DK163821B - POLYCARBONATE FORMULA WITH A COVERAGE AND PROCEDURE FOR PREPARING THEREOF - Google Patents
POLYCARBONATE FORMULA WITH A COVERAGE AND PROCEDURE FOR PREPARING THEREOF Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- Paints Or Removers (AREA)
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- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
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- Polymerisation Methods In General (AREA)
Description
DK 163821 BDK 163821 B
Opfindelsen angår et polycarbonatformlegeme med et overtræk af en polymer,opnået ved fotopolymerisering i nærværelse af en fotoinitiator, af en blanding af a) en acrylatmodificeret forbindelse, b) en yderligere umættet 5 forbindelse samt eventuelt yderligere c) en reaktiv forbindelse med molekylvægt under 400 og med i det mindste en acrylat-, metacrylat-, maleat- og/eller fumaratgruppe, og det ejendommelige er a) der som acrylatmodificeret forbindelse er anvendt en 10 urethanharpiks med molekylvægt 400-4000 i form af et kondensationsprodukt af (a.1) 1 mol hexamethylendiisocyanat og 2 mol tri- methylolpropandiacrylat, (a.2) 1 mol hexamethylendiisocyanat og 2 mol hydroxy· 15 ethylacrylat, eller (a.3) 1 mol toluendiisocyanat og 2 mol hydroxyethyl- acrylat, og b) der som yderligere umættet forbindelse er anvendt et N-vinylderivat af et ligekædet eller cyklisk sekun- 20 dært amid i en mængde på 5-60 vægt% beregnet på blandingens vægt.The invention relates to a polycarbonate mold body having a polymer coating obtained by photopolymerization in the presence of a photoinitiator, of a mixture of a) an acrylate-modified compound, b) a further unsaturated compound, and optionally a further c) a molecular weight reactive compound below 400 and with at least one acrylate, methacrylate, maleate and / or fumarate group, and the peculiar is a) an acrylate modified compound having a molecular weight 400-4000 urethane resin in the form of a condensation product of (a.1) 1 moles of hexamethylene diisocyanate and 2 moles of trimethylolpropane diacrylate, (a.2) 1 mole of hexamethylene diisocyanate and 2 moles of hydroxy · ethyl acrylate, or (a.3) 1 mole of toluene diisocyanate and 2 moles of hydroxyethyl acrylate, and b) which as a further unsaturated compound is used an N-vinyl derivative of a straight chain or cyclic secondary amide in an amount of 5-60% by weight based on the weight of the mixture.
Opfindelsen angår endvidere en fremgangsmåde til fremstilling af dette polycarbonatformlegeme, hvilken fremgangsmåde ifølge opfindelsen er ejendommelig ved, at 25 1) polycarbonatformiegernet overtrækkes med en blanding af (a) en urethanharpiks med molekylvægt 400-4000 i form af et kondensationsprodukt af (a.1) 1 mol hexamethylendiisocyanat og 2 mol tri-30 methylolpropandiacrylat, (a.2) 1 mol hexamethylendiisocyanat og 2 mol hydrox-vethylacrylat, eller (a.3) 1 mol toluendiisocyanat og 2 mol hydroxy-ethylacrylat, og 35 (b) et N-vinylderivat af et ligekædet eller cyk lisk sekundært amid i en mængde på 5-60 vægt%, beregnet på blandingens vægt, samt eventuelt yderligereThe invention further relates to a process for the preparation of this polycarbonate mold body which is characterized in that the 1) polycarbonate mold core is coated with a mixture of (a) a 400-4000 molecular weight urethane resin in the form of a condensation product of (a.1) 1 mole of hexamethylene diisocyanate and 2 moles of trimethylolpropane diacrylate, (a.2) 1 mole of hexamethylene diisocyanate and 2 moles of hydroxyethyl acrylate, or (a.3) 1 mole of toluene diisocyanate and 2 moles of hydroxyethyl acrylate, and (b) an N- vinyl derivative of a straight or cyclic secondary amide in an amount of 5-60% by weight, based on the weight of the mixture, and optionally further
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2 (c) en reaktionsdygtig forbindelse med molekylvægt under 400 og med i det mindste en acrylat-, metacry-lat-, maleat- og/eller fumaratgruppe, som er tilsat en fotoinitiator, og 5 2) blandingen fotopolymeriseres ved DV-bestråling.2 (c) a reactive compound having a molecular weight below 400 and having at least one acrylate, metacrylate, maleate and / or fumarate group added to a photoinitiator, and 2) the mixture is photopolymerized by DV irradiation.
Polycarbonater har, ved siden af fortrinlige egenskaber, såsom gennemsigtighed, slagstyrke og trækstyrke, de velkendte ulemper, som er forbundet med materialets overfladeegenskaber, såsom dets ringe mod-10 standsevne mod afslidning og ridsning og den ringe modstandsevne mod opløsningsmidler. Mere præcist ridses materialets overflade på grund af kontakt med slibende stoffer eller endda ved en blid kontakt med andre materialer, og har tilbøjelighed til at blive uklar. Nogle 15 få metoder til overvindelse af disse defekter er blevet foreslået, og sådanne fremgangsmåder baseredes på anvendelsen af særlige belægninger, som baseredes på siloxan- eller melaminharpikser. Disse belægninger medfører omkostningsproblemer, anvendelsesvanskeligheder 20 og utilfredsstillende egenskaber, eftersom disse er lakker i opløsningsmidler, som sædvanligvis kræver en varmebehandling ved mere eller mindre høje temperaturer til fremkaldelse af tværbinding, og nævnte behandling er af en sådan karakter, at polymerunderlagets egenska-25 ber forringes, mere præcist slagstyrken deraf.In addition to excellent properties such as transparency, impact resistance and tensile strength, polycarbonates have the well-known disadvantages associated with the surface properties of the material, such as its poor abrasion and scratch resistance and the poor solvent resistance. More precisely, the surface of the material is scratched due to contact with abrasive substances or even by gentle contact with other materials, and tends to become cloudy. Some 15 few methods for overcoming these defects have been proposed, and such methods were based on the use of special coatings based on siloxane or melamine resins. These coatings cause cost problems, application difficulties 20 and unsatisfactory properties since these are solvents in solvents which usually require a heat treatment at more or less high temperatures to induce crosslinking, and said treatment is of such a nature as to impair the properties of the polymer substrate. , more precisely its impact strength.
Fra WO-offentliggørelsesskrift 80/00942 kendes gennemsigtige formede polycarbonatprodukter, fremstillet ved overtrækning af et polycarbonat med en UV-hærdelig blanding af 30 1) en acrylatmodificeret polymer, og 2) i det mindste en polyfunktionel acrylsyreestermono-mer med den almene formelWO Publication 80/00942 discloses transparent shaped polycarbonate products prepared by coating a polycarbonate with a UV curable mixture of 1) an acrylate modified polymer, and 2) at least a polyfunctional acrylic acid ester monomer of the general formula
CH-, = CH - C - O - RCH- = CH - C - O - R
35- O n35- O n
Komponenten (1) kan gengives med følgende formelThe component (1) can be represented by the following formula
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Polymer- OPolymer-O
- 0 - C - CH * CH.- 0 - C - CH * CH.
— ^ X - (tilbagevendende enheder) 5 og typiske eksempler er: a) Acrylatpolyester med formlen » o o ch2-ch-0 - ich2)6 -- o - c - (CH2)4 - CO-(CH2)6 -- 0-c-ch-ch2 10 o o * b) Acrylatepoxider med formlen 4 15 O Γ OH CH3 oh o CH2=CH-C - 0 -- CH2-CH-CH2-0-0- c -0-0"" CH2-CH-CH2-OC-CH=CH2 L C‘H3 J n c) Acrylaturethaner med formlen 20 o Γ o q o ch2«ch-c-o-ch2 ck2jo-c-nh-0-nh - c - o-ch2 ch2--oc oh = CH2- and recurring units 5 and typical examples are: a) Acrylate polyester of the formula "oo ch2-ch-0 - ich2) 6 - o - c - (CH2) 4 - CO- (CH2) 6-0 -c-ch-ch2 10 oo * b) Acrylate epoxides of formula 4 O Γ OH CH3 oh o CH2 = CH-C - 0 - CH2-CH-CH2-0-0- c -0-0 "" CH2- CH-CH2-OC-CH = CH2 LC'H3 J nc) Acrylate ethanes of formula 20 o Γ oqo ch2 «ch-co-ch2 ck2jo-c-nh-0-nh - c - o-ch2 ch2 - oc oh = CH2
Det med overtræk forsynede polycarbonatlegeme ifølge opfindelsen har imidlertid overlegne afslidningsegenska-ber i forhold til et ifølge nævnte WO-skrift overtrukket; polycarbonatlegeme.However, the coated polycarbonate body of the invention has superior abrasion characteristics over a coating of the above-mentioned WO coating; polycarbonatlegeme.
Der henvises til nedenstående Eksempel 1, hvor en ^ bestemmelse af modstandsdygtigheden mod slid blev foretaget med en optisk metode efter ASTM D 1003, som er baseret på en måling af uklarhed.Reference is made to Example 1 below, in which a determination of wear resistance was made by an optical method according to ASTM D 1003, which is based on a measurement of haze.
Når en prøve af det ovennævnte kendte materiale og med en tykkelse på 0,3 mil ( 7,62 ym) blev underkastet samme uklarhedsprøve med samme slibehjul, men med en belastning på 500 g (i stedet for den dobbelte belastning på 1000 g som ved prøven i Eksem- 35When a sample of the aforementioned known material and with a thickness of 0.3 mil (7.62 µm) was subjected to the same cloud test with the same grinding wheel but with a load of 500 g (instead of the double load of 1000 g as at the sample in Eczema 35
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4 pel 1), blev der efter 100 gennemførelser af forsøget, i eksemplet betegnet forløb, opnået følgende resultater, jf. Tabel 2, side 23 i WO 80/00942: 5 Eksempel fra WO 80/00942 Oprivning (% uklarhed) 3 3,5 5 4,3 7 3,6 10 8 8,5 9 17,2 10 15,94 column 1), after 100 runs of the experiment, in the example referred to as the example, the following results were obtained, cf. Table 2, page 23 of WO 80/00942: 5 Example from WO 80/00942 Demolition (% obscurity) 3 3, 5 5 4.3 7 3.6 10 8 8.5 9 17.2 10 15.9
Det fremgår ved sammenligning af disse resultater med de nedenstående, at formlegemerne ifølge opfindelsen 15 har overlegne afslidningsegenskaber, specielt i betragtning af, at prøverne med formlegemerne ifølge opfindelsen er gennemført med en belastning, som er dobbelt så stor som hvad der blev anvendt ved afprøvningen af det kendte materiale.It is evident from comparing these results with the following that the mold bodies of the invention 15 have superior abrasion properties, especially considering that the tests of the mold bodies of the invention have been carried out at a load twice that of the test of the known material.
20 Fra US patentskrift nr. 3 874 906 kendes en frem gangsmåde til overtrækning af substrater, som f.eks. papir, metal, polymere, cellulose etc. med en blanding, som kan tværbindes ved aktinisk stråling. Den blanding, som anvendes til overtrækket, består i det væsentlige af 25 en polyesteracrylatharpiks og N-vinylpyrrolidon. Disse blandinger er helt forskellige fra de overtræk, som kommer i betragtning i forbindelse med nærværende ansøgning.20 U.S. Patent No. 3,874,906 discloses a method of coating substrates, such as e.g. paper, metal, polymers, cellulose etc. with a mixture which can be crosslinked by actinic radiation. The mixture used for the coating consists essentially of a polyester acrylate resin and N-vinylpyrrolidone. These mixtures are quite different from the coatings considered in the present application.
Som følge af anvendelsen af vinylpyrrolidon i forbindelse med polyesteracrylatharpikserne har dette kendte over-30 træksmateriale den ulempe, at det giver et overtræk med hydrofile egenskaber, som kvælder op ved berøring med vand og derfor ikke er vejrbestandigt. I modsætning hertil har det overraskende vist sig, at overtrækket, som opnås ved fremgangsmåden ifølge opfindelsen, også når 35 der anvendes vinylpyrrolidon, har god bestandighed mod vand.Due to the use of vinylpyrrolidone in conjunction with the polyester acrylate resins, this known coating material has the disadvantage of providing a coating with hydrophilic properties which swells upon contact with water and is therefore not weather resistant. In contrast, surprisingly, it has been found that the coating obtained by the process of the invention, even when vinyl pyrrolidone is used, has good water resistance.
Endelig kendes der fra US patentskrift 4 129 709 et overtræksmateriale omfattende en oligomer med formlenFinally, US Patent 4,129,709 discloses a coating material comprising an oligomer of the formula
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5 ° o * o o o o5 ° o * o o o o
I I N I ✓'vA » II I N I ✓'vA »I
CH2*CH—CO—CHjCHjOCNH f' S NHCO-fCHiCHjCHjCHjO^CNH f NHCOCHjCHj—OC-CH=CH2 9 9 CHj CHj CH3 CHj 5 sammen med N-vinyl-2-pyrrolidon og en acrylsyreester.CH2 * CH-CO-CH2CH2OCNH f S NHCO-fCHiCHjCHjCHjO ^ CNH f NHCOCHjCHj-OC-CH = CH2 9 9 CHj CHj CH3 CHj 5 together with N-vinyl-2-pyrrolidone and an acrylic acid ester.
Disse overtræksmaterialer angives at have god bestandighed mod slid og ridsning samt mod opløsningsmidler og at være egnede til overtrækning af blandt andet polycar-10 bonater. Ud fra den gengivne sammensætning vil det dog være klart, at der er tale cm ganske andre overtræksmaterialer, end hvad der benyttes som overtræk ved fremgangsmåden ifølge nærværende ansøgning.These coating materials are stated to have good resistance to abrasion and scratching as well as to solvents and to be suitable for coating, inter alia, polycarbonates. However, from the reproduced composition, it will be clear that these are quite different coating materials than those used as coatings in the process of the present application.
Det har vist sig, at en belægning på polycarbona-15 tet kan opnås ved anvendelse af fremgangsmåden ifølge opfindelsen til opnåelse af overtræk, som har overordentlig gode egenskaber med hensyn til vedhæftningsevne, hårdhed og afslidningsmodstandsevne, medens de ovennævnte ulemper afhjælpes.It has been found that a coating on the polycarbonate can be obtained by using the method of the invention to obtain coatings which have extremely good adhesion, hardness and abrasion resistance properties while alleviating the above drawbacks.
20 Polymerisationsreaktionen udføres under tilstede værelse af en fotoinitiator ved stuetemperatur.The polymerization reaction is carried out under the room of a room temperature photoinitiator.
Polymerisationsblandingen indeholder san nævnt eventuelt reaktive forbindelser, der har lav molekylvægt (mindre end 400), og som i deres molekyler indeholder mindst én 25 funktionel gruppe af typen acrylat, metacrylat, maleat eller fumarat. Eksempler på sådanne forbindelser er: butandioldiacrylat, ethylhexylacrylat, dimethylmaleat, diethylfumarat og ethylenglycoldiacrylat.The polymerization mixture, as mentioned, possibly contains low molecular weight reactive compounds (less than 400) and containing in their molecules at least one functional group of the type acrylate, metacrylate, maleate or fumarate. Examples of such compounds are: butanediol diacrylate, ethylhexyl acrylate, dimethyl maleate, diethyl fumarate and ethylene glycol diacrylate.
Ved fremgangsmåden til fremstilling af Dolycarbonatform-30 legemet med overtræk ifølge opfindelsen belægger man først poly-carbonatet med en blanding som beskrevet ovenfor, hvorpå man behandler det belagte produkt med UV-bestråling.In the process of preparing the dolycarbonate form body with coating according to the invention, the polycarbonate is first coated with a mixture as described above, after which the coated product is treated with UV irradiation.
Fremgangsmåden tillader, i modsætning til visse af de sædvanlige metoder, at blandingen hærdnes fuldkom-35 ment ved stuetemperatur, uden at man ændrer materialets grundlæggende egenskaber, såsom dets slagstyrke og gennemsigtighed.The process, unlike some of the conventional methods, allows the mixture to fully cure at room temperature without altering the basic properties of the material, such as its impact strength and transparency.
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Eksempler på N-vinylderivater af ligekædede eller cycliske sekundære amider er: N-vinylpyrrolidon, N-vinyl-caprolactam, N-vinyl-N-methylacetamid, N-vinyl-N-ethyl-propionamid og N-vinyl-N-methylpropionamid.Examples of N-vinyl derivatives of straight-chain or cyclic secondary amides are: N-vinylpyrrolidone, N-vinyl-caprolactam, N-vinyl-N-methylacetamide, N-vinyl-N-ethyl-propionamide and N-vinyl-N-methylpropionamide.
5 De fotoinitiatorer, der kan anvendes, omfatter forbindelser, der er i stand til at danne frie radikaler under indvirkning af UV-bestråling.The photoinitiators that can be used include compounds capable of forming free radicals under the influence of UV radiation.
Eksempler på disse er: benzoinisopropylether, benzoinethylether, benzyldimethylketal, benzophenon, 10 2,2-dimethyl-2-phenylacetophenon, 2-chlor-thioxanthon og antraquinon.Examples of these are: benzoin isopropyl ether, benzoin ethyl ether, benzyldimethyl ketal, benzophenone, 2,2-dimethyl-2-phenylacetophenone, 2-chloro-thioxanthone and anthraquinone.
Blandingen kan spredes på polycarbonatunderlaget ved udspredning, påsprøjtning eller neddypning: tykkelsen af belægningen kan variere mellem 5 og 200 ym.The mixture can be spread on the polycarbonate substrate by spreading, spraying or dipping: the thickness of the coating can vary between 5 and 200 µm.
15 Den til blandingens tværbindingsreaktion nødven dige UV-bestråling, kan let frembringes ved at man anvender kviksølvdamplamper, anvendt, under middel eller højt tryk. Det er også muligt at anvende andre typer bestråling (elektronstråler, røntgen og andet).The UV irradiation needed for the crosslinking reaction of the mixture can be readily obtained by using mercury vapor lamps used, under medium or high pressure. It is also possible to use other types of radiation (electron beams, X-rays and other).
20 Anvendelsesmulighederne for de ovennævnte sammen- ' sætninger, polycarbonatformlegemer med overtræk, er mangfoldige: gensigtige plader, maskin-dele og forskellige artikler. Den opnåede sammensætning tillader faktisk, at man forener polycarbonatemes grund-25 læggende og naturlige egenskaber (slagstyrke, gennemsigtighed og modstandsevne mod høje temperaturer) med meget gode overfladeegenskaber, såsom modstandsevne mod ridsning, afslidning, opløsningsmidler, bestråling og hydrolyse, således, at udendørsanvendelser af det 30 sammensatte materiale gøres muligt, idet det kan modstå vejrligets påvirkning og kontakt med kemikalier tillige.The applications of the above compositions, polycarbonate molding bodies with coatings, are manifold: transparent sheets, machine parts and various articles. The composition obtained actually allows the basic and natural properties of the polycarbonates (impact strength, transparency and resistance to high temperatures) to be combined with very good surface properties such as scratch resistance, abrasion, solvents, radiation and hydrolysis, so that outdoor applications of the 30 composite material is made possible as it can withstand the effects of the weather and contact with chemicals as well.
Opfindelsen illustreres med nogle få udførelseseksempler .The invention is illustrated by a few embodiments.
35 Eksempel 1Example 1
En urethanacrylatharpiks (harpiks A) anvendes som opnået ved kondensation af et mol hexamethylendiiso-cyanat med to mol trimethylolpropandiacrylat: produktetA urethane acrylate resin (resin A) is used as obtained by condensing one mole of hexamethylene diisocyanate with two moles of trimethylolpropane diacrylate: the product
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7 har en η 25°C = 13,500 Pa · s og en acrylisk funktionali- tet på 4 og en molekylvægt i intervallet 400-4000.7 has a η 25 ° C = 13,500 Pa · s and an acrylic functionality of 4 and a molecular weight in the range of 400-4000.
Harpiks A blandes med N-vinylpyrrolidon (VP) ifølge den følgende sammensætning: 5 Harpiks A 80 dele VP 20 deleResin A is mixed with N-vinylpyrrolidone (VP) according to the following composition: 5 Resin A 80 parts VP 20 parts
Benzyldimethylketal 5 deleBenzyldimethylketal 5 parts
Den således opnåede blanding har en η 25°C på 0,830 Pa * s og spredes over en prøve, der er 10 skåret ud af en plan extruderet plade af en typisk kommerciel polycarbonatvare, således at en belægningstykkelse på 30 ym opnås.The mixture thus obtained has a η 25 ° C of 0.830 Pa * s and is spread over a sample cut out of a flat extruded sheet of a typical commercial polycarbonate product so that a coating thickness of 30 µm is obtained.
Til denne proces anvendes en K-Control Coater filmspreder med spiralbjælker. Prøverne tværbindes ved 15 i nærværelse af luft at lade dem passere gennem en UV-tunnel med en kviksølvdamplampe, der har en styrke på 80 W/cm, som er anbragt i en afstand på 11 cm fra den overflade, der skal- tværbindes, idet fremføringshastigheden er 24 meter per minut. Prøvernes overflade-20 hårdhed (Konig hårdhed, PN Unichim Nr. 91) og ridsningsmodstand måles som funktion af antal passager gennem tunnelen. Ridsningsmodstanden måles ved aflæsning af den mindste belastning (i gram), som er nødvendig for at ridse overfladen, ved forsøg med en diamantspids 25 med en vinkel på 120°, der fremføres i en langsom, retlinet bevægelse.For this process, a K-Control Coater film spreader with spiral beams is used. The samples are crosslinked by passing them in the presence of air through a UV tunnel with a mercury vapor lamp having a power of 80 W / cm, spaced 11 cm from the surface to be crosslinked, with the feed rate is 24 meters per minute. The surface-20 hardness of the samples (Konig hardness, PN Unichim No. 91) and scratch resistance are measured as a function of the number of passages through the tunnel. Scratch resistance is measured by reading the smallest load (in grams) needed to scratch the surface by experimenting with a diamond tip 25 at an angle of 120 ° advanced in a slow, rectilinear motion.
De følgende resultater opnåedes:The following results were obtained:
Antal passager Konig hårdhed Ridsningsmodstand s g 2 169 26 4 170 29 8 176 32 12 178 33 16 181 34 35 20 185 35Number of passages Konig hardness Scratch resistance s g 2 169 26 4 170 29 8 176 32 12 178 33 16 181 34 35 20 185 35
Det kan ses, at overfladen har en stor hårdhed, og stor ridsningsmodstand efter allerede 2 passager.It can be seen that the surface has a great hardness and great scratch resistance after already 2 passes.
Den ubelagte prøves ridsningsmodstand er 6,2 g, så detThe scratch resistance of the uncoated sample is 6.2 g, so it
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8 fremgår, at belægningen forbedrer prøvernes ridsningsmodstand betragteligt. Belægningsfilmens vedhæftning til pladen, målt efter 20 tunnelpassager, er 100%, også med klæbestrimmel (måling efter FN UNICHIM Nr. 37 net) .8 shows that the coating significantly improves the scratch resistance of the samples. The coating film adhesion to the plate, measured after 20 tunnel passages, is 100%, also with adhesive strip (measurement according to UN UNICHIM No. 37 net).
5 Slagstyrken af prøverne, som er opnået på den ovenfor beskrevne måde, er den samme som for de ubelagte prøver (75 kg·cm/cm ), og det samme gælder for deres gennemsigtighed.5 The impact strength of the samples obtained in the manner described above is the same as for the uncoated samples (75 kg · cm / cm) and the same is true for their transparency.
Til bestemmelse af slagstyrken anvendtes Izod-10 metoden, ASTM-D-256.To determine the impact strength, the Izod-10 method, ASTM-D-256, was used.
Fremskyndede ældningsforsøg udførtes i et Weatherometer (WOM) og ved nedsænkning af prøverne i vand, og de følgende resultater opnåedes:Accelerated aging experiments were performed in a Weatherometer (WOM) and by immersing the samples in water, and the following results were obtained:
Efter 1.000 timer i WOM Vedhæftning uden strimmel 100% 15 do. med strinmel 100% RLdsningsmodstand 37 gAfter 1,000 hours in WOM Adhesion without strip 100% 15 do. with step flour 100% RL welding resistance 37 g
Farve uberørtColor untouched
Efter 10 døgn i vand ved 23°C Vedhæftning uden strinmel 100% do. med strinmel 100% 20 Afskrabningsmodstand 31 gAfter 10 days in water at 23 ° C Adhesion without step meal 100% do. with step meal 100% 20 Scrap resistance 31 g
Farve uberørtColor untouched
Det kan således konkluderes, at der ingen synlige ændringer er i prøverne under ældningsforløbet og vandnedsænkningen som udført. Hvis det samme forsøg 25 gentages under anvendelse af en belægning, der er sammensat af harpiks A alene, opnås en film, der har samme egenskaber som opstillet ovenfor, men vedhæft-ningen er lig 0. Forsøgene viser, at tilstedeværelsen af både harpiksen og vinylamidet er nødvendig, for at 30 også vedhæftningsegenskaberne kan blive tilfredsstillende.Thus, it can be concluded that there are no visible changes in the samples during the aging process and the water immersion as performed. If the same experiment 25 is repeated using a coating composed of resin A alone, a film having the same properties as set out above, but the adhesion is equal to 0. The tests show that the presence of both the resin and the vinyl amide is necessary for the adhesion properties to be satisfactory as well.
Den ovenfor beskrevne sammensætnings afslidnings-modstand måltes med et Taber Abrasionmeter, der har CS 10F slibehjul, ifølge ASTM-D10 44 standarden. Be-35 stemmelsen af afslidningen måltes ved en optisk metode, ifølge ASTM 1003 uklarhedsprøven.The abrasion resistance of the composition described above was measured with a Taber Abrasion Meter having CS 10F grinding wheel, according to the ASTM-D10 44 standard. The determination of the abrasion was measured by an optical method, according to the ASTM 1003 haze test.
De resultater, der er opnået for forskellige behandlingsforløb og ved anvendelse af den ovenfor be-The results obtained for different courses of treatment and using the above
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9 skrevne sammensætning belagt med harpiks A og vinyl-pyrrolidon, sammenlignet med et kommercielt polycarbonate belagt med en siloxanlakbelægning, er som følgende:9 written compositions coated with resin A and vinyl pyrrolidone, as compared to a commercial polycarbonate coated with a siloxane varnish coating, are as follows:
Antal forløb (Gennemførelse) Uklarhedsprøver, % 5 Polycarbonat + Kommerciel harpiks A + vinylpyrrolidon polycarbonat 10 1,2 1,2 20 2,5 1,6 40 3,8 3,9 10 60 5,0 5,6 100 7,5 10,0 150 10,8 15,6 200 13,9 26,8 15 Polycarbonat som sådan udviser under disse be tingelser allerede efter 10 forløb en værdi ved uklarhedsprøven, der er større end 20%. Disse resultater viser, at den ovenfor beskrevne sammensætning har en høj afslidningsmodstandsværdi,som er større end værdien 20 for de kommercielle lakbelagte artikler efter et vist antal forløb.Number of courses (Completion) Fuzziness tests,% 5 Polycarbonate + Commercial resin A + vinyl pyrrolidone polycarbonate 10 1.2 1.2 20 2.5 1.6 40 3.8 3.9 10 60 5.0 5.6 100 7.5 10.0 150 10.8 15.6 200 13.9 26.8 15 Polycarbonate, as such, already exhibits a value in the cloud sample greater than 20% after 10 cycles. These results show that the composition described above has a high abrasion resistance value which is greater than the value of 20 for the commercial varnish coated articles after a certain number of runs.
Eksempel 2Example 2
Ved at gå frem som i det foregående eksempel fremstilles en blanding med følgende sammensætning: 25 Harpiks A 50 dele vinylpyrrolidon 50 dele benzyldimethylketal 5 deleProceeding as in the previous example, a mixture of the following composition is prepared: 25 Resin A 50 parts vinyl pyrrolidone 50 parts benzyldimethyl ketal 5 parts
Blandingen har en viskositet ved 25°C på 0,075 Pa · s og spredes på de samme prøver, sådan at en tyk-30 kelse på 30 ym opnås. Efter 20 UV-tunnel passager, opnås en film, der har de følgende specifikationer:The mixture has a viscosity at 25 ° C of 0.075 Pa · s and is spread on the same samples to obtain a thickness of 30 µm. After 20 UV-tunnel passages, a film is obtained which has the following specifications:
Konig hårdhed 176 s vedhæftning uden strimmel 100 % vedhæftning med strimmel 100 % 35 ridsningsmodstand 24 g 10Konig hardness 176 s adhesive without strip 100% adhesion with strip 100% 35 scratch resistance 24 g 10
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Prøvernes slagstyrke og gennemsigtighed var de samme som for de ubelagte plader. Det ovenfor beskrevne forsøg gentoges med forskellige mængder af fotoinitiatoren eller i en nitrogenatmosfære, og efter 5 20 passager opnåedes følgende resultater: Hårdhed Vedhæftning Rids-The impact strength and transparency of the samples were the same as for the uncoated plates. The above described experiment was repeated with different amounts of the photoinitiator or in a nitrogen atmosphere, and after 5 passages the following results were obtained: Hardness
Uden med mod-SWithout mod-S
strimmel strimmel stan^ s % % g 10 Benzyldimethylketal 181 100 100 22 (2 dele)strip strip strip% g g Benzyldimethyl ketal 181 100 100 22 (2 parts)
Benzyldimethylketal 189 100 100 26 (2 dele + ^atmosfære) 15 Det kan konkluderes,.at indenfor de ovennævnte grænser, medfører initiatorkoncentrationen og tilstedeværelsen af nitrogen ingen nævneværdige ændringer i prøveegenskaberne .Benzyldimethylketal 189 100 100 26 (2 parts + ^ atmosphere) 15 It can be concluded that, within the above limits, the initiator concentration and the presence of nitrogen do not cause any appreciable changes in the test properties.
20 Eksempel 3Example 3
Fremgangsmåden er den samme som i eksempel 1, ved at blande N-vinylcaprolactam sammen med harpiks A, ifølge følgende sammensætning: harpiks A 60 dele 25 N-vinylcaprolactam 40 dele benzyldimethylketal 5 deleThe process is the same as in Example 1, by mixing N-vinylcaprolactam with resin A, according to the following composition: resin A 60 parts 25 N-vinylcaprolactam 40 parts benzyldimethyl ketal 5 parts
Der opnås en blanding, der har en n25°c ^*9 0,23 Pa-s, som spredes på polycarbonatplader, sådan at en tykkelse på 30 Um opnås.A mixture is obtained having a n25 ° c 2 9 0.23 Pa-s which is spread on polycarbonate plates to obtain a thickness of 30 µm.
30 Efter 20 UV-tunnel passager er resultatet en film, der har følgende egenskaber:30 After 20 UV tunnel passages, the result is a film that has the following properties:
Konig hårdhed 180 s vedhæftning uden strimmel 100 % vedhæftning med strimmel 100 % 35 ridsningsmodstand 27 gKonig hardness 180 s adhesive without strip 100% adhesion with strip 100% 35 scratch resistance 27 g
Prøvernes slagstyrke og gennemsigtighed er uændrede i forhold til det rene polycarbonat.The impact strength and transparency of the samples are unchanged from the pure polycarbonate.
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1111
Eksempel 4Example 4
Der fremstilles en blanding, som indeholder harpiks A plus de følgende bestanddele i de nedennævnte mængder: 5 harpiks A 70 dele N-vinylpyrrolidon 15 dele methylmaleat 15 dele benzoinethylether 5 deleA mixture is prepared containing resin A plus the following constituents in the amounts listed below: 5 resin A 70 parts N-vinylpyrrolidone 15 parts methyl maleate 15 parts benzoin ethyl ether 5 parts
Blandingen spredes på polycarbonat til en tykkelse på 10 30 ym og ved tværbinding efter 20 UV-tunnel passager opnås en film, der har de følgende egenskaber:The mixture is spread on polycarbonate to a thickness of 10 30 µm and by cross-linking after 20 UV tunnel passages a film having the following properties is obtained:
Konig hårdhed 177 s vedhæftning uden strimmel 100 % 15 vedhæftning med strimmel 100 % ridsningsmodstand 28 gKonig hardness 177 s adhesive without strip 100% 15 adhesion with strip 100% scratch resistance 28 g
Prøvernes slagstyrke og gennemsigtighed fandtes uændrede i forhold til værdierne for de ubehandlede polycarbo-natprøver.The impact strength and transparency of the samples were unchanged from the values of the untreated polycarbo night samples.
20 Eksempel 5Example 5
Den i eksempel 1 beskrevne harpiks A anvendes i en sammenblanding med N-vinyl-N-methylbutyramid i de følgende vægtforhold: harpiks A 70 dele 25 N-vinyl-N-methylbutyramid 30 dele benzyldimethylketal 5 deleThe resin A described in Example 1 is used in a mixture with N-vinyl-N-methylbutyramide in the following weight ratios: resin A 70 parts 25 N-vinyl-N-methylbutyramide 30 parts benzyldimethyl ketal 5 parts
Der fremstilles en film, der har en tykkelse på 5 ym med den ovennævnte blanding, og efter 10 UV-tunnel passager findes de følgende egenskaber: 30 Konig hårdhed 162 s vedhæftning uden strimmel 100 % vedhæftning med strimmel 100 % ridsningsmodstand 18 gA film having a thickness of 5 µm is made with the above mixture and after 10 UV tunnel passages the following properties are found: 30 Konig hardness 162 s adhesive without strip 100% adhesive with strip 100% scratch resistance 18 g
Prøvernes andre egenskaber svarer til de, der er be-35 skrevet i eksempel 1.The other properties of the samples are similar to those described in Example 1.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24354/80A IT1141029B (en) | 1980-08-29 | 1980-08-29 | POLYCARBONATE BASED COMPOSITION HAVING IMPROVED PROPERTIES AND METHOD FOR ITS OBTAINING |
| IT2435480 | 1980-08-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK356881A DK356881A (en) | 1982-03-01 |
| DK163821B true DK163821B (en) | 1992-04-06 |
| DK163821C DK163821C (en) | 1992-08-24 |
Family
ID=11213226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK356881A DK163821C (en) | 1980-08-29 | 1981-08-11 | POLYCARBONATE FORMULA WITH A COVERAGE AND PROCEDURE FOR PREPARING THEREOF |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5775857A (en) |
| AT (1) | AT381322B (en) |
| BE (1) | BE890097A (en) |
| BR (1) | BR8105413A (en) |
| CH (1) | CH655733A5 (en) |
| DE (1) | DE3134157C2 (en) |
| DK (1) | DK163821C (en) |
| ES (1) | ES8400474A1 (en) |
| FR (1) | FR2489345A1 (en) |
| GB (1) | GB2082606B (en) |
| IT (1) | IT1141029B (en) |
| NL (1) | NL8104013A (en) |
| NO (1) | NO156204C (en) |
| SE (1) | SE450002B (en) |
| ZA (1) | ZA815428B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5958035A (en) * | 1982-09-29 | 1984-04-03 | Mitsui Petrochem Ind Ltd | Curable coating resin composition |
| JPS59202229A (en) * | 1983-05-02 | 1984-11-16 | Sumitomo Bakelite Co Ltd | Production of transparent coating film |
| DE3415104A1 (en) * | 1984-04-21 | 1985-10-31 | Bayer Ag, 5090 Leverkusen | COATED PLASTIC FILM |
| US4954591A (en) * | 1987-11-06 | 1990-09-04 | Pilkington Visioncare Holdings, Inc. | Abrasion resistant radiation curable coating for polycarbonate article |
| US4929506A (en) * | 1987-12-31 | 1990-05-29 | General Electric Company | Coated polycarbonate articles |
| DE3819627A1 (en) * | 1988-06-09 | 1989-12-14 | Bayer Ag | UV-CARDABLE COATINGS FOR POLYCARBONATE FORMKOERPER |
| US5175030A (en) * | 1989-02-10 | 1992-12-29 | Minnesota Mining And Manufacturing Company | Microstructure-bearing composite plastic articles and method of making |
| US5104692A (en) * | 1990-04-20 | 1992-04-14 | Pilkington Visioncare Holdings, Inc. | Two-layer antireflective coating applied in solution |
| DE4025811C1 (en) * | 1990-08-16 | 1992-01-02 | Uvex Winter Optik Gmbh, 8510 Fuerth, De | |
| US5468820A (en) * | 1994-01-14 | 1995-11-21 | Isp Investments Inc. | Reactive diluent for radiation curing of film-forming polymers |
| DE4404616A1 (en) | 1994-02-14 | 1995-08-17 | Bayer Ag | Use of UV-curable coating agents for coating molded polycarbonate bodies |
| US6306504B1 (en) | 1994-02-14 | 2001-10-23 | Bayer Aktiengesellschaft | Polycarbonate molded articles coated with UV-curable compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3874906A (en) * | 1972-09-22 | 1975-04-01 | Ppg Industries Inc | Process for applying polyester-acrylate containing ionizing irradiation curable coatings |
| US4129709A (en) * | 1977-03-14 | 1978-12-12 | Gaf Corporation | Coating composition comprising N-vinyl-2-pyrrolidone and an oligomer |
| IT1162770B (en) * | 1979-08-10 | 1987-04-01 | Anic Spa | METHOD FOR COATING VARIOUS SURFACES AND MEANS SUITABLE FOR THE PURPOSE |
| US4319811A (en) * | 1979-10-01 | 1982-03-16 | Gaf Corporation | Abrasion resistance radiation curable coating |
-
1980
- 1980-08-29 IT IT24354/80A patent/IT1141029B/en active
-
1981
- 1981-08-06 ZA ZA815428A patent/ZA815428B/en unknown
- 1981-08-11 DK DK356881A patent/DK163821C/en not_active IP Right Cessation
- 1981-08-19 BR BR8105413A patent/BR8105413A/en unknown
- 1981-08-20 FR FR8116018A patent/FR2489345A1/en active Granted
- 1981-08-21 CH CH5412/81A patent/CH655733A5/en not_active IP Right Cessation
- 1981-08-24 NO NO812854A patent/NO156204C/en unknown
- 1981-08-25 GB GB8125945A patent/GB2082606B/en not_active Expired
- 1981-08-26 BE BE0/205775A patent/BE890097A/en not_active IP Right Cessation
- 1981-08-28 JP JP56134358A patent/JPS5775857A/en active Granted
- 1981-08-28 AT AT0374681A patent/AT381322B/en not_active IP Right Cessation
- 1981-08-28 SE SE8105109A patent/SE450002B/en not_active IP Right Cessation
- 1981-08-28 ES ES505479A patent/ES8400474A1/en not_active Expired
- 1981-08-28 NL NL8104013A patent/NL8104013A/en not_active Application Discontinuation
- 1981-08-28 DE DE3134157A patent/DE3134157C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2489345A1 (en) | 1982-03-05 |
| SE8105109L (en) | 1982-03-01 |
| BE890097A (en) | 1982-02-26 |
| DK356881A (en) | 1982-03-01 |
| NO812854L (en) | 1982-03-01 |
| ATA374681A (en) | 1986-02-15 |
| DK163821C (en) | 1992-08-24 |
| ES505479A0 (en) | 1983-10-16 |
| DE3134157A1 (en) | 1982-04-01 |
| FR2489345B1 (en) | 1984-12-28 |
| SE450002B (en) | 1987-06-01 |
| JPH0148935B2 (en) | 1989-10-23 |
| GB2082606B (en) | 1984-02-01 |
| BR8105413A (en) | 1982-05-11 |
| ES8400474A1 (en) | 1983-10-16 |
| DE3134157C2 (en) | 1987-01-22 |
| JPS5775857A (en) | 1982-05-12 |
| ZA815428B (en) | 1982-08-25 |
| AT381322B (en) | 1986-09-25 |
| NL8104013A (en) | 1982-03-16 |
| GB2082606A (en) | 1982-03-10 |
| NO156204B (en) | 1987-05-04 |
| CH655733A5 (en) | 1986-05-15 |
| IT1141029B (en) | 1986-10-01 |
| NO156204C (en) | 1987-08-12 |
| IT8024354A0 (en) | 1980-08-29 |
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