WO2000005284A1 - Acrylic polymer composition - Google Patents

Acrylic polymer composition Download PDF

Info

Publication number
WO2000005284A1
WO2000005284A1 PCT/GB1999/002206 GB9902206W WO0005284A1 WO 2000005284 A1 WO2000005284 A1 WO 2000005284A1 GB 9902206 W GB9902206 W GB 9902206W WO 0005284 A1 WO0005284 A1 WO 0005284A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylic
compound
polymerisable
composition
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB1999/002206
Other languages
English (en)
French (fr)
Inventor
Graeme Robertson
Ian Muir Fraser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Mitsubishi Chemical UK Ltd
Original Assignee
Imperial Chemical Industries Ltd
Ineos Acrylics UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd, Ineos Acrylics UK Ltd filed Critical Imperial Chemical Industries Ltd
Priority to EP99931382A priority Critical patent/EP1112295B1/en
Priority to US09/744,162 priority patent/US6794439B1/en
Priority to AU47918/99A priority patent/AU768611B2/en
Priority to PL345660A priority patent/PL199891B1/pl
Priority to JP2000561239A priority patent/JP2003529618A/ja
Priority to ES99931382T priority patent/ES2400230T3/es
Publication of WO2000005284A1 publication Critical patent/WO2000005284A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals

Definitions

  • the present invention relates to an abrasion resistant polymer composition and a process for its preparation.
  • Acrylic sheet materials are widely used for building and glazing applications and to form various shaped articles such as baths, sinks, vanity units and shower trays.
  • the abrasion resistance of the acrylic sheet used in such applications is normally required to be as high as possible.
  • One method that is currently used to improve the abrasion resistance of acrylic surfaces involves the application of an abrasion resistant coating to the surface of an acrylic sheet.
  • the coating is typically applied in solution to the acrylic sheet and is then cured, for example by radiation (UV), solvent evaporation or by thermal curing.
  • UV radiation
  • EP-A-571808 discloses antifogging film, plates and articles comprising an acrylic polymer support and a polymerised and UV reticulated abrasion resistant coating containing acrylic monomers and hydrophilic metal oxide(s).
  • abrasion-resistant coatings can enhance the performance of acrylic surfaces against abrasion, their use on acrylic sheet which is to be shaped, e.g. by thermoforming, may be limited by the relatively inelastic nature of the coating, which may cause cracking of the coating as the surface is deformed.
  • Conventional coating technology requires a two step process: polymerising the sheet o followed by coating and curing the abrasion resistant formulation. In practice, this often requires a clean room environment to ensure no dust particles become incorporated into the surface layer. There is therefore a significant manufacturing advantage to be gained for an abrasion resistant product which may be delivered in a one-step process.
  • the present invention provides an acrylic composition
  • an acrylic composition comprising at least 70% w/w of the residues of at least one polymerisable acrylic monomer, 0.2 - 5% w/w of a finely divided compound comprising at least one oxide selected from silicon, titanium, zirconium and aluminium oxides, and 0.2 - 25% w/w of at least one linking compound which is miscible with said polymerisable acrylic monomer and which is capable of bonding to the surface of the oxide compound.
  • the present invention provides a polymerisable composition
  • a polymerisable composition comprising at least 70% w/w of at least one polymerisable acrylic monomer, 0.2 - 5% w/w of a finely divided compound comprising at least one oxide selected from silicon, titanium, zirconium and aluminium oxides, and 0.2 - 25% w/w of at least one linking compound which is miscible with said polymerisable acrylic compound and which is capable of bonding to the surface of the oxide compound.
  • the present invention provides a process for forming an acrylic composition comprising the steps of:
  • the polymerisable acrylic monomers are alkyl (alk)acrylic acids and esters thereof, including functionalised monomers such as hydroxy, halogen or amine functionalised acrylate or methacrylate monomers.
  • the monomer(s) comprise one or more alkyl acrylates, alkyl methacrylates or acrylic or methacryiic acid, e.g. methyl, ethyl, hydroxyethyl, butyl, 2-ethylhexyl, cyclohexyi or phenyl esters of acrylic acid or methacryiic acid.
  • Suitable compounds include hydroxyethyl methacrylate (HEMA), hexanediol diacrylate, tripropylglycol methacrylate, ethylene glycol monopropylether, 3-aminopropyl trimethoxysilane and ethanolamine or mixtures thereof.
  • HEMA hydroxyethyl methacrylate
  • hexanediol diacrylate tripropylglycol methacrylate
  • ethylene glycol monopropylether 3-aminopropyl trimethoxysilane and ethanolamine or mixtures thereof.
  • Some compounds may perform the function of the linking compound adequately whilst having certain disadvantages in certain applications, e.g. the use of coloured compounds or compounds which develop a colour under the conditions of manufacture of the composition or any article made therefrom may be unsuitable when a clear product is required.
  • the finely divided oxide compound preferably has an average particle size between 1 and 50 nm, more preferably between 5 and 35 nm.
  • a preferred oxide compound is colloidal silica.
  • the oxide compound is preferably added to the acrylic monomer or polymer/monomer solution in the form of a dispersion in the linking compound.
  • Suitable dispersions are available commercially for use as coating compositions to provide abrasion resistant coatings. Examples of suitable commercial dispersions include the HIGHLINKTM compounds available from Clariant, e.g. Highlink OG 100-30.
  • the ratio of said linking compound to said finely divided oxide is preferably in the range 1:1 - 5:1 (more preferably 2:1 - 4:1) by weight.
  • the dispersion is preferably present at 0.2 to 10%, more preferably 2 to 8% by weight in the polymerisable composition.
  • the acrylic compositions can be made by conventional free radical, anionic or other polymerisation techniques, for example bulk, solution or suspension with the addition of suitable initiators and optionally chain transfer agents and/or other additives such as cross-linking additives, fillers, pigments, plasticisers, impact modifiers, stabilisers etc. Therefore the monomer(s) are caused to polymerise by initiating the polymerisation reaction, normally by means of activating the added initiator, and maintaining suitable conditions, e.g. an elevated temperature, pressure etc until the required degree of polymerisation has been achieved.
  • suitable conditions e.g. an elevated temperature, pressure etc until the required degree of polymerisation has been achieved.
  • suitable conditions e.g. an elevated temperature, pressure etc.
  • free-radical polymerisation is used, e.g.
  • the method of polymerising the polymer may also be selected from suspension polymerisation, solution polymerisation or by crushing or pelletising a bulk polymerised product.
  • Methods of forming acrylic polymers by suspension or solution polymerisation are well known in the art and therefore need not be further described.
  • AIBN 2,2 - azobisisobutyronitrile
  • HIGHLINKTM OG 100-30 from Clariant
  • MMA methylmethacrylate
  • the mixture was then post cured for 2 hours at 60 °C followed by 2 hours at 80 °C, followed by heating at a rate of 0.5 °C /min up to 118 °C and held at 118 °C for 1 hour.
  • the cell was then cooled and the glass sheets removed to release the resulting cast PMMA sheet.
  • a photoinitiator (DarocurTM 1173) was added at 2% w/w prior to coating. The coating was applied at a wet thickness of 4 microns and cured under UV light in a commercial UV coating apparatus. The coated samples were then tested as described in example 1. The results show that the abrasion resistance performance was comparable to that of Examples 1 & 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
PCT/GB1999/002206 1998-07-21 1999-07-09 Acrylic polymer composition Ceased WO2000005284A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP99931382A EP1112295B1 (en) 1998-07-21 1999-07-09 Acrylic polymer composition
US09/744,162 US6794439B1 (en) 1998-07-21 1999-07-09 Acrylic polymer composition
AU47918/99A AU768611B2 (en) 1998-07-21 1999-07-09 Acrylic polymer composition
PL345660A PL199891B1 (pl) 1998-07-21 1999-07-09 Kompozycja akrylowa i sposób jej wytwarzania
JP2000561239A JP2003529618A (ja) 1998-07-21 1999-07-09 アクリルポリマー組成物
ES99931382T ES2400230T3 (es) 1998-07-21 1999-07-09 Composición polimérica acrílica

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9815730.8 1998-07-21
GBGB9815730.8A GB9815730D0 (en) 1998-07-21 1998-07-21 Polymer composition

Publications (1)

Publication Number Publication Date
WO2000005284A1 true WO2000005284A1 (en) 2000-02-03

Family

ID=10835804

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/002206 Ceased WO2000005284A1 (en) 1998-07-21 1999-07-09 Acrylic polymer composition

Country Status (10)

Country Link
US (1) US6794439B1 (enExample)
EP (1) EP1112295B1 (enExample)
JP (1) JP2003529618A (enExample)
AU (1) AU768611B2 (enExample)
ES (1) ES2400230T3 (enExample)
GB (1) GB9815730D0 (enExample)
PL (1) PL199891B1 (enExample)
TW (1) TW505663B (enExample)
WO (1) WO2000005284A1 (enExample)
ZA (1) ZA200100485B (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1388550A1 (en) * 2002-08-08 2004-02-11 Kao Corporation Polymer composite particle
WO2005092967A1 (en) * 2004-03-25 2005-10-06 Jsr Corporation Curable liquid composition, cured film, and antistatic laminate

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19933098A1 (de) 1999-07-15 2001-01-18 Herberts Gmbh & Co Kg Mit Nanopartikeln modifizierte Bindemittel für Überzugsmittel und deren Verwendung
GB0612803D0 (en) * 2006-06-28 2006-08-09 Lucite Int Uk Ltd Polymeric composition
KR101464017B1 (ko) * 2007-05-01 2014-12-08 엑사테크 엘.엘.씨. 자외선 경화 인쇄 패턴을 가진 플라스틱 글레이징 패널과 상기 패널을 제조하는 방법
TW200932810A (en) * 2008-01-28 2009-08-01 Ind Tech Res Inst Silica-polymeric resin composite and method for manufacturing the same
ES2753723T3 (es) * 2016-03-24 2020-04-14 Sika Tech Ag Una composición de componentes individuales o múltiples para producir un hidrogel

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571808A2 (en) * 1992-05-26 1993-12-01 ELF ATOCHEM ITALIA S.r.l. No drop films or plates consisting of acrylic polymers and process for their preparation
EP0659530A2 (de) * 1993-12-22 1995-06-28 Röhm GmbH Verfahren zur Herstellung von hochgefülltem Kunststoff-Plattenmaterial
EP0685511A2 (en) * 1994-05-19 1995-12-06 Atohaas Holding C.V. Process for the preparation of antiscratch and antiabrasion shaped articles based on acrylic polymers
WO1996026238A1 (en) * 1995-02-23 1996-08-29 Aristech Chemical Corporation Acrylic sheet having uniform distribution of coloring and mineral filler before and after thermoforming
WO1997014749A1 (en) * 1995-10-17 1997-04-24 Ici Acrylics Inc. Acrylic compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4145477A (en) * 1974-11-11 1979-03-20 Rohm And Haas Company Rigidized acrylic articles and method
US5705552A (en) * 1993-11-26 1998-01-06 Aristech Chemical Corporation Thermoformable acrylic sheet having uniform distribution of color and mineral filler
KR960007660A (ko) * 1994-08-12 1996-03-22 아크릴계 시트, 아크릴계 접착시트 및 이들의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0571808A2 (en) * 1992-05-26 1993-12-01 ELF ATOCHEM ITALIA S.r.l. No drop films or plates consisting of acrylic polymers and process for their preparation
EP0659530A2 (de) * 1993-12-22 1995-06-28 Röhm GmbH Verfahren zur Herstellung von hochgefülltem Kunststoff-Plattenmaterial
EP0685511A2 (en) * 1994-05-19 1995-12-06 Atohaas Holding C.V. Process for the preparation of antiscratch and antiabrasion shaped articles based on acrylic polymers
WO1996026238A1 (en) * 1995-02-23 1996-08-29 Aristech Chemical Corporation Acrylic sheet having uniform distribution of coloring and mineral filler before and after thermoforming
WO1997014749A1 (en) * 1995-10-17 1997-04-24 Ici Acrylics Inc. Acrylic compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1388550A1 (en) * 2002-08-08 2004-02-11 Kao Corporation Polymer composite particle
US7153573B2 (en) 2002-08-08 2006-12-26 Kao Corporation Polymer composite particle comprising metal oxide and silicone and/or fluorine and method of producing the same
CN1324078C (zh) * 2002-08-08 2007-07-04 花王株式会社 复合聚合物粒子及其制造方法
WO2005092967A1 (en) * 2004-03-25 2005-10-06 Jsr Corporation Curable liquid composition, cured film, and antistatic laminate

Also Published As

Publication number Publication date
PL345660A1 (en) 2002-01-02
EP1112295A1 (en) 2001-07-04
JP2003529618A (ja) 2003-10-07
GB9815730D0 (en) 1998-09-16
ZA200100485B (en) 2002-01-17
US6794439B1 (en) 2004-09-21
PL199891B1 (pl) 2008-11-28
AU4791899A (en) 2000-02-14
TW505663B (en) 2002-10-11
EP1112295B1 (en) 2012-11-21
AU768611B2 (en) 2003-12-18
ES2400230T3 (es) 2013-04-08

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