CN116411476B - Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition - Google Patents

Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition Download PDF

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CN116411476B
CN116411476B CN202111668163.3A CN202111668163A CN116411476B CN 116411476 B CN116411476 B CN 116411476B CN 202111668163 A CN202111668163 A CN 202111668163A CN 116411476 B CN116411476 B CN 116411476B
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paper
monomer
barrier composition
polymer
meth
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CN116411476A (en
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刘伟时
林观生
石建伟
韩泽明
胡龙
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Guangzhou Shine Polymer Technology Co ltd
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Guangzhou Shine Polymer Technology Co ltd
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • 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
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

The invention discloses an anti-sticking barrier composition for paper and plastic, a preparation method thereof and a pulp molded product prepared from the composition. The anti-sticking barrier composition for paper and plastic comprises a polymer A, an alkaline substance B and a tackifying substance C, wherein the polymer A is formed by copolymerizing a (methyl) acrylic acid alkyl ester monomer a1, a vinyl aromatic monomer a2, an acrylic acid monomer a3 and a crosslinking vinyl monomer a 4. After the composition is coated on the surface of a paper-based product, a continuous compact film layer can be formed, and the tackifying substance can infiltrate into and fill the gaps of paper-based fibers when the coating is dried, so that the composition can endow the paper-based product with better anti-penetration performance (hot water, hot oil and steam prevention), has a hot-sticking prevention function, and particularly provides an effective solution to the problem of sticking rice on paper tableware, and the use of the composition does not influence pulping and recycling of the paper-based product.

Description

Anti-sticking barrier composition for paper and plastic, preparation method thereof and pulp molded product prepared from anti-sticking barrier composition
Technical Field
The invention relates to the field of high molecular polymers, in particular to an anti-sticking barrier composition for paper and plastic, a preparation method thereof and a pulp molding product prepared from the anti-sticking barrier composition.
Background
The paper pulp molding product (paper plastic) is a packaging material which is obtained by taking primary fiber or secondary fiber as a main raw material, dehydrating and molding the fiber by a special mold, and drying and shaping. The paper plastic product takes natural plant fiber as raw material, and the product can be recycled for many times or rapidly and naturally degraded, and more importantly, the paper plastic product replaces the foam plastic product which is extremely large in dosage and difficult to degrade and has pollution in the production process, thereby reducing the damage of human activities to the natural environment. Therefore, the production and application of the paper-plastic product accord with the modern green manufacturing concept, and the significance for reducing environmental pollution is great.
Because the paper-based fiber has hydroxyl and porous structure, the common paper-plastic product does not have the property of preventing liquid and gas from penetrating, and the common paper-plastic product must be subjected to permeation prevention treatment to meet the requirements of packaging use.
The traditional film coating process achieves the anti-seepage effect by coating a layer of plastic film on the surface of the paper product, but the used plastic film cannot be degraded in the nature, so that the film coating cannot fundamentally solve the problem of environmental pollution. The paper plastic industry adds waterproofing agent and fluorocarbon polymer oil-proofing agent into the pulp to achieve better waterproof and oil-proofing effects with smaller addition amount, but the method cannot solve the problems of gas permeation and thermal adhesion prevention, for example, after the paper snack box is filled with hot water and food, the snack box is softened quickly due to permeation of water vapor, meanwhile, hot food such as hot rice can be stuck on paper tableware, the transfer is difficult, even the hot rice can bring a small amount of paper fiber contacted with the hot rice out and is stuck on the rice, and consumers can feel difficult to swallow. In general, the research on the aspect of preventing gas permeation and thermal adhesion of paper-plastic products is very little in the industry at present, and the problem needs to be solved.
Disclosure of Invention
The invention provides an anti-sticking barrier composition for paper and plastic aiming at the problems existing in the prior art. The anti-sticking barrier composition has good anti-permeability and anti-sticking performance, and does not influence pulping recycling.
It is another object of the present invention to provide a method of preparing the anti-sticking barrier composition.
It is a further object of the present invention to provide the use of the anti-blocking composition.
It is another object of the present invention to provide a pulp molded article comprising the release barrier composition.
The above object of the present invention is achieved by the following technical scheme:
the anti-sticking barrier composition for paper and plastic comprises a polymer A, an alkaline substance B and a tackifying substance C, wherein the polymer A is formed by copolymerizing a (methyl) acrylic acid alkyl ester monomer a1, a vinyl aromatic monomer a2, an acrylic acid monomer a3 and a crosslinking vinyl monomer a 4;
the butanone insoluble component of the polymer A is more than 90 mass%;
the butanone soluble component of the polymer A has a weight average molecular weight Mw of 100000 ～ 200000, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, calculated as Mw/Mn, is 2.0 to 3.0;
the average particle diameter D50 of the polymer A is 100-200 nm.
The anti-sticking barrier composition for paper plastic provided by the invention endows paper-based products with better anti-permeation performance (hot water resistance, hot oil resistance and steam resistance) through reasonable collocation of the polymer A and the tackifying substances, has a function of heat adhesion resistance, and particularly provides an effective solution to the problem of rice adhesion of paper tableware. Meanwhile, the use of the composition does not affect the pulping recycling performance of paper-based products.
Preferably, the polymer A is polymerized from the following monomers in parts by weight: based on 100 parts of total monomer weight, the (methyl) acrylic acid alkyl ester monomer a1 is 30-50 parts, the vinyl aromatic monomer a2 is 40-65 parts, the acrylic acid monomer a3 is 3-5 parts, and the cross-linking vinyl monomer a4 is 0.1-3 parts.
The alkyl (meth) acrylate monomer a1 has a low glass transition temperature (Tg is-20 ℃ to-70 ℃ and the glass transition temperature of the copolymer can be calculated by using the FOX equation) of a homopolymer or a copolymer, so that the polymer A can be endowed with initial tackiness, film forming property and adhesive force.
Preferably, the alkyl (meth) acrylate monomer a1 is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, and lauryl (meth) acrylate.
The vinyl aromatic monomer a2 contains benzene ring in the molecular structure, and the homopolymer has higher glass transition temperature, and can improve the cohesion and heat-resistant temperature of the polymer by introducing the vinyl aromatic monomer a2 into the polymer A, plays an important role in heat adhesion prevention, and can improve the liquid permeation resistance of the coating.
Preferably, the vinylaromatic monomer a2 is one or more of styrene, alpha-methylstyrene, ethylstyrene, butylstyrene or dimethylstyrene.
The acrylic monomer a3 contains carboxyl groups, is polar groups and has strong hydrophilicity, and after being introduced into a polymer side chain, the acrylic monomer a3 tends to be distributed on the surface of latex particles to prevent the mutual bonding between ions, so that the formation of gel is inhibited, and the polymer A can be endowed with better stability and good dispersibility in an aqueous medium; meanwhile, carboxylate is generated by carboxyl groups and alkaline substances added subsequently, and carboxylate groups are mutually repelled to change a macromolecular chain from a curled state to an extended state, so that the viscosity of emulsion is increased, and therefore, the addition amount of the monomer a3 needs to be controlled to avoid the reduction of the water resistance of the finally formed coating of the polymer A due to more gel generation caused by excessive monomer a 3.
Preferably, the acrylic monomer a3 is one or more of (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid or maleic acid.
The cross-linking vinyl monomer a4 is used for introducing a cross-linking unit into a polymer A molecule, so that when the composition is applied to paper-plastic products, the surface of the paper-plastic products can be cross-linked to form a three-dimensional network structure in the drying process, the three-dimensional network structure can be better combined with paper-based fibers, the mechanical strength of the products is improved, and the coating loses viscosity when being heated for the second time, so that the products have anti-sticking performance.
The crosslinking vinyl monomer has at least one functional group capable of undergoing crosslinking reaction in addition to vinyl, and preferably the functional group is a hydroxyl group or a carbon-carbon double bond.
Some cross-linking vinyl monomers crosslink during the formation of polymer a, for example monomers having a carbon-carbon double bond as a cross-linking reactive functional group; some crosslinking vinyl monomers do not crosslink during polymer formation, but rather crosslink during baking after application to pulp molded articles, such as monomers having hydroxyl groups or the like as crosslinking reactive functional groups.
Preferably, the cross-linking vinyl monomer a4 is one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, N-methylolacrylamide, divinylbenzene, ethylene glycol di (meth) acrylate, allyl methacrylate, trimethylolpropane tri (meth) acrylate or triallyl cyanurate.
The preparation method of the polymer A preferably adopts a free radical polymerization method, and particularly adopts a conventional emulsion polymerization mode and a solution polymerization mode, and preferably adopts a pre-emulsification semi-continuous seed emulsion polymerization process. When emulsion polymerization is adopted, the reaction is carried out in the presence of a polymerization medium, an initiator is added to enable the polymerization to be carried out, and meanwhile, an emulsifier is also required to be added into the reaction medium.
The emulsifier may be nonionic emulsifier or anionic emulsifier, and the nonionic emulsifier may be fatty alcohol polyoxyethylene ether, alkyl phenyl polyoxyethylene ether, alkyl polyoxyalkylene polyoxyethylene ether, etc.; examples of the anionic emulsifier include sodium dodecyl sulfate, sodium dodecyl diphenyl ether disulfonate, sodium dodecyl polyether sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium hexadecyl diphenyl ether sulfonate, and sodium dioctyl succinate. At least one or two or more of them may be used. In the radical polymerization of the polymer a of the present invention, the emulsifier is used in an amount of 0.5 to 2 parts by mass based on 100 parts by mass of the total amount of the monomer a1, the monomer a2, the monomer a3 and the monomer a4 added.
The initiator may be at least one of an inorganic peroxide, an organic peroxide, and an azo initiator. Examples of the inorganic peroxide include hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like. Examples of the organic peroxide include dibenzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and t-butyl peroxypivalate. Examples of azo initiators include 2,2' -azobisisobutyronitrile, 2' -azobisisoheptonitrile, 4' -azobis (4-cyanovaleric acid), 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis (N, N ' -dimethylene isobutyramidine) dihydrochloride, and 2,2' -azobis [ N- (2-carboxymethyl) -2-methylpropionamidine ] hydrate. In the radical polymerization process of the polymer a of the present invention, the initiator is used in an amount of 0.5 to 1 part by mass based on 100 parts by mass of the total amount of the monomer a1, the monomer a2, the monomer a3 and the monomer a4 added.
In the process of forming the polymer a, a chain transfer agent may be added in order to control the molecular weight of the resulting polymer a. As the chain transfer agent, there may be mentioned an alkyl mercaptan compound such as dodecyl mercaptan, butyl mercaptan, octyl mercaptan, etc., and at least one of them may be used. In the radical polymerization process of the polymer a of the present invention, the chain transfer agent is used in an amount of 0.3 to 0.5 parts by mass based on 100 parts by mass of the total amount of the monomer a1, the monomer a2, the monomer a3 and the monomer a4 added.
In the step of forming the polymer A, a polymerization medium is selected according to the polymerization method and the kind of initiator. The polymerization medium may be an aqueous medium or an oily medium. As the aqueous medium, deionized water may be used. The oily medium may be one or more of ketone, alcohol, ether, and ester solvents, preferably propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, or their mixture. In the radical polymerization of the polymer a of the present invention, the polymerization medium is used in an amount of 150 to 400 parts by mass based on 100 parts by mass of the total amount of the monomer a1, the monomer a2, the monomer a3 and the monomer a4 added.
In the present invention, the alkaline substance B is an inorganic base or an organic base.
The alkaline substance B can be specifically selected from sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-swelling butylamine, ethanolamine, diethanolamine, triethanolamine and the like.
The basic substance B serves to neutralize the carboxyl groups in the polymer A and to adjust the pH of the composition to neutral.
From the viewpoint of improving the dispersion stability of the polymer a in an aqueous medium, the basic substance B is preferably sodium hydroxide or ammonia water.
The tackifying substance C is introduced into the invention, which not only can adjust the viscosity of the anti-blocking composition and improve the processing performance, but also can improve the film forming performance of the polymer A, and can infiltrate and fill the paper-based fiber gaps when the coating is dried, thereby having an auxiliary effect on the anti-permeation performance of the anti-blocking composition.
Preferably, the viscosity of the anti-sticking barrier composition for paper and plastic is 200 to 2000mPas.
The specific viscosity number of the release barrier composition may be based on the coating process selected subsequently, e.g. the viscosity may be tailored to the application process.
Preferably, the tackifying substance C can be selected from one or more of modified starch, polyvinyl alcohol, hydroxyethyl cellulose or sodium alginate.
Specifically, when the thickening material C is added to the composition, it is preferable that the thickening material C is prepared in advance with deionized water to form a gel having a mass concentration of 2 to 5%, and the amount of the gel to be added is 10 to 20 parts per 100 parts of the polymer a solution having a neutral pH.
The preparation method of the anti-sticking barrier composition for paper and plastic comprises the following steps: and (3) regulating the pH of the water dispersion solution of the polymer A to be neutral by using an alkaline substance B, and adding a tackifying substance C to regulate the viscosity to obtain the anti-sticking barrier composition for paper and plastic.
A pulp molded article having a release barrier coating formed from the release barrier composition for paper molding.
The preparation method of the pulp molding product comprises the following steps: and (3) carrying out surface coating on the paper pulp molding product by using the anti-sticking barrier composition for paper and plastic, and drying in an oven to form an anti-sticking barrier coating to obtain the paper pulp molding product.
In the present invention, the coating may be performed according to a process commonly used in the art, including various printing methods such as spin coating, casting, bar coating, roll coating, bar coating, dip coating, slot coating, micro gravure coating, capillary coating, spray coating, nozzle coating, screen printing, gravure printing, offset printing, lithography, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an anti-sticking barrier composition for paper and plastic. After the composition is coated on the surface of a paper-based product, a continuous compact film layer can be formed, and the tackifying substance can infiltrate into and fill the gaps of paper-based fibers when the coating is dried, so that the composition can endow the paper-based product with better anti-penetration performance (hot water, hot oil and water vapor prevention), has a hot-sticking prevention function, and particularly provides an effective solution to the problem of sticking rice on paper tableware, and the use of the composition does not influence pulping and recycling of the paper-based product.
Detailed Description
The invention is further illustrated in detail below in connection with specific examples which are provided solely for the purpose of illustration and are not intended to limit the scope of the invention. The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available. In the present specification, "part" and "%" respectively mean "part by mass" and "% by mass" unless otherwise specified. The embodiments of the present invention are not limited to the above-described embodiments, but any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the following embodiments, and are included in the scope of the present invention.
The physical properties of the present invention were measured as follows.
(1) Weight average molecular weight/number average molecular weight
Collecting a polymer A, refluxing with butanone in a Soxhlet extractor for 8 hours, filtering and separating butanone insoluble components, and calculating the butanone insoluble components; meanwhile, the butanone-soluble components were collected, dried at 80℃for 24 hours with a vacuum dryer, and the weight average molecular weight/number average molecular weight of the obtained polymer A was measured by Gel Permeation Chromatography (GPC). In GPC measurement, tetrahydrofuran (THF) was used as an eluent, and the temperature was 23.+ -. 2 ℃.
(2) Particle size test
Polymer a latex was added drop-wise to TopSizer laser particle size analyzer test cells using deionized water as the mobile phase to determine the average particle size D50 of the polymer a latex.
(3) Viscosity test
The viscosity of the release barrier composition was tested using a DNJ-1 rotational viscometer (rotor No. 1, speed 60 rpm, 25 ℃).
(4) Permeation resistance test
Soaking the bagasse board in water, fluffing the bagasse board by using a fiber standard dissociator after the bagasse board is fully swelled, pulping by using a pulping machine. And (3) molding, demolding, drying and shaping the prepared slurry to prepare a paper pulp molded product (paper cutlery box), coating the anti-sticking barrier composition on the surface of the paper cutlery box by using a spraying machine, and drying at 120 ℃ to prepare a sample to be tested.
Waterproof test: pouring hot water at 100 ℃ into the dried sample to be tested, standing for 30min, and observing whether the permeation phenomenon exists.
No penetration: the method is good;
no penetration has partial discoloration: generally;
the method comprises the following steps: and (3) difference.
Oil repellency test: pouring the peanut oil at 95 ℃ into the dried sample to be tested, standing for 30min, and observing whether the penetration phenomenon exists.
No penetration: the method is good;
no penetration has partial discoloration: generally;
the method comprises the following steps: and (3) difference.
And (3) waterproof steam test: pouring hot water at 100 ℃ into the dried sample to be tested, standing for 30min, and checking whether the sample becomes soft.
Does not soften: the method is good;
partially soft: generally;
softening: and (3) difference.
(5) Anti-sticking test
Soaking the bagasse board in water, fluffing the bagasse board by using a fiber standard dissociator after the bagasse board is fully swelled, pulping by using a pulping machine. And (3) molding, demolding, drying and shaping the prepared slurry to prepare a paper pulp molded product (paper cutlery box), coating the anti-sticking barrier composition on the surface of the paper cutlery box by using a spraying machine, and drying at 120 ℃ to prepare a sample to be tested.
And (3) hot tack prevention test: pouring the cooked rice heated at 95 ℃ into the dried sample to be tested, standing for 30min, stirring with a medicine spoon, and observing whether the cooked rice contacted with the surface of the sample brings out paper fibers and is stuck on the cooked rice.
No carry-over: the method is good;
partial carry-out: generally;
a large amount of carry-over: and (3) difference.
(6) Pulping recycling performance
Cutting the paper cutlery box coated with the anti-sticking barrier composition into fragments, soaking in water, fluffing by using a fiber standard dissociator after the paper cutlery box is fully swelled, pulping by using a pulping machine, making the pulp into paper sheets by using a sheet making machine, drying, and observing whether uncrushed pulp blocks exist on the surface of the paper sheets.
No lumps: the method is good;
part of the pulp block: generally;
a large number of pulp blocks: and (3) difference.
Example 1
Polymer a synthesis:
8 parts of monomer a1 methyl methacrylate, 40 parts of butyl acrylate, 45 parts of monomer a2 styrene, 4 parts of monomer a3 acrylic acid and 3 parts of monomer a4 hydroxyethyl methacrylate are weighed to form monomer components, and the monomer components are uniformly mixed with 0.2 part of fatty alcohol polyoxyethylene ether (AEO-9), 0.1 part of Sodium Dodecyl Sulfate (SDS), 0.5 part of dodecyl mercaptan (chain transfer agent) and 100 parts of deionized water, and are pre-emulsified at a high speed by a homogenizer to prepare a monomer emulsion. 0.8 part of potassium persulfate is weighed and dissolved in 20 parts of deionized water to prepare an initiator solution.
150 parts of deionized water as a solvent was added to a four-necked flask equipped with an electric stirrer, a constant pressure dropping funnel, a thermometer and a condenser, the stirrer was turned on, and 0.4 part of fatty alcohol polyoxyethylene ether (AEO-9) and 0.2 part of Sodium Dodecyl Sulfate (SDS) were weighed into the four-necked flask to be dissolved. Under the nitrogen atmosphere, adding 20% of monomer emulsion and 20% of initiator solution into a four-necked flask, reacting at 70 ℃, simultaneously dropwise adding the rest of monomer emulsion and initiator solution after blue light appears in reaction liquid in the flask, keeping the temperature for 2h after 3h dropwise adding, and cooling to room temperature to obtain polymer A solution. The pH of the polymer A solution was adjusted to neutral with ammonia.
Preparing a tackifying substance C: into a four-neck flask with an electric stirrer, a thermometer and a condenser tube, 95 parts of deionized water is added as a solvent, the stirrer is started, 5 parts of oxidized starch is weighed, the oxidized starch is added into the flask, and the mixture is stirred for 30min at 95 ℃ to obtain clear and transparent gelatinous gelatinized starch, so as to prepare a tackifying substance C.
The release barrier composition was prepared by mixing and stirring 80 parts of the pH neutral polymer a solution and 20 parts of the tackifying substance C.
Example 2
The monomer component in the step of preparing the polymer A in example 1 was changed to: 10 parts of isobutyl methacrylate monomer a1, 30 parts of isooctyl acrylate, 55 parts of styrene monomer a2, 4 parts of acrylic acid monomer a3 and 1 part of ethylene glycol di (meth) acrylate monomer a4, and the other steps are the same as in example 1.
Example 3
The monomer component in the step of preparing the polymer A in example 1 was changed to: 10 parts of isobutyl methacrylate monomer a1, 27.9 parts of isooctyl acrylate, 58 parts of styrene monomer a2, 4 parts of acrylic acid monomer a3 and 0.1 part of trimethylolpropane tri (meth) acrylate monomer a4, and the other steps are the same as in example 1.
Example 4
Polymer a synthesis: the same as in example 1.
Preparing a tackifying substance C: into a four-neck flask with an electric stirrer, a thermometer and a condenser tube, 95 parts of deionized water is added as a solvent, the stirrer is started, 5 parts of polyvinyl alcohol (PVA-235, alcoholysis degree is 87-89) is weighed, the mixture is added into the flask, and the mixture is stirred for 30min at 95 ℃ to obtain clear and transparent colloidal liquid, so as to prepare a tackifying substance C.
85 parts of a polymer A solution having a neutral pH and 15 parts of a tackifying substance C are mixed and stirred to prepare the anti-sticking barrier composition.
Example 5
Polymer a synthesis: the same as in example 1.
Preparing a tackifying substance C: 98 parts of deionized water is added into a four-neck flask with an electric stirrer, a thermometer and a condenser tube as a solvent, the stirrer is started, 2 parts of hydroxyethyl cellulose is weighed, the mixture is added into the flask, and the mixture is stirred for 30min at 95 ℃ to obtain clear and transparent colloidal liquid, so as to prepare a tackifying substance C.
90 parts of a polymer A solution having a neutral pH and 10 parts of a tackifying substance C are mixed and stirred to prepare the anti-sticking barrier composition.
Example 6
The monomer component in the step of preparing the polymer A in example 1 was changed to: 30 parts of isooctyl acrylate monomer a1, 65 parts of styrene monomer a2, 4 parts of acrylic acid monomer a3 and 1 part of methylol acrylamide monomer a 4N, and the other components are the same as in example 1.
Comparative example 1
The procedure of example 1 was repeated except that "0.5 part of dodecylmercaptan" in "Polymer A Synthesis" in example 1 was changed to "0 part of dodecylmercaptan".
Comparative example 2
The procedure of example 1 was repeated except that 0.4 part of fatty alcohol-polyoxyethylene ether (AEO-9) and 0.2 part of sodium dodecyl sulfate in the "Polymer A Synthesis" in example 1 were changed to "0.1 part of fatty alcohol-polyoxyethylene ether (AEO-9) and 0.05 part of sodium dodecyl sulfate".
Comparative example 3
Soaking the bagasse board in water, fluffing the bagasse board by using a fiber standard dissociator after the bagasse board is fully swelled, pulping by using a pulping machine. 1.5% of waterproof agent (AKD-15) and 1% of fluorocarbon oil-proofing agent (TG-8811) are added into the slurry in sequence, and the slurry is molded, demolded, dried and shaped to prepare the paper cutlery box (the paper cutlery box sample is an 8.86 disc, and the weight of the paper cutlery box sample is 14.5 g).
Preparation and evaluation of paper-Plastic articles
The molecular weight of the polymer A prepared in example and its particle diameter D50 in an aqueous dispersion were measured, the viscosity of the release barrier composition was tested, and the release barrier composition was applied to the surface of a paper cutlery box without the addition of a water repellent agent and an oil repellent agent in the slurry by spraying (six-axis coater, nozzle aperture 1.5mm, air pressure 0.3 to 0.8 MPa), the spraying amount was 10% (paper cutlery box sample was 8.86 disk, 14.5g weight), and oven-dried, and its barrier properties, release properties and repulping properties were measured. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, in examples 1 to 6, according to the different monomer ratios, different tackifying substances are selected, and in a reasonable viscosity range, the anti-sticking barrier composition with different viscosities is prepared, and can achieve good anti-sticking, anti-permeation and pulping recycling properties on the premise of ensuring reasonable molecular weight and distribution when applied to paper-plastic products. Comparative example 1 compared with example 1, since no molecular weight regulator (chain transfer agent) was added in comparative example 1, the molecular weight was large, and the anti-blocking and anti-permeation properties were good, but the beating recycling effect was poor. Comparative example 2 compared with example 1, the polymer particle size (D50) was large due to the low amount of emulsifier added (less than 0.5%) in comparative example 2, and when applied to paper-plastic products, a dense continuous film could not be formed, and barrier properties were poor. Comparative example 3 is a water and oil repellent process commonly used in the industry: the process of adding the waterproof agent and the fluorocarbon oil-proof agent into the slurry has good waterproof property, oil-proof property and pulping recycling property, but has poor steam-proof property and anti-sticking property.
The above examples are preferred embodiments of the present invention, but the present invention is not limited to these examples, and changes, modifications, substitutions, combinations, and simplifications made in the above examples are all considered to be equivalent substitution methods without departing from the spirit and principle of the present invention, and are all included in the scope of the present invention.
Industrial applicability
The anti-sticking barrier composition disclosed by the invention can be widely applied to the papermaking industry.

Claims (10)

1. The anti-sticking barrier composition for paper and plastic comprises a polymer A, an alkaline substance B and a tackifying substance C, wherein the polymer A is formed by copolymerizing a (methyl) acrylic acid alkyl ester monomer a1, a vinyl aromatic monomer a2, an acrylic acid monomer a3 and a crosslinking vinyl monomer a 4;
the butanone insoluble component of the polymer A is more than 90 mass%;
the butanone soluble component of the polymer A has a weight average molecular weight Mw of 100000 ～ 200000, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn, calculated as Mw/Mn, is 2.0 to 3.0;
the average particle diameter D50 of the polymer A is 100-200 nm.
2. The anti-sticking barrier composition for paper and plastic according to claim 1, wherein the polymer a is polymerized from the following monomers in parts by weight: based on 100 parts of total monomer weight, the (methyl) acrylic acid alkyl ester monomer a1 is 30-50 parts, the vinyl aromatic monomer a2 is 40-65 parts, the acrylic acid monomer a3 is 3-5 parts, and the cross-linking vinyl monomer a4 is 0.1-3 parts.
3. The anti-sticking barrier composition for paper and plastic according to claim 1, wherein the alkyl (meth) acrylate monomer a1 is one or more of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, and lauryl (meth) acrylate.
4. The anti-sticking barrier composition for paper and plastic according to claim 1, wherein the vinylaromatic monomer a2 is one or more of styrene, α -methylstyrene, ethylstyrene, butylstyrene, and dimethylstyrene.
5. The anti-sticking barrier composition for paper and plastic according to claim 1, wherein the acrylic monomer a3 is one or more of (meth) acrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, or maleic acid.
6. The release barrier composition for paper and plastic according to claim 1, wherein the cross-linked vinyl monomer a4 is one or more of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, N-methylolacrylamide, divinylbenzene, ethylene glycol di (meth) acrylate, allyl methacrylate, trimethylolpropane tri (meth) acrylate, or triallyl cyanurate.
7. The release barrier composition for paper and plastic according to claim 1, wherein the basic substance B is an inorganic base or an organic base.
8. The anti-sticking barrier composition for paper and plastic according to claim 1, wherein the tackifying substance C is one or more of modified starch, polyvinyl alcohol, hydroxyethyl cellulose or sodium alginate.
9. A process for the preparation of an anti-blocking composition for paper moulding according to any one of claims 1 to 8, characterized in that it comprises the following steps: and (3) regulating the pH of the water dispersion solution of the polymer A to be neutral by using an alkaline substance B, and adding a tackifying substance C to regulate the viscosity to obtain the anti-sticking barrier composition for paper and plastic.
10. A pulp molded article having a release barrier coating formed from the release barrier composition for paper molding of any one of claims 1 to 8.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009156341A1 (en) * 2008-06-24 2009-12-30 Basf Se Metal salt pigments containing paper coating agents containing aqueous dispersions of water-soluble copolymers
WO2010094641A1 (en) * 2009-02-19 2010-08-26 Basf Se Aqueous polymer dispersion made of a vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid
CN102015293A (en) * 2008-04-30 2011-04-13 米德韦斯瓦科公司 Water-based barrier coating compositions
CN106519144A (en) * 2016-08-31 2017-03-22 广州熵能创新材料股份有限公司 Vinyl grafted copolymer, resin composite containing same and preparation method of vinyl grafted copolymer
CN106519235A (en) * 2016-08-31 2017-03-22 广州熵能创新材料股份有限公司 Polysiloxane crosslinking agent, vinyl grafted copolymer powder prepared by using crosslinking agent and preparation method of vinyl grafted copolymer powder
CN111040072A (en) * 2019-11-27 2020-04-21 广州熵能创新材料股份有限公司 Vinyl fluorine-containing copolymer, water-and oil-repellent composition containing the same, and use thereof
KR20210023258A (en) * 2019-08-22 2021-03-04 주식회사 엘지화학 Acrylic emulsion pressure sensitive adhesive composition
KR102328902B1 (en) * 2021-06-03 2021-11-19 주식회사 서일 Gas barrier coating composition, and Gas barrier layer using this
KR20210148722A (en) * 2020-06-01 2021-12-08 주식회사 엘지화학 Acrylic emulsion pressure snsitive adhesive composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102015293A (en) * 2008-04-30 2011-04-13 米德韦斯瓦科公司 Water-based barrier coating compositions
WO2009156341A1 (en) * 2008-06-24 2009-12-30 Basf Se Metal salt pigments containing paper coating agents containing aqueous dispersions of water-soluble copolymers
WO2010094641A1 (en) * 2009-02-19 2010-08-26 Basf Se Aqueous polymer dispersion made of a vinylaromatic compound, conjugated aliphatic diene, and ethylenically unsaturated acid
CN106519144A (en) * 2016-08-31 2017-03-22 广州熵能创新材料股份有限公司 Vinyl grafted copolymer, resin composite containing same and preparation method of vinyl grafted copolymer
CN106519235A (en) * 2016-08-31 2017-03-22 广州熵能创新材料股份有限公司 Polysiloxane crosslinking agent, vinyl grafted copolymer powder prepared by using crosslinking agent and preparation method of vinyl grafted copolymer powder
KR20210023258A (en) * 2019-08-22 2021-03-04 주식회사 엘지화학 Acrylic emulsion pressure sensitive adhesive composition
CN111040072A (en) * 2019-11-27 2020-04-21 广州熵能创新材料股份有限公司 Vinyl fluorine-containing copolymer, water-and oil-repellent composition containing the same, and use thereof
KR20210148722A (en) * 2020-06-01 2021-12-08 주식회사 엘지화학 Acrylic emulsion pressure snsitive adhesive composition
KR102328902B1 (en) * 2021-06-03 2021-11-19 주식회사 서일 Gas barrier coating composition, and Gas barrier layer using this

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