CN111995912A - Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof - Google Patents
Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof Download PDFInfo
- Publication number
- CN111995912A CN111995912A CN202010849309.3A CN202010849309A CN111995912A CN 111995912 A CN111995912 A CN 111995912A CN 202010849309 A CN202010849309 A CN 202010849309A CN 111995912 A CN111995912 A CN 111995912A
- Authority
- CN
- China
- Prior art keywords
- coating
- coating liquid
- polyvinyl alcohol
- parts
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a moisture-proof high-oxygen-barrier water-based coating liquid and a preparation method thereof. Specifically, provided is an aqueous coating liquid of modified polyvinyl alcohol, which comprises: 1-20 parts by weight of polyvinyl alcohol; 0.1-10 parts by weight of nanoparticles; 0.01-3 parts by weight of a curing agent; 0.1-12 parts of cosolvent; and 75-100 parts by weight of water. The coating film using the coating liquid of the invention has extremely low oxygen permeability under high humidity conditions (the oxygen permeability under the conditions of 25 ℃, 85 percent RH is only 1-5 cm)3/m224h), heat resistance, boiling resistance, safety, no toxicity, environmental protection and very suitable useIt can be used as packaging material for food and medicine.
Description
Technical Field
The invention relates to the field of food packaging materials, in particular to a moisture-proof high-oxygen-barrier water-based coating liquid and a preparation method thereof.
Background
The barrier property of a material is generally referred to as the barrier effect of the material against oxygen and water vapor at a specified temperature and humidity, and is one of the important indicators of a packaging material. In the process of storing foods, medicines and the like, the existence and concentration of oxygen are key factors influencing the shelf life of the foods, the medicines and the like, and in recent years, the demand of high-barrier plastic packaging materials is increasing.
At present, the domestic high-barrier packaging materials mainly comprise aluminum foils, aluminum-plated films, five-layer co-extruded films of ethylene-vinyl alcohol copolymer (EVOH), and polyvinylidene chloride (PVDC) coated biaxially oriented nylon (BOPET) or Biaxially Oriented Polyester (BOPA) films.
The aluminum foil and the aluminum-plated film have excellent oxygen and water resistance, but have the defects of non-transparency, poor folding resistance, high cost and difficult recycling. The wide use of aluminum plastic paper composite packaging materials causes a huge amount of non-degradable wastes, and great pressure is exerted on environmental protection belts.
EVOH is an ethylene-vinyl alcohol copolymer, which has the easy processability of polyethylene and the gas barrier property of polyvinyl alcohol, and the barrier property of the EVOH depends on the content of ethylene in a copolymerization component, and the higher the content of ethylene is, the poorer the barrier property is, but the processability is improved. EVOH can be recycled, only carbon dioxide and oxygen are produced after combustion, and the EVOH is an excellent environment-friendly packaging material. However, EVOH contains a large amount of hydroxyl groups, so that the EVOH is very easy to absorb water under high humidity, so that the barrier property of the material is reduced rapidly, in order to avoid the influence of humidity, the EVOH needs to be placed in the middle layer of a co-extrusion composite film, and five or more EVOH co-extrusion films are generally used in practical application. At present, all EVOH resins used in China depend on import, and meanwhile, five-layer or more coextrusion equipment is expensive in investment, so that the cost of the film is always high.
PVDC exists in two forms of emulsion and resin, the localization technology of the PVDC emulsion is mature at present, but the resin mainly depends on import, and the PVDC emulsion has stronger acidity, needs special equipment for coating and has more complex process and can not be recycled; in addition, the adhesion between the emulsion and the BOPET and BOPA films is poor, and the films usually need a pre-coating process before coating, so that the process is complicated; most importantly: the waste materials can generate substances such as hydrogen chloride, dioxin and the like which are harmful to human beings and the environment when being combusted, and the development of PVDC is severely restricted.
The polyvinyl alcohol (PVA) resin has excellent adhesion with BOPET and BOPA films, but the coating is very easy to absorb moisture and swell under high humidity conditions (RH is more than or equal to 65 percent), the oxygen barrier effect is sharply reduced, and the application range is greatly limited.
Therefore, there is a strong need in the art to provide a coating liquid with high humidity resistance and high oxygen barrier, which is safe and environment-friendly.
Disclosure of Invention
The invention aims to provide a coating liquid which is safe, environment-friendly, high in humidity resistance and high in oxygen barrier.
In a first aspect of the present invention, there is provided an aqueous coating liquid of modified polyvinyl alcohol, comprising:
1-20 parts by weight of polyvinyl alcohol;
0.1-10 parts by weight of nanoparticles;
0.01-3 parts by weight of a curing agent;
0.1-12 parts of cosolvent; and
75-100 parts of water.
In another preferred embodiment, the polyvinyl alcohol is included by 2 to 10 parts by weight, preferably 3 to 8 parts by weight.
In another preferred embodiment, the amount of the nanoparticles is 1 to 6 parts by weight, preferably 2 to 5 parts by weight.
In another preferred embodiment, the curing agent is 0.1 to 2 parts by weight, preferably 0.3 to 1.5 parts by weight.
In another preferred embodiment, the cosolvent is 1 to 8 parts by weight, preferably 2 to 5 parts by weight.
In another preferred embodiment, the amount of the water is 80 to 95 parts by weight, preferably 85 to 94 parts by weight.
In another preferred embodiment, the polymerization degree of the polyvinyl alcohol is 400 to 2000, preferably 500 to 1900, and more preferably 1500 to 1800.
In another preferred embodiment, the alcoholysis degree of the polyvinyl alcohol is 88 to 99.9%, preferably 90 to 99.9%, and more preferably 95 to 99.9%.
In another preferred embodiment, the polymerization degree of the polyvinyl alcohol is 500 to 1900, and the alcoholysis degree is 88 to 99.9%.
In another preferred embodiment, the nanoparticles are selected from the group consisting of: nano-silica, nano-calcium carbonate, nano-titanium dioxide, nano-layered silicate, or a combination thereof.
In another preferred embodiment, the average particle size of the nanoparticles is 20 to 500nm, preferably 50 to 300nm, and more preferably 80 to 150 nm.
In another preferred embodiment, the curing agent is selected from the group consisting of: an amino resin, an alkyd resin, an isocyanate, or a combination thereof.
In another preferred embodiment, the co-solvent is selected from the group consisting of: a modifier, a dispersant, a defoamer, a leveling agent, or a combination thereof.
In another preferred embodiment, the cosolvent comprises the following components in parts by weight based on the total weight of the cosolvent:
in another preferred embodiment, the amount of the modifier is 1 to 8 parts by weight, preferably 2 to 5 parts by weight.
In another preferred embodiment, the dispersant is 0.3 to 1.5 parts by weight, preferably 0.5 to 1 part by weight.
In another preferred embodiment, the amount of the defoaming agent is 0.02 to 0.2 parts by weight, preferably 0.03 to 0.1 parts by weight.
In another preferred embodiment, the leveling agent is 0.005 to 0.2 parts by weight, preferably 0.008 to 0.1 parts by weight.
In another preferred embodiment, the coating fluid has one or more of the following characteristics:
(1) the dispersant is an acrylic copolymer, and preferably, the dispersant is selected from the following group: a polyester-acrylic copolymer, a polyester-methacrylic copolymer, a maleic anhydride-acrylic copolymer, or a combination thereof;
(2) the defoaming agent is selected from the following group: polyethers, organosiloxanes, polyether-modified organosiloxanes, or combinations thereof;
(3) the leveling agent is selected from the following group: polyester-modified organosiloxanes, polyether-modified organosiloxanes, alkyl-modified organosiloxanes, acrylic acids, alkyl fluorocarbons, or combinations thereof; and/or
(4) The modulator is selected from the group consisting of: ethanol, methanol, isopropanol, or a combination thereof.
In another preferred embodiment, the regulator is a mixture of isopropanol and ethanol, preferably, the ratio of isopropanol: 1: 0.5-2, preferably 1: 0.8 to 1.5.
In a second aspect of the present invention, there is provided a method for preparing a coating liquid according to the first aspect of the present invention, comprising the steps of:
(1) mixing polyvinyl alcohol resin, water, a defoaming agent and a regulator, heating to 80-100 ℃ for dissolving, and cooling to room temperature to obtain a mixture I;
(2) mixing the nano particles, a dispersing agent and water, grinding for 4-12 h to uniformly disperse the nano particles in the water to form a dispersion liquid I (the particle size of a dispersed phase is 20-500 nm); and
(3) and mixing the dispersion liquid I, the mixed liquid I, the curing agent and the flatting agent to obtain the coating liquid.
In a third aspect of the present invention, there is provided a binder composition for forming a coating liquid according to the first aspect of the present invention, the composition comprising:
in another preferred embodiment, the binder composition is mixed to obtain the coating solution according to the first aspect of the present invention.
In another preferred embodiment, the binder composition is used in the method according to the second aspect of the present invention to prepare a coating solution according to the first aspect of the present invention.
In a fourth aspect of the present invention, there is provided a coating layer obtained by coating with the coating liquid according to the first aspect of the present invention.
In a fifth aspect of the invention, there is provided an article comprising:
a base film, and the coating liquid according to the first aspect of the present invention or the coating layer according to the fourth aspect of the present invention coated on the base film.
In another preferred embodiment, the base film is selected from the group consisting of: BOPET film, BOPA film.
In another preferred embodiment, the thickness of the base film is 10 to 20 μm.
In another preferred embodiment, the article has one or more of the following features:
(1) the oxygen permeability is less than or equal to 10cm under the conditions of 25 ℃ and 85 percent RH3/m224h, preferably 1 to 5cm3/m224 h; and/or
(2) The oxygen permeability is 0.2-0.8 cm under the conditions of 25 ℃ and 0% RH3/m2·24h。
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
The inventors of the present invention have made extensive and intensive studies and, as a result, have provided a moisture-resistant high oxygen barrier aqueous coating liquid excellent in overall properties by a large number of screening and tests. According to the invention, a nano particle crosslinking modification method is adopted, and nano particles are uniformly dispersed into PVA resin, so that the barrier property of the film after coating is improved, meanwhile, abundant hydroxyl groups on the surface of the nano particles can form a large number of hydrogen bonds with the PVA and the surface of a base material, and the coating is endowed with excellent water resistance; in addition, the addition of the nano particles can accelerate the crystallization rate of PVA, so that the coating can be quickly crosslinked (solidified) into a film in a short time, and the coating is very suitable for on-line coating. The present invention has been completed based on this finding.
Term(s) for
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 invention belongs.
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Unless otherwise specified, the term room temperature means 4-40 ℃, preferably 20. + -. 5 ℃.
Coating liquid
The invention provides a coating liquid for a packaging material, which is particularly used for preparing a high-barrier packaging material and is suitable for enhancing the oxygen barrier property of a base film under a high-humidity condition.
The coating liquid of the present invention is obtained by modifying a polyvinyl alcohol (PVA) resin with nanoparticles and a curing agent (crosslinking agent).
Preferably, the coating liquid includes: 1-20 parts by weight of polyvinyl alcohol; 0.1-10 parts by weight of nanoparticles; 0.01-3 parts by weight of a curing agent; 0.1-12 parts of cosolvent; and 75-100 parts by weight of water.
As used herein, the terms "polyvinyl alcohol", "PVA", "polyvinyl alcohol resin" are used interchangeably to refer to a compound of formula (C)2H4O)nN represents the degree of polymerization. Preferably, the polymerization degree of the polyvinyl alcohol is 400-2000, preferably 500-1900, and more preferably 1500-1800. The alcoholysis degree of the polyvinyl alcohol is 88 to 99.9%, preferably 90 to 99.9%, and more preferably 95 to 99.9%.
Preferably, the nanoparticles include, but are not limited to: nano-silica, nano-calcium carbonate, nano-titanium dioxide, nano-layered silicate, or a combination thereof.
Preferably, the curing agent is a water-soluble curing agent, including but not limited to: an amino resin, an alkyd resin, an isocyanate, or a combination thereof.
Typically, the coating fluid also includes co-solvents commonly used in the art, including but not limited to: a modifier, a dispersant, a defoamer, a leveling agent, or a combination thereof. Thereby obtaining a coating liquid with particularly excellent comprehensive performance.
Preparation method
The coating liquid of the present invention can be prepared by a method comprising the steps of:
(1) mixing polyvinyl alcohol resin, water, a defoaming agent and a regulator, heating to 80-100 ℃ for dissolving, and cooling to room temperature to obtain a mixture I;
(2) mixing the nano particles, a dispersing agent and water, grinding for 4-12 h to uniformly disperse the nano particles in the water to form a dispersion liquid I (the particle size of a dispersed phase is 20-500 nm); and
(3) and mixing the dispersion liquid I, the mixed liquid I, the curing agent and the flatting agent to obtain the coating liquid.
More specifically, a preferred method for preparing a modified PVA coating liquid of the present invention comprises the steps of: (1) mixing polyvinyl alcohol resin, water, a defoaming agent and a regulator according to a certain proportion, heating to 80-100 ℃, keeping the temperature for 30-60 min to fully dissolve the resin, and cooling to room temperature; (2) mixing the nano particles, the dispersing agent and water according to a certain proportion, grinding for 4-12 hours, and uniformly dispersing the mixture in the water to form stable dispersion liquid, wherein the particle size of the dispersed phase is 40-500 nm; and (3) uniformly mixing the nano-particle dispersion liquid, the polyvinyl alcohol aqueous solution, the curing agent and the flatting agent according to a certain proportion to prepare the high-barrier coating.
Base composition
The present invention also provides a binder composition for forming the above coating liquid, the composition comprising:
coating, article
The invention also provides a coating layer formed by coating the PVA coating liquid and an article coated with the coating liquid.
The coating liquid of the present invention can be applied to a coating machine by a method commonly used in the art, and may include steps of coating, pre-drying and curing to form a film (coating).
Typically, the article comprises: a base film, and the coating liquid or coating layer coated on the base film.
Preferably, the coating amount of the coating liquid on the base film is 5 to 15g/m2Preferably, 8 to 12g/m2。
The coating liquid of the present invention has excellent adhesion and can be used for various packaging materials (such as food and medicine packaging materials, especially packaging materials used in a high-humidity environment) commonly used in the field, especially packaging films. Such as BOPET film, BOPA film, etc.
In another preferred embodiment, the article has one or more of the following features:
(1) the oxygen permeability is less than or equal to 10cm under the conditions of 25 ℃ and 85 percent RH3/m224h, preferably 1 to 5cm3/m224 h; and/or
(2) The oxygen permeability is 0.2-0.8 cm under the conditions of 25 ℃ and 0% RH3/m2·24h。
The main advantages of the invention include:
(1) the coating liquid of the invention exists in a state of high transparency and low viscosity, does not contain acid or alkali catalyst, has simple process, good economic benefit, environmental protection and saving, and can be used for industrial production on a large scale;
(2) the coating of the coating liquid has the advantages of high drying speed, high bonding strength with the surface of a base material and excellent barrier property, and the coated film can not generate the phenomena of reverse adhesion, swelling and the like under the conditions of high temperature and high humidity;
(3) the coating liquid disclosed by the invention has the advantages that the viscosity cannot change along with the time, the coating liquid is extremely stable, the coating liquid is suitable for long-term storage and use, the phenomena of easy skinning, unstable viscosity and the like on the surface of the conventional polyvinyl alcohol coating liquid are overcome, and the viscosity is stably kept at 5-15 cps after the coating liquid is kept for half a year;
(4) the coating liquid coating has excellent boiling resistance, can be boiled at 120 ℃ for 30min, has good barrier property of a coating film, and has oxygen permeability of only 0.2-0.8 cm under the conditions of 25 ℃ and 0% RH3/m2·24h。
(5) The coating liquid coating of the present invention is oxygen under high humidity conditionsThe air barrier property is excellent, and the oxygen permeability is only 1-5 cm under the conditions of 25 ℃ and 85% RH3/m2·24h。
(6) When the coating liquid is coated, the coating liquid can be dried in a drying tunnel to form a film and is compounded with a base material, so that the production efficiency is improved, and the cost and the process are saved; and the pre-coating and drying processes of the primer can be omitted.
The invention is further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
The coating method comprises the following steps: the coating liquid is put into a liquid tank of a scraper type coating machine, and the production process comprises the following steps: the linear speed is 100m/min, the transverse stretching temperature is 100-130 ℃, the transverse stretching time is 20-30 s, the heat setting temperature is 200-230 ℃, and the heat setting time is 3-6 s, and coating, pre-drying, curing and rolling are carried out. The coating weight was 10g/m2。
Oxygen permeability test method:
the instrument comprises the following steps: model 2/22 oxygen transmission rate analyzer (Mocon, USA)
The test method comprises the following steps: oxygen permeability test is carried out on the coating film by referring to GB/T31354-
Example 1
Coating solution 1 was prepared according to the formulation of table 1:
TABLE 1
| PVA | 6 portions of |
| Nanoparticles | 3 portions of |
| Curing agent | 0.5 portion |
| Dispersing agent | 0.6 part |
| Conditioning agents | 3 portions of |
| Defoaming agent | 0.05 part |
| Leveling agent | 0.01 part |
| Deionized water | 86.84 portions |
The polymerization degree of the polyvinyl alcohol resin is 599, and the alcoholysis degree is 99.9%;
the nano particles are layered nano silicate, namely montmorillonite, and the product brand DK-2, and the average particle size is 120nm after grinding treatment;
the curing agent is water-soluble amino resin, commercial product number CYMEL 365, solid content is 80%;
the dispersant is a water-soluble acrylic copolymer, trade mark
SD-10, solid content 40%;
the regulator is compounded by isopropanol and ethanol, and the volume ratio is 1: 1;
the defoaming agent and the leveling agent are polyether modified organic siloxane, and the trade marks are BYK028 and BYK 348.
After coating liquid 1 prepared in this example was coated with BOPET (12 μm) on line, the coating film was aged at 80 ℃ for 12 hours, and the BOPET coating film permeation was measured at 25 ℃ and 85% RHOxygen amount was 4.3cm3/m224h oxygen permeability of uncoated BOPET film 126cm3/m2·24h。
Example 2
Coating solution 2 was prepared according to the formulation of table 2:
TABLE 2
The polymerization degree of the polyvinyl alcohol resin is 1799, and the alcoholysis degree is 99.9%;
the nano particles are layered nano silicate, namely montmorillonite, and the product brand DK-4, and the average particle size is 100nm after grinding treatment;
the curing agent is hydrophilic aliphatic isocyanate with a trade mark
ultra 305；
The dispersant is a water-soluble acrylic copolymer, trade mark
A-6712, solid content 40%;
the regulator is compounded by isopropanol and ethanol, and the volume ratio is 1: 1;
the defoaming agent is polyether modified organosiloxane, and is sold under the trade name BYK 093;
the leveling agent is alkyl fluorocarbon, and the trade mark is CapstoneneTMFS-3100.
After coating liquid 2 prepared in this example was coated with BOPA (15 μm) on line, the coated film was aged at 80 ℃ for 12 hours, and the oxygen permeability was 1.8cm measured at 25 ℃ and 85% RH3/m224h oxygen permeability of uncoated BOPA film 83cm3/m2·24h。
Comparative examples 1 to 3
Coating solutions C1-C3 were prepared according to the recipe of Table 3, respectively:
TABLE 3
| COMPARATIVE EXAMPLE 1(C1) | COMPARATIVE EXAMPLE 2(C1) | COMPARATIVE EXAMPLE 3(C3) | |
| PVA | 4 portions of | 4 portions of | 4 portions of |
| Nanoparticles | - | 4 portions of | - |
| Curing agent | - | - | 1 part of |
| Dispersing agent | 0.8 portion of | 0.8 portion of | 0.8 portion of |
| Conditioning agents | 2 portions of | 2 portions of | 2 portions of |
| Defoaming agent | 0.05 part | 0.05 part | 0.05 part |
| Leveling agent | 0.01 part | 0.01 part | 0.01 part |
| Deionized water | 93.14 parts | 89.14 parts | 92.14 parts |
The PVA, nanoparticles, curing agent, dispersant, modifier, defoamer, and leveling agent were all the same as in example 2.
The coating liquids C1 to C3 prepared in comparative examples 1 to 3 were each coated with BOPA (15 μm) on line, and the coated films were aged at 80 ℃ for 12 hours and had oxygen permeabilities of 83cm each measured at 25 ℃ and 85% RH3/m2·24h、19cm3/m2·24h、84cm3/m2·24h。
In conclusion, the polyvinyl alcohol coating liquid modified by the nanoparticles and the curing agent has excellent comprehensive performance, high moisture resistance and high oxygen barrier performance, can well meet the oxygen barrier requirements of films such as BOPET (biaxially oriented polyethylene terephthalate) and BOPA (biaxially oriented polyamide) under high humidity conditions in the field of food packaging, is heat-resistant, steam-resistant, safe, nontoxic and environment-friendly, and is very suitable for packaging materials of foods and medicines.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (10)
1. An aqueous coating liquid for modified polyvinyl alcohol, characterized by comprising:
2. the coating liquid as claimed in claim 1, wherein the polymerization degree of the polyvinyl alcohol is 400 to 2000, preferably 500 to 1900, more preferably 1500 to 1800.
3. The coating solution as claimed in claim 1, wherein the degree of alcoholysis of the polyvinyl alcohol is 88 to 99.9%, preferably 90 to 99.9%, more preferably 95 to 99.9%.
4. The coating solution as claimed in claim 1, wherein the nanoparticles are selected from the group consisting of: nano-silica, nano-calcium carbonate, nano-titanium dioxide, nano-layered silicate, or a combination thereof.
5. The coating solution as claimed in claim 1, wherein the curing agent is selected from the group consisting of: an amino resin, an alkyd resin, an isocyanate, or a combination thereof.
6. The coating solution as defined in claim 1, wherein the co-solvent is selected from the group consisting of: a modifier, a dispersant, a defoamer, a leveling agent, or a combination thereof.
7. The method for preparing a coating liquid according to claim 1, comprising the steps of:
(1) mixing polyvinyl alcohol resin, water, a defoaming agent and a regulator, heating to 80-100 ℃ for dissolving, and cooling to room temperature to obtain a mixture I;
(2) mixing the nano particles, a dispersing agent and water, grinding for 4-12 h to uniformly disperse the nano particles in the water to form a dispersion liquid I (the particle size of a dispersed phase is 20-500 nm); and
(3) and mixing the dispersion liquid I, the mixed liquid I, the curing agent and the flatting agent to obtain the coating liquid.
8. A binder composition for forming the coating fluid of claim 1, wherein the composition comprises:
9. a coating layer which is obtained by coating with the coating liquid according to claim 1.
10. An article, characterized in that the article comprises:
a base film, and the coating liquid according to claim 1 or the coating layer according to claim 9 coated on the base film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010849309.3A CN111995912A (en) | 2020-08-21 | 2020-08-21 | Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010849309.3A CN111995912A (en) | 2020-08-21 | 2020-08-21 | Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111995912A true CN111995912A (en) | 2020-11-27 |
Family
ID=73473626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010849309.3A Pending CN111995912A (en) | 2020-08-21 | 2020-08-21 | Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111995912A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112900148A (en) * | 2021-01-15 | 2021-06-04 | 盐城工学院 | Method for improving water vapor barrier property of food packaging paper under high temperature and high humidity |
| CN115536892A (en) * | 2022-11-09 | 2022-12-30 | 江苏康辉新材料科技有限公司 | High-oxygen-resistance BOPET film and preparation method thereof |
| CN115895357A (en) * | 2022-12-15 | 2023-04-04 | 中山大学 | Novel degradable high-barrier film coating liquid and preparation method and application thereof |
| CN117384517A (en) * | 2023-12-07 | 2024-01-12 | 广东顺德德冠艺云科技有限公司 | Barrier aqueous coating liquid, barrier polyolefin film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410286A (en) * | 2018-03-27 | 2018-08-17 | 纳琳威纳米科技南通有限公司 | A kind of coating fluid and preparation method thereof being used to prepare high-barrier water boiling resistance film |
| CN109535867A (en) * | 2018-12-24 | 2019-03-29 | 福建师范大学福清分校 | A kind of high barrier PVA coating fluid and preparation method thereof |
-
2020
- 2020-08-21 CN CN202010849309.3A patent/CN111995912A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410286A (en) * | 2018-03-27 | 2018-08-17 | 纳琳威纳米科技南通有限公司 | A kind of coating fluid and preparation method thereof being used to prepare high-barrier water boiling resistance film |
| CN109535867A (en) * | 2018-12-24 | 2019-03-29 | 福建师范大学福清分校 | A kind of high barrier PVA coating fluid and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112900148A (en) * | 2021-01-15 | 2021-06-04 | 盐城工学院 | Method for improving water vapor barrier property of food packaging paper under high temperature and high humidity |
| CN115536892A (en) * | 2022-11-09 | 2022-12-30 | 江苏康辉新材料科技有限公司 | High-oxygen-resistance BOPET film and preparation method thereof |
| CN115895357A (en) * | 2022-12-15 | 2023-04-04 | 中山大学 | Novel degradable high-barrier film coating liquid and preparation method and application thereof |
| CN117384517A (en) * | 2023-12-07 | 2024-01-12 | 广东顺德德冠艺云科技有限公司 | Barrier aqueous coating liquid, barrier polyolefin film and preparation method thereof |
| CN117384517B (en) * | 2023-12-07 | 2024-02-23 | 广东顺德德冠艺云科技有限公司 | Barrier aqueous coating liquid, barrier polyolefin film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995912A (en) | Moisture-proof high-oxygen-barrier aqueous coating liquid and preparation method thereof | |
| CN109161363B (en) | High-resistance water-proof adhesive | |
| CN1089681C (en) | Readily bondable polyamide film | |
| CN108410286A (en) | A kind of coating fluid and preparation method thereof being used to prepare high-barrier water boiling resistance film | |
| CN107353605B (en) | Multifunctional graphene/PET composite film and preparation method thereof | |
| CN107880305A (en) | A kind of polymer composites of high air-liquid barrier property and preparation method thereof | |
| CN106883565B (en) | A kind of high-barrier composite film | |
| CN112250899B (en) | High-gas-barrier-property biodegradable oriented composite film | |
| JP2007504297A (en) | Non-elastic polymer barrier coatings and dispersed layered fillers in liquid carriers and coated articles | |
| CN112608502A (en) | High-toughness biaxially-oriented polylactic acid film, preparation method and application | |
| CN112334531B (en) | Aqueous ethylene-vinyl alcohol copolymer dispersion and oxygen barrier multilayer film coated with the same | |
| CN112318987A (en) | Transparent high-barrier food packaging composite film and preparation method thereof | |
| CN103122171A (en) | Method for preparing nano polyvinyl alcohol coating liquid by adopting sol-gel method and coating formed by nano polyvinyl alcohol coating liquid | |
| Zhu et al. | Fabrication and evaluation of melamine-formaldehyde resin crosslinked PVA composite coating membranes with enhanced oxygen barrier properties for food packaging | |
| CN114517049B (en) | Coating liquid with high barrier property and application thereof | |
| CN106867035A (en) | A kind of modified polyvinylalcohol packing film and preparation method thereof | |
| CN101280140B (en) | Non-aqueous high-obstructing coating liquid and high-obstructing hollow container prepared therefrom | |
| CN111393885A (en) | PET film with excellent gas barrier property and preparation process thereof | |
| EP2014733A1 (en) | Coating liquid, gas barrier film using same, gas barrier laminate, gas barrier multilayer film, and their production methods | |
| JP2005096353A (en) | Gas-barrier film | |
| CN214522534U (en) | Transparent high-barrier composite packaging film | |
| CN117384517B (en) | Barrier aqueous coating liquid, barrier polyolefin film and preparation method thereof | |
| JPS637946B2 (en) | ||
| CN115008853B (en) | Easily-recycled high-barrier paper aluminum composite packaging material and preparation method thereof | |
| CN116145472B (en) | High-biobased high-barrier biodegradable composite membrane material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201127 |