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WO1997046627A1 - Composition de formation de pellicules protectrices - Google Patents

Composition de formation de pellicules protectrices Download PDF

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Publication number
WO1997046627A1
WO1997046627A1 PCT/NL1997/000318 NL9700318W WO9746627A1 WO 1997046627 A1 WO1997046627 A1 WO 1997046627A1 NL 9700318 W NL9700318 W NL 9700318W WO 9746627 A1 WO9746627 A1 WO 9746627A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
composition according
composition
glass
Prior art date
Application number
PCT/NL1997/000318
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English (en)
Inventor
Toshihito Takahashi
Takashi Ukachi
Original Assignee
Dsm N.V.
Japan Synthetic Rubber Co., Ltd.
Japan Fine Coatings Co., 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 Dsm N.V., Japan Synthetic Rubber Co., Ltd., Japan Fine Coatings Co., Ltd. filed Critical Dsm N.V.
Priority to AU29818/97A priority Critical patent/AU2981897A/en
Publication of WO1997046627A1 publication Critical patent/WO1997046627A1/fr

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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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

  • the present invention relates to a composition for forming coating films having superior antibacterial and antifungal activities, free from yellowing due to lights and heat, and exhibiting excellent adhesion to various materials such as plastics, woods, papers, clothes, metals, and ceramics. Description of related Art Resins with antibacterial characteristics
  • antibacterial resins have conventionally been manufactured by incorporating an antibacterial agent into resins.
  • antibacterial resins are widely used as materials for floors, furniture, toilet stool, and miscellaneous goods which are used in the places where fungi may easily be produced or the places which should be kept clean.
  • Floors or furniture made of such an antibacterial resin may be coated with a paint.
  • the paint is applied to the surface of the resin in which an antibacterial agent has been incorporated by kneading.
  • the surface of the floor or furniture can exhibit an insufficient antibacterial effect.
  • a paint to be diluted with a solvent has been popular as the paint for coating floor and furniture in the past.
  • the solvent may vaporize and can be a cause of fires, explosions, poisoning, and air pollution.
  • the solvent used for the paint must be removed with expense of time and labor, requiring costs for securing safety of workers and heat energies for treatments.
  • Japanese Patent Application Laid-Open (kokai) No. 164368/1990 discloses an electron beam-curable type coating agent containing a metal-containing antibacterial agent.
  • Japanese Patent Application Laid-Open (kokai) No. 107972/1994 discloses a UV-curable type paint composition which contains fine particles of antibacterial or antifungal inorganic gel containing silver ion. These compositions exhibit an antibacterial activity against microorganisms such as E-coli and staphylococcus aureus.
  • This laid-open patent merely proposes the addition of the antibacterial glass powder to organic or inorganic materials, but does not disclose the antibacterial or antifungal activity of this glass powder, the composition for exhibiting film forming characteristics using this glass fiber, and improvement in the adhesion property to other materials such as plastics, woods, clothes, metals, and ceramics.
  • An object of the present invention is therefore to solve the above problems and provide a composition for forming coating films possessing superior antibacterial or antifungal activity, free from yellowing due to light and heat, and exhibiting excellent adhesion to other materials such as plastics, woods, clothes, metals, and ceramics.
  • This object has been achieved by the present invention by a composition for forming coating films comprising: (A) a urethane (meth)acrylate obtained by reacting a polyol having 2 to 6 hydroxyl groups in a molecule, a diisocyanate, and a (meth)acrylate having a hydroxyl group;
  • said composition further comprises one or more components selected from (D) a radiation polymerization initiator, (E) an antibacterial agent other than the component (C), and (F) an ultraviolet absorber.
  • the invention furthermore relates to cured coatings obtained by radiation curing of said coatings.
  • the urethane (meth)acrylate used in the composition of the present invention as the component (A) can be obtained by reacting (a) a polyol having 2 to 6 hydroxyl groups in a molecule, (b) a diisocyanate, and (c) a (meth)acrylate having a hydroxyl group.
  • a polyether polyol, a polyester polyol, a polycarbonate polyol, or a polycaprolactone polyol may be used as the component (a), which is the polyol having 2 to 6 hydroxyl groups in a molecule.
  • These polyols may be used either individually or in combination of two or more.
  • the manner of polymerization of each constitutional unit in these polyols is not specifically limited and may be random polymerization, block polymerization, or graft polymerization.
  • Aliphatic polyether polyols, alicyclic polyether polyols, and aromatic polyether polyols are given as the polyether polyols.
  • polyhydric alcohols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol, ethylene oxide addition triol of trimethylolpropane, propylene oxide addition triol of trimethylolpropane, ethylene oxide-propylene oxide addition triol of trimethylolpropane, dipentaeryth itol, ethylene oxide addition tetraol of pentaerythritol, and ethylene oxide addition hexaol of dipentaerythritol; and polyether polyols obtained by the ring-opening copolymerization of two or more ionic-polymerizable cyclic compounds.
  • the ionic-polymerizable cyclic compound include cyclic ethers such as ethylene oxide, propylene oxide, butene-1-oxide, is
  • ionic-polymerizable cyclic compounds include the combinations of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, propylene oxide and ethylene oxide, ethylene oxide and butene-1-oxide, and tetrahydrofuran and butene-1-oxide.
  • a cyclic imine such as ethylene imine
  • a cyclic lactone such as ⁇ -propiolactone and glycolic acid lactide
  • a dimethylcyclopolysiloxane dimethylcyclopolysiloxane
  • alicyclic polyether polyol examples include alkylene oxide addition diol of hydrogenated bisphenol A, alkylene oxide addition diol of hydrogenated bisphenol F, and alkylene oxide addition diol of 1 , 4-cyclohexane diol.
  • aromatic polyether polyol examples include alkylene oxide addition diol of bisphenol A, alkylene oxide addition diol of bisphenol F, alkylene oxide addition diol of hydroquinone, alkylene oxide addition diol of naphthohydroquinone, and alkylene oxide addition diol of anthrahydroquinone.
  • polyether polyols are commercially available.
  • Commercially available aliphatic polyether polyols include PTMGlOOO(tm) and PTMG2000(tm) (Mitsubishi Chemical Co., Ltd.); PPGlOOO(tm), EXCENOL 4020(tm), EXCENOL 3020(tm), EXCENOL 2020(tm), EXCENOL 1020 ⁇ tm) (Asahi Glass); PEGlOOO(tm), UNISAFE DCllOO(tm), UNISAFE DC1800(tm), UNISAFE DCB1100(tm) , UNISAFE DCB1800(tm) (Nippon Oil and Fats Co., Ltd.); PPTG4000(tm) , PPTG2000(tm) , PPTGlOOO(tm) , PTG2000(tm), PTG3000(tm), PTG650(tm), PTG400(tm), PTGL2000(tm
  • TMP30(tm), PNT4 Glycol(tm), EDA P4(tm), EDA P8( ' tm) (Nippon Emulsion Co., Ltd.); Quadrol(tm) (Asahi Denka Kogyo); and Tone Polyol 0200(tm), Tone Polyol 0221 (tm), Tone Polyol 0301(tm), Tone Polyol 0310(tm), Tone Polyol 2201 (tm), Tone Polyol 2221(tm) (Union Carbide Corp.).
  • polyester polyols can be obtained, for example, by reacting a polyhydric alcohol and a polybasic acid.
  • polyhydric alcohol examples include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,4-butene diol, 1,5-pentane diol, 1,6-hexane diol, 1,7-heptane diol, 1,8-octane diol, neopentyl glycol, 1,4-cyclohexane dimethanol, l,2-bis(hydroxyethyl)cyclohexane, 2,2-diethyl-l,3-propane diol, 3-methyl-l,5-pentane diol, 1,9-nonane diol, 2-methyl-l,8-octane diol, glycerin, trimethylolpropane, ethylene oxide addition compound of trimethylolpropane, propylene oxide addition compound of trimethylolpropane, ethylene oxide
  • polybasic acid examples include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, adipic acid, and sebacic acid.
  • Commercially available product of these polyester polyols include, for example, Korapole P-2010(tm), PMIPA(tm), PKA-A(tm), PKA-A2(tm), and PNA-2000(tm) (Kuraray Co. ) .
  • polycarbonate diols represented by the following formula (1) can be given.
  • R 1 is an alkylene group having 2 to 20 carbon atoms, a (poly)ethylene glycol residue, a (poly)propylene glycol residue, or a (poly)tetramethylene glycol residue, and m is an integer of 1 to 10.
  • R 1 are residues of the group such as 1,4-butane diol, 1,5-pentane diol, neopentyl glycol, 1,6-hexane diol, 1,4-cyclohexane dimethanol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol.
  • DN-980(tm), DN-981(tm), DN-982(tm), DN-983(tm) (Nihon Polyurethane) ; PC-8000(tm) (PPG); and PNOC1000(tm) , PNOC2000(tm) , PMClOO(tm), PMC2000(tm) (Kuraray Co.
  • polycaprolactone polyols obtained by the addition reaction of ⁇ -caprolactone and a diol such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,6-hexane diol, neopentyl ' glycol, 1,4-cyclohexane dimethanol, or 1,4-butane diol.
  • polycaprolactone diols can also be commercially available under the trademarks such as PLACCEL(tm) 205, 205AL, 212, 212AL, 220, 220AL (Daicell Co., Ltd.).
  • polyols other than those enumerated above are ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-butene diol, 1,5-pentane diol, 1,6-hexane diol, 1,7-heptane diol, 1,8-octane diol, neopentyl glycol, 1, 4-cyclohexane diol, 1,4-cyclohexane dimethanol,
  • polyether polyols and polycarbonate polyols are preferred, with particularly preferred being the ethylene oxide addition triol of trimethylolpropane.
  • the number average molecular weight of the polyols (a) is in the range of 50 to 15,000, and preferably 100 to 8,000.
  • the diisocyanate (b) are examples of the diisocyanate (b) are
  • diisocyantes particularly preferred are hydrogenated xylylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. These diisocyanates may be used either individually or in combination of two or more.
  • Examples of the (meth)acrylate having a hydroxyl group (c) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)aer late, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4-hydroxycyclohexyl (meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and (meth)acrylates represented by the following formula (2),
  • R 2 is a hydrogen atom or a methyl group and m denotes an integer of 1 to 15, preferably 1 to 4.
  • compounds obtained by an addition reaction between compounds containing a glycidyl group such as, alkyl glycidyl ether, allyl glycidyl ether, ' or glycidyl (meth)acrylate, and (meth)acrylic acid can also be used.
  • a glycidyl group such as, alkyl glycidyl ether, allyl glycidyl ether, ' or glycidyl (meth)acrylate, and (meth)acrylic acid
  • these (meth)acrylates having a hydroxyl group particularly preferred are 2-hydroxyethyl
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyl-tin-laurylate, triethylamine, 1,4-diazabicyclo[2.2.2]octane, or 1,4-diaza-2-methylbicyclo[2.2.2]octane is used, generally, in an amount of 0.01 to 1 part by weight for 100 parts by weight of the reaction raw materials.
  • the reaction temperature is normally in the range of 0-90°C, and preferably 10-80°C.
  • the urethane (meth)acrylate used in the present invention has a weight average molecular weight of 400 to 20,000, and preferably 600 to 10,000.
  • the urethane (meth)acrylate is incorporated in the composition of the present invention in an amount of 5 to 60% by weight. If the amount of the urethane (meth)acrylate is less than 5% by weight, coating films covering surfaces of various materials may have only poor flexibility and adhesion characteristics. If more than 60% by weight, the viscosity of the composition may be so great that it is difficult to obtain uniform coatings on the surfaces of various materials. In addition, too great an amount of the urethane (meth)acrylate makes soft coatings which are easily damaged.
  • the component (B), the reactive diluent can be a (meth)acrylate compound having at least one (meth)acryloyl group in the molecule, either mono-functional compounds having one (meth)acryloyl group or poly-functional compounds having two or more (meth)acryloyl groups or a compound having one or more vinyl groups such as vinylether or N-vinyl groups.
  • the reactive diluents can be used at a suitable proportion.
  • the monofunctional compounds are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (
  • R 2 is a hydrogen atom or a methyl group
  • R 3 is an alkylene group having 2 to 6 , preferably 2 to 4, carbon atoms
  • R 4 is a hydrogen atom or an alkyl group having 1 to 12, preferably 1 to 9, carbon atoms
  • m is an integer from 1 to 12, preferably 1 to 8;
  • R 2 has the same meaning as defined for formula (3), R 5 is an alkylene group having 2 to 8, preferably 2 to 5, carbon atoms; R 6 is a tetrahydrofurylgroup, and p is an integer from 1 to 8, preferably 1 to 4;
  • R 7 is a phenyl group, optionally substituted with an alkyl group having 1 to 12, preferably 1 to 9, carbon atoms;
  • R 2 and R 5 have the above defined meaning and q is an integer from 0 to 8; and R 8 and R 9 are individually a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, a group -R 10 -A, wherein R 10 is an alkylene group 5 containing 1 to 6 carbon atoms and A is a (meth)acryloyloxy group.
  • Suitable vinyl group-containing monomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl imidazole, vinyl pyridine, hydroxy butyl vinyl 0 ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and N-vinyl carbazole.
  • polyfunctional compounds examples include: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol
  • reactive diluents preferably comprising at least one (meth)acrylate compound; are preferably incorporated into the composition of the present invention in an amount of 30 to 90% by weight.
  • the inorganic antibacterial agent used as the component (C) in the composition of the present invention is a fine powder of glass containing silver ions.
  • specific examples are inorganic glass such as silicate glass, soda lime glass, borosilicate glass, or phosphosilicate glass, all containing silver ion as an essential component.
  • the amount of the silver ion contained in these inorganic antibacterial agents is normally 0.001 to 10% by weight, and preferably 0.01 to 5% by weight. If less than 0.001% by weight, the antibacterial effect is insufficient. It is difficult for glass to contain 10% by weight or more of silver ion in a stable manner, and such a glass can be manufactured only with difficulty.
  • These inorganic antibacterial agents comprising silver ion-containing glass may contain inorganic ions other than silver ion, such as copper ion, zinc ion, lead ion, tin ion, cadmium ion, calcium ion, magnesium ion, barium ion, bismuth ion, aluminum ion, germanium ion, lithium ion, sodium ion, potassium ion, cobalt ion, titanium ion, arsenic ion, antimony ion, and zirconium ion.
  • copper ion, zinc ion, calcium ion, magnesium ion, aluminum ion, sodium ion, potassium ion, cobalt ion, and titanium ion are preferred.
  • inorganic antibacterial agents of this type include, for example, antibacterial biocomposite glass fine powder manufactured by Koa Glass Co., Ltd. and IonPure(tm), WPA(tm) , and IP(tm), all manufactured by Ishizuka Glass Co., Ltd.
  • inorganic antibacterial agents may be used either individually or in combination of two or more, and incorporated in the composition of the present invention in an amount of 0.1 to 10% by weight, and preferably 0.5 to 5% by weight. If the amount of the inorganic antibacterial agents is less than 0.1% by weight, the composition may not exhibit sufficient antibacterial activity. If more than 10% by weight, light resistance of the composition may be impaired.
  • antibacterial agents are used in the form of fine powder dispersed in the composition.
  • the mean particle size of the fine powder is usually less than 50 ⁇ m, and preferably less than 20 ⁇ m.
  • composition of the present invention contains a radiation polymerization initiator as a component (D).
  • Radiation in this invention means infrared rays, visible lights, ultraviolet lights, X-rays, electron beam, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • the radiation polymerization initiators are benzophenone, benzoine ethyl ether, benzoine propyl ether, 1-hydroxycyclohexyl phenyl ketone, 2 ,2-dimethoxy-2-phenylacetophenone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4 '-dimethoxybenzophenone, 4 , 4 '-diaminobenzophenone, Michler 's ketone, 2-hydroxy-2-methyl-l-phenylpropan-l-one, 1-(4-dodecylphenyl)-2-hyd oxy-2-methylpropan-1-one, 4-(2-hydroxyethox )phenyl-(2-hydroxy-2-propyl)ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one,
  • the radiation polymerization initiator can be commercially available under the trademarks of IRGACURE(tm) 184, 261, 369, 500, 651, 907 (manufactured by Ciba Geigy); Lucirine LR8728(tm) (manufactured by BASF); Darocur(tm) 953, 1116, 1173, 1664, 2273, 2959, ZL1, 3331
  • radiation polymerization initiators may be used either individually or in combination of two or more, and incorporated in an amount less than 10% by weight, preferably 1 to 10% by weight, in the composition of the present invention.
  • an antibacterial agent other than the above-described inorganic antibacterial agent (C) can be incorporated in the composition of the present invention as component (E) .
  • This component (E) is not specifically limited so long as the component exhibits an antibacterial or antifungal activity. Coatings with a more excellent antifungal effect can be obtained by incorporating the component (E) as compared with the composition containing only the component (C). Either an organic or inorganic antibacterial agent can be used as the component (E).
  • the inorganic antibacterial agents used as the component (E) are fine powder of metal oxide such as zinc oxide and titanium oxide; metal alloys containing metals such as Co and Cu; and metal ions such as silver ion, copper ion, zinc ion, calcium ion, magnesium ion, aluminum ion, sodium ion, potassium ion, cobalt ion, or titanium ion carried on an inorganic compound such as zeolite, silica gel, alumina, apatite, titania, zirconium phosphate, calcium hydroxide, or magnesium hydroxide.
  • these antibacterial agents which are commercially available include Zeomic(tm) (manufactured by Shinanen Zeomic Co.
  • Bactekiller(tm) (manufactured by Kanebo Co., Ltd. ) which is an alminosilieate-type synthetic zeolite carrying silver ion or copper ion;
  • a ⁇ S(tm) (manufactured by Shokubai Kasei Co.) which is magnesium alminosilicate carrying silver ion, copper ion, or zinc ion;
  • Apatizer A(tm), Apatizer AW(tm), Apatizer A25(tm), Apatizer NB(tm) (manufactured by Sangi Co.
  • organic antibacterial agents used as the component (E) are: quaternary ammonium salts represented by the following formulas (7) or (8),
  • R 9 , R 10 , R 11 , and R 12 are individually an organic group consisting of 1 to 30 carbon atoms, 3 to 62 hydrogen atoms, 0 to 15 oxygen atoms, 0 to 5 nitrogen atoms, 0 to 3 silicon atoms, and 0 to 3 sulfur atoms, such as an alkyl group having 1 to 18 carbon atoms which may be substituted, a phenyl group, a substituted phenyl group with at least one C 1 to C 6 alkyl substituent, a naphthyl group, an amide bond-containing group of the formula -R 13 CONHR 14 - (wherein R 13 is an alkyl group having 1 to 18 carbon atoms or a phenyl group and R 14 represents an alkylene group having 1 to 8 carbon atoms), a trimethoxysilylalkyl group, a dimethoxysilylalkyl group, or a monomethoxysilylalkyl group, and X represents Cl, Br,
  • P + is a pyridinium group or a quinolinium group
  • R 15 is an alkyl group having 1 to 18 carbon atoms which links to the nitrogen atom of the pyridinium group or the quinolinium group
  • X represents Cl, Br , I, HS0 4 , or CH 3 S0 4
  • amphoteric surfactants such as carboxy betaine, sulfo betaine, aminocarboxylic acid, imidazolinium betaine, and lecithin
  • phenols such as phenol, catechol, resorcinol, cresol, 3,5-xylenol, pyrogallol, thymol, 2-benzyl-4-chlorophenol, 3-methyl-4-chlorophenol, (2,2 '-dihydroxy-5,5 '-dichloro)-diphenylmethane, 2-hydroxyphenyl-2 ',4 '-dichlorobenzyl ether, 2-phenylphenol , -na
  • 2-(4-thiazolyl)-benzimidazole, and methyl benzimidazolylcarbamate triazole derivatives such as 2-thiocyano-methylthiobenzthiazole, benzotriazole, tolyltriazole, and ⁇ -[2-(4-chlorophenyl)-ethyl]- ⁇ -(l,1-dimethylethyl)-lH-l,2, 4-triazol-1-yl-ethanol
  • guanidine derivatives such as chlorohexadine and polyhexamethylene biguanidine hydrochloride
  • zinc pyrithione, allyl isothiocyanate, ⁇ -thujaplicin, chitosan, and polylysine triazole derivatives such as 2-thiocyano-methylthiobenzthiazole, benzotriazole, tolyltriazole, and ⁇ -[2-(4-chlorophenyl)-ethyl]- ⁇ -(l,1-di
  • Preventol(tm) A2, A2-D, A3, A4-S, A5, A6, A7-D, A8, AS2, B2, BCM, BP, CMK, CMK-Na, CR, D2, D3, D4, D5, D6, D7, GD, O-Extra, O-N-Extra, OF, R80, R50, SB, WB, Z, CI3, CI4, CI5, CI6, CI7-100, CI8-100, Soblol(tm) A, A-Na, M, M-Na, P, P-Na, Bercoline(tm)
  • organic antibacterial agents are benzotriazole, tolyltriazole, ⁇ -[2-(4-chlorophenyl)-ethyl]- ⁇ -(1,1-dimethylethyl)-1H-1,2, 4-triazol-l-yl-ethanol, Biocut(tm) 210, and Preventol(tm) A8.
  • the antifungal activity of the composition can be improved by adding these oragnic antibacterial agents.
  • the antibacterial agents of component (E) can be used either individually or in combination of two or more, and can be incorporated into the composition of the present invention in an amount of less than 5% by weight, preferably 0.1 to 3% by weight, and particularly preferably 0.2 to 2% by weight. If incorporated more than 5% by weight, light resistance of the resulting composition is impaired.
  • the composition of the present invention may contain a UV absorber as component (F).
  • the UV absorbers include Tinuvin(tm) P, 213, 234, 320, 326, 327, 328, 329, 400 (Ciba Geigy); Seesorb(tm) 102, 103, 202, 501, 712 (manufactured by Shypro Kasei Kaisha, Ltd.); and Needral(tm) W-100, U-100 (Taki Chemical Co.).
  • the component (F) can be incorporated into the composition of the present invention in an amount of less than 5% by weight, preferably 0.1 to 3% by weight, and particularly preferably 0.2 to 2% by weight. The incorporation of the component (F) in the amount of 0.2 to 2% by weight can improve light resistance of the resulting composition without unduly impairing the curing rate.
  • a photo-sensitizer may be used, if necessary.
  • the photo-sensitizer are triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and commercially available products such as Uvecryl(tm) P102, P103, P104, and P105 (manufactured by UCB Co).
  • the photo-sensitizers are added in an amount of 0 to 5 parts by weight for 100 parts by weight of the composition of the present invention.
  • radical polymerizable compounds other than acryl or vinyl group-containing compounds as defined under (B) may be incorporated into the composition of the present invention.
  • Vinyl acetate, vinyl propionate, maleic acid anhydride, itaconic acid, fumaric acid, styrene, divinylbenzene, and unsaturated polyesters are given as examples of such compounds.
  • the unsaturated polyesters are esters of a dicarboxylic acid having a radical polymerizable double bond and an alcohol.
  • Maleic acid anhydride, itaconic acid, and fumaric acid are given as examples of the dicarboxylic acid having a radical polymerizable double bond.
  • the alcohol are monohydric alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-hexanol, cyclohexanol, and 2-ethylhexyl alcohol; (poly)ethylene glycols such as ethylene glycol, diethylene glycol, and triethylene glycol; (poly)propylene glycols such as propylene glycol, dipropylene glycol, and tripropylene glycol; dihydric alcohol such as 1,6-hexane diol; and trihydric alcohols such as glycerine and trimethylol propane.
  • monohydric alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol
  • additives are epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, chloroprene, polyether, polyester, pentadiene derivatives, SBS (styrene/butadiene/styrene block copolymer), hydrogenated SBS, SIS (styrene/isoprene/styrene block copolymer), petroleum resin, xylene resin, ketone resin, fluorine-containing oligomer, silicon-containing oligomer, polysulfide-type oligomer, and the like.
  • SBS styrene/butadiene/styrene block copolymer
  • SIS styrene/isoprene/styrene block copolymer
  • petroleum resin xylene resin
  • ketone resin fluorine-containing oligomer
  • silicon-containing oligomer silicon-containing oligomer
  • polysulfide-type oligomer
  • composition of the present invention may be formulated with various components, as required, such as antioxidants, photo-stabilizers, silane coupling agents, antifoaming agents, leveling agents, slipping agents, flatting agents, antistatic agents, surfactants, preservatives, thermal polymerization inhibitors, plasticizers, lubricants, solvents, fillers, coloring agents, wettability improvers, and coated surface improvers.
  • antioxidants which can be used are Irganox(tm) 245, 259, 565, 1010, 1035, 1076, 1081, 1098, 1222, 1330 (Ciba
  • the antioxidants can be used in an amount less than 2 % by weight of the composition of the present invention.
  • photo-stabilizers Tinuvin(tm) 144, 292, 622LD (Ciba Geigy), Sanol LS440, LS770 (Sankyo Chemical Co.), and Sumisorb(tm) TM-061 can be given as examples.
  • the photo-stabilizers can be used in an amount less than 5 % by weight of the composition of the present invention.
  • silane coupling agents which can be given are ⁇ -aminopropyltriethoxy silane, ⁇ -mercaptopropyltri-methoxy silane, ⁇ -methacryloxypropyltrimethoxy silane, and commercial products such as SH6062(tm), SH6030(tm) (Toray Silicone Co.) and KBE403(tm), KBE603(tm), KBE903(tm) (Shin-Etsu Chemical Co.).
  • the silane coupling agents can be added in an amount less than 2 parts by weight for 100 parts by weight of the composition of the present invention.
  • antifoaming agents organic copolymers which do not contain a silicon atom or a fluorine atom such as Florene(tm) AC-202, AC-300, AC-303, AC-326F, AC-900, AC-1190, AC-2000 (Kyoeisha Chemical Co.); silicon-type antifoaming agents such as Florene(tm) AC-901, AC-950, AC-1140, AO-3, AO-40H (Kyoeisha Chemical Co.) and FS1265(tm), SH200(tm), SC5550(tm), SC5540(tm), SC5570(tm), F-l(tm), SD5590(tm) (Toray Silicone Co.); and fluorine-containing antifoaming agents such as Megafac(tm) F-142D, F-144D, F-178K, F-179, F-815 (Dainippon Ink and Chemicals, Inc.).
  • the antifoaming agents can be added in an amount less than 1 part by weight for 100 parts by weight of the composition of the present invention.
  • Polyflow(tm) No. 7, No. 38, No. 50E, S, 75, No. 75, No. 77, NO. 90, No. 95, No. 300, No. 460, ATF, KL-425 (Kyoeisha Chemical Co.) are given as examples of the leveling agents.
  • the leveling agents can be added in an amount less than 2 parts by weight for 100 parts by weight of the composition of the present invention.
  • Granol(tm) 100, 115, 200, 400, 410, 440, B-1484 are given as examples of the slipping agents.
  • the slipping agents can be added in an amount less than 2 % parts by weight for 100 parts by weight of the composition of the present invention.
  • the glossing preventives are inorganic glossing preventives such as wet silica, dry silica, magnesium carbonate, and talc, and organic glossing preventives such as fine particles of polyethylene, polypropylene, polyurethane, poly(methyl methacrylate) , polycarbonate, urea-formaldehyde resin, benzoguanamine-formaldehyde resin, melamine-formaldehyde resin, and polytetrafluoroethylene.
  • inorganic glossing preventives such as wet silica, dry silica, magnesium carbonate, and talc
  • organic glossing preventives such as fine particles of polyethylene, polypropylene, polyurethane, poly(methyl methacrylate) , polycarbonate, urea-formaldehyde resin, benzoguanamine-formaldehyde resin, melamine-form
  • glossing preventives have an average particle diameter of 0.5 to 50 ⁇ m, preferably 1 to 20 ⁇ m. If the average particle size is less than 0.5 ⁇ m, no glossing preventive effects can be exhibited; if more than 50 ⁇ m, surface smoothness of the product is reduced.
  • the glossing preventives can be added in an amount less than 20% by weight, preferably less than 10% by weight, in the composition of the present invention. Strength of the coating film may be decreased, if the amount of the glossing preventives is greater than 20% by weight.
  • inorganic glossing preventives such as wet silica, dry silica, magnesium carbonate, and talc are preferred.
  • composition of the present invention may be used diluted with a solvent.
  • Preferred solvents are n-hexane, cyclohexane, toluene, xylene, methanol, ethanol, iso-propyl alcohol, 1-buthanol, 2-buthanol, iso-butyl alcohol, iso-pentyl alcohol, cyclohexanol, methyl cyclohexanol, methyl acetate, ethyl acetate, propyl acetate, iso-propyl acetate, butyl acetate, pentyl acetate, iso-pentyl acetate, methyl propionate, ethyl propionate, methyl 3-methoxypropionate, ethyl
  • composition of the present invention has a viscosity preferably of 10 to 10,000 mPa.s, and more preferably 50 to 5,000 mPa.s.
  • the composition of the present invention is preferably cured by radiation.
  • the composition should be cured by radiation such as X-rays, electron beams, ⁇ -rays, ⁇ -rays, or ⁇ -rays, preferably by electron beams.
  • the composition is cured by radiation such as visible lights, ultraviolet lights, X-rays, electron beams, ⁇ -rays, ⁇ - rays, or ⁇ -rays, preferably by ultraviolet lights.
  • Ultraviolet lights are irradiated at a dose preferably of 1 to 10,000 mJ/cm 2 .
  • a dose of 0.1 to 10 Mrad is preferably applied. Irradiation is preferably carried out using a conveyer irradiation device.
  • TMP30(tm), manufactured by Nippon Emulsion Co., Ltd. was added while controlling the temperature below 50°C. After the addition, the mixture was stirred for five hours while controlling the temperature at 50-60°C before terminating the reaction, thus obtaining urethane acrylate Al.
  • Component (B) BI 2-Acryloyloxyethyl succinate (NK Ester (tm), manufactured by Shin-Nakamura Chemical Co. )
  • Component (E) El: ⁇ -[2-(4-chlorophenyl )-ethyl]- ⁇ -(1, 1-dimethylethyl)-1H-1, 2 ,4-triazol-1-yl
  • FI TINUVIN400(tm) , manufactured by Ciba Geigy Other Component
  • the composition to be tested was applied to a flat, smooth glass plate using an applicator bar 15MIL(tm) (manufactured by Kumagairiki Kogyo) and irradiated by UV light at 1 J/cm 2 using a conveyer UV irradiation device equipped with a metal halide lamp (manufactured by Eye Graphics Co.).
  • the cured composition was peeled off from the glass plate to obtain a cured film with a thickness of about 200 ⁇ m.
  • An eye UV light integrating meter UVPF-36(tm) (manufactured by was used Eye Graphics Co.) was used for the measurement of irradiated UV light energy.
  • the composition was applied to a hard polyvinyl chloride board using a bar coater #10, followed by irradiation of UV light at 0.5 J/cm 2 from a conveyer UV irradiation device equipped with a mercury lamp (manufactured by Oak Manufacturing Co.) to obtain a cured film with a thickness of 15 ⁇ m.
  • the adhesion property was measured by the cross-cut adhesion test according to JIS K5400. The adhesion was indicated by the number of 1 mm x 1 mm squares left unpeeled among 100 squares. ⁇ Light resistance>
  • the composition was applied to a soft polyvinyl chloride board using a bar coater to produce a film with a thickness of about 30 ⁇ m, followed by irradiation of UV light at 0.5 J/cm 2 from a conveyer UV irradiation device equipped with a mercury lamp (manufactured by Oak Manufacturing Co.) to obtain a cured film with a thickness of about 30 ⁇ m.
  • the UV light irradiation energy was measured by ORC UV light luminometer UV-350(tm) (manufactured by Oak Manufacturing Co.).
  • the film was cut into pieces of 5 cm x 5 cm.
  • a bacterial solution containing about 106 cells/ml was applied to the test piece, which was allowed to stand at 35°C for 24 hours.
  • the bacterial solution on the test piece was washed out to count the number of living cells by microscope.
  • the same guantity of the bacterial solution as applied to the test piece was applied to a petri dish and allowed to stand 35°C for 24 hours, to count the number of living cells in the same manner.
  • E-coli and yellow staphylococcus were independently used as the test microorganisms.
  • Antifungal test Black mold (Aspergillus ni ⁇ er) and blue mold
  • Cell suspensions each containing a single cell-line in an amount of 1,000,000 to 200,000 cells per liter, were prepared using an inorganic base solution containing 0.7 g/1 of KH 2 P0 4 , 0.7 g/1 of K 2 HP0 4 , 0.7 g/1 of MgS0 4 .7H 2 0, 1.0 g/1 of NH 4 N0 3 , 0.05 g/1 of NaCl, 0.002 g/1 of FeS0 4 .7H 2 0, 0.002 g/1 of ZnS0 4 .7H 2 0, and 0.002 g/1 of MnS0 4 .7H 2 0.
  • a mixed cell line suspension was prepared by blending equivalent quantities of the single cell line suspensions.
  • test pieces used for the test for the antibacterial characteristics were placed in an inorganic agar medium prepared by solidifying the above inorganic base solution with the addition of 1.5% of agar.
  • the mixed cell line suspension was sprayed over the test pieces and cells were grown at 28-30°C, RH 85% for 14 days.
  • the growth of molds produced on the surface of the test pieces was microscopically observed to evaluate the growth of molds according to ASTM-G21. The results are indicated according the criteria shown in Table 3.
  • the results of the evaluations of antibacterial characteristics, antifungal characteristics, light resistance, and heat resistance are shown in Tables 4 and 5.
  • composition for forming coating films of the present invention has superior antibacterial and antifungal activities, is free from yellowing due to lights and heat, and exhibits excellent adhesion to various materials such as plastics, woods, papers, clothes, metals, and ceramics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

Une composition destinée à la formation de pellicules protectrices comprend: (A) un (méth)acrylate urétanique obtenu par réaction d'un polyol présentant 2 à 6 groupes hydroxyle dans une molécule, d'un diisocyanate, et d'un (méth)acrylate présentant un groupe hydroxyle; (B) un diluant réactif et (C) une poudre de verre fine contenant un ion argent en tant qu'agent antibactérien. La composition présente des activités antibactériennes et antifongiques supérieures, elle ne présente pas de jaunissement dû à la lumière et à la chaleur et elle présente une excellente adhésion à divers matériaux tels que le plastique, le bois, le papier, les tissus, les métaux et les céramiques.
PCT/NL1997/000318 1996-06-05 1997-06-05 Composition de formation de pellicules protectrices WO1997046627A1 (fr)

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JP8/143053 1996-06-05
JP14305396A JP3841232B2 (ja) 1996-06-05 1996-06-05 塗膜形成用組成物

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WO2000026312A1 (fr) * 1998-10-31 2000-05-11 Basf Coatings Ag Melanges de substances liquides et (co)polymeres, leur procede de production et leur utilisation pour la production de melanges reactifs a plusieurs substances
FR2795328A1 (fr) * 1999-06-23 2000-12-29 H F F F Haut Fourneau Forges E Procede et composition de protection contre la contamination pour articles sanitaires
EP1434804A4 (fr) * 2001-10-10 2006-08-02 Microban Products Revetement antimicrobien durcissable par exposition a des rayonnements
US7674817B2 (en) 2004-05-12 2010-03-09 Akzo Nobel Coatings International B.V. Antimicrobial acid-catalyzed coating compositions
US8728618B2 (en) 2007-06-26 2014-05-20 Fujikura Kasei Co., Ltd. Coating composition for metal thin film and photoluminescent coating film formed from same
US8734909B2 (en) 2010-03-10 2014-05-27 Eastman Chemical Company Methods and apparatus for coating substrates
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
CN104448994A (zh) * 2014-12-09 2015-03-25 苏州明轩地坪涂料有限公司 一种抗菌防霉涂料
US20160024333A1 (en) * 2014-07-25 2016-01-28 Nicole Richards Article With Reactive Metals Bound To Its Surface And Method Of Application
US9289795B2 (en) 2008-07-01 2016-03-22 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US9567676B2 (en) 2006-03-31 2017-02-14 Fujikura Kasei Co., Ltd. Hard coating composition for metal substrate
US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US9701802B2 (en) 2009-04-08 2017-07-11 Allnex Ip S.A.R.L. Reinforced UV-A curable composite compositions and methods
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
EP3334469A4 (fr) * 2015-08-13 2019-04-03 Dow Global Technologies LLC Composition de revêtement antimicrobien doté d'une résistance au jaunissement améliorée
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WO2022181492A1 (fr) * 2021-02-26 2022-09-01 パナソニックＩｐマネジメント株式会社 Composition polymérisable et matériau antibactérien
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Publication number Priority date Publication date Assignee Title
WO2000026312A1 (fr) * 1998-10-31 2000-05-11 Basf Coatings Ag Melanges de substances liquides et (co)polymeres, leur procede de production et leur utilisation pour la production de melanges reactifs a plusieurs substances
US7019052B1 (en) 1998-10-31 2006-03-28 Basf Coatings Ag Liquid substance mixtures and (co)-polymers, method for their production and use thereof for producing complex reactive mixtures
FR2795328A1 (fr) * 1999-06-23 2000-12-29 H F F F Haut Fourneau Forges E Procede et composition de protection contre la contamination pour articles sanitaires
WO2001000022A1 (fr) * 1999-06-23 2001-01-04 S.A.H.F.F.F. Haut Fourneau, Forges Et Fonderies Procede et composition de protection contre la contamination pour articles sanitaires
EP1434804A4 (fr) * 2001-10-10 2006-08-02 Microban Products Revetement antimicrobien durcissable par exposition a des rayonnements
US7098256B2 (en) 2001-10-10 2006-08-29 Microban Products Company Antimicrobial radiation curable coating
US7674817B2 (en) 2004-05-12 2010-03-09 Akzo Nobel Coatings International B.V. Antimicrobial acid-catalyzed coating compositions
US9567676B2 (en) 2006-03-31 2017-02-14 Fujikura Kasei Co., Ltd. Hard coating composition for metal substrate
US8728618B2 (en) 2007-06-26 2014-05-20 Fujikura Kasei Co., Ltd. Coating composition for metal thin film and photoluminescent coating film formed from same
US9289795B2 (en) 2008-07-01 2016-03-22 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US10576491B2 (en) 2008-07-01 2020-03-03 Precision Coating Innovations, Llc Pressurization coating systems, methods, and apparatuses
US9604251B2 (en) 2008-07-16 2017-03-28 Eastman Chemical Company Thermoplastic formulations for enhanced paintability, toughness and melt processability
US9701802B2 (en) 2009-04-08 2017-07-11 Allnex Ip S.A.R.L. Reinforced UV-A curable composite compositions and methods
US8734909B2 (en) 2010-03-10 2014-05-27 Eastman Chemical Company Methods and apparatus for coating substrates
US9616457B2 (en) 2012-04-30 2017-04-11 Innovative Coatings, Inc. Pressurization coating systems, methods, and apparatuses
US8865261B2 (en) 2012-12-06 2014-10-21 Eastman Chemical Company Extrusion coating of elongated substrates
US9919503B2 (en) 2012-12-06 2018-03-20 Eastman Chemical Company Extrusion coating of elongated substrates
US9744707B2 (en) 2013-10-18 2017-08-29 Eastman Chemical Company Extrusion-coated structural members having extruded profile members
US9920526B2 (en) 2013-10-18 2018-03-20 Eastman Chemical Company Coated structural members having improved resistance to cracking
US9758692B2 (en) * 2014-07-25 2017-09-12 Tommie Copper Ip, Inc. Article with reactive metals bound to its surface and method of application
EP3171865A4 (fr) * 2014-07-25 2018-02-21 Tommie Copper IP, Inc. Article ayant des métaux réactifs liés à sa surface, et procédé d'application
US20160024333A1 (en) * 2014-07-25 2016-01-28 Nicole Richards Article With Reactive Metals Bound To Its Surface And Method Of Application
CN104448994A (zh) * 2014-12-09 2015-03-25 苏州明轩地坪涂料有限公司 一种抗菌防霉涂料
EP3334469A4 (fr) * 2015-08-13 2019-04-03 Dow Global Technologies LLC Composition de revêtement antimicrobien doté d'une résistance au jaunissement améliorée
WO2021255128A1 (fr) * 2020-06-17 2021-12-23 Damir Ibrahimovic Revêtement réducteur de germes

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JP3841232B2 (ja) 2006-11-01
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