WO1998006783A1 - Compositions de resines durcissant sous l'effet de rayonnements - Google Patents

Compositions de resines durcissant sous l'effet de rayonnements Download PDF

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Publication number
WO1998006783A1
WO1998006783A1 PCT/BE1996/000084 BE9600084W WO9806783A1 WO 1998006783 A1 WO1998006783 A1 WO 1998006783A1 BE 9600084 W BE9600084 W BE 9600084W WO 9806783 A1 WO9806783 A1 WO 9806783A1
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WO
WIPO (PCT)
Prior art keywords
groups
meth
composition according
acrylate
radiation hardening
Prior art date
Application number
PCT/BE1996/000084
Other languages
English (en)
Inventor
Michio Kochi
Original Assignee
Ucb, S.A.
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 Ucb, S.A. filed Critical Ucb, S.A.
Priority to PCT/BE1996/000084 priority Critical patent/WO1998006783A1/fr
Publication of WO1998006783A1 publication Critical patent/WO1998006783A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C08L67/07—Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a radiation hardening type resin composition which is outstanding in its coating suitability and in its coated film properties. Radiation hardening resins are widely used in various fields both on account of their outstanding productivity and also because of the recent increased awareness of environmental issues.
  • the generally-used radiation hardening resin compositions which are a combination of oligomers of various kinds and ethylenically-unsaturated monomer, suffer from the problem of a lack of compatibility between the viscosity of compositions suitable for coating and the properties of the coated substrate and, additionally, the adhesion to the coated substrate is impaired by cure shrinkage at the time of curing especially when the substrate is poly ethylmethacrylate such as for Fresnel lenses Therefore a resolution of such problems is desirable.
  • oligomer (A) selected from urethane (meth) acrylates , epoxy (meth) acrylates and polyester (meth) acrylates
  • the urethane (meth) acrylate oligomer (A) may be obtained by the reaction between an organic isocyanate and a (meth) acrylate monomer having at least one hydroxyl group, optionally in the presence of a polyol. Specifically reaction can be carried out at normal pressure, at a temperature from about 60 to 80°C, and in the absence of a catalyst, but in order to promote the reaction there may be used from about 50 to 2000 ppm of a catalyst such as dibutyltin dilaurate.
  • a catalyst such as dibutyltin dilaurate.
  • organic isocyanate there can be cited aromatic, aliphatic and alicyclic dusocyanates such as tolylene dusocyanate, 4 , 4-d ⁇ phenylmethane dusocyanate, 1, 6-hexamethylene dusocyanate, xylylene dusocyanate and isophorone dusocyanate
  • (meth) acrylate monomer having at least one hydroxyl group there can be cited 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) acrylate, 2 -hydroxybutyl (meth) acrylate, 3-hydroxy-butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethyleneglycol mono (meth) acrylate, pentaerythritol di (meth) acrylate pentaeryth ⁇ tol tri (meth) acrylate and lactone-modifled 2 -hydroxyethyl (meth)
  • the epoxy (meth) acrylate oligomer (A) may be obtained by the reaction between an epoxy resin and a (meth) acrylate monomer with at least one functional group in the molecule which possesses reactivity for epoxy groups Specifically, such reaction may be carried out at normal pressure, at a temperature from about 100°C to about 140°C, using from about 0.5 to 3% of a catalyst such as triethylamme or triethylbenzylammonium chloride to promote the reaction.
  • a catalyst such as triethylamme or triethylbenzylammonium chloride
  • the aforesaid epoxy resin mention may be made of bisphenol- A type epoxy resins, novolak type epoxy resins, alicyclic epoxy resins and their modified derivatives.
  • the (meth) acrylate monomer with at least one functional group n the molecule which possesses reactivity for epoxy groups
  • the polyester (meth) acrylate oligomer (A) may be obtained by the reaction between (a) a polyol, (b) an organic acid with at least two carboxyl groups in the molecule, or the anhydride of such organic acid, and (c) a (meth) acrylate monomer with at least one carboxyl group in the molecule.
  • (a) , (b) and a solvent such as dichloroethane or a hydrocarbon used for the azeotropic removal of water are introduced into a reactor and an esterification reaction is carried out under reduced pressure, at a temperature from about 80°C to about 150°C From about 50 to 2000 ppm of a catalyst such as dibutyltin oxide may be used to promote the reaction
  • a catalyst such as dibutyltin oxide
  • the reaction may be performed at normal pressure, and no solvent for azeotropic removal of water is required.
  • (c) is added, and further reaction is carried out at a temperature of about 80°C to about 120°C. From 0 1 to 1% of a strong acid catalyst such as sulphuric acid or methanesulphonic acid may be added for promoting the reaction.
  • polystyrene resin examples of the polyol (a) .
  • polyethylene glycol examples of the polypropylene glycol, polytetramethylene glycol, ethylene glycol, propylene glycol, 1, 6-hexaned ⁇ ol , polyester-polyols, polycarbonate-polyols, and lactone-based polyester-polyols such as poly-caprolactone and polybutyrolactone .
  • organic acid (b) or anhydrides thereof there can be cited phthalic acid, adipic acid, phthalic anhydride, pyromellitic anhydride t ⁇ mellitic anhydride, isophthalic acid, terephthalic acid and the like
  • (meth) acrylate monomer (c) there can be cited acrylic acid, methacrylic acid, ⁇ -carboxyethyl acrylate, and the like
  • the oligomer (A) component comprises from about 95 to about 10 wt%, and preferably from 80 to 40 wt% of the composition of the invention
  • the oligomer (A) component comprises from about 95 to about 10 wt%, and preferably from 80 to 40 wt% of the composition of the invention
  • Polymer (B) thus preferably comprises from 20 to 60 wt% of the composition of the invention
  • the starting material monomer used for polymer (B) there can be cited styrene, acrylonitrile, methacrylonitrile, ethyl acrylate butyl acrylate, 2 -ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2- hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate, 2- hydroxyethyl methacrylate and the like.
  • a polymer (B) where terminal or side chain portions of the aforesaid polymer molecules have been modified (capped) by means of hydroxyl groups or polymerizable groups such as acryloyl groups, methacryloyl groups, allyl groups, styryl groups, vinyl benzyl groups, vinyl ether groups, vinyl silyl groups, dicyclopentadienyl groups, isopropenylphenyl groups, 5-norbornen-2-yl groups, or di ethylsiloxanyl groups, thus constituting what is commonly named a macromer .
  • hydroxyl groups or polymerizable groups such as acryloyl groups, methacryloyl groups, allyl groups, styryl groups, vinyl benzyl groups, vinyl ether groups, vinyl silyl groups, dicyclopentadienyl groups, isopropenylphenyl groups, 5-norbornen-2-yl groups, or di ethylsiloxanyl
  • any ethylenically unsaturated monomer can be added to the composition with the objective of adjusting the viscosity of the composition or improving the properties of the coated f lm
  • monomer there can be cited styrene, acrylonitrile, ethyl acrylate, butyl acrylate, 2 -ethylhexyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-chlorostyrene, 2,4- dichlorostyrene, acrylic acid, 2 -hydroxyethyl acrylate, methacrylic acid, butyl methacrylate, 2-hydroxyethyl methacrylate, 1, 6-hexaned ⁇ ol diacrylate, trimethylolpropane triacrylate, penta-eryth ⁇ tol triacrylate, dipentaerythritol hexaacrylate, and mixtures thereof
  • the radiation hardening resin composition of the present invention can be cured by ultraviolet radiation, electron beam, etc, and in the case of curing by ultraviolet radiation there can be added a photopolymerization initiator such as benzoin, benzoin methyl ether, benzyl dimethyl ketal, 2- hydroxy-2 -methyl-1-phenylpropan-l-one and benzophenone, etc Further, where required, there can also be used a photoactivator such as amines ureas, sulphur-containing compounds, phosphorus-containing compounds and sulphur- containing compounds, etc
  • the radiation-cured resin composition thus obtained constitute a second object of the present invention.
  • the radiation hardening and radiation cured resin compositions obtained by the present invention can be used in wide-ranging fields of industry such as for example in the composition of various kinds of coating agents, inks and paints
  • Example 1 444 g (2 mole) of isophorone dusocyanate (IPDI) and 0.05 g of stannous chloride were introduced into a reaction vessel provided with a stirrer, thermometer, dropping funnel and dry air supply inlet, and which was immersed m an oil bath When IPDI had reached 70°C, 530 g (1 mole) of Placcel 205, a polycaprolactone diol of molecular weight 530 marketed by Daicel Chemical Industries was added from the dropping funnel
  • polycaprolactone urethane prepolymer was produced by maintaining the internal temperature of the reaction vessel at 70°C until the residual NCO concentration reached the stoichiometric value. Subsequently, 232 g (2 mole) of 2-hydroxyethyl acrylate was added, after which maturation/ageing was carried out while maintaining the reaction vessel interior at 70°C, until the residual NCO concentration m a sample of extracted reaction product reached 0 1% or less In this way, a urethane acrylate oligomer (Al) was obtained.
  • Urethane acrylate oligomer (A2) was obtained in the same way as in Example 1 except that the IPDI was changed to 336 g (2 mole) of 1,6- hexamethylene dusocyanate.
  • Radiation hardening resin compositions were prepared by mixing the urethane acrylate oligomers obtained in Examples 1 and 2 with the amount of the various other components specified in Table 1.
  • Examples 7 and 8 are comparative.
  • UV curability UV irradiation conditions - high pressure mercury lamp 1 lamp lamp output 120 W/cm lamp irradiation distance 10 cm conveyor speed 10 m/min
  • the compositions were respectively coated to a thickness of 100 ⁇ m on glass plates, then UV irradiation carried out under the aforesaid conditions, after which in each case the surface of the coated film was assessed by touch for any tackiness .
  • a 100 ⁇ m thickness coated film was produced under the aforesaid UV irradiation conditions, and then tensile testing carried out based on standard method JIS K7113. The breaking strength, elongation at break, and Young's modulus were thus measured.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne des compositions de résines durcissant sous l'effet de rayonnements et comprenant, pour 10 % à 95 % de leur masse, au moins un oligomère (A) du groupe des (méth)acrylates d'uréthane, d'époxy et/ou de polyester, et pour 5 % à 90 % de leur masse, au moins un polymère (B) dont la masse moléculaire moyenne en nombres se situe dans la plage de 500 à 200.000 et qui s'obtient par polymérisation d'au moins un monomère du groupe des styrène, (méth)acrylonitrile et (méth)acrylate esters. Ces compositions, qui sont durcissables sous l'effet d'un rayonnement ultraviolet ou d'un faisceau d'électrons, conviennent particulièrement aux formulations d'agents de revêtement, d'encres et de peinture.
PCT/BE1996/000084 1996-08-12 1996-08-12 Compositions de resines durcissant sous l'effet de rayonnements WO1998006783A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/BE1996/000084 WO1998006783A1 (fr) 1996-08-12 1996-08-12 Compositions de resines durcissant sous l'effet de rayonnements

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/BE1996/000084 WO1998006783A1 (fr) 1996-08-12 1996-08-12 Compositions de resines durcissant sous l'effet de rayonnements

Publications (1)

Publication Number Publication Date
WO1998006783A1 true WO1998006783A1 (fr) 1998-02-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047655A1 (fr) * 1999-02-12 2000-08-17 Gil Technologies Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention
US8821841B2 (en) 2005-08-11 2014-09-02 Basf Se Copolymers for cosmetic applications

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2235989A1 (fr) * 1973-07-02 1975-01-31 Ford France
EP0006308A1 (fr) * 1978-06-08 1980-01-09 Ici Americas Inc. Composition pour revêtement en moule contenant des polymères liquides à groupes terminaux fonctionnels, et procédé de recouvrement avec cette composition des défauts de surface d'un article thermoplastique moulé
WO1990003988A1 (fr) * 1988-10-03 1990-04-19 Desoto, Inc. Melanges par exposition de polyurethanes d'ether vinylique et d'elastomeres non satures polymerisables aux ultra-violets, et revetements les contenant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2235989A1 (fr) * 1973-07-02 1975-01-31 Ford France
EP0006308A1 (fr) * 1978-06-08 1980-01-09 Ici Americas Inc. Composition pour revêtement en moule contenant des polymères liquides à groupes terminaux fonctionnels, et procédé de recouvrement avec cette composition des défauts de surface d'un article thermoplastique moulé
WO1990003988A1 (fr) * 1988-10-03 1990-04-19 Desoto, Inc. Melanges par exposition de polyurethanes d'ether vinylique et d'elastomeres non satures polymerisables aux ultra-violets, et revetements les contenant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047655A1 (fr) * 1999-02-12 2000-08-17 Gil Technologies Compositions de resine thermodurcies pour hyperfrequences transparentes, feuilles electriques derivees de ces compositions et leur procede d'obtention
US8821841B2 (en) 2005-08-11 2014-09-02 Basf Se Copolymers for cosmetic applications

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