CN105086872A - PVC (polyvinyl chloride) adhesive film and preparation method thereof - Google Patents
PVC (polyvinyl chloride) adhesive film and preparation method thereof Download PDFInfo
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Abstract
The invention provides a PVC (polyvinyl chloride) adhesive film which is used for packing matte plastic-powder baking-finish workpieces and has good water resistance, high viscosity and good atmosphere aging resistance. The PVC adhesive film comprises a PVC film and an adhesive adhering to the PVC film, wherein the adhesive is prepared from raw materials as follows: poly-1,4-butylene adipate glycol, 4,4 methylene diphenyl diisocyanate, triethylamine, dimethylolpropionic acid, butyl acrylate, methyl methacrylate, glycidyl methacrylate, hydroxypropyl acrylate, acyclic acid, N, N-dimethylformamide and potassium peroxodisulfate. The invention further provides a preparation method of the PVC adhesive film. The PVC adhesive film and the preparation method thereof have the benefits as follows: acrylic resin is modified by adopting polyurethane, N, N-dimethylformamide is taken as a medium, glycidyl methacrylate is taken as a cross-linking agent, the prepared adhesive cooperates with the PVC film, and the PVC adhesive film with low water absorption, high adhesive strength and excellent atmosphere aging resistance can be obtained.
Description
Technical field
The present invention relates to packing film field, specifically a kind of PVC glued membrane for sanding baking vanish workpiece packaging and preparation method thereof.
Background technology
Fire door mainly contains two kinds, and one is light baking vanish, and one is sub-light molding powder baking vanish.Fire door all needs to pack with special packing film before dispatching from the factory.PE glue film is the packing film that light baking vanish fire door is conventional, but then inapplicable on the fire door being used in sub-light molding powder baking vanish, and not only have no stickiness, once be subject to wind, product will be outside exposed, cannot reach the object of protection product.So can only be pasted onto on fire door by PE glue film with double faced adhesive tape now, then pack the fire door of sub-light molding powder baking vanish by the mode that packing bag is tied up, this packaging means not only takes time and effort, and also cannot ensure the reliability of packing.
Above-mentioned PE glue film is made at PE film coated glue, glue, i.e. aqueous coating glue, be using water as solvent by vinylformic acid or urethane resin by special emulsifying device, emulsification forms.Although cheap, have that film-forming properties is poor, viscosity is low, non-watertight, the fatal defects such as easily come unstuck.
The sizing agent of existing packing film is except glue, also has factice, i.e. oiliness coating adhesive, also claiming solvent-based adhesive, is using oil-based solvent toluene, DMF, butanone etc. as solvent, acrylate or urethane are dissolved and forms, after solvent evaporates, permanent mucous membrane can be formed, have that production technique is simple, water-fast, drying rate and the open hour are wide, first glutinous intensity feature that is high, easily some difficult glutinous surface wetting.But existing solvent-type acrylic ester sizing agent or solvent borne polyurethane sizing agent cannot be attached on PE film well, and single solvent-type acrylic ester sizing agent temperature tolerance is poor, moisture absorption ratio is high; Single solvent borne polyurethane sizing agent water resistance is poor.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of PVC glued membrane that sub-light molding powder baking vanish workpiece water-tolerant, viscosity are high for packing, resistance to weathering can be good and preparation method thereof.
In order to solve the problems of the technologies described above, one of the technical solution used in the present invention is: PVC glued membrane, comprise PVC film and be attached to the sizing agent in PVC film, described sizing agent is prepared from by the raw material of following weight part: poly-hexanodioic acid 1, 4-butanediol ester glycol 36 ~ 38 parts, 4, 4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, N, dinethylformamide 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part.
Another technical scheme that the present invention adopts is: the preparation method of PVC glued membrane, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 36 ~ 38 parts, 4,4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, DMF 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1 ~ 2h in reactor under 48 ~ 50 degrees Celsius, add poly-hexanodioic acid 1, 4-butanediol ester glycol and dimethylol propionic acid are also cooled to 50 ~ 60 degrees Celsius after continuing reaction 3 ~ 5h at 75 ~ 85 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add glycidyl methacrylate again, butyl acrylate, Potassium Persulphate is added after methyl methacrylate and vinylformic acid mix, be warming up to 81 ~ 84 degrees Celsius and be incubated 30min, obtain mixture,
Step 2, by step 1 gained mixture centrifugal 30min under 3200 ~ 3500r/min, obtain sizing agent;
Step 3, sizing agent to be applied in PVC film and dry, to obtain PVC glued membrane.
Another technical scheme that the present invention also adopts is: the preparation method of PVC glued membrane, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 37 parts, 4,4-methylenediphenyl diisocyanates 33 parts, triethylamine 5 parts, dimethylol propionic acid 33 parts, butyl acrylate 45 parts, methyl methacrylate 45 parts, glycidyl methacrylate 5 parts, Propylene glycol monoacrylate 2 parts, 6 parts, vinylformic acid, DMF 95 parts, Potassium Persulphate 2 parts;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1.5h in reactor under 49 degrees Celsius, add poly-hexanodioic acid 1,4-butanediol ester glycol and dimethylol propionic acid are also cooled to 55 degrees Celsius after continuing reaction 4h at 80 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add again after glycidyl methacrylate, butyl acrylate, methyl methacrylate and vinylformic acid mix and add Potassium Persulphate, be warming up to 83 degrees Celsius and be incubated 30min, obtaining mixture;
Step 2, by step 1 gained mixture centrifugal 30min under 3300r/min, obtain sizing agent;
Step 3, sizing agent is pressed surface covered 80m/min, spread 4.5g/m
2, bake out temperature is that the processing parameter of 55 degrees Celsius is applied to also drying in PVC film, obtains PVC glued membrane.
Beneficial effect of the present invention is: PVC glued membrane prepared by the preparation method of PVC glued membrane of the present invention adopts butyl acrylate as main soft monomer, methyl methacrylate is main hard monomer, vinylformic acid and Propylene glycol monoacrylate are functional monomer, with polyurethane-modified, glycidyl methacrylate does crosslinking and curing agent, Potassium Persulphate is as initiator, N, dinethylformamide is as solvent, the sizing agent drying and moulding prepared is rapid, the transparency is good, and weathering resistance, water tolerance, chemical proofing is splendid, resistance to weathering can be more excellent, easy to use, when using it in PVC film, owing to containing carboxyl, hydroxyl isopolarity group in sizing agent, can be combined with the polar group on sub-light molding powder baking vanish surface, form hydrogen bond action, considerably increase cohesive strength.After testing, water-intake rate of the present invention is below 3.9% ~ 4.2%, and PVC glued membrane T stripping strength can reach 29.1 ~ 30.5N/25mm, in an atmosphere more than 360 ~ 450 days not aging.
Embodiment
By describing technology contents of the present invention in detail, being realized object and effect, be explained below in conjunction with embodiment.
The design of most critical of the present invention is: with polyurethane modified acrylic resin, with N, dinethylformamide is as medium, by glycidyl methacrylate as linking agent, the sizing agent prepared coordinates with PVC film, can obtain the PVC glued membrane that water-intake rate is low, cohesive strength is high, resistance to weathering can be excellent.
The invention provides a kind of PVC glued membrane, comprise PVC film and be attached to the sizing agent in PVC film, described sizing agent is prepared from by the raw material of following weight part: poly-hexanodioic acid 1, 4-butanediol ester glycol 36 ~ 38 parts, 4, 4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, N, dinethylformamide 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part.
Mechanism of the present invention is: containing carbamate segment and ehter bond, urea key, ester bond isoreactivity group in polyurethane molecular, such constructional feature makes polyurethane material possess excellent physical and mechanical property, good winter hardiness, soft or hard degree is to temperature-insensitive, the advantages such as elasticity is large, but the water resistance of its film and mechanical strength are all not so good as acrylic resin, the water-tolerant of acrylic resin, but easily become fragile when having low temperature, easy stickness during high temperature, the shortcoming of snappiness difference, with polyurethane modified acrylic resin, complementary product of can gaining the upper hand.
Glycidyl methacrylate, as self-cross linking monomer, with other monomer copolymerizations, introduces crosslinkable epoxide group, makes sizing agent in film process, reach the object of self-crosslinking.Because glycidyl methacrylate is polyfunctional monomer, epoxide group in molecular structure can with the carboxyl on other monomers, hydroxyl generation opening, produce crosslinked, form tridimensional network, glycidyl methacrylate consumption increases, epoxide group increased number, and intermolecular cross-linking density increases, polymer molecule interchain space net structure is finer and close, thus improves the mechanical property of sizing agent.But when glycidyl methacrylate is excessive, stripping strength reduces on the contrary, this is because the second-order transition temperature of glycidyl methacrylate itself is higher, the increase of glycidyl methacrylate consumption improves the ratio of hard section in copolymer molecule chain, and then improve polymer glass temperature, under making normal temperature, copolymer adhesive film becomes fragile, polymer bonding degradation.
Glycidyl methacrylate is more, and cross-linking density is larger, and polymkeric substance becomes glued membrane compactness better, hinders the infiltration and diffusion of water molecules to glued membrane, causes water-intake rate to decline; The epoxide group of glycidyl methacrylate can, with the carboxyl generation crosslinking reaction in polymer molecular chain, make polymkeric substance carboxyl-content reduce, and also decreases the content of polar group simultaneously, glued membrane wetting ability is declined, and water-intake rate reduces.
Glycidyl methacrylate does crosslinking and curing agent, make the self-cross linking type polyacrylate adhesives of excellent performance, because the epoxide group accessed in molecular chain can react with the carboxyl in molecule long-chain, make between macromole, to form fine and close cross-linked structure, effectively improve glued membrane thermotolerance and water resistance, and greatly strengthen cohesive strength.Make that to can be applicable to PVC film bonding, there is high thermal resistance, dimensional stabilizing, free of contamination advantage.
Acrylic acid adding contributes to improving the water tolerance of film.Due to epoxide group and carboxyl, the hydroxyl generation open loop crosslinking reaction of glycidyl methacrylate, also can there is crosslinking reaction in carboxyl and hydroxyl.Increasing of acrylic acid content, the increased number of carboxyl, crosslinking degree increases, and forms continuously fine and close glued membrane, can effectively stop water molecules move in molecular chain and swelling, is conducive to the water resistance of raising acrylate glued membrane.But carboxyl is also hydrophilic radical, when vinylformic acid is excessive, too much carboxyl can not react with epoxide group or hydroxyl, is enriched in film coated surface, and along with the increase of vinylformic acid massfraction, film wetting ability strengthens, and contact angle reduces.
Acrylic acid content increases gradually, and the tensile strength of glued membrane presents the trend of increase, and elongation at break then reduces gradually.Carboxyl and glycidyl methacrylate epoxide group generation crosslinking reaction in acrylic molecules, cross-linked structure is there is in structure when making polymer film forming, along with increasing of vinylformic acid consumption, degree of crosslinking increases gradually, combine tightr between polymer molecule, make polymer molecule become three dimensional structure by linear structure, the tensile strength of film increases greatly, the crosslinked slippage fettering molecular chain simultaneously between macromolecular chain, causes the obvious reduction of elongation at break.
Acrylate copolymer molecule is alternately made up of mutually soft or hard section, give film snappiness and elasticity for soft section, and hard section gives its intensity.Therefore in acrylate, the mechanical property of ratio to acrylate films of soft section and hard section has a significant effect.Vinylformic acid is introduced and rigid structure in acrylate is increased, and hard section ratio increases, and thus mechanical property is more excellent.
Increase along with acrylic acid, carboxyl-content increases, and the crosslinking degree of system increases, and force of cohesion improves; In addition, the polar group of carboxyl and sub-light molding powder baking vanish workpiece surface forms hydrogen bond, makes stripping strength become large.The increase of acrylic acid content simultaneously also increases the ratio of hard section in molecule, when vinylformic acid is excessive, hard segment content is too high to work with these two factors of increase that are cross-linking set simultaneously, hinders acrylate Middle molecule chain movement, material hardens is become fragile, and adhesive property declines.Therefore acrylic acid content needs to control within the specific limits.
Propylene glycol monoacrylate is as a kind of active functional monomer, copolymerization can be carried out with other monomers, and hydroxyl is introduced in acrylate macromolecular chain, because hydroxyl can be rolled into a ball with glycidyl methacrylate epoxy group, and open loop crosslinking reaction occurs, also can occur crosslinked with the carboxylic group in macromole, form build macromole, also there is very large polarity, can form hydrogen bond structure with hydroxyl on molecular chain and fabric, therefore Propylene glycol monoacrylate is to improving self-crosslinked acrylate sizing agent and glue film performance plays vital effect.
Due to glycidyl methacrylate epoxide group can not only with carboxyl generation crosslinking reaction, also can with hydroxyl generation open loop crosslinking reaction, in addition also can there is crosslinking reaction in carboxyl and hydroxyl, when in glued membrane containing Propylene glycol monoacrylate time, system degree of crosslinking is low, and glued membrane water tolerance is general; Along with increasing of Propylene glycol monoacrylate content, the increased number of hydroxyl, crosslinking degree increases to some extent, and cross-linked structure becomes finer and close, stops water molecules to move in molecular chain further, is conducive to the water resistance improving polyurethane-acrylate glued membrane.But hydroxyl is also hydrophilic radical, when Propylene glycol monoacrylate is excessive, too much hydroxyl can not react with epoxide group or carboxyl, is enriched in film coated surface, plays hydrophilic effect, causes film water-absorbent to strengthen.
Can with the carboxyl generation crosslinking reaction in the epoxide group of glycidyl methacrylate glycidyl methacrylate and vinylformic acid due to Propylene glycol monoacrylate molecule having, cross-linked structure is there is in structure when making polymer film forming, along with increasing of Propylene glycol monoacrylate consumption, degree of crosslinking increases gradually, combine tightr between polymer molecule, polymer molecule is made to become three dimensional structure by linear structure, the tensile strength of film increases greatly, the crosslinked slippage fettering molecular chain simultaneously between macromolecular chain, causes decreasing of elongation at break; On the other hand, acrylate copolymer molecule is alternately made up of mutually soft or hard section, give film snappiness and elasticity for soft section, and hard section gives its intensity.Therefore in acrylate, the mechanical property of ratio to acrylate films of soft section and hard section has a significant effect.The introducing of Propylene glycol monoacrylate makes rigid structure in acrylate increase, and hard section ratio increases, and shows more excellent mechanical property.
The sizing agent that hardness is high, tensile strength is high, but unsuitable film forming, easily crisply easily to split; The sizing agent that hardness is too low, poor mechanical property, film forming is softer, if hard monomer too high levels, can not film forming under room temperature, stripping strength also sharply reduces.
The present invention selects butyl acrylate as main soft monomer, methyl methacrylate is as main hard monomer, soft monomer second-order transition temperature is low, and polymkeric substance long-chain kindliness can be made to improve, and gives sizing agent bonding characteristic, therefore increase sizing agent viscosity, but after film forming, the hardness of film is too little, and performance is bad: hard monomer second-order transition temperature is high, polymkeric substance long-chain mobility is weakened, increases the force of cohesion of sizing agent.Along with the increase of hard monomer content, stripping strength constantly increases, and film-forming properties improves.
From foregoing description, beneficial effect of the present invention is: PVC glued membrane prepared by the preparation method of PVC glued membrane of the present invention adopts butyl acrylate as main soft monomer, methyl methacrylate is main hard monomer, vinylformic acid and Propylene glycol monoacrylate are functional monomer, with polyurethane-modified, glycidyl methacrylate does crosslinking and curing agent, Potassium Persulphate is as initiator, N, dinethylformamide is as solvent, the sizing agent drying and moulding prepared is rapid, the transparency is good, and weathering resistance, water tolerance, chemical proofing is splendid, resistance to weathering can be more excellent, easy to use, when using it in PVC film, owing to containing carboxyl, hydroxyl isopolarity group in sizing agent, can be combined with the polar group on sub-light molding powder baking vanish surface, form hydrogen bond action, considerably increase cohesive strength.After testing, water-intake rate of the present invention is below 3.9% ~ 4.2%, and PVC glued membrane T stripping strength can reach 29.1 ~ 30.5N/25mm, in an atmosphere more than 360 ~ 450 days not aging.
Described sizing agent is prepared from by the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 37 parts, 4,4-methylenediphenyl diisocyanates 33 parts, triethylamine 5 parts, dimethylol propionic acid 33 parts, butyl acrylate 45 parts, methyl methacrylate 45 parts, glycidyl methacrylate 5 parts, Propylene glycol monoacrylate 2 parts, 6 parts, vinylformic acid, DMF 95 parts, Potassium Persulphate 2 parts.
Seen from the above description, adopt the raw material of aforementioned proportion to prepare sizing agent, the properties of sizing agent can be made best.
Further, the thickness of described sizing agent is 0.12 ~ 0.14mm.
Seen from the above description, by sizing agent gauge control at 0.12 ~ 0.14mm, not easily come unstuck after making PVC glued membrane pack sub-light molding powder baking vanish workpiece.
Another technical scheme that the present invention adopts is:
The preparation method of PVC glued membrane, is characterized in that, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 36 ~ 38 parts, 4,4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, DMF 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1 ~ 2h in reactor under 48 ~ 50 degrees Celsius, add poly-hexanodioic acid 1, 4-butanediol ester glycol and dimethylol propionic acid are also cooled to 50 ~ 60 degrees Celsius after continuing reaction 3 ~ 5h at 75 ~ 85 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add glycidyl methacrylate again, butyl acrylate, Potassium Persulphate is added after methyl methacrylate and vinylformic acid mix, be warming up to 81 ~ 84 degrees Celsius and be incubated 30min, obtain mixture,
Step 2, by step 1 gained mixture centrifugal 30min under 3200 ~ 3500r/min, obtain sizing agent;
Step 3, sizing agent to be applied in PVC film and dry, to obtain PVC glued membrane.
From foregoing description, beneficial effect of the present invention is: the preparation method of PVC glued membrane of the present invention is with N, dinethylformamide is medium, 4, 4-methylenediphenyl diisocyanates, poly-hexanodioic acid 1, the copolymerization under triethylamine katalysis of 4-butanediol ester glycol obtains urethane, adopt butyl acrylate as main soft monomer, methyl methacrylate is main hard monomer, vinylformic acid and Propylene glycol monoacrylate are functional monomer, with polyurethane-modified, glycidyl methacrylate does crosslinking and curing agent, Potassium Persulphate is as initiator, N, dinethylformamide is as solvent, the sizing agent drying and moulding prepared is rapid, the transparency is good, and weathering resistance, water tolerance, chemical proofing is splendid, resistance to weathering can be more excellent, easy to use, when using it in PVC film, owing to containing carboxyl, hydroxyl isopolarity group in sizing agent, can be combined with the polar group on sub-light molding powder baking vanish surface, form hydrogen bond action, considerably increase cohesive strength.After testing, water-intake rate of the present invention is below 3.9% ~ 4.2%, and PVC glued membrane T stripping strength can reach 29.1 ~ 30.5N/25mm, in an atmosphere more than 360 ~ 450 days not aging.
Further, the processing parameter of step 3 is: surface covered 80m/min, spread 4.5g/m
2, bake out temperature is 55 degrees Celsius.
Embodiment 1
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 36 parts, 4,4-methylenediphenyl diisocyanates 32 parts, triethylamine 4 parts, dimethylol propionic acid 32 parts, butyl acrylate 44 parts, methyl methacrylate 44 parts, glycidyl methacrylate 4 parts, Propylene glycol monoacrylate 1 part, 3 parts, vinylformic acid, DMF 90 parts, Potassium Persulphate 1 part;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1h in reactor under 48 degrees Celsius, add poly-hexanodioic acid 1,4-butanediol ester glycol and dimethylol propionic acid are also cooled to 50 degrees Celsius after continuing reaction 3h at 75 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add again after glycidyl methacrylate, butyl acrylate, methyl methacrylate and vinylformic acid mix and add Potassium Persulphate, be warming up to 81 degrees Celsius and be incubated 30min, obtaining mixture;
Step 2, by step 1 gained mixture centrifugal 30min under 3300r/min, obtain sizing agent;
Step 3, sizing agent is pressed surface covered 80m/min, spread 4.5g/m
2, bake out temperature is that the processing parameter of 55 degrees Celsius is applied to also drying in PVC film, obtains PVC glued membrane.
After testing, PVC glued membrane water-intake rate of the present invention is 4.2%, T stripping strength is 29.1N/25mm, in an atmosphere 410 days not aging.
Embodiment 2
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 38 parts, 4,4-methylenediphenyl diisocyanates 34 parts, triethylamine 6 parts, dimethylol propionic acid 35 parts, butyl acrylate 46 parts, methyl methacrylate 46 parts, glycidyl methacrylate 6 parts, Propylene glycol monoacrylate 3 parts, 9 parts, vinylformic acid, DMF 100 parts, Potassium Persulphate 3 parts;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 2h at 50 c in reactor, add poly-hexanodioic acid 1,4-butanediol ester glycol and dimethylol propionic acid are also cooled to 60 degrees Celsius after continuing reaction 5h at 85 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add again after glycidyl methacrylate, butyl acrylate, methyl methacrylate and vinylformic acid mix and add Potassium Persulphate, be warming up to 84 degrees Celsius and be incubated 30min, obtaining mixture;
Step 2, by step 1 gained mixture centrifugal 30min under 3300r/min, obtain sizing agent;
Step 3, sizing agent is pressed surface covered 80m/min, spread 4.5g/m
2, bake out temperature is that the processing parameter of 55 degrees Celsius is applied to also drying in PVC film, obtains PVC glued membrane.
After testing, PVC glued membrane water-intake rate of the present invention is 4.1%, T stripping strength is 29.8N/25mm, in an atmosphere 420 days not aging.
Embodiment 3
The preparation method of PVC glued membrane, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 37 parts, 4,4-methylenediphenyl diisocyanates 33 parts, triethylamine 5 parts, dimethylol propionic acid 33 parts, butyl acrylate 45 parts, methyl methacrylate 45 parts, glycidyl methacrylate 5 parts, Propylene glycol monoacrylate 2 parts, 6 parts, vinylformic acid, DMF 95 parts, Potassium Persulphate 2 parts;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1.5h in reactor under 49 degrees Celsius, add poly-hexanodioic acid 1,4-butanediol ester glycol and dimethylol propionic acid are also cooled to 55 degrees Celsius after continuing reaction 4h at 80 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add again after glycidyl methacrylate, butyl acrylate, methyl methacrylate and vinylformic acid mix and add Potassium Persulphate, be warming up to 83 degrees Celsius and be incubated 30min, obtaining mixture;
Step 2, by step 1 gained mixture centrifugal 30min under 3300r/min, obtain sizing agent;
Step 3, sizing agent is pressed surface covered 80m/min, spread 4.5g/m
2, bake out temperature is that the processing parameter of 55 degrees Celsius is applied to also drying in PVC film, obtains PVC glued membrane.
After testing, PVC glued membrane water-intake rate of the present invention is 3.9%, T stripping strength is 30.5N/25mm, in an atmosphere 450 days not aging.
The preparation method of PVC glued membrane of the present invention is with N, dinethylformamide is medium, 4, 4-methylenediphenyl diisocyanates, poly-hexanodioic acid 1, the copolymerization under triethylamine katalysis of 4-butanediol ester glycol obtains urethane, adopt butyl acrylate as main soft monomer, methyl methacrylate is main hard monomer, vinylformic acid and Propylene glycol monoacrylate are functional monomer, with polyurethane-modified, glycidyl methacrylate does crosslinking and curing agent, Potassium Persulphate is as initiator, N, dinethylformamide is as solvent, the sizing agent drying and moulding prepared is rapid, the transparency is good, and weathering resistance, water tolerance, chemical proofing is splendid, resistance to weathering can be more excellent, easy to use, when using it in PVC film, owing to containing carboxyl, hydroxyl isopolarity group in sizing agent, can be combined with the polar group on sub-light molding powder baking vanish surface, form hydrogen bond action, considerably increase cohesive strength.After testing, water-intake rate of the present invention is below 3.9% ~ 4.2%, and PVC glued membrane T stripping strength can reach 29.1 ~ 30.5N/25mm, in an atmosphere more than 360 ~ 450 days not aging.
In sum; provided by the inventionly the foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalents utilizing description of the present invention to do; or be directly or indirectly used in relevant technical field, be all in like manner included in scope of patent protection of the present invention.
Claims (6)
1.PVC glued membrane, it is characterized in that: comprise PVC film and be attached to the sizing agent in PVC film, described sizing agent is prepared from by the raw material of following weight part: poly-hexanodioic acid 1, 4-butanediol ester glycol 36 ~ 38 parts, 4, 4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, N, dinethylformamide 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part.
2. PVC glued membrane according to claim 1, is characterized in that: described sizing agent is prepared from by the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 37 parts, 4,4-methylenediphenyl diisocyanates 33 parts, triethylamine 5 parts, dimethylol propionic acid 33 parts, butyl acrylate 45 parts, methyl methacrylate 45 parts, glycidyl methacrylate 5 parts, Propylene glycol monoacrylate 2 parts, 6 parts, vinylformic acid, N, dinethylformamide 95 parts, Potassium Persulphate 2 parts.
3. PVC glued membrane according to claim 1, is characterized in that: the thickness of described sizing agent is 0.12 ~ 0.14mm.
The preparation method of 4.PVC glued membrane, is characterized in that, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 36 ~ 38 parts, 4,4-methylenediphenyl diisocyanates 32 ~ 34 parts, triethylamine 4 ~ 6 parts, dimethylol propionic acid 32 ~ 35 parts, butyl acrylate 44 ~ 46 parts, methyl methacrylate 44 ~ 46 parts, glycidyl methacrylate 4 ~ 6 parts, Propylene glycol monoacrylate 1 ~ 3 part, 3 ~ 9 parts, vinylformic acid, DMF 90 ~ 100 parts, Potassium Persulphate 1 ~ 3 part;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1 ~ 2h in reactor under 48 ~ 50 degrees Celsius, add poly-hexanodioic acid 1, 4-butanediol ester glycol and dimethylol propionic acid are also cooled to 50 ~ 60 degrees Celsius after continuing reaction 3 ~ 5h at 75 ~ 85 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add glycidyl methacrylate again, butyl acrylate, Potassium Persulphate is added after methyl methacrylate and vinylformic acid mix, be warming up to 81 ~ 84 degrees Celsius and be incubated 30min, obtain mixture,
Step 2, by step 1 gained mixture centrifugal 30min under 3200 ~ 3500r/min, obtain sizing agent;
Step 3, sizing agent to be applied in PVC film and dry, to obtain PVC glued membrane.
5. the preparation method of PVC glued membrane according to claim 4, is characterized in that: the processing parameter of step 3 is: surface covered 80m/min, spread 4.5g/m
2, bake out temperature is 55 degrees Celsius.
The preparation method of 6.PVC glued membrane, is characterized in that, comprises the steps:
Step 1, get out the raw material of following weight part: poly-hexanodioic acid BDO esterdiol 37 parts, 4,4-methylenediphenyl diisocyanates 33 parts, triethylamine 5 parts, dimethylol propionic acid 33 parts, butyl acrylate 45 parts, methyl methacrylate 45 parts, glycidyl methacrylate 5 parts, Propylene glycol monoacrylate 2 parts, 6 parts, vinylformic acid, DMF 95 parts, Potassium Persulphate 2 parts;
By 4, after 4-methylenediphenyl diisocyanates and Propylene glycol monoacrylate join and react 1.5h in reactor under 49 degrees Celsius, add poly-hexanodioic acid 1,4-butanediol ester glycol and dimethylol propionic acid are also cooled to 55 degrees Celsius after continuing reaction 4h at 80 degrees Celsius, now add triethylamine, N, dinethylformamide also stirs, add again after glycidyl methacrylate, butyl acrylate, methyl methacrylate and vinylformic acid mix and add Potassium Persulphate, be warming up to 83 degrees Celsius and be incubated 30min, obtaining mixture;
Step 2, by step 1 gained mixture centrifugal 30min under 3300r/min, obtain sizing agent;
Step 3, sizing agent is pressed surface covered 80m/min, spread 4.5g/m
2, bake out temperature is that the processing parameter of 55 degrees Celsius is applied to also drying in PVC film, obtains PVC glued membrane.
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