value is 8, adding the imino branched polymer after pulping, and uniformly mixing to obtain mixed pulp;
(4) mixing and stirring the mixed pulp, sodium carboxymethylcellulose and water according to the weight ratio of 1:3.5:100 to obtain a fiber stock solution, then carrying out net-feeding forming, and dehydrating and drying until the water content is 15% to obtain a paper sheet;
(5) carrying out double-sided coating on a paper sheet by using a filler comprising 200 parts of a polymerization sizing agent, 30 parts of polyvinyl acetate latex and 1 part of sodium stearate, and standing for 5 hours at normal temperature until the filler is completely fixed on the paper sheet, wherein the addition amount of the polymerization sizing agent is 4 wt%;
(6) and then dehydrating and drying until the water content is 3%, and calendering to obtain the large ink level printing bible paper.
Example 4
A production method of large ink position biblical paper comprises the following steps:
(1) under the protection of nitrogen, slowly dropwise adding diethylenetriamine into a methanol solution of methyl acrylate, wherein the molar ratio of the diethylenetriamine to the methyl acrylate is 1:3, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.5: 1; reacting for 4 hours at normal temperature, then distilling under reduced pressure to remove methanol, heating to 170 ℃, continuing to react for 4 hours under reduced pressure until the reaction is complete, and obtaining the imino branched polymer;
(2) adding a mixture of 0.1g of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into each milliliter of ethanol solution under the protection of nitrogen, adding the mixture into ethanol, and stirring and mixing to form a mixed solution, wherein the saponified polyvinyl acetate and the dimethoxy chlorosilylpropyl isocyanate are mixed according to a ratio of 1:8, the saponification degree of the saponified polyvinyl acetate is 40%, and the weight-average molecular weight is 3000; then reacting the mixed solution at 80 ℃ for 20 hours, and removing ethanol by reduced pressure distillation to obtain a polymerization sizing agent;
(3) mixing bleached softwood pulp and bleached hardwood pulp according to a weight ratio of 3:1, adding 2% titanium dioxide for pulping until the pulp grinding degree is 80 DEG SR, the centrifugal dryness is 40g, the wet weight is 5g, and the pH is 8.5, adding the imino branched polymer after pulping, and uniformly mixing to obtain mixed pulp;
(4) mixing and stirring the mixed slurry, sodium carboxymethylcellulose and water according to the weight ratio of 1:2:100 to obtain a fiber stock solution, then carrying out net-feeding forming, and dehydrating and drying until the water content is 10% to obtain a paper sheet;
(5) carrying out double-sided coating on a paper sheet by using a filler comprising 200 parts of a polymerization sizing agent, 20 parts of polyvinyl acetate latex and 1 part of sodium stearate, and standing for 5 hours at normal temperature until the filler is completely fixed on the paper sheet, wherein the addition amount of the polymerization sizing agent is 5 wt%;
(6) and then dehydrating and drying until the water content is 2%, and calendering to obtain the large ink level printing bible paper.
Comparative example 1
Comparative example 1 differs from example 3 in that comparative example 1 does not add the imino-branched polymer in step (1) and the remaining conditions are the same as in example 4.
Comparative example 2
Comparative example 2 differs from example 4 in that comparative example 2 added the sizing agent in step (4) as AKD sizing agent, and the remaining conditions were the same as in example 4.
Comparative example 3
Comparative example 3 differs from example 4 in that no imino-branched polymer was added in step (1) of comparative example 3 and the sizing agent added in step (4) was AKD sizing agent, all other conditions being the same as in example 4.
The performance parameters of the bible papers obtained in the different examples and comparative examples are shown in the following table:
| numbering | Quantitative (g/m)2） | Longitudinal tensile index (KN/m) | Transverse tensile index (KN/m) | Smoothness(s) | Water absorption Cobb (g/m) on paper surface2） |
| Example 1 | 28 | 2.3 | 1.5 | 105 | 4.0 |
| Example 2 | 31 | 2.2 | 1.5 | 110 | 3.5 |
| Example 3 | 28 | 2.5 | 1.7 | 108 | 3.4 |
| Example 4 | 29 | 2.6 | 1.7 | 112 | 3.1 |
| Comparative example 1 | 27 | 1.6 | 0.8 | 101 | 3.8 |
| Comparative example 2 | 27 | 2.1 | 1.1 | 73 | 10.2 |
| Comparative example 3 | 30 | 1.3 | 0.6 | 68 | 10.8 |
As can be seen from the table, the biblical papers prepared by the preparation method and the materials of the invention in examples 1 to 4 have good tensile index, smoothness and water absorption on the surface of the paper, and are suitable for being used as large ink level printing biblical papers; the bible paper prepared in comparative example 1, which did not contain the imino-branched polymer modifier, differed greatly in paper strength from the bible papers prepared in examples 1-4; the sizing agent on the surface of the bible paper prepared in the comparative example 2 is changed from a polymerization sizing agent to an AKD sizing agent, and the sizing agent is poor in smoothness and water absorption on the surface of the paper; the saint paper prepared in comparative example 3 has no imino-branched polymer modifier added thereto, and the surface sizing agent is changed from a polymeric sizing agent to an AKD sizing agent, which significantly reduces both the paper strength and the water repellency compared to the saint papers prepared in examples 1 to 4.
Claims (8)
1. A production method of large ink level printing biblical paper is characterized by comprising the following steps:
(1) mixing the fiber raw material and titanium dioxide, pulping, adding the imino branched polymer, and uniformly mixing to obtain mixed slurry;
(2) adding sodium carboxymethylcellulose and water into the mixed slurry, and mixing and stirring to obtain a fiber stock solution;
(3) forming the fiber stock solution on a net, dehydrating and drying to obtain paper sheets;
(4) coating the paper sheet with a filler comprising 100-200 parts of a polymerization sizing agent, 20-40 parts of a retention aid and 1-2 parts of a lubricant on both sides, and standing at normal temperature until the filler is completely fixed on the paper sheet, wherein the polymerization sizing agent is formed by polymerizing saponified polyvinyl acetate and dimethoxy chlorosilyl propyl isocyanate;
(5) dewatering, drying and press polishing to obtain big ink level printing bible paper;
the preparation method of the imino-branched polymer comprises the following steps:
(a) slowly dropwise adding diethylenetriamine and/or dimethylenetriamine into a methanol solution of methyl acrylate under the protection of nitrogen, and reacting for 2-5h at normal temperature to obtain a di-substituted or tri-substituted polymer monomer, wherein the molar ratio of the diethylenetriamine and/or the dimethylenetriamine to the methyl acrylate is 1:3-5, and the volume ratio of ethyl acrylate to methanol in a mixed solution of the methyl acrylate and the methanol is 0.3-0.5: 1;
(b) distilling under reduced pressure to remove methanol, heating to 130-170 ℃, continuing to react for 2-5h under reduced pressure until the reaction is complete, and obtaining the imino branched polymer;
the preparation method of the polymerization sizing agent comprises the following steps:
(i) adding the mixture of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate into ethanol in a molar ratio of 1:8-12 under the protection of inert gas, and stirring and mixing to form a mixed solution, wherein the amount of the mixture of saponified polyvinyl acetate and dimethoxy chlorosilylpropyl isocyanate added per milliliter of ethanol is 0.05-0.2 g;
(ii) and (3) reacting the mixed solution at 80-90 ℃ for 20-25 hours, and distilling under reduced pressure to remove ethanol to obtain the polymerization sizing agent.
2. The method for producing big ink level printing bible paper according to claim 1, wherein the fiber raw materials in the step (1) comprise bleached softwood pulp and bleached hardwood pulp, the weight ratio is 3-4:1-2, the adding amount of titanium dioxide is 1.5wt% -3wt%, the pulp refining degree is 75-85 ° SR, the centrifugal dryness is 20-30g, the wet weight is 2-5g, and the pH is 7.5-8.5.
3. The method for producing large ink level printing bible paper as claimed in claim 1, wherein the imino-branched polymer is added in the amount of 4-8 wt% in step (1).
4. The method as claimed in claim 3, wherein the weight average molecular weight of the saponified poly (vinyl acetate) is 3000-5000, and the saponification degree of the saponified poly (vinyl acetate) is 30-60%.
5. The method for producing large ink level printing biblical paper as claimed in claim 4, wherein in the step (4): the amount of polymeric sizing agent is 2.5-5wt%, and/or
Standing for 3-5 h.
6. The method for producing large ink level printing biblical paper as claimed in claim 1, wherein in the step (4): the retention aid is one or two of polyvinyl acetate latex and styrene-butadiene latex, and/or
The lubricant is calcium stearate.
7. The method for producing large ink level printing biblical paper as claimed in claim 1, wherein the mixed slurry, sodium carboxymethyl cellulose and water in step (2) are mixed according to a weight ratio of 1:2-5: 50-100.
8. The method for producing large ink level printing biblical paper according to any one of claims 1 to 7, wherein the water content of the large ink level printing biblical paper after the pre-dewatering and drying in the step (3) is 10-15wt%, and/or
In the step (5), the water content is 1-3wt% after dehydration and drying.
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| AU628651B2 (en) * | 1989-10-13 | 1992-09-17 | Idemitsu Kosan Co. Ltd | Styrene polymer composition |
| DE69415883T2 (en) * | 1993-07-16 | 1999-08-26 | Sumitomo Chemical Co | Paper coating composition |
| US6596809B2 (en) * | 2001-07-20 | 2003-07-22 | Symyx Technologies, Inc. | Cellulose copolymers that modify fibers and surfaces and methods of making same |
| CN101124175A (en) * | 2005-02-08 | 2008-02-13 | 莫门蒂夫功能性材料公司 | Sizing compositions for fibers utilizing low VOC silanes |
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