CN114016325A - Paper reinforcing agent and preparation method thereof, reinforced paper and preparation method thereof - Google Patents
Paper reinforcing agent and preparation method thereof, reinforced paper and preparation method thereof Download PDFInfo
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- CN114016325A CN114016325A CN202111208905.4A CN202111208905A CN114016325A CN 114016325 A CN114016325 A CN 114016325A CN 202111208905 A CN202111208905 A CN 202111208905A CN 114016325 A CN114016325 A CN 114016325A
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- 239000012744 reinforcing agent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 30
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 229920000881 Modified starch Polymers 0.000 claims abstract description 18
- 239000004368 Modified starch Substances 0.000 claims abstract description 18
- 235000019426 modified starch Nutrition 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 28
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 229940005740 hexametaphosphate Drugs 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 150000003839 salts Chemical group 0.000 claims description 5
- 239000004328 sodium tetraborate Substances 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- -1 hexametaphosphate Chemical compound 0.000 claims description 4
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 229960000250 adipic acid Drugs 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000003384 small molecules Chemical group 0.000 claims description 2
- 230000009172 bursting Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000001254 oxidized starch Substances 0.000 description 5
- 235000013808 oxidized starch Nutrition 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010295 mobile communication Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 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
- 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
- D21H21/18—Reinforcing agents
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/11—Halides
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
-
- 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
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
-
- 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
- D21H17/65—Acid compounds
-
- 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
- D21H17/66—Salts, e.g. alums
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The invention discloses a paper reinforcing agent, which comprises modified starch, polyvinyl alcohol and a cross-linking agent; the modified starch is oxidized, etherified or esterified starch; the cross-linking agent is a micromolecule with bifunctional groups or polyfunctional groups; the paper reinforcing agent is added in the papermaking step in the paper preparation process. The mass ratio of the modified starch, the polyvinyl alcohol and the cross-linking agent is 5 (5-10) to 0.1-0.5 in terms of solid mass. The invention also discloses a preparation method of the paper reinforcing agent, reinforced paper containing the paper reinforcing agent and a preparation method of the paper reinforcing agent. The invention solves the problem that PVA is difficult to retain in the papermaking process, improves the retention of PVA, effectively enhances the dry strength of paper, and particularly obviously improves the bursting strength of finished paper.
Description
Technical Field
The invention relates to the field of papermaking, and particularly relates to a paper reinforcing agent and a preparation method thereof, and reinforced paper and a preparation method thereof.
Background
The paper industry is the largest consumer of modified starch, which is treated with only one modification method, and is improved only in some properties, but has disadvantages in other aspects. If starch is modified by cross-linking, a starch molecular network with a three-dimensional structure is formed by bridging among parallel polyglucose molecules, so that the viscosity becomes very stable, the high temperature resistance is realized, and the shear resistance is greatly improved. However, the viscosity increased, the fluidity was poor, and the gelatinization temperature increased. After the starch is oxidized, molecules are degraded, the viscosity is reduced, the fluidity is good, the penetration and the gelatinization are easy, the carboxyl content is increased, the affinity to fibers is increased, and the adhesive force is enhanced. Multiple modifications can be made to achieve the desired combination of properties.
Starch and PVA are the most commonly used main sizing agents in the sizing of textile warps, and in production practice, in order to improve the performance deficiency of single starch sizing agent or PVA sizing agent, the two are often used in a mixed manner to obtain good sizing effect. However, starch and PVA are thermodynamically incompatible systems and are easily delaminated by direct mixing. Starch has poor compatibility with PVA, limiting the use of PVA in the papermaking field.
Polyvinyl alcohol is a linear polymer and contains abundant hydroxyl groups, but the application of the PVA-added pulp for enhancing paper products is less, because the hydraulic flushing force in the paper making process is large, the PVA is difficult to remain in the paper and is easy to run off, and the binding force between the PVA and fibers needs to be increased.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a paper reinforcing agent, which solves the problem that PVA is difficult to retain in the papermaking process, improves the retention property of PVA, effectively enhances the dry strength of paper, and particularly obviously improves the bursting strength of finished paper.
The second object of the present invention is to provide a method for producing the above paper reinforcing agent.
The invention also aims to provide reinforced paper containing the paper reinforcing agent.
The fourth purpose of the invention is to provide a preparation method of the reinforced paper.
The purpose of the invention is realized by the following technical scheme:
a paper reinforcing agent comprises modified starch, polyvinyl alcohol and a cross-linking agent;
the modified starch is oxidized, etherified or esterified starch;
the cross-linking agent is a small molecule cross-linking agent with double functional groups or multiple functional groups;
the paper reinforcing agent is added in the papermaking step in the paper preparation process.
Preferably, the mass ratio of the modified starch, the polyvinyl alcohol and the cross-linking agent is 5 (5-10) to 0.1-0.5 in terms of solid mass.
Preferably, the crosslinking agent is at least one of phosphorus oxychloride, trimetaphosphate, tripolyphosphate, borax, epichlorohydrin, formaldehyde, adipic acid, hexametaphosphate, glyoxal and divalent or trivalent anhydride.
More preferably, the crosslinking agent is at least one of adipic acid, hexametaphosphate, epichlorohydrin, formaldehyde, glyoxal and borax.
More preferably, the modified starch is oxidized starch, and the viscosity of the modified starch is 10-200 CP at 60 ℃ after gelatinization at the concentration of 15%.
The preparation method of the paper reinforcing agent comprises the following steps:
(1) fully gelatinizing the modified starch, and mixing the gelatinized modified starch with polyvinyl alcohol to obtain a mixture;
(2) adding a pH regulator into the mixture obtained in the step (1) to enable the pH value of the mixture to be 8-9, or 5-6; (3) adding a cross-linking agent, reacting for 1-2 hours at 60-80 ℃, cooling and discharging to obtain the paper reinforcing agent solution, standing for one week without layering and gelling.
Preferably, the preparation process is carried out under the condition of stirring, and the stirring speed is 300-500 rpm.
Preferably, the pH adjuster is a weak acid strong base salt or a metal hydroxide.
Preferably, the pH regulator is a dilute acid or a strong acid and weak base salt.
More preferably, the alkaline pH adjusting agent is sodium hydroxide; more preferably, the acidity regulator is dilute hydrochloric acid, dilute sulfuric acid or aluminum sulfate.
More preferably, the mixture of step (2) is added with a pH adjusting agent and then the pH of the mixture is 9/5.
The paper strengthening agent is added into the reinforced paper.
A method for preparing reinforced paper comprises the following steps: adding the paper reinforcing agent into paper pulp in a papermaking step; the mass of the paper reinforcing agent is 0.5-3% of that of the paper pulp.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the paper reinforcing agent adopts modified starch (which can be oxidized, etherified or esterified starch) containing more carboxyl groups and a cross-linking agent with bifunctional groups or polyfunctional groups to cross-link two hydroxyl groups of starch molecules, starch and two hydroxyl groups of PVA; the miscibility of the starch and the PVA is improved, the retention of the PVA is improved, the dry strength of the paper is effectively enhanced, and particularly, the bursting strength of the finished paper is obviously improved.
(2) Since the water flushing force in the papermaking process is large, PVA is difficult to remain in the paper and is easy to run off, and in order to increase the bursting strength of the paper, the prior art generally solves the problem by means of surface treatment on the finished paper. The paper reinforcing agent can be added in the papermaking process, so that the problem that PVA is difficult to retain in the papermaking process is solved, the PVA additive is directly added into pulp to obtain paper with high bursting strength, the production steps are simplified, the operation is simple and convenient, and the production period and the production cost are greatly reduced.
(3) The paper reinforcing agent prepared by the invention is not layered or gelled after being placed for one week, and has good stability.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The following components are calculated according to parts by mass.
A preparation method of a paper reinforcing agent comprises the following steps:
(1) after 30 parts of oxidized starch (15% by mass) was sufficiently gelatinized in water, 60 parts of PVA (15% by mass) was mixed to obtain a mixture, and the solid content of the obtained mixture was 15%.
(2) And adding sodium hydroxide into the mixture to ensure that the pH value of the mixture is 9, adding 0.5 part of epoxy chloropropane, reacting at 60 ℃ for 1.5 hours, cooling and discharging to obtain the paper reinforcing agent.
The obtained paper reinforcing agent is transparent light yellow liquid, and the viscosity is lower than 1000 cP.
And keeping low-speed stirring during preparation, wherein the low-speed stirring speed is 300-500 rpm.
A papermaking process: adding a needle blade pulp board into a cationic starch solution with the concentration of 1% for defibering for 1 minute, adding the paper reinforcing agent prepared in the embodiment into paper pulp with the addition amount of 1% (the solid content is not reduced, and the mass ratio of the paper reinforcing agent solution to the paper pulp) and uniformly mixing, and then, carrying out sheet making according to 100GSM to obtain a reinforced paper sample 1 in the embodiment;
after the needle blade pulp board is defibered, sheets are copied according to 100GSM as a blank 1;
after the needle blade pulp board is defibered, 2% of cationic starch solution dry strength agent (converted into solid content, mass ratio of dry strength agent to paper pulp) is added, and the mixture is uniformly mixed and then is sliced according to 100GSM (Global System for Mobile communications) to serve as a comparison 1.
The paper is subjected to performance tests according to GB/T1539 and GB/T2679.5-2002, and the results are as follows:
blank 1, burst index 0.9kPa.m2/g；
Comparative 1, burst index 1.5kPa.m 2/g;
sample 1, burst index 1.6kPa.m 2/g.
Example 2
The following components are calculated according to parts by mass.
A preparation method of a paper reinforcing agent comprises the following steps:
(1) after 30 parts of oxidized starch (15% by mass) was sufficiently gelatinized in water, 30 parts of PVA (15% by mass) was mixed to obtain a mixture, and the solid content of the obtained mixture was 15%.
(2) And adding dilute hydrochloric acid into the mixture to ensure that the pH value of the mixture is 5, adding 0.3 part of glyoxal, reacting at 60 ℃ for 1.5 hours, cooling and discharging to obtain the paper reinforcing agent.
The resulting paper strength agent was a clear colorless liquid with a viscosity of less than 1000 cP.
And keeping low-speed stirring during preparation, wherein the low-speed stirring speed is 300-500 rpm.
A papermaking process: adding a needle blade pulp board into a cationic starch solution with the concentration of 1% for defibering for 1 minute, adding the paper reinforcing agent prepared in the embodiment into paper pulp with the addition amount of 1% (the solid content is not reduced, and the mass ratio of the paper reinforcing agent solution to the paper pulp) and uniformly mixing, and then, carrying out sheet making according to 100GSM to obtain a reinforced paper sample 2 in the embodiment;
after the needle blade pulp board is defibered, sheets are copied according to 100GSM as a blank 2;
after the needle blade pulp board is defibered, 2% of cationic starch solution dry strength agent (by mass ratio of solid content and dry strength agent to paper pulp) is added, and the mixture is uniformly mixed and then is sliced according to 100GSM (Global System for Mobile communications) to serve as a comparison 2.
The paper is subjected to performance tests according to GB/T1539 and GB/T2679.5-2002, and the results are as follows:
blank 2, burst index 0.9kpa.m 2/g;
comparative 2, burst index 1.5kPa.m 2/g;
sample 2, burst index 1.5 kPa.m2/g.
Example 3
The following components are calculated according to parts by mass.
A preparation method of a paper reinforcing agent comprises the following steps:
(1) after 30 parts of oxidized starch (15% by mass) was sufficiently gelatinized in water, 60 parts of PVA (15% by mass) was mixed to obtain a mixture, and the solid content of the obtained mixture was 15%.
(2) And adding dilute hydrochloric acid into the mixture to ensure that the pH value of the mixture is 5, adding 0.3 part of glyoxal, reacting at 60 ℃ for 1.5 hours, cooling and discharging to obtain the paper reinforcing agent.
The resulting paper strength agent was a clear colorless liquid with a viscosity of less than 1000 cP.
And keeping low-speed stirring during preparation, wherein the low-speed stirring speed is 300-500 rpm.
A papermaking process: adding a needle blade pulp board into a cationic starch solution with the concentration of 1% for defibering for 1 minute, adding the paper reinforcing agent prepared in the embodiment into paper pulp with the addition amount of 1.5% (the solid content is not reduced, and the mass ratio of the paper reinforcing agent solution to the paper pulp) and uniformly mixing, and then, carrying out sheet making according to 100GSM to obtain a reinforced paper sample 3 of the embodiment;
after the needle blade pulp board is defibered, sheets are copied according to 100GSM as a blank 3;
after the needle blade pulp board is defibered, 2% of cationic starch solution dry strength agent (converted into solid content, mass ratio of dry strength agent to paper pulp) is added, mixed uniformly, and then the mixture is processed into sheets according to 100GSM (Global System for Mobile communications) as comparison 3.
The paper is subjected to performance tests according to GB/T1539 and GB/T2679.5-2002, and the results are as follows:
blank 3, burst index 0.9kpa.m 2/g;
comparison 3, burst index 1.5kPa.m 2/g;
sample 3, burst index 1.65 kPa.m2/g.
Example 4
The following components are calculated according to parts by mass.
A preparation method of a paper reinforcing agent comprises the following steps:
(1) after 30 parts of oxidized starch (15% by mass) was sufficiently gelatinized in water, a mixture was obtained by mixing with 50 parts of PVA (15% by mass), and the resulting mixture was made to have a solid content of 15%.
(2) And adding sodium hydroxide into the mixture to ensure that the pH value of the mixture is 9, adding 0.2 part of borax, reacting for 1 hour at 80 ℃, cooling and discharging to obtain the paper reinforcing agent.
The obtained paper reinforcing agent is transparent light yellow liquid, and the viscosity is lower than 1500 cP.
And keeping low-speed stirring during preparation, wherein the low-speed stirring speed is 400-500 rpm.
A papermaking process: adding a needle blade pulp board into a cationic starch solution with the concentration of 1% for defibering for 1 minute, adding the paper reinforcing agent prepared in the embodiment into paper pulp with the addition amount of 2% (the solid content is not reduced, and the mass ratio of the paper reinforcing agent solution to the paper pulp) and uniformly mixing, and then, carrying out sheet making according to 100GSM to obtain a reinforced paper sample 4 in the embodiment;
after the needle blade pulp board is defibered, sheets are taken according to 100GSM as a blank 4;
after the needle blade pulp board is defibered, 2% of cationic starch solution dry strength agent (converted into solid content, mass ratio of dry strength agent to paper pulp) is added, mixed uniformly, and then the mixture is processed into sheets according to 100GSM (Global System for Mobile communications) to serve as a comparison 4.
The paper is subjected to performance tests according to GB/T1539 and GB/T2679.5-2002, and the results are as follows:
blank 4, burst index 0.9kPa.m 2/g;
comparative 4, burst index 1.5kPa.m 2/g;
sample 4, burst index 1.7 kPa.m2/g.
Analysis of test results for each example:
as can be seen from comparison of the blank group and the sample group in each embodiment, the paper reinforcing agent used in the invention can greatly improve the dry strength of paper, wherein the burst index improvement range is about 60-80%; as can be seen from the comparative group and the sample group control of each example, compared with the commonly used cationic starch dry strength agent, the paper strengthening agent prepared by the invention has more excellent effect under the condition of 2% dosage, wherein the burst index is further improved by about 10-15%.
In the above embodiment, the crosslinking agent may also be at least one of phosphorus oxychloride, trimetaphosphate, tripolyphosphate, formaldehyde, adipic acid, hexametaphosphate, and di-or trivalent acid anhydride.
In the above embodiment, the pH adjuster may be an alkaline pH adjuster or an acidic pH adjuster. The alkaline pH regulator may also be weak acid, strong alkali salt or other metal hydroxide. Wherein, the acidity regulator is at least one of diluted acid and strong acid and weak base salt, and is more preferably diluted hydrochloric acid, diluted sulfuric acid and aluminum sulfate.
In the above embodiment, the modified starch may also be an etherified or esterified starch.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A paper reinforcing agent is characterized by comprising modified starch, polyvinyl alcohol and a cross-linking agent;
the modified starch is oxidized, etherified or esterified starch;
the cross-linking agent is a small molecule cross-linking agent with double functional groups or multiple functional groups;
the paper reinforcing agent is added in the papermaking step in the paper preparation process.
2. The paper reinforcing agent according to claim 1, wherein the mass ratio of the modified starch, the polyvinyl alcohol and the crosslinking agent is 5 (5-10) to 0.1-0.5, based on the solid content.
3. Reinforcing agent for paper according to claim 1, characterized in that the crosslinking agent is at least one of phosphorus oxychloride, trimetaphosphate, tripolyphosphate, borax, epichlorohydrin, formaldehyde, adipic acid, hexametaphosphate, glyoxal, di-or trivalent anhydride.
4. The paper reinforcing agent according to claim 1, wherein the crosslinking agent is at least one of adipic acid, hexametaphosphate, epichlorohydrin, formaldehyde, glyoxal, and borax.
5. The method for producing the paper reinforcing agent according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) fully gelatinizing the modified starch, and mixing the gelatinized modified starch with polyvinyl alcohol to obtain a mixture;
(2) adding a pH regulator into the mixture obtained in the step (1) to enable the pH value of the mixture to be 8-9, or 5-6;
(3) adding a cross-linking agent, reacting for 1-2 hours at 60-80 ℃, cooling and discharging to obtain the paper reinforcing agent solution.
6. The method for preparing the paper reinforcing agent according to claim 5, wherein the preparation process is carried out under stirring conditions, and the stirring speed is 300-500 rpm.
7. The method of claim 5, wherein the pH adjuster is a salt of a weak acid and a strong base or a metal hydroxide.
8. The method of claim 5, wherein the pH adjuster is a dilute acid or a salt of a strong acid and a weak base.
9. A reinforced paper characterized by adding the paper reinforcing agent according to any one of claims 1 to 4.
10. A preparation method of reinforced paper is characterized by comprising the following steps: adding the paper reinforcing agent according to any one of claims 1 to 4 to paper pulp in a papermaking step; the mass of the paper reinforcing agent is 0.5-3% of that of the paper pulp.
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