CN116876255A - Preparation process of oil-proof semitransparent paper - Google Patents
Preparation process of oil-proof semitransparent paper Download PDFInfo
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- CN116876255A CN116876255A CN202310833478.1A CN202310833478A CN116876255A CN 116876255 A CN116876255 A CN 116876255A CN 202310833478 A CN202310833478 A CN 202310833478A CN 116876255 A CN116876255 A CN 116876255A
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- paper
- sizing agent
- surface sizing
- oil
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000004513 sizing Methods 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000003490 calendering Methods 0.000 claims abstract description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 37
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 37
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 31
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 31
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 31
- 159000000000 sodium salts Chemical class 0.000 claims description 20
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 239000005871 repellent Substances 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 53
- 239000000123 paper Substances 0.000 description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000011087 paperboard Substances 0.000 description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- VPKQPPJQTZJZDB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C VPKQPPJQTZJZDB-UHFFFAOYSA-N 0.000 description 2
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- -1 polysiloxane structure Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002939 oilproofing Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/59—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 silicon
-
- 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
- D21H19/10—Coatings without pigments
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The application relates to the technical field of paper, and particularly provides a preparation process of oil-proof semitransparent paper. The preparation process of oil-proof semitransparent paper comprises the steps of applying a surface sizing agent to paper in a calendaring process; the surface sizing agent comprises, by weight, 100%: 2-5% of carboxymethyl cellulose, sodium salt thereof, 1-3% of amino silicone oil emulsion and the balance of water. The surface sizing agent of the present application may also comprise PVA and/or poly (meth) acrylic homo-or copolymers. The surface sizing agent can obviously improve the water resistance and oil resistance of paper after being applied to the surface of the paper, and has a certain effect on improving the tensile strength of the paper.
Description
Technical Field
The application relates to the technical field of paper, in particular to a preparation process of oil-proof semitransparent paper.
Background
Surface sizing is a procedure in the paper or paperboard processing process, and is usually positioned at the tail end of a drying part of a paper machine, so that a layer of glue solution is sprayed when paper sheets are not completely dried but have certain strength, and a layer of glue film is formed on the surface of the paper or paperboard after the drying procedure, thereby achieving the purposes of changing the surface properties of the paper or paperboard, such as oil resistance, strength improvement and the like.
In the prior art, a commonly used paper surface sizing agent is carboxymethyl cellulose (CMC), has good film forming property and integral film transferring property, and can form good sealing property and oil resistance on the surface of paper, but CMC also has the problems of high viscosity and strong viscosity. Although the problems of high viscosity and strong viscosity can be partially solved by adopting CMC with medium molecular weight at present, the problem can not be solved perfectly.
Disclosure of Invention
The application provides a preparation process of oil-proof semitransparent paper, which aims to solve the technical problems of high viscosity and strong viscosity of CMC (carboxyl methyl cellulose) serving as a paper surface sizing agent in the prior art.
The application adopts the following technical scheme:
a preparation process for applying surface semitransparent paper to paper in oil proofing is disclosed, wherein a sizing agent is applied to a calendaring process surface;
the surface sizing agent comprises, by weight, 100: 2-5% of carboxymethyl cellulose, sodium salt thereof, 1-3% of amino silicone oil emulsion and the balance of water.
Preferably, the weight percentage concentration ratio of the carboxymethyl cellulose and the sodium salt thereof to the amino silicone oil emulsion is 1:0.2-1.
Preferably, the carboxymethyl cellulose and its sodium salt have a viscosity of no more than 800cps at 2% by weight at 25 ℃ and a degree of substitution of 0.6 to 0.85.
Preferably, the amino silicone oil emulsion comprises 30-70% by weight.
Preferably, the surface sizing agent further comprises 1-3% polyvinyl alcohol.
More preferably, the polyvinyl alcohol has a polymerization degree of 1000 to 2000 and an alcoholysis degree of 98 to 99%.
Preferably, the surface sizing agent further comprises 1-3% of a poly (meth) acrylic acid homopolymer or a poly (meth) acrylic acid copolymer.
More preferably, the molar ratio of (meth) acrylic acid in the polymerized monomer of the poly (meth) acrylic acid copolymer is not less than 65%.
Further preferably, the polymerized monomers of the poly (meth) acrylic copolymer further comprise a polymer of the formula CH 2 =CR 1 COOR 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from C1-C18 alkyl or C1-C18 fluoro substituted alkyl.
An oil-repellent semi-transparent paper prepared by the process for preparing an oil-repellent semi-transparent paper according to any one of the embodiments described above.
In summary, the application has at least the following advantages:
1. the surface sizing agent disclosed by the application comprises carboxymethyl cellulose and sodium salt thereof and amino silicone oil emulsion, so that the problems of high viscosity and strong viscosity brought by using the carboxymethyl cellulose and sodium salt thereof as the surface sizing agent are solved, and the surface sizing agent has lower viscosity and viscosity.
2. The amino silicone oil emulsion is added into the surface sizing agent, so that the water and oil repellency of paper can be further improved, and the amino in the amino silicone oil and the carboxyl in the carboxymethyl cellulose and sodium salt thereof can generate stronger hydrogen bond action, so that the hydrophobic polysiloxane structure in the amino silicone oil molecule can cover and cover the surface and the outward facing side of the carboxymethyl cellulose and sodium salt thereof, thereby improving the water and oil repellency of the paper.
3. The surface sizing agent of the present application may further comprise homopolymers or copolymers of polyvinyl alcohol and/or poly (meth) acrylic acid. The polyvinyl alcohol allows better penetration of the surface sizing agent into the interior of the paper structure, thereby increasing the strength of the paper. The carboxyl in the homopolymer or copolymer of poly (methyl) acrylic acid can generate a plurality of hydrogen bonds with carboxymethyl cellulose and sodium salt thereof and amino silicone oil, thereby further improving the water and oil resistance of the paper.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail below.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
The application provides a preparation process of oil-proof semitransparent paper, wherein a surface sizing agent is applied to the paper in a calendaring process;
the surface sizing agent comprises the following components in percentage by weight: 2-5% of carboxymethyl cellulose, sodium salt thereof, 1-3% of amino silicone oil emulsion and the balance of water.
The carboxymethyl cellulose is used as a surface sizing agent for paper, has good film forming property and overall film transfer property, can form good sealing property and oil resistance on the surface of the paper, but also has the problems of high viscosity and high viscosity, and is unfavorable for sizing. In the application, amino silicone oil emulsion is added into the surface sizing agent, so that the problems of high viscosity and high viscosity caused by carboxymethyl cellulose and sodium salt thereof can be obviously reduced, and the water and oil resistance of paper can be improved after the surface sizing agent is sized on the surface of the paper. In the application, the dosage of the surface sizing agent for sizing paper is 10-50Kg per ton of paper.
In a preferred embodiment of the application, the weight percentage concentration ratio of the carboxymethyl cellulose and the sodium salt thereof to the amino silicone oil emulsion is 1:0.2-1. The weight percentage concentration ratio of the carboxymethyl cellulose and the sodium salt thereof to the amino silicone oil emulsion is controlled in the range, and the action between the carboxymethyl cellulose and the sodium salt thereof and the amino silicone oil is better. More preferably, the weight percent concentration ratio of carboxymethyl cellulose and its sodium salt to the aminosilicone emulsion is 1:0.2-0.6, for example, the weight percent concentration ratio may be 1:0.2, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.33, 1:0.35, 1:0.37, 1:0.4, 1:0.42, 1:0.45, 1:0.47, 1:0.5, 1:0.52, 1:0.55, 1:0.57, 1:0.6, etc.
In a preferred embodiment of the present application, the carboxymethyl cellulose and its sodium salt are medium viscosity carboxymethyl cellulose and its sodium salt, 2wt% viscosity at 25 ℃ is not more than 800cps, and substitution degree is 0.6-0.85. It is further preferred that the viscosity of 2wt% at 25 ℃ is no more than 600cps, and still further preferred that it is no more than 300cps. By way of example, the viscosity of carboxymethyl cellulose and its sodium salt at 25 ℃ at 2wt% may be 100cps, 150cps, 180cps, 200cps, 230cps, 250cps, 270cps, 280cps, 300cps, etc. Further preferably, the degree of substitution is 0.6 to 0.8, still further preferably, the degree of substitution is 0.6 to 0.75, and for example, the degree of substitution may be 0.6, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, or the like.
In a preferred embodiment of the application, the amino silicone oil emulsion comprises 30 to 70% by weight. In the application, the amino silicone oil emulsion not only comprises common amino silicone oil emulsion, namely amino silicone oil emulsion with milky appearance, but also comprises amino silicone oil microemulsion, namely amino silicone oil emulsion with semitransparent to transparent appearance. The ammonia value of the amino silicone oil in the amino silicone oil emulsion has an effect on yellowing of paper, and the higher the ammonia value, the more easily the paper becomes yellowing. In order to achieve both lower yellowing and not to affect the properties of the surface sizing agent, the ammonia value may be 0.1-1.5, or further, the ammonia value may be 0.2-1.2. The amino silicone oil emulsion of the application can be obtained from commercial products or self-made. The self-made method of the common amino silicone oil emulsion can be as follows: 100 parts by weight of amino silicone oil with the viscosity of 1000-10000mPa.s at 25 ℃ and the ammonia value of 0.2-1.2, 10 parts by weight of emulsifying agent (which can be composed of Tween80 and Span80 according to the weight ratio of 2:1-1:1) and 0.5 part by weight of n-butanol are uniformly mixed, 70-100 parts by weight of water is gradually added under high-speed stirring at 1200-2000rpm, the water is added, the stirring speed is adjusted to 200-300rpm, and stirring is continued for 10 minutes, so that the aqueous emulsion is obtained.
In a preferred embodiment of the present application, the above surface sizing agent may further contain 1 to 3% of polyvinyl alcohol. The polyvinyl alcohol PVA is further added into the surface sizing agent, so that the surface sizing agent can more easily permeate into the internal structure of the paper, and the tensile strength of the paper is improved.
In a more preferred embodiment of the application, the PVA has a degree of polymerization of 1000 to 2000 and an alcoholysis degree of 98 to 99%. For example, the polymerization degree of PVA may be 1200, 1500, 1700, etc., and specific PVA types may be PVA-1798, PVA-1799, etc.
In a preferred embodiment of the present application, the above surface sizing agent may further contain 1 to 3% of a poly (meth) acrylic acid homopolymer or a poly (meth) acrylic acid copolymer. The poly (methyl) acrylic acid homopolymer or the poly (methyl) acrylic acid copolymer is further added into the surface sizing agent, the poly (methyl) acrylic acid homopolymer or the poly (methyl) acrylic acid copolymer has better water solubility and can be dissolved in the sizing agent, and carboxyl groups in the poly (methyl) acrylic acid homopolymer or the poly (methyl) acrylic acid copolymer can form better hydrogen bonding with amino groups in amino silicone oil, carboxyl groups in carboxymethyl cellulose and sodium salt thereof, so that the amino silicone oil, the poly (methyl) acrylic acid homopolymer or the poly (methyl) acrylic acid copolymer, the carboxymethyl cellulose and sodium salt thereof can form multiple hydrogen bonding effects, and the three effects together improve the water and oil resistance of the surface sizing agent to paper and reduce the water absorption.
In a more preferred embodiment of the present application, the molar ratio of (meth) acrylic acid in the polymerized monomer of the poly (meth) acrylic acid copolymer is not less than 65%. The molar ratio of (methyl) acrylic acid in the polymerized monomer of the poly (methyl) acrylic acid copolymer is not less than 65 percent, and the copolymer has better water solubility. For example, the molar ratio of (meth) acrylic acid in the polymerized monomers of the poly (meth) acrylic acid copolymer may be 65%, 68%, 70%, 72%, 73%, 75%, 77%, 78%, 80%, 83%, 85%, 87%, 88%, 90%, 92%, 95%, 98%, etc.
In a further preferred embodiment of the application, the polymerized monomers of the poly (meth) acrylic acid copolymer comprise, in addition to (meth) acrylic acid, a polymer of the formula CH 2 =CR 1 COOR 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from C1-C18 alkyl or C1-C18 fluoro substituted alkyl. The copolymer containing the acrylate monomer structure as a hydrophobic structure is adopted, the hydrophilic structure in the copolymer and amino silicone oil, carboxymethyl cellulose and sodium salt thereof form a hydrogen bond effect, the hydrophobic structure stretches outwards to provide a hydrophobic effect for paper, and the water and oil resistance of the paper can be further improved. CopolymerizationWhen the hydrophobic structure contains the fluoroalkyl structure, the paper can be endowed with better water and oil resistance.
In the present application, the poly (meth) acrylic acid homopolymer can be prepared as follows: 50 parts by weight of (methyl) acrylic acid is added into 100 parts by weight of water, stirred and dissolved, an initiator ammonium persulfate accounting for 3% of the weight of the (methyl) acrylic acid is added, the temperature is raised to 70+/-2 ℃, the stirring reaction is carried out for 6 hours, the mixture is added into 2000 parts by weight of methanol for precipitation, and the precipitation is dried, thus obtaining the catalyst. Alternatively, the reaction system may be further concentrated by distillation under reduced pressure or the like, for example, the concentration may be concentrated to 50wt%, 60wt%, or the like, before being precipitated by addition to methanol.
In the present application, the poly (meth) acrylic copolymer may be prepared as follows: 50 parts by weight of (methyl) acrylic acid is added into 100 parts by weight of water, stirred and dissolved, an initiator ammonium persulfate accounting for 3% of the weight of the (methyl) acrylic acid is added, the temperature is raised to 70+/-2 ℃, the stirring reaction is carried out for 6 hours, then the corresponding parts by weight of acrylic ester monomers (such as butyl acrylate, perfluorooctyl ethyl acrylate and perfluorohexyl ethyl acrylate) are dropwise added, the reaction is continued for 5 hours, the mixture is added into 2500 parts by weight of methanol for precipitation, and the precipitation is dried, thus obtaining the catalyst. Alternatively, the reaction system may be further concentrated by distillation under reduced pressure or the like, for example, the concentration may be concentrated to 50wt%, 60wt%, or the like, before being precipitated by addition to methanol.
In another aspect, the application provides oil-resistant translucent paper, which is prepared by the preparation process of the oil-resistant translucent paper according to any one of the embodiments.
The paper sizing agent of the present application can be used for opaque paper, corrugated paper, etc., in addition to translucent paper.
The technical scheme of the application is described in detail below with reference to examples and comparative examples. Unless otherwise indicated, the parts in the examples and comparative examples below are parts by weight.
Example 1
100 parts of amino silicone oil with the viscosity of 750 mpa.s at 25 ℃ and the ammonia value of 0.4, 10 parts of emulsifying agent (composed of Tween80 and Span80 according to the weight ratio of 1.2:1) and 0.5 part of n-butanol are uniformly mixed, 100 parts of water is gradually added under high-speed stirring at 1500rpm, the water is added, the stirring speed is adjusted to 250rpm, and stirring is continued for 10 minutes, so that the amino silicone oil emulsion is obtained.
4 parts of medium-viscosity carboxymethyl cellulose CMC (viscosity 280cps at 25 ℃ at 2wt% concentration, substitution degree 0.65) is dissolved in 95 parts of water, 1 part of the amino silicone oil emulsion is added, and the mixture is stirred and mixed uniformly to obtain the surface sizing agent.
Example 2
In example 1, the amino silicone oil emulsion was adjusted to 2 parts, water was adjusted to 94 parts, and the remaining steps remained unchanged.
Example 3
The surface sizing agent in example 1 was dissolved by adding carboxymethyl cellulose, then added with 1 part of PVA-1798, the water was adjusted to 94 parts, finally added with amino silicone oil emulsion, and the rest steps remained unchanged.
Example 4
In example 3, PVA-1798 was adjusted from 1 part to 2 parts, the part of water was adjusted to 93 parts, and the rest of the procedure remained unchanged.
Example 5
The surface sizing agent in example 1 was dissolved by adding carboxymethyl cellulose and then added with 1 part of methacrylic acid homopolymer, the water was adjusted to 94 parts, and finally amino silicone oil emulsion was added, and the rest steps remained unchanged.
Example 6
The surface sizing agent in example 1 was dissolved by adding carboxymethyl cellulose and then added with 2 parts of methacrylic acid copolymer (the polymerized monomer consists of acrylic acid and perfluoro-hexyl ethyl acrylate in a molar ratio of 9:1), the water fraction was adjusted to 93 parts, finally amino silicone oil emulsion was added, and the rest steps remained unchanged.
Example 7
100 parts of amino silicone oil with the viscosity of 2700MPa.s at 25 ℃ and the ammonia value of 0.8, 8 parts of emulsifying agent (composed of Tween80 and Span80 according to the weight ratio of 1.3:1) and 0.5 part of n-butanol are uniformly mixed, 150 parts of water is gradually added under high-speed stirring at 1500rpm, water is added, the stirring speed is adjusted to 250rpm, and stirring is continued for 10 minutes, so that the amino silicone oil emulsion is obtained.
5 parts of medium-viscosity carboxymethyl cellulose (viscosity 280cps at 25 ℃ at 2wt% concentration, substitution degree 0.72) is dissolved in 93 parts of water, 2 parts of the amino silicone oil emulsion is added, and the mixture is stirred and mixed uniformly to obtain the surface sizing agent.
Example 8
5 parts of medium-viscosity carboxymethyl cellulose in example 7 is dissolved in 91.5 parts of water, 1.5 parts of methacrylic acid copolymer (a polymerization monomer consists of methacrylic acid and perfluorooctyl ethyl acrylate according to a molar ratio of 8:2) is added, stirring and dissolving are carried out, and then 2 parts of amino silicone oil emulsion in example 7 is added, stirring and mixing are carried out uniformly, so that the surface sizing agent is obtained.
Comparative example 1
4 parts of the medium-viscosity carboxymethyl cellulose in example 1 was dissolved in 96 parts of water to obtain a surface sizing agent.
Comparative example 2
4 parts of medium-viscosity carboxymethyl cellulose in example 1 was dissolved in 95 parts of water, 1 part of PVA-1798 was added thereto, and the mixture was stirred and mixed uniformly to obtain a surface sizing agent.
Comparative example 3
4 parts of medium-viscosity carboxymethyl cellulose in example 1 was dissolved in 94 parts of water, 2 parts of PVA-1798 was added thereto, and the mixture was stirred and mixed uniformly to obtain a surface sizing agent.
Comparative example 4
4 parts of the medium-viscosity carboxymethyl cellulose in example 1 was dissolved in 94 parts of water, 2 parts of the methacrylic acid copolymer in example 6 was added, and stirred and mixed uniformly to obtain a surface sizing agent.
The raw material compositions and viscosities (25 ℃) of the surface sizing agents of examples 1 to 8 and comparative examples 1 to 4 are shown in Table 1 below.
The viscosity was measured using a rotational viscometer NDJ-5S at 6rpm.
TABLE 1 raw material composition and viscosity of surface sizing agent
As can be seen from the results in Table 1, the surface sizing agent of the present application can significantly reduce the viscosity of the surface sizing agent after adding the amino silicone oil emulsion, and is more advantageous for construction.
The semitransparent paper is produced according to the following process: wood pulp, bagasse pulp and bleached waste paper pulp are added into 5m according to the weight ratio of 2:1:1 3 The pulper circulates and passes through the technological processes of beating the pulp tank before beating, pulping (five disc mills of a main line are connected in series), pulping tank, chemical product adding, pulp preparing tank, pulp tank before beating, surfing, squeezing, drying, coiling, wetting, calendaring, packaging, warehousing and the like.
In the above-mentioned steps of the process for producing translucent paper, 40Kg of the surface sizing agents of examples 1 to 8 and comparative examples 1 to 4 were added per ton of paper, respectively, in the calendering step.
Absorbency: the test was carried out according to GB/T1540-2002 determination of the absorbency of paper and cardboard (Lasiosphaera method).
Oil resistance: the test was carried out according to GB/T22805.2-2008 section 2 determination of the lipid resistance of paper and paperboard, surface repellency method.
Tensile strength: the test was carried out according to GB/T12914-2008 "determination of tensile Strength of paper and cardboard".
The results are shown in Table 2 below.
Table 2 performance test
As can be seen from the data in table 2, the surface sizing agent of the present application can reduce and improve the water resistance and oil resistance of paper and also improve the tensile strength to some extent after sizing on the surface of translucent paper in the calendering stage.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A preparation process of oil-proof semitransparent paper is characterized by comprising the following steps of: applying a surface sizing agent to the paper in a calendering process;
the surface sizing agent comprises, by weight, 100: 2-5% of carboxymethyl cellulose, sodium salt thereof, 1-3% of amino silicone oil emulsion and the balance of water.
2. The process for producing oil-repellent semi-transparent paper according to claim 1, wherein: the weight percentage concentration ratio of the carboxymethyl cellulose and the sodium salt thereof to the amino silicone oil emulsion is 1:0.2-1.
3. The process for producing oil-repellent semi-transparent paper according to claim 1, wherein: the viscosity of the carboxymethyl cellulose and sodium salt thereof is not more than 800cps at 25deg.C and 2wt%, and the substitution degree is 0.6-0.85.
4. The process for producing oil-repellent semi-transparent paper according to claim 1, wherein: the weight percentage of the amino silicone oil emulsion is 30-70%.
5. The process for producing oil-repellent semi-transparent paper according to claim 1, wherein: the surface sizing agent also contains 1-3% of polyvinyl alcohol.
6. The process for producing oil-repellent semi-transparent paper according to claim 5, wherein: the polymerization degree of the polyvinyl alcohol is 1000-2000, and the alcoholysis degree is 98-99%.
7. The process for producing oil-repellent semi-transparent paper according to claim 1, wherein: the surface sizing agent also contains 1-3% of poly (meth) acrylic acid homopolymer or poly (meth) acrylic acid copolymer.
8. The process for producing oil-repellent semi-transparent paper according to claim 7, wherein: the molar ratio of (meth) acrylic acid in the polymerized monomer of the poly (meth) acrylic acid copolymer is not less than 65%.
9. The process for producing oil-repellent semi-transparent paper according to claim 8, wherein: the polymerized monomers of the poly (meth) acrylic copolymer further comprise a polymer of the formula CH 2 =CR 1 COOR 2 Wherein R is 1 Selected from H or C1-C4 alkyl, R 2 Selected from C1-C18 alkyl or C1-C18 fluoro substituted alkyl.
10. An oil-resistant translucent paper, characterized in that: obtained by the process for producing oil-repellent semi-transparent paper according to any one of claims 1 to 9.
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