CN104371508A - Weather-resistant coating composite film - Google Patents
Weather-resistant coating composite film Download PDFInfo
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- CN104371508A CN104371508A CN201410607543.XA CN201410607543A CN104371508A CN 104371508 A CN104371508 A CN 104371508A CN 201410607543 A CN201410607543 A CN 201410607543A CN 104371508 A CN104371508 A CN 104371508A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
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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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09D175/06—Polyurethanes from polyesters
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- 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
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
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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 relates to a weather-resistant coating composite film which comprises a radiation-curing undercoat and a thermocuring weather-resistant layer applied onto the undercoat. The undercoat is prepared from the following raw materials in parts by weight: 30-90 parts of polyester base, 5-50 parts of diluter, 0.1-10 parts of initiator and 0.1-10 parts of first assistant. The polyester base is one or mixture or more of epoxy acrylate polymers, polyurethane acrylate polymers and unsaturated polyester resins. By using the polyester base composed of the epoxy acrylate polymers, polyurethane acrylate polymers or unsaturated polyester resins, the undercoat can react with the weather-resistant layer, so that the weather-resistant layer has favorable adhesive force on the undercoat. The undercoat is formed by radiation curing, and thus, has the characteristics of high speed and environmental protection; and the weather-resistant layer is formed by thermocuring, thereby ensuring the compactness and certain surface matting degree of the coating.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of combined films, be specifically related to a kind of weathering resistance coatings combined films.
Background technology
There is a lot of thin-film material in market, PET film, PA film, PP film, HDPE film and PVC film etc. can be divided into according to material therefor difference.Some film can be used alone, as agriculture production polyethylene film, also have for palletization or the shrink film tied up.But in the more common scenario, the film due to differing materials has respective performance characteristics, therefore multiple film combines and is used more, as food packaging film, blooming and industrial packaging film etc.
The technique that multiple film combines is had a lot, and as recombining process, coating process etc., but in these techniques, always so that wherein a kind of film is as basement membrane, other films fit on basement membrane again.Basement membrane generally chooses harder, thick film, as polyester film, polypropylene film, polyamide layer etc.Basement membrane requires heat-resisting solvent resistant, stable performance, to be conducive to the enforcement of subsequent production technique.The multiple film composite membrane produced that combines has the performance of various film concurrently, take PET film as basement membrane as food packaging film, be compounded with aluminium foil to obtain, PET film has better toughness and impressionability, and aluminium foil has extremely outstanding barrier property, the food packaging film that two kinds of Film laminateds are produced together has had the performance of each side concurrently, to meet food packaging requirement.
Coating technique is the comparatively simple method realizing combining between the different film of attribute, and we can carry out the performance of comprehensive basement membrane and coated membrane at coating on base films one deck or which floor coating, realize the specific function of film.If optical thin film is coated on adhesive coated on basement membrane in advance, then be pasted onto together with basement membrane on liquid crystal panel, play the effect of protection liquid crystal surfactant; Paper as a kind of material of cheapness, have porousness, water-absorbent, surface tension higher, can the characteristic such as viscosity, the paper being coated with PE film then avoids porousness and absorptive characteristic, may be used for the production of disposable tableware and water tumbler; If paper surface is coated with one deck silicone oil coating, then reduce the surface tension of paper, make it have not viscosity, the protective layer of the viscous material such as adhesive tape or printed matter can be used as.
At present, still there are some problems in the existing combined films utilizing coating technique to prepare: the sticking power of such as basement membrane is poor, erosion resistance is poor, make between whole combined films and other differing materials cohesiveness variation etc.This just needs to develop a kind of combined films and is coated on basement membrane to overcome the unfavorable factor that basement membrane uses out of doors for a long time.
Summary of the invention
The present invention seeks to provide a kind of weathering resistance coatings combined films with outstanding sticking power, weathering resistance and erosion resistance to overcome the deficiencies in the prior art.
For achieving the above object, the technical solution used in the present invention is: a kind of weathering resistance coatings combined films, it comprises by the shaping undercoat of radiation curing and is coated on weathering layer shaping through thermofixation on undercoat, and the composition of raw materials of described undercoat comprises the component of following parts by weight:
Polyester matrix 30 ~ 90 parts;
Thinner 5 ~ 50 parts;
Initiator 0.1 ~ 10 part;
First auxiliary agent 0.1 ~ 10 part;
Described polyester matrix is the mixture of one or several compositions in epoxy acrylic ester polymer, urethane acrylate polymer, unsaturated polyester resin.
Optimally, the composition of raw materials of described weathering layer comprises the component of following parts by weight:
Acrylic resin modified 30 ~ 80 parts;
Mineral filler 5 ~ 40 parts;
Second auxiliary agent 0.1 ~ 5 part;
Solvent 0.1 ~ 50 part;
1 ~ 50 part, solidifying agent.
Optimally, described thinner is ethyl acrylate, acrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, 1, 3-butylene glycol diacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexanediyl ester, diethylene glycol diacrylate, neopentylglycol diacrylate, polyethyleneglycol diacrylate, peopentyl ester acid diacrylate, tri (propylene glycol) diacrylate, cyanacrylate, Viscoat 295, tetramethylol methane tetraacrylate, dipentaerythritol six acrylate, triethyleneglycol divinylether, 1, 4-cyclohexane dimethanol divinyl ether, 4-hydroxy butyl vinyl ether, dodecyl vinyl, propylene carbonate allyl ethers, 1, 3, 5-triallyl s-triazine-2, 4, mixtures of one or several compositions in 6-triketone and triallyl isocyanuric acid ester, the relative molecular mass of described polyethyleneglycol diacrylate is 100 ~ 1000.
Optimally, described initiator is st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, 1-hydroxy-cyclohexyl phenyl ketone, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, two benzoylphenyl phosphine oxide, benzophenone, 2, 4-dihydroxy benaophenonel, Michler's keton, sulfo-propoxy-thioxanthone, isopropyl thioxanthone, diaryl group iodized salt, triaryl salt compounded of iodine, mixtures of one or several compositions in alkyl salt compounded of iodine and the luxuriant iron hexafluorophosphate of isopropyl benzene.
Optimally, described first auxiliary agent is silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organo-siloxane, vinylformic acid flow agent or fluorine richness flow agent.
Optimally, also comprise the vibrin of 10 ~ 50 parts of parts by weight in the composition of raw materials of described weathering layer, described vibrin is the straight chain saturated polyester resin containing aromatic hydrocarbon structure.
Further, the second-order transition temperature of described vibrin is 0 ~ 50 DEG C, and hydroxyl value is 1 ~ 50mgKOH/g, and molecular weight is 3000 ~ 50000.
Optimally, described acrylic resin modified be in trifluorochloroethylene-vinyl ether co-polymer, trifluorochloroethylene-vinyl ester copolymer, tetrafluoroethylene-Ethylene base ether copolymer, tetrafluoroethylene-Ethylene base ester copolymer, tetrafluoroethylene-Ethylene base ether-vinyl ester copolymer, tetrafluoroethylene and polyvinylidene difluoride (PVDF) one or more composition mixtures.
Optimally, described acrylic resin modified be that the one or more combination being polymerized by one or more in olefin(e) acid esters monomer or being polymerized by olefin(e) acid esters monomer in the polymkeric substance that formed forms.
Optimally, described acrylic resin modified second-order transition temperature is 0 ~ 70 DEG C, and molecular weight is 1000 ~ 10000, and hydroxyl value is 10 ~ 150 mgKOH/g.
Because technique scheme is used, the present invention compared with prior art has following advantages: weathering resistance coatings combined films of the present invention, use the polyester matrix of epoxy acrylic ester polymer, urethane acrylate polymer or unsaturated polyester resin composition on the one hand, undercoat and weathering layer can be reacted to each other, make the sticking power of weathering layer on undercoat excellent; Undercoat is formed by radiation curing on the other hand, have the feature of quick environmental protection, and weathering layer is formed by thermofixation, has the compactness and certain surface matte degree that ensure coating.
Embodiment
Weathering resistance coatings combined films of the present invention, comprise the shaping undercoat of radiation curing and be coated on the shaping weathering layer of thermofixation on undercoat, the composition of raw materials of described undercoat comprises the component of following parts by weight: polyester matrix 30 ~ 90 parts; Thinner 5 ~ 50 parts; Initiator 0.1 ~ 10 part; First auxiliary agent 0.1 ~ 10 part; Described polyester matrix is the mixture of one or several compositions in epoxy acrylic ester polymer, urethane acrylate polymer, unsaturated polyester resin.Wherein the polymericular weight of epoxy acrylic ester polymer, unsaturated polyester resin and urethane acrylate is preferably 1000 ~ 10000, the too high Homogeneous phase mixing being unfavorable for them of molecular weight.One aspect of the present invention uses the polyester matrix of epoxy acrylic ester polymer, urethane acrylate polymer or unsaturated polyester resin composition, undercoat and weathering layer can be reacted to each other, make the sticking power of weathering layer on undercoat excellent; Undercoat is formed by radiation curing on the other hand, there is the feature of quick environmental protection, and weathering layer is formed by thermofixation, there is the compactness and certain surface matte degree that ensure coating, and solving the binding property problem of undercoat and other material (as hot melt adhesive EVA, PE etc.), environment for use for a long time can the solution of viscosity out of doors to provide base material.
In order to improve the sticking power between undercoat and weathering layer further, now carried out optimizing further to the composition of raw materials of weathering layer, the composition of raw materials being specially described weathering layer comprises the component of following parts by weight: acrylic resin modified 30 ~ 80 parts, mineral filler 5 ~ 40 parts, the second auxiliary agent 0.1 ~ 5 part, solvent 0.1 ~ 50 part, 1 ~ 50 part, solidifying agent.Use the acrylic resin modified weathering resistance that can improve weathering layer at the composition of raw materials of weathering layer, be namely conducive to strengthening the opposing of weathering layer to factors such as illumination, cold and hot, wind and rain, bacteriums; Utilize the interaction between polyester matrix in acrylic resin modified and undercoat, thus improve their weathering resistance and sticking power.
The thinner of described undercoat preferably has the ester class of unsaturated link(age), ethers, ketone or there is the low-molecular weight polymer of similar quality, such as ethyl acrylate, acrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, 1,3 butyleneglycol diacrylate, 1,4 butanediol diacrylate, 1,6-hexanediyl ester, diethylene glycol diacrylate, neopentylglycol diacrylate, peopentyl ester acid diacrylate, tri (propylene glycol) diacrylate, Viscoat 295, cyanacrylate, tetramethylol methane tetraacrylate, dipentaerythritol six acrylate, triethyleneglycol divinylether, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, 4-hydroxy butyl vinyl ether, dodecyl vinyl, propylene carbonate allyl ethers, 1,3,5-triallyl s-triazine-2,4,6-triketone and triallyl isocyanuric acid ester, the mixture of one or several compositions in polyethyleneglycol diacrylate, the relative molecular mass of described polyethyleneglycol diacrylate is 100 ~ 1000.Such thinner can be used in dispersible polyesters matrix on the one hand, can produce chemical reaction on the other hand under the effect of initiator, thus the toughness of raising undercoat, intensity and the sticking power with other material.Initiator is for selecting universal optical initiator, mainly select radical photoinitiator, such as st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, 1-hydroxy-cyclohexyl phenyl ketone, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, two benzoylphenyl phosphine oxide, benzophenone, 2, 4-dihydroxy benaophenonel, Michler's keton, sulfo-propoxy-thioxanthone, isopropyl thioxanthone, diaryl group iodized salt, triaryl salt compounded of iodine, mixtures of one or several compositions in alkyl salt compounded of iodine and the luxuriant iron hexafluorophosphate of isopropyl benzene.Such undercoat gets final product curing molding in the mode such as employing UV light source or EB electron beam irradiation etc. after on basement membrane that is coated on, and greatly simplifies the technique at basement membrane painting bottom coating, is beneficial to scale operation.
In the present invention, the material of basement membrane is comparatively extensive, such as the blend of polyamide (PA), polymethylmethacrylate (PMMA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), cyclohexanedimethanol's dimethyl ester (PCT), polystyrene (PS), one or more compositions of PEN (PEN).Described first auxiliary agent can select those routines, such as silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organo-siloxane, vinylformic acid flow agent or fluorine richness flow agent.The vibrin of 10 ~ 50 parts of parts by weight is also comprised in the composition of raw materials of described weathering layer, described vibrin is the straight chain saturated polyester resin containing aromatic hydrocarbon structure, the second-order transition temperature of described vibrin is 0 ~ 50 DEG C, hydroxyl value is 1 ~ 50mgKOH/g, molecular weight is 3000 ~ 50000, thus intensity and the toughness of weathering layer can be improved, but the content of vibrin can not be too high, otherwise the tack of weathering layer can be reduced.Described acrylic resin modified second-order transition temperature is 0 ~ 70 DEG C, and molecular weight is 1000 ~ 10000, and hydroxyl value is 10 ~ 150 mgKOH/g, acrylic resin modified can be trifluorochloroethylene-vinyl ether co-polymer, trifluorochloroethylene-vinyl ester copolymer, tetrafluoroethylene-Ethylene base ether copolymer, tetrafluoroethylene-Ethylene base ester copolymer, tetrafluoroethylene-Ethylene base ether-vinyl ester copolymer, mixtures of one or more compositions in tetrafluoroethylene and polyvinylidene difluoride (PVDF), also can be that the one or more combination being polymerized by one or more in olefin(e) acid esters monomer or being polymerized by olefin(e) acid esters monomer in the polymkeric substance that formed forms, or be the two mixture, above-mentioned olefin(e) acid esters monomer comprises methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, butyl methacrylate, lauryl methacrylate(LMA), N-Hexyl methacrylate, stearyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hy-droxybutyl, the own ester of vinylformic acid hydroxyl, vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, Rocryl 410, hydroxyethyl methylacrylate, Rocryl 410, methacrylate, the own ester of hydroxyethyl methacrylate, hydroxyethyl methacrylate ester in the last of the ten Heavenly stems, vinylformic acid, methacrylic acid, butenoic acid, acrylate propyl ester, vinylformic acid diethylin propyl ester, dimethylaminoethyl acrylate, dimethylaminoethyl propyl ester, methacrylic acid diethylin propyl ester, dimethylaminoethyl methacrylate, fluoroalkyl base ester, cyano ethyl acrylate, vinylformic acid tetrahydrofuran (THF) methyl esters and vinylformic acid ethoxyquin DCPA.
Described solvent is selected containing oxygen kind solvent, as ester class, ethers or ketone, but can not use alcoholic solvent.Solidifying agent in weathering resistance coatings is preferably one or more mixtures in isocyanate curing agent, acid catalysis amino curing agent, peroxide initiator, benzophenone and st-yrax ethers initiator, these solidifying agent are all thermo-sensitivity, namely can make the weathering layer curing molding be coated on undercoat in a heated condition, the curing process that other solidifying agent is corresponding different can certainly be selected.Described second auxiliary agent is universal auxiliary agent, as flow agent, dispersion agent, defoamer, wetting agent etc., makes weathering layer raw material in layoutprocedure, avoid producing too much foam, mineral filler is uniformly dispersed, is conducive to even spread etc.
Below will the present invention is described in detail by specific embodiment.
Embodiment 1
The preparation of undercoat:
At polyester matrix (by 40kg epoxy acrylic resin, 30kg polyurethane acrylate resin and 20kg bisphenol A-type unsaturated polyester Homogeneous phase mixing form, above-mentioned polymericular weight is 1000) in add 10kg1, 6-hexanediyl ester, 20kg cyanacrylate, 20kg tetramethylol methane tetraacrylate, 6kg benzophenone, 4kg photosensitizers 1173 and 2kg flow agent TEGO Flow300, after mixing, as bottom coating B-1, bottom coating B-1 is coated on the PET basement membrane of 250 micron thickness, coating thickness is 10 microns, through uv light irradiation 30 seconds curing moldings of 5kw,
The preparation of weathering layer:
20kg titanium dioxide is added in 50kg trifluorochloroethylene-vinyl ether co-polymer, and 1kg second auxiliary agent (being specially dispersant B YK-163), 10 microns are less than with utmost dispatch sand milling to titanium dioxide particle diameter in sand mill, add remaining 4kg second auxiliary agent more successively and (comprise 1kg flow agent TEGO Glide 100, 1kg wetting agent TEGO Wet270, 2kg defoamer TEGO Foamex840), 30kg Hydroxylated acrylic resin, (second-order transition temperature is 50 DEG C to 50kg polyethylene terephthalate, hydroxyl value is 50mgKOH/g, molecular weight is 50000), be uniformly dispersed with the stirring velocity of 800 revs/min, obtained weathering layer coating A-1, 50kg acetone, 50kg tolylene diisocyanate is added in A-1 coating, NCO/OH ratio is made to be approximately 1.05, be uniformly coated on subsequently on the undercoat of curing molding, coating thickness is 50 microns, through 150 DEG C of hot blast drying tunnel dry solidifications 3 minutes, obtain basement membrane PET and weathering resistance coatings combined films integration sample S-1.
Embodiment 2
In the present embodiment, undercoat is roughly the same with the preparation method of weathering layer, different unlike its composition of raw materials, is specially:
Undercoat is:
Polyester matrix: 30 kg epoxy acrylic resins, molecular weight is 10000;
Thinner: 1kg ethyl acrylate, 1kg acrylic acid-beta-hydroxy ethyl ester, 1kg senecioate-hydroxypropyl acrylate, 1kg 1,3 butyleneglycol diacrylate, 1kg 1,4 butanediol diacrylate;
Initiator: 0.1kg benzoin dimethylether;
First auxiliary agent: 0.05kg flow agent Irgaflow100 and 0.05kg flow agent HENSIC H-143.
Weathering layer is:
Acrylic resin modified: methyl methacrylate, fluoroalkyl base ester, Propylene glycol monoacrylate and methacrylate four kinds of monomer equal proportion mixing post polymerization form, 30kg altogether, second-order transition temperature is 0 DEG C, and molecular weight is 1000, and hydroxyl value is 150 mgKOH/g;
Mineral filler: 5kg titanium dioxide
Second auxiliary agent: 0.1kg defoamer TEGO Foamex840
Solvent: 0.1kg butanone;
Solidifying agent: 1kg HDI solidifying agent 3390.
Sample S-2 is formed by the method preparation in embodiment 1 by above-mentioned composition of raw materials.
Embodiment 3
In the present embodiment, undercoat is roughly the same with the preparation method of weathering layer, different unlike its composition of raw materials, is specially:
Undercoat is:
Polyester matrix: 30 kg epoxy acrylic resins and 20kg polyurethane acrylate resin, molecular weight is 5000;
The acid of thinner: 5kg 1,6-hexanediyl ester, 5kg diethylene glycol diacrylate, 5kg neopentylglycol diacrylate, 5kg peopentyl ester diacrylate, 5kg tri (propylene glycol) diacrylate, 5kg cyanacrylate;
Initiator: 1kg Benzoin ethyl ether, 1kg benzoin isopropyl ether, 1kg 1-hydroxy-cyclohexyl phenyl ketone, 1kg α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, 1kg α, α-diethoxy acetophenone;
First auxiliary agent: 0.5 kg silicone oil, 1kg polydimethylsiloxane, 1kg BT-3193 water-soluble silicon oil (i.e. organic silicon modified by polyether oxygen alkane), 0.5 kg HP-8100 alkyl-silicone oil, 2kg KE-401-45 Organosilicon wax.
Weathering layer is:
Acrylic resin modified: to be mixed by 10kg tetrafluoroethylene-Ethylene base ester copolymer, 10kg tetrafluoroethylene-Ethylene base ether-vinyl ester copolymer, 20kg tetrafluoroethylene and 20kg polyvinylidene difluoride (PVDF);
Vibrin: 10kg gathers 1,6-hexanodioic acid 1,6-hexylene glycol ester (second-order transition temperature is 0 DEG C, hydroxyl value is 1mgKOH/g, molecular weight be 3000);
Mineral filler: 10kg aerosil
Second auxiliary agent: 0.5kg defoamer TEGO Foamex840,0.5kg sodium lauryl sulphate (wetting agent), 0.5kg dispersion agent HLD-10 and 0.5kg flow agent Irgaflow100;
Solvent: 10kg ethyl acetate;
Solidifying agent: the 5kg benzoyl peroxide tert-butyl ester, 5kg benzophenone.
Sample S-3 is formed by the method preparation in embodiment 1 by above-mentioned composition of raw materials.
Embodiment 4
In the present embodiment, undercoat is roughly the same with the preparation method of weathering layer, different unlike its composition of raw materials, is specially:
Undercoat is:
Polyester matrix: 20 kg epoxy acrylic resins and 20kg polyurethane acrylate resin, molecular weight is 3000;
Thinner: 5kg tri (propylene glycol) diacrylate, 5kg Viscoat 295,5kg tetramethylol methane tetraacrylate, 5kg dipentaerythritol six acrylate, 5kg triethyleneglycol divinylether, 5kg Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether;
Initiator: 1kg alpha-hydroxyalkyl benzophenone, 1kg α-amine alkyl phenones, 1kg aroyl phosphine oxide, 1kg two benzoylphenyl phosphine oxide, 1kg benzophenone, 1kg 2,4 dihydroxyl benzophenone, 1kg Michler's keton, 1kg sulfo-propoxy-thioxanthone;
First auxiliary agent: 1kg polydimethylsiloxane, 1kg BT-3193 water-soluble silicon oil (i.e. organic silicon modified by polyether oxygen alkane), 2kg KE-401-45 Organosilicon wax.
Weathering layer is:
Acrylic resin modified: 5kg trifluorochloroethylene-vinyl ether co-polymer, 5kg tetrafluoroethylene-Ethylene base ether-vinyl ester copolymer, 5kg tetrafluoroethylene and 5kg polyvinylidene difluoride (PVDF); Lauryl methacrylate(LMA), hy-droxybutyl, the own ester of vinylformic acid hydroxyl, vinylformic acid hydroxyl ester in the last of the ten Heavenly stems, propyl methacrylate, β-dimethyl-aminoethylmethacrylate, hydroxyethyl methacrylate ester in the last of the ten Heavenly stems are polymerized rear equal proportion respectively and mix, altogether 20kg;
Vibrin: 10kg gathers 1,6-hexanodioic acid 1,6-hexylene glycol ester (second-order transition temperature is 30 DEG C, hydroxyl value is 20mgKOH/g, molecular weight be 10000);
Mineral filler: 5kg aerosil and 3kg titanium dioxide;
Second auxiliary agent: 0.5kg defoamer TEGO Foamex840,0.5kg sodium lauryl sulphate (wetting agent), 0.5kg dispersion agent HLD-10 and 0.5kg flow agent Irgaflow100;
Solvent: 10kg ether;
Solidifying agent: 5kg 3,3-diaminodiphenylsulfone(DDS).
Sample S-4 is formed by the method preparation in embodiment 1 by above-mentioned composition of raw materials.
Embodiment 5
In the present embodiment, undercoat is roughly the same with the preparation method of weathering layer, different unlike its composition of raw materials, is specially:
Undercoat is:
Polyester matrix: 30 kg epoxy acrylic resins and 20kg polyurethane acrylate resin;
Thinner: 5kg cyanacrylate, 5kg 4-hydroxy butyl vinyl ether, 5kg dodecyl vinyl, 5kg propylene carbonate allyl ethers, 5kg 1,3,5-triallyl s-triazine-2,4,6-triketone, 5kg triallyl isocyanuric acid ester, 1kg relative molecular mass is the polyethyleneglycol diacrylate of 100;
Initiator: 1kg isopropyl thioxanthone, 1kg diaryl group iodized salt, 1kg triaryl salt compounded of iodine, 1kg second class salt compounded of iodine, the luxuriant iron sodium hexafluoro phosphate of 1kg isopropyl benzene;
First auxiliary agent: 0.5 kg silicone oil, 1kg polydimethylsiloxane, 1kg BT-3193 water-soluble silicon oil (i.e. organic silicon modified by polyether oxygen alkane), 0.5 kg HP-8100 alkyl-silicone oil, 2kg KE-401-45 Organosilicon wax.
Weathering layer is:
Acrylic resin modified: lauryl methacrylate(LMA), N-Hexyl methacrylate, stearyl methacrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate five kinds of monomer equal proportion mixing post polymerization form, 40kg altogether; Second-order transition temperature is 70 DEG C, and molecular weight is 10000, and hydroxyl value is 10 mgKOH/g;
Vibrin: 10kg poly terephthalic acid 1,6-hexylene glycol ester (second-order transition temperature is 40 DEG C, hydroxyl value is 25mgKOH/g, molecular weight be 20000);
Mineral filler: 10kg aerosil
Second auxiliary agent: 0.5kg defoamer TEGO Foamex840,0.5kg sodium lauryl sulphate (wetting agent), 0.5kg dispersion agent HLD-10 and 0.5kg flow agent Irgaflow100;
Solvent: 10kg ethyl acetate;
Solidifying agent: the 5kg benzoyl peroxide tert-butyl ester, 5kg benzophenone.
Sample S-3 is formed by the method preparation in embodiment 1 by above-mentioned composition of raw materials.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. a weathering resistance coatings combined films, is characterized in that: it comprises by the shaping undercoat of radiation curing and is coated on weathering layer shaping through thermofixation on undercoat, and the composition of raw materials of described undercoat comprises the component of following parts by weight:
Polyester matrix 30 ~ 90 parts;
Thinner 5 ~ 50 parts;
Initiator 0.1 ~ 10 part;
First auxiliary agent 0.1 ~ 10 part;
Described polyester matrix is the mixture of one or several compositions in epoxy acrylic ester polymer, urethane acrylate polymer, unsaturated polyester resin.
2. weathering resistance coatings combined films according to claim 1, is characterized in that: the composition of raw materials of described weathering layer comprises the component of following parts by weight:
Acrylic resin modified 30 ~ 80 parts;
Mineral filler 5 ~ 40 parts;
Second auxiliary agent 0.1 ~ 5 part;
Solvent 0.1 ~ 50 part;
1 ~ 50 part, solidifying agent.
3. weathering resistance coatings combined films according to claim 1, is characterized in that: described thinner is ethyl acrylate, acrylic acid-beta-hydroxy ethyl ester, senecioate-hydroxypropyl acrylate, 1,3 butyleneglycol diacrylate, 1,4 butanediol diacrylate, 1,6-hexanediyl ester, diethylene glycol diacrylate, neopentylglycol diacrylate, polyethyleneglycol diacrylate, peopentyl ester acid diacrylate, tri (propylene glycol) diacrylate, cyanacrylate, Viscoat 295, tetramethylol methane tetraacrylate, dipentaerythritol six acrylate, triethyleneglycol divinylether, Isosorbide-5-Nitrae-cyclohexane dimethanol divinyl ether, 4-hydroxy butyl vinyl ether, dodecyl vinyl, propylene carbonate allyl ethers, 1,3, mixtures of one or several compositions in 5-triallyl s-triazine-2,4,6-triketone and triallyl isocyanuric acid ester, the relative molecular mass of described polyethyleneglycol diacrylate is 100 ~ 1000.
4. weathering resistance coatings combined films according to claim 1, it is characterized in that: described initiator is st-yrax, benzoin dimethylether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, 1-hydroxy-cyclohexyl phenyl ketone, α, alpha, alpha-dimethyl oxygen base-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, two benzoylphenyl phosphine oxide, benzophenone, 2, 4-dihydroxy benaophenonel, Michler's keton, sulfo-propoxy-thioxanthone, isopropyl thioxanthone, diaryl group iodized salt, triaryl salt compounded of iodine, mixtures of one or several compositions in alkyl salt compounded of iodine and the luxuriant iron hexafluorophosphate of isopropyl benzene.
5. weathering resistance coatings combined films according to claim 1, is characterized in that: described first auxiliary agent is silicone oil, polydimethylsiloxane, polyether polyester modified organic silicon oxygen alkane, alkyl-modified organo-siloxane, vinylformic acid flow agent or fluorine richness flow agent.
6. weathering resistance coatings combined films according to claim 2, is characterized in that: the vibrin also comprising 10 ~ 50 parts of parts by weight in the composition of raw materials of described weathering layer, and described vibrin is the straight chain saturated polyester resin containing aromatic hydrocarbon structure.
7. weathering resistance coatings combined films according to claim 6, is characterized in that: the second-order transition temperature of described vibrin is 0 ~ 50 DEG C, and hydroxyl value is 1 ~ 50mgKOH/g, and molecular weight is 3000 ~ 50000.
8. weathering resistance coatings combined films according to claim 2, is characterized in that: the described acrylic resin modified mixture for one or more compositions in trifluorochloroethylene-vinyl ether co-polymer, trifluorochloroethylene-vinyl ester copolymer, tetrafluoroethylene-Ethylene base ether copolymer, tetrafluoroethylene-Ethylene base ester copolymer, tetrafluoroethylene-Ethylene base ether-vinyl ester copolymer, tetrafluoroethylene and polyvinylidene difluoride (PVDF).
9. weathering resistance coatings combined films according to claim 2, is characterized in that: described acrylic resin modified be that the one or more combination being polymerized by one or more in olefin(e) acid esters monomer or being polymerized by olefin(e) acid esters monomer in the polymkeric substance that formed forms.
10. weathering resistance coatings combined films as claimed in claim 2, it is characterized in that: described acrylic resin modified second-order transition temperature is 0 ~ 70 DEG C, molecular weight is 1000 ~ 10000, and hydroxyl value is 10 ~ 150 mgKOH/g.
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| CN104817950A (en) * | 2015-05-19 | 2015-08-05 | 太仓市金新涂料有限公司 | Energy-saving and environment-friendly roller coating paint for printing plate and application method of energy-saving and environment-friendly roller coating paint |
| CN104910792A (en) * | 2015-05-27 | 2015-09-16 | 天津市美冠科技有限公司 | Aqueous UV coating material and preparation method thereof |
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| CN107383798A (en) * | 2017-07-25 | 2017-11-24 | 合肥华盖光伏科技有限公司 | A kind of solar cell backboard film and preparation method thereof |
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| CN113956781A (en) * | 2021-09-22 | 2022-01-21 | 杭州梵因科技有限公司 | Preparation method of nano enhanced ultraviolet curing antifogging agent |
| CN114752309A (en) * | 2022-03-29 | 2022-07-15 | 安徽屹珹新材料科技有限公司 | Multilayer film and preparation method thereof |
| CN116836438A (en) * | 2023-07-11 | 2023-10-03 | 江西塔益莱高分子材料有限公司 | PCB dry film resin and preparation method thereof |
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