CN109837036A - A kind of anti-scratch anti-pollution TPU vehicle body protective film and its production technology - Google Patents
A kind of anti-scratch anti-pollution TPU vehicle body protective film and its production technology Download PDFInfo
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Abstract
The invention discloses a kind of anti-scratch anti-pollution TPU vehicle body protective films; glue-line including substrate layer and set on substrate layer lower part; it is characterized by: the substrate layer is TPU film; the upper surface of TPU film is equipped with anti-scratch anti-pollution layer, the composition and mass fraction of the anti-scratch anti-pollution layer are as follows: 50 ~ 85 parts of matrix resin；Initiator or/and 0.01 ~ 5 part of crosslinking agent；5 ~ 50 parts of filler；0 ~ 20 part of auxiliary agent；0 ~ 30 part of solvent；The filler includes nano-high molecule microballon of the autonomous assembling at micro-nano cluster；The matrix resin is the composition of polyester polyurethane or/and acrylic resin.The present invention is by forming a kind of novel anti-scratch anti-pollution TPU vehicle body protective film to the improvement being formulated in anti-scratch anti-pollution layer; for anti-scratch anti-pollution layer makes the TPU vehicle body protective film compare existing protective film in the invention, anti-scratch and anti-pollution effect can be had both simultaneously.
Description
Technical field
The present invention relates to protective film, especially a kind of anti-scratch anti-pollution TPU vehicle body protective film and its production technology.
Background technique
TPU is a kind of macromolecular material, referred to as the Novel environment-friendlymaterial material of 21st century.The particular molecule of TPU
Structure determines that he has excellent physical characteristic, such as: high resiliency, wearability, high intensity, strong hardness, ductile property and excellent
Thermal adaptability；And nontoxicity, waterproof, ventilative, oil resistant, water-fast, resistance to mould.And temperature tolerance is good, can -60 DEG C -
Elasticity is kept within the scope of 200 DEG C for a long time.Therefore TPU material is favored in more and more industries, using TPU as the vehicle body of substrate
Paste more and more be used in automobile industry.
With the continuous development of materials industry, simple TPU structure has been insufficient for vast consumption market for protecting
The functional requirement of cuticula.TPU film has certain toughness, but film itself is more soft, is easy because of the higher power of intensity
Lead to scratch, or even scratches.And the appearance of automobile is vulnerable to external environmental, it is difficult to keep permanent clean state, therefore
It is many it is artificial allow the love vehicle of oneself to seem clean beauty, continually vehicle body can be cleaned, degrease grease stain, then right
Vehicle body waxing, envelope glaze etc..Waxing and envelope glaze can make vehicle body bright, not easy to pollute, damage resistant, easy cleaning.But these behaves
Protection period is not permanent, and such as period of waxing is 7 ~ 15 days；The period for sealing glaze is 3 ~ 6 months；The period of cleaning is shorter.In addition,
Every primary such body care of progress can all bring primary damage to bodywork surface, and vehicle surface can be made by such as continually cleaning to wipe
There is trace；The alkali components contained in vehicle wax can make vehicle body become crow；Body polish, stock removal polishing can must be made to paint before envelope glaze
Thinning 3 ~ 5 microns of face.
The patent of invention of Patent No. 201510645557.5 discloses a kind of TPU protective film containing anti-scratch coating,
Including substrate layer, glue-line, attached bottom, substrate layer is TPU film, and anti-scratch coating is contained on TPU film surface, and anti-scratch coating is pressed
Mass fraction includes following component: six functional groups polyurethane acrylic resin, trifunctional polyurethane acrylic resin, two functions
Reunion urethane acrylate resin silicone resin, acrylic monomers, coalescing agent, plasticizer, photoinitiator, leveling auxiliary agent, adhesive force
Promotor.The invention increases antiscratch coatings, increases the scratch resistance energy on the surface TPU, while ensure that increase TPU film
The high tenacity of TPU film is not reduced while scratch resistance energy again.But anti-scratch coating therein cannot be provided simultaneously with anti-pollution energy
Power still needs to carry out vehicle body regular cleaning to keep vehicle body clean degree, to also affect the use of anti-scratch coating indirectly
Service life.
Summary of the invention
A kind of anti-scratch anti-pollution TPU vehicle body protective film, the glue-line including substrate layer and set on substrate layer lower part, the substrate layer
Upper surface for TPU film, TPU film is equipped with anti-scratch anti-pollution layer, the composition of the anti-scratch anti-pollution layer are as follows:
50 ~ 85 parts of matrix resin；
Initiator or/and 0.01 ~ 5 part of crosslinking agent；
5 ~ 50 parts of filler；
0 ~ 20 part of auxiliary agent；
0 ~ 30 part of solvent；
The filler includes nano-high molecule microballon of the autonomous assembling at micro-nano cluster, such as PMMA microballon,
And silica and/or aluminum oxide；
The matrix resin is the composition of polyester polyurethane and/or acrylic resin；
Wherein polyester polyurethane be polycarbonate polyurethane or fluorine-carbon modified polyester polyurethane, the acrylic resin
Composition includes six functional groups polyurethane acrylic resin, trifunctional polyurethane acrylic resin and two functional polyurethanes third
Olefin(e) acid resin；
Preferably, the composition of anti-scratch anti-pollution layer are as follows:
60 ~ 80 parts of matrix resin；
Initiator or/and 1 ~ 5 part of crosslinking agent；
20 ~ 30 parts of filler；
10 ~ 20 parts of auxiliary agent；
20 ~ 30 parts of solvent；
Preferably, for photocuring system, initiator is selected, the initiator is alpha-hydroxyalkyl benzophenone class initiator, α-amine alkane
Base benzophenone class initiator or acyl group phosphorus oxidation species initiator；Wherein alpha-hydroxyalkyl benzophenone class initiator is as 1- hydroxy-cyciohexyl-
Phenyl ketone, 2- hydroxy-methyl=phenyl-propane -1- ketone, α-amine alkylbenzene ketone initiator is as 2- phenyl benzyl -2- dimethyl amine -
1-(4- morpholine benzyl phenyl) butanone, acyl group phosphorus oxidation species initiator is as 2,4,6(trimethylbenzoyls) diphenyl phosphate oxidation,
Bis- (2,4,6 --- trimethylbenzoyl)-phenylphosphine oxide.For heat cured system, crosslinking agent is selected, the crosslinking agent is
Aziridine, organosilicon cross-linking agent, epoxy silane coupling agent or multi-functional polycarbodiimide crosslinkers.For photocuring and thermosetting
Change the system combined, selects the mixture of initiator and crosslinking agent, wherein the proportion of initiator and crosslinking agent is in 1:1 to 1:5
In the range of.
Preferably, the polyester polyurethane is polycarbonate polyurethane or fluorine-carbon modified polyester polyurethane.
Preferably, the composition of the acrylic resin further includes four-functional group polyurethane acrylic resin and/or 3 points
Five function reunion urethane acrylate resins.
Preferably, the auxiliary agent is one of levelling agent, coalescing agent, adhesion promoter, defoaming agent or a variety of.
Preferably, the levelling agent is one or more of acrylate, polysiloxanes or organic fluothane, the film forming
Auxiliary agent is alkoxide or alcohol ethers coalescing agent, and the adhesion promoter is phosphate promotor, and the defoaming agent is organic
Silicone resin.
In photocuring system, it is not necessarily to solvent.
In aqueous systems, the solvent is water.
In oleaginous system, the solvent is ethyl acetate, toluene, dimethylbenzene, repefral, dipropylene glycol
One or more in methyl ether, the preferably mixture of ethyl acetate and phthalic acid dimethyl ether matches as ethyl acetate: adjacent benzene
Dioctyl phthalate dimethyl ether=30:20.
Preferably, the glue-line lower part is equipped with release film.Release film is bonded with TPU film by glue-line, described anti-scratch anti-
Dirty coating is equipped with protective layer.Release film be PET release film, PC release film, PS release film, PMMA release film, PP release film,
PVC release film, PE release film or PA release film.Its bottom surface is mechanical wire-drawing surface, physical frosted face or frosted coating.When winding,
The anti-scratch coating surface of anti-pollution is equipped with the protective layer of low adhesion.To enable protective film to arrange when winding by rough surface
Air out reaches the winding effect of smooth bubble-free, and protective layer can prevent bottom surface coarse under impaction state to coating
Damage.
A kind of production technology of anti-scratch anti-pollution TPU vehicle body protective film as described in claim 1, step is to carry out TPU membrane
High-voltage corona processing；By any one mode in web coatable, transfer coated, slit type extrusion coated TPU membrane electricity
Anti-scratch anti-pollution layer is coated in dizzy process face, coating weight is 10 ~ 20g/m2, and the viscosity of coating is controlled in 300 ~ 400cps；Pass through
Any one mode in hot-air seasoning, photocuring or both, which combines, solidifies anti-scratch anti-pollution layer, the hot-air seasoning
Temperature control be 80 ~ 105 DEG C, a length of 340 ~ 370nm of the light wave of the photocuring；To the TPU membrane for containing anti-scratch anti-pollution layer
It cut, packed.
The coating of the web coatable, specially cylinder, is to use diameter for 45 ~ 55mm, and mesh number is 50 ~ 60, depth 100
Anti-scratch anti-pollution layer is applied in TPU membrane by ~ 300 μm of dimple roller.
It further include the process for paste by pressure-sensitive adhesive layer release film to TPU membrane, which can carry out high pressure in TPU membrane
It is carried out before sided corona treatment, can also be after the solidification of anti-scratch anti-pollution layer, and carried out before cutting.
Further include pasting protective layer on anti-scratch anti-pollution layer, the step can anti-scratch anti-pollution layer solidification after, and
It carries out, can also be carried out simultaneously with cutting before cutting.
After TPU membrane is bonded by pressure-sensitive adhesive layer with release film, protective layer is first pasted on anti-scratch anti-pollution layer, then carry out
The cutting of TPU membrane, packaging.
The present invention by forming a kind of novel anti-scratch anti-pollution TPU vehicle body protective film to the improvement being formulated in anti-scratch anti-pollution layer,
For anti-scratch anti-pollution layer makes the TPU vehicle body protective film compare existing protective film in the invention, it can have both simultaneously anti-scratch
With the effect of anti-pollution.
It embodies in the following areas:
1) high molecular nanometer microballon, silica, aluminium dioxide can coating surface-assembled at micro-nano clustering architecture, reduce
The surface energy of coating, forms similar lotus leaf surface, makes oily water dirt be difficult to soak tiling on it, greatly improve protection membrane coat
Pollution resistance, and these macromolecule microballons are gathered in coating surface can also improve the anti-scratch performance of coating.High molecular nanometer microballon,
Silica, aluminium dioxide can reside in the inside of coating, can be used as contact and connect different resin segments, improve coating
Ductility and flexibility
2) using the polyester polyurethane and/or acrylic resin with low-surface-energy, wherein polyurethane resin is with higher
Elasticity and self-repairability, acrylic resin have stronger hardness, these resins being modified, which assign, applies layered low-surface energy and one
Fixed hard elastics, so as to improve the stain resistance of coating.
Using polycarbonate polyurethane as matrix resin, the hardness of polycarbonate and the soft bullet of polyurethane can be taken into account
Property, guarantee that coating has certain anti-scratch ability and certain scratch repair ability.Fluorine-carbon modified polycarbonate polyurethane
With low-surface-energy, guarantee the pollution resistance of coating.
Using the composition of polyfunctional group polyurethane acrylic resin as matrix resin, network knot is formed by crosslinking curing
Structure.It also may include four-functional group and/or three points five using six functional groups, trifunctional, two functional polyurethane acrylic resins
Functional polyurethane acrylic resin limits functional group's number more reasonablely and each function is reunited compared with traditional coating
The component content of urethane acrylate resin guarantees cross-linked network structure so as to control the crosslink density of cross-linked network structure
Coating have stronger hardness and flexibility, it is available to have both anti-pollution, anti-scratch, scratch self-repair function coating.
Further, since the elongation at break of the coating is up to 140% ~ 183%, tensile strength is up to 90N/25mm ~ 120N/
25mm, so that its anti-scratch aspect of performance is improved, and aqueous systems or body of light system can be used in coating, takes water as a solvent or not
Solvent is needed, it is more environmentally friendly.
The present invention also provides a kind of for producing the technique of anti-scratch anti-pollution TPU vehicle body protective film, can be made by the technique
The anti-scratch superior TPU body sticker of antifouling property is obtained, specific advantage is embodied in the following aspects:
(1) TPU membrane progress high-voltage electricity is pressed into processing, can be improved the activity on TPU membrane surface, so that it is attached on film to improve coating
Ability.
(2) web coatable, transfer coated and slit type extrusion coated belong to accurate coating, and coating weight is low, and coating is uniformly, full
Requirement of the foot to coating transparent, because low coating weight can make coating thin, the transparency is good, but requires the viscosity of coating paste
It is low, coating viscosity is controlled thus in the range of 300 ~ 400cps.
(3) optimize coating method, cylinder coating, using dimple roller, mesh number and depth meet this patent and be coated with to coating
Requirement.
(4) coating can be solidified in such a way that photocuring and heat cure combine, using heat cured system
The initiator of crosslinking agent and photocuring system is blended in coating paste, rationally controls the proportion of crosslinking agent and initiator, is guaranteed
Curing of coatings is thorough.Before this to curing of coatings in a manner of heat cure, high temperature is conducive to accelerate the levelling of coating, improves coating
Glossiness, after with photocuring to curing of coatings, the curing efficiency of photocuring is high, can overcome the disadvantages that heat cure is difficult thoroughly insufficient.
It (5), can be according to the demand of customer, in the back of TPU under the premise of the positive coated anti-scratch anti-pollution layer of TPU
Face applies and scrapes different pressure-sensitive glues, or has passed through after pressure-sensitive adhesive layer is bonded with release film in TPU, can according to the demand of customer,
In the coating of the front coating different function of TPU, it is also an option that covering protective layer or not covering protective layer, and covered not in cutting
Same protective layer can save raw material, cost by diversified process to meet the needs of different.
Specific embodiment
Embodiment one
A kind of anti-scratch anti-pollution TPU vehicle body protective film, including TPU film, pressure-sensitive adhesive layer and frosted PET release film, TPU film
Upper surface is equipped with anti-scratch anti-pollution layer, the composition of the anti-scratch anti-pollution layer are as follows:
75 parts of matrix resin polyester polyurethane；
10 parts of filler PMMA microballon；Partial size is 10 μm
4.5 parts of crosslinking agent aziridine；
1.5 parts of levelling agent acrylate
Aqueous solvent 20.0.
Processing step:
1) TPU membrane is subjected to high-voltage corona processing；
2) processing is dusted to TPU membrane；
3) anti-scratch anti-pollution layer, coating weight 10g/m are coated on the sided corona treatment face of TPU membrane by cylinder coating method2, apply
The viscosity of layer slurry is controlled in 300cps；
4) anti-scratch anti-pollution layer is solidified by hot-air seasoning mode, temperature control is 80 ~ 105 DEG C；
5) protective layer is pasted on anti-scratch anti-pollution layer after hardening；
6) the resulting TPU membrane of step 5) is bonded by pressure-sensitive adhesive layer with frosted PET release film；
7) it cuts, pack.
Coating have it is anti-scratch have an anti-pollution effect, it is anti-scratch functional, gently brushed using steel brush, scratch disappears in 12 seconds,
Three drop blue ink of drop can be wiped away by paper handkerchief in coating surface, not stay blue Polluted area.System aqueous, environmental protective.Coating
Elongation at break is 183%, tensile strength 120N/25mm.
Embodiment two
A kind of anti-scratch anti-pollution TPU vehicle body protective film, including TPU film, pressure-sensitive adhesive layer and wire drawing PET release film, TPU film
Upper surface is equipped with anti-scratch anti-pollution layer, the composition of the anti-scratch anti-pollution layer are as follows:
25 parts of matrix resin six functional groups polyurethane acrylic resin, 35 parts of trifunctional polyurethane acrylic resin and two officials
Can reunite 10 parts of urethane acrylate resin acrylic resin composition
8 parts of filler PMMA microballon
1.5 parts of filler-silicon dioxide
0.2 part of ketone of photoinitiator 1- hydroxy-cyclohexyl-phenyl
0.5 part of levelling agent acrylate
.5 parts of adhesion promoter phosphoesterase 30
Processing step:
1) two sides of TPU membrane is subjected to high-voltage corona processing；
2) TPU membrane is bonded by pressure-sensitive adhesive layer with wire drawing PET release film；
3) processing is dusted to TPU membrane obtained by step 2；
4) anti-scratch anti-pollution layer is coated in another sided corona treatment face of TPU membrane by transfer coated mode, coating weight 15g/m2,
The viscosity of coating paste is controlled in 300cps；
5) anti-scratch anti-pollution layer is solidified using photocuring mode, the wavelength of photocuring is 350nm;
6) the resulting TPU membrane of step 5) is cut, while pastes protective layer, packed.
Coating have it is anti-scratch have anti-pollution effect, gently brushed using steel brush, scratch disappears in 20 seconds, drop three drop blue inks applying
Layer surface, can be wiped away by paper handkerchief, not stay blue Polluted area.System does not have any solvent, environmental protection.It is disconnected when coating failure
Splitting elongation is 140%, tensile strength 90N/25mm.
Embodiment three
A kind of anti-scratch anti-pollution TPU vehicle body protective film, including TPU film, pressure-sensitive adhesive layer and frosted PET release film, TPU film
Upper surface is equipped with anti-scratch anti-pollution layer, the composition of the anti-scratch anti-pollution layer are as follows:
20 parts of matrix resin six functional groups polyurethane acrylic resin, three points five 20 parts of function reunion urethane acrylate resins, two
20 parts of functional polyurethane acrylic resin of 2.0 parts of acrylic acid resin composition crosslinking agent aziridine
Initiator 2,4,6(trimethylbenzoyl) 0.1 part of diphenyl phosphate oxidation
10 parts of filler PMMA microballon
3 parts of filler aluminum oxide
12 parts of diluent ethyl acetate
8 parts of diluent phthalic acid dimethyl ether
Processing step:
1) TPU membrane is subjected to high-voltage corona processing；
2) processing is dusted to TPU membrane；
3) anti-scratch anti-pollution layer, coating weight 12g/m are coated on the sided corona treatment face of TPU by web coatable2, coating paste
Viscosity control be 300cps；
4) anti-scratch anti-pollution layer is solidified by photocuring mode, the wavelength control of photocuring is 350nm；
5) again anti-scratch anti-pollution layer is continued to solidify by hot-air seasoning mode, the temperature control of hot-air seasoning is 80 ~ 105 DEG C；
6) the resulting TPU membrane of step 5) is bonded with frosted PET release film；
7) the resulting TPU membrane of step 6) is cut, while pastes protective layer on anti-scratch anti-pollution layer, packed.
In such a way that photocuring and hot wind solidification combine, guarantee that coating sufficiently solidifies, coating has anti-scratch antifouling property, adopts
It is gently brushed with steel brush, scratch disappears in 18 seconds, and three drop blue ink of drop can be wiped away by paper handkerchief in coating surface, not stay blue
Polluted area.Elongation at break when coating failure is 162%, tensile strength 110N/25mm.
Foregoing description has illustrated illustrating and describing for invention.It is not configured to limit the invention to disclosed
Form and mode.According to above mode, it can be modified or be changed accordingly.Discuss that example is to be better described
The principle of the present invention and the practicality, to be carry out various modifications using the present invention and meet other specific demands.It is all this
A little modifications and variations are interpreted when according to fair and legal right, and according to accessory claim, these modifications and variations are all
It is within the scope of the present invention.
Claims (10)
1. a kind of anti-scratch anti-pollution TPU vehicle body protective film, the glue-line including substrate layer and set on substrate layer lower part, it is characterised in that:
The substrate layer is TPU film, and the upper surface of TPU film is equipped with anti-scratch anti-pollution layer, the composition of the anti-scratch anti-pollution layer are as follows:
50 ~ 85 parts of matrix resin；
Initiator or/and 0.01 ~ 5 part of crosslinking agent；
5 ~ 50 parts of filler；
0 ~ 20 part of auxiliary agent；
0 ~ 30 part of solvent；
The filler includes autonomous assembling into the nano-high molecule microballon and silica of micro-nano cluster and/or three oxidations two
Aluminium；
The matrix resin is the composition of polyester polyurethane and/or acrylic resin；
Wherein polyester polyurethane be polycarbonate polyurethane or fluorine-carbon modified polyester polyurethane, the acrylic resin
Composition includes six functional groups polyurethane acrylic resin, trifunctional polyurethane acrylic resin and two functional polyurethanes third
Olefin(e) acid resin；
The initiator is that alpha-hydroxyalkyl benzophenone class initiator, α-amine alkylbenzene ketone initiator or acyl group phosphorus oxidation species cause
Agent；The crosslinking agent is aziridine, organosilicon cross-linking agent, epoxy silane coupling agent or multi-functional polycarbodiimide crosslinkers.
2. anti-scratch anti-pollution TPU vehicle body protective film as described in claim 1, it is characterised in that: the combination of the acrylic resin
Object further includes four-functional group polyurethane acrylic resin and/or three points five function reunion urethane acrylate resins.
3. anti-scratch anti-pollution TPU vehicle body protective film as described in claim 1, it is characterised in that: the auxiliary agent is levelling agent, film forming
One of auxiliary agent, adhesion promoter, defoaming agent are a variety of；The levelling agent is acrylate, polysiloxanes or Organic fluoride
One of alkane is a variety of, and the coalescing agent is alkoxide or alcohol ethers coalescing agent, and the adhesion promoter is phosphoric acid
Ester promotor, the defoaming agent are organic siliconresin.
4. anti-scratch anti-pollution TPU vehicle body protective film as described in claim 1, it is characterised in that: the solvent is water, acetic acid second
It is ester, toluene, dimethylbenzene, repefral, one or more in dipropylene glycol methyl ether.
5. a kind of production technology of anti-scratch anti-pollution TPU vehicle body protective film as described in claim 1, it is characterised in that: including following
Step:
1) TPU membrane is subjected to high-voltage corona processing；
2) by any one mode in web coatable, transfer coated, slit type extrusion coated in the sided corona treatment face of TPU membrane
The upper anti-scratch anti-pollution layer of coating, coating weight are 10 ~ 20g/m2, the viscosity control of coating is in 300 ~ 400cps；
3) it is combined by any one mode or both in hot-air seasoning, photocuring and anti-scratch anti-pollution layer is solidified, institute
The temperature control for stating hot-air seasoning is 80 ~ 105 DEG C, a length of 340 ~ 370nm of the light wave of the photocuring；
4) TPU membrane containing anti-scratch anti-pollution layer cut, packed
In the step 2, the coating of the web coatable, specially cylinder, is use diameter for 45 ~ 55mm, mesh number for 50 ~
60, depth is that anti-scratch anti-pollution layer is applied in TPU membrane by 100 ~ 300 μm of dimple roller.
6. the production technology of anti-scratch anti-pollution TPU vehicle body protective film as claimed in claim 5, it is characterized in that: in above-mentioned steps 1)
Before, first TPU membrane is bonded by pressure-sensitive adhesive layer with release film.
7. the production technology of anti-scratch anti-pollution TPU vehicle body protective film as claimed in claim 5, it is characterized in that: in above-mentioned steps 3)
Later, first TPU membrane is bonded by pressure-sensitive adhesive layer with release film, then carries out above-mentioned steps 4).
8. the production technology of the anti-scratch anti-pollution TPU vehicle body protective film as described in any one of claim 5 ~ 7, it is characterized in that:
In above-mentioned steps 3) after, protective layer is pasted on anti-scratch anti-pollution layer, then carry out step 4).
9. the production technology of the anti-scratch anti-pollution TPU vehicle body protective film as described in any one of claim 5 ~ 7, it is characterized in that:
Carry out above-mentioned steps 4) in cutting while, paste protective layer on anti-scratch anti-pollution layer.
10. the production technology of anti-scratch anti-pollution TPU vehicle body protective film as claimed in claim 7, it is characterized in that: pass through in TPU membrane
After pressure-sensitive adhesive layer is bonded with release film, protective layer is first pasted on anti-scratch anti-pollution layer, then carry out step 4).
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