CN106893474A - A kind of freeze-resistant packs the preparation method of film composition - Google Patents
A kind of freeze-resistant packs the preparation method of film composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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- 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
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- 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
- C09D7/65—Additives macromolecular
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses the preparation method that freeze-resistant packs film composition, including following operation：1）At room temperature to IPDI etc. is added in the first reactor, primary product is obtained；2）To adding dihydromethyl propionic acid in primary product, then vacuum distillation is carried out, obtain secondary product；3）Secondary product is scattered in the second reactor, the diethylenetriamine aqueous solution is added, Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained；4）To Ludox and Aliphatic Polyester Aqueous Polyurethane Dispersions are added in the 3rd reactor, mixed emulsion is obtained, it is standby；5）To appropriate acrylic acid copolymer sodium salt etc. is added in the 4th reactor, obtain mixing bottom liquid；6）To mixed emulsion is added in mixing bottom liquid, freeze-resistant packaging film composition is obtained.There is stronger cohesive force, good strippable property, coating strength higher and preferable safety and environmental protection performance using film composition is packed obtained in the present invention.
Description
Technical field
The present invention relates to decorating field, the preparation method of film composition is packed more particularly, to freeze-resistant.
Background technology
To prevent material or half product under the atmospheric environment to be contaminated, corrode and damage, and increase the service life, it will usually there is the coating of good protective and strippable property in their surface smear it is carried out effective and interim to seal protection up for safekeeping.In this way, can both isolate air, salt fog, the invasion of microorganism in the external world, antiseptic effect is reached；The effect of decontamination can be cleaned to reach by adsorbing pollutant again.For compared with solvent-borne type protective coating, aqueous protective coating has more security and the feature of environmental protection, thus is widely used in the decorating field of product.But, existing aqueous protective coating still has the shortcomings that coating strength is low, strippable property is poor and barrier propterty is single.
The content of the invention
The purpose of the present invention is the defect for overcoming above-mentioned prior art; the preparation method that freeze-resistant packs film composition is provided; effective closing protection can be carried out to protected object using film composition is packed obtained in the present invention, has the advantages that strippable property is good, coating strength is high, cohesive force is strong.
The purpose of the present invention is achieved through the following technical solutions：
Freeze-resistant packs the preparation method of film composition, including following operation：
1）At room temperature to addition IPDI, polypropylene glycol, polyethylene glycol, dibutyl tin laurate and butanone in the first reactor, temperature is risen to 58 ~ 80 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 220 ~ 260min is reacted, then cools the temperature to 38 ~ 43 DEG C, addition triethylamine；Again by temperature control at 79 ~ 80 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, obtains secondary product, standby；
3）To addition operation 2 in the second reactor for filling distilled water）The secondary product of gained simultaneously makes secondary product be scattered in distilled water, adds the diethylenetriamine aqueous solution, and Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained, standby；
4）At room temperature to addition Ludox and operation 3 in the 3rd reactor）The Aliphatic Polyester Aqueous Polyurethane Dispersions of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtain mixed emulsion, standby；
5）To adding the swollen acrylic thickener of appropriate acrylic acid copolymer sodium salt, alkali soluble and organic silicon modified by polyether in the 4th reactor for filling distilled water, by the 4 ~ 10min of rotating speed stirring mixing of 200 ~ 300r/min, add appropriate titanium dioxide, mica, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min, obtain mixing bottom liquid, it is standby；
6）To operation 5）Operation 4 is added in the mixing bottom liquid of gained）The mixed emulsion of gained, by the 12 ~ 22min of rotating speed stirring mixing of 350 ~ 500r/min；Appropriate neopelex, polyether-modified dimethyl siloxane, alkali soluble is swollen acrylic thickener, aqueous silicone oil, organic silicon modified by polyether are added, by the rotating speed stirring 15 ~ 20min of mixing of 200 ~ 300r/min, freeze-resistant packaging film composition is obtained；
The Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained by the raw material of following quality proportioning：40 ~ 80 parts of IPDI, 25 ~ 40 parts of polypropylene glycol, 25 ~ 80 parts of polyethylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of diethylenetriamine, 3 ~ 9 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The freeze-resistant packaging film composition is obtained by the raw material of following mass fraction：Aliphatic Polyester Aqueous Polyurethane Dispersions 60 ~ 80%, Ludox 5 ~ 10%, titanium dioxide 2 ~ 5%, mica 3 ~ 5%, aqueous silicone oil 1 ~ 3%, neopelex 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether-modified dimethyl siloxane 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
The present invention first mixes each auxiliary agent during freeze-resistant packaging film composition is prepared in distilled water, then to adding color stuffing to form finely dispersed mixing bottom liquid in it, mixed emulsion is well mixed with mixing bottom liquid again finally.This kind of production technology can reduce the resistance of motion of various auxiliary agents, especially wetting agent and dispersant so that they can preferably be adsorbed onto color stuffing surface, and then can greatly improve the decentralization of color stuffing, it is to avoid the problem of particle agglomeration.In the preparation process of Aliphatic Polyester Aqueous Polyurethane Dispersions, by operation 2）Vacuum distillation can remove butanone solvent, and remaining solvent as cosolvent, the Aliphatic Polyester Aqueous Polyurethane Dispersions for so being formed more security and the feature of environmental protection.Aqueous protective coating is mainly made up of film forming matter, color stuffing, auxiliary agent and solvent.Wherein, film forming matter is the nucleus of protective coating, and the present invention, as film forming matter, can improve mechanical strength, strippable property and the tolerance to acid-base salt solution of coating from Aliphatic Polyester Aqueous Polyurethane Dispersions and Ludox compounding.The following raw material is selected in the preparation of Aliphatic Polyester Aqueous Polyurethane Dispersions：The reaction of isocyanate groups and hydroxyl is carried out with polyethylene glycol from IPDI and polypropylene glycol, the mechanical property and water resistance of film forming can be improved.In the reaction, butanone is added to reduce the viscosity of primary product.Because when the temperature of the reaction is higher than 80 DEG C, though the content of-NCO can be rapidly reached theoretical value, now side reaction is more, so easily makes unstable product quality；And when reaction is less than 58 DEG C, production efficiency can be influenceed because reaction speed is relatively slow again.Therefore, by reaction temperature control at 58 ~ 80 DEG C.From diethylenetriamine as chain extender, it can carry out chain extension to secondary product, can so improve the tensile strength of coating film.The addition of Ludox can make in the nano-silica filled film to coating, and the segment of silica can constitute the network-like structure for mutually running through with the organic high molecular polymer in coating and mica, so, the pliability of organic polymer can be improved, meanwhile, coating film bulk strength and hardness can also be improved.Because the permeability of Ludox is fabulous, it can be penetrated into inside protected base material so that coating film is securely attached on base material.Ludox can also improve the consistency of coating film, can so prevent moisture and other media from invading, and then improve the corrosion resistance of film.
Color stuffing is indispensable part in formulation for coating material, and coloring and filling effect are played in coating.Titanium dioxide is the very good Chinese white of covering power, and with good ultraviolet radiation absorption function of shielding.From mica as filler, the performances such as hardness, intensity, wearability and the base material adhesive force of coating film can be improved.Alkali soluble is swollen, and acrylic thickener can improve the viscosity of dispersion, be conducive to dispersion of the mica in system, prevent mica from sinking to luming；The denseness of coating can also be increased simultaneously, the stability of coating is improved.The base material adhesive force of adjusting coating film is capable of in the use of aqueous silicone oil, film is had preferable peeling effect.Used as wetting agent, it can reduce the surface tension of coating film to neopelex, coating film cissing phenomenon is occurred, is prevented from making application uneven because protected object is unclean with soaking base material, reduction well.Because color stuffing all has hydrophobicity, thus their less stables in water, easily reunite and sink.And pass through to add acrylic acid copolymer sodium salt, then can keep dispersiveness of the color stuffing in water.Polyether-modified dimethyl siloxane is used as levelling agent, it is possible to decrease the interfacial tension between coating and ground, improves the phenomenons such as coating is bad to shrinkage cavity that by the wetability of ground, reduction causes by ground, adhesive force.Coating is required for various artificial and mechanically actuateds in production, storage and work progress, foam is so easily caused to produce, and foam can hinder the dispersion of mica, and film coated surface is caused to form pin hole and shrinkage cavity, so as to influence the outward appearance of coating film, anti-corrosive properties and weatherability.And add the organic silicon modified by polyether can be then effectively improved above mentioned problem.
To ensure isocyanate group-NCO and being smoothed out that the hydroxyl-OH reacts, further, the mol ratio of the isocyanate group-NCO and hydroxyl-OH is 2.6 ~ 4 in the raw material of the Aliphatic Polyester Aqueous Polyurethane Dispersions:1.As-NCO/-OH ＜ 2.6, the viscosity of product can be increased, and be difficult dispersion；And as-NCO/-OH ＞ 4, the easy gel of Aliphatic Polyester Aqueous Polyurethane Dispersions reduces storage period.
To reach good neutralization, further, the addition of the triethylamine and the dihydromethyl propionic acid equimolar amounts.
It is that balance is reached between adhesive force and peel strength, further, the Ludox is 1 with the mass ratio of the Aliphatic Polyester Aqueous Polyurethane Dispersions:4.The consumption of Ludox directly affects the combination property and production cost of coating.Specifically, when the addition of Ludox is excessive, not only result in film and become fragile, film adhesive is excessive, be unfavorable for peeling off；The stability of coating system can be also influenceed, increases the production cost of coating.And Ludox consumption it is very few when, active force of the nano-particle in coating is weaker, so causes the performance improvement effect of coating unobvious.Therefore consumption of the Ludox in coating must be rationally appropriate.When the present invention is from the ratio, may be such that the tensile strength and elongation at break of coating film is strengthened, while moderate peel strength is also maintained, good acid and alkali-resistance salt performance.
To improve stability of the color stuffing in system, further, the addition of the acrylic acid copolymer sodium salt is the 2 ~ 4% of the titanium dioxide and mica total amount.
Further, the operation 1）The temperature control of middle hybrid reaction is at 78 ~ 80 DEG C, and the hybrid reaction time is 100 ~ 150min.Because the reactivity of IPDI is relatively low, thus need operation 1）Reaction temperature should be higher than that 75 DEG C, along with the boiling point of butanone is 79.6 DEG C, thus can be by temperature control at 78 ~ 80 DEG C.
Effectively to control operation 1）In reaction-reaction rate of NCO group, further, the operation 1）In also comprise the following steps：During hybrid reaction, every 5 ~ 8min measurements once in first reactor-NCO group accounts for the weight/mass percentage composition of system.
The invention has the advantages that：There is stronger cohesive force, good strippable property, coating strength higher and preferable safety and environmental protection performance using freeze-resistant packaging film composition obtained in the present invention; it can carry out effective closing protection to protected object, prevent protected object to be contaminated, corrode and damage.Simultaneously, moreover it is possible to good decontamination cleaning is carried out to protected object.Specifically, mechanical strength, strippable property and the tolerance to acid-base salt solution of coating can be improved as film forming matter from Aliphatic Polyester Aqueous Polyurethane Dispersions and Ludox compounding.From mica as filler, the performances such as hardness, intensity, wearability and the base material adhesive force of coating film can be improved.The viscosity of dispersion can be improved from the swollen acrylic thickener of alkali soluble, increases the denseness of coating, improve the stability of coating.From aqueous silicone oil as remover, the base material adhesive force of energy adjusting coating film improves the rippability of film.From neopelex as wetting agent, coating can be enable film cissing phenomenon occur with soaking base material, reduction well.From acrylic acid copolymer sodium salt as dispersant, dispersiveness of the color stuffing in water can be kept.From polyether-modified dimethyl siloxane as levelling agent, it is possible to decrease the interfacial tension between coating and ground, coating is improved to by the wetability of ground.From organic silicon modified by polyether as defoamer, the generation of foam can be reduced, so as to improve the outward appearance of coating film, anti-corrosive properties and weatherability.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
Freeze-resistant packs the preparation method of film composition, including following operation：
1）At room temperature to addition IPDI, polypropylene glycol, polyethylene glycol, dibutyl tin laurate and butanone in the first reactor, temperature is risen to 58 ~ 80 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 220 ~ 260min is reacted, then cools the temperature to 38 ~ 43 DEG C, addition triethylamine；Again by temperature control at 79 ~ 80 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, obtains secondary product, standby；
3）To addition operation 2 in the second reactor for filling distilled water）The secondary product of gained simultaneously makes secondary product be scattered in distilled water, adds the diethylenetriamine aqueous solution, and Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained, standby；
4）At room temperature to addition Ludox and operation 3 in the 3rd reactor）The Aliphatic Polyester Aqueous Polyurethane Dispersions of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtain mixed emulsion, standby；
5）To adding the swollen acrylic thickener of appropriate acrylic acid copolymer sodium salt, alkali soluble and organic silicon modified by polyether in the 4th reactor for filling distilled water, by the 4 ~ 10min of rotating speed stirring mixing of 200 ~ 300r/min, add appropriate titanium dioxide, mica, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min, obtain mixing bottom liquid, it is standby；
6）To operation 5）Operation 4 is added in the mixing bottom liquid of gained）The mixed emulsion of gained, by the 12 ~ 22min of rotating speed stirring mixing of 350 ~ 500r/min；Appropriate neopelex, polyether-modified dimethyl siloxane, alkali soluble is swollen acrylic thickener, aqueous silicone oil, organic silicon modified by polyether are added, by the rotating speed stirring 15 ~ 20min of mixing of 200 ~ 300r/min, freeze-resistant packaging film composition is obtained；
The Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained by the raw material of following quality proportioning：40 ~ 80 parts of IPDI, 25 ~ 40 parts of polypropylene glycol, 25 ~ 80 parts of polyethylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of diethylenetriamine, 3 ~ 9 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The freeze-resistant packaging film composition is obtained by the raw material of following mass fraction：Aliphatic Polyester Aqueous Polyurethane Dispersions 60 ~ 80%, Ludox 5 ~ 10%, titanium dioxide 2 ~ 5%, mica 3 ~ 5%, aqueous silicone oil 1 ~ 3%, neopelex 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether-modified dimethyl siloxane 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
The present invention first mixes each auxiliary agent during freeze-resistant packaging film composition is prepared in distilled water, then to adding color stuffing to form finely dispersed mixing bottom liquid in it, mixed emulsion is well mixed with mixing bottom liquid again finally.This kind of production technology can reduce the resistance of motion of various auxiliary agents, especially wetting agent and dispersant so that they can preferably be adsorbed onto color stuffing surface, and then can greatly improve the decentralization of color stuffing, it is to avoid the problem of particle agglomeration.In the preparation process of Aliphatic Polyester Aqueous Polyurethane Dispersions, by operation 2）Vacuum distillation can remove butanone solvent, and remaining solvent as cosolvent, the Aliphatic Polyester Aqueous Polyurethane Dispersions for so being formed more security and the feature of environmental protection.Aqueous protective coating is mainly made up of film forming matter, color stuffing, auxiliary agent and solvent.Wherein, film forming matter is the nucleus of protective coating, and the present invention, as film forming matter, can improve mechanical strength, strippable property and the tolerance to acid-base salt solution of coating from Aliphatic Polyester Aqueous Polyurethane Dispersions and Ludox compounding.The following raw material is selected in the preparation of Aliphatic Polyester Aqueous Polyurethane Dispersions：The reaction of isocyanate groups and hydroxyl is carried out with polyethylene glycol from IPDI and polypropylene glycol, the mechanical property and water resistance of film forming can be improved.In the reaction, butanone is added to reduce the viscosity of primary product.Because when the temperature of the reaction is higher than 80 DEG C, though the content of-NCO can be rapidly reached theoretical value, now side reaction is more, so easily makes unstable product quality；And when reaction is less than 58 DEG C, production efficiency can be influenceed because reaction speed is relatively slow again.Therefore, by reaction temperature control at 58 ~ 80 DEG C.From diethylenetriamine as chain extender, it can carry out chain extension to secondary product, can so improve the tensile strength of coating film.The addition of Ludox can make in the nano-silica filled film to coating, and the segment of silica can constitute the network-like structure for mutually running through with the organic high molecular polymer in coating and mica, so, the pliability of organic polymer can be improved, meanwhile, coating film bulk strength and hardness can also be improved.Because the permeability of Ludox is fabulous, it can be penetrated into inside protected base material so that coating film is securely attached on base material.Ludox can also improve the consistency of coating film, can so prevent moisture and other media from invading, and then improve the corrosion resistance of film.
Color stuffing is indispensable part in formulation for coating material, and coloring and filling effect are played in coating.Titanium dioxide is the very good Chinese white of covering power, and with good ultraviolet radiation absorption function of shielding.From mica as filler, the performances such as hardness, intensity, wearability and the base material adhesive force of coating film can be improved.Alkali soluble is swollen, and acrylic thickener can improve the viscosity of dispersion, be conducive to dispersion of the mica in system, prevent mica from sinking to luming；The denseness of coating can also be increased simultaneously, the stability of coating is improved.The base material adhesive force of adjusting coating film is capable of in the use of aqueous silicone oil, film is had preferable peeling effect.Used as wetting agent, it can reduce the surface tension of coating film to neopelex, coating film cissing phenomenon is occurred, is prevented from making application uneven because protected object is unclean with soaking base material, reduction well.Because color stuffing all has hydrophobicity, thus their less stables in water, easily reunite and sink.And pass through to add acrylic acid copolymer sodium salt, then can keep dispersiveness of the color stuffing in water.Polyether-modified dimethyl siloxane is used as levelling agent, it is possible to decrease the interfacial tension between coating and ground, improves the phenomenons such as coating is bad to shrinkage cavity that by the wetability of ground, reduction causes by ground, adhesive force.Coating is required for various artificial and mechanically actuateds in production, storage and work progress, foam is so easily caused to produce, and foam can hinder the dispersion of mica, and film coated surface is caused to form pin hole and shrinkage cavity, so as to influence the outward appearance of coating film, anti-corrosive properties and weatherability.And add the organic silicon modified by polyether can be then effectively improved above mentioned problem.
To ensure isocyanate group-NCO and being smoothed out that the hydroxyl-OH reacts, it is preferable that the mol ratio of the isocyanate group-NCO and hydroxyl-OH is 2.6 ~ 4 in the raw material of the Aliphatic Polyester Aqueous Polyurethane Dispersions:1.As-NCO/-OH ＜ 2.6, the viscosity of product can be increased, and be difficult dispersion；And as-NCO/-OH ＞ 4, the easy gel of Aliphatic Polyester Aqueous Polyurethane Dispersions reduces storage period.
To reach good neutralization, it is preferable that the addition of the triethylamine and the dihydromethyl propionic acid equimolar amounts.
It is that balance is reached between adhesive force and peel strength, it is preferable that the Ludox is 1 with the mass ratio of the Aliphatic Polyester Aqueous Polyurethane Dispersions:4.The consumption of Ludox directly affects the combination property and production cost of coating.Specifically, when the addition of Ludox is excessive, not only result in film and become fragile, film adhesive is excessive, be unfavorable for peeling off；The stability of coating system can be also influenceed, increases the production cost of coating.And Ludox consumption it is very few when, active force of the nano-particle in coating is weaker, so causes the performance improvement effect of coating unobvious.Therefore consumption of the Ludox in coating must be rationally appropriate.When the present invention is from the ratio, may be such that the tensile strength and elongation at break of coating film is strengthened, while moderate peel strength is also maintained, good acid and alkali-resistance salt performance.
To improve stability of the color stuffing in system, it is preferable that the addition of the acrylic acid copolymer sodium salt is the 2 ~ 4% of the titanium dioxide and mica total amount.
Preferably, the operation 1）The temperature control of middle hybrid reaction is at 78 ~ 80 DEG C, and the hybrid reaction time is 100 ~ 150min.Because the reactivity of IPDI is relatively low, thus need operation 1）Reaction temperature should be higher than that 75 DEG C, along with the boiling point of butanone is 79.6 DEG C, thus can be by temperature control at 78 ~ 80 DEG C.
Effectively to control operation 1）In reaction-reaction rate of NCO group, it is preferable that the operation 1）In also comprise the following steps：During hybrid reaction, every 5 ~ 8min measurements once in first reactor-NCO group accounts for the weight/mass percentage composition of system.
Above content is to combine the further description that specific preferred embodiment is made to the present invention, it is impossible to assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, the other embodiment drawn in the case where technical scheme is not departed from should be included within the scope of the present invention.
Claims (1)
1. freeze-resistant packs the preparation method of film composition, it is characterised in that：
Including following operation：
1）At room temperature to addition IPDI, polypropylene glycol, polyethylene glycol, dibutyl tin laurate and butanone in the first reactor, temperature is risen to 58 ~ 80 DEG C again, their-NCO% values in hybrid reaction to system in the first reactor is no longer changed, obtain primary product, it is standby；
2）By temperature control at 80 DEG C, to operation 1）Dihydromethyl propionic acid is added in the primary product of gained and 220 ~ 260min is reacted, then cools the temperature to 38 ~ 43 DEG C, addition triethylamine；Again by temperature control at 79 ~ 80 DEG C, pressure is controlled in -0.095 ~ -0.085 MPa, carries out vacuum distillation, until solid content reaches 80 ~ 95%, obtains secondary product, standby；
3）To addition operation 2 in the second reactor for filling distilled water）The secondary product of gained simultaneously makes secondary product be scattered in distilled water, adds the diethylenetriamine aqueous solution, and Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained, standby；
4）At room temperature to addition Ludox and operation 3 in the 3rd reactor）The Aliphatic Polyester Aqueous Polyurethane Dispersions of gained, by the rotating speed stirring 50 ~ 70min of mixing of 200 ~ 300r/min, obtain mixed emulsion, standby；
5）To adding the swollen acrylic thickener of appropriate acrylic acid copolymer sodium salt, alkali soluble and organic silicon modified by polyether in the 4th reactor for filling distilled water, by the 4 ~ 10min of rotating speed stirring mixing of 200 ~ 300r/min, add appropriate titanium dioxide, mica, by the 35 ~ 42min of rotating speed stirring mixing of 1500 ~ 1800r/min, obtain mixing bottom liquid, it is standby；
6）To operation 5）Operation 4 is added in the mixing bottom liquid of gained）The mixed emulsion of gained, by the 12 ~ 22min of rotating speed stirring mixing of 350 ~ 500r/min；Appropriate neopelex, polyether-modified dimethyl siloxane, alkali soluble is swollen acrylic thickener, aqueous silicone oil, organic silicon modified by polyether are added, by the rotating speed stirring 15 ~ 20min of mixing of 200 ~ 300r/min, freeze-resistant packaging film composition is obtained；
The Aliphatic Polyester Aqueous Polyurethane Dispersions are obtained by the raw material of following quality proportioning：40 ~ 80 parts of IPDI, 25 ~ 40 parts of polypropylene glycol, 25 ~ 80 parts of polyethylene glycol, 3 ~ 10 parts of dihydromethyl propionic acid, 50 ~ 80 parts of butanone, 5 ~ 12 parts of diethylenetriamine, 3 ~ 9 parts of triethylamine, 1 ~ 3 part of dibutyl tin laurate, 40 ~ 80 parts of distilled water；The freeze-resistant packaging film composition is obtained by the raw material of following mass fraction：Aliphatic Polyester Aqueous Polyurethane Dispersions 60 ~ 80%, Ludox 5 ~ 10%, titanium dioxide 2 ~ 5%, mica 3 ~ 5%, aqueous silicone oil 1 ~ 3%, neopelex 0.1 ~ 0.5%, alkali soluble is swollen acrylic thickener 0.5 ~ 1%, polyether-modified dimethyl siloxane 0.3 ~ 0.6%, acrylic acid copolymer sodium salt 0.1 ~ 0.5%, organic silicon modified by polyether 0.1 ~ 0.5%, balance of distilled water.
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| CN201510952753.7A CN106893474A (en) | 2015-12-20 | 2015-12-20 | A kind of freeze-resistant packs the preparation method of film composition |
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| CN201510952753.7A CN106893474A (en) | 2015-12-20 | 2015-12-20 | A kind of freeze-resistant packs the preparation method of film composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019147519A1 (en) * | 2018-01-25 | 2019-08-01 | Covestro Llc | Temporary decorative automotive/protective paint based on polyurethane dispersions |
| US11008468B2 (en) | 2018-01-25 | 2021-05-18 | Covestro Llc | Temporary decorative automotive/protective paint based on polyurethane dispersions |
-
2015
- 2015-12-20 CN CN201510952753.7A patent/CN106893474A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019147519A1 (en) * | 2018-01-25 | 2019-08-01 | Covestro Llc | Temporary decorative automotive/protective paint based on polyurethane dispersions |
| CN111615533A (en) * | 2018-01-25 | 2020-09-01 | 科思创有限公司 | Temporary decorative automotive/protective coatings based on polyurethane dispersions |
| US11008468B2 (en) | 2018-01-25 | 2021-05-18 | Covestro Llc | Temporary decorative automotive/protective paint based on polyurethane dispersions |
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Application publication date: 20170627 |