CN105086872B - PVC glued membranes and preparation method thereof - Google Patents
PVC glued membranes and preparation method thereof Download PDFInfo
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- CN105086872B CN105086872B CN201510630811.4A CN201510630811A CN105086872B CN 105086872 B CN105086872 B CN 105086872B CN 201510630811 A CN201510630811 A CN 201510630811A CN 105086872 B CN105086872 B CN 105086872B
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Abstract
Of the invention to provide a kind of PVC glued membranes for being used to pack that matt molding powder baking vanish workpiece water-tolerant, viscosity are high, resistance to weathering energy is good, including PVC film and the adhesive being attached in PVC film, the adhesive is prepared from by the following raw material：Polyadipate Isosorbide-5-Nitrae butyl glycol ester diol, 4,4 methylenediphenyl diisocyanates, triethylamine, dihydromethyl propionic acid, butyl acrylate, methyl methacrylate, GMA, hydroxypropyl acrylate, acrylic acid, N, N dimethylformamides and potassium peroxydisulfate.The present invention also provides a kind of preparation method of PVC glued membranes.The beneficial effects of the present invention are：With polyurethane modified acrylic resin, with N, N dimethylformamides are used as crosslinking agent as medium with GMA, the adhesive prepared coordinates with PVC film, can obtain the PVC glued membranes that water absorption rate is low, adhesion strength is high, resistance to weathering can be excellent.
Description
Technical field
The present invention relates to packaging film field, specifically a kind of PVC glued membranes packed for sanding baking vanish workpiece and its
Preparation method.
Background technology
Fire resistant doorsets mainly have two kinds, and one kind is light baking vanish, and one kind is matt molding powder baking vanish.Fire resistant doorsets are all needed before dispatching from the factory
Packed with special packaging film.PE glue films are the conventional packaging films of light baking vanish fire resistant doorsets, but used in matt molding powder
Do not applied to then on the fire resistant doorsets of baking vanish, not only have no stickiness, once by wind, product will it is exposed outside, it is impossible to reach guarantor
Protect the purpose of product.So PE glue films can only be pasted onto now on fire resistant doorsets with double faced adhesive tape, then the side tied up with packaging bag
Formula packs the fire resistant doorsets of matt molding powder baking vanish, and this manner of packing not only takes time and effort, and can not also ensure the reliability of packaging.
Above-mentioned PE glue films are made in PE film coated glues, glue, i.e. aqueous coating glue, be using water as
Solvent is by acrylic acid or polyurethane resin by special emulsifying device, and emulsification is formed.Although cheap, there is film forming
Difference, viscosity are low, non-watertight, the fatal defects such as easy degumming.
The adhesive of existing packaging film is except glue, also factice, i.e. oiliness coating adhesive, also referred to as solvent-borne type gluing
Agent, is using oil-based solvent toluene, DMF, butanone etc. as solvent, by acrylate or polyurethane dissolving
Into after the volatilization of, solvent, permanent mucous membrane can be formed, with simple production process, water-fast, rate of drying and the open hour it is wide,
Just glutinous intensity is high, easily soak the characteristics of some hardly possiblies stick surface.But existing solvent-type acrylic ester adhesive or solvent-borne type are poly-
Urethane adhesive can not be perfectly adhered on PE films, and single solvent-type acrylic ester adhesive temperature tolerance is poor, the moisture absorption
Rate is high；Single solvent borne polyurethane adhesive water resistance is poor.
The content of the invention
The technical problems to be solved by the invention are：There is provided it is a kind of be used to packing matt molding powder baking vanish workpiece water-tolerant,
PVC glued membranes that viscosity is high, resistance to weathering can be good and preparation method thereof.
In order to solve the above-mentioned technical problem, one of the technical solution adopted by the present invention is：PVC glued membranes, including PVC film and
The adhesive in PVC film is attached to, the adhesive is prepared from by the raw material of following parts by weight：Polyadipate 1,4- fourths two
36~38 parts of alcohol esterdiol, 4,4- 32~34 parts of methylenediphenyl diisocyanates, 4~6 parts of triethylamine, dihydromethyl propionic acid
32~35 parts, 44~46 parts of butyl acrylate, 44~46 parts of methyl methacrylate, GMA 4~6
Part, 1~3 part of hydroxypropyl acrylate, 3~9 parts of acrylic acid, 90~100 parts of DMF, 1~3 part of potassium peroxydisulfate.
Another technical scheme that the present invention is used for：The preparation method of PVC glued membranes, comprises the following steps：
Step 1, the raw material for getting out following parts by weight：36~38 parts of polyadipate BDO esterdiol, 4,4- is sub-
32~34 parts of methyldiphenyl diisocyanate, 4~6 parts of triethylamine, 32~35 parts of dihydromethyl propionic acid, butyl acrylate 44~
46 parts, 44~46 parts of methyl methacrylate, 4~6 parts of GMA, 1~3 part of hydroxypropyl acrylate, third
3~9 parts of olefin(e) acid, 90~100 parts of DMF, 1~3 part of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor Celsius 48~50
After 1~2h of the lower reaction of degree, add polyadipate BDO esterdiol and dihydromethyl propionic acid and 75~85 degrees Celsius after
50~60 degrees Celsius are cooled to after 3~5h of continuous reaction, triethylamine, DMF is now added and stirs, then
Add after GMA, butyl acrylate, methyl methacrylate and acrylic acid are well mixed and add over cure
Sour potassium, is warming up to 81~84 degrees Celsius and is incubated 30min, obtain mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3200~3500r/min, obtain adhesive；
Step 3, by adhesive be applied in PVC film and dry, obtain PVC glued membranes.
Another technical scheme for also using of the present invention for：The preparation method of PVC glued membranes, comprises the following steps：
Step 1, the raw material for getting out following parts by weight：37 parts of polyadipate BDO esterdiol, 4,4- methylene
33 parts of diphenyl diisocyanate, 5 parts of triethylamine, 33 parts of dihydromethyl propionic acid, 45 parts of butyl acrylate, methyl methacrylate
45 parts, 5 parts of GMA, 2 parts of hydroxypropyl acrylate, 6 parts of acrylic acid, 95 parts of DMF,
2 parts of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor under 49 degrees Celsius
React after 1.5h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and after 80 degrees Celsius are continued to react 4h
55 degrees Celsius are cooled to, triethylamine, DMF is now added and stirs, add Glycidyl methacrylate
Potassium peroxydisulfate is added after glyceride, butyl acrylate, methyl methacrylate and acrylic acid are well mixed, 83 degrees Celsius are warming up to
And 30min is incubated, obtain mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3300r/min, obtain adhesive；
Step 3, by adhesive press coating speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius of work
Skill parameter is applied in PVC film and dried, and obtains PVC glued membranes.
The beneficial effects of the present invention are：PVC glued membranes prepared by the preparation method of PVC glued membranes of the present invention use acrylic acid fourth
Ester is as main soft monomer, and methyl methacrylate is main hard monomer, and acrylic acid and hydroxypropyl acrylate are functional monomer,
With polyurethane-modified, GMA does crosslinking and curing agent, and potassium peroxydisulfate is used as initiator, N, N- dimethyl methyls
Acid amides is as solvent, and the adhesive drying and moulding prepared is rapid, and the transparency is good, and weatherability, water resistance, chemical proofing
Splendid, resistance to weathering can be more excellent, easy to use；When using it in PVC film, due in adhesive containing carboxyl,
Hydroxyl isopolarity group, can be combined with the polar group on matt molding powder baking vanish surface, formed hydrogen bond action, considerably increased and cohere
Intensity.After testing, water absorption rate of the present invention is below 3.9%~4.2%, and PVC glued membrane T peel strengths are up to 29.1~30.5N/
25mm, in an atmosphere not aging in more than 360~450 days.
Embodiment
To describe technology contents, the objects and the effects of the present invention in detail, it is explained below in conjunction with embodiment.
The design of most critical of the present invention is：With polyurethane modified acrylic resin, using DMF as
Medium, with GMA as crosslinking agent, the adhesive prepared coordinates with PVC film, can be absorbed water
The PVC glued membranes that rate is low, adhesion strength is high, resistance to weathering can be excellent.
The present invention provides a kind of PVC glued membranes, including PVC film and the adhesive being attached in PVC film, the adhesive
It is prepared from by the raw material of following parts by weight：36~38 parts of polyadipate BDO esterdiol, 4,4- methylenediphenyls
32~34 parts of diisocyanate, 4~6 parts of triethylamine, 32~35 parts of dihydromethyl propionic acid, 44~46 parts of butyl acrylate, methyl
44~46 parts of methyl acrylate, 4~6 parts of GMA, 1~3 part of hydroxypropyl acrylate, acrylic acid 3~9
Part, 90~100 parts of DMF, 1~3 part of potassium peroxydisulfate.
The mechanism of the present invention is：Contain carbamate segment and ehter bond, urea bond, ester bond isoreactivity in polyurethane molecular
Group, such design feature causes polyurethane material to possess excellent physical and mechanical property, good cold resistance, soft or hard degree
To temperature-insensitive, the advantages of elasticity is big, but the water resistance and mechanical strength of its film are all not so good as acrylic resin, acrylic acid
The water-tolerant of resin, but easily become fragile when having low temperature, easy stickness during high temperature, the shortcoming of pliability difference, with polyurethane-modified
Acrylic resin, the product for the complementation that can gain the upper hand.
GMA, with other monomers copolymerization, introduces crosslinkable epoxy radicals as self-cross linking monomer
Group, makes adhesive reach the purpose of self-crosslinking in film forming procedure.Because GMA is multifunctional single group
With the carboxyl in other monomers, hydroxyl opening can occur for the epoxide group in body, molecular structure, produce crosslinking, shape
Into tridimensional network, the increase of GMA consumption, epoxide group number increases, and intermolecular cross-linking density increases
Greatly, polymer molecule interchain space net structure is finer and close, so as to improve the mechanical property of adhesive.But work as metering system
When acid glycidyl ester is excessive, peel strength is reduced on the contrary, and this is due to the vitrifying of GMA in itself
Temperature is higher, and the increase of GMA consumption improves the ratio of hard section in copolymer molecule chain, Jin Erti
High polymer glass temperature so that copolymer adhesive film becomes fragile under normal temperature, polymer bonding hydraulic performance decline.
GMA is more, and crosslink density is bigger, and polymer institute is better into glued membrane compactness, hinders
Infiltration and diffusion of the hydrone to glued membrane, cause water absorption rate to decline；The epoxide group of GMA can be with gathering
Carboxyl in adduct molecule chain crosslinks reaction so that polymer carboxyl-content is reduced, while also reducing polar group
Content so that glued membrane hydrophily declines, water absorption rate reduces.
GMA does crosslinking and curing agent, and the self-cross linking type polyacrylate gluing of excellent performance is made
Agent, because the epoxide group accessed in strand can react with the carboxyl in molecule long-chain, makes to form fine and close between macromolecular
Cross-linked structure, effectively improve glued membrane heat resistance and water resistance, and greatly strengthen bond strength.Being made to apply
In PVC film bonding, with heat-resisting quantity, dimensionally stable, free of contamination advantage.
The addition of acrylic acid is favorably improved the water resistance of film.Due to the epoxide group of GMA
Occurs open loop cross-linking reaction with carboxyl, hydroxyl, carboxyl can also crosslink reaction with hydroxyl.Acrylic acid content increases, carboxyl
Number increase, crosslinking degree increase forms continuous fine and close glued membrane, can effectively prevent hydrone from being migrated into strand
Be swelled, be conducive to improve acrylate glued membrane water resistance.But carboxyl is also hydrophilic radical, when propylene excessive acid,
Excessive carboxyl can not react with epoxide group or hydroxyl, be enriched in film coated surface, with the increasing of acrylic acid mass fraction
Greatly, film hydrophily strengthens, and contact angle reduces.
Acrylic acid content gradually increases, and the trend of increase is presented in the tensile strength of glued membrane, and elongation at break is then gradually reduced.
Carboxyl crosslinks reaction with GMA epoxide group in acrylic molecules so that tied during polymer film forming
Occur cross-linked structure in structure, with increasing for acrylic acid consumption, the degree of cross linking gradually increases, combined between polymer molecule tighter
It is close, polymer molecule is become three-dimensional-structure by linear structure, the tensile strength of film is greatly increased, while the friendship between macromolecular chain
Connection has fettered the sliding of strand, causes the obvious reduction of elongation at break.
Acrylate copolymer molecule is alternateed by soft and hard segments to be constituted, and soft segment assigns film pliability and elasticity, and hard
Section assigns its intensity.Therefore the ratio of soft segment and hard section has a significant effect to the mechanical property of acrylate films in acrylate.
Acrylic acid is introduced into so that rigid structure increases in acrylate, and hard section ratio increases, thus mechanical property is more excellent.
With increasing for acrylic acid, carboxyl-content increase, the crosslinking degree increase of system, cohesive force is improved；In addition, carboxyl
With the polar group formation hydrogen bond of matt molding powder baking vanish workpiece surface, peel strength is set to become big.The increase of acrylic acid content simultaneously
The ratio of hard section in molecule is also increased, when propylene excessive acid, hard segment content is too high and the increase of crosslinking points the two factors
Work simultaneously, hinder molecular chain movement in acrylate, material is hardened and become fragile, adhesive property declines.Therefore acrylic acid
Content needs to control within the specific limits.
Hydroxypropyl acrylate can carry out copolymerization, and hydroxyl is drawn as a kind of active functional monomer with other monomers
Enter in acrylate macromolecular chain, because open loop crosslinking can occur with GMA epoxide epoxy group group for hydroxyl instead
Should, it can also be crosslinked with the carboxylic group in macromolecular, form build macromolecular, also with very big polarity, energy and molecule
Hydroxyl formation hydrogen bond structure on chain and fabric, therefore hydroxypropyl acrylate is to improving self-crosslinked acrylate adhesive and glued membrane
Vital effect can be played.
, also can be with hydroxyl because the epoxide group of GMA can not only crosslink reaction with carboxyl
Generation open loop cross-linking reaction, in addition carboxyl and hydroxyl can also crosslink reaction, when in glued membrane without hydroxypropyl acrylate
When, the system degree of cross linking is low, and glued membrane water resistance is general；With increasing for hydroxypropyl acrylate content, the number of hydroxyl increases, crosslinking
Degree has increased, and cross-linked structure becomes finer and close, further prevents hydrone from being migrated into strand, is conducive to carrying
The water resistance of high polyurethane-acrylate glued membrane.But hydroxyl is also hydrophilic radical, when hydroxypropyl acrylate is excessive, mistake
Many hydroxyls can not react with epoxide group or carboxyl, be enriched in film coated surface, play hydrophilic effect, cause film to be inhaled
Aqueous enhancing.
Can be with GMA GMA due to having on hydroxypropyl acrylate molecule
Epoxide group and acrylic acid in carboxyl crosslink reaction so that occur crosslinking net knot during polymer film forming in structure
Structure, with increasing for hydroxypropyl acrylate consumption, the degree of cross linking gradually increases, and is combined more closely between polymer molecule, makes polymer
Molecule becomes three-dimensional-structure by linear structure, and the tensile strength of film is greatly increased, while the crosslinking between macromolecular chain has been fettered point
The sliding of subchain, causes decreasing for elongation at break；On the other hand, acrylate copolymer molecule is mutual by soft and hard segments
Alternately constitute, soft segment assigns film pliability and elasticity, and hard section assigns its intensity.Therefore in acrylate soft segment and hard section ratio
Example has a significant effect to the mechanical property of acrylate films.Hydroxypropyl acrylate be introduced into so that in acrylate rigid structure increase
Many, the increase of hard section ratio shows more excellent mechanical property.
The high adhesive of hardness, tensile strength is high, but unsuitable film forming, brittle easily to split；The too low adhesive of hardness, mechanical property
Can be poor, film forming is softer, if hard monomer too high levels, film forming is unable at room temperature, peel strength is also strongly reduced.
The present invention is from butyl acrylate as main soft monomer, and methyl methacrylate is used as main hard monomer, soft list
Body glass transition temperature is low, and polymeric long chain compliance can be made to improve, and assigns adhesive bonding characteristic, therefore increase adhesive is sticked
Degree, but after film forming, the hardness of film is too small, and performance is bad：Hard monomer glass transition temperature is high so that polymer long-chain mobility subtracts
It is weak, increase the cohesive force of adhesive.With the increase of hard monomer content, peel strength constantly increases, and film forming improves.
It was found from foregoing description, the beneficial effects of the present invention are：PVC prepared by the preparation method of PVC glued membranes of the present invention
Glued membrane is using butyl acrylate as main soft monomer, and methyl methacrylate is main hard monomer, acrylic acid and acrylic acid hydroxyl
Propyl ester is functional monomer, with polyurethane-modified, and GMA does crosslinking and curing agent, and potassium peroxydisulfate is as drawing
Agent is sent out, DMF is as solvent, and the adhesive drying and moulding prepared is rapid, and the transparency is good, and it is weatherability, resistance to
Aqueous, chemical proofing is splendid, and resistance to weathering can be more excellent, easy to use；When using it in PVC film, due to
Contain carboxyl, hydroxyl isopolarity group in adhesive, can be combined with the polar group on matt molding powder baking vanish surface, form hydrogen bond and make
With considerably increasing bond strength.After testing, water absorption rate of the present invention is below 3.9%~4.2%, PVC glued membrane T peel strengths
Up to 29.1~30.5N/25mm, in an atmosphere not aging in more than 360~450 days.
The adhesive is prepared from by the raw material of following parts by weight：37 parts of polyadipate BDO esterdiol, 4,
33 parts of 4- methylenediphenyl diisocyanates, 5 parts of triethylamine, 33 parts of dihydromethyl propionic acid, 45 parts of butyl acrylate, methyl-prop
45 parts of e pioic acid methyl ester, 5 parts of GMA, 2 parts of hydroxypropyl acrylate, 6 parts of acrylic acid, N, N- dimethyl formyls
95 parts of amine, 2 parts of potassium peroxydisulfate.
Seen from the above description, adhesive is prepared using the raw material of aforementioned proportion, the properties of adhesive can be made optimal.
Further, the thickness of the adhesive is 0.12~0.14mm.
Seen from the above description, by adhesive thickness control in 0.12~0.14mm so that PVC glued membranes pack matt molding powder
Degumming is difficult after baking vanish workpiece.
Another technical scheme that the present invention is used for：
The preparation method of PVC glued membranes, it is characterised in that comprise the following steps：
Step 1, the raw material for getting out following parts by weight：36~38 parts of polyadipate BDO esterdiol, 4,4- is sub-
32~34 parts of methyldiphenyl diisocyanate, 4~6 parts of triethylamine, 32~35 parts of dihydromethyl propionic acid, butyl acrylate 44~
46 parts, 44~46 parts of methyl methacrylate, 4~6 parts of GMA, 1~3 part of hydroxypropyl acrylate, third
3~9 parts of olefin(e) acid, 90~100 parts of DMF, 1~3 part of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor Celsius 48~50
After 1~2h of the lower reaction of degree, add polyadipate BDO esterdiol and dihydromethyl propionic acid and 75~85 degrees Celsius after
50~60 degrees Celsius are cooled to after 3~5h of continuous reaction, triethylamine, DMF is now added and stirs, then
Add after GMA, butyl acrylate, methyl methacrylate and acrylic acid are well mixed and add over cure
Sour potassium, is warming up to 81~84 degrees Celsius and is incubated 30min, obtain mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3200~3500r/min, obtain adhesive；
Step 3, by adhesive be applied in PVC film and dry, obtain PVC glued membranes.
It was found from foregoing description, the beneficial effects of the present invention are：The preparation method of PVC glued membranes of the present invention is with N, N- diformazans
Base formamide is medium, and 4,4- methylenediphenyl diisocyanates, polyadipate BDO esterdiol are urged in triethylamine
The lower copolymerization of change effect obtains polyurethane, and using butyl acrylate as main soft monomer, methyl methacrylate is main hard monomer,
Acrylic acid and hydroxypropyl acrylate are functional monomer, with polyurethane-modified, and GMA does crosslinking curing
Agent, potassium peroxydisulfate is as initiator, and DMF is as solvent, and the adhesive drying and moulding prepared is rapid, thoroughly
Bright property is good, and weatherability, water resistance, chemical proofing are splendid, and resistance to weathering can be more excellent, easy to use；Used
When in PVC film, due to containing carboxyl, hydroxyl isopolarity group, polarity that can be with matt molding powder baking vanish surface in adhesive
Group is combined, and is formed hydrogen bond action, is considerably increased bond strength.After testing, water absorption rate of the present invention 3.9%~4.2% with
Under, PVC glued membrane T peel strengths are up to 29.1~30.5N/25mm, in an atmosphere not aging in more than 360~450 days.
Further, the technological parameter of step 3 is：Coating speed 80m/min, spread 4.5g/m2, drying temperature is 55
Degree Celsius.
Embodiment 1
Step 1, the raw material for getting out following parts by weight：36 parts of polyadipate BDO esterdiol, 4,4- methylene
32 parts of diphenyl diisocyanate, 4 parts of triethylamine, 32 parts of dihydromethyl propionic acid, 44 parts of butyl acrylate, methyl methacrylate
44 parts, 4 parts of GMA, 1 part of hydroxypropyl acrylate, 3 parts of acrylic acid, 90 parts of DMF,
1 part of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor under 48 degrees Celsius
React after 1h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and dropped after continuing to react 3h at 75 degrees Celsius
Temperature adds triethylamine, DMF to 50 degrees Celsius, now and stirred, and adds Glycidyl methacrylate sweet
Potassium peroxydisulfate is added after grease, butyl acrylate, methyl methacrylate and acrylic acid are well mixed, 81 degrees Celsius are warming up to simultaneously
30min is incubated, mixture is obtained；
Step 2, step 1 gained mixture centrifuged into 30min under 3300r/min, obtain adhesive；
Step 3, by adhesive press coating speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius of work
Skill parameter is applied in PVC film and dried, and obtains PVC glued membranes.
After testing, PVC glued membranes water absorption rate of the present invention is that 4.2%, T peel strengths are 29.1N/25mm, 410 days in an atmosphere
Not aging.
Embodiment 2
Step 1, the raw material for getting out following parts by weight：38 parts of polyadipate BDO esterdiol, 4,4- methylene
34 parts of diphenyl diisocyanate, 6 parts of triethylamine, 35 parts of dihydromethyl propionic acid, 46 parts of butyl acrylate, methyl methacrylate
46 parts, 6 parts of GMA, 3 parts of hydroxypropyl acrylate, 9 parts of acrylic acid, 100 parts of DMF,
3 parts of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor at 50 c
React after 2h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and dropped after continuing to react 5h at 85 degrees Celsius
Temperature adds triethylamine, DMF to 60 degrees Celsius, now and stirred, and adds Glycidyl methacrylate sweet
Potassium peroxydisulfate is added after grease, butyl acrylate, methyl methacrylate and acrylic acid are well mixed, 84 degrees Celsius are warming up to simultaneously
30min is incubated, mixture is obtained；
Step 2, step 1 gained mixture centrifuged into 30min under 3300r/min, obtain adhesive；
Step 3, by adhesive press coating speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius of work
Skill parameter is applied in PVC film and dried, and obtains PVC glued membranes.
After testing, PVC glued membranes water absorption rate of the present invention is that 4.1%, T peel strengths are 29.8N/25mm, 420 days in an atmosphere
Not aging.
Embodiment 3
The preparation method of PVC glued membranes, comprises the following steps：
Step 1, the raw material for getting out following parts by weight：37 parts of polyadipate BDO esterdiol, 4,4- methylene
33 parts of diphenyl diisocyanate, 5 parts of triethylamine, 33 parts of dihydromethyl propionic acid, 45 parts of butyl acrylate, methyl methacrylate
45 parts, 5 parts of GMA, 2 parts of hydroxypropyl acrylate, 6 parts of acrylic acid, 95 parts of DMF,
2 parts of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor under 49 degrees Celsius
React after 1.5h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and after 80 degrees Celsius are continued to react 4h
55 degrees Celsius are cooled to, triethylamine, DMF is now added and stirs, add Glycidyl methacrylate
Potassium peroxydisulfate is added after glyceride, butyl acrylate, methyl methacrylate and acrylic acid are well mixed, 83 degrees Celsius are warming up to
And 30min is incubated, obtain mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3300r/min, obtain adhesive；
Step 3, by adhesive press coating speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius of work
Skill parameter is applied in PVC film and dried, and obtains PVC glued membranes.
After testing, PVC glued membranes water absorption rate of the present invention is that 3.9%, T peel strengths are 30.5N/25mm, 450 days in an atmosphere
Not aging.
The preparation method of PVC glued membranes of the present invention is using DMF as medium, and 4,4- methylenediphenyls two are different
The copolymerization under triethylamine catalytic action of cyanate, polyadipate BDO esterdiol obtains polyurethane, using butyl acrylate
As main soft monomer, methyl methacrylate is main hard monomer, and acrylic acid and hydroxypropyl acrylate are functional monomer, are used
Polyurethane-modified, GMA does crosslinking and curing agent, and potassium peroxydisulfate is used as initiator, N, N- dimethyl formyls
Amine is as solvent, and the adhesive drying and moulding prepared is rapid, and the transparency is good, and weatherability, water resistance, chemical proofing pole
Good, resistance to weathering can be more excellent, easy to use；When using it in PVC film, due to containing carboxyl, hydroxyl in adhesive
Base isopolarity group, can be combined with the polar group on matt molding powder baking vanish surface, form hydrogen bond action, considerably increased and cohered by force
Degree.After testing, water absorption rate of the present invention is below 3.9%~4.2%, and PVC glued membrane T peel strengths are up to 29.1~30.5N/
25mm, in an atmosphere not aging in more than 360~450 days.
In summary, what the present invention was provided the foregoing is only embodiments of the invention, not thereby limit the present invention's
The scope of the claims, the equivalents that every utilization present specification is made, or directly or indirectly it is used in the technology of correlation
Field, is included within the scope of the present invention.
Claims (6)
1.PVC glued membranes, it is characterised in that：Including PVC film and the adhesive being attached in PVC film, the adhesive is by such as
The raw material of lower parts by weight is prepared from：36~38 parts of polyadipate BDO esterdiol, 4,4- methylenediphenyls two are different
32~34 parts of cyanate, 4~6 parts of triethylamine, 32~35 parts of dihydromethyl propionic acid, 44~46 parts of butyl acrylate, metering system
Sour 44~46 parts of methyl esters, 4~6 parts of GMA, 1~3 part of hydroxypropyl acrylate, 3~9 parts of acrylic acid, N,
90~100 parts of dinethylformamide, 1~3 part of potassium peroxydisulfate.
2. PVC glued membranes according to claim 1, it is characterised in that：The adhesive is prepared by the raw material of following parts by weight
Form：37 parts of polyadipate BDO esterdiol, 4,4- 33 parts of methylenediphenyl diisocyanates, 5 parts of triethylamine, two
33 parts of hydroxymethyl propionic acid, 45 parts of butyl acrylate, 45 parts of methyl methacrylate, 5 parts of GMA, propylene
Sour 2 parts of hydroxypropyl acrylate, 6 parts of acrylic acid, 95 parts of DMF, 2 parts of potassium peroxydisulfate.
3. PVC glued membranes according to claim 1, it is characterised in that：The thickness of the adhesive is 0.12~0.14mm.
The preparation method of 4.PVC glued membranes, it is characterised in that comprise the following steps：
Step 1, the raw material for getting out following parts by weight：36~38 parts of polyadipate BDO esterdiol, 4,4- methylene
32~34 parts of diphenyl diisocyanate, 4~6 parts of triethylamine, 32~35 parts of dihydromethyl propionic acid, butyl acrylate 44~46
Part, 44~46 parts of methyl methacrylate, 4~6 parts of GMA, 1~3 part of hydroxypropyl acrylate, propylene
3~9 parts of acid, 90~100 parts of DMF, 1~3 part of potassium peroxydisulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor under 48~50 degrees Celsius
React after 1~2h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and continue anti-at 75~85 degrees Celsius
Answer and 50~60 degrees Celsius are cooled to after 3~5h, now add triethylamine, DMF and stir, add
Potassium peroxydisulfate is added after GMA, butyl acrylate, methyl methacrylate and acrylic acid are well mixed,
It is warming up to 81~84 degrees Celsius and is incubated 30min, obtains mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3200~3500r/min, obtain adhesive；
Step 3, by adhesive be applied in PVC film and dry, obtain PVC glued membranes.
5. the preparation method of PVC glued membranes according to claim 4, it is characterised in that：The technological parameter of step 3 is：Coating
Speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius.
The preparation method of 6.PVC glued membranes, it is characterised in that comprise the following steps：
Step 1, the raw material for getting out following parts by weight：37 parts of polyadipate BDO esterdiol, 4,4- methylene hexichol
33 parts of group diisocyanate, 5 parts of triethylamine, 33 parts of dihydromethyl propionic acid, 45 parts of butyl acrylate, methyl methacrylate 45
Part, 5 parts of GMA, 2 parts of hydroxypropyl acrylate, 6 parts of acrylic acid, 95 parts of DMF, mistake
2 parts of potassium sulfate；
4,4- methylenediphenyl diisocyanates and hydroxypropyl acrylate are added in reactor and reacted under 49 degrees Celsius
After 1.5h, add polyadipate BDO esterdiol and dihydromethyl propionic acid and cool after continuing to react 4h at 80 degrees Celsius
To 55 degrees Celsius, now add triethylamine, DMF and stir, add methyl propenoic acid glycidyl
Potassium peroxydisulfate is added after ester, butyl acrylate, methyl methacrylate and acrylic acid are well mixed, 83 degrees Celsius is warming up to and protects
Warm 30min, obtains mixture；
Step 2, step 1 gained mixture centrifuged into 30min under 3300r/min, obtain adhesive；
Step 3, by adhesive press coating speed 80m/min, spread 4.5g/m2, drying temperature is 55 degrees Celsius of technological parameter
It is applied in PVC film and dries, obtains PVC glued membranes.
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| CN107805462B (en) * | 2017-10-28 | 2020-11-13 | 浙江世窗光学薄膜制造有限公司 | Paint surface protective film and preparation method and application thereof |
| CN116376373A (en) * | 2023-03-30 | 2023-07-04 | 濮阳展辰新材料有限公司 | High-adhesion nitro white primer and preparation method and application thereof |
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| CN103012728B (en) * | 2012-12-11 | 2014-10-29 | 广东工业大学 | Method for preparing ultraviolet light cured pressure sensitive adhesive |
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