CN101375162A - High optical purity copolymer film - Google Patents
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- CN101375162A CN101375162A CNA200780003643XA CN200780003643A CN101375162A CN 101375162 A CN101375162 A CN 101375162A CN A200780003643X A CNA200780003643X A CN A200780003643XA CN 200780003643 A CN200780003643 A CN 200780003643A CN 101375162 A CN101375162 A CN 101375162A
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Abstract
The invention relates to a high optical purity toughened copolymer film or coating. The copolymer is a graft or block copolymer, preferably acrylic, preferably produced by a controlled radical polymerization having an extremely low degree of particulate contamination and excellent optical properties. The film or coating is preferably formed by solvent-casting on a temporary substrate or solvent-coating on a permanent substrate.
Description
Invention field
The present invention relates to a kind of high optical purity, toughened film or coating based on multipolymer.This multipolymer is grafting or segmented copolymer, preferably, the acrylic acid grafting or the segmented copolymer that form by controllable free-radical polymerisation technology preferably,, it has the particle contamination of utmost point low degree.Described film or coating preferably form by solvent cast (casting) or solvent coating, and show good optical characteristics.
Background of invention
Acrylic acid composition and by its goods made from transparent, have surface gloss, UV degradation, anti-cut and well-known.Also known their shock strengths are low, fragility, poor ductility are arranged.
Can improve impact strength and ductility by in acrylic substrate, adding anti-impact modifier, nucleocapsid (core shell) anti-impact modifier that anti-impact modifier is for example described in the United States Patent (USP) 6,420,033.This method can be used for by molten condition processing as melt extrudes lamella or film and injection moulding making film or coating.Also can be used for preparing film or coating by the solvent cast or the solvent coating of dispersion soln.Yet known core-shell impact modifiers can cause the optical clarity problem.Their transparent (clarity) degree is based on the index matched degree between adjuvant and the matrix, and this depends on temperature to a great extent.After melt process (for example thermoforming, extrude or injection moulding), its outward appearance is relatively poor.Relatively poor outward appearance can be that for example surface haze height or glossiness are low.Core-shell impact modifiers also can produce albefaction (whitening) under stress condition.Similar or during greater than this thickness, these effects are especially obvious when the thickness of particle diameter and film or coating.At last, containing the film of nucleocapsid adjuvant or the optical purity of coating can't improve by microfiltration (fine filtration), because filtration step can be removed these nucleocapsid correctivess.
Also the segmented copolymer anti-impact modifier can be added in the acryl resin to improve impact resistance and toughness.European patent 1475397 has been described use methacrylate/acrylate block copolymer, and this multipolymer forms by controlled radical polymerization technique.Segmented copolymer can be used as the anti-impact modifier in the thermoplastic matrix or himself can be thermoformed into bar, sheet, film or extrusion molding product.
WO 2004/087796 has described the segmented copolymer that utilizes at least 95% content in the acryl resin and toughness is provided and has solved usually and some relevant transparency problems of use nucleocapsid modifier.The self-organization in Nano grade of these segmented copolymers provides good transparency for material in very large-scale temperature.Handle disclosed block polymer with smelting process.
United States Patent (USP) 6,239,226 described by just-segmented copolymer that oxyl (n-oxyl) free radical forms, but it is used for producing transparent or semitransparent film or the mechanograph (molding) with high impact strength (especially at low temperatures).With coextrusion, extrude or the method for melt processing of injection moulding is processed these films.
European patent 1348735 has been described the acrylic block copolymers of the anti-impact modifier that can be used as thermoplastic.Described the acrylic acid (segmented copolymer) of impact resistance, be used for thermoforming pipe, lamellar membrane and fibrous product through modification.
Toughness, be usually used in sheltering and protect other plastic material through the acrylic film of impact modification or coating, to utilize good acrylic properties.
Toughness, use the transparency of the level of also having relatively high expectations and do not have foreign particle or optical defect that gel causes through some of the acrylic film of impact modification or coating.The melting mixing of the routine of describing with this area is extruded, injection moulding, pressing mold (compressing molding) or calendering (calendaring) processing acryhic material cause to a certain degree defective, for example dust and part (formation) gel through regular meeting.For the meticulousst filtration, preferred polymers solution because for polymer melt the lower viscosity of easier acquisition.Need a kind of shock proof acrylic film or coating with high-optical-purity.
Unexpectedly, find that available leading portion copolymer compositions based on solvent can form toughness reinforcing film and coating in solvent cast and solvent coating process.Preferred described film and coating are acrylic acid (acrylic).Can remove after filtration greater than the particle of setting diameter based on the segmented copolymer of solvent, no matter this diameter is to arrive greater than 50 microns less than 1 micron, this multipolymer is used to produce the film and the coating of high-optical-purity then.Any requirement maybe needs the place of low defective film and coating can use the film and the coating of this high-optical-purity.Based on the film of solvent and another advantage of coating is to make the variation in thickness of film and coating littler than film and the coating that existing melting method makes.
Find, can under several conditions, keep good transparency based on the material of segmented copolymer.Under mechanical stress, their transparency can keep, and this is with opposite based on the material of nucleocapsid modifier.In addition, thermoformed components can not form turbidity owing to this parts attenuation makes the shock resistance correctives move to the surface in process.
The solution coatings that adopts acrylic block copolymers to prepare to have appropriate balance between multifrequency nature or the film of solvent cast are also described at present in this area, and described characteristic comprises the transparency in toughness, serviceability temperature and stress and the process.Solvent cast or solvent coating can provide film and the coating that is of high quality, because with respect to other film build method, have carried out microfiltration before forming film.
The invention summary
The present invention relates to the toughness reinforcing co-polymer membrane and the coating of high-optical-purity, it comprises block or the graft copolymer with hard and soft segment, and the visual defects that wherein said film and coating are every square feet is less than 0.5.
The invention still further relates to and be used to form, said method comprising the steps of based on the toughened film of acrylic copolymer or the method for coating:
A) by incompatible formation block of controlled radical polymerization or graft copolymer, it has hard and soft segment;
B) stable polymer/solvent mixture of described block of formation or graft copolymer in solvent;
C) the described polymer/solvent mixture of optional filtration;
D) described polymer/solvent mixture is coated on the base material;
E) the described solvent of evaporation is to form film or coating.
Detailed Description Of The Invention
The present invention relates to the block that will obtain by controlled radical polymerization technique or graft copolymer and be used for film or the coating that solvent cast or solvent coating process obtain high-optical-purity.
" segmented copolymer " used herein both referred to real block polymer, can be diblock, three blocks or multi-block polymer; The cladodification segmented copolymer also claims known as linear star; And gradient polymer (gradient).Gradient polymer is a linear polymer, and its composition gradually changes along polymer chain, may be from disordered structure to the block spline structure.Each block of segmented copolymer itself may be homopolymer, random copolymers, random terpolymer or gradient polymer.
Term " polymer " used herein " comprise homopolymer, multipolymer, terpolymer and by the polymkeric substance that forms more than three kinds of monomers.
Segmented copolymer is made up of at least a " firmly " block and at least a " soft " block.The glass transition temperature of hard block (Tg) is generally greater than 20 ℃, more preferably greater than 50 ℃.Hard block can be selected from any thermoplastic polymer (thermopolymer) who meets this Tg requirement.Hard block preferably mainly is made up of methacrylate unit, styrene units or its potpourri.Can be used for methacrylate of the present invention and include but not limited to methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the secondary butyl ester of methacrylic acid, the metering system tert-butyl acrylate, the methacrylic acid pentyl ester, the metering system isoamyl valerate, the just own ester of methacrylic acid, cyclohexyl methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid pentadecyl ester, lauryl methacrylate, IBOMA, the methacrylic acid phenylester, the methacrylic acid benzyl ester, methacrylic acid phenoxy group ethyl ester (phnoxyethyl methacrylate), methacrylic acid-2-hydroxyethyl ester or methacrylic acid-2-methoxy ethyl ester.Styrene units comprises styrene and derivant thereof, such as but not limited to α-Jia Jibenyixi and p-methylstyrene.Hard block preferably contains at least 60 weight %, the more preferably methyl methacrylate units of at least 80 weight %, and all the other are the acrylic acid alkyl ester units.Can select copolymer type and quantity to think that given terminal applies provides concrete Performance Characteristics.
The Tg of soft segment is generally less than 20 ℃, preferably less than 0 ℃.Preferred soft segment comprises the polymkeric substance and the multipolymer of alkyl acrylate, diene, styrene (styrenics) and composition thereof.Preferred soft segment mainly is made of acrylic ester unit.The acrylic ester unit that can be used for forming soft segment includes but not limited to methyl acrylate, ethyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, the acrylic acid pentyl ester, the acrylic acid isopentyl ester, the just own ester of acrylic acid, cyclohexyl acrylate, acrylic acid-2-ethyl caproite, acrylic acid pentadecyl ester, dodecylacrylate, isobornyl acrylate, phenyl acrylate, the acrylic acid benzyl ester, acrylic acid phenoxy group ethyl ester (phnoxyethyl methacrylate), 2-hydroxyethyl acrylate or acrylic acid-2-methoxy ethyl ester.The preferred acrylate unit is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid-2-ethyl caproite and 2-ethyl hexyl acrylate.Useful diene includes but not limited to isoprene and butadiene.
In a kind of preferred implementation, segmented copolymer is formed by methyl methacrylate and butyl acrylate block.Content of butyl acrylate in the fine-tuning segmented copolymer is to obtain good anti-cut performance.
Segmented copolymer of the present invention has controlled molecular weight and molecular weight distribution.The molecular weight of preferred copolymer is 1,000-1, and 000,000g/mol most preferably is 5,000-300,000g/mol.The molecular weight distribution of measuring with Mw/Mn or polydispersity is generally less than 4.0, preferably is lower than 3.0.
The ratio of hard block and soft segment is that 5:95 is to 95:5 in the multipolymer.Preferred this ratio is 40:60-90:10, most preferably is 65:35-85:15.
In principle, any activity (living) or controlled polymerization technique all can be used for preparing segmented copolymer.Yet, consider the practicality of controlling acrylic acid (ester) class, segmented copolymer of the present invention preferably forms by controlled radical polymerization technique (CRP).These technology generally with the combination of typical radical initiator and compound with the control polymerization process and form have specific composition, controlled molecular weight and the polymkeric substance of narrow molecular weight range.These used radical initiators can be known in the art, include but not limited to can provide after the thermal decomposition per-compound, superoxide, hydroperoxides (hydroperoxide) and the azo-compound of free radical.In one embodiment, initiating agent also can comprise controlling agent.
The example that those skilled in the art know controlled radical polymerization technique includes but not limited to the polymerization (NMP) of atom transfer radical polymerization (ATRP), RAFT polymerization (RAFT), nitroxide (nitroxide) mediation, the polymerization and the catalytic chain transfer polymerization (CCT) of boron mediation.The description of these polymerization techniques and comparison visible " ACS symposium series (Symposium Series) 768 ", the name be called " Controlled/Living Radical Polymerization:Progress in ATRP; NMP; and RAFT (controlled/active free radical polymerization: the progress of ATRP, NMP and RAFT) ", the KrzystofMatyjaszewski chief editor, American Chemical Society, Washington, 2000.
A kind of method for optimizing of controlled radical polymerization technique is the CRP of nitroxide-mediated.The polymerization of nitroxide-mediated can take place in body, solvent and polymerizable aqueous, can be in existing equipment use and reaction time and temperature and other Raolical polymerizable similar.The advantage of the CRP of nitroxide-mediated is that nitroxide generally is nontoxic, and can be retained in the reaction mixture, and other CRP Technology Need is removed controlled compound from final polymkeric substance.
The mechanism of this control mode can be illustrated as follows:
Wherein M represents polymerisable monomer, the polymer chain in the P representative growth.
The key of this controlling mechanism and constant K
Deact, k
ActAnd k
pRelevant (T.Fukuda and A.Goto, big molecule,, 32,618-623 page or leaf in 1999).If k
Deact/ k
ActRatio too high, then can hinder polymerization, if k
p/ k
DeactThe too high or k of ratio
Deac/ k
ActRatio too low, then polymerization is out of hand.
Find (P.Tordo etc., Polym.Prep.1997,38,729-730 page or leaf; C.J.Hawker etc., Polym.mater.Sci.Eng., 1999,80,90-91), the alkoxyamine of β-replacement can cause and control the polymerization of the monomer of several types effectively, and based on the alkyl amine of TEMPO (as " big molecule " 1996,29, the 5245-5254 page or leaf mention (as 2 ', 2 ', 6 ', 6 '-tetramethyl-1 '-piperidyl oxygen (piperidyloxy)-) toluene) only control the polymerization of styrene and styrene derivative.TEMPO and be not suitable for the controllable polymerization of acrylic compounds based on the alkyl amine of TEMPO.
The CRP method of nitroxide-mediated is described in US 6,255,448, US 2002/0040117 and WO00/71501, and they insert herein by reference in full.Above-mentioned patent has been described the polymerization of carrying out nitroxide-mediated by several different methods.In these methods each all can be used for synthetic polymkeric substance of the present invention.
In one approach, (know as is known to the person skilled in the art) under the normal condition of related a kind of monomer or multiple monomer and carry out free radical polymerization or instrument, different is the stabilized radical that adds β-replacement in potpourri.According to one or more monomers of wanting polymerization, may need in polyblend, to add traditional radical initiator, this is well known to those skilled in the art.
Another method has been described and has been used the alkoxyamine that obtains from the nitroxide of β-replacement to carry out the polymerization of one or more related monomers, and the nitroxide of described β-replacement is suc as formula shown in the I, and wherein A represents monovalence or multivalence structure, R
LRepresent molecular weight greater than 15 and be the monovalence free radical, 1 of n.
Another kind method described based on polyfunctional monomer (such as but not limited to acrylate monomer and alkoxyamine) under controllable temperature reaction and form the multivalence alkoxyamine of formula (I).When n 2 the time, the multifunctional alkoxyamine of formula (I) can be used for from one or more the related monomer synthesizing linear stars and the polymeric material and the copolymeric material of cladodification.
Another kind method has been described the preparation of multimodal distribution (multimodal) polymkeric substance, at least a in (multiple) monomer of wherein being considered carries out free radical polymerization in the presence of several alkoxyamines, described alkoxyamine comprises the sequence of formula (I), wherein n is the non-zero integer, and alkoxyamine has different n values.
Above-mentioned alkoxyamine and nitroxyl (nitroxyl) (nitroxyl also can prepare separately by known method from corresponding alkoxyamine) are well known in the art.Their synthesis example is as being described in U.S. Patent number 6,255, and 448 and WO 00/40526.
Segmented copolymer of the present invention is inserted with the elastic body fragment in propenoic acid main chain, these segmented copolymers can use or can be used as anti-impact modifier separately and mix in the thermoplastic compounds.In one embodiment, thermoplastic is as the matrix of segmented copolymer.Thermoplastic through impact modification can contain the described segmented copolymer of 5-95 weight %, preferred 20-80 weight % and the described matrix polymer of 5-95 weight %, preferred 20-80 weight %.Matrix and segmented copolymer all can be added in the solution, filter to produce polymkeric substance (mixing) solution of high-optical-purity.Available thermoplastic matrix includes but not limited to polycarbonate, acrylic polymers, polystyrene (PS), high impact polystyrene (HIPS), Polyvinylchloride (PVC), polyvinylidene fluoride (PVDF), the PVDF-acrylic copolymer, imidization (imidized) acrylic polymers, cyclenes copolymer (COC), polyolefin, impact modified polyolefin, polyester is (as PET, PBT, APET), styrene-acrylonitrile (SAN), AN-AE, acrylonitrile methyl meth acrylat copolymer, copolymer of methyl methacrylatestyrene, other styrene polymer or the multipolymer that comprise α-Jia Jibenyixi, glycol-modified polyethylene terephthalate (polyethylene terephthalate-glycolmodified) (PETG), methacrylate-butadiene-styrene trimer, acrylonitrile-styrene-acrylic ester (ASA) trimer, acronitrile-butadiene-styrene (ABS) trimer, poly-ring-hexyl ethene and their potpourri.Preferred matrix is the homopolymer or the multipolymer of methyl methacrylate.
Solvent cast as herein described or solvent coating are meant a kind of technology, wherein with polymer dissolution, disperse or be mixed in organic solvent or the aqueous solvent to form solution or dispersion liquid.Term used herein " solution " and " polymer solution " are used to describe polymer/solvent mixture, and it can be stable solution, dispersion liquid, suspension, emulsion, inverse emulsion (inverse emulsion) form or other stable form.Then the solution that forms is put on base material, remove and desolvate to produce film or coating.Useful solvent includes but not limited to any potpourri of water, alkane, aromatic, ketone, ester class, ethers, acids, amine, alcohols, dimethyl formamide, halogen derivatives and these solvents.
Except that segmented copolymer, also can there be other adjuvant that is generally used in the thermoplastic, comprise pigment, dyestuff, plastifier, antioxidant, thermal stabilizer, ultra-violet stabilizer, processing aid or lubricant.In one embodiment, need a kind of transparent goods, do not have pigment.Though being used for the adjuvant of polymer solution can be the adjuvant of any size, recognize also that if polymer solution will filter adjuvant needs to be filtered off outside the solution avoiding enough for a short time so before using.An advantage that adds adjuvant to solution among the present invention is that the viscosity in the operation of viscosity ratio melting mixing is much smaller.This makes mixed process be easier to operation, and faster, more thorough, thereby can for example (can obtain) high composition of filling to make the concentration of adjuvant much higher under the condition that more low-shearing force mixes.
Segmented copolymer of the present invention especially can be used in the application of high-optical-purity.Acrylic block copolymers solution or the segmented copolymer that is blended in thermoplastic polymer's matrix can be filtered, and produce very pure solution, but this solution curtain coating to base material or as solvent coating, apply, to prepare transparent (" zero-fault ") film or coating.
Segmented copolymer also provides the means of production toughened acrylic film or coating, because this segmented copolymer can not be leached into outside the solution.
Available means known in the art are filtered, for example, and membrane filtration and utilize gradient cartridge filter (gradientfiter cartridge).According to the needs of terminal applies, the filtration of polymer solution can be used for removing the particle of any size.Can select filter medium, for example remove particle greater than 50 microns, greater than 30 microns particle, greater than 5 microns particle, greater than 1 micron particle, or any other required purity.Use when block copolymer-modified when the impact resistance of thermoplastic, filtered polymer solution can contain segmented copolymer and linear polymer.
Solvent cast produces gross thickness at the film between the 2-200 micron, between the preferred 10-120 micron.With the film curtain coating on smooth substrate surface, the metal aluminium for example of polyester film (PET) or polishing for example.Select base material to make it not by degrading solvent.In one embodiment, the turbidity of film is lower than 2.In another embodiment, the breaking elongation of acrylic film (elongation at break) is greater than 50%.Solvent cast technology provides good THICKNESS CONTROL, form 100 microns+/-5 microns or even+/-3 microns film, this being controlled in the smelting process is impossible realize.Film should can easily use or handle described film on base material by curtain coating on base material, maybe film can be coated on the base material so that nonvolatil level and smooth top layer to be provided, because through filtering, this top layer can have very high optical purity and very low defective.The base material that can apply permanent toughening thin film of the present invention comprises acrylic substrate, PVC, polycarbonate, glass, metal, timber, pottery, leather, timber/polymer complex and other plastics and compound.
Useable solvents curtain coating or coating processes (comprising that brushing, roller coat, spraying, injection coating, groove dye (slotdie), intaglio printing, anti-roller coat (reverse roller) and impregnating) apply segmented copolymer (or segmented copolymer/thermoplastic mixture) solution.
Current, also the acrylic acid of high-optical-purity of no use (ester) carries out the coating that shock resistance is regulated, and the compositions and methods of the invention provide the means of producing a kind of like this coating, because anti-impact modifier of the present invention can not be filtered off outside the solution.The Polyvinylchloride oilcloth (vinyltarps), canvas, glass of solvent coating-provide anti-cut characteristic and optical clarity, flexible PVC (especially when segmented copolymer coatings volatile organic compounds solution contains ultraviolet light absorber) and metal are provided available toughness reinforcing acrylic acid (ester) (with the high optical purity form of filtering or the filtered version not) base material that applies.In one embodiment, coating is used for biologic applications, for example is used for the capsule (cassettes for kidneys) of kidney.
Toughened film of the present invention or coating have high-optical-purity, produce the hyaline membrane or the coating that do not have defective." not having defective " used herein, " no particle " or " zero-fault " refer to the visual defects of every square feet of described film or coating less than 0.5, and preferred every square feet defective is less than 0.01.Visible " defective " used herein refer to diameter greater than (dry) but film thickness half, maximum gauge is less than any defective of the detected size of naked eyes.Generally, naked eyes can be seen the defective of 20-30 micron.Visual defects can be caused that circumgranular certain zone in film or coating is irregular owing to the effect of particle in addition by any particle.In other of the very pure optical characteristics of needs (light scattering is low, distortion (distortion) low) used, limited field even can be littler.
In the application of transparent (non-pigment) and interpolation pigment, all can relate to optical purity.For example, in the black film of high gloss, the comparative films that does not have high-optical-purity of the present invention can be seen a little or defective under some light condition.Another example of optical purity is that film of the present invention or coating are further processed, for example, with film-stack of the present invention on base material, thermoforming then, will can not form turbidity on the surface through hot formed parts, but this situation will appear in film or coating that nucleocapsid (modifier) is regulated owing to thereby film attenuation anti-impact modifier in the thermoforming process moves to.
Film of the present invention and coating do not contain particle, toughness, little, the excellent optical characteristics of variation in thickness.
With respect to can be by the permission of extruding or the blown film hot-working method obtains (tolerance), the film that forms by solvent cast or solvent coating or the thickness of coating be controlled in the nearer permission scope.Almost do not have at the very high optical clarity of needs in some application of incident light distortion, this control is especially favourable.
Film of the present invention and coating can be used for production optical grade product (low scattering), and these products keep transparency under mechanical pressure and in the very wide temperature range.
One of this class optical application is DVD production.Can form or apply transparent propene sorrel toughness, anti-cut on DVD, it not only protects DVD but also as lens or focus layer, this uses especially favourable for small wavelength laser.
Toughened film of the present invention also can be used as the coverture (capping agent) of high-optical-purity, anti-cut and shock resistance characteristic are provided and do not influence the characteristic of base material.
The application of other proposal of block copolymer film or coating includes but not limited to insert molding (insertmolding), as flat-panel monitor or the outer field film of LED, membrane switch (membranes switches), applique (decals) or transfer membrane, instrument panel and smart card.In a kind of embodiment, graphic designs can be printed onto on the toughened film of the present invention and put on base material.Can be by stacked or film is applied on the base material with bonding agent.
Embodiment 1:
In the presence of alkoxyamine based on nitroxide SG1, in body, synthesize the segmented copolymer of making by butyl polyacrylate and polymethylmethacrylate (polymer A) by controlled radical polymerization technique, and be separated into particle (pellet) by extruding.Because this preparation process, a small part material is made of insoluble particle or pollutant.
Prepare sample 1 with following step.By the polymer A solution of 1-micron filter cartridge in methyl ethyl ketone (MEK) and 2-methylpentanone (MIBK) potpourri, then with this solution casting to polyester base material.The base material of curtain coating is passed through the multi-region baking oven, and the temperature and the residence time are suitable for concrete solvent system, so that the wet film drying.Peel dry film to obtain independently (free-standing) film from polyester base material, average thickness is 95 microns+/-4 microns.
Prepare sample 2 (comparative example) with following step.At first, melt extrude polymer A with 400 purposes sieve filtrator.Then, use conventional processing condition at the acrylic acid thermoplastic polymer, by fluoropolymer resin is extruded-curtain coating is converted into film with fluoropolymer resin to chromium roller coat device.The final thickness of extruded film is 80 microns+/-10 microns.
For analyzing size greater than 10 microns but, sample 1 and sample 2 are flat on the microscope stage less than 30 microns defective, by optical microscope with differing analyzing defect.Estimate the numbers of particles of giving sizing in five zones of each membrane sample.According to the known area in five zones, calculate the average defect concentration (the defective number on each area) of each film.Select this five zones at random.For greater than 30 microns Analysis on defects, visual check membrane sample on bigger area.Confirm defect area with microscope and image analysis software.The digital proof of table 1 film of solvent cast be the cleanliness (cleanliness) of sample 1.
Table 1
The defect concentration defect concentration
(size between the 10-30 micron) (size〉30 micron)
Defective/square millimeter defective/square feet
Sample 150
Sample 2 (comparative example) 32 50
Claims (19)
1. the toughness reinforcing co-polymer membrane or the coating of a high-optical-purity, it comprises block or the graft copolymer with hard and soft segment, and every square feet of visual defects that contains of wherein said film or coating is less than 0.5.
2. high-optical-purity film as claimed in claim 1 or 2 or coating is characterized in that, described film is formed by solvent cast membrane process or solvent coating technology.
3. each described high-optical-purity film or coating in the claim as described above is characterized in that described hard block mainly comprises methyl methacrylate units, and described soft segment mainly comprises the acrylic acid alkyl ester units.
4. each described high-optical-purity film or coating in the claim as described above are made up of block or graft copolymer.
5. each described high-optical-purity film or coating in the claim as described above contain the thermoplastic matrix polymer of described block or graft copolymer and the 5-95 weight % of 5-95 weight %.
6. each described high-optical-purity film or coating in the claim as described above is characterized in that the Tg of described hard block is preferably greater than 50 ℃ greater than 20 ℃, and the Tg of described low Tg block preferably is lower than 0 ℃ less than 20 ℃.
7. each described high-optical-purity film or coating in the claim as described above is characterized in that the molecular weight of described block or graft copolymer is 1,000-1,000,000g/mol.
8. each described high-optical-purity film or coating in the claim as described above is characterized in that described block or graft copolymer are to form by controlled radical polymerization technique.
9. each described high-optical-purity film or coating in the claim as described above is characterized in that, described block or graft copolymer are that the controlled radical polymerization technique by nitroxide-mediated forms.
10. each described high-optical-purity film or coating in the claim as described above is characterized in that described film does not contain the particle greater than 30 microns, preferably do not contain the particle greater than 5 microns.
11. each described high-optical-purity film or coating in the claim is characterized in that the variation in thickness of described film is not more than 3% of film thickness as described above.
12. each described high-optical-purity film or coating in the claim as described above, it is characterized in that described film or coating also contain one or more adjuvants that are selected from down group: pigment, dyestuff, plastifier, antioxidant, thermal stabilizer, ultra-violet stabilizer, processing aid, lubricant and anti-impact modifier.
13. each described high-optical-purity film or coating in the claim is characterized in that as described above, described film or coating keep its original optical characteristics in mechanical stress with in hot procedure.
14. one kind is used to form based on the toughened film of acrylic copolymer or the method for coating, said method comprising the steps of:
A) form block or graft copolymer by controlled free radical polymerization with hard and soft segment;
B) stable polymer/solvent mixture of described block of formation or graft copolymer in solvent;
The described polymer/solvent mixture of optional filtration;
C) described polymer/solvent mixture is coated on the base material;
D) the described solvent of evaporation is to form film or coating.
15. method as claimed in claim 14 is characterized in that, by solvent cast or solvent coating described polymer/solvent mixture is coated on the described base material.
16., also be included in before applying by 30 microns or littler filtrator filtration step b as claim 14 or 15 described methods) described in the step of polymer/solvent mixture.
17., also be included in described coating step c as each described method among the claim 14-16) step of before described block or graft copolymer being mixed with thermoplastic matrix polymer.
18., it is characterized in that the solvent evaporation of described step d) forms toughened film as each described method among the claim 14-17, remove striping from base material then, to be processed into film in the end article or on the end article.
19. as each described method among the claim 14-18, it is characterized in that described step d) forms toughness reinforcing coating, this coating adheres on the described base material.
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| US76265506P | 2006-01-27 | 2006-01-27 | |
| US60/762,655 | 2006-01-27 | ||
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| CN105518089A (en) * | 2013-09-09 | 2016-04-20 | 阿科玛法国公司 | Process for producing thick nanostructured films obtained from a block copolymer composition |
| TWI769691B (en) * | 2016-01-25 | 2022-07-01 | 中國商肖特玻璃科技（蘇州）有限公司 | Glass substrate and use of glass substrate |
| CN116694128A (en) * | 2023-06-28 | 2023-09-05 | 鹤山市炎墨科技有限公司 | Anti-welding ink containing block copolymer and preparation method thereof |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105518089A (en) * | 2013-09-09 | 2016-04-20 | 阿科玛法国公司 | Process for producing thick nanostructured films obtained from a block copolymer composition |
| TWI769691B (en) * | 2016-01-25 | 2022-07-01 | 中國商肖特玻璃科技（蘇州）有限公司 | Glass substrate and use of glass substrate |
| CN116694128A (en) * | 2023-06-28 | 2023-09-05 | 鹤山市炎墨科技有限公司 | Anti-welding ink containing block copolymer and preparation method thereof |
| CN116694128B (en) * | 2023-06-28 | 2023-11-24 | 鹤山市炎墨科技有限公司 | Anti-welding ink containing block copolymer and preparation method thereof |
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