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WO2015190544A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2015190544A1
WO2015190544A1 PCT/JP2015/066839 JP2015066839W WO2015190544A1 WO 2015190544 A1 WO2015190544 A1 WO 2015190544A1 JP 2015066839 W JP2015066839 W JP 2015066839W WO 2015190544 A1 WO2015190544 A1 WO 2015190544A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
compound
component
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/066839
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English (en)
Japanese (ja)
Inventor
佐内　康之
祐子 大田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toagosei Co Ltd
Original Assignee
Toagosei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Priority to KR1020167035079A priority Critical patent/KR102396700B1/ko
Priority to JP2016527854A priority patent/JP6465316B2/ja
Priority to CN201580030555.3A priority patent/CN106459329B/zh
Publication of WO2015190544A1 publication Critical patent/WO2015190544A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • 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

Definitions

  • the present invention relates to a curable composition containing urethane (meth) acrylate, and belongs to the technical field of active energy ray curable composition and paint / coating.
  • a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design.
  • the forming method is used.
  • the 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, it is required that the surface of the plastic substrate is coated with a coating composition and is subjected to a so-called hard coat treatment to impart scratch resistance and improve surface hardness.
  • an active energy ray-curable composition comprising (meth) acrylate having an alicyclic skeleton excellent in hardness of a cured film is known (Patent Document 1 and the same). 2).
  • Patent Document 3 a coating agent using photo-cationic polymerization of cyclic ether is known (Patent Document 3). It is disclosed in the Examples that this method has better adhesion and curl resistance than a coating agent using photoradical polymerization of (meth) acrylate.
  • a method of combining 4- (meth) acryloylmorpholine with tri- or higher functional (meth) acrylate having one or more hydroxyl groups is known as a coating agent that is not easily affected by humidity and has good adhesion (Patent Document 4). ). Good adhesion is obtained by using 4- (meth) acryloylmorpholine.
  • (Meth) acrylates having an alicyclic skeleton have a high glass transition point (Tg) and good hardness in many cases, but there is a tendency that adhesion to a substrate is difficult to obtain due to a large stress during active energy ray curing. is there.
  • Tg glass transition point
  • the adhesiveness with respect to a plastic base material is not disclosed in the Example.
  • a reactive polymer is produced in advance using a thermal polymerization initiator. If the thermal polymerization initiator used at this time remains, an active energy ray-curable composition is used. May be cured by polymerization during storage, and cannot be said to have sufficient stability.
  • the present inventors have intensively studied in order to find a curable composition having a cured film excellent in hardness, adhesion and flexibility, and having better curl resistance.
  • the inventors of the present invention have produced a urethane (meth) acrylate-containing reaction product that has excellent storage stability without producing turbidity even when produced without using an organic solvent. In order to find out the manufacturing method of the thing, earnest examination was performed.
  • the reason why the storage stability is reduced is the low molecular weight compound contained in the urethane (meth) acrylate-containing reaction product. It has been found that in order to reduce the molecular weight compound, this can be prevented by setting the hydroxyl value in the (meth) acrylic acid adduct of the starting aliphatic polyhydric alcohol compound to a specific value.
  • the curable composition containing the urethane (meth) acrylate-containing reaction product has flexibility that the cured film is excellent in hardness, adhesion and followability to deformation of the substrate, and has curl resistance. As a result, the present invention was completed. Hereinafter, the present invention will be described in detail.
  • the curable composition of the present invention since it is excellent in storage stability that does not generate turbidity during storage, it has good handling properties when used as a blending raw material for paints, coatings, and the like, and is further obtained.
  • the cured film has high hardness and excellent adhesion, flexibility and curl resistance.
  • the present invention relates to a (meth) acrylic acid adduct of pentaerythritol having a hydroxyl value of 180 to 300 mgKOH / g (hereinafter referred to as “compound (a1)”) and a polyvalent isocyanate compound (a2). )
  • compound (a2) relates to a curable composition containing a urethane (meth) acrylate-containing reaction product (A) obtained by reaction.
  • this invention relates also to the manufacturing method of the urethane (meth) acrylate containing reaction product which heats and mixes a compound (a1) and a compound (a2).
  • the raw material urethane (meth) acrylate-containing reaction product is preferably produced without using an organic solvent in an object or application in which it is preferable that the raw material does not contain an organic solvent or contains a small amount. That is, the organic solvent is not contained or the composition does not require a drying step, or the composition containing a small amount of the organic solvent can simplify the drying step.
  • a composition containing no or a small amount of an organic solvent can be suitably used in applications requiring thick coating.
  • a composition that does not contain an organic solvent contains a compound having a single (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) as a component of the composition.
  • the above-described curable composition of the present invention has excellent storage stability such that turbidity does not occur during storage. It has been found that when it is used as a raw material, it has good handling properties, and the resulting cured film has high hardness and excellent adhesion, flexibility and curl resistance.
  • the component (A) which is an essential component, other components, usage methods, and the like will be described.
  • the component (A) is a urethane (meth) acrylate-containing reaction product obtained by reacting the compound (a1) and the compound (a2).
  • the weight average molecular weight (hereinafter also referred to as “Mw”) of the component (A) is preferably 800 to 100,000, more preferably 1,000 to 10,000, and 1,200 to 5 Is more preferably 1,500, and particularly preferably 1,500 to 3,000.
  • Mw in the present invention means a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”).
  • GPC gel permeation chromatography
  • Compound (a1) is a (meth) acrylic acid adduct of pentaerythritol and has a hydroxyl value of 180 to 300 mgKOH / g.
  • the hydroxyl value of the compound (a1) is from 180 to 300 mgKOH / g, preferably from 190 to 290 mgKOH / g, and more preferably from 200 to 280 mgKOH / g.
  • the hydroxyl value of the compound (a1) is less than 180 mgKOH / g, the storage stability of the obtained component (A) is lowered, and the cured film of the resulting composition has hardness and adhesion to the substrate.
  • the followability to the deformation of the base material and the curl resistance are insufficient.
  • the hydroxyl value of the compound (a1) exceeds 300 gKOH / g, the molecular weight of the urethane (meth) acrylate in the component (A) obtained by the urethanization reaction becomes too high, and surface smoothness is obtained when it is used as a coating agent. It becomes worse or becomes incompatible with other components.
  • the hydroxyl value a value measured according to a method defined in JIS K0070-1992 is adopted.
  • the compound (a1) is preferably a compound obtained by an esterification reaction of pentaerythritol and (meth) acrylic acid.
  • (Meth) acrylic acid used in the reaction may be either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid, but only acrylic acid should be used. Is preferred.
  • (meth) acrylic acid instead of (meth) acrylic acid, (meth) acrylic acid equivalent, (meth) acrylic acid halide, (meth) acrylic anhydride, (meth) acrylic acid are used. Esters may be used.
  • the proportion of (meth) acrylic acid used is such that the hydroxyl value of the resulting (meth) acrylic ester is 180 to 300 mgKOH.
  • the molar amount of (meth) acrylic acid used is preferably less than the molar amount of the hydroxyl group of pentaerythritol to be used, preferably 0.75 to 1.25 molar equivalents relative to the total number of hydroxyl groups of pentaerythritol, More preferably, it is 0.85 to 1.15 molar equivalent.
  • Compound (a1) includes pentaerythritol tetra (meth) acrylate having no hydroxyl group (hereinafter referred to as “PETet”) and pentaerythritol tri (meth) acrylate having one hydroxyl group (hereinafter referred to as “PETri”). It is preferable to contain at least PETet, PETri, and more preferably at least dipentaerythritol di (meth) acrylate (hereinafter referred to as “PEDi”) having two hydroxyl groups.
  • PETet pentaerythritol tetra (meth) acrylate having no hydroxyl group
  • PETri pentaerythritol tri (meth) acrylate having one hydroxyl group
  • the proportion of PETet and PETri in the compound (a1) is preferably 50% by weight or more, more preferably 65% by weight or more, and still more preferably 80% by weight or less as the total amount of PETet and PETri. Furthermore, the ratio of PETet, PETri and PEDi in the compound (a1) is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 93% by weight or more as the total amount of PETet, PETri and PEDi. .
  • a catalyst an acid catalyst can be preferably exemplified.
  • a stabilizer well-known polymerization inhibitors, such as hydroquinone monomethyl ether, can be mentioned suitably.
  • oxygen is also preferable to use oxygen as a stabilizer, particularly a polymerization inhibitor.
  • unnecessary polymerization of (meth) acrylic acid or (meth) acrylate can be prevented by producing the compound (a1) in an oxygen-containing atmosphere.
  • the oxygen content in the atmosphere is preferably 1 to 20% by volume, more preferably 1 to 10% by volume.
  • the manufacturing method of a compound (a1) includes the method of refine
  • a compound having a hydroxyl value of 180 to 300 mgKOH / g can be easily produced.
  • the compound (a2) is a polyvalent isocyanate compound.
  • the compound (a2) is preferably a divalent isocyanate compound, and is preferably an aliphatic polyvalent isocyanate compound.
  • Specific examples of the preferred compound (a2) include aliphatic divalent isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and norbornane diisocyanate.
  • Aromatic divalent isocyanates such as xylene diisocyanate and diphenylmethane diisocyanate, and nurate trimers of these compounds.
  • a compound (a2) may be used individually by 1 type or may use 2 or more types together, it is preferable to use it individually by 1 type.
  • Component (A) is produced by urethanization of the hydroxyl group in compound (a1) and the isocyanate group in compound (a2).
  • the hardness of the obtained cured film is more excellent as it is the said aspect.
  • (A) component There is no restriction
  • the compound (a1) and the compound (a2) may be heated and stirred.
  • the obtained component (A) can be excellent in storage stability.
  • urethanization catalysts include organotin compounds such as dibutyltin dilaurate; acetylacetonate metal complexes such as iron acetylacetonate, zinc acetylacetonate and ruthenium acetylacetonate; metal organic weak acid salts such as lead naphthenate and potassium acetate And triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5; -Tertiary amine compounds such as diazabicyclo [4.3.0] nonene-5; and trialkylphosphine compounds such as triethylphosphine.
  • organotin compounds such as dibutyltin dilaurate
  • acetylacetonate metal complexes such as iron acetylacetonate, zinc
  • the ratio of the urethanization catalyst may be appropriately set according to the compound (a1), the compound (a2), the catalyst, etc. to be used, but is preferably 0.01 to 1,000 ppm by weight with respect to the reaction solution. Is 0.1 to 1,000 wtppm.
  • the reaction temperature may be appropriately set according to the type and ratio of the compound (a1), compound (a2) and catalyst used, and is preferably 60 to 130 ° C, more preferably 70 to 90 ° C.
  • reaction solvent can be blended in the reaction component.
  • the reaction solvent is preferably one that does not participate in the urethanization reaction, and examples thereof include aromatic compounds such as toluene and xylene, and organic solvents such as dimethylformamide.
  • the amount of the organic solvent to be used may be appropriately set according to the viscosity of the component (A), but is preferably set to be 0 to 70% by weight in the reaction solution.
  • the reaction solution means the total amount of the raw material compound when only the raw material compound is used, and means the total amount including these when the reaction solvent or the like is used in addition to the raw material compound. Specifically, it is used to mean a solution in which the compound (a1), the compound (a2) and a reaction solvent used as necessary are combined.
  • a small amount of a chain extender can be blended for the purpose of adjusting the molecular weight.
  • the chain extender those usually used in a urethanization reaction can be used.
  • Specific examples of the chain extender include low molecular weight polyols, polyether polyols, polycarbonate polyols and polyester polyols.
  • the low molecular weight polyol include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane, and the like.
  • Examples include polyols such as alkylene oxide adducts.
  • Examples of the polyether polyol include polyalkylene glycol having 3 or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • Examples of the polycarbonate polyol include a reaction product of carbonate and diol. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the diol include the low molecular weight polyol described above.
  • polyester polyol examples include a reaction product of an acid component with at least one selected from the group consisting of the low molecular weight polyol, the polyether polyol, and the polycarbonate polyol.
  • the acid component examples include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof.
  • the ring-opening reaction product of polycarbonate diol and caprolactone is also mentioned.
  • the proportion of the chain extender used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the total component (A) finally obtained.
  • the component (A) does not have an isocyanate group or a small amount of the isocyanate group is preferable from the viewpoint of hardness and stability.
  • a compound having two or more (meth) acryloyl groups hereinafter also referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) may be added.
  • hydroxyl group-containing polyfunctional (meth) acrylate various compounds can be used, which are (meth) acrylates derived from a trihydric or higher polyhydric alcohol, having two or more (meth) acryloyl groups, It is preferable that it is (meth) acrylate which has 1 or more.
  • hydroxyl group-containing polyfunctional (meth) acrylate examples include trimethylolpropane di (meth) acrylate, di (meth) acrylate of trimethylolpropane alkylene oxide adduct, di- or tri (meth) acrylate of pentaerythritol, penta Di or tri (meth) acrylate of alkylene oxide adduct of erythritol, di or tri (meth) acrylate of ditrimethylolpropane, di or tri (meth) acrylate of alkylene oxide adduct of ditrimethylolpropane, dipentaerythritol di, Di, tri, tetra or penta (meth) acrylate and isocyanurate alkylene oxide of tri, tetra or penta (meth) acrylate, dipentaerythritol alkylene oxide adduct Di (meth) acrylate of adduct, dipent
  • examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of ditrimethylolpropane and di, tri, tetra or penta (meth) acrylate of dipentaerythritol Preferably mentioned.
  • Component (A) is a urethane (meth) acrylate-containing reaction product, and PETri [tri (meth) acrylate of pentaerythritol] having one hydroxyl group contained in compound (a1) and PEDi [
  • urethane (meth) acrylate obtained by reacting a hydroxyl group such as di (meth) acrylate of pentaerythritol and an isocyanate group of compound (a2)
  • PETet penentaerythritol tetra (meth) acrylate
  • the component (A) preferably contains at least urethane (meth) acrylate and PETet, and contains at least urethane (meth) acrylate obtained by reacting PETri having one hydroxyl group with the compound (a2) and PETet.
  • at least acrylate and PETet are included.
  • the component (A) is preferably a mixture of urethane (meth) acrylate and PETet.
  • the hardness and adhesiveness of the cured film obtained are more excellent in the above range.
  • a compound having a molecular weight distribution of 1,000 or less in a molecular weight distribution measured by GPC of 20 area% or less is excellent in storage stability and has other ethylenically unsaturated groups This is preferable because the compatibility of the cured film is good and the adhesion of the resulting cured film to the substrate is good. This ratio is more preferably 5 to 18 area%.
  • a component having a molecular weight of 500 or less in the molecular weight distribution measured by GPC is 18 area% or less because it has excellent storage stability and can impart flexibility to the cured film. preferable. This ratio is more preferably 10 to 13 area%.
  • the molecular weight distribution measured by GPC in the present invention means a value measured under the following conditions.
  • ⁇ Detector Differential refractometer (RI detector) -Column type: Cross-linked polystyrene column-Column temperature: within the range of 25-50 ° C-Eluent: Tetrahydrofuran (hereinafter referred to as "THF")
  • the viscosity of the component (A) may be appropriately set according to the purpose.
  • the viscosity is preferably 8,000 to 600,000 mPa ⁇ s, more preferably 8,000 to 400,000 mPa ⁇ s. .
  • the viscosity of the component (A) when no organic solvent is contained means a value measured at 50 ° C. using an E-type viscometer.
  • the viscosity of the organic solvent solution of the component (A) may be appropriately set according to the purpose and depends on the concentration of the component (A).
  • the value measured at 25 ° C. using an E-type viscometer is preferably 10 to 600,000 mPa ⁇ s.
  • Curable composition The present invention relates to a curable composition containing the component (A) as an essential component.
  • a manufacturing method of a composition what is necessary is just to follow a conventional method, for example, it can manufacture by stirring and mixing (A) component and another component as needed. In this case, heating can be performed as necessary.
  • the heating temperature may be appropriately set according to the components contained in the composition to be used, the substrate on which the composition is coated, the purpose of use, etc., but is preferably 30 ° C. to 80 ° C.
  • the viscosity of the composition may be appropriately set according to the purpose, and is preferably 200 to 600,000 mPa ⁇ s for both a solventless composition containing no organic solvent and a solvent composition containing an organic solvent. More preferably, it is 200 to 400,000 mPa ⁇ s.
  • the above-mentioned viscosity range is preferable.
  • a value measured at 25 ° C. using an E-type viscometer 200 to 3,000 mPa ⁇ s is preferable.
  • the cured product of the composition of the present invention is excellent in hardness, flexibility and curl resistance.
  • the hardness has an effect that the pencil hardness of a cured film having a thickness of 1 to 30 ⁇ m formed on a plastic film having a thickness of 100 ⁇ m is H or more.
  • flexibility there exists an effect that the crack and peeling of a cured film are not seen in the core rod of diameter 5mm in a mandrel bending test.
  • the curl resistance has the effect that when the 100 ⁇ m thick plastic film with a cured film with a thickness of 1 to 30 ⁇ m is cut into 10 cm ⁇ 10 cm, the raised heights of the four corners are 8 mm or less. It is what you play.
  • composition of the present invention can be used as an active energy ray-curable composition and a thermosetting composition, and can be preferably used as an active energy ray-curable composition.
  • the composition of the present invention contains the component (A) as an essential component, but various components can be blended depending on the purpose.
  • Preferable examples of other components include compounds having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as “component (B)”], photopolymerization initiator [hereinafter referred to as “(C)”.
  • component (B) compounds having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as “component (B)”], photopolymerization initiator [hereinafter referred to as “(C)”.
  • Component ”] thermal polymerization initiator
  • component (E) ” organic solvent
  • component (B) component is a compound which has an ethylenically unsaturated group other than (A) component, and mix
  • the ethylenically unsaturated group in component (B) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, with a (meth) acryloyl group being preferred.
  • “monofunctional” means a compound having one ethylenically unsaturated group
  • “X function” means a compound having X ethylenically unsaturated groups
  • “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.
  • specific examples of the monofunctional ethylenically unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ⁇ -carboxy-polycaprolactone mono (meth) acrylate, monohydroxy phthalate Ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2- Ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of alkylphenol alkylene oxide adduct ) Acrylate, cyclohexyl (me
  • bifunctional (meth) acrylate compound examples include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tetramethylene glycol.
  • epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.
  • trifunctional or higher functional (meth) acrylate compound specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and tris (2- (meth) acryloyloxyethyl) isocyanurate.
  • a polyfunctional ethylenically unsaturated compound is included from a viewpoint of the hardness of the cured film obtained, and it is more preferable that a polyfunctional (meth) acrylate compound is included.
  • the component (B) preferably contains an ethylenically unsaturated compound having a hydroxyl group from the viewpoint of adhesion of the resulting cured film to the substrate and curl resistance, and a (meth) acrylate compound having a hydroxyl group It is more preferable that a monofunctional (meth) acrylate compound having a hydroxyl group is more preferable.
  • Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate are particularly preferable.
  • the component (B) is preferably a monofunctional ethylenically unsaturated compound and / or a bifunctional ethylenically unsaturated compound.
  • a component may contain individually by 1 type, or may contain 2 or more types.
  • the content ratio of the component (B) is preferably 3 to 60 parts by weight, more preferably 4 to 45 parts by weight, with respect to 100 parts by weight of the total amount of the components (A) and (B). It is particularly preferable that the amount be ⁇ 30 parts by weight. Within the above range, the cured film obtained is more excellent in curling resistance and hardness.
  • (C) Component When the composition of the present invention is used as an active energy ray curable composition and further used as an electron beam curable composition, the component (C) (photopolymerization initiator) is not contained, and the electron It can also be cured by a wire. When using the composition of this invention as an active energy ray hardening-type composition, it is preferable to further contain (C) component from a viewpoint of the ease of hardening or cost.
  • various known photopolymerization initiators can be used as the component (C) in the present invention.
  • the component (C) is preferably a radical photopolymerization initiator.
  • component (C) examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-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- (2-hydroxy-2-methylpropionyl) benzyl] pheny ⁇ Acetophenone compounds such as 2-methylpropan-1-one; Benzophenone compounds such as benzophenone, 4-phenylbenzophen
  • Phosphine oxide compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2- Acetophenone / benzophenone hybrid photoinitiators such as methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2- And oxime ester photopolymerization initiators such as octanedione; and camphorquinone.
  • benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether
  • titanocene compounds 1- [4- (4-benz
  • acetophenone compounds Among these, acetophenone compounds, benzophenone compounds, and phosphine oxide compounds are preferable, and acetophenone compounds are particularly preferable.
  • the component (C) only one type may be used, or two or more types may be used in combination.
  • the content ratio of the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the total amount of the curable components. It is particularly preferred that the amount be ⁇ 5 parts by weight.
  • the composition has excellent curability and the resulting cured film has excellent scratch resistance.
  • hardenable component is a component hardened
  • thermosetting composition When using a thermal-polymerization initiator composition as a thermosetting composition, a thermal-polymerization initiator can be mix
  • the composition of this invention can mix
  • Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
  • organic peroxide examples include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m
  • azo compound examples include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane, and the like. These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.
  • the amount of these thermal polymerization initiators used is preferably not more than 10 parts by weight with respect to 100 parts by weight of the total amount of curable components.
  • the thermal polymerization initiator may be carried out in accordance with conventional means of normal radical thermal polymerization.
  • the thermal polymerization initiator is used in combination with a photopolymerization initiator and photocured for the purpose of further improving the reaction rate. Curing can also be performed.
  • composition of the present invention preferably further contains (E) an organic solvent from the viewpoints of applicability and handleability of the composition.
  • organic solvent Various known organic solvents can be used as the organic solvent in the present invention.
  • As a component what melt
  • Preferred specific examples of the component (E) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, Aromatic compounds such as toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Is mentioned.
  • an alkylene glycol monoether compound and a ketone compound are preferable, and an alkylene glycol monoether compound is more preferable.
  • component (E) only one type may be used, or two or more types may be used in combination.
  • the content of component (E) is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is part by weight.
  • the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.
  • composition of the present invention may further contain other components other than the components (A) to (E).
  • known additives can be used.
  • Other components described later may be used alone or in combination of two or more.
  • UV absorber examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) 1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyl
  • benzotriazole ultraviolet absorbers are particularly preferable.
  • the content of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1 to 2 parts by weight.
  • a known light stabilizer can be used.
  • a hindered amine light stabilizer HALS
  • Specific examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
  • the content ratio of the ultraviolet absorber is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is 1 to 1 part by weight.
  • the composition of this invention is excellent in the adhesive material to base materials, such as a plastics, adhesiveness can be improved further by adding an acidic substance.
  • the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, and the like.
  • inorganic acids or organic acids are preferable, organic sulfonic acid compounds are more preferable, aromatic sulfonic acid compounds are more preferable, and p-toluenesulfonic acid is particularly preferable.
  • the content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and more preferably 0.0005 to 100 parts by weight of the total amount of the curable components. More preferably, it is 0.5 parts by weight. Within the above range, the adhesion to the substrate is excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.
  • metal oxide particles are preferable.
  • the metal oxide particles are preferably metal oxide particles or composite metal oxide particles made of one or more metals selected from the group consisting of silicon, zirconium, titanium, antimony, tin, cerium, aluminum, zinc and indium. Can be mentioned.
  • the average particle size of the inorganic particles may be selected according to the use, but is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and particularly preferably 10 to 100 nm. Within the above range, the transparency and appearance of the cured film are good.
  • the average particle diameter of the inorganic particles means a particle diameter when assuming that the particles are true spherical particles from the specific surface area of the sample obtained by the BET method.
  • the inorganic particles may be surface-modified particles.
  • the surface modifier a known one can be used, and a silane coupling agent, a titanium coupling agent, and the like are preferable.
  • a silane coupling agent is more preferable, and a compound having an ethylenically unsaturated group and an alkoxysilyl group is particularly preferable. It is excellent in the hardness and curl resistance of the cured film obtained as it is the said aspect.
  • Specific examples of the silane coupling agent include the same compounds as those described below.
  • the surface modification amount of the inorganic particles is not particularly limited, but the ratio of the surface modifier to the inorganic particles is 1.0 to 45.0% by weight with respect to the total weight of the surface modifier and the inorganic particles. It is preferable to have made it react with.
  • the content of the inorganic particles is preferably 25 to 400 parts by weight, more preferably 30 to 200 parts by weight, and more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably. It is excellent in transparency, adhesiveness, abrasion resistance, and curl resistance of the cured film obtained as it is the said aspect.
  • the composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
  • an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
  • examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • Preferred examples of the phenolic antioxidant include hindered phenols such as di-t-butylhydroxytoluene.
  • Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
  • phosphorus antioxidant examples include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like.
  • examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010.
  • Etc examples of the sulfur-based antioxidant include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
  • the content of the antioxidant is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable components.
  • the composition is excellent in stability, and curability and adhesive strength are good.
  • the composition of the present invention may further contain a silane coupling agent for the purpose of improving the adhesion to the substrate.
  • the silane coupling agent used in the present invention is not particularly limited, and a known silane coupling agent can be used.
  • silane coupling agent examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Sidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyltrimeth
  • the content of the silane coupling agent is preferably 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable components. It is excellent in adhesiveness with a base material as it is the said range.
  • a surface modifier may be added for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like.
  • the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. . Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred.
  • silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain silicone polymers and oligomers having a silicone chain and a polyester chain
  • fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
  • a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.
  • the content ratio of the surface modifier is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the total amount of the curable components. It is excellent in the surface smoothness of a coating film as it is the said range.
  • the composition of the present invention may further contain a polymer other than the component (A) for the purpose of further improving the curl resistance of the resulting cured film.
  • Suitable polymers include (meth) acrylic polymers, 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.
  • the content ratio of the polymer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable components. It is excellent in the curl resistance of the cured film obtained as it is the said range.
  • the composition of the present invention can be cured by irradiation with active energy rays or by heating to obtain a cured product.
  • the composition is applied to a substrate to be applied by a normal coating method, and then in the case of an active energy ray-curable composition, an active energy ray.
  • a method of heating and curing may be used.
  • the composition is injected into a predetermined mold and then cured in the case of an active energy ray curable composition by irradiation with active energy rays, or a thermosetting composition.
  • the method of heating and hardening etc. is mentioned.
  • a general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
  • (C) component (photopolymerization initiator) and (D) component (thermal polymerization initiator) are used in combination with the composition, irradiated with active energy rays, and then heat-cured, thereby adhering to the substrate.
  • a method for improving the property can also be adopted.
  • the substrate to which the composition of the present invention can be applied is applicable to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
  • plastics include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
  • the wood include natural wood and synthetic wood.
  • the metal examples include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
  • metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
  • inorganic materials include glass, mortar, concrete, and stone. Among these, a plastic substrate is particularly preferable.
  • the method of applying the composition of the present invention to the substrate may be appropriately set according to the purpose, and is a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma.
  • the coating method include a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, and a micro gravure coater.
  • the thickness of the cured film may be selected according to the use of the substrate to be used or the substrate having the produced cured film, but is preferably 1 to 100 ⁇ m, more preferably 5 to 40 ⁇ m. .
  • the composition is an active energy ray-curable composition and contains an organic solvent
  • it is heated and dried to evaporate the organic solvent.
  • the drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation.
  • Examples of the active energy rays for curing the composition of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are particularly preferable.
  • Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (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 2,000 mJ / cm 2 is more preferable.
  • composition of the present invention can be used for various applications, preferably as an active energy ray-curable composition, and specifically, coating agents such as paints, inks, nanoimprints, and lens sheets.
  • coating agents such as paints, inks, nanoimprints, and lens sheets.
  • examples include resins, resin films, and adhesives.
  • a cured product obtained by curing the active energy ray-curable composition of the present invention, particularly a cured film, is excellent in hardness, adhesion to a substrate, followability to deformation of the substrate, and curl resistance. It can be preferably used as a coating agent.
  • a so-called hard coat coating agent based on a plastic can be preferably used.
  • 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.
  • Examples of using metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.
  • the resin film produced from the composition of the present invention can be preferably used particularly as an optical film.
  • the optical film formed from the composition of the present invention can be used for various optical applications. More specifically, a film used for a liquid crystal display device such as a polarizer protective film for a polarizing plate, a support film for a prism sheet, and a light guide film, and a touch panel integrated liquid crystal display device, various functional films (for example, hard coat) Films, decorative films, transparent conductive films) and surface films (for example, moth-eye type antireflection films and films with a texture structure for solar cells), light resistance for outdoor use such as solar cells (weather resistance) ) Applications such as films, films for LED lighting / organic EL lighting, and transparent heat-resistant films for flexible electronics.
  • a film used for a liquid crystal display device such as a polarizer protective film for a polarizing plate, a support film for a prism sheet, and a light guide film, and a touch panel integrated liquid crystal display device
  • a transparent conductive film in a cover-integrated touch panel in which a touch sensor such as ITO is directly formed on the cover glass of the touch panel, plastic is used as the cover material instead of glass, and the touch sensor such as ITO is directly applied to the plastic. It can also be used for so-called OPS (One Plastic Solution).
  • OPS One Plastic Solution
  • Production example 1 Raw material production example 1 [ Production of compound (a1)] Since nitrogen gas containing 5% by volume of oxygen was not blown into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a blower, 301 parts (4.18 mol) of acrylic acid, pentaerythritol [Kouei Chemical Co., Ltd. ) Made. Hereinafter, it is referred to as “PE”. 167 parts (1.23 mol), 7 parts of sulfuric acid, 0.14 part of hydroquinone monomethyl ether (hereinafter referred to as “MEHQ”) and 224 parts of toluene were mixed, and the reaction temperature was about 80 ° C.
  • MEHQ hydroquinone monomethyl ether
  • Raw material production example 2 [ Production of compound (a1)] Condensed water was used under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 moles) of acrylic acid, 167 parts (1.23 moles) of PE, 7 parts of sulfuric acid, 0.14 parts of MEHQ and 224 parts of toluene were used. While removing, the reaction was continued until 30% of all hydroxyl groups in the PET were esterified. The generated condensed water was 18 parts, and 83.5 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
  • Raw material production example 3 [ Production of compound (a1)] Condensation under the same conditions as in Raw Material Production Example 1 except that 301 parts (4.18 moles) of acrylic acid, 167 parts (1.23 moles) of PE, 7 parts of sulfuric acid, 0.14 parts of MEHQ and 224 parts of toluene are used. While removing water, the reaction was continued until 15% of all hydroxyl groups in the PET were esterified. The generated condensed water was 10 parts, and 101 parts of unreacted PE was recovered. After completion of the reaction, 870 parts of toluene was added.
  • reaction mixture was cooled and a 20% aqueous sodium hydroxide solution (32 parts) was added to the reaction solution to neutralize the strong acid catalyst.
  • reaction liquid (1,959 parts) into a separatory funnel, then add cyclohexane (600 parts), methyl ethyl ketone (2,400 parts), and further water (1,250 parts), mix, and leave the liquid to stand. Separation was performed and the lower layer was extracted to separate the organic phase.
  • an equimolar amount of 20% aqueous sodium hydroxide solution (840 parts) was added with stirring to the acid content of the organic phase to carry out neutralization treatment.
  • the organic phase was separated and washed with water. After washing with water, the organic phase was again separated and heated under reduced pressure to distill off the solvent.
  • the obtained acrylate was 874 parts, and the hydroxyl value was 280 mgKOH / g.
  • the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-1)”) had a molecular weight measured by GPC under the following conditions of polystyrene conversion, Mw of 2,026, and a viscosity at 50 ° C. of 13, It was 800 mPa ⁇ s.
  • Components having a molecular weight of 1000 or less obtained by GPC measurement under the following conditions were 16 area%, and components having a molecular weight of 500 or less were 14 area%.
  • ⁇ GPC measurement conditions / apparatus GPC system name manufactured by Waters Co., Ltd. 1515 2414 717P RI Detector: RI detector
  • Production Example 4 [Production of Component (A)] Same as Production Example 1 except that 100 parts of the compound (a1) (hydroxyl value: 224 mgKOH / g) obtained in Raw Material Production Example 2 was used and 42 parts of isophorone diisocyanate (hereinafter referred to as “IPDI”) was appropriately reduced. The urethanization reaction was performed. The resulting urethane acrylate-containing reaction product (hereinafter referred to as “(UA-4)”) had an Mw of 2,290 and a viscosity at 50 ° C. of 350,000 mPa ⁇ s. Components having a molecular weight of 1,000 or less obtained by GPC measurement were 14 area%, and components having a molecular weight of 500 or less were 13 area%.
  • IPDI isophorone diisocyanate
  • (UA-5) Mw of the obtained urethane acrylate-containing reaction product (hereinafter referred to as “(UA-5)”) is 3,825, and the viscosity at 25 ° C. of an EtOA solution containing 61% by weight of (UA-5) is 168 mPa ⁇ It was s.
  • Components having a molecular weight of 1000 or less obtained by GPC measurement were 7.5 area%, and components having a molecular weight of 500 or less were area 6.9%. This value is a value excluding the solvent EtOA.
  • (UA′-1) had an Mw of 1,350 and a viscosity at 25 ° C. of 29,900 mPa ⁇ s.
  • Components having a molecular weight of 1,000 or less obtained by GPC measurement were 32 area%, and components having a molecular weight of 500 or less were 26 area%.
  • Comparative production example 2 [ Production of urethane acrylate other than component (A)] A urethanization reaction was carried out in the same manner as in Production Example 1 except that 100 parts of an acrylate of pentaerythritol having a hydroxyl value of 163 mg KOH / g obtained in Comparative Raw Material Production Example 1 was used and 23 parts of HDI was appropriately adjusted.
  • the resulting urethane acrylate-containing reaction product (hereinafter referred to as “(UA′-2)”) had an Mw of 1,650 and a viscosity at 50 ° C. of 5,500 mPa ⁇ s.
  • Components having a molecular weight of 1,000 or less obtained by GPC measurement were 18 area%, and components having a molecular weight of 500 or less were 16 area%.
  • Tables 1 and 2 summarize the physical properties of the raw material compounds used and the resulting urethane acrylate-containing reaction products in Production Examples 1 to 6 and Comparative Production Examples 1 to 3.
  • the storage stability was evaluated by the following method. In a 100 ml screw can, 60 g of urethane acrylate reaction product was placed and allowed to stand at room temperature. The lid was periodically opened, and the time course of the reaction product was visually observed to confirm the presence or absence of precipitates.
  • the obtained composition was applied to a polyethylene terephthalate film A-4300 (film thickness: 100 ⁇ m, hereinafter referred to as “PET film”) manufactured by Toyobo Co., Ltd. using a bar coater # 8 so that the film thickness after drying was 5 ⁇ m. And dried for 3 minutes in a dryer at 100 ° C. After drying, using a high-pressure mercury lamp equipped with a conveyor (H06-L 41 manufactured by Eye Graphics Co., Ltd., lamp output 80 W / cm), UV-A illuminance 450 mW / cm 2 and irradiation energy 200 mJ / cm 2 Was irradiated. The obtained cured film was used and evaluated according to the following method. The results are shown in Tables 3 and 4.
  • Flexibility According to a mandrel test (JIS K5600-5-1), a PET film having a cured film formed around a core rod having a diameter of 3 mm to 10 mm was wound, and the minimum diameter at which the cured film was not cracked or peeled was evaluated.
  • the composition of the present invention is excellent in all of hardness, adhesion, scratch resistance, curl resistance and flexibility, and maintains a good surface hardness. However, it had both flexibility.
  • the compositions of Comparative Examples 1 to 3 are compositions containing urethane acrylate produced from a raw material having a hydroxyl value of less than 180 mgKOH / g, and the compositions of Comparative Examples 1 and 2 have a hardness of
  • the composition of Comparative Example 3 is excellent in hardness, adhesion, scratch resistance, and flexibility, but is inferior in curling resistance, although it is excellent in scratch resistance. Hardness and flexibility were not compatible.
  • composition of the present invention can be used for various uses such as a coating agent, ink, shaping resin, resin film and adhesive, preferably as an active energy ray hardening composition, and the resulting cured film has a surface hardness. , Since it can achieve both adhesion and flexibility, it can be preferably used as a coating agent composition.

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Abstract

[Problème] Le problème abordé par la présente invention est la fourniture d'une composition durcissable ayant une dureté, une adhérence et une flexibilité supérieures d'un film durci de celle-ci, ayant une plus grande supériorité de résistance au roulage, et une stabilité de conservation supérieure de sorte qu'un trouble n'apparaisse pas, même après une conservation à long terme. [Solution] La présente invention concerne une composition durcissable qui contient un produit de réaction d'uréthane-(méth)acrylate (A) résultant de la réaction de : un composé (a1) qui est le résultat de l'ajout d'acide (méth)acrylique à du pentaérythritol et qui a un indice d'hydroxyle de 180 à 300 mgKOH/g ; et un composé d'isocyanate polyvalent (a2).
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017002102A (ja) * 2015-06-04 2017-01-05 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
JP2017002104A (ja) * 2015-06-04 2017-01-05 Dic株式会社 ウレタン（メタ）アクリレート樹脂及び積層フィルム
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