WO2006006402A1 - Composition de résine polymèrisable par rayons d’énergie active, procédé pour la fabrication de celle-ci, et composition de revêtement utilisant celle-ci - Google Patents

Composition de résine polymèrisable par rayons d’énergie active, procédé pour la fabrication de celle-ci, et composition de revêtement utilisant celle-ci Download PDF

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Publication number
WO2006006402A1
WO2006006402A1 PCT/JP2005/011944 JP2005011944W WO2006006402A1 WO 2006006402 A1 WO2006006402 A1 WO 2006006402A1 JP 2005011944 W JP2005011944 W JP 2005011944W WO 2006006402 A1 WO2006006402 A1 WO 2006006402A1
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compound
meth
group
resin composition
active energy
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PCT/JP2005/011944
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English (en)
Japanese (ja)
Inventor
Toshirou Noda
Hitoshi Matsunami
Hiromitsu Koumoto
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The Nippon Synthetic Chemical Industry Co., Ltd.
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Application filed by The Nippon Synthetic Chemical Industry Co., Ltd. filed Critical The Nippon Synthetic Chemical Industry Co., Ltd.
Priority to KR1020077003026A priority Critical patent/KR100998116B1/ko
Publication of WO2006006402A1 publication Critical patent/WO2006006402A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints

Definitions

  • the present invention relates to an active energy one-line curable resin composition containing a polysiloxane-containing polyisocyanate derivative, more specifically, excellent antifouling properties, coating film hardness, and scratch resistance.
  • the present invention relates to an active energy one-line curable resin composition useful for forming a coating layer having excellent properties, solvent resistance, and adhesion, a method for producing the same, and a coating agent composition using the same.
  • Examples of the resin composition used in such a coating agent include, for example, a photocurable (meth) acrylate resin, a photocurable polysiloxane urethane (meth) acrylate resin, and a photocurable silicone block.
  • a resin composition containing a (meth) acrylate-based resin and a photopolymerization initiator has been proposed (see, for example, JP-A-2003-192751).
  • the technique disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2003-192751 is mainly polyisocyanate and polydimethyl having one hydroxyl group at both ends.
  • an active energy useful for forming a coating layer having excellent antifouling properties and excellent coating film hardness, scratch resistance, solvent resistance, and adhesiveness under such a background is to provide a lug-line curable resin composition, a method for producing the composition, and a coating agent composition using the composition.
  • the present inventor has conducted extensive studies in view of intensive efforts.
  • the polysiloxane compound (al) having a hydroxyl group at one end represented by the following general formula (1), a polyisocyanate compound, and a hydroxyl group
  • a polysiloxane-containing polyisocyanate derivative [A] obtained by reacting a containing (meth) acrylate compound and a compound [B] having one or more ethylenically unsaturated groups in one molecule
  • the present inventors have found that the active energy ray-curable resin composition meets the above-mentioned purpose and completed the present invention.
  • R 1 represents an alkyl group
  • R 2 independently represents an alkyl group, a cycloalkyl group or a phenyl group
  • R 3 represents a hydrocarbon group or an organic group containing an oxygen atom.
  • a is an integer of 1 or more
  • b is an integer of 1 to 3.
  • a polysiloxane compound (cl) having a hydroxyl group at both ends represented by the following general formula (2), a polyisocyanate compound, and a hydroxyl group-containing (meth) acrylate compound It is preferable in terms of transparency and scratch resistance that it contains a polyisocyanate derivative [C] obtained by reaction.
  • each R 4 independently represents an organic group containing a hydrocarbon group or an oxygen atom
  • each R 5 independently represents an alkyl group, a cycloalkyl group, or a full group
  • c is 1 or more. It is an integer
  • d and e are integers of 1 to 3.
  • the compound [B] having one or more ethylenically unsaturated groups in one molecule is represented by the urethane (meth) atalylate compound (B1) and Z represented by the following general formula (3):
  • an ethylenically unsaturated monomer (excluding (B1)) (B2) is preferred from the viewpoint of coating film hardness, and further, a urethane (meth) acrylate compound represented by the following general formula (4) [D]
  • the combination of these is preferred in terms of flexibility and crack resistance.
  • R ° is a urethane bond residue of the polyisocyanate compound (bl)
  • R 7 is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b2)
  • f is an integer of 2 to 50 It is.
  • R 8 is a urethane bond residue of a polyisocyanate compound (dl)
  • R 9 is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound (d2)
  • R 1Q is a polyol compound ( d3) urethane bond residue
  • g is an integer of 1 to 50
  • h is an integer of 2 to 50.
  • the active energy ray-curable resin composition of the present invention comprises a polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1), a polyisocyanate compound, Because it contains a polysiloxane-containing polyisocyanate derivative [A] obtained by reacting a hydroxyl group-containing (meth) acrylate compound and a compound [B] having one or more ethylenically unsaturated groups in one molecule The resulting coating film is excellent in antifouling properties and exhibits excellent effects in coating film hardness, scratch resistance, solvent resistance, and adhesion.
  • Paint, ink, protective coating agent, anchor coating agent It is useful as various film forming materials such as magnetic powder coating binders, pressure-sensitive adhesives, adhesives, and adhesives. Especially, it is very useful as a coating agent composition for top coating of various plastics and optical films.
  • the active energy ray-curable resin composition of the present invention comprises a polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule. is there.
  • the polyisocyanate derivative [A] includes a polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1), a polyisocyanate compound, and a hydroxyl group-containing (meth) atariate. It is obtained by reacting a rate compound.
  • the powerful polysiloxane compound (al) is not particularly limited as long as it is a compound having a structure represented by the general formula (1).
  • R 1 represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.)
  • each R 2 independently represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group).
  • a butyl group, etc.) a cycloalkyl group or a phenyl group
  • R 3 represents a hydrocarbon group or an organic group containing an oxygen atom.
  • a is an integer of 1 or more, preferably 9 to 120
  • b is an integer of 1 to 3, preferably 1 to 2.
  • the weight average molecular weight of the polysiloxane compound (al) used in the present invention is not particularly limited.
  • the force is preferably 100-30, 000, particularly 500 to 10,000, more preferably 1,000.
  • a power of -10,000 S is preferred.
  • the weight average molecular weight is less than 100, the antifouling performance is lowered.
  • the weight average molecular weight is more than 30,000, the coating film hardness is undesirably lowered.
  • polysiloxane compound (al) represented by the general formula (1) examples include Shin-Etsu Chemical Co., Ltd. “-22-1700”, “X-22-4015” manufactured by Kogyo Co., Ltd. “Silaplane FM-0411”, “Silaplane FM—0412”, “Silaplane FM—0425” manufactured by Chisso Corporation , “Sylaplane FM—DA11”, “Silaplane FM—DAI 2”, “Silaplane FM—DA25”, etc.
  • the polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates.
  • an isocyanate compound having three or more isocyanate groups in one molecule is required to have a coating film hardness, scratch resistance and solvent resistance. , And more preferable because it can reduce unreacted low molecular weight components that cause bleeding.
  • polyols examples include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene dallicol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, poly Butylene glycol, 1,6-hexane diol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, polypropylene, trimethylololeethane, trimethylololepropane, polytrimethylololepropane , Pentaerythritol, polypentaerythritol, sonolebithonole, mannitol, glycerin, poly Polyhydric alcohols such as glycerin and polytetramethylene glycol, polyether polyols having a structure of at least one of block or random copolymerization of polyethylene oxide, polypropylene oxide,
  • Polyester polyols which are condensates with polybasic acids such as itaconic anhydride, itaconic acid, adipic acid, isophthalic acid, etc.
  • Caplatato-modified polyols such as force prolatatone-modified polytetramethylene polyol, polyolefin-based polyols, hydrogenated polybutadiene polyols Examples thereof include polybutadiene-based polyols.
  • polyol for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4 dihydroxybenzoic acid, 3,5 dihydroxybenzoic acid, 2,2 bis (hydroxymethyl) propion Acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenol) acetic acid, 4,4-bis (4-hydroxyphenol) -Ru) Powerful ruxyl group-containing polyols such as pentanoic acid and homogentisic acid, and sulphonic acid group or sulfonate group-containing polyols such as sodium 1,4 butanediol sulfonate.
  • Powerful ruxyl group-containing polyols such as pentanoic acid and homogentisic acid, and sulphonic acid group or sulfonate group-containing polyols such as sodium 1,4 butanediol sulfonate.
  • a reaction product of a polyisocyanate and a polyol when used, for example, it may be used as a urethane polyol obtained by reacting the polyol with the polyisocyanate.
  • a metal catalyst such as dibutyltin dilaurate or an amine catalyst such as 1,8 diazabicyclo [5.4.0] undecene-7 is used for the purpose of accelerating the reaction. Also preferred to use.
  • the hydroxyl group-containing (meth) acrylate compound used in the present invention is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 Hydroxybutyl (meth) atarylate, 4 Hydroxybutyl (meth) atrelate, 2-Hydroxyethyl allyloyl phosphate, 2- (meth) atariloy cicchitil— 2 Hydroxypropyl phthalate, 2 Hydroxy 1- (meth) atariloy Roxypropyl (meth) acrylate, force prolataton modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, cap latataton modified dipentaerythritol penta (Meta) Atarirate, Power Rataton modified pen Examples include t
  • the method for producing the polysiloxane-containing polyisocyanate derivative [A] is not particularly limited.
  • the (mouth) method is preferable.
  • reaction temperature is preferably 30 to 90 ° C, particularly preferably 40 to 70 ° C.
  • the weight average molecular weight of the obtained polyisocyanate derivative [A] is preferably 500 to 50,000, and moreover, The force S is preferably 500 to 30,000.
  • the weight average molecular weight is less than 500, the film forming property is deteriorated.
  • the weight average molecular weight is more than 50,000, the viscosity becomes high and the film is difficult to handle.
  • the weight average molecular weight of the polyisocyanate derivative [A] is a weight average molecular weight in terms of standard polystyrene molecular weight, and is determined by high performance liquid chromatography (Nippon “Waters 2695 (main unit)” and “Waters 2414 (detector)” manufactured by Orters Co., Ltd.), column: Shodex GPC KF—806L (exclusion limit molecular weight: 2 X 10 7 , separation range: 100-2 X 1 0
  • Theoretical plate number 10,000 plate Z Measured by using three series of Z, filler material: styrene-dibutylbenzene copolymer, filler particle size: 10 m).
  • Sarako contains a compound [B] having one or more ethylenically unsaturated groups in one molecule. It is necessary in terms of coating film hardness, and such a compound [B] is not particularly limited, but is a urethane (meth) acrylate compound (B1) represented by the above general formula (3) and Z or ethylenically unsaturated Monomers [excluding (B1)] (B2) are preferred.
  • a compound [B] is not particularly limited, but is a urethane (meth) acrylate compound (B1) represented by the above general formula (3) and Z or ethylenically unsaturated Monomers [excluding (B1)] (B2) are preferred.
  • R 6 is a urethane bond residue of the polyisocyanate compound (bl)
  • R 7 is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b2)
  • f is 2 to 50 It is an integer.
  • the urethane (meth) acrylate compound (B1) represented by the general formula (3) is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.
  • the isocyanate compound is not particularly limited, and examples thereof include those similar to the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound is not particularly limited, but the hydroxyl group-containing (meth) acrylate is not particularly limited. Examples thereof are the same as those of the series compounds.
  • any monomer having one or more ethylenically unsaturated groups in one molecule may be used.
  • Bifunctional monomers and tri- or higher functional monomers are listed.
  • Examples of the monofunctional monomer include styrene, butyltoluene, chlorostyrene, a -methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, butyl acetate, 2-hydroxyethyl ( (Meth) attalylate, 2-hydroxypropyl (meth) attali
  • bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol Type A di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 6-hexanediol ethylene oxide modified di (meta ) Atari Glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene diol diglycidy
  • tri- or higher functional monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate.
  • acrylic acid Michael-added products or 2-ataryl oxychetyl dicarboxylic acid monoester examples include acrylic acid Michael-added products or 2-ataryl oxychetyl dicarboxylic acid monoester.
  • acrylic acid Michael adducts include acrylic acid dimer, methacrylic acid dimer, acrylic acid.
  • examples include acid trimer, methacrylic acid trimer, acrylic acid tetramer, and methacrylic acid tetramer.
  • the 2-ataryl oxyschetil dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyl oxystilyl succinic acid monoester, 2-methacryloyl oxysche.
  • Tylsuccinic acid monoester 2-Atalyloxyxetyl phthalic acid monoester, 2-Methacryloyl oxychetyl phthalic acid monoester, 2-Atalyloxyxetylhexahydrophthalic acid monoester, 2-methacryloyl Oxetylhexahydrophthalic acid monoester and the like.
  • other oligoester acrylates are also included.
  • urethane (meth) acrylate compounds (B1) and ethylenically unsaturated monomers (except (B1)) (B2) may be used alone or in combination of two or more. Also good.
  • the content is not particularly limited, but the polysiloxane-containing polyisocyanate derivative [A ] 100 weight ⁇ for 1 ⁇ : LO, 000 weight ⁇ ⁇ Special ⁇ MA 5 ⁇ 5,000 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ This is preferably 10 to 5,000 parts by weight 1 weight If it is less than 10 parts by weight, no improvement in coating film hardness is observed, and if it exceeds 10,000 parts by weight, the antifouling performance is lowered, which is not preferable.
  • Ethylenically unsaturated monomer (excluding (B1)) ( ⁇ 2)
  • polysiloxane-containing polyisocyanate derivatives [A] 100 parts by weight [In contrast, 1 to: LO, 000 wt. It is preferable that the amount is 10 to 5,000 parts by weight. If the amount is less than 1 part by weight, the coating film hardness is not improved, and if it exceeds 10,000 parts by weight, the antifouling performance is lowered.
  • urethane (meth) acrylate compound (B1) represented by the general formula (3) and the ethylenically unsaturated monomer (excluding ( ⁇ 1)) ( ⁇ 2) are used in combination
  • each of the above range forces may be appropriately selected and used.
  • polyisocyanate derivative [ ⁇ ] 100 parts by weight 2 to 20,000 parts by weight, particularly 5 to L0,000 parts by weight is preferable in terms of coating film hardness.
  • the polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1) from the viewpoint of achieving both antifouling properties and coating film hardness.
  • Particularly preferred are a polysiloxane compound (al) 1 to 20% by weight, a polyisocyanate compound 10 to 40% by weight, and a hydroxyl group-containing (meth) acrylate compound 50 to 89% by weight.
  • the present invention further comprises a polysiloxane compound (cl) having a hydroxyl group at both ends represented by the general formula (2), a polyisocyanate compound, and a hydroxyl group-containing (meth) atrelate compound.
  • the polysiloxane-containing polyisocyanate derivative [C] obtained by reaction is preferably contained in terms of antifouling property, transparency and scratch resistance.
  • the polysiloxane compound (cl) having hydroxyl groups at both ends represented by the general formula (2) is not particularly limited as long as it is a compound having a structure represented by the general formula (2).
  • General formula ( In 2) R 4 represents a hydrocarbon group or an organic group containing an oxygen atom, and R 5 each independently represents an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group), a cycloalkyl group or a phenyl group.
  • c is an integer of 1 or more, preferably 9 to 120
  • d and e are integers of 1 to 3, preferably 1 to 2.
  • the weight average molecular weight of the polysiloxane compound (cl) used in the present invention is not particularly limited.
  • the force is preferably 100-30, 000, particularly 500 to 10,000, more preferably 1,000.
  • a power of -10,000 S is preferred.
  • the weight average molecular weight is less than 100, the antifouling performance is lowered, and when it exceeds 30,000, transparency and scratch resistance are lowered.
  • polysiloxane compound (cl) represented by the general formula (2) include "X-22-160AS”, “KF-6001”, “KF-” manufactured by Shin-Etsu Chemical Co., Ltd. “6002”, “KF—6003”, “Silaplane FM—4411”, “Silaplane FM—4412”, “Silaplane FM—4425” manufactured by Chisso Corporation, “Macromonomer HK” manufactured by Toagosei Co., Ltd. — 20 ”and so on.
  • the polyisocyanate compound used in the present invention is not particularly limited, and examples thereof include those similar to the above polyisocyanate compound.
  • Examples of the hydroxyl group-containing (meth) acrylate compound include It is not particularly limited, and examples thereof include those similar to the above hydroxyl group-containing (meth) acrylate compound.
  • the production method is not particularly limited,
  • the (mouth) method is preferable.
  • reaction temperature is preferably 30 to 90 ° C, particularly preferably 40 to 70 ° C.
  • the weight average molecular weight of the obtained polyisocyanate derivative [C] is preferably 500 to 50,000, and moreover, The force S is preferably 500 to 30,000.
  • the weight average molecular weight is less than 500, the film-forming property is deteriorated.
  • the weight average molecular weight is more than 50,000, the viscosity becomes high and it is difficult to handle, and the hardness and scratch resistance of the cured coating film are remarkably inferior.
  • the content of the strong polyisocyanate derivative [C] is not particularly limited.
  • the polyisocyanate derivative [A] is 1 to 500 parts by weight, particularly 1 to: LOO weight with respect to 100 parts by weight. 1 to 50 parts by weight is preferred. If the amount is less than 1 part by weight, the solvent resistance is not improved, and if it exceeds 500 parts by weight, the repellency of the cured coating film surface decreases, which is not preferred.
  • a blend of a polysiloxane-containing polyisocyanate derivative [A], a compound [B] having at least one ethylenically unsaturated group and a polysiloxane-containing polyisocyanate derivative [C] In such cases, (1) a method in which [A], [B], and [C] obtained separately are combined, or (2) [A], [B], and [C] are reacted in the same reaction system [ A), [B] and [C] are produced and blended, and (2) is preferred in terms of production stability and transparency of the paint! / ,.
  • the polysiloxane compound (al) having a hydroxyl group at one end represented by the general formula (1) from the viewpoint of achieving both antifouling properties and coating film hardness.
  • Particularly preferred ratios are as follows: polysiloxane compound (al) 1-20% by weight, polysiloxane compound (cl) 1-20% by weight, polyisocyanate compound 10-40% by weight, hydroxyl group-containing (meth) It is 50 to 88% by weight of the attalylate compound.
  • a urethane (meth) acrylate compound [D] represented by the general formula (4) is further contained.
  • R 8 is a urethane bond residue of a polyisocyanate compound (dl)
  • R 9 is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound (d2)
  • R 1Q is a polyol compound.
  • D3 urethane bond residue
  • g is an integer of 1 to 50
  • h is an integer of 2 to 50.
  • the urethane (meth) acrylate compound [D] represented by the general formula (4) is obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound and a polyol compound.
  • the polyisocyanate compound is not particularly limited, and examples thereof include those similar to the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound is not particularly limited. Although the same thing as the said hydroxyl-containing (meth) acrylate-type compound is mentioned, Although it does not specifically limit as a polyol-type compound, The thing similar to said polyol is mentioned.
  • the content of the urethane (meth) acrylate compound [D] represented by the general formula (4) is not particularly limited.
  • the polysiloxane-containing polyisocyanate derivative [A] is 100 parts by weight. , 0.1 ⁇ : LOO weight ⁇ ⁇ special ⁇ ⁇ or ⁇ 5 ⁇ 5 5 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ 5 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Flexibility is not obtained, and if it exceeds 100 parts by weight, the scratch resistance is lowered, which is preferable.
  • the photopolymerization initiator [ ⁇ ] used in the present invention is not particularly limited as long as it generates a radical by the action of light.
  • the amount of the photopolymerization initiator [E] is such that the polysiloxane-containing polyisocyanate derivative [A] and one or more ethylenically unsaturated groups per molecule.
  • the polysiloxane-containing polyisocyanate derivative [A] the compound having one or more ethylenically unsaturated groups in one molecule [B]
  • the polysiloxane-containing polyisocyanate In addition to isocyanate derivatives [C], urethane (meth) acrylate compounds [D], photoinitiators [E], fillers, electrolyte salts, dyes, pigments, oils, plasticizers, waxes, dry Agents, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, antifoaming agents, leveling agents, thixotropic agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, crosslinkers Etc. can also be blended.
  • unsaturated polyester resin vinyl urethane resin, vinyl ester urethane resin, polyisocyanate, polyepoxide, acrylic resin, alkyd for the purpose of suppressing the curing shrinkage of the coating film.
  • the polysiloxane-containing polyisocyanate derivative of the present invention [A] and a compound having at least one ethylenically unsaturated group in one molecule [B], preferably a polysiloxane-containing polyisocyanate.
  • An active energy ray-curable resin composition containing an nate-based derivative [C] and a urethane (meth) acrylate-based compound [D] is obtained.
  • this composition can be used by blending an organic solvent and adjusting the viscosity.
  • organic solvents include cellosolves such as ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and ethyl acetate sorb.
  • Examples include propylene glycolenoatenoles such as propylene glycolenomonomethylenoatenole and diacetone alcohol. These can be used alone or in combination.
  • the active energy ray-curable resin composition of the present invention is cured by irradiating with an active energy ray after applying it to an object.
  • polyethylene polypropylene
  • Polyolefin resin such as licyclopentagen
  • polycarbonate polycarbonate
  • polyester polyolefin resin
  • Examples include ABS resin, acrylic resin, molded products (films, sheets, cups, etc.), metals, and glass.
  • active energy rays to be generated in addition to electromagnetic rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays and infrared rays, X rays and ⁇ rays, electron rays, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of irradiation equipment, price, etc. In addition, when performing electron beam irradiation, it can be cured without using a photopolymerization initiator [ ⁇ ].
  • a high-pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm
  • an ultra-high pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, etc. Irradiation with about 100 to 3000 mjZcm 2 is sufficient.
  • heating can be performed as necessary to complete the curing.
  • the active energy ray-curable resin composition of the present invention comprises a polysiloxane-containing polyisocyanate derivative [A] and a compound having one or more ethylenically unsaturated groups in one molecule [B].
  • it further comprises a polysiloxane-containing polyisocyanate derivative [C] N-urethane (meth) atalylate compound [D], so that it is excellent in antifouling properties, and has coating film hardness and scratch resistance.
  • An active energy one-line curable resin composition that forms a coating layer with excellent solvent resistance and adhesion. Paint, ink, protective coating agent, anchor coating agent, magnetic powder coating binder, adhesive, adhesive It is useful as various film forming materials such as adhesives. Among them, it is very useful as a coating agent for various plastics and optical film top coats.
  • Example 1 An active energy one-line curable resin composition that forms a coating layer with excellent solvent resistance and adhesion. Paint, ink, protective coating agent, anchor coating agent, magnetic powder
  • Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) 77. lg (0.13) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet Mol) and dibutyltin dilaurate (0.10 g) and methyl ethyl ketone (500 g), and dipentaerythritol pentaatalylate (mixture of dipentaerythritol pentaatalylate and dipentaerythritol hexaatalylate acrylate (hydroxyl group) at 60 ° C or lower.
  • isophorone diisocyanate (isocyanate group content 21.3%) 96.
  • Og (0.43 mol) and dibutyltin dilaurate 0 10 g and 500 g of methyl ethyl ketone were charged, and pentaerythritol triatalylate [mixture of pentaerythritol triatalylate and pentaerythritol tetraatalylate (hydroxyl value 120 mg KOH / g)] at 60 ° C or lower 404.
  • Og (0.43 mol) and dibutyltin dilaurate 0 10 g and 500 g of methyl ethyl ketone were charged, and pentaerythritol triatalylate [mixture of pentaerythritol triatalylate and pentaerythritol tetraatalylate (hydroxyl value 120 mg KOH / g)] at
  • Trimer of hexamethylene diisocyanate (isocyanate group content 21.0%) 88.7 g (0.15) in a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet Mol), polydimethylsiloxanediol having one hydroxyl group at both ends (cl) (manufactured by Shin-Etsu Chemical Co., Ltd., “KF6003”) 377.
  • Og (0.074 mol)
  • dibutyltin dilaurate 0.10 g, methyl Ethyl ketone 500g was charged and reacted at 60 ° C for 2 hours.
  • Polysiloxane-containing polyisocyanate derivative [A], compound having one or more ethylenically unsaturated groups in one molecule [B], polysiloxane-containing polyisocyanate derivative [C], urethane ( The meta) acrylate compound [D] and the photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) are adjusted to the ratio shown in Table 1 in terms of solid content.
  • the active energy ray-curable resin composition solution was obtained by blending and diluting with methyl ethyl ketone so that the solid content excluding the photopolymerization initiator was 30%.
  • a mixture of the above polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) was adjusted to the ratio shown in Table 1 in terms of solid content, and the solid content excluding the photopolymerization initiator was adjusted to a concentration of 30%. Dilution with ethyl ketone gave an active energy ray-curable resin composition solution.
  • a mixture of the above polysiloxane-containing polyisocyanate derivative [A] and a compound [B] having one or more ethylenically unsaturated groups in one molecule and a photopolymerization initiator [E] (Ciba 'Specialty' Chemicals Co., Ltd., “Darocur 1173”) was adjusted to the ratio shown in Table 1 in terms of solid content, and the methyl ethyl ketone was adjusted so that the solid content excluding the photopolymerization initiator would be 30% concentration.
  • the cured coating film was reciprocated once with blue magic ink, and then left for 24 hours.
  • the coating film after wiping with a waste cloth was observed and evaluated as follows.
  • the pencil hardness was measured according to JIS K 5600-5-4.
  • the cured film was visually observed for the degree of scratching on the surface after steel wool # 0000 with a load of 500 g was reciprocated 10 times on the surface of the cured film, and evaluated as follows.
  • the surface of the cured coating film was wiped 10 times with a cloth soaked with ethanol, and then the above ink wiping property was observed.
  • the coating film was observed and evaluated as follows.
  • the obtained active energy ray-curable resin composition was coated on a polycarbonate panel using a bar coater No. 14 so that the film thickness after drying was 5 m, After drying at 60 ° C for 5 minutes, using a high pressure mercury lamp lamp 80 W, 1 lamp, 2 passes of UV irradiation (cumulative irradiation dose 450 mi / cm 2 ) from a height of 18 cm at a conveyor speed of 5. lm / min As a result, a cured coating film was formed and the following evaluation was performed.
  • Table 1 shows the evaluation results of Examples and Comparative Examples.
  • Examples 7 to 8 were better than Examples 1 to 6. However, the transparency in the cured coating film was good in both Examples and Comparative Examples.
  • the active energy ray-curable resin composition of the present invention has an excellent antifouling property and an active energy ray-curable resin that forms a coating layer having excellent coating film hardness, scratch resistance, solvent resistance, and adhesion. It becomes a composition and is useful as a coating film forming material such as paints, inks, protective coating agents, anchor coating agents, magnetic powder coating binders, adhesives, adhesives, and adhesives. Among them, it is very useful as a coating agent for various plastics and optical film top coats.

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

Abstract

Est décrite une composition de résine polymérisable par rayons d’énergie active qui est utile pour former une couche de revêtement ayant d’excellentes propriétés d’antisalissure, dureté de la pellicule de revêtement, résistance à l’abrasion, résistance aux solvants et adhésivité. Sont également décrits un procédé pour la fabrication d’une telle composition de résine et une composition de revêtement utilisant une telle composition de résine. Est spécifiquement décrite une composition de résine polymérisable par rayons d’énergie active contenant un dérivé de polyisocyanate contenant du polysiloxane [A] obtenu en faisant réagir un composé de polysiloxane (a1) représenté par la formule générale (1) ci-dessous et ayant un groupe terminal hydroxyle, un composé polyisocyanate et un composé (méth)acrylate contenant un groupe hydroxyle, et un composé [B] ayant un ou plusieurs groupes à insaturation éthylénique dans une molécule. Sont également décrits un procédé pour la fabrication d’une telle composition de résine et une composition de revêtement utilisant une telle composition de résine. [Dans la formule, R1 représente un groupe alkyle ; les R2 représentent indépendamment un groupe alkyle, un groupe cycloalkyle ou un groupe phényle ; R3 représente un groupe hydrocarbure ou un groupe organique contenant un atome d’oxygène ; a représente un entier supérieur à 1 ; et b représente un entier compris entre 1 et 3].
PCT/JP2005/011944 2004-07-08 2005-06-29 Composition de résine polymèrisable par rayons d’énergie active, procédé pour la fabrication de celle-ci, et composition de revêtement utilisant celle-ci WO2006006402A1 (fr)

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WO2013082399A1 (fr) * 2011-12-02 2013-06-06 Ppg Industries Ohio, Inc. Procédé permettant de limiter l'accumulation de glace sur un substrat
US9090797B2 (en) 2011-12-02 2015-07-28 Ppg Industries Ohio, Inc. Method of mitigating ice build-up on a substrate
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US9090797B2 (en) 2011-12-02 2015-07-28 Ppg Industries Ohio, Inc. Method of mitigating ice build-up on a substrate
RU2592896C2 (ru) * 2011-12-02 2016-07-27 Ппг Индастриз Огайо, Инк. Способ снижения обледенения подложки
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US8911832B2 (en) 2011-12-02 2014-12-16 Ppg Industries Ohio, Inc. Method of mitigating ice build-up on a substrate
WO2013082399A1 (fr) * 2011-12-02 2013-06-06 Ppg Industries Ohio, Inc. Procédé permettant de limiter l'accumulation de glace sur un substrat
WO2013082393A1 (fr) * 2011-12-02 2013-06-06 Ppg Industries Ohio, Inc. Procédé d'atténuation de l'accumulation de glace sur un substrat
WO2015148876A1 (fr) * 2014-03-27 2015-10-01 Ppg Industries Ohio, Inc. Procédé de limitation de la formation de glace sur un substrat
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WO2022065019A1 (fr) * 2020-09-23 2022-03-31 信越化学工業株式会社 Composition de silicone durcissable aux ultraviolets et produit durci
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CN115976877B (zh) * 2022-12-27 2023-10-13 广东利宏达包装有限公司 一种包装盒的表面处理工艺

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