WO2014157070A1 - Active-energy-ray-curable coating composition - Google Patents
Active-energy-ray-curable coating composition Download PDFInfo
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- 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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- 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
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- 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
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- 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
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- 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.
Abstract
Description
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.
一般に、プラスチック基材は、軽量であり、耐衝撃性及び易成形性等に優れているが、表面が傷つきやすく硬度が低いため、そのまま使用すると外観を著しく損なうという欠点がある。このため、プラスチック基材の表面を塗料組成物で塗装し、いわゆるハードコート処理して、耐磨耗性及び耐擦傷性等を付与することが多い。 In recent years, glass has been used for displays such as touch panels and smartphones, which are rapidly spreading, but studies are underway to replace them with plastics for the purpose of reducing weight and preventing glass scattering when broken. .
In general, a plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since 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.
ここで、プラスチック基材へのハードコート剤としては、紫外線硬化型のアクリル系ハードコート剤、熱硬化型のシリコーン系ハードコート剤等が提案されている。
熱硬化型のシリコーン系ハードコート剤は耐磨耗性及び耐擦傷性に優れるものの、硬化時間が長く生産性に劣ること、及び硬化時に高温を必要とするため基材の変形が生じる場合がある等の問題がある。これに対して、紫外線硬化型のアクリル系ハードコート剤は、一般に耐磨耗性及び耐擦傷性が劣るものの硬化時間が短く生産性に優れている。 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.
Here, as 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. On the other hand, 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.
例えば、組成物に、コロイダルシリカを配合したり、(メタ)アクリロイルオキシ基を有するシラン化合物を配合する方法が知られている。
具体的には、コロイダルシリカ、(メタ)アクリロイルオキシ基を有するアルコキシシラン及びアクリレートを含む紫外線硬化型塗料組成物(特許文献1)、イソシアネート含有アルコキシシランと分子内に水酸基と3個以上のアクリロイル基を有する多官能アクリレートとの反応物、3個以上のアクリロイル基を有する多官能アクリレート及びコロイダルシリカを含む紫外線硬化型塗料組成物(特許文献2)が知られている。
しかしながら、これら塗料組成物は、従来の紫外線硬化型塗料組成物と比較して硬化膜の耐磨耗性及び耐擦傷性に優れるものの、耐磨耗性及び耐擦傷性の両方を同時に満足できなかったり、実用上満足な性能を有していなかったりするものであった。また、使用する基材によっては密着性が不十分となることがあった。 As described above, 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.
Specifically, 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 There is known an ultraviolet curable coating composition (Patent Document 2) containing a reaction product with a polyfunctional acrylate having a polyfunctional acrylate, a polyfunctional acrylate having three or more acryloyl groups, and colloidal silica.
However, 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.
一般に、有機溶剤の代わりに反応性モノマー等を配合して組成物の粘度を調整した場合には、硬化物の硬度や耐擦傷性が低下するため、得られる硬化膜は、ハードコートとしては十分満足するものではなかった。このため、無溶剤系であって、硬度や耐擦傷性を満足し、電子線、紫外線等の活性エネルギー線により硬化が可能な塗料組成物が求められていた。 However, 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.
In addition, 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.
〔1〕(A)下記一般式(1)で表される(メタ)アクリロイル基含有ケイ素化合物(a1)と、下記一般式(2)で表されるケイ素化合物(a2)とを、上記ケイ素化合物(a1)1モルに対して、上記ケイ素化合物(a2)0.3~1.8モルの割合で、加水分解共重縮合させて得られる有機ケイ素化合物、
SiY4 ・・・(2)
(一般式(2)において、Yはシロキサン結合生成基であり、複数のYは互いに同一であっても異なっていても良い。)
(B)3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を2個以上有し、水酸基を1個以上有する(メタ)アクリレートと、ポリイソシアネートとの付加反応で得られるウレタンアダクト化合物(b1)、及び、3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を3個以上有し、水酸基を有さない(メタ)アクリレート(b2)から構成される(メタ)アクリレート混合物、
並びに、
(C)分子内に窒素原子を有するラジカル重合性不飽和化合物であって、上記成分(A)及び上記成分(B)以外の化合物、を含有し、
上記成分(A)、上記成分(B)及び上記成分(C)の含有量は、これらの合計を100重量部としたときに、上記成分(A)が5~50重量部、上記成分(B)が30~90重量部、上記成分(C)が5~35重量部である活性エネルギー線硬化型塗料組成物。
〔2〕上記化合物(a1)は、一般式(1)におけるXがアルコキシ基であり且つnが0である化合物であり、
上記化合物(a2)は、一般式(2)におけるYがアルコキシ基である上記〔1〕に記載の活性エネルギー線硬化型塗料組成物。
〔3〕上記成分(C)が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも1種の化合物(C1)を含む上記〔1〕又は〔2〕に記載の活性エネルギー線硬化型塗料組成物。
〔4〕上記化合物(C1)が、アクリロイルモルホリン、N-ビニルホルムアミド、N-ビニルアセトアミド及びN-ビニル-ε-カプロラクタムから選ばれた少なくとも1種である上記〔3〕に記載の活性エネルギー線硬化型塗料組成物。
〔5〕上記成分(C)が、イソシアヌル環を有する化合物(C2)を含み、該化合物(C2)の含有量が5~30重量部である上記〔1〕~〔4〕のいずれかに記載の活性エネルギー線硬化型塗料組成物。
〔6〕上記化合物(C2)が、アルキレンオキシド又はカプロラクトンにより変性されたラジカル重合性不飽和化合物である上記〔5〕に記載の活性エネルギー線硬化型塗料組成物。
〔7〕上記成分(C)の含有量が、上記成分(A)、上記成分(B)及び上記成分(C)の合計を100重量部としたときに、10~35重量部であり、上記成分(C)が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも1種の化合物(C1)と、イソシアヌル環を有する化合物(C2)とからなり、両者の合計を10~35重量部とした場合に、上記化合物(C1)の含有割合が5~30重量部であり、上記化合物(C2)の含有割合が5~30重量部である上記〔1〕~〔6〕のいずれかに記載の活性エネルギー線硬化型塗料組成物。
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;
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 radically polymerizable unsaturated compound having a nitrogen atom in the molecule, which contains a compound other than the component (A) and the component (B),
The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight of the component (A) when the total of these components is 100 parts by weight. ) Is 30 to 90 parts by weight, and the active component (C) is 5 to 35 parts by weight.
[2] 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.
[3] The above [1] or [2], wherein 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 active energy ray-curable coating composition described in 1.
[4] The active energy ray curing according to the above [3], wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide and N-vinyl-ε-caprolactam. Mold paint composition.
[5] 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.
[7] 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, When the total amount of both is 10 to 35 parts by weight, the content of the compound (C1) is 5 to 30 parts by weight, and the content of the compound (C2) is 5 to 30 parts by weight [1 ] The active energy ray-curable coating composition according to any one of [6] to [6].
また、本発明の他態様の組成物によれば、プラスチック等の各種基材に対して、高い硬度を有し、耐擦傷性及び耐衝撃性にも優れた硬化膜を形成することが可能となる。
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.
In addition, according to 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.
(A)成分を5~50重量部、
(B)成分を30~90重量部及び
(C)成分を5~35重量部
含有する。
以下、それぞれの成分及び組成物の詳細について説明する。
尚、本明細書においては、アクリロイル基又はメタクリロイル基を「(メタ)アクリロイル基」と表し、アクリレート又はメタクリレートを「(メタ)アクリレート」と表す。 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.
Hereinafter, the detail of each component and a composition is demonstrated.
In the present specification, an acryloyl group or a methacryloyl group is represented as “(meth) acryloyl group”, and an acrylate or methacrylate is represented as “(meth) acrylate”.
本発明に係る成分(A)は、下記一般式(1)で表される(メタ)アクリロイル基含有ケイ素化合物(a1)(以下、「化合物(a1)」という)と下記一般式(2)で表されるケイ素化合物(a2)(以下、「化合物(a2)」という)とを、化合物(a1)1モルに対して、化合物(a2)0.3~1.8モルの割合で、加水分解共重縮合させて得られる有機ケイ素化合物である。
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.
(一般式(2)において、Yはシロキサン結合生成基であり、複数のYは互いに同一であっても異なっていても良い。) 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.)
これらの中でも、炭素数1~6のアルキル基が好ましく、得られる組成物の硬化膜が耐磨耗性に優れる点で、メチル基がより好ましい。
R2は炭素数1~6の2価の飽和炭化水素基であり、アルキレン基が好ましい。アルキレン基としては、得られる組成物の硬化膜が耐磨耗性に優れるものとなり、原料コストの点から、トリメチレン基がより好ましい。R3は水素原子又はメチル基である。
Xは加水分解性基であり、複数のXは互いに同一であっても異なっていても良い。加水分解性基としては、加水分解性を有する基であれば種々の基が可能である。具体的には、水素原子、アルコキシ基、シクロアルコキシ基、アリールオキシ基及びアリールアルコキシ基が挙げられる。これらの中でもアルコキシ基が好ましく、炭素数1~6のアルコキシ基がより好ましい。アルコキシ基の具体例としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基及びヘキシルオキシ基等が挙げられる。
また、nは0又は1であり、得られる組成物の硬化膜が耐磨耗性に優れる点で、好ましくは0である。 In the general formula (1) representing the compound (a1), 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.
Among these, 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. As the 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. As 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. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Further, n is 0 or 1, and is preferably 0 in that the cured film of the resulting composition is excellent in wear resistance.
シロキサン結合生成基としては、アルコキシ基が好ましい。アルコキシ基の好ましい例としては、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基及びsec-ブトキシ基等の炭素数1~4のアルコキシ基が挙げられる。
化合物(a2)の好ましい具体例は、テトラ-n-プロポキシシラン、トリメトキシ-n-プロポキシシラン、ジメトキシジ-n-プロポキシシラン、メトキシトリ-n-プロポキシシラン等のn-プロポキシ基を有するアルコキシシラン化合物である。
n-プロポキシ基含有アルコキシシラン化合物は、1種の化合物でも、n-プロポキシ基を有し、他のアルコキシ基を有する化合物の混合物でも良い。
n-プロポキシ基含有アルコキシシラン化合物の混合物は、複数種の成分を混合して使用することもできるが、アルコール交換によって製造したものをそのまま使用することもできる。例えば、上記一般式(2)で表されるケイ素化合物であり、且つn-プロポキシ基を有さない化合物(例えば、テトラメトキシシラン)を、1-プロパノール中でアルコール交換反応させることにより得ることができる。また、この反応により得られた反応生成物をそのまま用いることもできる。 In the general formula (2) showing the compound (a2), Y is a siloxane bond-forming group, and a plurality of siloxane bond-forming groups in one molecule may be the same or different.
As the siloxane bond-forming group, an alkoxy group is preferable. Preferable examples of 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.
Preferable specific examples of 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. For example, it can be obtained by subjecting a silicon compound represented by the above general formula (2) and having no n-propoxy group (for example, tetramethoxysilane) to alcohol exchange reaction in 1-propanol. it can. Moreover, the reaction product obtained by this reaction can also be used as it is.
上記第1工程をアルカリ性条件下で進めることにより反応後のゲル化を防止することができ、高収率で成分(A)を製造することができる。
アルカリ性条件は、具体的には、反応系のpHが7を超える値であり、好ましくはpHが8以上であり、更に好ましくはpHが9以上である。尚、上限は、通常、pH13である。反応系を上記pHとすることにより、保存安定性に優れた成分(A)を高い収率で製造することができる。
酸性条件下(pH7未満)で加水分解共重縮合させて得られる有機ケイ素化合物は、保存安定性に劣る場合がある。
また、中性条件下(pH7付近)では、加水分解共重縮合反応が進行し難い場合がある。 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. By reacting at this ratio, the component (A) can be efficiently produced without causing gelation during and after the reaction.
By proceeding the first step under alkaline conditions, gelation after the reaction can be prevented, and the component (A) can be produced in a high yield.
Specifically, the alkaline condition is such that the pH of the reaction system exceeds 7, preferably 8 or more, more preferably 9 or more. The upper limit is usually pH 13. By setting the reaction system to the above pH, 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.
しかしながら、所定量以上のMモノマーを併用することで、ゲル化は回避できても、得られる有機ケイ素化合物の無機的性質は低下する傾向にある。
一方、アルカリ性条件による製造方法によれば、化合物(a1)と化合物(a2)をゲル化させずに共重縮合させることができ、その上、得られる硬化物の無機的性質を低下させることがないという効果を奏する。 Conventionally, a method for producing an organosilicon compound under acidic conditions is known, but it is difficult to uniformly react both the compound (a1) and the compound (a2) of the raw material compound, and a gel is likely to be generated. . Therefore, a method of avoiding gelation by causing a silicon compound having only one siloxane bond-forming group (hereinafter referred to as “M monomer”), such as trimethylalkoxysilane or hexamethyldisiloxane, to act as an end-capping agent. It has been known.
However, even when gelation can be avoided by using a predetermined amount or more of the M monomer, the inorganic properties of the resulting organosilicon compound tend to decrease.
On the other hand, according to the production method under alkaline conditions, the compound (a1) and the compound (a2) can be copolycondensed without gelation, and the inorganic properties of the resulting cured product can be reduced. There is no effect.
(第2工程)第1工程で得られた反応液を、酸により中和する工程。
(第3工程)第2工程で得られた中和液から揮発性成分を除去する工程。
(第4工程)第3工程で得られた濃縮物と、洗浄用有機溶剤とを、混合及び接触させて、少なくとも成分(A)を洗浄用有機溶剤に溶解する工程。
(第5工程)第4工程で得られた有機系液を水により洗浄した後、成分(A)を含む有機溶液を得る工程。
(第6工程)第5工程で得られた有機溶液から揮発性成分を除去する工程。
成分(A)の製造方法は、第1工程、第2工程及び第5工程を含むことが好ましい。 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.
(5th process) The process of obtaining the organic solution containing a component (A), after wash | cleaning the organic type liquid obtained at the 4th process with water.
(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.
成分(A)の含有割合を5~50重量部とすることで、硬度と耐擦傷性に優れた硬化膜を与える組成物とすることができる。 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.
By setting the content of component (A) to 5 to 50 parts by weight, a composition that provides a cured film having excellent hardness and scratch resistance can be obtained.
本発明に係る成分(B)は、3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を2個以上有し、水酸基を1個以上有する(メタ)アクリレートとポリイソシアネートとの付加反応で得られるウレタンアダクト化合物(b1)(以下、「成分(b1)」という)、及び、3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を3個以上有し、水酸基を有さない(メタ)アクリレート(b2)(以下、「成分(b2)」という)から構成される(メタ)アクリレート混合物である。 2. Ingredient (B)
Component (B) according to the present invention 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. .
水酸基含有多官能(メタ)アクリレートの原料化合物である3価以上の脂肪族多価アルコールとしては、種々の化合物が使用でき、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン及びジペンタエリスリトール等が挙げられる。
水酸基含有多官能(メタ)アクリレートとしては、種々の化合物が使用でき、具体的には、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールのジ又はトリ(メタ)アクリレート、ジトリメチロールプロパンのジ又はトリ(メタ)アクリレート及びジペンタエリスリトールのジ、トリ、テトラ又はペンタ(メタ)アクリレート等が挙げられる。
これらの中でも、硬化膜が硬度と耐擦傷性に優れる点で、3個以上の(メタ)アクリロイル基を有し、水酸基を1個有する化合物が好ましく、具体的には、ペンタエリスリトールトリ(メタ)アクリレート、ジトリメチロールプロパントリ(メタ)アクリレート及びジペンタエリスリトールペンタ(メタ)アクリレート等が挙げられる。 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”).
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. .
As the 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.
好ましいポリイソシアネートの例としては、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、4,4′-ジシクロヘキシルメタンジイソシアネート、ノルボルナンジイソシアネート、2,4-トリレンジイソシアネート及びこれらのヌレート型三量体等が挙げられる。 Various compounds can be used as polyisocyanate, which is another synthetic raw material for component (b1).
Examples of preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, and their nurate type trimers.
成分(b2)の原料化合物である3価以上の脂肪族多価アルコールとしては、上記で挙げたものと同様のものが使用できる。
成分(b2)の具体例としては、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート及びジペンタエリスリトールヘキサ(メタ)アクリレート等が挙げられる。
これらの中でも、硬化膜が耐磨耗性と耐擦傷性に優れる点で、4個以上の(メタ)アクリロイル基を有する化合物が好ましく、具体的には、ペンタエリスリトールテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート及びジペンタエリスリトールヘキサ(メタ)アクリレート等が挙げられる。 Component (b2) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol.
As 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.
Among these, a compound having four or more (meth) acryloyl groups is preferable in that the cured film is excellent in wear resistance and scratch resistance. Specifically, pentaerythritol tetra (meth) acrylate and ditrimethylol are preferable. Examples include propanetetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
成分(b1)及び(b2)の割合は目的に応じて適宜設定すれば良い。上記成分(B)は、好ましくは(b1):(b2)=10:90~75:25の重量比で含む混合物であり、より好ましくは(b1):(b2)=30:70~70:30の重量比で含む混合物である。
成分(b1)及び(b2)の重量比をこの範囲とすることで、硬度と耐擦傷性に優れた硬化膜を与える組成物を得ることができる。 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 component (B) is preferably a mixture containing (b1) :( b2) = 10: 90 to 75:25, more preferably (b1) :( b2) = 30: 70 to 70: It is a mixture containing at a weight ratio of 30.
By setting the weight ratio of components (b1) and (b2) within this range, a composition that gives a cured film having excellent hardness and scratch resistance can be obtained.
成分(B)の含有割合を30~90重量部とすることで、硬度と耐擦傷性に優れた硬化膜を与える組成物とすることができる。 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.
By setting the content ratio of component (B) to 30 to 90 parts by weight, a composition that provides a cured film excellent in hardness and scratch resistance can be obtained.
本発明に係る成分(C)は、分子内に窒素原子を有するラジカル重合性不飽和化合物(以下、「不飽和化合物(C)」ともいう)であって、上記成分(A)及び上記成分(B)以外の化合物である。
上記不飽和化合物(C)を用いることにより、硬度及び耐擦傷性に優れた硬化膜を与える活性エネルギー線硬化型塗料組成物とすることが可能となる。また、後述する特定の化合物(C1)を含有する場合には、粘度が十分に低い組成物とすることができ、後述する特定の化合物(C2)を含有する場合には、硬度及び耐擦傷性を低下させることなく、硬化膜の耐衝撃性を向上させることができる。 3. Ingredient (C)
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).
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. Moreover, when 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.
このような単官能不飽和化合物の具体例としては、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N,N-ジメチルアミノプロピルアクリルアミド、N-ビニルホルムアミド、N-ビニルアセトアミド、ダイアセトン(メタ)アクリルアミド等のアミド基含有単量体;ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート等のアミノ基含有単量体;N-ビニルピロリドン;N-ビニル-ε-カプロラクタム等のラクタム化合物;(メタ)アクリロイルモルホリン等のモルホリニル基含有単量体;(メタ)アクリロニトリル、N-シクロヘキシルマレイミド、N-フェニルマレイミド等が挙げられる。これら化合物は単独で用いてもよいし、2種以上を併用してもよい。 In the present invention, 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.
Specific examples of such monofunctional unsaturated compounds include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxy. Methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl acrylamide, N-vinylformamide, N-vinylacetamide, diacetone (meth) acrylamide, etc. Amide group-containing monomer; Amino group-containing monomer such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; N-vinylpyrrolidone; N-vinyl-ε -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.
尚、化合物(C2)が有するラジカル重合性不飽和基の数は、特に制限されず、1個でも、2個以上でもよい。本発明においては、硬度が高く、耐擦傷性も良好な硬化膜が得られ易い点から、ラジカル重合性不飽和基を2個以上有する化合物が好ましい。 As the compound (C2), alkylene oxide-modified (meth) acrylates and ε-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.
不飽和化合物(C)を5~35重量部含有することで、硬度及び耐擦傷性に優れた硬化膜を得ることができる。 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.
By containing 5 to 35 parts by weight of the unsaturated compound (C), a cured film having excellent hardness and scratch resistance can be obtained.
不飽和化合物(C)が化合物(C2)のみからなる場合、より優れた耐衝撃性を有する硬化膜が得られることから、その含有割合は、成分(A)、(B)及び(C)の合計を100重量部としたときに、好ましくは5~30重量部、より好ましくは8~30重量部、更に好ましくは10~25重量部である。 In the present invention, when 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. When 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.
When 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) When 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.
本発明の活性エネルギー線硬化型塗料組成物は、有機溶剤を含む組成物、及び、有機溶剤を含まない組成物のいずれでもよく、成分(C)の種類により、有機溶剤を含有する組成物とすることもできる。例えば、成分(C)が化合物(C1)を含む場合には、有機溶剤を含有しない組成物とすることができる。また、成分(C)が化合物(C2)を含む場合、あるいは、化合物(C1)及び(C2)の両方を含む場合には、有機溶剤を含有することが好ましい。使用可能な有機溶剤は後述される。 4). Active energy ray-curable coating composition The active energy ray-curable coating composition of the present invention 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. For example, when component (C) contains compound (C1), it can be set as the composition which does not contain an organic solvent. Moreover, 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.
光重合開始剤の配合量を0.1~10重量部とすることで、組成物が硬化性に優れるものとなり、硬度と耐擦傷性に優れた硬化膜を与える組成物とすることができる。 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.
When 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.
1分子中に1個のラジカル重合性不飽和基を有する化合物の具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート、スチレン、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、フェノールのアルキレンオキサイド付加物の(メタ)アクリレート、アルキルフェノールのアルキレンオキサイド付加物の(メタ)アクリレート等が挙げられる。 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 phenol, (meth) acrylate of an alkylene oxide adduct of alkylphenol, and the like.
他の多官能不飽和化合物におけるラジカル重合性不飽和基の数は、硬度及び耐擦傷性を低下させない観点から、1分子中に3~20個であることが好ましい。 In addition, a compound having two or more radically polymerizable unsaturated groups in one molecule (hereinafter referred to as “other polyfunctional unsaturated compound”) 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.
具体例としては、ビスフェノールAのアルキレンオキサイド付加物のジ(メタ)アクリレート、ビスフェノールFのアルキレンオキサイド付加物のジ(メタ)アクリレート、ビスフェノールZのアルキレンオキサイド付加物のジ(メタ)アクリレート、ビスフェノールSのアルキレンオキサイド付加物のジ(メタ)アクリレート、チオビスフェノールのアルキレンオキサイド付加物のジ(メタ)アクリレート、ビスフェノールAのジ(メタ)アクリレート、ビスフェノールFのジ(メタ)アクリレート、ビスフェノールZのジ(メタ)アクリレート、ビスフェノールSのジ(メタ)アクリレート、チオビスフェノールのジ(メタ)アクリレート、トリシクロデカンジメチロールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、グリセリンのアルキレンオキサイド付加物のジ(メタ)アクリレート、ダイマー酸ジオールジ(メタ)アクリレート、シクロヘキサンジメチロールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンのアルキレンオキサイド付加物のトリ(メタ)アクリレート、ペンタエリスリトールのトリ及びテトラアクリレート、ペンタエリスリトールのアルキレンオキサイド付加物のトリ及びテトラアクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ及びペンタアクリレート、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、末端に(メタ)アクリロイル基を有するシリコーン樹脂等が挙げられる。 As another polyfunctional unsaturated compound, 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. Di (meth) acrylate of alkylene oxide adduct, di (meth) acrylate of alkylene oxide adduct of thiobisphenol, di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol F, di (meth) of bisphenol Z Acrylate, di (meth) acrylate of bisphenol S, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (meth) acrylate, ethylene glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, di (meth) acrylate of glycerin alkylene oxide adduct, dimer acid diol di (meth) acrylate, cyclohexane dimethylol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate, pentaerythritol tri- and tetraacrylate, pentaerythritol Alkylene oxide adduct tri- and tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, Examples thereof include silicone resins having a (meth) acryloyl group.
ここで、ポリオールとしては、低分子量ポリオール、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール等が挙げられる。
低分子量ポリオールとしては、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、シクロヘキサンジメチロール、3-メチル-1,5-ペンタンジオール、及びグリセリン等が挙げられる。
ポリエーテルポリオールとしては、ポリプロピレングリコールやポリテトラメチレングリコール等が挙げられる。
ポリエステルポリオールとしては、これら低分子量ポリオール及び/又はポリエーテルポリオールと、アジピン酸、コハク酸、フタル酸、ヘキサヒドロフタル酸及びテレフタル酸等の二塩基酸又はその無水物等の酸成分との反応物が挙げられる。
有機ポリイソシアネートとしては、トリレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、4,4′-ジフェニルメタンジイソシアネート、4,4′-ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート、及びイソホロンジイソシアネート等が挙げられる。
ヒドロキシル基含有(メタ)アクリレートとしては、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレートのヒドロキシル基含有(メタ)アクリレート等が挙げられる。 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.
Here, 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.
Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol.
As the 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.
Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of 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.
有機溶剤の配合量を10~1000重量部とすることにより硬化性組成物の粘度が十分低減されるため、公知の塗布方法(バーコート、ロールコート、スピンコート、ディップコート、グラビアコート、ダイコート、フローコート、スプレーコート等)に対応した塗料組成物を調製し易い。 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.
本発明の活性エネルギー線硬化型塗料組成物は、基材に対して密着性の高い塗装皮膜の形成に好適である。
本発明の組成物は、種々の材料からなる基材に適用することができる。そして、好ましい基材としては、木材、金属、無機材料及びプラスチック等が挙げられる。
無機材料としては、モルタル、コンクリート及びガラス等が挙げられる。
プラスチックの具体例としては、ポリメチルメタクリレート等のアクリル樹脂、ポリエチレンテレフタレート等のポリエステル樹脂、ポリ塩化ビニル、ポリカーボネート樹脂、エポキシ樹脂及びポリウレタン樹脂等が挙げられる。 5. Coating method 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.
また、硬化膜を形成する具体的な方法としては、組成物を基材に塗布した後に、塗膜に活性エネルギー線を照射する方法等が挙げられる。尚、必要に応じて、活性エネルギー線の照射前に、塗膜の乾燥工程又は予備加熱工程を経ても良い。 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.
Moreover, as 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.
乾燥温度又は予備加熱温度は、適用する基材が変形等の問題を生じない温度以下であれば特に限定されるものではない。 The coating film and the film thickness after drying may be appropriately set according to the purpose, but are generally about 5 to 300 μm.
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.
紫外線照射装置としては、高圧水銀ランプ、メタルハライドランプ、UV無電極ランプ、LED等が挙げられる。
照射エネルギーは、活性エネルギー線の種類や配合組成に応じて適宜設定すべきものであるが、一例として高圧水銀ランプを使用する場合を挙げると、UV-A領域の照射エネルギーで100~5,000mJ/cm2が好ましく、200~1,000mJ/cm2がより好ましい。
電子線により硬化させる場合には、使用できる電子線(EB)照射装置としては種々の装置を使用することができ、例えば、コックロフトワルトシン型、バンデグラフ型及び共振変圧器型の装置等が挙げられ、電子線としては50~1,000eVのエネルギーを与えるものが好ましく、より好ましくは100~300eVである。 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.
In the case of curing with an electron beam, various devices can be used as 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.
例えば、表示板用前面板、建材用途、照明器具、携帯電話及びスマートフォン等のディスプレイや筐体、家電製品の筐体、眼鏡等の各種レンズが挙げられる。
表示板用前面板の具体例としては、電光掲示板、ディスプレイ、看板、広告及び標識等が挙げられる。
基材として木材を使用した例としては、階段、床及び家具等の木工製品が挙げられる。基材として金属を使用した例としては、台所用キッチンパネル及びステンレスシンク等の金属製品等が挙げられる。
The cured film obtained by using the composition of the present invention is excellent in hardness and scratch resistance. For example, 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.
For example, 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.
Examples of using wood as a base material include woodwork products such as stairs, floors and furniture. Examples of using metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.
また、以下において「部」とは重量部を意味し、「%」とは重量%を意味する。 Hereinafter, the present invention will be specifically described based on examples. In addition, this invention is not limited by these Examples.
In the following, “part” means part by weight, and “%” means percent by weight.
製造例1(MAC-TQの製造)
攪拌機及び温度計を備えた反応器に、アルコール交換反応用の1-プロパノール150gとテトラメトキシシラン(以下、「TMOS」という)36.53g(0.24モル)とを仕込んだ後、これらを撹拌しながら、25%水酸化テトラメチルアンモニウムメタノール溶液4.37g(メタノール0.1モル、水酸化テトラメチルアンモニウム12ミリモル)を徐々に加えて、温度25℃、pH9で6時間反応させた。その後、内温を60℃にして攪拌しながら更に1時間反応させた。ここで、反応液をガスクロマトグラフ分析(TCD検出器)したところ、TMOSに含まれるメトキシ基の1~4個がn-プロポキシ基に置換された1置換体、2置換体、3置換体又は4置換体の各化合物及び未反応のTMOSが検出された。TMOSは痕跡量しか検出されなかった。これらのうちのn-プロポキシ基含有化合物(n-プロポキシ基含有アルコキシシラン)の割合は、合計でほぼ100%であった。ガスクロマトグラムにおける生成物のピーク面積に基づいて、1-プロパノールの置換数(n-プロポキシ基含有化合物1分子あたりのn-プロポキシ基の数の平均)を求めたところ、2.7であった。
次に、上記反応液に、3-メタクリロキシプロピルトリメトキシシラン59.62g(0.24モル)を加え、さらに水30.2gを加えた。そして、25%水酸化テトラメチルアンモニウムメタノール溶液7.88g(メタノール0.18モル、水酸化テトラメチルアンモニウム21.6ミリモル)を加えて、撹拌しながら、温度25℃、pH9で24時間反応させた。その後、10%硝酸水溶液22.2g(35.3ミリモル)を加えて中和した。次いで、この中和液を、ジイソプロピルエーテル120g及び水180gの混合液の中に加えて抽出を行った。このジイソプロピルエーテル層を水洗することで塩類や過剰の酸を除去し、その後、重合禁止剤として和光純薬工業社製N-ニトロソフェニルヒドロキシルアミシアルミニウム塩「Q-1301」(商品名)を11.5mg加えた。得られたジイソプロピルエーテル溶液から、減圧下で有機溶剤を留去し、無色透明な固体の有機ケイ素化合物(以下、「MAC-TQ」という)を得た。その収量は57.72gであった。 1. 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. Thereafter, the internal temperature was set to 60 ° C., and the reaction was further continued for 1 hour with stirring. Here, when the reaction solution was subjected to gas chromatographic analysis (TCD detector), 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. Based on the peak area of the product in the gas chromatogram, 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.
Next, 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane was added to the reaction solution, and 30.2 g of water was further added. Then, 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. . Thereafter, 22.2 g (35.3 mmol) of 10% nitric acid aqueous solution was added for neutralization. Next, this neutralized solution was added to a mixed solution of 120 g of diisopropyl ether and 180 g of water for extraction. The diisopropyl ether layer is washed with water to remove salts and excess acid, and then N-nitrosophenylhydroxylami aluminum salt “Q-1301” (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is used as a polymerization inhibitor. .5 mg was added. From the obtained diisopropyl ether solution, the organic solvent was distilled off under reduced pressure to obtain a colorless and transparent solid organosilicon compound (hereinafter referred to as “MAC-TQ”). The yield was 57.72g.
MAC-TQの1H-NMRチャートから算出したアルコキシ基(ケイ素原子に結合したn-プロポキシ基)の含有割合は、仕込み原料に含まれていたアルコキシ基の全体に対して2.5%に相当する量であった。
また、ゲルパーミエーションクロマトグラフィー(GPC)により、MAC-TQの平均分子量を測定したところ、標準ポリスチレン換算のMnは9,600であった。 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.
製造例2(HDI-M305の製造)
攪拌装置及び空気の吹き込み管を備えた0.5Lセパラブルフラスコに、ペンタエリスリトールトリアクリレート(以下、「PETri」という)とペンタエリスリトールテトラアクリレート(以下、「PETet」という)との混合物(PETri0.3モル及びPETet0.2モルを含有する)である、東亞合成社製「アロニックスM-305」(商品名、以下、「M-305」という。)159.2g、2,6-ジ-tert-ブチル-4-メチルフェノール(以下、「BHT」という)0.092g、及びジブチルスズジラウレート(以下、「DBTL」という)0.055gを仕込み、液温を70~75℃とした後、これらを攪拌しながら、ヘキサメチレンジイソシアネート(以下、「HDI」という)25.2g(0.15モル)を滴下し、反応させた。
HDIの滴下終了後、内温を80℃として更に反応を継続し、3時間攪拌した。そして、反応生成物のIR(赤外吸収)分析でイソシアネート基が消失していることを確認して反応を終了した。以下、この反応生成物を「HDI-M305」と呼ぶ。 2. Production of Component (B) Production Example 2 (Production of HDI-M305)
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, a mixture of pentaerythritol triacrylate (hereinafter referred to as “PETri”) and pentaerythritol tetraacrylate (hereinafter referred to as “PETet”) (PETri0.3). "Aronix M-305" (trade name, hereinafter referred to as "M-305") manufactured by Toagosei Co., Ltd., and 2,6-di-tert-butyl. 0.092 g of -4-methylphenol (hereinafter referred to as “BHT”) and 0.055 g of dibutyltin dilaurate (hereinafter referred to as “DBTL”) were charged and the liquid temperature was adjusted to 70 to 75 ° C., and these were stirred. , 25.2 g (0.15 mol) of hexamethylene diisocyanate (hereinafter referred to as “HDI”) ) Was added dropwise and reacted.
After completion of the dropwise addition of HDI, the reaction was further continued at an internal temperature of 80 ° C. and stirred for 3 hours. The reaction was completed after confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. Hereinafter, this reaction product is referred to as “HDI-M305”.
上記で得られたMAC-TQ及びHDI-M305と、表1に示す成分とを用いて、活性エネルギー線硬化型塗料組成物を製造し、各種評価に供した。 3. Production and evaluation of active energy ray curable coating composition Using the MAC-TQ and HDI-M305 obtained above and the components shown in Table 1, an active energy ray curable coating composition was produced and evaluated in various ways. It was used for.
各原料を、表2に示す割合で用いて、常法に従い、常温で攪拌・混合し、活性エネルギー線硬化型塗料組成物を調製した。
その後、得られた各組成物の25℃における粘度をE型粘度計により測定し、得られた値を各表に併記した。 Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4
Each raw material was used in the proportions shown in Table 2 and stirred and mixed at room temperature according to a conventional method to prepare an active energy ray-curable coating composition.
Thereafter, the viscosity of each composition obtained at 25 ° C. was measured with an E-type viscometer, and the obtained values were listed in each table.
紫外線照射は、アイグラフィックス社製紫外線照射機(高圧水銀ランプ)を使用し、ランプ高さを19cm、コンベア速度2.3m/分で片面1パスずつ照射した。1パス当りの照射エネルギーを、EIT社製の光度計「UV POWER PUCK」により測定したところ、UV-A領域で900mJ/cm2であった。また、ピーク照度は、UV-A領域で170mW/cm2であった。
得られた硬化膜について、鉛筆硬度、耐擦傷性及び密着性を、以下に示す方法で評価した。それらの評価結果を表2に示す。 Thereafter, each composition was hung on the surface of one side of a 7 cm × 15 cm × 50 μm polyethylene terephthalate film, and a 50 μm-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 μm, 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.
For ultraviolet 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.
JIS K 5600-5-4に準じて鉛筆硬度を測定した。 (1) Pencil hardness Pencil hardness was measured according to JIS K 5600-5-4.
硬化膜の表面に、日本スチールウール社製スチールウール「ボンスター#0000」を配置した状態で、に1200g/4cm2の荷重をかけながら、400往復擦ったときの傷の数を計測した。この傷の数を用いて、下記基準に基づき耐擦傷性を評価した。ここで、評価「A」又は「B」を耐擦傷性良好とした。
A:傷が全くなかった。
B:傷が1~9本あった。
C:傷が10本以上あった。 (2) Scratch resistance The number of scratches when rubbing 400 reciprocating times while applying a load of 1200 g / 4 cm 2 to the surface of the cured film with steel wool “Bonster # 0000” manufactured by Nippon Steel Wool Co., Ltd. Was measured. Using the number of scratches, scratch resistance was evaluated based on the following criteria. Here, the evaluation “A” or “B” was defined as good scratch resistance.
A: There was no scratch.
B: There were 1 to 9 scratches.
C: There were 10 or more scratches.
比較例3及び4は、本発明に係る成分(C)の含有量が本発明で規定した範囲を外れた場合の実験例である。成分(C)の含有量が少なすぎる比較例3では、組成物の粘度を十分低減することができず、逆に、成分(C)の含有量が多すぎる比較例4では、硬化膜の鉛筆硬度及び耐擦傷性が低いものであった。 On the other hand, since 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. In 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.
各原料を、表3に示す各原料を、表3に示す割合で用いて、常法に従い、常温で攪拌・混合し、活性エネルギー線硬化型塗料組成物を調製した。尚、比較例5の組成物は、比較例1の組成物と同じである。各組成物の粘度を測定し、以下のように区分された基準により塗工適性を判定した。その結果を表3に併記した。
A:粘度が100mPa・s以上10,000mPa・s以下であった
B:粘度が10,000mPa・sを超えて15,000mPas以下であった
C:粘度が15,000mPa・sを超えて20,000mPas以下であった
D:粘度が20,000mPa・sを超えた
その後、実施例1と同様にして、ポリエチレンテレフタレートフィルムの両面に硬化膜を形成した。そして、上記(1)硬度及び(2)耐擦傷性に加えて、下記(3)耐衝撃性の評価を行った。これらの評価結果を表3に示す。 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.
A: The viscosity was 100 mPa · s to 10,000 mPa · s B: The viscosity was more than 10,000 mPa · s to 15,000 mPas or less C: The viscosity was more than 15,000 mPa · s to 20, D: Viscosity exceeded 20,000 mPa · s. Thereafter, in the same manner as in Example 1, cured films were formed on both surfaces of the polyethylene terephthalate film. In addition to the above (1) hardness and (2) scratch resistance, the following (3) impact resistance was evaluated. These evaluation results are shown in Table 3.
硬化膜の表面に対して、10cmの高さからJIS B 1501に準じた25gの鉄球を落とした。硬化膜に割れやクラックが発生しないときは、5cmずつ高さを上昇させて鉄球を落とす操作を繰り返し、割れやクラックが発生しなかった高さの最高値を記録した。この試験を5枚の硬化物について行い、割れやクラックが発生しなかった最高値の平均値を算出することにより耐衝撃性を評価した。
尚、試験は、23℃及び50%RHの恒温恒湿条件下で実施した。 (3) Impact resistance (falling ball test)
A 25 g iron ball according to JIS B 1501 was dropped from a height of 10 cm on the surface of the cured film. When no cracks or cracks occurred in the cured film, the operation of raising the height by 5 cm and dropping the iron ball was repeated, and the maximum height at which no cracks or cracks occurred was recorded. This test was conducted on five cured products, and the impact resistance was evaluated by calculating the average value of the highest values at which no cracks or cracks occurred.
The test was conducted under constant temperature and humidity conditions of 23 ° C. and 50% RH.
On the other hand, 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.
Claims (7)
- (A)下記一般式(1)で表される(メタ)アクリロイル基含有ケイ素化合物(a1)と、下記一般式(2)で表されるケイ素化合物(a2)とを、前記ケイ素化合物(a1)1モルに対して、前記ケイ素化合物(a2)0.3~1.8モルの割合で、加水分解共重縮合させて得られる有機ケイ素化合物、
SiY4 ・・・(2)
(一般式(2)において、Yはシロキサン結合生成基であり、複数のYは互いに同一であっても異なっていても良い。)
(B)3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を2個以上有し、水酸基を1個以上有する(メタ)アクリレートと、ポリイソシアネートとの付加反応で得られるウレタンアダクト化合物(b1)、及び、3価以上の脂肪族多価アルコールから誘導される(メタ)アクリレートであって、(メタ)アクリロイル基を3個以上有し、水酸基を有さない(メタ)アクリレート(b2)から構成される(メタ)アクリレート混合物、
並びに、
(C)分子内に窒素原子を有するラジカル重合性不飽和化合物であって、前記成分(A)及び前記成分(B)以外の化合物、を含有し、
前記成分(A)、前記成分(B)及び前記成分(C)の含有量は、これらの合計を100重量部としたときに、前記成分(A)が5~50重量部、前記成分(B)が30~90重量部、前記成分(C)が5~35重量部である活性エネルギー線硬化型塗料組成物。
(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) are converted into the silicon compound (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;
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 radically polymerizable unsaturated compound having a nitrogen atom in the molecule, which contains a compound other than the component (A) and the component (B),
The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight of the component (A) when the total of these components is 100 parts by weight. ) Is 30 to 90 parts by weight, and the component (C) is 5 to 35 parts by weight.
- 前記化合物(a1)は、一般式(1)におけるXがアルコキシ基であり且つnが0である化合物であり、
前記化合物(a2)は、一般式(2)におけるYがアルコキシ基である請求項1に記載の活性エネルギー線硬化型塗料組成物。
The compound (a1) is a compound in which X in the general formula (1) is an alkoxy group and n is 0,
2. The active energy ray-curable coating composition according to claim 1, wherein in the compound (a2), Y in the general formula (2) is an alkoxy group.
- 前記成分(C)が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも1種の化合物(C1)を含む請求項1又は2に記載の活性エネルギー線硬化型塗料組成物。
The active energy ray according to claim 1 or 2, wherein the component (C) includes at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer, and a lactam compound. A curable coating composition.
- 前記化合物(C1)が、アクリロイルモルホリン、N-ビニルホルムアミド、N-ビニルアセトアミド及びN-ビニル-ε-カプロラクタムから選ばれた少なくとも1種である請求項3に記載の活性エネルギー線硬化型塗料組成物。
The active energy ray-curable coating composition according to claim 3, wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. .
- 前記成分(C)が、イソシアヌル環を有する化合物(C2)を含み、該化合物(C2)の含有量が5~30重量部である請求項1~4のいずれかに記載の活性エネルギー線硬化型塗料組成物。
The active energy ray-curable type according to any one of claims 1 to 4, wherein the component (C) includes a compound (C2) having an isocyanuric ring, and the content of the compound (C2) is 5 to 30 parts by weight. Paint composition.
- 前記化合物(C2)が、アルキレンオキシド又はカプロラクトンにより変性されたラジカル重合性不飽和化合物である請求項5に記載の活性エネルギー線硬化型塗料組成物。
The active energy ray-curable coating composition according to claim 5, wherein the compound (C2) is a radically polymerizable unsaturated compound modified with alkylene oxide or caprolactone.
- 前記成分(C)の含有量が、前記成分(A)、前記成分(B)及び前記成分(C)の合計を100重量部としたときに、10~35重量部であり、
前記成分(C)が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも1種の化合物(C1)と、イソシアヌル環を有する化合物(C2)とからなり、両者の合計を10~35重量部とした場合に、前記化合物(C1)の含有割合が5~30重量部であり、前記化合物(C2)の含有割合が5~30重量部である請求項1~6のいずれかに記載の活性エネルギー線硬化型塗料組成物。 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,
The component (C) consists of at least one compound (C1) selected from morpholinyl group-containing monomers, amide group-containing monomers, and lactam compounds, and a compound (C2) having an isocyanuric ring. The content ratio of the compound (C1) is 5 to 30 parts by weight and the content ratio of the compound (C2) is 5 to 30 parts by weight when the total of both is 10 to 35 parts by weight. The active energy ray-curable coating composition according to any one of 1 to 6.
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JP2018150522A (en) * | 2017-03-13 | 2018-09-27 | 三洋化成工業株式会社 | Photocurable resin composition |
CN109369880A (en) * | 2018-10-08 | 2019-02-22 | 武汉大学 | A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application |
WO2021138191A1 (en) * | 2019-12-31 | 2021-07-08 | Dow Silicones Corporation | Method of preparing silicone-acrylate hybrid composition and hybrid composition formed thereby |
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JP6186032B1 (en) * | 2016-03-31 | 2017-08-23 | ハリマ化成株式会社 | Coating agent and coating film |
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JP5150759B1 (en) | 2011-09-06 | 2013-02-27 | 株式会社豊田自動織機 | Curable coating composition |
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WO2011048776A1 (en) * | 2009-10-21 | 2011-04-28 | 株式会社豊田自動織機 | Curable coating material composition |
WO2011048775A1 (en) * | 2009-10-21 | 2011-04-28 | 株式会社豊田自動織機 | Vehicle member and process for production thereof |
JP2011088996A (en) * | 2009-10-21 | 2011-05-06 | Toagosei Co Ltd | Photocurable coating composition |
WO2013035265A1 (en) * | 2011-09-06 | 2013-03-14 | 株式会社豊田自動織機 | Curable coating composition |
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JP2018150522A (en) * | 2017-03-13 | 2018-09-27 | 三洋化成工業株式会社 | Photocurable resin composition |
CN109369880A (en) * | 2018-10-08 | 2019-02-22 | 武汉大学 | A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application |
WO2021138191A1 (en) * | 2019-12-31 | 2021-07-08 | Dow Silicones Corporation | Method of preparing silicone-acrylate hybrid composition and hybrid composition formed thereby |
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CN104981525A (en) | 2015-10-14 |
TW201443172A (en) | 2014-11-16 |
JPWO2014157070A1 (en) | 2017-02-16 |
KR20150135243A (en) | 2015-12-02 |
CN104981525B (en) | 2017-03-08 |
JP6075443B2 (en) | 2017-02-08 |
KR102158660B1 (en) | 2020-09-22 |
TWI617630B (en) | 2018-03-11 |
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