[go: up one dir, main page]

WO1986002652A1 - Compositions de revetement polymerisables aux ultraviolets contenant un additif polymerisable aux ultraviolets - Google Patents

Compositions de revetement polymerisables aux ultraviolets contenant un additif polymerisable aux ultraviolets Download PDF

Info

Publication number
WO1986002652A1
WO1986002652A1 PCT/US1985/002041 US8502041W WO8602652A1 WO 1986002652 A1 WO1986002652 A1 WO 1986002652A1 US 8502041 W US8502041 W US 8502041W WO 8602652 A1 WO8602652 A1 WO 8602652A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
recited
composition
diacrylate
silicone
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/US1985/002041
Other languages
English (en)
Inventor
Frank A. Leo
Elias P. Moschovis
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.)
DeSoto Inc
Original Assignee
DeSoto Inc
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 DeSoto Inc filed Critical DeSoto Inc
Publication of WO1986002652A1 publication Critical patent/WO1986002652A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • This invention relates to ultraviolet curable curable coating compositions which are modified to improve the flow, leveling, wetting, mar resistance and flexibility of the coatings.
  • Background Art Liquid ultraviolet curable coatings do not wet substrates well, especially when they do not contain volatile organic solvent, and it is usually . desired to substantially eliminate the use of such solvents in order to minimize pollution, hazard and unnecessary expense. This lack of good wetting of the substrate persists even when the unsaturated coating composition which is used is of low viscosity. As a result, the wet coatings crawl and flow over the substrate is poor, causing all sorts of coating defects like pinholing and orange peel. As a result, liquid radiation curable coatings are modified to include flow control agents which improve the capacity of the coating to wet the substrate.
  • a radiation-curable liquid coating composition comprising polymerizable ethylenically unsaturated material containing a major weight proportion (more than 50%) of a polyacrylate or the corresponding polymethacrylate, which is preferably a liquid, is modified by the addition of from 0.1% to 2.5%, preferably from 0.2% to 1.0%, of a silicone dicarbinol diurethane diacrylate or dimethacrylate in which the carbinol groups are carried by an ethoxylate or propoxylate constituting from 30% to 70% of the silicone.
  • the preferred composition contains polyacrylates or methacrylates having at least 2.4 unsaturated groups per molecule to provide a relatively hard coating after curing with radiation which is preferably ultraviolet radiation.
  • the preferred coating compositions are substantially free of volatile inert organic solvent, but some of the problems which have been noted persist even when volatile solvent is present, and this is especially true when the proportion of solvent is small.
  • polyacrylates and polymethacrylates are well known to identify a plurality of acrylic or methacrylic acid ester groups.
  • the proportion of the silicone polyurethane diacrylate or dimethacrylate is critical because very little is used, and larger amounts are counterproductive because such larger amounts soften the cured coating which is an undesirable effect since hardness is important to obtaining mar resistance.
  • the crucial component in this invention is a silicone dicarbinol diurethane diacrylate or dimethacrylate, the diacrylate being preferred.
  • These silicone-containing compounds are based on organic polysiloxanes having two substituents having a carbinol-terminal group.
  • the carbinol group is provided by starting with a dihydroxy-ter inated organic polysiloxane and alkoxylating it with ethylene oxide or propylene oxide so that the alkoxylate constitutes from 30% to 70% of the dicarbinol which is produced.
  • the carbinol functionality in the alkoxylate is reacted with an organic diisocyanate, such as 2,4-toluene diisocyanate or isophorone diisocyanate, and also with an hydroxy-functional acrylate or methacrylate, such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, to provide a diacrylate- unctional diurethane derivative of the silicone dicarbinol.
  • an organic diisocyanate such as 2,4-toluene diisocyanate or isophorone diisocyanate
  • an hydroxy-functional acrylate or methacrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate
  • the sequence of the above reactions is known to be variable, it being permissible to react the silicone dicarbinol with excess diisocyanate and then with the hydroxy acrylate, or to prereact the hydroxy acrylate with a molar proportion of the diisocyanate to form an unsaturated monoisocyanate which is reacted with the dicarbinol in a stoichiometric amount based on isocyanate and carbinol functionalities.
  • the usual organic polysiloxanes which are available in commerce are methyl or phenyl substituted (methyl substitution is preferred and will be used in the examples) and have, a molecular weight in the range of 600 to 10,000.
  • the valences of the silicon atoms in the polysiloxane carry inert organic substituents, such as methyl and/or phenyl substituents, except for the two hydroxy groups which are ethoxylated to provide the terminal carbinol groups.
  • the initial polysiloxane can be dihydroxy terminated and alkoxylated directly or first prereacted with a monoepoxide, such as propylene oxide or butylene oxide to provide carbinol termination for further alkoxylation.
  • the carbinol groups are then adducted with from 30% to 70%, preferably from 40% to 60%, of ethylene oxide or propylene oxide to form the polyalkoxylates utilized herein after conversion to a urethane acrylate.
  • the polymerizable ethylenically unsaturated material including a major weight proportion of liquid polyacrylate or polymethacrylate
  • radiation curable compounds containing an average of more than 2.4 acrylate or methacrylate groups per molecule are preferred to provide hard cured coatings.
  • polyacrylates which are at least approximately tri unctional, such as trimethylol propane triacrylate or pentaerythritol tri- or tetra-acrylate.
  • Acrylate unsaturation is preferred because it provides a more rapid radiation cure, especially when photoinitiators are used to enable an ultraviolet cure.
  • especially hard and mar resistant coatings are obtained using from 70% to 85% of trimethylol propane triacrylate.
  • from 5% to 15% of a carboxylic acid which contains acrylic or methacrylic acid unsaturation, especially acrylic acid itself, is used to improve adhesion to surfaces having a basic nature, and such carboxyl-functional material is also useful herein.
  • the acrylation of the p.referred polyacrylate e.g., trimethylol propane triacrylate
  • the preferred trimethylol propane is acrylated to provide an average of at least 2.4 acrylate groups per molecule, preferably about 2.8 acrylate groups per molecule.
  • polyacrylate component from 1% to 12%, preferably 3% to 7%, of an epoxy diacrylate or dimethacrylate, preferably of a diglycidyl ether of a bisphenol in which the molecular weight of the diglycidyl ether is less than about 600, such as about 400 as in the Shell product Epon 828, since this also maximizes hardness and adhesion.
  • an epoxy diacrylate or dimethacrylate preferably of a diglycidyl ether of a bisphenol in which the molecular weight of the diglycidyl ether is less than about 600, such as about 400 as in the Shell product Epon 828, since this also maximizes hardness and adhesion.
  • the corresponding dimethacrylates are also useful. Preferred proportions are from 1% to 6%, and the preferred diacrylate is 1,6-hexanediol diacrylate. Isobornyl acrylate may also be present in small amount to enhance rapid radiation cure, flexibility, and to enhance the liquidity of the composition or one of its components.
  • the photoinitiators are themselves well known and are preferably ketonic in character. It is preferred to employ photoinitiators which comprise benzophenone so that the ultraviolet cure can be carried out in air instead of in a nitrogen or other inert atmosphere. Acetophenone and benzophenone will illustrate ketonic photoinitiators in this well known class. Substituted acetophenones are particularly effective, especially those which are hydroxy-substituted. A large number of substituted acetophenones are disclosed in U. S. Pats. Nos. 4,284,485 and 4,318,791.
  • This invention will be exemplified using the commercial ketonic photoinitiator, Irgacure 184 which is available from Ciba-Geigy (the compound 1-hydroxycyclohexyl phenyl ketone).
  • This compound is a substituted acetophenone.
  • substituted acetophenones are preferably used in combination with benzophenone to enable rapid and complete cure in an oxygen-containing atmosphere.
  • Epoxy diacrylate (1) 6. 0 6. 0

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

Compositions liquides de revêtement polymérisables par des radiations, comprenant une substance polymérisable éthyléniquement insaturée, contenant une proportion pondérale importante de polyacrylate ou polyméthacrylate de préférence liquide, contenant de préférence au moins 2,4 groupes acrylate ou méthacrylate par molécule, pour former un revêtement polymérisé qui est relativement dur, cette composition étant sensiblement exempte de solvants organiques inertes volatils, et de 0,1 % à 2,5 % d'un diacrylate ou diméthacrylate de diuréthane dicarbinol silicone dans lequel les groupes carbinol sont véhiculés par un éthoxylate ou propoxylate constituant de 30 à 70 % du silicone. Cette modification permet d'obtenir une amélioration du mouillage et de la lubrification en surface tout en conservant la dureté lorsque le diacrylate de silicone est soumis à polymérisation par radiation. La polymérisation est effectuée de préférence sous lumière ultraviolette et ceci requiert la présence d'un photo-initiateur.
PCT/US1985/002041 1984-10-22 1985-10-22 Compositions de revetement polymerisables aux ultraviolets contenant un additif polymerisable aux ultraviolets Ceased WO1986002652A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US66354684A 1984-10-22 1984-10-22
US663,546 1984-10-22

Publications (1)

Publication Number Publication Date
WO1986002652A1 true WO1986002652A1 (fr) 1986-05-09

Family

ID=24662296

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1985/002041 Ceased WO1986002652A1 (fr) 1984-10-22 1985-10-22 Compositions de revetement polymerisables aux ultraviolets contenant un additif polymerisable aux ultraviolets

Country Status (1)

Country Link
WO (1) WO1986002652A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6288129B1 (en) 1998-11-03 2001-09-11 Th. Goldschmidt Ag Process for preparing acrylic esters and/or methacrylic esters of hydroxy-functional siloxanes and/or polyoxyalkylene-modified siloxanes and their use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4130708A (en) * 1977-12-09 1978-12-19 Ppg Industries, Inc. Siloxane urethane acrylate radiation curable compounds for use in coating compositions
US4201808A (en) * 1978-06-12 1980-05-06 Union Carbide Corporation Radiation curable silicone release compositions
US4218294A (en) * 1973-09-24 1980-08-19 Design Cote Corp. Radiation curable coating composition
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4218294A (en) * 1973-09-24 1980-08-19 Design Cote Corp. Radiation curable coating composition
US4130708A (en) * 1977-12-09 1978-12-19 Ppg Industries, Inc. Siloxane urethane acrylate radiation curable compounds for use in coating compositions
US4201808A (en) * 1978-06-12 1980-05-06 Union Carbide Corporation Radiation curable silicone release compositions
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DOW CORNING, "Organofunctional silicone fluids-silicone polycarbinols-" New Product Information, 01 February 1975 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6288129B1 (en) 1998-11-03 2001-09-11 Th. Goldschmidt Ag Process for preparing acrylic esters and/or methacrylic esters of hydroxy-functional siloxanes and/or polyoxyalkylene-modified siloxanes and their use

Similar Documents

Publication Publication Date Title
EP0181528B1 (fr) Revêtements réticulant par radiation ultraviolette et résistant à l'abrasion
US4932750A (en) Single-coated optical fiber
JP2540708B2 (ja) 放射線硬化性組成物および使用方法
CA1143095A (fr) Resines durcissables derivees de lactone
JP2632783B2 (ja) 放射線硬化性組成物を使用する被覆方法
CA1259725A (fr) Enduits radiodurcissables a prise ulterieure
JPS59156942A (ja) 光フアイバ−用の可剥性被覆組成物
EP0114982A2 (fr) Revêtement externe pour fibre optique comprenant une couche tampon
KR960010731A (ko) 긁힘 방지성 및 내마모성 필름으로 피복된 아크릴 중합체 기재 성형 제품의 제조방법
JPH09272707A (ja) 活性エネルギー線硬化型（メタ）アクリレート組成物
KR960010798A (ko) 분체 도료용 결합제
JPS60118759A (ja) 輻射線硬化性液体コーテイング組成物
JPH0759677B2 (ja) 低粘度液体状の紫外線硬化性コーティング組成物
WO1986002652A1 (fr) Compositions de revetement polymerisables aux ultraviolets contenant un additif polymerisable aux ultraviolets
WO1991003498A1 (fr) Oligomeres polymerisables et revetement a base de butadiene
JPH08259644A (ja) 活性エネルギー線硬化型樹脂組成物
CA1127345A (fr) Compositions photocurables
KR101719043B1 (ko) 듀얼 경화형 고신율 자외선 경화형 코팅제 조성물 및 그를 이용한 코팅방법
JPS59170155A (ja) 放射線硬化性コ−テイング組成物
US4564666A (en) Urethane acrylates based on polyepichlorohydrin polyether diols and optical fiber coatings based thereon
JPH06184267A (ja) 密着性に優れた光硬化型樹脂組成物
JPS59170154A (ja) 放射線硬化性コ−テイング組成物
JPS6354412A (ja) 光硬化性樹脂組成物
JPH05214299A (ja) 紫外線硬化型粘着性組成物
JP2002226519A (ja) エネルギー線硬化型樹脂組成物及びそれを用いた塗料

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP