CN1942512A - Barrier layer to prevent the loss of additives in an underlying layer - Google Patents

Abstract

The present invention provides a protected layered system for a component assembly. The protected layered system includes a plastic panel and at least two protective layers formed integrally with the plastic panel. One protective layer is configured as a barrier layer that reduces the loss of an additive suspended, and not covalently bonded, in the structure of any underlying protective layer or the plastic panel. The weathering performance exhibited by the component assembly is similar for various colored or tinted plastic panels or protective layers.

Description

Be used to prevent the sealing coat of the additive losses of lower floor

Technical field

The present invention relates to a kind of sealing coat of additive losses of lower floor of the plastic plate that prevents to be used for automobile assembling assembly (component assembly).

Background of the present invention

Plastics are used to make many trolley parts and element at present as polycarbonate (PC) and polymethylmethacrylate (PMMA), as the B-post, and head lamp, and skylight.The automotive window assembly has represented these plastics because of various advantages and in styleization/design, weight savings, and a purposes that is just occurring in security/security fields.More specifically, plastics provide by functional element is integrated into to the automaker and reduce the window assembly complicacy in the moulded plastic assembly, and make its vehicle be different from the ability of rival's vehicle by increasing overall design and form fit rerum natura.The application of light plastic window assembly can help to reduce the center of gravity (vehicle performance and safety preferably) and the improved fuel economy of vehicle.At last, occupant or passenger more are inclined to maintenance in the vehicle with plastic window assembly when relating to overthrow accident, and this further increases security.

Although exist and use the relevant many advantages of plastic window, these plastics assemblies satisfied existing rule of establishing for glass port (as, title 49, the 5 chapters, federal motor vehicle standard No.205; The 571.205th part of ANSI-Z26.1, American National Standards Institute-1977) can not carry out the scale commercial applications widely the time.The minimum requirements of having established that plastic window is used for automobile gathers at table 1.

Table 1

	Requirement
		Wear resistance (Δ % mist degree)	≤ 2.0, in the place ahead of B-post;
	≤ 10.0, at the rear of B-post
		Optical delivery rate (%)	〉=90.0%, clarification,
	〉=70.0, daylight,
			〉=20%, secret,
Initial mist degree (%)	≤1.0
		The coating adhesivity keeps (%)	100
Life time (year in the Florida or Arizona)	＞5
		Colour-change (Δ YI)	＜2.0
Shock-resistance	Ductility

In order to satisfy the requirement of defined in the table 1, must with protective layer (as, coating or film) be applied on the plastic window assembly to overcome several limitations that plastics are had.These limitations comprise that to be exposed to ultraviolet (UV) radiation caused rotten, exemplify to be variable color, and optical delivery descends and fragility increases (shock-resistance declines), and the wear resistance and the stability to hydrolysis of limiting to.The too early destruction that the protective layer system for example shows as delamination or adhesivity loss causes the work-ing life of plastic window assembly limited by quickening aforementioned mechanism of degradation.The color of plastic window or the difference of tone, for example, transparent clarification; daylight (green); and secret (black), can promote the too early destruction of protective layer system, this estimates that the temperature in the environment exposure process takes place between plastic window and the protective layer system by being increased in.This suggestion can be used for equally versicolor other opaque plastics element (as, moulded work, B-post, the follow-up assembly, the body plate, etc.) viewed failure mechanisms.

Therefore, industrially need that exploitation is a kind of to be made the plastic window assembly satisfy automobile attemperator to window to require and too early destructive protective layer firmly do not occur.

Summary of the present invention

The invention provides a kind of protection layered system that is used for making-up unit.This layered system comprises the leaching of the additive in the structure that is not joined to any following protective layer or plastic plate base material or one deck at least that loss plays buffer action.The performance of this layered system is irrelevant with the color or the tone of plastic plate or additive layer basically.Plastic plate and additive layer can be transparent, opaque, or its mixed form.

In certain embodiments, making-up unit is to comprise transite plate, and dispensable protection additive layer and its performance satisfy the window assembly of the sealing coat that is used for automobile occasion performance requriements.

Other characteristics and advantage are according to following detailed description and appended claims and draw with reference to the accompanying drawings and obviously.

Brief description of the drawings

Fig. 1 is to having plastic plate, additive layer and according to several diagrams that may how much of the protection laminate structure of the making-up unit of sealing coat of the present invention.

Fig. 2 has and does not have the plastic plate of sealing coat and UV light absorption ratio that the additive layer system an is had figure as the function of UV radiation amount.

Fig. 3 be have and do not exist UV light absorption ratio that the plastic plate of sealing coat and additive layer system had when being exposed to about 70 ℃ of temperature as total time (hour) the figure of function.

Detailed description of the present invention

Preferred embodiment described below only is illustrative and has no intention to limit by any way the present invention or its purposes or application.

According to the present invention, the protection layered system has improved the service life of plastics load modules, if one deck is as the additive leaching in anti-any following additive layer and the plastic plate or the separation layer of loss. Fig. 1 has provided several possibility geometric configurations of the structure of protection layered system. Separation layer 30 (" B ") can be outermost layer, play a part to prevent any below the separation layer of additive leaching of additive layer 20 and/or plastic plate 10, as shown in Figure 1A and 1B. Separation layer 30 also can be sandwiched between additive layer 20 and the plastic plate 10, plays a part to prevent the separation layer of additive additive layer 20 or plastic plate 10 leachings below only, shown in Fig. 1 C and 1D. In special embodiment, separation layer 30 is that outermost layer is to provide extra wearability benefit to load module. Load module can comprise a plurality of additive layers, and a plurality of separation layer.

For buffer action being described and to having and do not have the various plastic plates 10 of separation layer 30 and performance that additive layer 20 has to compare, select several specific plastic resins (R1-R6), additive layer (A1-A9), and separation layer (B1-B2) provides in table 2. These resins and additive layer along with two may separation layers 30 should not exemplify for limiting scope of the present invention, and various embodiments of the present invention are described just. Nomenclature for the composition of confirming selected protection layered system for buffer action is described provides for specific plastic resin, and additive layer, and each mark of separation layer are as described in Table 2. For example, the protection layered system that is designated as R2+A2A7 comprises plastic resin plate R2 and additive layer A2 and A7. The protection layered system that is designated as R1+A8+B1 comprises plastic resin plate R1, additive layer A8, and separation layer B1.

Conventional sealing coat coating attempts to permeate to coated substrate from environment through coating as water or oxygen by preventing molecule.These environmental pollutant have molecular diameter usually and are lower than 150 picometres (that is molecular diameter O, ₂～121 picometres and molecular diameter H ₂O～108 picometres) small size.But sealing coat 30 can see through these molecules that appear in the environment.For example, in particular embodiment, the make vapor transmission rate of sealing coat 30 under about 37.8 ℃ and about 100% relative humidity is about 3.7gms/m ²-day (Permatran W 3/31, MOCON, Minneapolis, MN).

Table 2

	Substrate resin	Manufacturers
			R1	Limpid polycarbonate	LS2, GE Plastics, Mount Vernon, Indiana USA or AL2647, Bayer AG, Germany
R2	Limpid polycarbonate	M2808, Bayer AG, Germany or 101-111N, GE Plastics, Mount Vernon, Indiana USA
			R3	Daylight dyeing (green) polycarbonate	LS2, GE Plastics, Mount Vernon, Indiana USA or AL2647, Bayer AG, Germany
R4	Gray colored (daylight) polycarbonate	R2+ gray background (plate)
			R5	Secret dyeing (black) polycarbonate	LS2, GE Plastics, Mount Vernon, Indiana USA or AL2647, Bayer AG, Germany
R6	Black colorant (secret) polycarbonate	R2+ black background (printing ink or plate)

	Additive layer	Manufacturers
			A1	Vinylformic acid	Exatec SHP-9X，Exatec LLC，Wixom，Michigan USA
A2	Vinylformic acid	SHP401，GE Silicones，Waterford，New York USA
			A3	Vinylformic acid	UVHC 3000，GE Silicones，Waterford，New York USA
A4	Vinylformic acid	SHP470，GE Silicones，Waterford，New York USA
			A5	Vinylformic acid	PR-800，SDC Technologies，Inc.，Anaheim，CA USA
A6	The siloxanes hard coat	Exatec SHX，Exatec LLC，Wixom，Michigan USA
			A7	The siloxanes hard coat	AS4000，GE Silicones，Waterford，New York USA
A8	The siloxanes hard coat	PHC587，GE Silicones，Waterford，New York USA
			A9	The siloxanes hard coat	MP-101，SDC Technologies，Inc.，Anaheim，CA USA

	Sealing coat	Manufacturers
			B1	The Si that applies by plasma body enhanced chemical vapor deposition wO xC yH z	Exatec LLC，Wixom，Michigan USA
B2	The siloxanes hard coat	AS4700，GE Silicones，Waterford，New York USA

Conventional sealing coat coating is to seeing through from the macromole that descends finishing coat or base material to be diffused into the environment by coating.The sealing coat coating that is used for the microelectronics manufacturing makes the polymer unwinds product be diffused into environment by the sealing coat coating.For example, in order to form air gap between conductive metal wire in the microelectronics manufacturing processed, the high molecular degradation production of polynorbornene is diffused in the surrounding environment by top dielectric (sealing coat) coating easily.

Sealing coat 30 is found and unexpectedly reduces or prevent that molecular diameter from leaching into the environment from following additive layer and plastic plate by sealing coat greater than the additive of 150 picometres.Preferably, sealing coat 30 reduces or prevents molecular diameter greater than about 200 picometres, or in certain embodiments, greater than the additive leaching of about 300 picometres.

Prevent that additive from can increase the corresponding work-ing life of making-up unit from plastic plate and the leaching of any additives layer.Work-ing life of making-up unit according to color (jaundice index=YI) and aspect the shock-resistance characteristic size of viewed performance variation measure, as described in Table 1.Mainly, jaundice index (YI) change to surpass approximately+5 units or begin to show impact fracture (as, fragility causes) plastic plate of sign is considered to reach the useful work-ing life of making-up unit.

Most of plastics are easy to go bad by the process that photochemistry drives.Usually, these degradation processes cause forming the colour characteristics that can influence plastics or the molecular substance of shock-resistance.The process that drives at these photochemistry is usually by with uv-absorbing (" UVA ") molecule introducing body plastics or be administered in the additive layer on the frosting and protect.If the UVA molecule is applied in the protection additive layer, delamination between this additive layer and the plastic plate or adhesivity loss are considered to a kind of destruction, cause producing restriction the useful work-ing life relevant with making-up unit.

The kind of the UVA molecule in the protection additive layer and the useful work-ing life that concentration is represented making-up unit inherently.The UVA molecule can reach the photochemistry inertia stage or exist concentration the mechanism of degradation that photochemistry drives to occur to stop fully not too greatly along with the past of time.The initial zone that is present in the non-absorbent any UV radiation degradation of UVA molecule in the additive layer is represented at interface between additive layer and the plastics.Because the degraded at this interface helps the delamination of additive layer, the destruction height of additive layer depends on the concentration and the work-ing life of the UVA molecule that is introduced in the additive layer.According to the present invention, the jaundice index (YI) greater than+5 units of plastic plate increases the delamination that has been found and has protected additive layer, and brittle beginning is consistent.

Reach colour-change (Δ YI)+5 units and additive layer delaminations or impact and destroy required UV radiant exposure (UV _EXP) amount can use following equation 1 to estimate.In this equation, D is meant rate of fall-off, and Ao is meant the light absorption ratio value of initial mensuration, and T _FBe meant the described color change that causes " unprotected " plastic plate or the radiation quantity of impact fracture.By the exposure (UV that uses this equation to determine _EXP) amount provide with megajoule (MJ).T _FValue measure the colour-change of " unprotected " plastic plate or impact property easily by experiment and determine as the function of radiant exposure.

${\mathrm{UV}}_{\mathrm{EXP}}=(1/D)\log [({10}^{\left(D{T}_F\right)}+{10}^{(-A_O)}-1)/{10}^{\left({-A}_O\right)}]---\left(1\right)$

According to the present invention, sealing coat 30 increases the UV radiation quantity about 63% that plastic plate can stand before the destruction of the colour-change that for example is expressed as excessive+5 unit (that is Δ YI).Comprising polycarbonate (R2) plate that the additive layer (A2A7) of UVA molecule protected is found by being exposed to the 8MJ uv-radiation and reaches+the jaundice index variation (Δ YI) (referring to test #01, table 3) of 5 units.Comparatively speaking, when sealing coat 30 encapsulation contains the protective additive layer of UVA molecule, identical plastic plate (R2+A2A7) be found in be exposed to greater than the uv-radiation of 12MJ reach+YI of 5 units changes (test #02, table 3).As shown in table 3, the plate destructive actual measurement time is found very approaching with the predetermined time to rupture that calculates according to equation 1.

Table 3

Δ (YI) 〉=+5 units of delta (YI) 〉=+5 unit

Measure and calculate equation 1

(megajoule) (megajoule)

8.0	8.9
		13.0	12.5
62.5％	40.4％

#01 R2+A2A7 #02 R2+A2A7+B1 buffer action

According to the present invention, sealing coat 30 increases plastic plate and is reaching the UV radiation quantity about 42% that can stand before " fragility " or the shock-resistance destruction.Only the plastic plate (R2) by the additive layer that comprises the UVA molecule (A2A7) protection is found by exposing the 10.3MJ uv-radiation in the breakdown point that reaches shock-resistance.Comparatively speaking, identical plastic plate (R2+A2A7) is found by being exposed to the breakdown point that about 14.6MJ uv-radiation reaches shock-resistance, if sealing coat 30 is sealed this protection additive layer.

Further according to the present invention, the rate of fall-off that sealing coat 30 reduces the additive in the protection layered system surpasses about 20%.For example, be present in rate of fall-off obviously decline of the relative UV light absorption ratio that the UVA molecule showed in the additive layer by using sealing coat defined herein.In this case, rate of fall-off (D) is defined as every megajoule (MJ) UV radiation that plate or window assembly exposed (wavelength=340nm), the decline of absorption (ABS) units of being measured at the UVA molecule in the additive layer.Comprising plastic plate (R1) that the additive layer (A2A7) of UVA molecule protected is found and has the UVA molecule rate of fall-off when being exposed to the UV radiation that equals pact-0.20ABS/MJ exposure, (referring to test #03) as shown in Figure 2.Comparatively speaking, identical plastic plate (R1+A2A7) is found when sealing coat 30 and seals the rate of fall-off (referring to test #04) that the protection UVA that comprises additive layer divides the period of the day from 11 p.m. to 1 a.m to have to equal pact-0.11ABS/MJ.Therefore, sealing coat 30 being applied in the additive layer that comprises the UVA molecule reduced rate of fall-off about 41% under this particular case.

According to the present invention, sealing coat 30 is found and unexpectedly makes the opaque plastics plate and the transparent plastics window that comprise different tinting materials and tone respectively similar on performance.In other words, the performance of dyeing or painted plastic plate and additive layer combination when adopting sealing coat by normalization method.Be characterized by clarification (＞90% transparency) respectively, the plastic plate of daylight grey and secret black (R6) measure having and do not exist under the situation of sealing coat 30 for R2, R4 by the rate of fall-off of the UVA molecule in the protection additive layer on (A2A7 or A1A6).Under the situation that does not have sealing coat, the rate of fall-off (D) of the UVA molecule in the protection additive layer is found the tendency of following D clarification＞D daylight＞D secret.For example, only protect additive layer (A1A6) if plastic plate scribbles, for clarifying to the secret coloring board, rate of fall-off is measured as 0.03 to 0.05ABS/MJ so.UV light absorption ratio rate of fall-off is relevant to the difference of the surface temperature that the dependency of protection color of layered system or tone can be experienced with plastic plate.For example, 20 ℃ of differences are present in and just experience the acceleration climatic test, and ASTM G155 is between the clarification and secret coloring board in cycle 1 (GMOD).In this special test, the temperature of clarification and secret plate is found and is respectively 70 ℃ and 90 ℃.According to various embodiments of the present invention, sealing coat makes that the life time of plastic plate is substantially similar, if the surface temperature of plastic plate is between about 20 ℃ and about 120 ℃.

If sealing coat 30 is applied on the protection additive layer, rate of fall-off (D) is found follows D _{Clarification}-D _Daylight-D _SecretTendency.For example, if plastic plate scribbles protection additive layer (A1A6) and sealing coat B1, rate of fall-off is measured as about 0.02ABS/MJ, for all (clarifying to secret) coloring boards.In all cases, rate of fall-off reduces above about 20% by using sealing coat 30, and is as shown in table 4.Sealing coat 30 reduces the effect of the surface temperature of plastic plate to the rate of fall-off of the UV light absorption ratio of protection layered system effectively.

Table 4

The decline of UVA rate of fall-off

#05 R2+A2A7+B1 22％

#06 R4+A2A7+B1 27％

#07 R6+A2A7+B1 27％

#08 R2+A1A6+B1 42％

#09 R4+A1A6+B1 75％

#10 R6+A1A6+B1 40％

Further according to the present invention, the isolation performance that sealing coat 30 is shown can be determined by measuring at elevated temperatures relatively the additive relative loss of exposure duration.Sealing coat prevents that additive losses is to being lower than about 0.15% (being exposed to after 70 ℃ at 100 hours), preferred about 0.50% (after 300 hours), or more preferred about 0.80% (after 500 hours).The specific performance of additive can be used as the function of time and monitored relative loss with definite additive.For example, if additive is the UVA molecule, can measure the UVA absorbance units as the time that is exposed to 70 ℃ of temperature (hour) loss of function to be to determine relative loss.Sealing coat 30 under this particular case, be found prevent below the UVA molecule loss of additive layer (A2A7) and plastic plate (R2) to being lower than 0.157%, 0.470% and 0.780%, expose about 100 down at about 70 ℃ respectively, after 300 and 500 hours (referring to test #16, table 5).In a word, sealing coat 30 reduces the lower floor that contains additive and the additive losses speed of plastic plate surpasses about 300%.

Plastic plate 10 can comprise any thermoplasticity or thermosetting polymer resin.Plastic plate can be opaque, transparent or its mixed form.Fluoropolymer resin can include but not limited to polycarbonate, vinylformic acid, poly-arylide polyester, polysulfones, urethane, siloxanes, epoxy, polymeric amide, poly-alkane alkene, and acrylonitrile-butadiene-styrene (ABS) (ABS), with and multipolymer, blend, and mixture.Preferably transparent, thermoplastic resin includes but not limited to polycarbonate resin, acrylic resin, poly-arylide resin, vibrin, and polysulfone resin, and multipolymer and its mixture.Plastic plate can further comprise various additives, as tinting material, and rheology control agent, releasing agent, antioxidant, uv-absorbing (UVA) molecule and IR absorb or reflective paint, and other.Plastic plate can be by using the known any technology of those skilled in the art, as extrusion molding, and molding (comprising injection moulding, blowing, and compression moulding), or thermosetting (comprising thermoforming, vacuum forming, and cold-forming) and be shaped to making-up unit.

Additive layer 20 can include but not limited to siloxanes, urethane, vinylformic acid, polyester, epoxy and its mixture or multipolymer.Additive layer can be extruded or casting becomes film or use as discrete coatings.A plurality of coatings that contain additive comprise that acrylic primer and siloxanes hard coat or urethane middle layer can be used for increasing the protection of plastic plate.The example of a plurality of additive coatings comprise acrylic primer (SHP401, GE Silicones, Waterford, NY) and the combination of siloxanes hard coat (AS4000, GE Silicones).Additive in the additive layer can be tinting material (tone), rheology control agent, and releasing agent, antioxidant, uv-absorbing (UVA) molecule and IR absorb or reflective paint, and other.Additive coating can be by dip-coating, flow coat, spraying, heavy curtain coating, or known other technology of those skilled in the art and using.The thin film of additive layer can pass through in-mold decoration, film insert molding, casting, or known other technology of those skilled in the art and using.

Its loss preferably comprises uv-absorbing (UVA) molecule by the additive that uses sealing coat 30 to control, and other.The UVA molecule can include, but not limited to hydroxy benzophenone, polyphenyl formyl radical Resorcinol, or its combination, and 2-ethylhexyl-2-cyano group-3, the derivative of 3-phenylbenzene cyanoacrylate.If the UVA molecule so that the UVA molecular linkage is received in the coated mesh structure, is preferably about 5% as not being keyed in the reticulated structure so that sealing coat has the ratio of the UVA molecule that the additive of remarkable effect exists by silylation.

Sealing coat 30 can comprise any known conduction or dielectric materials, Inorganic Dielectric Material wherein, and organic dielectric materials, or its mixture and blend are preferred.The example of Inorganic Dielectric Material includes but not limited to aluminum oxide, barium fluoride, boron nitride, hafnia, lanthanum fluoride, magnesium fluoride, magnesium oxide, Scium trioxide, silicon monoxide, silicon-dioxide, silicon nitride, silicon oxynitride, siloxicon, silicon carbide, tantalum oxide, titanium oxide, stannic oxide, indium tin oxide target, yttrium oxide, zinc oxide, zinc selenide, zinc sulphide, zirconium white, zirconia titanate, or glass and its mixture or blend.Organic dielectric materials can include but not limited to diamond-like-carbon and " intensive " polymeric system, as urethanum, and epoxide, acrylate, siloxanes and its mixture or blend.Polymeric system is considered to " intensive " polymeric system, if it satisfies the standard of performance to sealing coat 30 defined herein.

Sealing coat 30 can be used by the known any suitable technique of those skilled in the art.These technology comprise from reactive materials, as are used for vacuum aided depositing operation and atmosphere coating process those, as are used for sol-gel paint is administered to those reactive materials depositions on the base material.The example of vacuum aided depositing operation includes but not limited to plasma body enhanced chemical vapor deposition, ion auxiliary plasma deposition, magnetron sputtering, electron beam evaporation, and ion beam sputtering.The example of atmosphere coating process includes but not limited to the heavy curtain coating, spraying, spin coating, dip-coating and the coating of flowing.

Have plastic plate, the example of the protection layered system of two additive coatings and sealing coat 30 comprises polycarbonate/acrylonitrile acid/siloxanes/" glassy " system.In these systems, polycarbonate is represented transite plate, and two additive layer 20 are represented in vinylformic acid and siloxanes middle layer, and " glassy " outer layer expression sealing coat 30.

The thickness of sealing coat 30 can be about 1 micron to about 100 microns.The optimum thickness of sealing coat 30 depends on that this layer prevents the effectiveness of additive losses of lower floor and the optical property that this layer had.Have transite plate, total window assembly of any additives layer and sealing coat 30 preferably satisfies the optics requirement for mist degree and light transmission of table 1 defined.Equally, the thickness of additive layer can be about 1 micron to about 100 microns, depends on the performance of its optical property and the overall window assembly of influence.

Following object lesson is used to illustrate the present invention and should not be construed as limiting the scope of the invention.

Embodiment 1-specimen preparation

The dull and stereotyped commercial polycarbonate resin (LS2 that uses, GE Plastics, MountVernon, Indiana or AL2647, Bayer AG, German) or be mixed with this resin (M2808, Bayer AG, Germany or the 101-111 N that in wavelength region 315-360 nanometer, has the special type of the UV absorption spectrum that is lower than about 1 absorbance units (ABS), GE Plastics, MountVernon, Indiana, USA) molding.The every kind of resin that is used for forming plastic sheets further identifies as R1 to R6 at table 2.

The polycarbonate resin that is used to form each plate is clarifying (R1 and R2), painted (R3 and R5), or painted (R4 and R6).Resin in the dyed plate comprises color additives or tinting material, produces the plate that is coloured to this color like this.Coloring board is by to the back up coloring printing ink of clarification (R1 and R2) plate or adhere to coloring film (as, plate) and make.

Made plate is coated with subsequently with one or more additive coatings, as table 2 as shown in the A1 to A9.After using each additive coating, with coating " flash distillation " or dry air 20-30 minute, then at the about 110-130 ℃ of about 30-60 of following thermofixation minute.Use commercially available coating and solidify according to the condition of manufacturer recommendation.

The plate of the combination that scribbles each additive layer or additive layer of half is used sealing coat 30 subsequently, and the character of this layer is described in table 2.Sealing coat 30 is according to M.Schaepkens, S.Selenzneva, P.Moeleker, condition and parameter described in the article of publishing with C.D.lacovangelo are applied or deposit on the surface of outermost additive layer: magazine vacuum science and technology A, 21 (4), 2003, pgs 1266-1271, its whole contents is incorporated the present invention into as a reference at this.

Be used for subsequent embodiment subsequently with the assessment buffer action by various resins (R1-R6) molding with scribbling various additive layer (A1-A9) and being with or without all plates of using sealing coat 30.Ductile and satisfy in table 1 optical delivery (%) and initial mist degree (%) requirement of regulation on Zhi Bei all transparent panels in this embodiment.

Embodiment 2-buffer action: thermosteresis

A part of plate that will prepare in embodiment 1 is exposed to heat under 70 ℃ in convection furnace.Each plate uses spectrometer to be used for 0,24 in the temperature that is exposed to rising, and 72,144,312,648, checked afterwards in 1008,1368 and 1728 hours.Cary 500 scanning UV-Vis-NIR spectrometers are used in spectroscopic analysis, and (Varian, Palo Alto CA) carry out under scanning speed 300 nm/minute in wavelength region 215-500 nanometer.

For each plate of being assessed, 10 powers that obtain the UV light absorption ratio deduct 1 logarithm (Log[10 ^ABS-1]) is exposed to the figure of 70 ℃ time length relatively.An example of this mapping provides at two plates that are designated as R2+A2A7 (test #13) and R2+A2A7+B1 (test #16) in Fig. 3.The linear regression curve fitting analysis is used to obtain the slope and the y-intercept of each plate of assessing.The slope of this line is represented the speed of additive (UVA molecule) loss, represents with ABS/ hour units.In some specified time interval, calculate subsequently additive losses percentage ratio and exist with the situation that does not have sealing coat 30 under more identical resin and additive layer system.

At a plurality of additive layer systems that have and do not use sealing coat 30, determine the percentage ratio of the speed of additive losses and additive losses as the function of time, as shown in table 5.The various additive layer combination (test #11-13) of not using sealing coat 30 is confirmed as it and absorbs UV radiating ability and descend about 0.3 to 0.6% after 100 hours being exposed to 70 ℃; After 300 hours about 0.9 to 1.8%; With after about 500 hours about 1.4 to 3.0%.The speed of the additive absorption loss of these various additive layer combinations (test #11-13) is 1.0 * 10 ^-4To 8.9 * 10 ^-5ABS/ hour.

Comparatively speaking, the same additives layer combination in the presence of sealing coat 30 (test #14-16) is found the additive losses speed with obvious decline.The various additive layer combination (test #14-16) of using sealing coat 30 is confirmed as it and absorbs UV radiating ability and descend about 0.05 to 0.2% after 100 hours being exposed to 70 ℃; After 300 hours about 0.2 to 0.5%; With after 500 hours about 0.3 to 0.8%.Additive absorption loss speed (test #14-16) with these various additive layer combinations of sealing coat 30 is 1.0 * 10 ^-5To 2.0 * 10 ^-5ABS/ hour.The overall function of sealing coat 30 in this object lesson (referring to Fig. 3) is, compare with the identical system that does not have sealing coat (test #11-13), after being exposed to the temperature specific time of rising, making additive (UVA molecule) layer absorb UV radiating ability in the presence of sealing coat (test #14-16) increases greater than 300%.

Table 5

In time (hour) the ABS loss (%) that changes, in 70 ℃			The slope of linear regression fitting of a curve (ABS/ hour)
				100 hours	300 hours	500 hours

Additive layer

0.280％	0.860％	1.400％	-0.0001000
				0.196％	0.588％	0.980％	-0.0000700
0.598％	1.790％	2.989％	-0.0000891

#11 R2+A5A9 #12 R2+A1A6 #13 R2+A2A7

Add sealing coat

0.050％	0.160％	0.267％	-0.0000200
				0.000％	0.000％	0.000％	-0.0000100
0.157％	0.470％	0.780％	-0.0000179

#14 R2+A5A9+B1 #15 R2+A1A6+B1 #16 R2+A2A7+B1

Buffer action

560％	538％	524％
			＞1000％	＞1000％	＞1000％
381％	381％	383％

#11-#14 #12-#15 #13-#16

This embodiment explanation, sealing coat 30 prevent that additive losses is to being lower than about 0.15% (after 70 ℃ expose 100 hours down), preferably about 0.50% (after about 300 hours) and more preferably from about 0.80% (after about 500 hours).This embodiment further specify sealing coat 30 at different following additive layer (as, A1A6, A2A7, and A5A9) show similar ability.

Embodiment 3-buffer action: rate loss (ABS/MJ)

A part of plate that will prepare in embodiment 1 is exposed to the UV-visible light in several different natural and acceleration climatic tests.In a kind of therein test, plate (test #17-24) is in the AtlasC5000i weatherometer, use ASTM G155 cycle 1 (GMOD) artificial climate program to use following specified conditions to carry out the UV-visible light: (1) UV source is an xenon arc, have in the borosilicate and the outer spectral filter of borosilicate, spectral intensity 0.75W/m ², at 340nm; (2) blackboard temperature is 75 ℃; (3) relative humidity 30%; (4) dry-bulb temperature is 55 ℃.Use ASTM D 3359-92a at every 1.2MJ/m ²Check whether all plates exist crack splitting after the UV exposure, spontaneous delamination, or adhesivity is destroyed.In case destroy, plate withdrawn test.

The plate of the another part that will prepare in embodiment 1 (test #25-28) is exposed to outdoor natural climate in Florida and Arizona under 5 degree angles.Use ASTM D 3359-92a to check whether each plate crack splitting occur in per 6 months, spontaneous delamination, or adhesivity is destroyed.In case destroy, plate withdrawn test.

The plate of the another part that will prepare in embodiment 1 (test #25-28) uses the ASTM G90 cycle 3 (ASTM D4141), and (Q-PANEL, Cleveland OH) are exposed to the outdoor weather of acceleration on the equipment at QTRAC in the Arizona.Use ASTM D 3359-92a to check whether each plate crack splitting occur in per 6 months, spontaneous delamination, or adhesivity is destroyed.In case destroy, plate withdrawn test.

At last, another part plate that will in embodiment 1, prepare, and uncoated resin (R1-R6) plate uses QUV spraying weatherometer, and (Q-Panel Lab Products, Cleveland OH) are exposed to the UV-visible light.ASTM G154。Cycles 4 artificial climate program is used for this test, but a variation is arranged.This variation comprises, uses luminescent lamp to be exposed to spectral intensity 1.35W/m continuously under the 340nm wavelength plate ²Vision and utilize spectrographic technique to check all plates 0,24,72,144,312,648, the weather infringement after the exposure in 720 and 1440 hours (as, crackly split and be coated with delamination layer).

The spectroscopic analysis of plate use Cary 500 scanning UV-visible-(Varian, Palo Alto CA) carry out under scanning speed 300nm/min in wavelength region 215-500nm the NIR spectrometer.Yellowness index uses ASTM E313-00 (being used for calculating from the color coordinates of Instrument measuring the standard practice of yellow degree and whiteness index), uses BYK colour index (colour system: CIELab; Index: YE 313-98, illumination/viewer: D65/10 °) determines.

The absorption (ABS) of the mensuration that the yellowness index of uncoated (not additive layer) polycarbonate plate is caused by the UV radiant exposure under wavelength 340nm relatively changes mapping.The linear regression fitting of a curve is applied to this mapping, and the gained slope is as light-Fries correction factor.This correction factor is used for determining under 340nm the corrected absorbance that produces in the loss of the plate that comprises polycarbonate resin and various additive layer owing to the UVA molecule.At each plate of assessing, use the corrected absorbance value, 10 powers of light absorption ratio are deducted 1 logarithm (that is Log[10, ^ABS-1]) relative UV radiant exposure (MJ/m ²) mapping.An example of this mapping provides at plate that is designated as R1+A2A7 (test #03) and the plate that is designated as R1+A2A7+B1 (testing #04) in Fig. 2.Rate of fall-off or absorption loss speed (ABS/MJ) are defined as deriving from the slope of the linearity curve of this analysis.

At last, the wear resistance of another part plate of preparation in embodiment 1 (test #17-24) is according to ASTM D1044 (1000 cycles, CSF10 wheel) test.

The test-results that the plate of preparation obtains after being exposed to above-mentioned various acceleration and natural climate condition among the embodiment 1 provides in table 6.The plate that will have polycarbonate resin (R3) and various additive layer, as A1A6 (test #17), A2A7 (test #18 and 25), A8 (test #21 and 27), and A3 (test #23), having and do not adding sealing coat (referring to test #18,20,22,24,26 and 28) directly compare under the situation.This embodiment explanation, the existence of sealing coat 30 obviously increases additive layer and the stability of resin board under weather condition.

Table 6

The ASTM G155 cycle (GMOD)
				Destroy (MJ/m 2In 340nm)	Additive layer thickness (micron)	Absorption loss rate (ABS/MJ is in 340nm)	Δ % mist degree (Taber, 1000 cycles, CSF10 wheel)
5.0	7.3	-0.03	12％
				13.8	7.2	-0.02	2％
8.6	4.9	-0.20	10％
				12.9	4.7	-0.12	2％
4.9	4.2	-0.24	8％
				5.4	4.2	-0.11	1％
6.5	7.0	-0.54	20％
				7.0	7.4	-0.07	1％

#17 R3+A1A6 #18 R3+A1A6+B1 #19 R3+A2A7 #20 R3+A2A7+B1 #21 R3+A8 #22 R3+A8+B1 #23 R3+A3 #24 R3+A3+B1

The ASTM G90 cycle 3 (QTRAC)		The Florida weather aging		The Arizona weather aging
						Destroy (MJ/m 2 TUVR)	Additive layer thickness (micron)	Lost efficacy (year)	Additive layer thickness (micron)	Fallure (year)	Additive layer thickness (micron)
836	6.3	1.5	7.5	2.0	6.2
						1704	6.4	2.5	7.7	3.5	6.2
570	4.4	2.0	4.5	1.5	4.4
						710	4.6	2.5	4.6	2.5	4.4

#25 R3+A2A7 #26 R3+A2A7+B1#27 R3+A8#28 R3+A8+B1

ASTM G154, the cycle 4 (QUVA)
	The decline of absorption loss rate (% Δ ABS/MJ is in 340nm)
40％
	50％
27％
	71％

#29 R3+A2A7+B1 #30 R3+A8+B1#31 R3+A4+B2#32 R3+A4+B2B1

The existence of sealing coat 30 increases the UV radiating amount (MJ/m that plate can expose in ASTM G155 cycle 1 (GMOD) test process ²).This increases, and directly the increase in the work-ing life in the use of reality is relevant with transparent panel or window.This increase is that about 10% (will test #21 to #22 and #23 to #24 relatively) will be extremely greater than 50% (will test #17 to #18 and #19 to #20 relatively).Similarly, the absorption loss speed of each plate in the UV exposure process descends when having sealing coat 30.This decline (ABS/MJ) of loss speed is found greater than about 30%, for all additive systems that (will test #21 and #22, #23 and #24, #17 and #18 and #19 and #20 comparison) assess in the presence of sealing coat 30.The thickness of the additive layer of the plate of each of carrying out in analytic process in relatively is almost suitable, has eliminated the possibility that existing relatively large additive can bring viewed performance difference like this.For example, the thickness of the additive layer on the plate among the test #17 (7.3 μ m) is similar to the thickness of the additive layer on the plate of testing among the #18 (7.2 μ m).

The existence of sealing coat 30 increases plate at ASTM G90, cycle 3 (QTRAC) test, Florida natural climate, Arizona natural climate and ASTM G154, the UV radiation quantity that can expose in cycle 4 (QUVA) test process.This increase that increases directly with transparent panel or window work-ing life in actual use is relevant.In the QTRAC test, this increase is that 25% (comparison test #27 to #28) is to about 100% (comparison test #25 to #26).In Florida and Arizona natural climate test, this increase is about 25% (in the Florida, for test #27 and #28) to (, (test #25 and #26 and #27 and #28 comparison) greater than 50% for test #25 and #26 with in the Arizona in the Florida.

In QUVA test, the decline of the rate of fall-off of viewed uv-absorbing molecule is greater than about 27%, shown in test #29-32 when adopting sealing coat 30.In all these tests, the percentage of rate of fall-off (ABS/MJ) changes by having and not existing the same system of sealing coat 30 to compare and obtains.In test #32, the existence of two sealing coats (B1B2) is found the rate of fall-off that reduces the uv-absorbing molecule the biglyyest and reaches 71%.The thickness of each of carrying out in analysis in all cases, additive layer relatively is suitable.

The application of sealing coat (B1) increases the wear resistance of additive layer and plate.As shown in table 6, the wear resistance of additive layer increases and surpasses 100%, for all direct comparisons (referring to test #17 to #18, #19 is to #20, #21 to #22 and #23 to #24).This embodiment explanation, sealing coat 30 can increase wear resistance.

Embodiment 4-buffer action: to the refusal of color change

A part of plate that will prepare in embodiment 1 is exposed to the outdoor weather of nature and carries out ASTM G155 cycle 1 (GMOD) test under 5 degree angles in the Florida.Each plate that will carry out weather in the Florida used ASTM D 3359-92a to check crack splitting whether occur in per 6 months, spontaneous delamination, or adhesivity is destroyed.Similarly, at every 1.2MJ/m ²All plates that will carry out the GMOD test after the UV exposure carry out the inspection of above-mentioned failure mode aspect.The gained result of Ping Gu each provides in table 7 in this embodiment.

Table 7

The existence of sealing coat 30 makes plastic plate and additive layer absorb relatively large UV radiation before reaching breakdown point.This increase is relevant with the increase of the expected service life of protection layered system or plastic window.The time shutter that daylight dyed plate with sealing coat 30 is found in before destroying has 26% to increase (comparison test #34 to #33).Similarly, divide other to have a time shutter that sealing coat 30 secret coloring boards (relatively #38 to #37) and secret dyed plate (relatively #36 to #35) be found in before destroying 116% and 200% increase is arranged.This embodiment explanation, a kind of predictive role of sealing coat 30 is that cancellation plate or additive layer color influence making-up unit any effect in work-ing life.In other words, the performance of dyeing or painted plastic plate and additive layer combination when adopting sealing coat 30 by normalization method.Dyeing daylight (test #34) and dyeing secret (test #36) performance of protection lamellated plate in the presence of sealing coat 30 are found and all were normalized to life time about 3 years.

Those skilled in the art can recognize according to above description, under the situation that does not deviate from the determined scope of the invention of following claim, can improve and change the preferred embodiments of the invention.Those skilled in the art further recognize, the measurement to the additive rate loss that for example is described in preferred embodiment is the canonical measure that can obtain by various test method.The test method that is described in embodiment is represented only a kind of method that can be used for obtaining each required observed value.

Claims (59)

1. a protection layered system that is used for making-up unit comprises: plastic plate; At least two protective layers that are integrated into plastic plate; One of them protective layer is the sealing coat that reduces the additive losses that is suspended, and covalent linkage is not connected in the structure of any following protective layer or plastic plate.

2. the protection layered system of claim 1, wherein the rate of fall-off during additive losses is limited to about 95% of the additive losses rate of fall-off that is lower than when not having sealing coat by this sealing coat.

3. the protection layered system of claim 2, wherein the rate of fall-off during additive losses is limited to about 90% of the additive losses rate of fall-off that is lower than when not having sealing coat by this sealing coat.

4. the protection layered system of claim 3, wherein the rate of fall-off during additive losses is limited to about 85% of the additive losses rate of fall-off that is lower than when not having sealing coat by this sealing coat.

5. the protection layered system of claim 1 wherein descends exposure in the time of about 500 hours for about 70 ℃ in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.8% volume.

6. the protection layered system of claim 1 wherein descends exposure in the time of about 300 hours for about 70 ℃ in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.5% volume.

7. the protection layered system of claim 1 wherein descends exposure in the time of about 100 hours for about 70 ℃ in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.15% volume.

8. the protection layered system of claim 1, wherein sealing coat reduces the loss of molecular diameter greater than the additive of about 150 micromicrons.

9. the protection layered system of claim 8, wherein sealing coat reduces the loss of molecular diameter greater than the additive of about 200 micromicrons.

10. the protection layered system of claim 9, wherein sealing coat reduces the loss of molecular diameter greater than the additive of about 300 micromicrons.

11. the protection layered system of claim 1, wherein the thickness of sealing coat is about 1 micron to 100 microns.

12. the protection layered system of claim 1, wherein plastic plate is painted, dyeing, or its mixed form.

13. the protection layered system of claim 12, if wherein the surface temperature of plastic plate is between about 20 ℃ and about 120 ℃, sealing coat makes that the life time of plastic plate is substantially similar.

14. the protection layered system of claim 12, wherein for any painted or coloured plastics plate, sealing coat makes that the work-ing life of plastic plate is substantially similar.

15. the protection layered system of claim 14, wherein the coloured plastics plate be initial level of haze be lower than about 1% and transparence greater than about 20% window assembly.

16. the window assembly of claim 15 wherein is lower than about 10% in the variation that is exposed to 1000 period T aber test (CSF10 wheel) mist degree % afterwards.

17. the window assembly of claim 16 wherein is lower than about 2% in the variation that is exposed to 1000 period T aber test (CSF10 wheel) mist degree % afterwards.

18. the window assembly of claim 15, wherein the transparence of window assembly is greater than about 70%.

19. the window assembly of claim 18, wherein the transparence of window assembly is greater than about 90%.

20. the protection layered system of claim 14, wherein the coloured plastics plate is opaque.

21. the protection layered system of claim 1, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than making-up unit and Duos about more than 10% in GMOD test.

22. the window assembly of claim 1, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than making-up unit and Duos about more than 25% in QTRAC test.

23. the protection layered system of claim 1, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than making-up unit and Duos about more than 40% in QUVA test.

24. the protection layered system of claim 1, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than making-up unit and Duos about more than 25% in natural weathering test.

25. the protection layered system of claim 1, wherein plastic plate is to be selected from polycarbonate resin, acrylic resin, poly-arylide resin, vibrin, polysulfone resin and its mixture, blend or multipolymer a kind of.

26. the protection layered system of claim 1, wherein protective layer is to be selected from coating, cast film, or a kind of in the extruded film.

27. the protection layered system of claim 26, wherein protective layer is to be selected from the siloxanes hard coat, a kind of in polyurethane coating and acrylic acid coatings or its combination.

28. the protection layered system of claim 1, wherein sealing coat is to be selected from electro-conductive material, Inorganic Dielectric Material, organic dielectric materials, or a kind of in its mixture and the blend.

29. the protection layered system of claim 28, wherein Inorganic Dielectric Material is selected from aluminum oxide, barium fluoride, boron nitride, hafnia; lanthanum fluoride, magnesium fluoride, magnesium oxide, Scium trioxide, silicon monoxide; silicon-dioxide, silicon nitride, silicon oxynitride, siloxicon, silicon carbide; tantalum oxide, titanium oxide, stannic oxide, indium tin oxide target; yttrium oxide, zinc oxide, zinc selenide, zinc sulphide; zirconium white, zirconia titanate, glass, or its mixture or blend.

30. the protection layered system of claim 28, wherein organic dielectric materials is selected from diamond-like-carbon or intensive polymkeric substance.

31. the protection layered system of claim 30, wherein intensive polymkeric substance is selected from urethanum, epoxide, acrylate, siloxanes, or its mixture or blend.

32. the protective layer of claim 1, wherein additive is to be selected from dispersion agent, tensio-active agent, and softening agent, flowing additive, releasing agent, antioxidant, the uv-absorbing molecule, IR absorbs pigment, or the IR reflective paint.

33. the protective layer of claim 32, wherein the uv-absorbing molecule is selected from the hydroxy benzophenone derivative, polyphenyl formyl radical resorcinol derivatives, 2-ethylhexyl-2-cyano group-3,3-phenylbenzene cyanoacrylate, or its mixture or blend.

34. the protective layer of claim 33, wherein the derivative of hydroxy benzophenone or polyphenyl formyl radical Resorcinol is used greater than about 5% residual non covalent bond and is received UVA silylanizing in the additive layer structure.

35. the protection layered system of claim 1, wherein sealing coat is the outermost layer in the protection layered system.

36. the protection layered system of claim 1, wherein sealing coat is between another protective layer and plastic plate.

37. the protection layered system of claim 1 wherein protects layered system to comprise the sealing coat that surpasses one deck.

38. a protection layered system that is used for making-up unit comprises: plastic plate; With at least one protective layer, this layer be used for reducing the loss of the additive that is suspended and not covalent linkage be connected on the sealing coat of the structure of plastic plate.

39. the protection layered system of claim 38, wherein the rate of fall-off during additive losses is limited to about 95% of the additive losses rate of fall-off that is lower than when not having sealing coat by this sealing coat.

40. the protection layered system of claim 38, wherein the rate of fall-off during additive losses is limited to about 90% of the additive losses rate of fall-off that is lower than when not having sealing coat by this sealing coat.

41. the protection layered system of claim 38, wherein about 70 ℃ exposure is in the time of about 500 hours down in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.8% volume.

42. the protection layered system of claim 38, wherein about 70 ℃ exposure is in the time of about 300 hours down in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.5% volume.

43. the protection layered system of claim 38, wherein about 70 ℃ exposure is in the time of about 100 hours down in temperature, and additive losses is limited to by this sealing coat and is lower than about 0.15% volume.

44. the protection layered system of claim 38, wherein sealing coat reduces the loss of molecular diameter greater than the additive of about 150 micromicrons.

45. the protection layered system of claim 38, wherein the thickness of sealing coat is about 1 micron to 100 microns.

46. the protection layered system of claim 38, wherein plastic plate is painted, dyeing, or its mixed form.

47. the protection layered system of claim 46, wherein for any painted or coloured plastics plate, sealing coat makes that the work-ing life of plastic plate is substantially similar.

48. the protection layered system of claim 47, wherein the coloured plastics plate be initial level of haze be lower than about 1% and transparence greater than about 20% window assembly.

49. the protection layered system of claim 48 wherein is lower than about 10% in the percentage variation that is exposed to 1000 period T aber test (CSF10 wheel) mist degrees afterwards.

50. the protection layered system of claim 48, wherein the transparence of window assembly is greater than about 70%.

51. the protection layered system of claim 47, wherein the coloured plastics plate is opaque.

52. the protection layered system of claim 38, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than window assembly and Duos about more than 10% in GMOD test.

53. the protection layered system of claim 38, wherein making-up unit destroys the UV radiant exposure limit that UV radiation quantity that ground exposes established under the situation that does not have sealing coat than making-up unit and Duos about more than 25% in QTRAC test.

54. the protection layered system of claim 38, wherein the making-up unit UV radiation quantity that can not expose in the QUVA test UV radiant exposure limit of being established under the situation that does not have sealing coat than making-up unit is Duoed about more than 40% with destroying.

55. the protection layered system of claim 38, wherein making-up unit does not destroy the UV radiant exposure limit that UV radiation quantity that ground can expose established under the situation that does not have sealing coat than making-up unit and Duos about more than 25% in natural weathering test.

56. the protection layered system of claim 38, wherein plastic plate is selected from polycarbonate resin, acrylic resin, poly-arylide resin, vibrin, polysulfone resin, or its mixture, blend or multipolymer.

57. the protection layered system of claim 38, wherein sealing coat is to be selected from electro-conductive material, Inorganic Dielectric Material, organic dielectric materials, or its mixture and blend.

58. the protection layered system of claim 38, wherein Inorganic Dielectric Material is selected from aluminum oxide, barium fluoride, boron nitride, hafnia; lanthanum fluoride, magnesium fluoride, magnesium oxide, Scium trioxide, silicon monoxide; silicon-dioxide, silicon nitride, silicon oxynitride, siloxicon, silicon carbide; tantalum oxide, titanium oxide, stannic oxide, indium tin oxide target; yttrium oxide, zinc oxide, zinc selenide, zinc sulphide; zirconium white, zirconia titanate, glass, or its mixture or blend.

59. the protection layered system of claim 38, wherein additive is selected from dispersion agent, tensio-active agent, and softening agent, flowing additive, releasing agent, antioxidant, the uv-absorbing molecule, IR absorbs pigment, or the IR reflective paint.

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