CN116783255A - Hydrophilic coating composition and method for preparing same - Google Patents

Hydrophilic coating composition and method for preparing same Download PDF

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Publication number
CN116783255A
CN116783255A CN202380008818.5A CN202380008818A CN116783255A CN 116783255 A CN116783255 A CN 116783255A CN 202380008818 A CN202380008818 A CN 202380008818A CN 116783255 A CN116783255 A CN 116783255A
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China
Prior art keywords
coating composition
hydrophilic
resin
hydrophilic coating
modified
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朴柄瑞
朴相赫
赵延基
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Nissin Wells Ltd
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Nissin Wells Ltd
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C09J161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The present disclosure relates to a hydrophilic coating composition including a thermoplastic resin modified with a hydrophilic substance, with which a coating film excellent in scratch resistance, long-term persistence of no dripping, transparency, and non-tackiness can be obtained.

Description

Hydrophilic coating composition and method for preparing same
Technical Field
The present disclosure relates to a hydrophilic coating composition excellent in dripless and scratch resistance, a method for preparing the same, and a coating film using the same.
Background
Most thermoplastic films used as plastic greenhouses are hydrophobic and condense when the ambient temperature is less than or equal to the dew point of the water vapor, thus condensing water droplets on the film surface. Due to this phenomenon, there is a problem that the transmittance of sunlight is lowered, condensed water drops drop onto crops, and thus the growth of crops is delayed or spoilage is caused.
Korean laid-open patent KR10-2003-0093013A uses additives called dripless, anti-drip agents, antifogging agents, etc. in the film formation, which are added together with the resin at the time of film formation, and after film formation, the additives migrate to the surface while exerting a dripless effect. The drop-free agent has a function of suppressing condensation of water droplets and improving transmittance by forming a thin water layer when water droplets contact the surface by lowering the surface tension of the film. The additive type drip-free agent functions while the raw material migrates to the film surface, and therefore the initial drip-free property is good, but after the raw material is completely consumed, the function is lost. Therefore, when an agricultural film manufactured by the conventional means is used, there is a problem that the water vapor condensation phenomenon occurs again after a certain time.
In order to solve such problems, korean laid-open patent KR 10-2019-011143A discloses a technology for preparing a hydrophilic coating agent using inorganic colloidal sols such as silica, alumina, etc., and organosilanes, surfactants. Since the hydrophilic colloidal particles are not adhered to the hydrophobic plastic film as a substrate, a silane coupling agent is used as an adhesive to improve adhesion to the film in order to strongly adhere the colloidal particles to the substrate. On the other hand, the composition containing them reduces the water contact angle of the plastic film or sheet and improves the hydrophilicity, but has problems such as poor scratch resistance, high-temperature hydrophilicity, transparency, and the like after coating.
Disclosure of Invention
An object of one embodiment is to provide a hydrophilic coating composition that is excellent in scratch resistance, and has no dripping for a long period of time.
An object of one embodiment is to provide a method for producing a hydrophilic coating composition excellent in scratch resistance and having no dripping for a long period of time.
An object of an embodiment is to provide a coating film comprising the above hydrophilic coating composition.
In order to achieve the above-mentioned object,
in one aspect, the present invention provides a hydrophilic coating composition comprising: a thermosetting resin derived from a resin containing 1 or more monomers selected from the group consisting of primary amine groups, secondary amine groups, and hydroxyl groups, an inorganic colloidal sol, and a silane coupling agent; the thermosetting resin is modified by hydrophilic substances.
In this case, the thermosetting resin may include 1 or more selected from the group consisting of phenol resin, polyurethane resin, melamine resin, urea resin, modified phenol resin, modified melamine-urea resin, modified phenol-urea resin, and modified polyurethane resin.
In addition, the monomer may include melamine or phenol.
In addition, the above hydrophilic substances may include saccharide compounds, polyols, or may include all of them.
The above composition may comprise 0.1 to 20 wt% of a thermosetting resin modified with a hydrophilic additive, relative to the total weight of the composition; 50 to 90 wt% inorganic colloidal sol; and 0.1 to 5 wt% of a silane coupling agent.
The above composition may further comprise a surfactant, and may comprise 0.1 to 10 wt% of the above surfactant, relative to the total weight of the composition.
The inorganic colloid sol is selected from the group consisting of Al 2 O 3 、SiO 2 、ZnO、ZrO 2 、BaTiO 3 、TiO 2 、Ta 2 O 5 、Ti 3 O 5 、ITO、IZO、ATO、ZnO-Al、Nb 2 O 3 One or a combination of two or more of the group consisting of SnO and MgO.
In another aspect of the present invention, there is provided a method for preparing a hydrophilic coating composition, comprising the steps of: (a) Mixing a hydrophilic substance with a monomer containing 1 or more selected from the group consisting of a primary amine group, a secondary amine group and a hydroxyl group to prepare a thermosetting resin modified with the hydrophilic substance; and (b) mixing the above-described modified thermosetting resin in a mixed solution containing an inorganic colloidal sol and a silane coupling agent.
At this time, the above step (a) may be performed under a pH of 3 to 7.
In addition, in the above (a), the monomer and the hydrophilic substance may be mixed in a weight ratio of 1:01 to 1:2.
Still another aspect of the present invention provides a coating film comprising: a base film; and a coating layer comprising the hydrophilic coating composition on the base film.
In this case, the base film may include a thermoplastic resin, and the thermoplastic resin may be a polyolefin resin.
In addition, the coating film may be an agricultural coating film.
The present disclosure relates to a hydrophilic coating composition comprising a thermoplastic resin modified with a hydrophilic substance, with which a coating film excellent in scratch resistance, long-term persistence of dripless properties, transparency, and non-tackiness can be obtained.
Detailed Description
The present invention will be described in detail below.
On the other hand, the embodiment of the present invention may be modified in various ways, and the scope of the present invention is not limited to the embodiment described below. Furthermore, embodiments of the present invention are provided to more fully illustrate the invention to those skilled in the art. In the present invention, the term "comprising" means that other components may be further included, and that other components are not excluded unless otherwise stated.
In one aspect, the present invention provides a hydrophilic coating composition comprising: a thermosetting resin derived from a resin containing 1 or more monomers selected from the group consisting of primary amine groups, secondary amine groups, and hydroxyl groups; an inorganic colloidal sol; and a silane coupling agent, wherein the thermosetting resin is modified by a hydrophilic substance.
In this case, the monomer is a monomer that can react with a hydrophilic substance, and is not particularly limited as long as it contains any one or more of a primary amine group, a secondary amine group, and a hydroxyl group, and may include melamine, phenol, or urea, for example. For example, the thermosetting resin may be a phenol resin, a polyurethane resin, a melamine resin, a urea resin, a modified phenol resin, a modified melamine-urea resin, a modified phenol-urea resin, or a modified polyurethane resin. The thermosetting resin may preferably be a reaction product of a compound composed of the monomer and a hydrophilic substance. In one embodiment of the present invention, the hydrophilic substance containing hydroxyl groups is used in the condensation reaction with melamine instead of aldehyde such as formaldehyde, thereby imparting high hydrophilicity to the resin, so that the resin is strongly fixed on the surface of the film, thereby improving the scratch resistance of the film, and significantly improving the effects of initial dripless, long-term dripless, repeated dripless (water resistance).
As an example of the above monomer, melamine (melamine) is excellent in crosslinking ability, and thus is used as a crosslinking agent in various industrial fields. However, since melamine has no hydrophilicity, there is a problem that although durability is higher and dripless is reduced as the amount of addition increases, in the case where an excessive amount of melamine is used, dripless are reduced in a short time, and thus the amount of addition may be limited.
The hydrophilic substance may include, for example, a saccharide compound, a polyhydric alcohol, or may include all of them, and specifically may be a monosaccharide, a disaccharide, a polysaccharide, glucose, fructoseSucrose, maltoseLactose, dextrose, maltose-> Trehalose, fructose->A C1-20 polyol, a C1-15 polyol, a C1-10 polyol, a C1-5 polyol, or a mixture of 2 or more thereof. The polyhydric alcohol is not particularly limited as long as it contains two or more hydroxyl groups (-OH) in the molecule, and may be, for example, glycerin, diglycerin, triglycerin, polyglycerol, sorbitol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol (butylene glycol), pentylene glycol, hexylene glycol, pentaerythritol, xylitol, mannitol, pentaerythritol, but is not necessarily limited thereto.
The hydrophilic coating composition may contain 0.1 to 20 wt% of the thermosetting resin modified with the hydrophilic substance with respect to the total weight of the composition, but is not necessarily limited to the above weight range, and may contain 0.1 to 15 wt%, 0.5 to 15 wt%, 3 to 15 wt%, or 5 to 15 wt%. In addition, in the hydrophilic coating composition, the inorganic colloidal sol may be contained in an amount of 50 to 90 wt% with respect to the total weight of the composition, but is not necessarily limited to the above weight range, and may be contained in an amount of 60 to 90 wt%, or 65 to 85 wt%. In addition, the hydrophilic coating composition may contain 0.1 to 5 wt% of the silane coupling agent with respect to the total weight of the composition, but is not necessarily limited to the above weight range, and may contain 0.1 to 4 wt%, 0.1 to 3 wt%, and 0.1 to 2 wt%.
The hydrophilic coating composition may also contain a surfactant. The above surfactant may be selected from conventionally used nonionic, cationic, anionic, or zwitterionic surfactants. The above surfactant may be contained in an amount of 0.1 to 10 wt% relative to the total weight of the composition, but is not necessarily limited to the above weight range, and may be contained in an amount of 0.5 to 8 wt%, 1 to 7 wt%, or 2 to 6 wt%.
The inorganic colloidal sol may include at least one inorganic substance capable of reacting with the silane coupling agent, and the inorganic substance may be inorganic nanoparticles having an average particle diameter of 1 to 100 nm. The inorganic nanoparticles may be, for example, metal oxides, al 2 O 3 、SiO 2 、ZnO、ZrO 2 、BaTiO 3 、TiO 2 、Ta 2 O 5 、Ti 3 O 5 、ITO、IZO、ATO、ZnO-Al、Nb 2 O 3 SnO or MgO. The inorganic nanoparticles are uniformly formed in the coating film, and thus the mechanical properties such as scratch resistance and pencil hardness can be improved. The inorganic colloidal sol may be used as it is, or may be commercially available, or may be used in the form of a dispersion in a solvent at a concentration of 10 to 80% by weight when the commercially available sol is used. Alternatively, the colloidal sol may include alumina sol and silica sol, or may include all of them, and a solid content of 10% to 50%, or 10% to 30% may be used.
The silane coupling agent (Silan coupling agent) has a hydrolysis group having affinity or reactivity with an inorganic material (silica, glass, metal, etc.) and an organic functional group chemically bonded to an organic material (organic synthetic resin, etc.), and functions to bond the inorganic material and the organic material, and to improve mechanical strength, water resistance, adhesion, etc. The silane coupling agent may be, for example, an epoxy silane, a silane ester, or an acrylic silane. As a specific example of the silane coupling agent, may be glycidoxymethyl trimethoxysilane, 3-glycidoxypropyl dimethylhydroxy silane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl dimethoxymethylsilane, 3-glycidoxypropyl dimethylmethoxysilane, 3-glycidoxypropyl trimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, 5, 6-epoxyhexyl triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, triethylvinylsilane, triethoxysilane, 3-diethoxysilane, dimethyldiethoxysilane, 3-diethoxysilane, diethoxysilane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, butyl trimethoxy silane, butyl triethoxy silane, phenyl triethoxy silane, or 3-acryloxypropyl trimethoxy silane. The silane coupling agent may be combined with the inorganic substance by a sol-gel process. The hydrolytic group is hydrolyzed into silanol groups (Si-OH) by water and then forms hydrogen bonds with-OH on the surfaces of inorganic matters such as inorganic colloid sol particles, so that the effect of improving the combination force of organic matters and inorganic matters which are difficult to adhere is achieved, and the organic functional groups react with the reactive groups on the surfaces of the films, so that the coating is not easy to be carried away by water.
In one embodiment of the present invention, a condensation reaction is performed by reacting with a hydrophilic substance containing a hydroxyl group to impart high hydrophilicity to a thermosetting resin, and by using an inorganic colloidal sol, a silane coupling agent and the above-mentioned thermosetting resin modified with a hydrophilic substance together, the coating composition is strongly fixed to the film surface, whereby a film having improved scratch resistance, maintained dripless properties for a long period of time, high transparency and non-tackiness, and no blocking between film surfaces can be produced.
In another aspect of the present invention, there is provided a method for preparing a hydrophilic coating composition, comprising the steps of: a step of mixing a hydrophilic substance with a monomer containing 1 or more selected from the group consisting of a primary amine group, a secondary amine group and a hydroxyl group, to prepare a thermosetting resin modified with the hydrophilic substance; and a step of mixing the modified thermosetting resin in a mixed solution containing an inorganic colloidal sol and a silane coupling agent.
The method for producing the hydrophilic coating composition will be described in detail.
The method for producing the hydrophilic coating composition includes a step of mixing 1 or more monomers selected from the group consisting of primary amine groups, secondary amine groups and hydroxyl groups with a hydrophilic substance to prepare a thermosetting resin modified with the hydrophilic substance (hereinafter also referred to as a modification step). This step may be performed under a condition of pH3 to 7, but is not necessarily limited to this condition, and may be performed under a condition of 4 to 7, or 5 to 7, for example. In order to adjust the pH range, in the above-mentioned modification step, a pH adjustor may be used together, and the pH adjustor is not particularly limited as long as it can adjust the pH of the mixed solution of the monomer and the hydrophilic substance to a range of 3 to 7, but acetic acid (acetic acid), citric acid, phosphoric acid, hydrochloric acid, tartaric acid, succinic acid, malic acid, glycolic acid, fumaric acid, oxalic acid, itaconic acid, tricarballylic acid, stearic acid, pyruvic acid, acetoacetic acid, glutaconic acid, mellitic acid, isocitric acid, ascorbic acid, iminoacetic acid, propionic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, palmitic acid, or salts thereof may be used.
In the above-mentioned modification step, a conventional solvent may be used together, and the kind of the solvent is not particularly limited, and for example, distilled water may be used; or an organic solvent selected from ethanol, methanol, acetone, dichloromethane, acetonitrile, hexane, cyclohexane, benzene, ethyl acetate, diethyl ether, tetrahydrofuran, butanol, toluene, carbon tetrachloride, chloroform, and dichloromethane.
In the above-mentioned modification step, the mixed solution is stirred at 30℃to 100℃for 30 minutes to 120 minutes, whereby a thermoplastic resin solution modified with a hydrophilic substance can be obtained, and the above-mentioned temperature conditions are not necessarily limited thereto, and for example, may be performed at 30℃to 80℃40℃to 70℃or 40℃to 60℃and the above-mentioned time conditions are not necessarily limited thereto, and for example, may be stirred for 30 minutes to 100 minutes 40 minutes to 90 minutes 50 minutes to 80 minutes.
In the modification step, the monomers and the hydrophilic substance may be mixed in a weight ratio of 1:0.1 to 1:2, 1:0.1 to 1:1.5, 1:0.5 to 1:1.5, or 1:0.7 to 1:1.3, but not necessarily limited thereto.
The method for preparing the hydrophilic coating composition includes a step of mixing the modified thermosetting resin in a mixed solution including an inorganic colloidal sol and a silane coupling agent.
The mixed solution containing the inorganic colloidal sol and the silane coupling agent may contain a conventional organic solvent, and the kind of the organic solvent is not particularly limited, and for example, may be selected from distilled water, ethanol, methanol, acetone, methylene chloride, acetonitrile, hexane, cyclohexane, benzene, ethyl acetate, diethyl ether, tetrahydrofuran, butanol, toluene, carbon tetrachloride, chloroform, or methylene chloride.
When the modified thermosetting resin is mixed with the mixed solution containing the inorganic colloidal sol and the silane coupling agent, the mixture may be mixed by adding a surfactant together. Then, the step of stirring at 30 to 80 ℃ for 60 to 300 minutes may be included, and the above temperature conditions are not necessarily limited thereto, and may be performed at 30 to 70 ℃, 40 to 70 ℃, or 40 to 60 ℃, and the above time conditions are not necessarily limited thereto, and may be performed for 100 to 280 minutes, 120 to 240 minutes, 150 to 210 minutes, for example.
Another aspect of the present invention provides a coating film comprising: a base film; a coating comprising the hydrophilic coating composition described above.
The base film may include a thermoplastic resin, and the thermoplastic resin may include, for example, a polyolefin resin, a polyvinyl chloride resin, a polyester resin, and the like. Examples of the polyolefin resin include polyethylene, polypropylene, and ethylene copolymers, specifically, linear Low Density Polyethylene (LLDPE), low Density Polyethylene (LDPE), high Density Polyethylene (HDPE), ethylene-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, ethylene- (meth) acrylate copolymer, and metal salt (ionomer) of ethylene- (meth) acrylate copolymer, the polyvinyl chloride resin may be polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-methyl methacrylate copolymer, and polyvinylidene chloride, and the polyester resin may be polyethylene terephthalate (PET), polyethylene naphthalate (PBT), polybutylene terephthalate (PBT), and polybutylene naphthalate (PBN).
When the hydrophilic coating composition is coated on the base film, the composition may be diluted in water, and for example, the composition may be diluted in such a manner that the dilution ratio of the coating composition to water is 1:2 to 1:20, 1:10 to 1:20, or 1:12 to 1:18. In general, the surface of a thermoplastic film such as a polyolefin film is hydrophobic, and thus surface treatment may be performed to form a reactive group. The surface treatment method includes chemical treatment, corona discharge treatment, mechanical treatment, ultraviolet (UV) treatment, active plasma treatment, glow discharge treatment, etc., and may be selected and performed as appropriate.
As a method of applying the coating layer containing the above hydrophilic coating composition to the base film, a known coating method can be used, and for example, can be performed by gravure (gravure) coating, spray (spray) coating, dip (dip) coating (immersion coating), flow (flow) coating, roll-to-roll (roll to roll) coating, doctor blade (doctor blade) coating, or air knife (air knife) coating. The above-mentioned coating may further include a step of hot air drying at 50 to 100 ℃ for 30 to 5 minutes, and the above-mentioned temperature conditions are not necessarily limited thereto, and may be, for example, 60 to 90 ℃, and the time conditions are not necessarily limited thereto, and may be, for example, 30 to 180 seconds, or 60 to 180 seconds.
The above-mentioned coating film can be used as an agricultural film. The agricultural film may be, for example, a film or sheet for mounting an agricultural plastic booth. In this case, in the production of the above film, additives for agricultural film production such as drip-free agents, drip-resistant agents, and antifogging agents may be used. Modes for carrying out the invention
Hereinafter, examples and experimental examples of the present invention are specifically illustrated. However, the examples and experimental examples described below are only illustrative of a part of the present invention, and the present invention is not limited thereto.
< example 1-1> preparation of hydrophilic coating composition-1
Step 1: preparation of modified thermosetting resin (melamine resin)
3g of liquid melamine and 6g of ethanol were mixed, the pH was set to 6 using acetic acid, and then 3g of glucose was added as a hydrophilic substance. Then, the mixture was stirred at 50℃for 1 hour to prepare a modified dense ammonia resin solution as a modified thermosetting resin.
Step 2: preparation of hydrophilic coating compositions
First, 70% by weight of a colloidal sol (colloidal silica, colloidal alumina), 10% by weight of distilled water, 2% by weight of ethanol, and 0.5% by weight of a silane coupling agent ((3-glycidoxypropyl) trimethoxysilane) were mixed, and the mixed solution was stirred at 300rpm for 6 hours, thereby obtaining an opaque white solution. To this solution, 3 wt% of a nonionic surfactant LA-7 (polyoxyethylene alkyl (C12-14) ether/ethoxylated (C12-14) alcohol, cas No. 68439-50-9) and 9.5 wt% of the modified dense ammonia resin solution prepared in the above step 1 were added, followed by stirring at 50 ℃ for 3 hours, thereby preparing a hydrophilic coating composition.
< example 1-2> preparation of hydrophilic coating composition-2
A hydrophilic coating composition was prepared in the same manner as in example 1-1 except that fructose was added instead of glucose in step 1 of example 1-1.
< examples 1-3> preparation of hydrophilic coating composition-3
A hydrophilic coating composition was prepared in the same manner as in example 1-1 except that sucrose was added instead of glucose in step 1 of example 1-1.
< examples 1-4> preparation of hydrophilic coating composition-4
A hydrophilic coating composition was prepared in the same manner as in example 1-1 except that glycerol was added instead of glucose in step 1 of example 1-1.
< examples 1-5> preparation of hydrophilic coating composition-5
A hydrophilic coating composition was prepared in the same manner as in example 1-1 except that diglycerol was charged in place of glucose in step 1 of example 1-1.
< examples 1-6> preparation of hydrophilic coating composition-6
A hydrophilic coating composition was prepared in the same manner as in example 1-1 except that pentaerythritol was added instead of glucose in step 1 of example 1-1.
< examples 1-7> preparation of hydrophilic coating composition-7
A hydrophilic coating composition was prepared by the same method as in example 1-1 above except that in step 1 of example 1-1, phenol aldehyde was used instead of melamine.
< examples 1-8> preparation of hydrophilic coating composition-8
A hydrophilic coating composition was prepared in the same manner as in example 1-1 above, except that in step 1 of example 1-1, phenol aldehyde was used instead of melamine and sucrose was used instead of glucose.
Comparative example 1-1> preparation of coating composition comprising unmodified thermosetting resin-1
A coating composition was prepared in the same manner as in example 1-1 above, except that in step 1 of example 1-1, no hydrophilic substance and no acetic acid were added.
Comparative examples 1-2> preparation of coating composition comprising unmodified thermosetting resin-2
In examples 1 to 7, hydrophilic coating compositions were prepared in the same manner as in examples 1 to 7 above, except that hydrophilic substances and acetic acid were not added.
The thermosetting resins and hydrophilic materials of the above examples 1-1 to 1-8 and comparative examples 1-1 to comparative examples 1-2 were arranged in the following Table 1.
[ Table 1 ]
Thermosetting resin Hydrophilic substance
Example 1-1 Melamine Glucose
Examples 1 to 2 Melamine Fructose
Examples 1 to 3 Melamine Sucrose
Examples 1 to 4 Melamine Glycerol
Examples 1 to 5 Melamine Diglycerol
Examples 1 to 6 Melamine Pentaerythritol
Examples 1 to 7 Phenolic aldehyde Glucose
Examples 1 to 8 Phenolic aldehyde Sucrose
Comparative example 1-1 Melamine -
Comparative examples 1 to 2 Phenolic aldehyde -
< examples 2-1 to 2-8> production of films coated with hydrophilic coating compositions
Each of the hydrophilic coating compositions prepared in examples 1-1 to 1-8 above was diluted with water at 1:15 for use. The surface of a linear Low Density Polyethylene (LDPE) film having a thickness of 0.1T was subjected to discharge treatment under conditions of Load control (Load-adj) 6, load current (Load-current) 4A, and treatment bar 0.4m using a corona discharge processor (manufactured by Song motor, corona surface voltage (Corona surface voltage) 220V, load control (Load-adj) 0 to 10, load current (Load-current) 0 to 10A, treatment bar 0.4 m). After the surface treatment, the film having a surface tension of 40 to 50mN/m was immersed in the coating liquid composition to be coated (dip-coating), and dried with hot air in an oven at 80℃for 2 minutes. The dried film was left at room temperature for 12 hours or more.
< comparative examples 2-1 to 2> production of films coated with coating composition
Using the coating compositions prepared in comparative examples 1-1 to 1-2 described above, films coated with the coating compositions were produced by the same method as in example 2-1 described above.
< Experimental example 1> initial dripless analysis of coating film
To confirm the initial dripless degree of the coating film, after a 40℃incubator was set in a 20℃laboratory, the films of examples 2-1 to 2-8 and comparative examples 2-1 to 2-2 were attached to the upper part of the transversal 25 cm. Times.longitudinal 40 cm-width incubator in an unfolded manner by tilting by 30 ℃. The time taken from the setting of the thermostatic bath until the condensation area of the water droplets reached 10% was measured, and the results of the evaluation according to the following criteria are shown in table 2 below. In this case, the shorter the elapsed time, the more excellent the initial dripless property.
A: less than 10 minutes after set up
B: after setting, the time is greater than or equal to 10 minutes and less than 20 minutes
C: after setting, the water content is greater than or equal to 20 minutes and less than 30 minutes
D: after setting, the time is greater than or equal to 30 minutes
< Experimental example 2> long-term dripless analysis of coating film
To confirm whether or not the dripless properties of the coating film were maintained for a long period of time, after a 40℃incubator was set in a 20℃laboratory, the films of examples 2-1 to 2-8 and comparative examples 2-1 to 2-2 were attached to the upper part of the incubator having a width of 25cm in the transverse direction and 40cm in the longitudinal direction by tilting at 30℃so as not to be folded. The degree of condensation of water droplets on the surface of the inner film 20 days after the installation of the thermostatic bath was visually observed, and the results of the evaluation according to the following criteria are shown in table 2 below.
A: transparent state with little condensation of water droplets
B: the condensation area of the water drops is less than or equal to 25 percent
C: a state in which the condensation area of the water droplets is 25% to 50%
D: the condensation area of the water drops is 50% or more
< Experimental example 3> repeated dripless analysis of coating film
To confirm the water resistance of the coating film, after a 40℃incubator was set in a 20℃laboratory, the films of examples 2-1 to 2-8 and comparative examples 2-1 to 2-2 were attached to the upper part of the incubator having a width of 25cm in the transverse direction and 40cm in the longitudinal direction by tilting at 30 ℃. After the constant temperature bath was set for 3 days, the film was removed, and after the film was completely dried at normal temperature, the film was set in the constant temperature bath again, and the degree of condensation of water droplets on the film surface was visually observed, and the results of the evaluation according to the following criteria were shown in table 2 below.
A: the condensation area of the water drops is less than or equal to 10 percent
B: a state in which the condensation area of the water droplets is 10% to 30%
C: a state in which the condensation area of the water droplets is 30 to 60%
D: the condensation area of the water drops is more than or equal to 60 percent
< Experimental example 4> scratch resistance analysis of coating film
The degree of abrasion resistance of the coating was evaluated using an abrasion (rubber) tester (model: COAD.108, power (Power): AC220V 60 Hz). A 200g weight was used to apply a load, and friction was repeated 40 times at a constant speed. After a constant temperature bath of 40℃was set in a laboratory of 20℃and the film to be measured was attached to the upper part of the constant temperature bath by tilting by 30℃and then the area of the film to be measured having no drop caused by friction was visually observed, the results of the evaluation according to the following criteria are shown in Table 2 below.
A: the stripping area of the coating is less than 10 percent of the whole
B: the stripping area of the coating is between 10 and 40 percent of the whole
C: the stripping area of the coating is between 40% and 80% of the whole
D: the peeling area of the coating is more than or equal to 80 percent of the whole
Experimental example 5> film coating force analysis of coating composition
In examples 2-1 to 2-8 and comparative examples 2-1 to 2-2, the films subjected to hot air drying after dip coating were visually observed, and the results evaluated according to the following criteria are shown in table 2 below.
A: uniform coating throughout the membrane area
B: the area of the flower spots is less than 10 percent of the whole area
C: the area of the flower spots is between 10 and 50 percent of the whole area
D: the area of the flower spots is more than or equal to 50 percent of the whole area
< Experimental example 6> adhesive force analysis of coating film
To confirm the adhesive force of the coated surfaces, the films of examples 2-1 to 2-8 and comparative examples 2-1 to 2-2 were laminated so as to face each other between the coated surfaces, and then a 20kg weight was applied, and after storage in an oven at 80℃for 24 hours, the force required for 180℃peeling (peeling) was measured using UTM. At this time, when the film is stretched with high adhesion, blocking phenomenon occurs between the coated surfaces. The measurement results are shown in table 2 below.
< Experimental example 7> analysis of transparency of coating film
In order to confirm the transparency of the films of examples 2-1 to 2-8 and comparative examples 2-1 to 2-2, the results of measurement using a color difference meter (colorimeter) are shown in table 2 below. At this time, the lower the result value, the more transparent.
[ Table 2 ]
From the above table 2, it was confirmed that the film coated with the hydrophilic coating composition containing the thermosetting resin modified with the hydrophilic substance is excellent in initial, long-term, repeated dripless and scratch resistance, and can be usefully used for the production of agricultural films and the like, is excellent in transparency and coatability, and has an advantage of easy coating production process.
On the other hand, it was found that comparative examples 2-1 and 2-2, in which films were coated with a composition comprising a thermosetting resin not modified with a hydrophilic substance, were excellent in initial dripless but poor in long-term, repeated dripless, and were not suitable for agricultural films requiring continuous dripless.
The present invention has been described in detail by way of preferred embodiments and experimental examples, but the scope of the present invention is not limited to the characteristic embodiments and should be construed by the appended claims. Further, those skilled in the art will appreciate that numerous modifications and variations may be made without departing from the scope of the invention.

Claims (15)

1. A hydrophilic coating composition comprising:
a thermosetting resin derived from a resin containing 1 or more monomers selected from the group consisting of primary amine groups, secondary amine groups and hydroxyl groups,
an inorganic colloidal sol, and
a silane coupling agent;
the thermosetting resin is modified by hydrophilic substances.
2. The hydrophilic coating composition according to claim 1, wherein,
the thermosetting resin includes 1 or more selected from the group consisting of a phenolic resin, a polyurethane resin, a melamine resin, a urea resin, a modified phenolic resin, a modified melamine-urea resin, a modified phenolic-urea resin, and a modified polyurethane resin.
3. The hydrophilic coating composition according to claim 1, wherein,
the monomer comprises melamine or phenolic.
4. The hydrophilic coating composition according to claim 1, wherein,
the hydrophilic substance includes a saccharide compound or a polyol.
5. The hydrophilic coating composition according to claim 1, wherein,
comprising 0.1 to 20 wt% of a thermosetting resin modified with a hydrophilic substance, relative to the total weight of the composition; 50 to 90 wt% inorganic colloidal sol; and 0.1 to 5 wt% of a silane coupling agent.
6. The hydrophilic coating composition according to claim 1, wherein,
the hydrophilic coating composition further comprises a surfactant.
7. The hydrophilic coating composition according to claim 6, wherein,
the hydrophilic coating composition comprises 0.1 to 10 wt% of the surfactant, relative to the total weight of the composition.
8. The hydrophilic coating composition according to claim 1, wherein,
the inorganic colloid sol is selected from the group consisting of Al 2 O 3 、SiO 2 、ZnO、ZrO 2 、BaTiO 3 、TiO 2 、Ta 2 O 5 、Ti 3 O 5 、ITO、IZO、ATO、ZnO-Al、Nb 2 O 3 One or a combination of two or more of the group consisting of SnO and MgO.
9. A method of preparing a hydrophilic coating composition comprising the steps of:
(a) Mixing a hydrophilic substance with a monomer containing 1 or more selected from the group consisting of a primary amine group, a secondary amine group and a hydroxyl group to prepare a thermosetting resin modified with the hydrophilic substance; and
(b) The modified thermosetting resin is mixed in a mixed solution containing an inorganic colloidal sol and a silane coupling agent.
10. The method for producing a hydrophilic coating composition according to claim 9, wherein,
the step (a) is performed at a pH of 3 to 7.
11. The method for producing a hydrophilic coating composition according to claim 9, wherein,
in the step (a), the monomer and the hydrophilic substance are mixed in a weight ratio of 1:01 to 1:2.
12. A coating film comprising:
a base film; and
a coating layer coated on the base film comprising the hydrophilic coating composition of claim 1.
13. The coating film according to claim 12, wherein,
the base film includes a thermoplastic resin.
14. The coating film according to claim 12, wherein,
the thermoplastic resin is a polyolefin resin.
15. The coating film according to claim 12, wherein,
the coating is an agricultural coating.
CN202380008818.5A 2022-01-17 2023-01-12 Hydrophilic coating composition and method for preparing same Pending CN116783255A (en)

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