WO2014157070A1 - Composition de revêtement durcissable par rayon d'énergie active - Google Patents

Composition de revêtement durcissable par rayon d'énergie active Download PDF

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Publication number
WO2014157070A1
WO2014157070A1 PCT/JP2014/058050 JP2014058050W WO2014157070A1 WO 2014157070 A1 WO2014157070 A1 WO 2014157070A1 JP 2014058050 W JP2014058050 W JP 2014058050W WO 2014157070 A1 WO2014157070 A1 WO 2014157070A1
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Prior art keywords
compound
meth
component
group
acrylate
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PCT/JP2014/058050
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English (en)
Japanese (ja)
Inventor
絹子 小倉
昭憲 北村
尚正 古田
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東亞合成株式会社
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Priority to JP2015508473A priority Critical patent/JP6075443B2/ja
Priority to CN201480007642.2A priority patent/CN104981525B/zh
Priority to KR1020157023145A priority patent/KR102158660B1/ko
Publication of WO2014157070A1 publication Critical patent/WO2014157070A1/fr

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    • 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
    • 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
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • the present invention relates to an active energy ray-curable coating composition, and belongs to the technical field of an active energy ray-curable composition and a coating material.
  • a plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like.
  • the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, the surface of a plastic substrate is often painted with a coating composition and subjected to a so-called hard coat treatment to impart abrasion resistance, scratch resistance, and the like.
  • the conventional coating composition uses a coating composition in which a resin is dissolved in a solvent, and is applied to a substrate and then dried to form a resin film. For the purpose of improving productivity, etc. Further, photocurable compositions and thermosetting compositions have been studied.
  • a hard coating agent for a plastic substrate an ultraviolet curable acrylic hard coating agent, a thermosetting silicone hard coating agent, and the like have been proposed.
  • Thermosetting silicone hard coat agent is excellent in abrasion resistance and scratch resistance, but the curing time is long and the productivity is inferior, and the substrate may be deformed because a high temperature is required at the time of curing. There are problems such as.
  • the ultraviolet curable acrylic hard coat agent is generally inferior in abrasion resistance and scratch resistance, but has a short curing time and excellent productivity.
  • the ultraviolet curable acrylic hard coating agent is superior to the thermosetting composition in terms of productivity and energy saving. Investigations have been made to improve wear and scratch resistance. For example, a method of blending a composition with colloidal silica or a silane compound having a (meth) acryloyloxy group is known.
  • colloidal silica an ultraviolet curable coating composition containing an alkoxysilane and acrylate having a (meth) acryloyloxy group (Patent Document 1), an isocyanate-containing alkoxysilane, a hydroxyl group and three or more acryloyl groups in the molecule
  • Patent Document 2 an ultraviolet curable coating composition containing a reaction product with a polyfunctional acrylate having a polyfunctional acrylate, a polyfunctional acrylate having three or more acryloyl groups, and colloidal silica.
  • these coating compositions are excellent in abrasion resistance and scratch resistance of the cured film as compared with conventional UV curable coating compositions, but cannot satisfy both abrasion resistance and scratch resistance at the same time. Or did not have satisfactory performance in practice. In addition, the adhesion may be insufficient depending on the substrate used.
  • Patent Document 3 a photocurable coating composition containing a specific organosilicon compound as a hard coat agent excellent in abrasion resistance, scratch resistance, adhesion to a substrate, and the like.
  • the photocurable coating composition described in Patent Document 3 requires an organic solvent in order to adjust the viscosity of the composition and impart coating suitability. For this reason, for example, when thick film coating is performed, it may take time to evaporate the solvent, and there is room for improvement. Generally, when the viscosity of a composition is adjusted by adding a reactive monomer or the like in place of an organic solvent, the hardness and scratch resistance of the cured product are reduced, and the resulting cured film is sufficient as a hard coat. I was not satisfied. Therefore, there has been a demand for a coating composition that is solvent-free, satisfies hardness and scratch resistance, and can be cured by active energy rays such as electron beams and ultraviolet rays.
  • the present invention is an active energy ray-curable coating composition that does not contain an organic solvent, the viscosity of which is sufficiently reduced to allow coating, and the cured film when applied to a substrate such as plastic. It is an object to provide an active energy ray-curable coating composition exhibiting sufficient hardness and scratch resistance.
  • the present invention is sufficiently reduced in viscosity to enable coating, and when applied to a substrate such as plastic, the cured film exhibits sufficient hardness and scratch resistance, and has an impact resistance. It is an object of the present invention to provide an active energy ray-curable coating composition having excellent properties.
  • the present inventors have used a composition containing a compound having a nitrogen atom and a radically polymerizable unsaturated group, so that the composition can be obtained without using an organic solvent. It was found that the product can be adjusted to a viscosity that can be sufficiently applied, and a cured product having excellent hardness and scratch resistance can be obtained. In addition, the present inventors have obtained a cured film having high hardness and excellent scratch resistance and impact resistance by using a composition containing a compound having an isocyanuric ring and a radically polymerizable unsaturated group. As a result, the present invention has been completed.
  • the present invention is as follows. [1] (A) A (meth) acryloyl group-containing silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) (A1) An organosilicon compound obtained by hydrolytic copolycondensation at a ratio of 0.3 to 1.8 mol of the silicon compound (a2) with respect to 1 mol; (In General Formula (1), R 1 is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 2 is an organic group having 1 carbon atom.
  • R 3 is a hydrogen atom or a methyl group
  • X is a hydrolyzable group
  • a plurality of X may be the same or different from each other
  • SiY 4 (2) (In General Formula (2), Y is a siloxane bond-forming group, and a plurality of Y may be the same or different from each other.)
  • B a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups, and polyisocyanate Adduct compound (b1) obtained by addition reaction with (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having 3 or more (meth) acryloyl groups, (Meth) acrylate mixture composed of (meth) acrylate (b2) not having And (C) a
  • the compound (a1) is a compound in which X in the general formula (1) is an alkoxy group and n is 0.
  • the said compound (a2) is an active energy ray hardening-type coating composition as described in said [1] whose Y in General formula (2) is an alkoxy group.
  • the component (C) comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer, and a lactam compound.
  • the component (C) includes the compound (C2) having an isocyanuric ring, and the content of the compound (C2) is 5 to 30 parts by weight.
  • Active energy ray-curable coating composition [6] The active energy ray-curable coating composition according to the above [5], wherein the compound (C2) is a radical polymerizable unsaturated compound modified with alkylene oxide or caprolactone.
  • the content of the component (C) is 10 to 35 parts by weight when the total of the component (A), the component (B) and the component (C) is 100 parts by weight,
  • Component (C) comprises a morpholinyl group-containing monomer, an amide group-containing monomer, and at least one compound (C1) selected from lactam compounds, and a compound (C2) having an isocyanuric ring,
  • the content of the compound (C1) is 5 to 30 parts by weight
  • the content of the compound (C2) is 5 to 30 parts by weight
  • the active energy ray-curable coating composition according to any one of [6] to [6].
  • the composition of one embodiment of the present invention can be a composition that does not contain an organic solvent, and forms a cured film having high hardness and excellent scratch resistance with respect to various substrates such as plastics. It becomes possible to do.
  • the composition of another embodiment of the present invention it is possible to form a cured film having high hardness and excellent scratch resistance and impact resistance on various substrates such as plastics. Become.
  • the active energy ray-curable coating composition of the present invention comprises the above components (A), (B) and (C) with respect to a total of 100 parts by weight.
  • (A) 5 to 50 parts by weight of component, 30 to 90 parts by weight of component (B) and 5 to 35 parts by weight of component (C) are contained.
  • component (C) 5 to 35 parts by weight of component (C)
  • an acryloyl group or a methacryloyl group is represented as “(meth) acryloyl group”
  • an acrylate or methacrylate is represented as “(meth) acrylate”.
  • the component (A) according to the present invention includes a (meth) acryloyl group-containing silicon compound (a1) (hereinafter referred to as “compound (a1)”) represented by the following general formula (1) and the following general formula (2). Hydrolysis of the represented silicon compound (a2) (hereinafter referred to as “compound (a2)”) at a ratio of 0.3 to 1.8 mol of compound (a2) with respect to 1 mol of compound (a1). It is an organosilicon compound obtained by copolycondensation.
  • compound (a1) represented by the following general formula (1)
  • compound (2) Hydrolysis of the represented silicon compound (a2) (hereinafter referred to as “compound (a2)”) at a ratio of 0.3 to 1.8 mol of compound (a2) with respect to 1 mol of compound (a1). It is an organosilicon compound obtained by copolycondensation.
  • R 1 is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms
  • R 2 is an organic group having 1 carbon atom.
  • R 3 is a hydrogen atom or a methyl group
  • X is a hydrolyzable group
  • a plurality of X may be the same or different from each other, and n Is 0 or 1.
  • SiY 4 (2) (In General Formula (2), Y is a siloxane bond-forming group, and a plurality of Y may be the same or different from each other.)
  • R 1 is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
  • an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable in that the cured film of the resulting composition is excellent in wear resistance.
  • R 2 is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group.
  • a cured film of the resulting composition has excellent wear resistance, and a trimethylene group is more preferable from the viewpoint of raw material cost.
  • R 3 is a hydrogen atom or a methyl group.
  • X is a hydrolyzable group, and a plurality of X may be the same as or different from each other.
  • the hydrolyzable group various groups can be used as long as they are hydrolyzable groups. Specific examples include a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, and an arylalkoxy group. Among these, an alkoxy group is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
  • n is 0 or 1, and is preferably 0 in that the cured film of the resulting composition is excellent in wear resistance.
  • Specific examples of the compound of the general formula (1) in which n is 0 and X is an alkoxy group include 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxy Examples thereof include silane and 3- (meth) acryloyloxypropylethyltriethoxysilane.
  • Y is a siloxane bond-forming group, and a plurality of siloxane bond-forming groups in one molecule may be the same or different.
  • an alkoxy group is preferable.
  • the alkoxy group include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group and sec-butoxy group.
  • the compound (a2) are alkoxysilane compounds having an n-propoxy group such as tetra-n-propoxysilane, trimethoxy-n-propoxysilane, dimethoxydi-n-propoxysilane, methoxytri-n-propoxysilane and the like.
  • the n-propoxy group-containing alkoxysilane compound may be a single compound or a mixture of compounds having an n-propoxy group and other alkoxy groups.
  • the mixture of n-propoxy group-containing alkoxysilane compounds can be used by mixing a plurality of types of components, but can also be used as it is produced by alcohol exchange.
  • the reaction product obtained by this reaction can also be used as it is.
  • Component (A) is a compound obtained by hydrolytic copolycondensation of compound (a1) and compound (a2) at a ratio of 0.3 to 1.8 mol of compound (a2) with respect to 1 mol of compound (a1).
  • first step The reaction conditions for the hydrolytic copolycondensation are not particularly limited, but are preferably alkaline conditions.
  • the first step under alkaline conditions will be described.
  • the reaction ratio of the compound (a1) to the compound (a2) is 0.3 to 1.8 mol of the compound (a2) with respect to 1 mol of the compound (a1), preferably 0.8% of the compound (a2).
  • the amount of the compound (a2) is preferably 1 to 1.4 mol in a proportion of ⁇ 1.6 mol.
  • the component (A) having excellent storage stability can be produced in a high yield.
  • An organosilicon compound obtained by hydrolytic copolycondensation under acidic conditions (less than pH 7) may be inferior in storage stability. Further, under neutral conditions (around pH 7), the hydrolysis copolycondensation reaction may hardly proceed.
  • the condensation rate of the compound (a1) and the compound (a2) can be 92% or more, more preferably 95% or more, and still more preferably 98% or more.
  • the siloxane bond-forming groups including hydrolyzable groups
  • the upper limit of the condensation rate in the first step is usually 99.9%.
  • the component (A) is produced by using the first step as an essential component, but the production method of the component (A) can further include the following steps as necessary.
  • (Second step) A step of neutralizing the reaction solution obtained in the first step with an acid.
  • (Third step) A step of removing volatile components from the neutralized liquid obtained in the second step.
  • (Fourth step) A step of mixing and contacting the concentrate obtained in the third step with a cleaning organic solvent to dissolve at least the component (A) in the cleaning organic solvent.
  • (Sixth Step) A step of removing volatile components from the organic solution obtained in the fifth step. It is preferable that the manufacturing method of a component (A) includes a 1st process, a 2nd process, and a 5th process.
  • the reaction system of the first step the reaction solution containing the component (A) after the first step, the neutralization solution after the second step, the organic solution after the fourth step, and the fifth step
  • a polymerization inhibitor that inhibits polymerization of the (meth) acryloyl group may be added to at least one of the later organic solutions.
  • the content ratio of the component (A) in the composition of the present invention is 5 to 50 parts by weight, preferably 5 to 5 parts when the total of the components (A), (B) and (C) is 100 parts by weight.
  • the amount is 40 parts by weight, more preferably 10 to 35 parts by weight.
  • Component (B) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having two or more (meth) acryloyl groups and one or more hydroxyl groups ( Urethane adduct compound (b1) obtained by addition reaction of (meth) acrylate and polyisocyanate (hereinafter referred to as “component (b1)”) and (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol And a (meth) acrylate mixture composed of (meth) acrylate (b2) (hereinafter referred to as “component (b2)”) having 3 or more (meth) acryloyl groups and no hydroxyl group. .
  • the raw material compound of component (b1) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having two or more (meth) acryloyl groups and one or more hydroxyl groups (meta) ) Acrylate (hereinafter referred to as “hydroxyl-containing polyfunctional (meth) acrylate”).
  • hydroxyl-containing polyfunctional (meth) acrylate Various compounds can be used as the trihydric or higher aliphatic polyhydric alcohol which is a raw material compound of a hydroxyl group-containing polyfunctional (meth) acrylate, and examples include trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. .
  • hydroxyl group-containing polyfunctional (meth) acrylate various compounds can be used, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane di- or tri- Examples include (meth) acrylate and dipentaerythritol di, tri, tetra, or penta (meth) acrylate. Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable in that the cured film is excellent in hardness and scratch resistance. Specifically, pentaerythritol tri (meth) is preferable. Examples include acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.
  • polyisocyanate which is another synthetic raw material for component (b1).
  • preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, and their nurate type trimers.
  • Component (b1) is synthesized by an addition reaction between a hydroxyl group-containing polyfunctional (meth) acrylate and polyisocyanate.
  • this addition reaction can be performed without a catalyst, the reaction may be carried out in the presence of a catalyst such as a tin compound such as dibutyltin dilaurate or an amine compound such as triethylamine in order to advance the reaction efficiently.
  • a catalyst such as a tin compound such as dibutyltin dilaurate or an amine compound such as triethylamine in order to advance the reaction efficiently.
  • Component (b2) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol.
  • the trivalent or higher aliphatic polyhydric alcohol which is a raw material compound of the component (b2) the same as those mentioned above can be used.
  • Specific examples of the component (b2) include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • a compound having four or more (meth) acryloyl groups is preferable in that the cured film is excellent in wear resistance and scratch resistance.
  • pentaerythritol tetra (meth) acrylate and ditrimethylol are preferable.
  • Examples include propanetetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
  • Component (B) according to the present invention is a mixture of components (b1) and (b2).
  • the ratio of components (b1) and (b2) may be set as appropriate according to the purpose.
  • the content ratio of the component (B) in the composition of the present invention is 30 to 90 parts by weight, preferably 40 to 90 parts by weight with respect to 100 parts by weight as a total of the components (A), (B) and (C). Part, more preferably 50 to 85 parts by weight.
  • the component (C) according to the present invention is a radically polymerizable unsaturated compound having a nitrogen atom in the molecule (hereinafter also referred to as “unsaturated compound (C)”), and the component (A) and the component ( Compounds other than B).
  • unsaturated compound (C) By using the unsaturated compound (C), it is possible to obtain an active energy ray-curable coating composition that gives a cured film having excellent hardness and scratch resistance.
  • it contains the specific compound (C1) mentioned later it can be set as a composition whose viscosity is low enough, and when it contains the specific compound (C2) mentioned later, hardness and scratch resistance The impact resistance of the cured film can be improved without lowering.
  • the number of radically polymerizable unsaturated groups that the unsaturated compound (C) has is not particularly limited, but when the viscosity of the composition is relatively low, a compound having one radically polymerizable unsaturated group So-called monofunctional unsaturated compounds are preferred.
  • monofunctional unsaturated compounds include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxy.
  • Amide group-containing monomer Amino group-containing monomer such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; N-vinylpyrrolidone; N-vinyl- ⁇ -Caprolactam Lactam compound of; (meth) acrylate morpholinyl group-containing monomers such as acryloyl morpholine, (meth) acrylonitrile, N- cyclohexyl maleimide, N- phenylmaleimide, and the like. These compounds may be used independently and may use 2 or more types together.
  • the amide group-containing monomer, the lactam compound, and the morpholinyl group-containing monomer (hereinafter referred to as these) from the point that the Tg of the homopolymer is high and the hardness and scratch resistance of the resulting cured film are good.
  • compound (C1) dimethyl (meth) acrylamide, N-vinylformamide, N-vinylacetamide, and (meth) acryloylmorpholine are more preferable.
  • N-vinylformamide and N-vinylacetamide which are amide group-containing monomers, are more preferable because they have a high effect of reducing not only the performance of the cured product but also the viscosity of the composition.
  • the unsaturated compound (C) is a radically polymerizable unsaturated compound having an isocyanuric ring in the molecule (hereinafter also referred to as “compound (C2)”) alone or in combination with the compound (C1). Preferred component.
  • this compound (C2) isocyanuric acid EO modified
  • ⁇ -caprolactone-modified tris [2- (meth) acryloxyethyl] isocyanurate for example, “Aronix M-327” manufactured by Toagosei Co., Ltd., “NK Ester A” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • ⁇ -caprolactone-modified (meth) acrylates such as “-9300-1CL”
  • alkylene oxide-modified (meth) acrylates and ⁇ -caprolactone-modified (meth) acrylates are more preferable because the resulting cured film has better impact resistance.
  • the number of radically polymerizable unsaturated groups that the compound (C2) has is not particularly limited, and may be one or two or more. In the present invention, a compound having two or more radically polymerizable unsaturated groups is preferred because a cured film having high hardness and good scratch resistance can be easily obtained.
  • the content ratio of the unsaturated compound (C) in the composition of the present invention is 5 to 35 parts by weight, preferably 100 parts by weight of the sum of the components (A), (B) and (C), preferably 5 to 30 parts by weight, more preferably 8 to 25 parts by weight.
  • a cured film having excellent hardness and scratch resistance can be obtained.
  • the unsaturated compound (C) comprises only the compound (C1)
  • the viscosity of the composition is reduced to such an extent that it can be applied without containing an organic solvent.
  • the total of (A), (B) and (C) is 100 parts by weight, it is preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight, and still more preferably 8 to 25 parts by weight.
  • the unsaturated compound (C) consists only of the compound (C2), a cured film having better impact resistance can be obtained. Therefore, the content ratio of the components (A), (B) and (C)
  • the total is 100 parts by weight, it is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight.
  • the unsaturated compound (C) is composed of the compounds (C1) and (C2), a cured film excellent in all of hardness, scratch resistance and impact resistance can be obtained. Therefore, a preferable content ratio of these compounds Is shown below.
  • the content of the compound (C1) is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, still more preferably 8 to 25 parts by weight.
  • the content of compound (C2) is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, and still more preferably 10 to 25 parts by weight.
  • the viscosity of the composition is reduced to such an extent that it can be applied without using an organic solvent, and the hardness, scratch resistance and impact resistance are excellent. A cured film can be obtained.
  • Active energy ray-curable coating composition may be either a composition containing an organic solvent or a composition not containing an organic solvent, and depending on the type of component (C), It can also be set as the composition containing an organic solvent.
  • component (C) contains compound (C1)
  • component (C2) when a component (C) contains a compound (C2) or when both a compound (C1) and (C2) are included, it is preferable to contain an organic solvent.
  • Usable organic solvents will be described later.
  • the composition of the present invention essentially comprises the components (A), (B) and (C), but depending on the purpose, a photopolymerization initiator, a pigment, a dye, a surface conditioner, and an ultraviolet absorber.
  • a photopolymerization initiator such as an agent, a light stabilizer such as HALS, a compound having a radical polymerizable unsaturated group other than components (A), (B) and (C), and an organic polymer can also be blended.
  • Various compounds can be used as the photopolymerization initiator. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone Oligo ⁇ 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone ⁇ and 2-hydroxy-1- ⁇ 4- [4- ( Acetophenone compounds such as -hydroxy-2-methylpropionyl) benzyl] phenyl ⁇ -2-methyl-propan-1-one
  • a preferable blending amount of the photopolymerization initiator is 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight when the total of components (A), (B) and (C) is 100 parts by weight. 7 parts by weight, particularly preferably 1 to 5 parts by weight.
  • the blending amount of the photopolymerization initiator is 0.1 to 10 parts by weight, the composition has excellent curability, and a composition that gives a cured film having excellent hardness and scratch resistance can be obtained.
  • the surface conditioner has an effect of enhancing leveling properties when the composition of the present invention is applied, an effect of enhancing the antifouling property and slipperiness of the cured coating film, and the like.
  • a silicone-based surface conditioner or a fluorine-based surface conditioner is suitable. Specific examples include a silicone polymer having a silicone chain and a polyalkylene oxide chain, a fluorine polymer having a perfluoroalkyl group and a polyalkylene oxide chain, and a fluorine polymer having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Can be mentioned.
  • a preferable blending amount of the surface conditioner is 0.01 to 3 parts by weight, more preferably 0.02 to 0 when the total of the components (A), (B) and (C) is 100 parts by weight. .5 parts by weight.
  • the compound having another radical polymerizable unsaturated group is not particularly limited as long as it is a compound having at least one radical polymerizable unsaturated group in one molecule.
  • Specific examples of the compound having one radical polymerizable unsaturated group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, 2-hydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate of an alkylene oxide adduct of
  • a compound having two or more radically polymerizable unsaturated groups in one molecule improves adhesion, hardness and scratch resistance to the substrate. Can do.
  • the number of radically polymerizable unsaturated groups in the other polyfunctional unsaturated compound is preferably 3 to 20 in one molecule from the viewpoint of not reducing the hardness and scratch resistance.
  • a compound having two or more (meth) acryloyl groups in one molecule is preferable.
  • Specific examples include di (meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, di (meth) acrylate of an alkylene oxide adduct of bisphenol Z, and bisphenol S.
  • polyester (meth) acrylate examples include a dehydration condensate of a polyester polyol and (meth) acrylic acid.
  • the polyester polyol examples include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, or Reaction products obtained using these polyol components such as alkylene oxide adducts and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof And dehydration condensates of various dendrimer type polyols with (meth) acrylic acid.
  • epoxy (meth) acrylate As epoxy (meth) acrylate, (meth) acrylic acid adduct of bisphenol A type epoxy resin, (meth) acrylic acid adduct of hydrogenated bisphenol A type epoxy resin, (meth) acrylic of phenol or cresol novolac type epoxy resin Acid addition products, (meth) acrylic acid addition products of biphenyl type epoxy resins, (meth) acrylic acid addition products of diglycidyl ether of polyethers such as polytetramethylene glycol, (meth) acrylic acid addition of diglycidyl ether of polybutadiene , (Meth) acrylic acid adduct of polybutadiene internal epoxidized product, (meth) acrylic acid adduct of silicone resin having epoxy group, (meth) acrylic acid adduct of limonene dioxide, 3,4-epoxycyclohexylmethyl- 3,4-epoch Shi cyclohexanecarboxylate (meth) acrylic acid adduct and the like.
  • Examples of the urethane (meth) acrylate include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and compounds obtained by addition reaction of organic polyisocyanate, polyol and hydroxyl group-containing (meth) acrylate.
  • examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.
  • Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, and glycerin.
  • polyether polyol examples include polypropylene glycol and polytetramethylene glycol.
  • polyester polyol a reaction product of these low molecular weight polyols and / or polyether polyols and an acid component such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or a dibasic acid or its anhydride. Is mentioned.
  • organic polyisocyanate examples include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • hydroxyl group-containing (meth) acrylates include hydroxyl group-containing (meta) of hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate and the like.
  • the organic polymer has an action of reducing warpage during curing while maintaining transparency.
  • a preferred organic polymer is a (meth) acrylic polymer, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- (2 -(Meth) acryloxyethyl) tetrahydrophthalimide and the like.
  • glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
  • composition of the present invention does not contain an organic solvent, it may be excellent in coating properties and handling properties, but for the purpose of further improving these performances, or for the purpose of adjusting the viscosity of the composition, Organic solvents can be used.
  • an organic solvent what dissolve
  • preferred organic solvents include alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as toluene and xylene; Examples thereof include ester compounds such as glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; N-methylpyrrolidone and the like.
  • alcohols such as ethanol and isopropanol
  • alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether
  • acetone alcohols such as diacetone alcohol
  • aromatic compounds such as toluene and xylene
  • ester compounds such as glycol monomethyl ether acetate,
  • a preferable blending amount of the organic solvent is 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, further preferably 100 parts by weight when the total of components (A), (B) and (C) is 100 parts by weight. Is 50 to 300 parts by weight. Since the viscosity of the curable composition is sufficiently reduced by setting the blending amount of the organic solvent to 10 to 1000 parts by weight, a known coating method (bar coating, roll coating, spin coating, dip coating, gravure coating, die coating, It is easy to prepare a coating composition corresponding to flow coat, spray coat, etc.
  • the viscosity (25 ° C.) measured by the E-type viscometer of the active energy ray-curable coating composition of the present invention is preferably 20,000 mPa ⁇ s or less, more preferably 15,000 mPa ⁇ s, from the viewpoint of coating properties. s or less, more preferably 10,000 mPa ⁇ s or less. The lower limit is usually 100 mPa ⁇ s.
  • the production method of the active energy ray-curable coating composition of the present invention may be in accordance with a conventional method.
  • Component (A), Component (B), Component (C), and other components used as necessary Can be made into a manufacturing method provided with processes, such as stirring and mixing.
  • the active energy ray-curable coating composition of the present invention is suitable for forming a coating film having high adhesion to a substrate.
  • the composition of the present invention can be applied to a substrate made of various materials. And as a preferable base material, wood, a metal, an inorganic material, a plastics, etc. are mentioned. Examples of the inorganic material include mortar, concrete, and glass.
  • Specific examples of the plastic include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride, polycarbonate resins, epoxy resins, and polyurethane resins.
  • the method for coating the base material with the composition of the present invention is not particularly limited, and may be a conventional method. For example, bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, spray coating, and the like can be applied.
  • a specific method of forming the cured film there may be mentioned a method of irradiating the coating film with active energy rays after applying the composition to the substrate. In addition, you may pass through the drying process or preheating process of a coating film before irradiation of an active energy ray as needed.
  • the coating film and the film thickness after drying may be appropriately set according to the purpose, but are generally about 5 to 300 ⁇ m.
  • the drying temperature or preheating temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause problems such as deformation.
  • Examples of active energy rays for curing the coating film made of the composition of the present invention include electron beams, ultraviolet rays, visible rays, and X-rays, but ultraviolet rays are preferable because inexpensive devices can be used.
  • Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
  • the irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm 2 is preferable, and 200 to 1,000 mJ / cm 2 is more preferable.
  • an electron beam (EB) irradiation device that can be used, for example, Cockloft-Waltsin type, Bandegraph type, and resonance transformer type devices.
  • the electron beam preferably gives an energy of 50 to 1,000 eV, more preferably 100 to 300 eV.
  • the cured film obtained by using the composition of the present invention is excellent in hardness and scratch resistance.
  • the pencil hardness measured according to JIS K 5600-5-4 is usually 8H or more, and scratches due to contact with a metal member or the like are also suppressed.
  • the material having the cured film can be used for various applications by taking advantage of this characteristic.
  • the display panel front plate building material applications, lighting fixtures, displays and cases such as mobile phones and smartphones, home appliance cases, and various lenses such as glasses.
  • Specific examples of the front plate for the display board include an electric bulletin board, a display, a signboard, an advertisement, and a sign.
  • wood as a base material include woodwork products such as stairs, floors and furniture.
  • metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.
  • part means part by weight
  • % means percent by weight
  • Production of Component (A) Production Example 1 (Production of MAC-TQ) A reactor equipped with a stirrer and a thermometer was charged with 150 g of 1-propanol for alcohol exchange reaction and 36.53 g (0.24 mol) of tetramethoxysilane (hereinafter referred to as “TMOS”), and then stirred. Then, 4.37 g of a 25% tetramethylammonium hydroxide methanol solution (0.1 mol of methanol, 12 mmol of tetramethylammonium hydroxide) was gradually added and reacted at a temperature of 25 ° C. and pH 9 for 6 hours.
  • TMOS tetramethoxysilane
  • the internal temperature was set to 60 ° C., and the reaction was further continued for 1 hour with stirring.
  • TCD detector gas chromatographic analysis
  • 1 to 4 methoxy groups contained in TMOS were substituted with n-propoxy groups, 1-substituted, 2-substituted, 3-substituted or 4 Substituted compounds and unreacted TMOS were detected. Only trace amounts of TMOS were detected. Of these, the ratio of the n-propoxy group-containing compound (n-propoxy group-containing alkoxysilane) was almost 100% in total.
  • the number of 1-propanol substitutions (average of the number of n-propoxy groups per molecule of n-propoxy group-containing compound) was determined to be 2.7.
  • 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane was added to the reaction solution, and 30.2 g of water was further added.
  • 7.88 g of a 25% tetramethylammonium hydroxide methanol solution (0.18 mol of methanol, 21.6 mmol of tetramethylammonium hydroxide) was added and reacted for 24 hours at a temperature of 25 ° C. and a pH of 9 while stirring. .
  • a 1 H-NMR analysis of MAC-TQ revealed that the 3-methacryloxypropyltrimethoxysilane used as the compound (a1) and the n-propoxy group-containing alkoxysilane used as the compound (a2) stoichiometrically. It was confirmed to be a copolycondensate obtained by reaction.
  • the content ratio of alkoxy groups (n-propoxy groups bonded to silicon atoms) calculated from the 1 H-NMR chart of MAC-TQ corresponds to 2.5% of the total alkoxy groups contained in the raw materials. It was the amount to be. Further, when the average molecular weight of MAC-TQ was measured by gel permeation chromatography (GPC), Mn in terms of standard polystyrene was 9,600.
  • each composition was hung on the surface of one side of a 7 cm ⁇ 15 cm ⁇ 50 ⁇ m polyethylene terephthalate film, and a 50 ⁇ m-thick release film made of polyethylene terephthalate and transmitting ultraviolet rays was placed thereon. It was. Subsequently, it passed through the laminating roll so that the film thickness after curing was about 50 ⁇ m, and the thickness of the coating film was adjusted. A coating film was formed on the other surface of the polyethylene terephthalate film in the same manner. Then, the cured film was created on both surfaces of the polyethylene terephthalate film by irradiating with ultraviolet rays through the release film under the following conditions.
  • UV irradiation an ultraviolet ray irradiator (high pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. was used, and irradiation was performed one pass on each side at a lamp height of 19 cm and a conveyor speed of 2.3 m / min.
  • the irradiation energy per pass was measured with a photometer “UV POWER PUCK” manufactured by EIT, and found to be 900 mJ / cm 2 in the UV-A region.
  • the peak illuminance was 170 mW / cm 2 in the UV-A region.
  • About the obtained cured film, pencil hardness, abrasion resistance, and adhesiveness were evaluated by the method shown below. The evaluation results are shown in Table 2.
  • Pencil hardness Pencil hardness was measured according to JIS K 5600-5-4.
  • compositions of Examples 1 to 5 showed a viscosity of 10,850 mPa ⁇ s or less even though no organic solvent was used, and the viscosity was sufficiently reduced to a level capable of being applied. Further, it was confirmed that the cured film had a good pencil hardness of 8H to 10H, and was excellent in wear resistance and scratch resistance.
  • NVF N-vinylformamide
  • Examples 3 to 5 using N-vinylformamide (NVF) as the component (C) have a reduced viscosity of the composition, which is advantageous for coating properties during various coatings. It was.
  • Comparative Example 1 does not contain the component (C) according to the present invention, it has a very high viscosity of 34,400 mPa ⁇ s, and is diluted with an organic solvent or the like at the time of handling and coating. It was highly necessary.
  • Comparative Example 2 using 1,6-hexanediol diacrylate (HDDA), which is an unsaturated compound containing no nitrogen atom, both the pencil hardness and scratch resistance of the cured film were reduced.
  • Comparative Examples 3 and 4 are experimental examples when the content of the component (C) according to the present invention is outside the range defined in the present invention. In Comparative Example 3 in which the content of the component (C) is too small, the viscosity of the composition cannot be sufficiently reduced. Conversely, in Comparative Example 4 in which the content of the component (C) is too large, the pencil of the cured film is used. Hardness and scratch resistance were low.
  • Examples 6 to 11 and Comparative Example 5 Using each raw material shown in Table 3 in the ratio shown in Table 3, the active energy ray-curable coating composition was prepared by stirring and mixing at room temperature according to a conventional method.
  • the composition of Comparative Example 5 is the same as the composition of Comparative Example 1.
  • the viscosity of each composition was measured, and the coating suitability was determined according to the criteria classified as follows. The results are also shown in Table 3.
  • Comparative Example 5 is an experimental example of a composition that does not contain the component (C) according to the present invention.
  • the viscosity of the composition is high, and the obtained cured film has excellent hardness and scratch resistance, but a falling ball test.
  • the value of was as low as 15 cm and was inferior in impact resistance.
  • the active energy ray-curable coating composition of the present invention can be suitably used for coating various substrates such as wood, metal, inorganic materials, and plastics.

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Abstract

L'invention concerne une composition de revêtement durcissable par rayon d'énergie active qui comprend les composants (A) à (C) suivants à un rapport de teneur spécifié : (A) un composé organosilicium obtenu par l'hydrolyse et la copolycondensation d'un composé du silicium à teneur en groupe (méth)acryloyle (a1) représenté par la formule générale (1) et un composé du silicium (a2) représenté par la formule SiY4 (où Y représente un groupe apte à générer une liaison siloxane) au rapport de 0,3 à 1,8 mole du composant (a2) pour 1 mole du composant (a1); (B) un mélange (méth)acrylate constitué d'un composé d'addition d'uréthane (b1) et d'un (méth)acrylate (b2), où le composant (b1) est obtenu par la réaction d'addition d'un (méth)acrylate qui est issu d'un alcool polyhydrique aliphatique ayant une valence de 3 ou plus et a au moins deux groupes (méth)acryloyle et au moins un groupe hydroxy avec un polyisocyanate et le composant (b2) a au moins trois groupes (méth)acryloyle et n'a pas de groupe hydroxy; et (C) un composé insaturé polymérisable par voie radicalaire ayant un atome d'azote dans la molécule.
PCT/JP2014/058050 2013-03-26 2014-03-24 Composition de revêtement durcissable par rayon d'énergie active WO2014157070A1 (fr)

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CN109369880A (zh) * 2018-10-08 2019-02-22 武汉大学 一种可光固化的甲基苯基有机硅改性聚氨酯(甲基)丙烯酸酯树脂及其制备方法和应用
WO2021138191A1 (fr) * 2019-12-31 2021-07-08 Dow Silicones Corporation Procédé de préparation d'une composition hybride silicone-acrylate et composition hybride ainsi formée

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JP6186032B1 (ja) * 2016-03-31 2017-08-23 ハリマ化成株式会社 コーティング剤およびコーティング膜

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CN109369880A (zh) * 2018-10-08 2019-02-22 武汉大学 一种可光固化的甲基苯基有机硅改性聚氨酯(甲基)丙烯酸酯树脂及其制备方法和应用
WO2021138191A1 (fr) * 2019-12-31 2021-07-08 Dow Silicones Corporation Procédé de préparation d'une composition hybride silicone-acrylate et composition hybride ainsi formée

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