CN109536058A - A kind of wear-resistant protection film and the article protected using the film - Google Patents
A kind of wear-resistant protection film and the article protected using the film Download PDFInfo
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- CN109536058A CN109536058A CN201710671721.9A CN201710671721A CN109536058A CN 109536058 A CN109536058 A CN 109536058A CN 201710671721 A CN201710671721 A CN 201710671721A CN 109536058 A CN109536058 A CN 109536058A
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- protective film
- polyurethane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2427/00—Presence of halogenated polymer
- C09J2427/006—Presence of halogenated polymer in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of protective film, including layer of polyurethane, wherein under the test condition of 1Hz frequency, the storage modulus of the layer of polyurethane within the scope of 25~2000MPa, and the layer of polyurethane with a thickness of 12~55 microns；And according to GB/T1768 standard, use CS-17 grinding wheel with 750g loading with the revolving speed of 67r/min when rotation 1000 rotates into row wearability test on the protective film, the wear weight loss of the protective film is not more than 100mg.The present invention also provides the method for preparing protective film and use the article of protective film.
Description
Technical field
The present invention relates to a kind of protective films, more particularly to wear-resisting protective film.The invention further relates to use the protective film
The article of protection.
Background technique
With the improvement of living standards, people are bought and increased considerably using the quantity of automobile, and people are for automobile
The requirement of maintenance is also higher and higher.In order to make love vehicle bright as new always, people mention frequently with modes such as waxing, envelope glaze, plated films
The lacquer painting brightness of high vehicle body reduces lacquer painting damage.However, these method effects are all not obvious generally also not lasting enough enough, especially
Being can be ineffective quickly after multiple carwash, nor can assign lacquer painting wearability well.Carwash itself can not
The lacquer painting of automobile is caused to wear with avoiding, automobile also occurs that automobile case scratch phenomenon in driving procedure, on the way high speed
When driving also due to the collision friction of sand particles and lacquer painting is come to harm, park occasion sometimes also and can occur by people therefore
Meaning scratches the destruction of automobile.The modes such as waxing, envelope glaze, plated film not can be well solved these problems.These problems one
Denier occurs, and can all influence the beauty of automobile entirety, repairs also troublesome, it is necessary to it is a series of time-consuming to carry out spray painting processing etc.
Expensive process could be restored.
In order to solve problem above, it is developed body paint surface protective film.This body paint surface protective film passes through high score
Sub- polymeric material is attached at surface of vehicle paint, achievees the purpose that the former paint of protection, decoration vehicle body, and can remove easily at any time, has just
In construction, flexibility, durability, the resistance to chemical corrosion many advantages, such as, thus the former paint for the vehicle that adequately protects.However, existing
Automobile painting surface protective film itself it is not wear-resisting enough and easy scuffing, slighter collision can all make the surface damage of protective film, shadow
Ring its appearance and use.
Therefore, it is necessary to develop a kind of more wear-resisting protective film, can be used to protect the vehicle body lacquer painting of automobile, avoid or
The abrasion and/or scratch of lacquer painting are reduced, and is convenient for surface cleaning.More advantageously, it is desirable to which car body coating can be replaced by developing one kind
Protective film, to reduce the use of volatile organic compounds, so that the manufacture and maintenance of automobile are more environmentally-friendly, conveniently.
Summary of the invention
It is surprisingly found by the inventors that by using the protective film containing layer of polyurethane and by the storage modulus of layer of polyurethane
It is controlled in particular range respectively with thickness, it is available with protection film for automobile that is good wear-resistant and/or scratching.
In one aspect, the present invention provides a kind of protective film, including layer of polyurethane, wherein in the test condition of 1Hz frequency
Under, the storage modulus of the layer of polyurethane is within the scope of 25~2000MPa, and the layer of polyurethane is micro- with a thickness of 12~55
Rice；And according to GB/T1768 standard, use CS-17 grinding wheel with 750g loading with the revolving speed of 67r/min in the protective film
When upper rotation 1000 rotates into row wearability test, the wear weight loss of the protective film is not more than 100mg.
On the other hand, the present invention provides a kind of article, including substrate and protective film with surface, the protective film
It is covered on the surface of the substrate.
By the present invention in that being provided a kind of with improvement with the layer of polyurethane with storage modulus and thickness specific combination
Wear-resisting property protective film.
Specific embodiment
Numberical range herein includes using a unit from lower value to high value as increment and including described lower
All values of value and the high value.For example, should be considered as will be all individual if numberical range is 100 to 500
Value such as 100,101,102 ... 498,499 and 500 is listed one by one, also should be considered as listing all subranges such as 100 to
144,155 to 170,197 to 200,268 to 390,420 to 500 etc..
Protective film
Protective film of the invention includes the layer of polyurethane with specific storage modulus and thickness, wherein in the survey of 1Hz frequency
Under the conditions of examination, the storage modulus of the layer of polyurethane within the scope of 25~2000MPa, and the layer of polyurethane with a thickness of 12~
55 microns；And according to GB/T1768 standard, use CS-17 grinding wheel with 750g loading with the revolving speed of 67r/min in the guarantor
When rotation 1000 rotates into row wearability test on cuticula, the wear weight loss of the protective film is not more than 100mg.
In a preferred embodiment, according to GB/T1768 standard, use CS-17 grinding wheel with 750g loading with 67r/
When rotation 1000 rotates into row wearability test on the protective film, the wear weight loss of the protective film is not more than the revolving speed of min
75mg, preferably no greater than 25mg, more preferably no more than 15mg.
Come according to the present invention it is possible to be adjusted combination to the storage modulus of layer of polyurethane and thickness in appropriate range
Reach desired better effect.In a specific embodiment, under the test condition of 1Hz frequency, the polyurethane
Layer storage modulus within the scope of 25~1000MPa, and the layer of polyurethane with a thickness of 12~55 microns, preferably 20~55 is micro-
Rice, more preferable 20~40 microns.In another specific embodiment, under the test condition of 1Hz frequency, the layer of polyurethane
Storage modulus within the scope of 1000~2000MPa, and the layer of polyurethane with a thickness of 25~45 microns.It is specific at another
In embodiment, under the test condition of 1Hz frequency, the storage modulus of the layer of polyurethane within the scope of 1500~2000MPa,
And the layer of polyurethane with a thickness of 20~40 microns.
According to the present invention, the layer of polyurethane can be used alone, and can also use with other materials or substrate combination.
In one embodiment, protective film of the invention further includes the gluing oxidant layer laminated with the layer of polyurethane.
In another embodiment, protective film of the invention further includes the basal layer laminated with the layer of polyurethane.It is excellent
Selection of land, protective film of the invention further include polymeric substrate layers and optional gluing oxidant layer, and the polymeric substrate layers include the
One surface and the second surface opposite with the first surface, the layer of polyurethane are attached to the first of the polymeric substrate layers
On surface, the optional gluing oxidant layer is attached on the second surface of the polymeric substrate layers.
It can according to need and use any suitable polymeric substrate layers.Polymeric substrate layers can provide more for protective film
Good mechanical support effect can also provide some additional benefits, such as impact resistance, sound insulation, heat-insulated, insulation, decoration etc..
For example, being suitable for the invention polymeric substrate layers may include one of following material or a variety of or by following material
One or more compositions: polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polymethyl acrylate, poly-vinegar
Vinyl acetate, polyethylene terephthalate, polyurethane and combinations thereof.In a preferred embodiment, the polymer
Basal layer is polyvinyl chloride layer.
The thickness of polymeric substrate layers, which can according to need, to be determined.In one embodiment, the polymer matrix
Bottom with a thickness of 10~200 microns, preferably 15~150 microns, more preferable 25~100 microns, even more preferably 50~80 is micro-
Rice.
In the present invention, the layer of polyurethane is preferably dual-component polyurethane layer.In a preferred embodiment, described
Layer of polyurethane includes to be selected from one of polyester based polyurethanes, polycarbonate-based polyurethane, polyether based polyurethanes or a variety of.It is preferred that
Ground, the layer of polyurethane are at least partly crosslinked, such as at least 5%, preferably at least 10%, more preferably at least 15%
Crosslink density.Crosslink density can be by that will have the weight of the reactive component of three or more degrees of functionality divided by polyurethane
Total weight is calculated multiplied by 100 (with reference to WO2015/175911).
In certain embodiments, the layer of polyurethane is the reaction product of polyalcohol and polyisocyanates.In some realities
It applies in scheme, the polyalcohol is aliphatic polyol.In some embodiments, the polyisocyanates is preferably aliphatic
Polyisocyanates.In some preferred embodiments, the layer of polyurethane is the pure and mild aliphatic polyisocyante of aliphatic polybasic
Reaction product.
The example of suitable polyalcohol includes can be with trade name DESMOPHEN from city, Pittsburgh, Pennsylvania
The commercially available material of the Bayer company of (Pittsburgh, PA).Polyalcohol can be polyester polyol (such as DESMOPHEN
631A, 650A, 651A, 670A, 680,110 and 1150；XCP-35EBD, the XCP-1000NB of Suzhou Xu Chuan Chemical Co., Ltd.,
XCP-2000NB, XCP-500, XCP-2000, XCP-2325, XCP-1500NH), polyether polyol (such as DESMOPHEN
550U, 1600U, 1900U and 1950U), polycarbonate polyol (such as can be with trade name PC-1122, PC-1167 and PC-
1733 derive from the Picassian Polymers of Massachusetts classic city (Boston, MA) or with trade name DESMOPHEN
2020E derives from those of Bayer company polycarbonate polyol) and their combination.Reactive (such as-OH) degree of functionality
The selection of degree (such as difunctionality) will usually be selected according to the required crosslinking degree of gained polyurethane.
The example of suitable polyisocyanates includes the aliphatic polyisocyante based on hexamethylene diisocyanate, example
It such as, but not limited to, can be with trade name MONDUR or DESMODUR (such as DESMODUR N3800, DESMODUR N75, DESMODUR
N3390 and DESMODUR 3400) it is commercially available from the Bayer company of city, Pittsburgh, Pennsyivania (Pittsburgh, PA)
Polyisocyanates and their any combination.
Catalyst can be used to promote the reaction between polyalcohol and polyisocyanates.It is suitable for the invention catalyst
Including but not limited to aluminium, bismuth, tin, vanadium, zinc or Zirconium-base catalyst.Particularly preferred tin-based catalyst, because tin-based catalyst can be bright
It is aobvious to reduce the amount to deaerate in polyurethane.In one embodiment, the catalyst is dibutyltin compound, such as but unlimited
In dibutyltin diacetate, dibutyl tin dilaurate, diacetyl acetonation dibutyl tin, two dibutyltin mercaptides, two octanoic acids
Dibutyl tin, two dibutyitin maleates, acetonyl acetonation dibutyl tin and dibutyltin oxide.The dosage of catalyst can
To be determined as needed by those skilled in the art.
The type of polyalcohol, hydroxy functionality, molecular weight and the type of isocyanates, isocyanate functionality, polymerization
Type, the degree of cross linking of body are likely to influence the storage modulus of layer of polyurethane.Change the chemical structure of isocyanates, such as will be different
The linear fraction (HDI) of cyanate changes into alicyclic structure (IPDI), so that it may since increase layer of polyurethane storage modulus.This
It outside, can also be by adjusting the ratio containing different structure isocyanate chemical structure, to adjust the storage modulus of layer of polyurethane.
The storage modulus of layer of polyurethane can also be changed by changing the degree of polymerization.Those skilled in the art can be in conjunction with the normal of this field
Know storage modulus required for obtaining by suitable means.
In the present invention, gluing oxidant layer can be used to so that protective film with protected object body convenient for combining, and optionally
Enhance the impact resistance of film and/or assigns some possible additional benefits.Gluing suitable for protective film according to the present invention
Agent includes but is not limited to one of acrylic tackifier, rubber based adhesives, organic silicon adhesive or a variety of.
In some embodiments, the gluing oxidant layer may include pressure-sensitive adhesive and/or non-depressed sensitive adhesive.At this
Wen Zhong, " pressure-sensitive adhesive ", which refers to only, has permanent and aggressive tack adhesive to various substrates after applying slight pressure.
It has bonding, cohesion, four aspect comprehensive performances of stretching and elasticity, its use in generally room temperature (i.e. about 20-30 DEG C)
At a temperature of be usually viscosity.Pressure-sensitive adhesive generally also has the opening time viscosity (open by day, usually in terms of the moon or year
Time tack) (i.e. adhesive is the sticky time at room temperature).A kind of quantitative description of the approval of pair of pressure-sensitive adhesive by
(referring to pressure-sensitive adhesive technical manual, the second edition, D.Satas is edited Dahlquist criterion line, Van Nostrand
Reinhold, New York, NY, 1989,171-176 pages) it provides, it points out that storage modulus is less than about 3 × 105Pascal (
With the measurement of 10 radian per seconds at a temperature of about 20-22 DEG C) material generally there is pressure-sensitive adhesive performance, and storage modulus is more than
The material of this value does not have pressure-sensitive adhesive performance generally.Herein, " non-depressed sensitive adhesive " refers in the molten state not
Non-adhesive polymer material and adhesive polymer material with pressure-sensitive, or there is adhesiveness at room temperature but be unsatisfactory for
The other materials of above-mentioned Dahlquist criterion.The storage modulus of this material at least about 3 × 105Pascal is (at about 20-22 DEG C
At room temperature with 10 radian per seconds measurement).These materials can be elasticity or stiff non-tacky thermoplastic's material.Alternatively, it
Can be inviscid elastomer.
Example especially suitable for adhesive of the invention such as acrylic tackifier includes but is not limited to alkyl acrylate
Base ester (such as n-butyl acrylate, 2-EHA, ethyl acrylate, Isooctyl acrylate monomer) and acrylic acid or alkyl
The copolymer of vinyl acetate (such as vinyl acetate, vinyl propionate, vinyl butyrate, isooctyl acid vinyl acetate), particularly preferred third
Olefin(e) acid 2- ethylhexyl or ethyl acrylate and vinyl acetate or vinyl propionate copolymer, most preferably acrylic acid 2- ethyl hexyl
Ester and vinyl propionate copolymer.The example of rubber based adhesives include but is not limited to butadiene-styrene rubber, polyisoprene rubber,
One of polyisobutene and butyl rubber, neoprene and nitrile rubber or it is a variety of based on resin adhesive, it is especially excellent
Choosing with one of butadiene-styrene rubber, polyisoprene rubber and polyisobutene or it is a variety of based on resin adhesive, most preferably
The adhesive of resin based on butadiene-styrene rubber.The example of organic silicon adhesive includes but is not limited to that the end of polymer chain includes
The high molecular weight dimethyl silicone polymer or polydimethyldiphenylsiloxane of residual silane alcohol functionalities (SiOH), or comprising poly-
The block copolymer of two organosiloxane soft segments and the hard section of urea sealing end.
In one embodiment, the gluing oxidant layer with a thickness of 5~100 microns, preferably 10~70 microns, most preferably
20~50 microns.
Protective film of the invention can further include release layer, the gluing in the case where including gluing oxidant layer
Oxidant layer can be attached on the release layer.
The preparation method of protective film
The preparation method of protective film of the present invention is not particularly limited.For example, applicable method may include:
Layer of polyurethane is provided, wherein under the test condition of 1Hz frequency, the storage modulus of the layer of polyurethane 25~
Within the scope of 2000MPa, and the layer of polyurethane with a thickness of 12~55 microns；And according to GB/T1768 standard, using CS-17
Number grinding wheel with 750g loading with the revolving speed of 67r/min when rotation 1000 rotates into row wearability test on the protective film, it is described
The wear weight loss of protective film is not more than 100mg.
In one embodiment, the method also includes the attachment glues on a surface of the layer of polyurethane
Layer.
In an alternative embodiment, the method also includes:
There is provided polymeric substrate layers, the polymeric substrate layers include first surface and opposite with the first surface the
Two surfaces；
Adhere to the layer of polyurethane on the first surface of the polymeric substrate layers；
The attachment glue layer optionally on the second surface of the polymeric substrate layers.
Layer of polyurethane can be used conventional method and be formed, such as by way of solution coating or other possible sides
Formula is formed.Polyurethane solutions can be applied directly in polymeric substrate layers, or can be coated to smooth surface
To obtain the polyurethane film or sheet material of self-supporting on releasable carrier (such as release film), then again with polymeric substrate layers into
Row is laminated.Can be used conventional equipment well known by persons skilled in the art for example knife type coater, roll coater, inverse roll coater,
Notched bar coaters, curtain coater, roto-gravure coaters, rotary printing machines etc. carry out solution coating.In a preferred embodiment
In, the layer of polyurethane is formed and/or is attached to by way of solution coating on the first surface of the polymeric substrate layers.
In the present invention, polymeric substrate layers can be preformed or commercially available finished film, be also possible to
The casting films that scene is formed by way of solution or melt coating or the blown film formed by extrusion-blown modling.
In the present invention, gluing oxidant layer can be used conventional method and form and/or be attached to the layer of polyurethane or institute
It states on the second surface of polymeric substrate layers.For example, the gluing oxidant layer can be by way of solution coating or other sides
Formula is formed directly on the layer of polyurethane or the second surface of the polymeric substrate layers, or be can be and be coated to light
On the releasable carrier (such as release film or release paper) on sliding surface then again with the layer of polyurethane or the polymeric substrates
The second surface of layer is laminated, or is also possible to preformed so as to being directly covered in the layer of polyurethane or described poly-
On the second surface of polymer substrates layer.In a preferred embodiment, gluing oxidant layer shape by way of solution coating
At on the layer of polyurethane or the second surface of the polymeric substrate layers.In a further preferred embodiment, the glue
Adhesive layer is coated in the releasable carrier with smooth surface (such as release film or release paper), then again with the polyurethane
Layer or the second surface of the polymeric substrate layers are laminated.Conventional equipment well known by persons skilled in the art such as scraper can be used
Coating machine, roll coater, inverse roll coater, notched bar coaters, curtain coater, roto-gravure coaters, rotary printing machines etc. carry out
The solution coating of adhesive.
Use the article of protective film
The present invention also provides a kind of articles comprising substrate and protective film according to the present invention with surface, the guarantor
Cuticula is covered on the surface of the substrate.
In one embodiment, the substrate is selected from one of metal, plastics, glass, ceramics or a variety of.
In one embodiment, the substrate has painted surface, and the protective film is covered on the substrate
On painted surface.
Protective film of the invention be particularly suitable for protect the vehicles for example automobile, bullet train, urban track traffic,
The car body and vehicle window of aircraft, water carrier etc..
Protective film of the invention can be sized and certain shapes, to comply with the table of vehicle body part
Face, the vehicle body part have need surface to be protected, such as painted surface and glass surface.
Embodiment
Certain specific embodiments of the invention are explained below with reference to embodiment, so that this field skill
Art personnel are more clearly understood that technical solution of the present invention and its advantage, but are not formed in any way to limit of the invention
System.Unless specifically stated otherwise, the ratio in the present invention, number, content are by weight.
Used material is described as follows in embodiment:
1. the preparation of protective film
The preparation of 1.1 dual-component polyurethane solution
1) preparation of component solution A:
It takes 0.494kg propylene glycol monomethyl ether acetate, 0.527kg butanone to be added in 5L barrels respectively, 0.15kg is added later
CAB 381.01 is stirred to powder and is completely dissolved, and 0.4kg XCP-1000NB, 0.4kg XCP-500N and 0.4kg is then added
CAPA-3031 is stirred evenly, spare as component A.
2) preparation of bi-component polyurethane ester solution:
It takes component A 10g and polyisocyanate curing agent several respectively, and two laurels of the 126ppm in terms of solid part is added
Sour dibutyl tin is stirred evenly as catalyst, is configured to coating solution.Kind based on used polyisocyanate curing agent
Class and dosage difference, obtain solution 1-10, as shown in table 1.
1 bi-component polyurethane ester solution of table
1.2 coating process
First of coating:
By dual-component polyurethane solution by scraper for coating method, control different gap is adjusted, is coated on poly- with backing
In the air surface of vinyl chloride film (6650FC comes from 3M), 25~55 μm of thickness of dry film is formed, drying temperature condition is set as 40
DEG C, 80 DEG C, 100 DEG C, 130 DEG C, the linear velocity of coating apparatus is 1.5m/min.
Backing is torn, exposes the polychloroethylene film in backing face, 200mJ/cm is carried out to it2Sided corona treatment, obtain part
A。
Second coating:
Acrylic adhesive solution (with CSA3050 partial cross-linked solution as main component, coming from 3M) is passed through into scraper
Rubbing method is coated in the layer upper surface of release paper with 25~30 μm of dry film of thickness, obtains part B.
It is laminated:
The corona treated surface of part A is contacted with the surface opposite with release paper of part B, and passes through press equipment
(Rollscroller flatbed laminator) makes part A and part B be laminated together to form protection with the laminating pressure of 75psi
Film.Referring specifically to the protective film embodiment 1-15 in table 4.
2. performance test
The test of 2.1 storage modulus:
It is coated with bi-component polyurethane ester solution to be tested in release paper with scraper for coating method, about 60 μm of wet-film thickness, it
It is dried 5 minutes at 120 DEG C afterwards.40-50 μm of thickness of dry film.Dry film is taken off from release paper when test, be cut into length 10~
The batten of 17mm, width 5.45mm, thickness vernier caliper measurement.Storage modulus survey is carried out on DMA Q800 (TA Co.)
Examination, test condition are as follows: 5 DEG C/min of heating rate, 1 hertz of frequency.
By the film 1-10 being coated with of the bi-component polyurethane ester solution 1-10 in table 1 crosslink density and storage modulus such as
Shown in table 2, middle crosslink density, which passes through, will have the weight of the reactive component of three or more degrees of functionality divided by polyurethane
Total weight is calculated multiplied by 100 (with reference to WO2015/175911).
The crosslink density and storage modulus of 2 two component polyurethane solution coating of table
| Number | Crosslink density (%) | Storage modulus (MPa) |
| Film 1 | 65 | 78.9 |
| Film 2 | 69 | 407.0 |
| Film 3 | 64 | 446.9 |
| Film 4 | 64 | 641.6 |
| Film 5 | 65 | 781.7 |
| Film 6 | 65 | 923.1 |
| Film 7 | 66 | 1159.0 |
| Film 8 | 67 | 1608.0 |
| Film 9 | 68 | 2344.0 |
| Film 10 | 69 | 29.93 |
As previously mentioned, the type of many factors such as polyalcohol, the kind of hydroxy functionality, molecular weight and isocyanates
All there may be shadows for the storage modulus of class, isocyanate functionality, polymeric type, the degree of cross linking to the resulting polyurethane of coating
It rings.Such as the chemical structure by changing isocyanates, as the linear fraction (HDI) of isocyanates changes into alicyclic structure
(IPDI), the storage modulus of polyurethane coating film can be increased.The isocyanates as used in solution 2 be HDI trimer (N75), be by
The hexamethylene diisocyanate of straight chain is polymerized, and the storage modulus of gained polyurethane coating film 2 is 407MPa；And 3 institute of solution
It is different by the isophorone two containing saturation hexatomic ring with the IPDI tripolymer (Z4470) of fraction is contained in isocyanates
Cyanate is polymerized, even if the total amount of isocyanates is less than the amount of isocyanates used in solution 2, gained polyurethane coating film 3
Storage modulus still increase to 446.9MPa.Furthermore, it is possible to by adjusting the ratio containing different chemical structures isocyanates,
The storage modulus of polyurethane coating film is adjusted, such as solution 5-9, by being stepped up the ratio of Z4470, polyurethane coating film 5-9's
Storage modulus increases to 2344MPa by 781.7MPa.
2.2 wearability test
According to GB/T1768 standard, using JM-IV type abrasion instrument (Shanghai Modern Environmental Engineering Technology Co., Ltd.'s manufacture),
CS17# grinding wheel is chosen, using 750g loading, sets 1000 turns, wearability test is carried out to sample with 67rpm revolving speed.It surveys later
Weightlessness before examination mill after mill: Δ W (mg)=W0 (before mill, mg)-W1 (after mill, mg), and judged according to following standard:
3 wear weight loss of table and evaluating abrasion resistance grade
| Grade | Weightless Δ W (mg) | Wearability |
| I | <25 | It is fabulous |
| II | >=25 and<75 | It is good |
| III | >=75 and≤100 | It is acceptable |
| IV | >100 | Difference, it is unacceptable |
Table 4 lists the protective film and its evaluating abrasion resistance obtained by the dual-component polyurethane solution coating in table 1.
The evaluating abrasion resistance of 4 protective film of table
*: using ProGage Electronic Thickness thickness gauge, 6 points are randomly selected on sample, are surveyed
Amount reads mean value.
As can be seen from Table 4, when the storage modulus of layer of polyurethane in protective film is in 25~2000MPa, layer of polyurethane
Thickness is in 12~55 μm, available wearability acceptable protective film.When the energy storage mould of layer of polyurethane in protective film
When amount is higher than 2000MPa, the brittleness of film increases, and fails to obtain the protective film with acceptable wearability.When poly- in protective film
When the thickness of urethane layer is less than 12 μm, also fail to obtain the protective film with acceptable wearability.
In conclusion the present invention provides at least following implementation:
1. a kind of protective film, including layer of polyurethane, wherein under the test condition of 1Hz frequency, the storage of the layer of polyurethane
Can modulus within the scope of 25~2000MPa, and the layer of polyurethane with a thickness of 12~55 microns；And it is marked according to GB/T1768
Standard is used CS-17 grinding wheel to be rotated 1000 on the protective film with the revolving speed of 67r/min with 750g loading and rotates into row wearability
When test, the wear weight loss of the protective film is not more than 100mg.
2. according to protective film described in item 1, wherein under the test condition of 1Hz frequency, the energy storage mould of the layer of polyurethane
Amount within the scope of 25~1000MPa, and the layer of polyurethane with a thickness of 20~55 microns.
3. according to protective film described in item 1, wherein under the test condition of 1Hz frequency, the energy storage mould of the layer of polyurethane
Amount within the scope of 1000~2000MPa, and the layer of polyurethane with a thickness of 25~45 microns.
4. the protective film according to any one of item 1-3, wherein according to GB/T1768 standard, using CS-17 grinding wheel
With 750g loading with the revolving speed of 67r/min on the protective film rotation 1000 rotate into row wearability test when, the protective film
Wear weight loss be not more than 75mg.
5. the protective film according to any one of item 1-4, wherein according to GB/T1768 standard, using CS-17 grinding wheel
With 750g loading with the revolving speed of 67r/min on the protective film rotation 1000 rotate into row wearability test when, the protective film
Wear weight loss be not more than 25mg.
6. the protective film according to any one of item 1-5 further includes the gluing oxidant layer laminated with the layer of polyurethane.
It further include polymeric substrate layers and optional gluing oxidant layer 7. the protective film according to any one of item 1-6,
The polymeric substrate layers include first surface and the second surface opposite with the first surface, and the layer of polyurethane is attached to
On the first surface of the polymeric substrate layers, the optional gluing oxidant layer is attached to the second table of the polymeric substrate layers
On face.
8. according to protective film described in item 7, wherein the polymeric substrate layers include or by one of following material or
A variety of compositions: polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polymethyl acrylate, polyvinyl acetate
Ester, polyethylene terephthalate, polyurethane.
9. according to protective film described in item 7, wherein the polymeric substrate layers are polyvinyl chloride layers.
10. the protective film according to any one of item 7-9, wherein the polymeric substrate layers with a thickness of 25~100
Micron.
11. the protective film according to any one of item 1-10, wherein the layer of polyurethane is dual-component polyurethane layer, packet
Containing selected from one of polyester based polyurethanes, polycarbonate-based polyurethane, polyether based polyurethanes or a variety of.
12. the protective film according to any one of item 1-11, wherein the layer of polyurethane is the pure and mild rouge of aliphatic polybasic
The reaction product of fat race polyisocyanates.
13. the protective film according to any one of item 1-12, wherein the layer of polyurethane is by way of solution coating
It is formed.
14. a kind of article, including the substrate with surface and the protective film according to any one of item 1-13, the guarantor
Cuticula is covered on the surface of the substrate.
15. according to article described in item 14, wherein the substrate be selected from one of metal, plastics, glass, ceramics or
It is a variety of.
16. wherein the substrate has painted surface, and the protective film is covered on institute according to the article of item 14 or 15
It states on the painted surface of substrate.
Claims (16)
1. a kind of protective film, including layer of polyurethane, wherein under the test condition of 1Hz frequency, the energy storage mould of the layer of polyurethane
Amount within the scope of 25~2000MPa, and the layer of polyurethane with a thickness of 12~55 microns；And according to GB/T1768 standard,
It uses CS-17 grinding wheel to rotate 1000 on the protective film with the revolving speed of 67r/min with 750g loading and rotates into the survey of row wearability
When examination, the wear weight loss of the protective film is not more than 100mg.
2. protective film according to claim 1, wherein under the test condition of 1Hz frequency, the energy storage of the layer of polyurethane
Modulus within the scope of 25~1000MPa, and the layer of polyurethane with a thickness of 20~55 microns.
3. protective film according to claim 1, wherein under the test condition of 1Hz frequency, the energy storage of the layer of polyurethane
Modulus within the scope of 1000~2000MPa, and the layer of polyurethane with a thickness of 25~45 microns.
4. protective film according to any one of claim 1-3, wherein according to GB/T1768 standard, using CS-17 sand
The protection with the revolving speed of 67r/min when rotation 1000 rotates into row wearability test on the protective film is taken turns with 750g loading
The wear weight loss of film is not more than 75mg.
5. protective film according to any one of claim 1-3, wherein according to GB/T1768 standard, using CS-17 sand
The protection with the revolving speed of 67r/min when rotation 1000 rotates into row wearability test on the protective film is taken turns with 750g loading
The wear weight loss of film is not more than 25mg.
6. protective film according to any one of claim 1-3 further includes the adhesive laminated with the layer of polyurethane
Layer.
7. protective film according to any one of claim 1-3 further includes polymeric substrate layers and optional adhesive
Layer, the polymeric substrate layers include first surface and the second surface opposite with the first surface, and the layer of polyurethane is attached
On the first surface of the polymeric substrate layers, the optional gluing oxidant layer is attached to the of the polymeric substrate layers
On two surfaces.
8. protective film according to claim 7, wherein the polymeric substrate layers include or by one of following material
Or a variety of compositions: polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polymethyl acrylate, poly-vinegar acid second
Enester, polyethylene terephthalate, polyurethane.
9. protective film according to claim 7, wherein the polymeric substrate layers are polyvinyl chloride layers.
10. protective film according to claim 7, wherein the polymeric substrate layers with a thickness of 25~100 microns.
11. protective film according to any one of claim 1-3, wherein the layer of polyurethane is dual-component polyurethane layer,
Comprising selected from one of polyester based polyurethanes, polycarbonate-based polyurethane, polyether based polyurethanes or a variety of.
12. protective film according to any one of claim 1-3, wherein the layer of polyurethane is the pure and mild rouge of aliphatic polybasic
The reaction product of fat race polyisocyanates.
13. protective film according to any one of claim 1-3, wherein the layer of polyurethane is by way of solution coating
It is formed.
14. a kind of article, described including substrate and protective film according to claim 1 to 13 with surface
Protective film is covered on the surface of the substrate.
15. article according to claim 14, wherein the substrate is selected from one of metal, plastics, glass, ceramics
Or it is a variety of.
16. 4 or 15 article according to claim 1, wherein the substrate has painted surface, and the protective film is covered on
On the painted surface of the substrate.
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| CN201710671721.9A CN109536058A (en) | 2017-08-08 | 2017-08-08 | A kind of wear-resistant protection film and the article protected using the film |
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| CN201710671721.9A CN109536058A (en) | 2017-08-08 | 2017-08-08 | A kind of wear-resistant protection film and the article protected using the film |
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ID=65827765
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111844998A (en) * | 2020-08-18 | 2020-10-30 | 江苏吉腾新材料科技有限公司 | Antistatic release film |
| CN112795325A (en) * | 2020-12-31 | 2021-05-14 | 中科院长春应化所黄埔先进材料研究院 | Wear-resisting resistant stealthy car clothing that deforms |
| CN113801593A (en) * | 2020-06-12 | 2021-12-17 | 苏州高泰电子技术股份有限公司 | Single-sided protective film adhesive tape and preparation method and application thereof |
| CN113978402A (en) * | 2020-07-27 | 2022-01-28 | 和美汽车零部件青县有限公司 | Protective film for vehicle body |
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| CN106103526A (en) * | 2014-03-26 | 2016-11-09 | 3M创新有限公司 | Urethane composition, film and method thereof |
| TW201712056A (en) * | 2015-09-28 | 2017-04-01 | Teikoku Printing Inks Mfg Co Ltd | Crosslinked coating film having scratch resistance and flexibility, and resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104768997A (en) * | 2012-11-08 | 2015-07-08 | 沙特基础全球技术有限公司 | Methods of making polyurethane coated articles, and articles made therefrom |
| CN106103526A (en) * | 2014-03-26 | 2016-11-09 | 3M创新有限公司 | Urethane composition, film and method thereof |
| TW201712056A (en) * | 2015-09-28 | 2017-04-01 | Teikoku Printing Inks Mfg Co Ltd | Crosslinked coating film having scratch resistance and flexibility, and resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113801593A (en) * | 2020-06-12 | 2021-12-17 | 苏州高泰电子技术股份有限公司 | Single-sided protective film adhesive tape and preparation method and application thereof |
| CN113978402A (en) * | 2020-07-27 | 2022-01-28 | 和美汽车零部件青县有限公司 | Protective film for vehicle body |
| CN111844998A (en) * | 2020-08-18 | 2020-10-30 | 江苏吉腾新材料科技有限公司 | Antistatic release film |
| CN112795325A (en) * | 2020-12-31 | 2021-05-14 | 中科院长春应化所黄埔先进材料研究院 | Wear-resisting resistant stealthy car clothing that deforms |
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