CN102811866A - Low ghosting dry erase article and use thereof - Google Patents
Low ghosting dry erase article and use thereof Download PDFInfo
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- CN102811866A CN102811866A CN2011800147000A CN201180014700A CN102811866A CN 102811866 A CN102811866 A CN 102811866A CN 2011800147000 A CN2011800147000 A CN 2011800147000A CN 201180014700 A CN201180014700 A CN 201180014700A CN 102811866 A CN102811866 A CN 102811866A
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- xerotripsis
- writing
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- radiation
- label
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L1/00—Repeatedly-usable boards or tablets for writing or drawing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
- B43L1/00—Repeatedly-usable boards or tablets for writing or drawing
- B43L1/002—Repeatedly-usable boards or tablets for writing or drawing chemical details
Abstract
Dry erase articles having a writing surface that exhibits good writing receptivity and good resistance to ghosting and method of using such articles.
Description
Technical field
The present invention relates to the purposes of a kind of xerotripsis goods and this based article, said xerotripsis goods have the good acceptance of writing to the xerotripsis ink and also even after between writing and wiping, experiencing for a long time still are easy to remove the xerotripsis ink.
Background technology
Because the convenience and the versatility of xerotripsis plate, it is existing for many years as writing surface.Said plate provides a kind of expression device, and it has eliminated the dirty and messy of chalk board and trouble.
The xerotripsis label of on the xerotripsis plate, writing should form dark-coloured solid line and Cheng Zhu not.If the xerotripsis ink becomes pearl on writing surface, then it will stay dotted line or hole in the gained written image.Expectation has the xerotripsis ink xerotripsis plate of Cheng Zhu not above that.
Xerotripsis goods on the market are numerous.Schematic writing surface on this based article comprises porcelain steel, melamine, japanning metal, glass and the acrylate coatings that solidifies through UV.These surfaces can provide the effective wetting of many commercially available xerotripsis labels and enough erasabilities, if after on writing soon (for example in several hours) promptly wipe.Yet,, write and more and more be difficult to wipe with eraser with becoming if stay a couple of days or several weeks onboard.The result stays light written image, is sometimes referred to as " ghosting (ghosting) ", and it must remove with special liquid cleaner.
Existence is to not only providing the good needs of writing acceptance but also the xerotripsis writing surface of good low ghosting property being provided.
Summary of the invention
The invention provides a kind of xerotripsis goods; Said xerotripsis goods have the good acceptance of writing; The good wettability that has xerotripsis label printing ink above that when promptly writing, and even between writing and wiping experience still be easy to remove the xerotripsis mark after long-time with dried eraser, promptly hang down ghosting.Also provide to obtain still NO so far xerotripsis performance and the method for using that is easy to the combination of usability, in certain embodiments, novel high-performance xerotripsis label is provided.
In brief, xerotripsis goods of the present invention comprise and show to have the good writing surface of writing acceptance and good anti-ghosting property.Xerotripsis goods of the present invention have wetting tension and are lower than about 38mJ/m
2, be usually less than about 32mJ/m
2, be about 20 to about 30mJ/m in certain embodiments
2Writing surface.Such wetting tension characteristic is lower than those wetting tension characteristics of the writing surface of known available xerotripsis goods, it is believed that the wetting tension of the writing surface of known available xerotripsis goods is at least about 38mJ/m
2Or it is higher.
Required surface characteristic obtains through following method: apply the coating that produces the writing surface with required character or writing to the surface of writing member and mix selected component in the member and have required character so that its front surface shows.
In brief, method of the present invention comprises:
A) a kind of xerotripsis goods described in this paper are provided;
B) use comprise surface tension be lower than writing surface the surface can the xerotripsis label of printing ink on writing surface, write first and write thing; With
C) use dried eraser wipe said first write thing at least a portion, normally wipe solidly and be no more than 2 times, preferably only 1 time with hand, make write thing said part on the xerotripsis goods no longer it is thus clear that.
According to the present invention, said method can be used to obtain low ghosting performance, or even under the situation of write the back existing several hours, a couple of days or longer time.
The present invention also provides the xerotripsis label, and in brief, said xerotripsis label uses surface tension significantly to be lower than the fluid of used fluid in the conventional xerotripsis label.
Found that the writing surface described in this paper has wonderful performance.Some advantages of xerotripsis goods of the present invention comprise good writing property and good anti-ghosting property.In addition, when with inappropriate writing implement such as so-called permanent marker rather than xerotripsis label marking, xerotripsis goods of the present invention are resistant more.Possibly need solvent such as isopropyl alcohol to come to remove permanent marker, but the person's handwriting of conventional xerotripsis label can be through only wiping one or remove for twice with conventional dried eraser from xerotripsis goods of the present invention.In addition, xerotripsis goods of the present invention show to have excellent mechanical endurance and anti-aging yellowing property usually.
The accompanying drawing summary
In conjunction with accompanying drawing the present invention is further specified, wherein:
Fig. 1 is the cross sectional representation of an illustrative examples of the present invention.
This figure not to scale (NTS) is drawn, and only is intended to signal rather than restrictive.
The specific embodiment
For the following term that provides definition, be as the criterion with these definition, only if provided different definition in addition at claims or other parts in this manual.
Except as otherwise noted, all numerals of character, reaction conditions or the like such as the amount of used expression composition, for example molecular weight all are interpreted as being modified by term " about " in all cases otherwise in specification and claims.Therefore, only if opposite explanation is arranged, otherwise the numerical parameter of in above-mentioned specification and accessory claim, listing is approximation, and these approximations can change with the characteristic that those skilled in the art uses instruction content of the present invention to seek to obtain.On minimum level, each numerical parameter is not intended to limit the application of doctrine of equivalents on claims protection domain, should explain each numerical parameter according to the significant digit of institute's numerical values recorded with through usual rounding-off method at least.Although setting forth the number range and the parameter of broad range of the present invention is approximation, numerical value will as far as possible accurately be narrated described in the instantiation.Yet any numerical value has comprised owing to be present in them inherently tests standard deviation and unavoidable some mistake in measuring separately.
% weight, weight %, % (by weight) etc. are synonym, refer to that substance weight takes advantage of 100 material concentrations that obtain again divided by composition weight.
Number range by the end points statement comprises all numerical value (for example, 1 to 5 comprises 1,1.5,2,2.75,3,3.80,4 and 5) that comprise in this scope.Such as in this specification and additional claims use, only if in have in addition clearly statement, the word of singulative " " and " said " comprise the object of plural words and phrases indication.Therefore, this expression way of composition that for example, comprises " a kind of compound " comprises the mixture that comprises two or more this compounds.Such as in this specification and additional claims use, term " or " generally with comprise " and/or " the meaning use, only if in have in addition clearly statement.
The xerotripsis article configurations
Fig. 1 shows a kind of schematic xerotripsis goods of the present invention, wherein shows to comprise the xerotripsis goods 10 of writing member 12 and the backing member of choosing wantonly 14.According to the present invention, write the front 16 of member 12, i.e. writing surface had not only shown that having good writing acceptance but also show had good anti-ghosting property.In certain embodiments, backing member 14 comprises that structural elements 18 and optional priming coat 20 are to obtain writing the required layer-to-layer adhesion of member 12.In certain embodiments, goods 10 can for example be shown on the back side of backing member 14 also on its back side here, comprise optional adhesive 22, and adhesive 22 provides and adheres to the measure of goods 10 in adherend as required.In certain embodiments, goods 10 can also on one or more marginal portions, comprise framing component 24 with the component pieces of consolidated article 10 in together, be convenient to goods 10 grasping, the device of attached goods 10 in area supported etc. is provided.
Goods of the present invention can be as required with the various embodiments manufacturing, and schematically instance comprises sheet material independent or cushioning (for example similar with paper, film, stickers), is attached in file, otecase, the xerotripsis goods etc.
Allow printing ink on writing surface 16, not have the printing ink pearl and form " wetability " that can be defined as the xerotripsis writing surface as written indicia.Wetability is meant along with solvent seasoning can keep its shape and the successional lines of writing.Solvent makes lines move inward or interrupts at some points from drying of writing surface, thereby causes the space in writing in the thing.If the surface tension of solvent composition in the ability greater than flag printing ink of the surface of writing surface then realizes qualified wetability (or not having writing of drying) usually.Wetting tension method of testing ASTM D 2578-08 " the wetting tension standard method of test of polyethylene and polypropylene screen " is the direct measurement of surface wettability.In this method of testing, the liquid of known surface tension force is applied to the surface.If this liquid does not become pearl or dries after 2 seconds, then say this wetted surface.After 2 seconds not the surface tension of the peak surface tension liquid of Cheng Zhu be regarded as wetting of surfaces tension force.
Solvent compositions in the xerotripsis label is listed on the label usually or is recorded in the MSDS that is used for label.The general solvent that is used for the xerotripsis label comprises (for example) ethanol, isopropyl alcohol, methyl iso-butyl ketone (MIBK) and n-butyl acetate.Having high capillary a kind of solvent is n-butyl acetate, and it has about 25mJ/m
2Surface tension.Therefore, in certain embodiments, can be about 25mJ/m through surface tension
2Or lower solvent comes wetting xerotripsis surface.In one embodiment, the surface of writing surface can be at about 26mJ/m
2To being lower than about 38mJ/m
2Scope in.In another embodiment, the surface of writing surface can be at about 30mJ/m
2To being lower than about 38mJ/m
2Scope in.
The writing surface of goods of the present invention provides " erasability " that allows the user when no longer needing, (for example to use dried cloth or dried eraser) to wipe the level of the mark of writing with the xerotripsis label in addition., then realize qualified erasability if thereby the surface of writing surface can enough lowly avoid the binding agent in the marking ink to adhere to writing surface with strong effect of other solids.As used herein, good erasability be considered to dried eraser hand wipe be no more than 2 times, preferably only promptly wipe basically fully for 1 time and write thing.Eraser is wiped and once is defined as the eraser folk prescription to passing through on the writing surface.The meaning with hand is meant about 0.4N/cm
2Power.If use lighter power, then possibly need to increase the number of times of wiping.The needs of the strong scouring action that the wonderful erasable performance that writing surface of the present invention provides has been avoided usually running into when wiping make it be easier to be the wearing and tearing on more people's institute's use and minimizing eraser and the writing surface.In addition, owing to obtained to be easy to wiping property, so thereby the user needn't clean writing surface with more powerful cleaning agent with bad smell and the instrument that possibly often make the writing surface variation shorten its surface lifetime.
Can use multiple dried eraser type among the present invention.The illustrative example of eraser material comprises the compacting and the woven felt of synthetic and/or natural (for example wool) material, has used cellulose, foam rubber, neoprene, cloth, pile, melamine fiber and similar material.Preferably, selected eraser material is not an abrasion, so that improve the durability of writing surface.
Writing surface of the present invention also provides the maintenance of label person's handwriting in the surface (holdout).In the time of in marking ink penetrates into the surface, the ghosting of xerotripsis person's handwriting possibly take place, make to be difficult to maybe can not remove through simply wiping with dried eraser.If this infiltration then often takes place in writing surface porous or softness.The invention provides porous not and highly cross-linked writing surface to prevent causing ghosting in the writing surface because of solvent penetrates into.Therefore, the writing surface of goods of the present invention shows to have excellent anti-ghosting property.
Optional backing member 14 is chosen as gives required performance, for example gives writing surface and gives reflectivity and improved projection ability etc. with color background, under xerotripsis goods situation.
In certain embodiments, the xerotripsis goods comprise on a side of backing member 14 writes member 12, and optional adhesive (not shown) is arranged on second side of backing member 14, and optional release liner (not shown) is arranged on the back side of adhesive.
In certain embodiments, the xerotripsis goods have adhesive on the part of one of which side, having the base material of solidified coating on the part of the opposite side of said base material, and wherein said goods are laminated into second base material, and it adds upper frame then and processes the xerotripsis plate.
Write member
The favourable beneficial effect apparatus of the present invention obtains just like the member of writing of the writing surface described in this paper.Said writing surface can also solidify or form through the cured film that forms from supporting from said composition through for example applying said composition to base material from curable coating composition.
In a typical embodiment, write member and comprise coating or film from the coating formation of radiation-hardenable.The coating of said radiation-hardenable comprises acrylate monomer and other polymerisable monomers or polymer and at least a polymerisable low-surface-energy monomer, oligomer or polymer.This low-surface-energy monomer, oligomer or polymer can be fluorohydrocarbon, organosilicon or hydrocarbon.In preparation, add said low-surface-energy monomer, oligomer or polymer and be for the surface that reduces radiation-curable couting can, but still xerotripsis label complete wetting from the teeth outwards is provided.After the curing, as it is measured to press ASTM D 2578-08, and the wetting tension of face coat is about 30 to being lower than about 38mJ/m
2
In another embodiment, the present invention includes the coating of the radiation-hardenable on a kind of film or the paper base material, the wetting tension of said coating is about 20 to about 30mJ/m
2, be called " ultralow wetting tension " xerotripsis goods in this article.An advantage of this " ultralow wetting tension " xerotripsis goods is that permanent marker will dry or Cheng Zhu, thereby sends the signal that has used wrong label to the user.Yet commercially available xerotripsis label can wetting effectively such writing surface, but becomes pearl so that in person's handwriting, form the space.Therefore, to provide at wetting tension be about 20 to about 30mJ/m to one aspect of the present invention
2" ultralow wetting tension " surface on wetting xerotripsis label.Wetting can the realization with the surface tension that reduces printing ink through preparing marking ink again for example mixed surfactant in printing ink on such writing surface.Such printing ink will be wetting effectively on such writing surface, but even still be easy to after on staying in said surface for a long time wipe.
When using conventional xerotripsis label, expect that usually writing surface 16 has more than or equal to about 26mJ/m
2The surface ability.This writing surface surface can will prevent on writing surface, to become pearl from the printing ink of typical xerotripsis and permanent marker.Admit written indicia with pantostrat, thereby avoid one-tenth pearl or " gap " in the line that forms written indicia.Typical xerotripsis label solvent comprises ethanol, isopropyl alcohol, methyl iso-butyl ketone (MIBK) and n-butyl acetate.For making not Cheng Zhu of the wetting effectively xerotripsis of label surface, the surface tension of the solvent in the necessary greater than flag printing ink of surface ability on xerotripsis surface.The solvent that has highest face temperature tension force in the above-mentioned tabulation is a n-butyl acetate, and it has about 25mJ/m
2Surface tension.Therefore, in one embodiment, the writing surface of xerotripsis goods has more than or equal to about 26mJ/m
2The surface ability.In the embodiment that substitutes, as it is measured to press ASTM D 2578-08, and the writing surface of xerotripsis goods has more than or equal to about 30mJ/m
2The surface ability.In addition, can be preferably wipe and minimum xerotripsis goods printing ink absorption comes to remove written indicia apace from the xerotripsis goods with minimum., then realize the qualified removable property of printing ink if thereby the surface of writing surface can enough lowly avoid the binding agent in the marking ink to adhere to writing surface with strong effect of other solids.Therefore, in one embodiment, the writing surface of xerotripsis goods has and is less than or equal to about 38mJ/m
2The surface ability.In the embodiment that substitutes, as it is measured to press ASTM D 2578-08, and the writing surface of xerotripsis goods has and is less than or equal to about 35mJ/m
2The surface ability.
In certain embodiments, write the crosslinked polymer layer that member cannot not comprise stickingly.This polymeric layer makes from the coating formulation of radiation-hardenable, and said preparation contains at least a low-surface-energy monomer, oligomer or the polymer that is selected from polymerisable fluorohydrocarbon, organosilicon or hydrocarbon monomer.When radiation curing, said not sticking crosslinked polymer layer provides printing ink to accept the surface, and improved erasability and anti-ghosting property are provided simultaneously.
Said not sticking crosslinked polymer layer can form through the polymerization precursor composition, but also can use additive method (for example using chemical or ionising radiation to carry out the crosslinked of polymer or its blend).Available precursor composition comprises one or more polymerizable materials (for example monomer and/or oligomer, it can be simple function and/or polyfunctional), curing agent and optional inorganic particle usually.But polymerizable material can be for example free redical polymerization, cationically polymerizable and/or polycondensation.Available polymerizable material comprises the for example oligomer and the polymer of acrylic acid ester and methacrylate, epoxides, polyisocyanates and trialkoxysilane-capped.Preferably, said polymerizable material comprises the material of free redical polymerization.
The material of available free redical polymerization comprises the for example monomer and/or the oligomer of free redical polymerization, its arbitrary or the two can be simple function or polyfunctional.The monomer of exemplary free redical polymerization comprises styrene and substituted styrene (for example AMS); Vinyl esters (for example vinylacetate); Vinyl ethers (for example butyl vinyl ether); N-vinyl compound (for example N-vinyl-2-Pyrrolidone, N-caprolactam); Acrylamide and substituted acrylamide (for example N, N-dialkyl group acrylamide); With acrylic acid ester and/or methacrylate (promptly close in this article and be called (methyl) acrylic acid ester) (for example (methyl) Isooctyl acrylate monomer, nonyl phenol ethoxylation (methyl) acrylic acid ester, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) acrylic acid binaryglycol ester, (methyl) IBOA, (methyl) acrylic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) 2-EHA, (methyl) lauryl acrylate, list (methyl) acrylic acid butanediol ester, (methyl) propenoic acid beta-carboxylic ethyl ester, (methyl) isobutyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylonitrile, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) n-butyl acrylate, (methyl) methyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid, (methyl) acrylic acid stearyl, hydroxy-functional polycaprolactone (methyl) acrylic acid ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid hydroxyl methyl esters, (methyl) hydroxypropyl acrylate, (methyl) acrylic acid hydroxyl isopropyl ester, (methyl) acrylic acid hydroxy butyl ester, (methyl) acrylic acid hydroxyl isobutyl ester, (methyl) tetrahydrofurfuryl acrylate, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid hexylene glycol ester, two (methyl) acrylic acid triglycol ester, two (methyl) acrylic acid 1; Ammediol ester, two (methyl) acrylic acid TEG ester, trimethylolpropane tris (methyl) acrylic acid ester, two (methyl) acrylic acid 1; 4-cyclohexanediol ester, two (methyl) acrylic acid 1,5-pentadiol ester, ethoxylated trimethylolpropane three (methyl) acrylic acid ester, three (methyl) acrylic acid glyceride, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, five (methyl) acrylic acid, two pentaerythrityl esters and two (methyl) acrylic acid DOPCP).
The oligomer of exemplary free redical polymerization comprises UCB Chemicals; Smyrna; Those and Sartomer Company that Georgia (for example with trade name " EBECRYL ") sells; Exton, those that Pennsylvania (for example with trade name " KAYARAD " or " CN ") sells.
Depend on the selection of polymerizable material, precursor composition can randomly contain the curing agent that one or more help the said polymerizable material of polymerization.For specific polymerizable material, but the chemical property of copolymeric material is depended in the selection of curing agent.For example, with regard to epoxy resin, select to become known for curing agent for epoxy resin (for example dicyandiamide, salt or polymercaptan) usually.With regard to the resin of free redical polymerization, free radical thermal initiator and/or light trigger are available curing agent.
Usually, optional curing agent uses with the amount of effective promotion monomer polymerization, and said amount will be with the molecular weight of the type of for example curing agent, curing agent and polymerization and different.Optional curing agent is included in the precursor composition to the amount of about 10 weight % with about 0.01 weight % of accounting for the precursor composition gross weight usually, but also can use higher and lower amount.Precursor composition can for example solidify through being exposed to thermal source (for example heat, infra-red radiation), electromagnetic radiation (for example ultraviolet and/or visible radiation) and/or particle radiation (for example gamma-emitting electron beam).
Should solidify fully to keep label on the surface from its coating composition that forms writing surface, here it can be easy to remove through directly contacting with dried eraser.Especially, that part of composition that forms writing surface at least should solidify fully.Those skilled in the art know multiple curing strategy and can easily select suitable strategy, and this part depends on the characteristic of curable coating composition, the miscellaneous part and the manufacturing facility of goods.The schematic technology of the curing of maximization UV cure coating compositions be included in nitrogen under solidify, use new UV bulb, use before cleaning UV bulb, the output spectrum that makes the UV bulb be complementary and processing and/or processing long period under low speed with the absorption of initator.In certain embodiments, because the xerotripsis goods are at room temperature aging, so as time passes, a certain amount of exposure back possibly take place solidify.
The state of cure of the xerotripsis goods that are coated can stop through person's handwriting before wiping carries out the xerotripsis described in the Test Methods section on the sample of a time and tests.If the xerotripsis goods are wiped after solidify the back better, then initial solidification maybe be not enough.Therefore except that above-mentioned first solidifies, possibly also need second cured.Second curing can use the radiation source identical with first curing or its can use different radiation sources.Preferred second curing comprises heat, electron beam and gamma-rays processing.
If optional curing agent is a radical initiator, then the amount of curing agent preferably at about 1 weight % of precursor composition gross weight to about 5 weight % scopes, but also can use higher and lower amount.Available free radical photo-initiation for example comprises benzoin ether (like styrax methyl ether and benzoin isobutyl propyl group ether), substituted benzoin ether (for example anisoin methyl ether), substituted acetophenone (for example 2,2-dimethoxy-2-phenyl acetophenone), substituted α-keto-alcohol (for example 2-methyl-2-hydroxypropiophenonepreparation), benzophenone derivates (for example benzophenone) and acylphosphine oxide.Exemplary commercially available light trigger comprises with trade name " IRGACURE " (IRGACURE for example
TM651, IRGACURE
TM184 and IRGACURE
TM819) or " DAROCUR " (DAROCUR for example
TM1173, DAROCUR
TM4265) from (the Ciba Specialty Chemicals of vapour Bagong department of New York Tarrytown; Tarrytown; New York) with the BASF (BASF of trade name " LUCIRIN " (for example " LUCIRIN TPO ") from New Jersey Pa Xipani; Parsippany, New Jersey) those.
Exemplary free radical thermal initiator comprises: peroxide; For example benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, cyclohexane peroxide, methyl-ethyl-ketone peroxide, hydroperoxides (for example TBHP) and hydrogen phosphide cumene, di-cyclohexylperoxy di-carbonate, t-butyl perbenzoate and azo-compound (for example 2; 2 ,-azo-two (isobutyronitrile)).
Low-surface-energy monomer, oligomer or polymer can be selected from fluorohydrocarbon, organosilicon or hydrocarbon monomer.Be suitable for fluorohydrocarbon monomer of the present invention and include but not limited to perfluorinated acrylate or perfluoro-methyl acrylic acid ester, for example based on C
4F
9The sulfonamide acrylic acid ester and based on C
3F
7The sulfonamide acrylic acid ester.The illustrative example of available fluorohydrocarbon monomer comprises C among this paper
4F
9SO
2N (CH
3) C
2H
4O-CONHC
6H
5-CH
2C
6H
5NHCO-OC
2H
4OCOCH=CH
2(also claiming MeFBSE-MDI-HEA), C4F9SO2N (CH3) C2H4O-CONH (CH2) 6NHCO-OC2H4OCOCMe=CH2, C
4F
9SO
2N (CH
3) C
2H
4O-CONH (CH
2)
6NHCO-OC
12H
24OCOCH=CH
2And CF
3CH
2O-CONHC
6H
5CH
2C
6H
5NHCO-OC
2H
4OCOCH=CH
2Be applicable to that perfluorinated acrylate of the present invention comprises C
1To C
6Perfluoroalkyl acrylate or RSO
2NMeC
2H
4OC (O) CH=CH
2Type, wherein R is C
nF2
N+1, n is 1 to 6 integer.
The suitable fluorochemical monomer of another series is at United States Patent(USP) No. 7,279, and 210 people such as () Hulteen and No.7 state among 199,197 people such as () Caldwell.These fluorinated acrylate monomers are expressed from the next:
Wherein, n is 1 to 6 integer (comprising end points), and p is 2 to 30 integer (comprising end points); R' is H, CH
3Or F, A be alkylene and
Wherein, R is H or the alkyl with 1 to 4 carbon atom; M is 2 to 8 integer (comprising end points); R
fBe C
nF2
N+1Y is 0 to 6 integer (comprising end points); Q is 1 to 8 integer (comprising end points).
In certain embodiments, A Xuan Zi – C
6H
12–,
Be applicable to that other fluorochemical additives of the present invention comprise United States Patent(USP) No. 7,173, the PFPE urethane acrylate of describing among 778 people such as () Jing.
Being applicable to that fluorochemical oligomer in the xerotripsis goods of the present invention comprises can (3M Company, St.Paul MN.) be purchased the FLUORAD of acquisition from the 3M in Sao Paulo, Minnesota State company
TMFC-4430 and FC-4432.
Be applicable to that the fluorochemical polymer in the xerotripsis goods of the present invention comprises having the PFPE polymer that gathers (alkylene oxide) repetitive, for example described in PCT application No.WO2009/076389 people such as () Yang.
Be applicable to that organic silicon monomer of the present invention includes but not limited to the organic silicon acrylic ester monomer.The exemplary organic silicon acrylic ester that is suitable among this paper comprises (the BYK-Chemie GmBH of Bi Ke chemical company from German Wei Saier; Wesel, the reactive organosilicon surface additive of Germany) BYK-371, the reactive organosilicon surface additive of BYK-373, the reactive organosilicon surface additive of BYK-377, be used for radiation curable system BYK-UV 3500 surface additives, be used for radiation curable system BYK-UV 3530 surface additives, be used for BYK-UV 3570 surface additives and the BYK SILCLEAN of radiation curable system
TM3710 surface additives are to improve surperficial cleanablity.Other suitable organic silicon monomers comprise win wound Gao Shi Mitt USA Corporation (Evonik Goldschmidt Corporation, Hopewell, TEGORAD VA) from Virginia Hope Wei Er
TM2100, TEGORAD
TM2200N, TEGORAD
TM2250 and TEGORAD
TM2300 organic silicon acrylic ester monomers.
Can use hydrocarbon monomer to reduce the surface ability of coating.These hydrocarbon monomers are characterised in that the long side chain that can form crystal structure from the teeth outwards.Suitable hydrocarbon monomer includes but not limited to the acrylic acid stearyl.
In one embodiment of the invention, be about 26 to about 36mJ/m with low-surface-energy monomer, oligomer or polymer to be enough to produce wetting tension
2The concentration of solidified coating be added in the coating formulation.The wetting tension of preferred said solidified coating is about 30 to about 36mJ/m
2
In certain embodiments; The material of radiation-hardenable comprises aforementioned one or more oligomer, one or more monomers and/or one or more polymer and a certain amount of optional particle or nano particle in one or more solvents, for example write hardness and the durability that member improves to give.
Nano particle can be through surface modification, and this refers to that nano particle has surface through modification so that nano particle provides the fact of stabilising dispersions." stabilising dispersions " refers to such dispersion: in said dispersion, the colloid nano particle is not for example reunited after having and leaving standstill for example about 24 hours of a period of time under the extreme electromagnetic force at room temperature (about 20 to about 22 ℃), atmospheric pressure under environmental condition.
In but the colloid nano particle of surface modification can randomly be present in as the polymer coating of the coating composition among this paper and nano particle exist with the amount of the durability that strengthens finished product or optical element effectively.The colloid nano particle through surface modification described in this paper can have multiple required attribute, for example comprises: but the compatibility of nano particle and coating composition, but so that nano particle forms stable dispersion in coating composition; But the reactivity of nano particle and coating composition, thereby make that this compound is more durable; Low with viscosity influence to uncured composition.Can use the combination of surface modification to come the uncured and curing properties of control combination thing.But can improve the optics and the physical property of coating composition through the nano particle of surface modification, for example improve the mechanical strength of resin, in improving curable compositions, make the viscosity minimize variations in the solid volume carrying capacity and in improving curable compositions, keep optical clarity in the solid volume carrying capacity.
In certain embodiments, nano particle is the nano particle through surface modification.The suitable colloid nano particle through surface modification can comprise oxide particle.For given material, nano particle can have a series of granularities on known size distribution.In certain embodiments, particle mean size can be at about 1nm to about 100nm scope.Granularity and size distribution can be confirmed in known manner, for example comprise and confirming through transmission electron microscope (" TEM ").Suitable nano particle can comprise any material in the multiple material, for example is selected from the metal oxide of aluminium oxide, tin oxide, antimony oxide, silica, zirconia, titanium dioxide and aforementioned both or more persons' combination.Colloid nano particle through surface modification can condense basically fully.
In certain embodiments, the granularity of Nano particles of silicon dioxide can be about 5 to about 100nm.In certain embodiments, the granularity of Nano particles of silicon dioxide can be about 10 to about 30nm.But Nano particles of silicon dioxide can about amount of 10 to about 100phr be present in the coating composition.In certain embodiments, but Nano particles of silicon dioxide can about amount of 30 to about 90phr be present in the coating composition.Be applicable to that but the Nano particles of silicon dioxide in the coating composition of the present invention can ProductName NALCO
TM(Nalco Chemical Co. (Naperville, IL)) is purchased acquisition in the Nalco Chemical Co of COLLOIDAL SILICAS Na Boweier from the Illinois.Suitable silica product comprises NALCO product 1040,1042,1050,1060,2327 and 2329.Suitable pyrogenic silica product comprises the goldschmidt chemical corporation DeGussa AG that for example can derive from Hanau, Germany, (Hanau, Germany) with AEROSIL
TMProduct that series OX-50 ,-130 ,-150 and-200 the sells and (CAB-O-SPERSE of Cabot Corp. (Tuscola, IL)) of Cabot Co.,Ltd that can derive from Illinois Ta Sikela
TM2095, CAB-O-SPERSE
TMA105 and CAB-O-SIL
TMMS.But the surface treatment to nanoscale particle can be provided at the stable dispersion in the coating composition (for example fluoropolymer resin).Preferably, surface treatment makes the nano particle stabilisation, but so that these particles are dispersed in the coating composition well and obtain the composition of homogeneous basically.In addition, can at least a portion of nanoparticle surface, carry out modification with surface conditioning agent, but so that stabilized particle in solidification process can with coating composition copolymerization or reaction.
Nano particles of silicon dioxide usable surface inorganic agent is handled.But the surface conditioning agent that is suitable for the particle in said coating composition comprises compound, like isooctyltrimethoxysi,ane, N-(3-triethoxysilylpropyltetrasulfide) methoxy ethoxy ethoxyethyl group carbamate (PEG3TES), SILQUEST
TMA1230; N-(3-triethoxysilylpropyltetrasulfide) methoxy ethoxy ethoxyethyl group carbamate (PEG2TES); 3-(methacryloxy) propyl trimethoxy silicane; 3-acryloxy propyl trimethoxy silicane; 3-(methacryloxy) propyl-triethoxysilicane; 3-(methacryloxy) propyl group methyl dimethoxysilane; 3-(acryloxy propyl group) methyl dimethoxysilane; 3-(methacryloxy) propyl-dimethyl Ethoxysilane; 3-(methacryloxy) propyl-dimethyl Ethoxysilane; Vinyl-dimethyl base oxethyl silane; Phenyltrimethoxysila,e; The n-octyl trimethoxy silane; The dodecyl trimethoxy silane; The octadecyl trimethoxy silane; Propyl trimethoxy silicane; The hexyl trimethoxy silane; Vinyl methyl diacetoxy silane; The vinyl methyldiethoxysilane; Vinyltriacetoxy silane; VTES; Vinyl silane triisopropoxide; Vinyltrimethoxy silane; Vinyl triple phenoxyl silane; Vinyl three tert-butoxy silane; Vinyl three isobutoxy silane; Vinyl three iso-propenyloxysilanes; Vinyl three (2-methoxy ethoxy) silane; The styryl ethyl trimethoxy silane; Mercaptopropyl trimethoxysilane; The 3-glycidoxypropyltrimewasxysilane; Acrylic acid; Methacrylic acid; Oleic acid; Stearic acid; Dodecylic acid; 2-[2-(2-methoxy ethoxy) ethyoxyl] acetate (MEEAA); Propenoic acid beta-carboxyl ethyl ester; 2-(2-methoxy ethoxy) acetate; Methoxybenzene guanidine-acetic acid and aforementioned both or more persons' mixture.
In certain embodiments, particle mean size (for example particle diameter) can be at about 1nm to about 1000nm scope.Except that aforementioned granularity, it will also be appreciated that the particle mean size that use is littler or bigger.In an embodiment of the present invention, at least a portion aforementioned particles can be carried out surface modification with above-described mode.In other embodiments, all particles are all through surface modification.Also in other embodiment, all particles are all without surface modification.
As will understand, be used for making the coating composition of writing member of the present invention and can comprise optional additive and come to strengthen as required or control characteristic, for example rheology modifier such as JAYLINK
TMRheology modifier, colouring agent (like dyestuff and/or pigment), fire retardant, anti-oxidant, stabilizing agent, antiozonant, plasticizer, UV absorbent, resistance amine light stabilizer (HALS) etc.
Backing member
In certain embodiments; For example when write member be not fully from when supporting maybe when needing other character of xerotripsis goods; In the time of for example need giving magnetic, curling resistance, wear resistant, dimensional stability, color etc., the xerotripsis goods should be also comprise backing member writing on the back surface of member.Depend on embodiment, backing member can be single or multiple lift.
The illustrative example that is used as the suitable substrate of backing member includes but not limited to glass, paper, coated paper, paper rete compound, polymer film, polymer sheet and metal forming, metal sheet, ceramics material etc.Polymer film and sheet material include but not limited to polyester, polypropylene, polyethylene, polystyrene, cellulose acetate, Merlon, polyacrylate and polyvinyl chloride.Polymer film and sheet material can comprise copolymer, blend or the coextruded multilayer film of above-mentioned polymer or other polymer.If desired, backing can on surface thereafter, comprise adhesive or even form by adhesive, to promote the bonding of gained xerotripsis goods to base material or surface.
Need therein to write preferred substantial transparent of member and backing member and have reflection characteristic among the embodiment of good projection performance of xerotripsis goods.For example, the U.S. Patent application No.12/684 that submitted on December 15th, 2009, disclosed projection means can be used in the xerotripsis goods of the present invention in 565.
If desired, backing member can be opaque and/or coloured, to give gained xerotripsis goods required outward appearance.In addition; Decoration or organization chart, header etc. can be provided so that visible in goods, for example be embedded in and write in the member, write the legend that goes up on the surface, the backing front surface is first-class behind the member and required decorative pattern, information heading (for example " NAME ", " IN ", " OUT " etc.) the observer.
The xerotripsis label
In certain embodiments, xerotripsis goods of the present invention can use with multiple conventional xerotripsis label.
The surface tension of commercially available xerotripsis label printing ink is usually less than about 30mJ/m
2Common xerotripsis label has two types, promptly based on the label of alcoholic solvent with based on the label of ketone solvent.Solvent in the alcohol label is generally ethanol and isopropyl alcohol.Be generally methyl iso-butyl ketone (MIBK) and n-butyl acetate based on the solvent in the label of ketone.The surface tension value of these solvents is listed in following table.
The surface tension of table 1. label solvent
For making xerotripsis label complete wetting, the wetting tension of xerotripsis plate needs the surface tension of greater than flag printing ink.Therefore, as it is measured to press ASTM D2578, and wetting from the teeth outwards for making commercially available label, wetting of surfaces tension force usually should be greater than 25mJ/m
2
To have ultralow moistened surface tension force be that moistened surface tension force is lower than about 30mJ/m to writing surface therein
2Some embodiment of the invention in, one or more surfactants that can in the printing ink in the xerotripsis label, add effective dose are to reduce the surface tension of ink formulations.Said surfactant can be anionic, cationic or non-ionic.Owing to the selection of the label that can be used on the surface of the ultralow wetting tension of this type, effectively write is limited; So this type xerotripsis goods will be avoided the attempt of coating and drawing at random above that or avoid inadvertently using wrong label, for example use permanent marker rather than xerotripsis label.
The illustrative example of suitable surfactant includes but not limited to: from 3M Company, and St.Paul, the FLUORAD of MN
TMFC-170C, FC-430 and FC-171; The industry of win wound (Evonik Industries, Parsippany, SIVENTODYNASYLAN NJ) from New Jersey Pa Xipani
TMF8810; Ausimont company (Ausimont Inc., Thorofare, FOMBLIN NJ) from plug sieve Fil, New Jersey
TMC; Gelest company (Gelest Inc., Kent, Silane B-1092 ME) from Kent, Maine State fort; Solvay Solexis company (Solvay Solexis, West Deptford, FLUOROLINK NJ) from west, New Jersey Paterson
TM3; With the Huls U.S. (Huls America, Cincinnati, DYNASYLAN OH) from the Cincinnati, Ohio
TMFC-8261.In ink formulations more according to the present invention, can use above-mentioned FLUORAD
TMFC-4430 and FC-4432 are as surfactant.
Instance
Further explain the present invention with schematic limiting examples below.
Test method
Use following method of testing.
Label dries: with comprise that 14 different markers things of 7 xerotripsis label brands mark on the xerotripsis surface.These xerotripsis labels are: AVERY
TMMARKS-A-LOT
TM(AVERY DENNISON of California Pasadena (Avery-Dennison, Pasadena, Cal.)), BEIFA
TMOwn Brand label (the Bei Fa company of Tokyo (Beifa, Tokyo, Japan)), BICTM xerotripsis label (BIC Corp. of Connecticut State Penelope Milford (BIC Corporation, Milford, Conn.)), DIXON
TMXerotripsis label (the Dixon Tai Kangde scholar lattice company of Heathrow, Florida State (Dixon Ticonderoga Co., Heathrow, Fla.)), EXPO
TMBold (the Sang Fude company of Illinois Bellwood (Sanford Corp., Bellwood, IL)), EXPO
TMLow Odor (Sang Fude company (Sanford Corp.)) and QUARTET
TMMark (the Acco company of Lincolnshire, thing Illinois (Acco, Inc, Lincolnshire, IL)).All labels all have the cusp of scalpriform.From the label of two kinds of colors of each brand selection, one is black, and another is red, green or blue.Typical xerotripsis sample is the size of about a piece of paper.For each label brand, on sample, this label brand reserved the horizontal space of high about 2.5cm.On the left-hand side in the high space of this 2.5cm, write label brand name with first label, and on the right-hand side in the high space of this 2.5cm, write same label brand name with second label.Like this, all person's handwritings from each label brand are arranged in an erasable horizontal line.
After marking on the xerotripsis of the present invention surface, check the situation of drying of every printing ink line.Xerotripsis printing ink dry or Cheng Zhu is confirmed by the contraction that occurs gap or ink line in the printing ink line.The sum of the label that calculating is dried.Write and used 14 different markers things in the test, therefore the possible score scope of drying is 0 to 14.For example, if there is not label to dry, then dry to such an extent that be divided into zero.If 10 labels dry, then must be divided into 10.
The xerotripsis person's handwriting removes: as writing on the writing surface that is tried and behind aging person's handwriting under the room temperature, testing the removable property of xerotripsis person's handwriting by being described below indicatedly.Sample is placed on the hard flat surface.Use EXPO
TMDried eraser (Sanford Corp.) comes erasing handwriting.The eraser area that contacts with writing surface is about 12.5cm * 5cm.On eraser, place 12.5cm * 5cm brass counterweight of a heavy 2.5kg, thereby produce 0.4N/cm
2Pressure.Let this eraser that has added load on article one line of label person's handwriting, pass through, do not apply hand in addition.Article one line of person's handwriting comprises the person's handwriting from two labels of number one brand.Counting removes the required eraser number of pass times of most label person's handwriting spots.If person's handwriting is still readable after eraser has been walked 10 strokes, then stop to wipe.Continue to wipe with hygenic towelette then, at the most 10 strokes.Write down the stroke sum of each label brand and with the stroke sum addition of seven brands.In some cases, single eraser stroke promptly removes all person's handwritings from two labels.In other cases, removing said person's handwriting has spent above a stroke.Minimum xerotripsis removes to such an extent that be divided into 7, because always have 7 xerotripsis label person's handwriting lines.
Wetting tension: press ASTM D 2578-08 (on September 1st, 2009) and measure xerotripsis wetting of surfaces tension force of the present invention.At first with isopropyl alcohol and paper handkerchief cleaning all surface.Let dry tack free 10 minutes.(UVProcess Control, Chicago IL) obtain the wetting tension pen, cover 30 to 48mJ/m from the UV in Chicago, Illinois process control company
2Scope, step is 2mJ/m
2The neat solvent measurement of listing in the use table 2 is lower than 30mN/m
2Moistened surface tension force.
The surface tension of table 2. neat liquid
With pen or cotton swab said liquid is applied on the dry surface.If if liquid not exclusively becomes pearl or liquid to keep gapless continuous film to reach 2 seconds, then be the wetted surface.The wetting tension of film is that wetting film reaches 2 seconds the highest face temperature tension force pen or the surface tension of liquid.
Adhesion to the xerotripsis surface: the standard adhesive tape is to relative peel adhesion the measuring for this surperficial apparent surface ability of writing surface.Measure 3M
TMSCOTCH
TM810 magical adhesive tapes are to the peel adhesion of writing surface.The surface is cleaned and dried overnight under 23 ℃ (73 ℉) and 50%RH with isopropyl alcohol earlier.(she steps on the Minnesota State in the following clamp of MTS in the Prey (MTS, Eden Prairie, MN)) and inserts ball slide rail (ball slide) to cupping machine.Apply 3M to this ball slide rail
TMHigh/Low Tack 9415 two-sided tapes let repositionable adhesive up.Then the xerotripsis surface is applied to this 9415 adhesive tape.810 adhesive tapes of certain-length, wide 2.54cm are adhered to the xerotripsis surface, and letting at least, the adhesive tape of 20cm is suspended in outside the leading edge on surface.2kg rubber covered roll with standard is pressed onto this adhesive tape roller on the film, and this roller passes through four times separately with the speed of about 64cm/min.The free end of adhesive tape is attached to the last clamp of cupping machine.In under 90 ° with the speed of 30cm/min stripping tape from the film, move ball slide rail through phase same rate and keep 90 ° to peel off with 30cm/min.Write down average peel adhesion value.
Material
The material that uses in instance and the comparative example is shown in the table 3.
Table 3. material
Label: for making xerotripsis label complete wetting, xerotripsis wetting of surfaces tension force needs the surface tension of greater than flag logistics body.Usually, for all labels of on the xerotripsis surface, writing, wetting of surfaces tension force need be greater than about 28mJ/m
2
Preparation contains the aqueous isopropanol of 10 weight %FC-4432 surfactants.With syringe to black and green EXPO
TMInject the 0.5mL surfactant solution in the point of low smell xerotripsis label and let its infiltration and mixing spend the night.
Prepare functionalized nano silicon: the 3000g colloidal silica aqueous solution of in 12 liters of flasks, packing into is (for example from the NALCO of Ondeo Nalco Co. (Nalco Company)
TM2327) and begin to stir.Add 3591g 1-methoxyl group-2-propyl alcohol then (for example from Dow Chemical (Dow Chemical, Midland, DOWANOL MI) of available
TMPM).In independent container, with 189.1g 3-methyl allyl acyloxypropyl trimethoxysilane (for example from Myto Hi-tech Materials Co., Ltd (Momentive Performance Materials, Wilton, the SILQUEST of CT of Connecticut State Wilden
TMA-174)) mix with 455g 1-methoxyl group-2-propyl alcohol.This premixed solution is added in the flask, with 455g 1-methoxyl group-2-propyl alcohol flushing.With mixture be heated to 80 ℃ about 16 hours.Mixture is cooled to 35 ℃.With receiving flask mixture is carried out vacuum distillation (30-35 holds in the palm (4000-4700Pa), 35-40 ℃).In still-process, other 1813.5g 1-methoxyl group-2-propyl alcohol is added reaction flask.Collect the 6784g distillate altogether.Through in 105 ℃ of baking ovens in the taring aluminum pot with the dry solid % that measured mixture in 60 minutes of small amount of sample.Record mixture and comprise 52.8% solid.Add other 250g 1-methoxyl group-2-propyl alcohol and stir the mixture.Measure solid %, the result is 48.2%.Collect mixture through filtering, to remove granular debris with cheese cloth.
Instance 1 – has 906 hard coatings of 0.075%HFPO-UA: HFPO-UA synthesizes at United States Patent(USP) No. 7,173, states in 778.In MEK, HFPO-UA is diluted to 25 solid %.In the solution of 906 hard coatings, add the solution of HFPO-UA in MEK, have the ultimate density of 0.075%HFPO-UA solid based on 906 hard coating solids to produce.With ethyl acetate this solution is diluted to 25 solid % then.On the wide continuous coating machine of 9in (23cm), be coated with said preparation, this coating machine comprises and is used to be coated with, dry, UV solidifies and coated film is batched station.Through the coating die head coating formulation is applied on the thick white polyester film of 3 mils (76 microns).After the coating, let film pass through the long convection oven of 30ft (9.1m) and dry down in 130 ℉ (54 ℃).Let film pass through the UV curing room that nitrogen purges then, the H+ bulb is arranged in this curing room.Oxygen concentration in the curing room is lower than 100ppm.Linear velocity on the coating machine is 50 feet per minute clocks (15.2m/min), and the dried thick of coating is 2 μ m on the film.
Instance 2 – have 10%MeFBSEA (C 4 F 9 SO 2 NMeC 2 H 4 OC (O) CH=CH 2 ) 906 hard coatings: it is synthetic that MeFBSEA presses the program of describing among PCT application No.WO200130873 people such as () Savu.In 906 hard coatings, add MeFBSEA to count 10% value based on solid.After the mixing, solution is diluted to 30 solid % with MEK.With No. 6 Mayer rods with this solution coat to 2 mils (50 microns) transparent polyester film.Will be following dry one minute in 100 ℃ through the film of coating.Let the film of band dry coating pass through the UV curing room that nitrogen purges, the H bulb is arranged in this curing room.
Instance 3 – have 15%MeFBSEA (C 4 F 9 SO 2 NMeC 2 H 4 OC (O) CH=CH 2 ) 906 hard coatings: MeFBSEA is synthetic by the program of describing among the PCT application No.WO200130873.In 906 hard coatings, add MeFBSEA to count 15% value based on solid.After the mixing, solution is diluted to 30 solid % with MEK.With No. 6 Meier rods with this solution coat to 2 mil transparent polyester films.Film through coating is following dry one minute in 100 ℃.Let the film of band dry coating pass through the UV curing room that nitrogen purges, the H bulb is arranged in this curing room.
Instance 4 – have the hard coating 2 of 0.075%HFPO-UA: the hard coating 2 of pressing the formulation 30 solid % in the table 4.Being prepared in the instance part of functionalized nano silicon described.The solution of the HFPO-UA that in solution, adds some 25 solid % in MEK is so that be 0.075% based on solid meter HFPO-UA.With ethyl acetate said preparation is diluted to 25 solid % then.By with instance 1 in identical method coating, dry and solidify said preparation.
The prescription of table 4. hard coating 2
| Material | Prescription (weight %) | Percent solids |
| Functionalized nano silicon | 19.9% | 35.9% |
| IRGACURE TM184 | 0.6% | 2.5% |
| SR?444 | 13.3% | 53.2% |
| SR?344 | 2.1% | 8.3% |
| Isopropyl alcohol | 24.6% | 0.0% |
| Ethyl acetate | 39.4% | 0.0% |
Instance 5 – have the hard coating 2 of 0.075%HFPO-PEG: being prepared among the PCT application No.WO 2009/076389 of HFPO-PEG monomer stated.Press the hard coating 2 of the formulation 30 solid % in the table 4.The solution of the HFPO-PEG that in hard coating 2 solution, adds some 25 solid % in MEK is so that be 0.075% based on solid meter HFPO-PEG.With ethyl acetate said preparation is diluted to 25 solid % then.Press the method coating of describing in the instance 1, dry and curing said preparation.
Instance 6 – have the hard coating 2 of 1.4%HFPO-UA: the hard coating 2 of pressing the formulation 30 solid % in the table 4.The solution of the HFPO-UA that in solution, adds some 25 solid % in MEK is so that be 1.4% based on solid meter HFPO-UA.With ethyl acetate said preparation is diluted to 25 solid % then.By with instance 1 in identical method coating, dry and solidify said preparation.
Instance 7: use the 906 hard coating system films that contain 0.15%HFPO-UA based on the solid meter.In 3M 906 hard coatings, add the solution of HFPO-UA in MEK, obtain having the concentration of 0.075%HFPO-UA solid based on 906 hard coating solid meters.With ethyl acetate this hard coating is diluted to 25 solid %.Described in instance 1, on the experimental coating machine said preparation is being applied on the white PET film of 3 mil thick.
Instance 8: the hard coating 2 for preparing 30 solid % by the method in the instance 4.The solution of FC-4430 in MEK that in solution, adds some 25 solid % is so that the solids ratio of FC-4430 is 1.5% in the preparation.With ethyl acetate said preparation is diluted to 25 solid % then.By with instance 1 in identical method coating, dry and solidify said preparation.Dry coating thickness is 2.0 μ m.
Instance 9: the hard coating 2 for preparing 30 solid % by the method in the instance 4.The solution of FC-4430 in MEK that in solution, adds some 25 solid % is so that the solids ratio of FC-4430 is 2.5% in the preparation.With ethyl acetate said preparation is diluted to 25 solid % then.By with instance 1 in identical method coating, dry and solidify said preparation.Dry coating thickness is 2.0 μ m.
Instance 10 – have the hard coating 3 of 1%MeFBSEA: the hard coating of pressing this 30 solid of the formulation % in the table 4.Being prepared in the instance part of functionalized nano silicon described.Solid MeFBSEA is dissolved in the solution of preparation 25 solid % in the ethyl acetate.In big stainless steel beaker, add five kinds of listed in the table 5 materials and mixing.In same beaker, preparation is diluted to 25 solid % with ethyl acetate.By with instance 1 in identical method coating, dry and solidify said preparation.After the coating, film was heated two days down in 50 ℃.
The prescription of table 5. hard coating 3
| Material | Prescription (weight %) | Percent solids |
| Functionalized nano silicon | 26.7% | 40.0% |
| IRGACURE TM184 | 0.73% | 2.4% |
| SR?351LV | 17.0% | 56.6% |
| MeFBSEA | 0.30% | 1.0% |
| Ethyl acetate | 55.3% | 0.0% |
Comparative example C1 – 906 hard coatings: with ethyl acetate 906 hard coatings are diluted to 25 solid %.On the experimental coating machine said preparation is being applied on the white PET film of 3 mil thick.By with instance 1 in identical method coating, dry and solidify said preparation.The dry coating thickness of hard coating is 2 μ m.
Comparative example C2 – hard coating 2: instance 4 hard coatings 2 preparations that prepare 25 solid %.By with instance 1 in identical method coating, dry and solidify said preparation.The dry coating thickness of hard coating is 2 μ m.
Comparative example C3-QUARTET TM But complete wiping board (Total Erase Board): this plate is from Acco Corp., and it comprises the polyfunctional acrylic ester coating on the coated paper on the medium density fibre board (MDF).
Comparative example C4: JFE porcelain steel plate, can derive from Tokyo JFE metallic article and engineering company (JFE Metal products and Engineering Inc., Tokyo, Japan).
Comparative example C5: from Polyvision company (Polyvision Corp., Suwanee, POLYVISION GA) of Georgia State Su Wanni
TMPorcelain steel xerotripsis plate.
The result
Illustrated in the table 6 the xerotripsis writing surface wetting tension, dry and the adhesive tape adhesion.
Table 6. wetting tension, dry and the adhesive tape adhesion
The writing property result of the xerotripsis label that has mixed surfactant has been shown in the table 7.
Table 7.EXPO
TM
Low scent marking thing wetting on example film
| The label color | Institute adds surfactant | Wetting on instance 1 film | Wetting on instance 7 films |
| Black | Do not have | Be | Not |
| Black | FC-4432 | Be | Be |
| Green | Do not have | Be | Not |
| Green | FC-4432 | Be | Be |
The selected instance of test is the removing of xerotripsis person's handwriting (table 8) after experience on the instance surface one day and two all time of staying.Dried eraser promptly removes all xerotripsis label person's handwritings through seven times and shows that person's handwriting is easy to remove.The score that removes that surpasses seven times shows, eraser is through stay the ghosting of one or more labels after once onboard.
The xerotripsis test of the selected instance of table 8.
Although the present invention is combined its preferred embodiment and carried out comprehensive description with reference to accompanying drawing, should notice that variations and modifications are conspicuous to those skilled in the art.This variation and modification are interpreted as being contained in by in the defined scope of the present invention of appended claims, only if they depart from the scope of the present invention.
The complete disclosure of all patents, patent document and the publication of quoting among this paper is all incorporated into way of reference in full.Providing above-mentioned detailed description and instance has been merely and has been expressly understood the present invention.Should be appreciated that for the present invention, these are described and embodiment does not have unnecessary restriction.And the present invention is not limited to that this paper shows and described detail, and various variations of the present invention will become apparent to those skilled in the art that these variations all are included in the present invention by in the scope that claims defined.
Claims (21)
1. xerotripsis goods, said xerotripsis goods have moistened surface tension force and are lower than about 38mJ/m
2Writing surface.
2. goods according to claim 1, the moistened surface tension force of wherein said writing surface are about 26 to being lower than about 38mJ/m
2
3. goods according to claim 1, the moistened surface tension force of wherein said writing surface are about 30 to being lower than about 38mJ/m
2
4. goods according to claim 1, the moistened surface tension force of wherein said writing surface are about 20 to about 30mJ/m
2
5. goods according to claim 1, wherein said writing surface comprise the radiation curing product of the coating composition of radiation-hardenable, and the coating composition of said radiation-hardenable comprises at least a low-surface-energy monomer, oligomer or polymer.
6. goods according to claim 5, the coating composition of wherein said radiation-hardenable comprise at least a polyfunctional acrylic ester monomer.
7. goods according to claim 5, the coating composition of wherein said radiation-hardenable randomly comprises the Nano particles of silicon dioxide of Nano particles of silicon dioxide or acrylate-functional.
8. goods according to claim 5, at least a portion of the coating of the said radiation-hardenable at wherein said writing surface place is solidified fully.
9. second curing that goods according to claim 5, wherein said radiation curing product stand to choose wantonly, the said second optional curing is realized by heat, IR radiation, UV radiation, electron beam or gamma-rays radiation.
10. goods according to claim 5, wherein said low-surface-energy monomer, oligomer or polymer are the fluorochemical with one or more side chains, said side chain has formula C
nF
N-1, wherein n is 1 to 6 integer.
11. goods according to claim 5, wherein said low-surface-energy monomer, oligomer or polymer are the organic silicon acrylic ester material.
12. goods according to claim 5, wherein said low-surface-energy monomer, oligomer or polymer are the long chain hydrocarbon that contains at least one polymerizable acrylate group.
13. goods according to claim 12, wherein said long chain hydrocarbon are the acrylic acid stearyl.
14. a method, said method comprises:
A) xerotripsis goods according to claim 1 are provided;
B) use comprise surface tension be lower than said writing surface the surface can the xerotripsis label of printing ink on said writing surface, write first and write thing; With
C) let dried eraser through be no more than wipe for 2 times said first write thing at least a portion.
15. method according to claim 14, wherein in said erase process, said dried eraser stands about at the most 0.4N/cm
2Pressure.
16. method according to claim 14, wherein said writing with hand carried out.
17. method according to claim 14, the surface tension of wherein said xerotripsis label fluid is about 20mJ/m
2To about 30mJ/m
2
18. method according to claim 17, wherein said xerotripsis label printing ink contain surfactant with the surface tension that reduces said printing ink to the surface ability that is lower than said writing surface.
19. method according to claim 14, wherein said erase step carries out during at least about 6 hours after writing step said.
20. method according to claim 14, wherein said erase step carries out during at least about 24 hours after writing step said.
21. method according to claim 14, wherein said erase step carries out during at least about 7 days after writing step said.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29843310P | 2010-01-26 | 2010-01-26 | |
| US61/298,433 | 2010-01-26 | ||
| PCT/US2011/022618 WO2011094342A1 (en) | 2010-01-26 | 2011-01-26 | Low ghosting dry erase article and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102811866A true CN102811866A (en) | 2012-12-05 |
Family
ID=43754791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800147000A Pending CN102811866A (en) | 2010-01-26 | 2011-01-26 | Low ghosting dry erase article and use thereof |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2528751A1 (en) |
| JP (1) | JP5936552B2 (en) |
| KR (1) | KR101891835B1 (en) |
| CN (1) | CN102811866A (en) |
| BR (1) | BR112012018603A2 (en) |
| WO (1) | WO2011094342A1 (en) |
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| CN104275899A (en) * | 2014-07-03 | 2015-01-14 | 毛伟生 | Nano coating simulation painting and calligraphy paper and manufacture method thereof |
| CN105658441A (en) * | 2013-10-30 | 2016-06-08 | 3M创新有限公司 | Rollable, self-adhesive dry erase sheet assembly and method of use |
| CN106398353A (en) * | 2016-09-20 | 2017-02-15 | 浙江世窗光学薄膜制造有限公司 | Coating composition and preparation method thereof |
| CN110290932A (en) * | 2017-02-15 | 2019-09-27 | 3M创新有限公司 | Xerotripsis product |
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- 2011-01-26 KR KR1020127021926A patent/KR101891835B1/en active IP Right Grant
- 2011-01-26 JP JP2012551272A patent/JP5936552B2/en not_active Expired - Fee Related
- 2011-01-26 EP EP11703962A patent/EP2528751A1/en not_active Withdrawn
- 2011-01-26 BR BR112012018603A patent/BR112012018603A2/en not_active Application Discontinuation
- 2011-01-26 WO PCT/US2011/022618 patent/WO2011094342A1/en active Application Filing
- 2011-01-26 CN CN2011800147000A patent/CN102811866A/en active Pending
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| CN1902244A (en) * | 2003-12-31 | 2007-01-24 | 3M创新有限公司 | Water- and oil-repellent fluoroacrylates |
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| CN101027705A (en) * | 2004-07-27 | 2007-08-29 | 3M创新有限公司 | Dry erase substrate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658441A (en) * | 2013-10-30 | 2016-06-08 | 3M创新有限公司 | Rollable, self-adhesive dry erase sheet assembly and method of use |
| CN105658441B (en) * | 2013-10-30 | 2018-02-09 | 3M创新有限公司 | Roll-type self-adhesion mould assembly dry-erase board material component and application method |
| CN104275899A (en) * | 2014-07-03 | 2015-01-14 | 毛伟生 | Nano coating simulation painting and calligraphy paper and manufacture method thereof |
| CN106398353A (en) * | 2016-09-20 | 2017-02-15 | 浙江世窗光学薄膜制造有限公司 | Coating composition and preparation method thereof |
| CN106398353B (en) * | 2016-09-20 | 2021-06-15 | 浙江世窗光学薄膜制造有限公司 | Coating composition and preparation method thereof |
| CN110290932A (en) * | 2017-02-15 | 2019-09-27 | 3M创新有限公司 | Xerotripsis product |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112012018603A2 (en) | 2016-04-05 |
| EP2528751A1 (en) | 2012-12-05 |
| JP5936552B2 (en) | 2016-06-22 |
| KR20120120335A (en) | 2012-11-01 |
| JP2013517972A (en) | 2013-05-20 |
| KR101891835B1 (en) | 2018-08-24 |
| WO2011094342A1 (en) | 2011-08-04 |
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