WO2019151123A1 - モノマー混合物、及びそれを含む硬化性組成物 - Google Patents
モノマー混合物、及びそれを含む硬化性組成物 Download PDFInfo
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- WO2019151123A1 WO2019151123A1 PCT/JP2019/002386 JP2019002386W WO2019151123A1 WO 2019151123 A1 WO2019151123 A1 WO 2019151123A1 JP 2019002386 W JP2019002386 W JP 2019002386W WO 2019151123 A1 WO2019151123 A1 WO 2019151123A1
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
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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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/18—Oxetanes
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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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
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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
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
Definitions
- the present invention relates to a monomer mixture and a curable composition containing the monomer mixture.
- the ink jet recording method in which printing is performed by flying ink droplets onto a recording medium to form recording dots, is suitably used for applications in which a large number of products are printed in small quantities because an original plate is not required.
- inkjet inks used in this inkjet recording method cationic curable inks and radical curable inks are known.
- the radical curable ink has been frequently used because it has a fast curing property and has many types of monomers.
- low-viscosity ink is used from the viewpoint of dischargeability, and oxygen easily diffuses and enters the ink from the atmosphere.
- the ink is printed as small droplets, the surface area is increased and the ink is easily exposed to oxygen. Therefore, the inhibition of curing due to oxygen becomes remarkable, and there is a problem in that a large amount of unreacted monomer that causes bleeding or odor remains.
- Another problem is that the substrate adhesion is low and it is necessary to process the substrate surface in order to improve the adhesion of the ink.
- the cationic curable ink is not inhibited by oxygen from being cured.
- the substrate adhesion is superior to radical curable inks.
- a cation curable composition containing alicyclic epoxy compound, di- or trivinyl ether compound, and 3-alkyl-3-hydroxyalkyloxetane as monomers has low viscosity and was used as an inkjet ink. In some cases, it is described that it exhibits excellent ejection properties, and is cured rapidly by irradiating with ultraviolet rays to form a cured product having excellent substrate adhesion and high hardness.
- the cured product of the cationic curable composition described in Patent Document 1 is excellent in adhesion to plastics, but has low adhesion to metals and glass. It was necessary to perform surface processing such as primer treatment on glass and glass. Further, it was found that the inhibition of curing is remarkable in a high humidity environment where the humidity is 50% RH or more.
- the object of the present invention is as a raw material of a curable composition that cures quickly even in a high humidity environment and forms a cured product having excellent adhesion to not only paper and plastic but also metal and glass. It is to provide a useful monomer mixture. Another object of the present invention is to provide a curable composition comprising the monomer mixture and a curing catalyst. Another object of the present invention is to provide a curable composition useful as an ultraviolet curable inkjet ink, a coating agent, or an adhesive. Another object of the present invention is to provide a cured product having excellent adhesion to metal and glass as well as paper and plastic. Another object of the present invention is to provide a cured product or a molded product of the curable composition. Another object of the present invention is to provide a structure provided with a cured product of the curable composition on a substrate.
- a monomer mixture containing a specific cationic polymerizable monomer in a specific ratio has excellent curing sensitivity when added with a curing catalyst. It has been found that by irradiating, a cured product having excellent adhesion to not only paper and plastic but also metal and glass can be formed even in a high humidity environment. The present invention has been completed based on these findings.
- the present invention is a monomer mixture composed of two or more kinds of cationically polymerizable monomers, wherein the cationically polymerizable monomer includes a compound (A) having a vinyl ether group and a hydroxyl group, and a compound having an oxetanyl group and a hydroxyl group.
- (B) and the following formula (c) (Wherein X represents a single bond or a linking group)
- the total content of the compound (A), the compound (B), and the compound (C) is 50% by weight or more of the total amount of the monomer mixture, and the compound (A) Provided is a monomer mixture in which the content [A] and the content [B] of the compound (B) satisfy the following formula (1).
- the present invention also provides a monomer (D) (excluding a compound having a hydroxyl group) in which two or more vinyl ether groups are bonded to an alicyclic skeleton or a non-aromatic heterocyclic skeleton as a cationic polymerizable monomer.
- a monomer mixture as described above containing 1-10% by weight of the total mixture.
- the present invention also provides the monomer mixture further containing, as a cationic polymerizable monomer, a compound (E) having two or more oxetanyl groups (excluding compounds having a hydroxyl group) in an amount of 15 to 40% by weight based on the total amount of the monomer mixture.
- a compound (E) having two or more oxetanyl groups excluding compounds having a hydroxyl group
- I will provide a.
- the present invention also provides a curable composition containing the monomer mixture and a curing catalyst.
- the present invention also provides the curable composition containing a sensitizer or a sensitizer and a sensitization aid.
- the present invention also provides the curable composition containing a coloring material.
- the present invention also provides the above curable composition containing a dispersant.
- the present invention also provides the curable composition as described above, which is an ultraviolet curable inkjet ink.
- the present invention also provides the above curable composition which is a coating agent.
- the present invention also provides the above curable composition which is an adhesive.
- the present invention also provides a cured product of the curable composition.
- the present invention is also a cured product of a curable composition containing a cationically polymerizable monomer, and has adhesion to a paper substrate, a plastic substrate, a metal substrate, and a glass substrate according to JISJK 5600-5-5.
- a cured product having a classification of 0 to 2 in a 6-stage classification test by a cross-cut method according to 6 is provided.
- the present invention also provides a molded article made of the cured product.
- the present invention also provides a molded article made of a cured product of the curable composition through a step of ejecting the curable composition by an inkjet method and then curing the ejected curable composition.
- a method for producing a molded article is provided.
- the present invention also provides a structure provided with the above cured product on the surface of a substrate.
- the “oxetanyl group” is a group having a 4-membered saturated aliphatic hydrocarbon ring structure containing one oxygen atom
- the “epoxy group” is containing one oxygen atom. This is a group having a 3-membered saturated aliphatic hydrocarbon ring structure.
- the curable composition obtained by blending the curing catalyst with the monomer mixture of the present invention having the above-described structure is low in viscosity and excellent in coating properties before being irradiated with ultraviolet rays, and is irradiated with ultraviolet rays even in a high humidity environment. It can be cured rapidly to form a cured product having excellent adhesion to not only paper and plastic but also metal and glass. Therefore, the said curable composition can be used conveniently as an ultraviolet curable inkjet ink, a coating agent, an adhesive agent, etc.
- the monomer mixture of the present invention is extremely useful as a raw material for a curable composition having the above characteristics.
- the curable composition is used as an ultraviolet curable ink-jet ink, it has a low viscosity and excellent ejection properties. Even under high humidity, it can be applied directly to the surface of a metal or glass, and then cured. An ink film having high accuracy and excellent adhesion can be formed.
- the cured product of the present invention has excellent adhesion to metal and glass as well as paper and plastic. Therefore, if the hardened
- the monomer mixture of the present invention is a monomer mixture composed of two or more kinds of cationically polymerizable monomers, and has, as the cationically polymerizable monomer, a compound (A) having a vinyl ether group and a hydroxyl group, an oxetanyl group and a hydroxyl group.
- the compound (B) and the compound (C) represented by the formula (c) are contained.
- the monomer mixture of the present invention may further contain a compound (D) in which two or more vinyl ether groups are bonded to an alicyclic skeleton or a non-aromatic heterocyclic skeleton, and does not have a hydroxyl group. Moreover, it may further contain a compound (E) having two or more oxetanyl groups and not having a hydroxyl group.
- the compound (A) is a compound having at least one vinyl ether group and a hydroxyl group, and is a cationically polymerizable monomer.
- the cured product obtained by curing the curable composition containing the compound (A) has high hardness and toughness because the vinyl ether group and the hydroxyl group of the compound (A) are polymerized to form a highly crosslinked structure. Have.
- the compound (a) having one vinyl ether group and one hydroxyl group in one molecule from the viewpoints of increasing the hardness of the cured product, reducing the shrinkage of curing, and improving adhesion. Is preferred.
- the compound (a) is represented by the following formula, for example. HO—R a —CH ⁇ CH 2 (a-1) (Wherein, R a represents a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which these are bonded via a single bond or a linking group)
- the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
- divalent aliphatic hydrocarbon group examples include a linear or branched alkylene group having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- a linear or branched alkenylene group having 2 to 18 carbon atoms such as vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene group; ethynylene, propynylene, 3- Examples thereof include linear or branched alkynylene groups having 2 to 18 carbon atoms such as methyl-1-propynylene, butynylene and 1,3-butadienylene groups.
- the alicyclic ring constituting the divalent alicyclic hydrocarbon group includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring.
- the polycyclic hydrocarbon ring includes a spiro hydrocarbon ring, a ring An aggregated hydrocarbon ring, a bridged cyclic hydrocarbon ring, a fused ring hydrocarbon ring, and a bridged fused ring hydrocarbon ring are included.
- Examples of the divalent alicyclic hydrocarbon group include groups obtained by removing two hydrogen atoms from the structural formula of the alicyclic ring.
- Examples of the monocyclic hydrocarbon ring include C 3-12 cycloalkane rings such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane; C 3-12 cycloalkene rings such as cyclopentene and cyclohexene. Is mentioned.
- spiro hydrocarbon ring examples include C 5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, and spirobicyclohexane.
- ring assembly hydrocarbon ring examples include a ring assembly hydrocarbon ring including two or more C 5-12 cycloalkane rings such as bicyclohexane .
- bridged cyclic hydrocarbon ring examples include pinane, bornane, norpinane, norbornane, norbornene, bicycloheptane, bicycloheptene, bicyclooctane (bicyclo [2.2.2] octane, bicyclo [3.2.1] octane, etc.
- Bicyclic hydrocarbon rings such as homobredane, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [4.3.1.1 2,5 ] undecane, etc. Ring: Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodecane, tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene, and the like.
- Examples of the condensed cyclic hydrocarbon ring include 5 to 8 members such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydrophenalene and the like. Examples thereof include a condensed ring in which a plurality of cycloalkane rings are condensed.
- bridged condensed cyclic hydrocarbon ring examples include diene dimers (for example, dimers of cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like.
- diene dimers for example, dimers of cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene
- hydrogenated products thereof and the like.
- divalent aromatic hydrocarbon group examples include arylene groups having 6 to 18 carbon atoms such as a phenylene group, a biphenylene group, and a naphthylene group.
- the hydrocarbon group includes various substituents [for example, halogen atom, oxo group, substituted oxy group (for example, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxy group). Carbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] Good.
- the carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- an aromatic or non-aromatic heterocyclic ring may be condensed with the alicyclic ring constituting the alicyclic hydrocarbon group or the aromatic ring constituting the aromatic hydrocarbon group.
- the heterocyclic ring constituting the divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring.
- a heterocyclic ring containing an oxygen atom as a hetero atom for example, a 4-membered ring such as an oxetane ring) Ring; 5-membered ring such as furan ring, tetrahydrofuran ring, oxazole ring, isoxazole ring, ⁇ -butyrolactone ring; 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; benzofuran ring, iso-ring Condensed ring such as benzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring; 3-oxatricyclo [4.3.1.1 4,8 ] undecan-2-one ring, 3-oxatricyclo
- the heterocyclic group may be an alkyl group (for example, a C 1-4 alkyl group such as a methyl group or an ethyl group), a cycloalkyl group, an aryl group (For example, a phenyl group, a naphthyl group, etc.) may be included.
- alkyl group for example, a C 1-4 alkyl group such as a methyl group or an ethyl group
- a cycloalkyl group for example, a phenyl group, a naphthyl group, etc.
- divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the structural formula of the heterocyclic ring.
- linking group examples include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (-OCOO-) and the like.
- R a is preferably a divalent hydrocarbon group, or a divalent group in which two or more of the hydrocarbon groups are bonded via a linking group, particularly preferably a divalent aliphatic hydrocarbon group, Or a divalent group in which two or more aliphatic hydrocarbon groups are bonded via a linking group, most preferably a linear or branched alkylene group having 1 to 18 carbon atoms, or a C 1 to 18 carbon group.
- a group in which two or more linear or branched alkylene groups are bonded via a linking group particularly preferably a linear or branched alkylene group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms are groups in which two or more of the linear or branched alkylene groups are bonded via a linking group.
- the linking group is preferably an ether bond.
- the compound (A) preferably contains at least one selected from the compounds represented by the following formulas (a-1-1) to (a-1-3).
- the compound (B) is a compound having at least one oxetanyl group and a hydroxyl group, and is a cationically polymerizable monomer.
- the compound (B) does not include a compound containing a vinyl ether group.
- the curable composition containing the compound (B) is excellent in curability, and the cured product obtained by curing the curable composition has excellent adhesion to metal and glass.
- the compound (B) having one oxetanyl group and one hydroxyl group is preferable in that the obtained cured product has both high hardness and low curing shrinkage.
- the compound (b) is represented by the following formula (b-1), for example.
- HO—R b —Y (b-1) (In the formula, R b represents a divalent hydrocarbon group, a divalent heterocyclic group, or a divalent group in which these are bonded via a single bond or a linking group, and Y represents an oxetanyl group)
- R b examples include the same examples as R a described above.
- R b is preferably a divalent hydrocarbon group, particularly preferably a divalent aliphatic hydrocarbon group, most preferably a linear or branched alkylene group having 1 to 18 carbon atoms, especially A linear or branched alkylene group having 1 to 6 carbon atoms is preferred.
- Compound (C) is a compound represented by the following formula (c) and is a cationically polymerizable monomer.
- the compound (C) does not include a compound containing a vinyl ether group or an oxetanyl group.
- the curable composition containing the compound (C) has fast curability, and the cured product obtained by curing the curable composition has high hardness.
- X represents a single bond or a linking group.
- the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group (—CO—), an ether bond (—O—), Examples include an ester bond (—COO—), a carbonate bond (—O—CO—O—), an amide bond (—CONH—), and a group in which a plurality of these are linked.
- Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms.
- Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
- Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, and a 1,2-cyclohexylene group. Cycloalkylene groups (including cycloalkylidene groups) such as 1,3-cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.
- alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and the like.
- the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
- a substituent may be bonded to the cyclohexene oxide group in the above formula (c).
- the substituent include a halogen atom, a C 1-10 alkyl group, a C 1-10 alkoxy group, C 2 -10 alkenyloxy group (excluding vinyl ether group), C 6-14 aryloxy group, C 7-18 aralkyloxy group, C 1-10 acyloxy group, C 1-10 alkoxycarbonyl group, C 6-14 aryloxycarbonyl Group, C 7-18 aralkyloxycarbonyl group, epoxy group-containing group, C 1-10 acyl group, isocyanate group, sulfo group, carbamoyl group, oxo group and the like.
- Representative examples of the compound represented by the above formula (c) include (3,4,3 ′, 4′-diepoxy) bicyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2- Epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxycyclohexane-1-yl) propane, 1,2-bis (3,4- And epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (c-1) to (c-8).
- L represents an alkylene group having 1 to 8 carbon atoms (preferably a linear or branched chain having 1 to 3 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group, etc. A chain-like alkylene group).
- n 1 and n 2 each represent an integer of 1 to 30.
- Compound (D) is a compound (D) in which two or more vinyl ether groups are bonded to an alicyclic skeleton or a non-aromatic heterocyclic skeleton, and is a cationically polymerizable monomer.
- the compound (D) does not include a compound containing a hydroxyl group or a compound containing an epoxy group.
- the curable composition containing the compound (D) has fast curability, and the cured product obtained by curing the curable composition has high hardness.
- Examples of the compound (D) include compounds represented by the following formula (d).
- s-valent alicyclic hydrocarbon group or a non-aromatic heterocyclic group examples similar to the above R a is Can be mentioned.
- s-valent (s ⁇ 3) alicyclic hydrocarbon group or non-aromatic heterocyclic group from the structural formula of the divalent alicyclic hydrocarbon group or non-aromatic heterocyclic group. , (S-2) groups excluding hydrogen atoms.
- the s-valent alicyclic hydrocarbon group or non-aromatic heterocyclic group may have a substituent (for example, an alkyl group having 1 to 3 carbon atoms).
- the compound (D) includes, among others, a compound in which two or more vinyl ether groups are bonded to a non-aromatic heterocyclic skeleton and / or a compound in which two or more vinyl ether groups are bonded to an alicyclic skeleton.
- the compound (D) it is particularly preferable to contain at least the compound (d), and in particular, a compound represented by the above formula (d-1) and / or a compound represented by the above formula (d-2). It is preferable to contain at least.
- Compound (E) is a compound having two or more oxetanyl groups.
- the compound (E) does not include a compound containing a hydroxyl group, a compound containing an epoxy group, or a compound containing a vinyl ether group.
- the curable composition containing the compound (E) is excellent in curability, and the cured product obtained by curing the curable composition has excellent adhesion to metal and glass.
- Examples of the compound (E) include compounds represented by the following formula (e).
- R e- (Y) t (e) (Wherein, R e represents a t-valent organic group, Y .t showing an oxetanyl group is an integer of 2 or more)
- the t-valent organic group in R e includes a t-valent hydrocarbon group, a t-valent heterocyclic group, and a t-valent group in which two or more of these are bonded through a single bond or a linking group.
- Examples of the t-valent hydrocarbon group and the t-valent heterocyclic group include a divalent hydrocarbon group and a divalent heterocyclic group in Ra above, and a t-valent group corresponding thereto.
- Examples of the linking group include the same examples as the linking group for Ra .
- As the linking group an ether bond is preferable.
- These groups may have a substituent, and examples of the substituent include the same examples as the substituent which the hydrocarbon group in Ra may have.
- T represents an integer of 2 or more, for example, an integer of 2 to 5, preferably 2.
- the compound (E) preferably contains at least a compound having two oxetanyl groups (for example, a compound in which t in the above formula (e) is 2). ) And / or a compound represented by the following formula (e-2).
- the compound (E) for example, commercially available products such as “Aron Oxetane OXT-221” and “Aron Oxetane OXT-121” (above, manufactured by Toagosei Co., Ltd.) can be used.
- the monomer mixture of the present invention may contain one or more other cationic polymerizable monomers in addition to the compounds (A) to (E).
- a monomer having two or more cationic polymerizable groups for example, a group selected from a vinyl ether group, an oxetanyl group, and an epoxy group
- a polyfunctional cationic polymerizable monomer is curable.
- the following compounds are preferable, for example.
- Compound having 2 or more glycidyl ether groups Two or more ethylene oxide groups
- Examples of the compound (1) having three or more alicyclic epoxy groups include compounds represented by the following formulas (1-1) and (1-2).
- N 3 to n 8 in the formula each represents an integer of 1 to 30.
- Examples of the compound (3) having two or more glycidyl ether groups include aromatics such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenol type epoxy compounds, phenol novolac type epoxy compounds, and cresol novolac type epoxy compounds.
- Compounds represented by formulas (3-1) to (3-5) trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, dipenta Aliphatic epoxy compounds such Risuri tall hexa glycidyl ether.
- Examples of the compound (4) having two or more ethylene oxide groups include a compound represented by the following formula (4-1).
- R ′′ is a group obtained by removing p hydroxyl groups from the structural formula of p-valent alcohol (p-valent organic group), and p and n 9 each represent a natural number.
- the alcohol [R ′′ (OH) p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (polyhydric alcohols having 1 to 15 carbon atoms, etc.).
- p is preferably 1 to 6
- n 9 is preferably 1 to 30.
- n 9 in each [] (inside square brackets) may be the same or different.
- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol specifically, trade name “EHPE3150” (manufactured by Daicel Corporation), etc.] and the like.
- Examples of the compound (5) in which two or more vinyl ether groups are bonded to the aliphatic hydrocarbon group or the alicyclic hydrocarbon group include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, Examples include triethylene glycol divinyl ether and cyclohexane dimethanol divinyl ether.
- the monomer mixture of the present invention is a monomer mixture composed of two or more kinds of cationically polymerizable monomers, and contains at least the compound (A), the compound (B), and the compound (C) as the cationically polymerizable monomer.
- the monomer mixture of the present invention may contain the above-mentioned compound (D) and / or compound (E) in addition to the compound (A), the compound (B), and the compound (C) as a cationic polymerizable monomer. it can.
- the total content of the compound (A), the compound (B) and the compound (C) is 50% by weight or more of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture). In view of particularly excellent curability in a humidity environment, 55% by weight or more is preferable, particularly preferably 60% by weight or more, and most preferably 65% by weight or more. Further, the total content of the compound (A), the compound (B) and the compound (C) is 90% by weight or less of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture). It is preferable in terms of particularly excellent curability in a high humidity environment, particularly preferably 85% by weight or less, most preferably 80% by weight or less, and particularly preferably 75% by weight or less.
- the content [A] of the compound (A) and the content [B] of the compound (B) satisfy the following formula (1).
- the value calculated by the above formula (1) or the ratio of the content [A] of the compound (A) in the total content [A + B] of the compound (A) and the compound (B) is the high humidity environment. It is preferably 0.5 or more, particularly preferably 0.7 or more, most preferably 0.8 or more, and particularly preferably 0.85 or more in view of particularly excellent curability underneath. Moreover, it is preferable that it is less than 1.0 at the point which is especially excellent in the adhesiveness with respect to a metal or glass, Especially preferably, it is 0.95 or less, Most preferably, it is 0.90 or less.
- the total content [A + B] of the compound (A) and the compound (B) is, for example, 20 to 55% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture), and is based on the metal or glass.
- it is more than 30% by weight and preferably 55% by weight or less, particularly preferably 32 to 55% by weight. Further, it is particularly preferably 32% by weight or more and less than 40% by weight, particularly preferably 32 to 38% by weight, in that it is particularly excellent in adhesion to metals and glass and is particularly excellent in curability in a high humidity environment. It is.
- the content [A] of the compound (A) is, for example, 10 to 45% by weight of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture), and is particularly excellent in adhesion to metals and glass. Is preferably 15 to 40% by weight, particularly preferably 20 to 40% by weight, most preferably 25 to 35% by weight, particularly preferably more than 25% by weight and not more than 35% by weight.
- the content of the compound (a-1-1) is, for example, 10 to 45% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture), and is particularly excellent in adhesion to metals and glass. In this respect, it is preferably 15 to 40% by weight, particularly preferably 20 to 40% by weight, most preferably 25 to 35% by weight, particularly preferably more than 25% by weight and not more than 35% by weight.
- the total content of the cationic polymerizable monomer containing a hydroxyl group is, for example, 20 to 55% by weight of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture). In particular, it is preferably 23 to 45% by weight, more preferably more than 25% by weight, 45% by weight or less, particularly preferably 30 to 45% by weight, most preferably 30% by weight or more, 40% by weight. Is less than.
- the content [B] of the compound (B) is, for example, 1 to 15% by weight of the total amount of the monomer mixture (or the total amount of the cationically polymerizable monomer contained in the monomer mixture), and is particularly effective for curability in a high humidity environment. From the viewpoint of superiority, it is preferably 1 to 10% by weight, particularly preferably 2% by weight or more and less than 10% by weight, most preferably 2 to 8% by weight, particularly preferably 3 to 8% by weight.
- the content of the compound (b-1-1) is, for example, 1 to 15% by weight of the total amount of the monomer mixture (or the total amount of the cationically polymerizable monomer contained in the monomer mixture), and is curable in a high humidity environment.
- it is preferably 1 to 10% by weight, particularly preferably 2% by weight or more and less than 10% by weight, most preferably 2 to 8% by weight, particularly preferably 3 to 8% by weight.
- the content of the compound (C) is, for example, 15 to 45% by weight of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture), and is particularly excellent in curability in a high humidity environment. It is preferably 20 to 45% by weight, particularly preferably 25 to 45% by weight, and most preferably 30 to 40% by weight.
- the content of the compound (c ′) is, for example, 15 to 45% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture), and is particularly excellent in curability in a high humidity environment. It is preferably 20 to 45% by weight, particularly preferably 25 to 45% by weight, and most preferably 30 to 40% by weight.
- the content of the compound (D) is, for example, 1 to 10% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture), and is 1 to 2 in terms of particularly excellent adhesion to metals and glass. It is preferably 8% by weight, particularly preferably 2 to 7% by weight, most preferably 3 to 6% by weight.
- the content of the compound (d) is, for example, 1 to 10% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture), and is 1 to 2 in terms of particularly excellent adhesion to metals and glass. It is preferably 8% by weight, particularly preferably 2 to 7% by weight, most preferably 3 to 6% by weight.
- the total content of the compound represented by the formula (d-1) and the compound represented by the formula (d-2) is, for example, 1 of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture). From 1 to 8% by weight, preferably from 1 to 8% by weight, particularly preferably from 2 to 7% by weight, and most preferably from 3 to 6% by weight, in view of particularly excellent adhesion to metals and glass.
- the content of the compound (E) is, for example, 15 to 40% by weight of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture), and is particularly excellent in curability in a high humidity environment. It is preferably 15 to 35% by weight, particularly preferably 20 to 35% by weight, most preferably 25 to 35% by weight, particularly preferably 30 to 35% by weight.
- the total content of the compound represented by the formula (e-1) and the compound represented by the formula (e-2) is, for example, 15 of the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture). It is preferably 40 to 40% by weight, and is preferably 15 to 35% by weight, particularly preferably 20 to 35% by weight, most preferably 25 to 35% by weight, and particularly preferably 30% in view of particularly excellent curability in a high humidity environment. ⁇ 35% by weight.
- the content of the compound represented by the formula (e-1) is, for example, 15 to 40% by weight of the total amount of the monomer mixture (or the total amount of the cation polymerizable monomer contained in the monomer mixture), and is used in a high humidity environment. From the viewpoint of excellent curability, it is preferably 15 to 35% by weight, particularly preferably 20 to 35% by weight, most preferably 25 to 35% by weight, and particularly preferably 30 to 35% by weight.
- the content of the cation polymerizable monomer having an oxetanyl group and / or an epoxy group is the total amount of the monomer mixture (or the monomer mixture).
- the total amount of cationically polymerizable monomers contained is, for example, 50 to 90% by weight, more preferably 55 to 90% by weight, particularly preferably 55 to 85% by weight, and most preferably 60 to 85% by weight.
- the content of the cationic polymerizable monomer having a vinyl ether group is, for example, the total amount of the monomer mixture (or the total amount of the cationic polymerizable monomer contained in the monomer mixture). It is 10 to 50% by weight, more preferably 15 to 45% by weight, particularly preferably more than 20% by weight, 45% by weight or less, most preferably 25 to 45% by weight.
- the proportion of the total content of compound (A), compound (B), compound (C), compound (D), and compound (E) in the total amount of the monomer mixture of the present invention is, for example, 75% by weight or more, preferably It is 80% by weight or more, particularly preferably 85% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more. Accordingly, the cationic polymerizable monomer other than the compound (A), the compound (B), the compound (C), the compound (D), and the compound (E) in the total amount of the monomer mixture of the present invention (for example, the above other cationic polymerizable compounds).
- the proportion of the content of the monomer) (when two or more are contained, the total amount thereof) is, for example, 25% by weight or less, preferably 20% by weight or less, particularly preferably 15% by weight or less, most preferably 10% by weight or less, Particularly preferred is 5% by weight or less.
- the monomer mixture of the present invention comprises the above compound (A), compound (B), compound (C) and, if necessary, other monomers, a self-revolving stirring deaerator, a homogenizer, a planetary mixer, a roll mill, a bead mill. It can manufacture by mixing uniformly using the generally known mixing apparatuses, such as. Each component may be mixed simultaneously or sequentially.
- the monomer mixture of the present invention is useful as a raw material for a cured composition having the above-described characteristics.
- the curable composition of this invention contains the said monomer mixture and a curing catalyst.
- the content of the monomer mixture is, for example, 50 to 99.9% by weight, preferably 70 to 98% by weight, based on the total amount (100% by weight) of the curable composition of the present invention.
- the curing catalyst includes a known or conventional photocationic polymerization initiator and a photoradical polymerization initiator.
- the curable composition of the present invention preferably contains at least a photocationic polymerization initiator as a curing catalyst. Moreover, you may contain radical photopolymerization initiator with a photocationic polymerization initiator, Thereby, the hardening reaction of a curable composition may be able to advance more efficiently, and the hardness of the hardened
- Examples of the cationic photopolymerization initiator include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds. Etc.
- trade names “CPI-101A”, “CPI-100P”, “CPI-110P” manufactured by San Apro Co., Ltd.
- photo radical polymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2- Propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin phenyl Ether, benzyldimethylke Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone
- the amount of the cationic photopolymerization initiator used is preferably, for example, 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and further preferably 1 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture. is there.
- the amount of the photo radical polymerization initiator used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the monomer mixture. Particularly preferred is 0.5 to 3 parts by weight, and most preferred is 0.5 to 2 parts by weight.
- the curable composition of the present invention may further contain a solvent, it does not contain a solvent, or suppressing the content of the solvent can improve the drying property, and is easily deteriorated by the solvent. It is preferable in that it can be applied to a substrate and can prevent generation of odor due to volatilization of the solvent.
- the content of the solvent is preferably 10% by weight or less of the total amount of the curable composition (100% by weight). More preferably, it is 5% by weight or less, particularly preferably 1% by weight or less.
- the curable composition of the present invention may contain other components as required in addition to the monomer mixture and the curing catalyst.
- other components include well-known and conventional sensitizers (for example, acridine compounds, benzoflavins, perylenes, anthracenes, thioxanthone compounds, laser dyes, etc.), sensitization aids, and surface conditioners (leveling agents).
- Agents antifoaming agents, antioxidants, stabilizers such as amines, silane coupling agents, fillers, flame retardants and the like.
- the curable composition of the present invention when used for the purpose of curing by irradiating UV-LED, it may contain a sensitizer and, if necessary, a sensitization aid. These are preferable in that the light absorption rate can be improved and the curability can be improved, and the content thereof (the total amount when two or more are contained) is, for example, 0.05 to The amount is 10 parts by weight, preferably 0.1 to 5 parts by weight.
- a sensitizer for example, when a compound represented by the following formula (f-1) and a compound represented by the following formula (f-2) are used in combination, coloring of the resulting cured product is suppressed extremely low.
- the curability can be improved, and the combined ratio of these compounds [compound represented by formula (f-1) / compound represented by formula (f-2); weight ratio] is: For example, it is 0.01 to 1.0, preferably 0.1 to 0.5, particularly preferably 0.2 to 0.5.
- the compound represented by the following formula (f-1) for example, trade name “Anthracure UVS-1331” (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) can be used.
- trade name “Anthracure UVS-581” manufactured by Kawasaki Kasei Kogyo Co., Ltd.
- the curable composition of the present invention is used as a color ink of an ultraviolet curable ink jet ink, it is preferable to further contain a coloring material.
- Color materials include pigments and dyes.
- it does not contain a color material it can be used as a clear ink.
- any pigment that is generally known as a pigment and can be dispersed in the curable composition can be used without particular limitation.
- the average particle diameter of the pigment is preferably 300 nm or less, for example, from the viewpoint of excellent ejection properties, ink flying properties, and print reproducibility.
- the pigment may have a magnetic property, a fluorescent property, a conductive property, a dielectric property, etc. in addition to the coloring and coloring properties. In this case, various functions can be given to the image.
- Usable pigments include, for example, earthen pigments (eg, ocher, amber, etc.), lapis lazuli, azurite, chalk, pepper, lead white, vermilion, ultramarine, viridan, cadmium red, carbon pigments (eg, carbon black, Carbon refined, carbon nanotubes, etc.), metal oxide pigments (eg, iron black, cobalt blue, zinc oxide, titanium dioxide, chromium oxide, iron oxide, etc.), metal sulfide pigments (eg, zinc sulfide, etc.), metallic sulfuric acid Inorganic pigments such as salts, metal carbonates (eg, calcium carbonate, magnesium carbonate, etc.), metal silicates, metal phosphates, metal powders (eg, aluminum powder, bronze powder, zinc powder, etc.); insoluble azo pigments ( For example, monoazo yellow, monoazo red, monoazo violet, disazo yellow Disazo orange, pyrazolone pigment, etc.), soluble azo pigment (eg, azo
- Pigment for example, isoindoline yellow
- dioxazine pigment for example, dioxazine violet
- thioindigo pigment anthraquinone pigment
- quinophthalone pigment for example, quinophthalone yellow
- metal complex pigment dike Organic pigments such as topyrrolopyrrole pigments, phthalocyanine pigments (for example, phthalocyanine blue and phthalocyanine green), dye lake pigments; fluorescent pigments such as inorganic phosphors and organic phosphors, and the like. These can be used alone or in combination of two or more.
- dye examples include nitroaniline, phenyl monoazo, pyridone azo, quinophthalone, styryl, anthraquinone, naphthalimido azo, benzothiazolyl azo, phenyl disazo azo, and thiazolyl azo dyes. . These can be used alone or in combination of two or more.
- the content of the coloring material (the total amount when two or more are contained) is, for example, 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the monomer mixture.
- the curable composition of the present invention is used as an ultraviolet curable ink-jet ink
- a dispersing agent in order to improve the dispersibility of the dispersing agent.
- the dispersant include, for example, nonionic surfactants, ionic surfactants, charging agents, polymer dispersants (for example, trade names “Solsperse 24000”, “Solsperse 32000”, manufactured by Abyssia Co., Ltd., “Asper PB821”, “Azisper PB822”, “Azisper PB824”, “Azisper PB881”, “Azisper PN411”, “Azisper PN411”, and the like, manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like. These can be used alone or in combination of two or more.
- the content of the dispersing agent is, for example, 1 to 50 parts by weight, preferably 3 to 30 parts by weight, and particularly preferably 5 to 10 parts by weight with respect to 100 parts by weight of the color material.
- the surface tension (at 30 ° C. and 1 atm) of the curable composition of the present invention is, for example, 10 to 50 mN / m.
- the viscosity [at 25 ° C., shear rate 100 (1 / s)] of the curable composition of the present invention is, for example, 1 to 1000 mPa ⁇ s, preferably 1 to 500 mPa ⁇ s, particularly preferably 1 to 100 mPa ⁇ s. Most preferably, it is 1 to 50 mPa ⁇ s, and particularly preferably 1 to 30 mPa ⁇ s. Therefore, the curable composition of this invention is excellent in fluidity
- the curable composition of the present invention is used in a high humidity environment (for example, humidity 50 to 90% RH, preferably humidity 65 to 90% RH, particularly preferably humidity 70 to 90% RH, most preferably humidity 75 to 90% RH).
- a high humidity environment for example, humidity 50 to 90% RH, preferably humidity 65 to 90% RH, particularly preferably humidity 70 to 90% RH, most preferably humidity 75 to 90% RH.
- the resin can be quickly cured by irradiation with ultraviolet rays to form a cured product. Therefore, when used as an ultraviolet curable ink-jet ink, it is possible to prevent the occurrence of bleeding and odor and to form an ink film excellent in print quality.
- the ultraviolet light source may be any light source that can generate acid in the curable composition by irradiating light, such as a UV-LED, a low, medium, or high pressure mercury lamp.
- a UV-LED a low, medium, or high pressure mercury lamp.
- the ultraviolet irradiation amount is, for example, 10 to 5000 mJ / cm 2 .
- the curable composition of the present invention may be further subjected to heat treatment after being irradiated with ultraviolet rays.
- heat treatment By performing the heat treatment, the degree of curing can be further improved.
- the heating temperature is about 40 to 200 ° C., and the heating time is about 1 minute to 15 hours.
- the degree of curing can also be improved by leaving it to stand at room temperature (20 ° C.) for about 1 to 48 hours after irradiation with ultraviolet rays.
- the curable composition of the present invention can form a cured product having excellent adhesion to a wide range of substrates.
- the cured product of the curable composition of the present invention includes, for example, plastic (for example, polyethylene, polypropylene, polyethylene terephthalate (PET), vinyl chloride resin, polycarbonate, ABS resin, etc.), natural rubber, butyl rubber, foam (for example, polyurethane) , Polychloroprene rubber, etc.), wood, woven fabric, non-woven fabric, cloth, paper (for example, fine paper, glassine paper, kraft paper, Japanese paper, etc.), silicon wafers, ceramics, and composites thereof, of course, Excellent adhesion to glass and metal (for example, aluminum foil, copper foil, SUS plate, etc.).
- plastic for example, polyethylene, polypropylene, polyethylene terephthalate (PET), vinyl chloride resin, polycarbonate, ABS resin, etc.
- natural rubber butyl rubber, foam (for example, polyurethane)
- the curable composition of the present invention includes ultraviolet curable ink-jet ink materials, adhesives, coating agents (or paints), sealing materials, civil engineering and building materials, laminates and other electrical and electronic parts, photoresists and solders. It can be suitably used as a resist, an interlayer component for a multilayer wiring board, an insulating material, a concrete building repair material, a casting material, a sealant, an optical modeling material, an optical material such as a lens or an optical waveguide, and the like.
- the curable composition of the present invention is used as, for example, an ultraviolet curable ink-jet ink, it is highly accurate with no particular limitation on the substrate to be printed and in a high humidity environment, while suppressing the generation of odor.
- a high hardness ink film can be formed.
- the cured product of the present invention is a cured product of a curable composition containing a cationic polymerizable monomer.
- the cured product of the present invention has excellent adhesion to the substrate, and exhibits excellent adhesion to paper and plastic substrates, as well as surface treatment (for example, primer treatment) for improving adhesion. Excellent adhesion to metal and glass substrates that are not used.
- the adhesion of the cured product of the present invention to a paper substrate, a plastic substrate, a metal substrate, and a glass substrate can be classified, for example, in a six-stage classification test by a cross-cut method in accordance with JIS K5600-5-6. 0-2.
- the cationically polymerizable monomer contained in the curable composition forming the cured product of the present invention two or more kinds of cationically polymerizable monomers may be contained, and in particular, extremely excellent substrate adhesion is exhibited. In this respect, it is preferable to contain the monomer mixture.
- the curable composition forming the cured product of the present invention preferably contains a curing catalyst together with the cationic polymerizable monomer.
- the curable composition of the present invention is particularly preferable as the curable composition. Therefore, the cured product of the present invention is preferably a cured product of the above-described curable composition of the present invention.
- the molded product of the present invention comprises a cured product of the above curable composition.
- the molded product of the present invention can be produced through a step of discharging the curable composition by an inkjet method and then curing the discharged curable composition.
- the shape and thickness of the molded product can be appropriately adjusted according to the application.
- the curable composition has a fast curing property, when used for forming a molded product (for example, a three-dimensional molded product), a molded product having a desired shape can be easily and efficiently produced.
- the molded product of the present invention is composed of a cured product of the above curable composition, and is particularly excellent in adhesion to metal and glass.
- the structure of this invention has the structure provided with the hardened
- the said structure can be manufactured through the process of discharging the said curable composition to the base-material surface by an inkjet system, and hardening the discharged curable composition after that, for example.
- the shape and thickness of the cured product can be appropriately adjusted according to the application.
- the above-mentioned substrates can be used without any particular limitation. Since the structure of the present invention is formed using the curable composition, it has excellent adhesion to a substrate (not only to paper and plastic but also to metal and glass). For example, in the 6-step classification test by the cross-cut method (conforming to JIS K 5600-5-6), the adhesion with respect to is 0 to 2, for example.
- the said curable composition has quick-curing property, a structure (For example, the structure which has the printing and coating film which consist of hardened
- the cured product of the curable composition is particularly excellent in adhesion to metal and glass, it is not necessary to subject the substrate surface to surface treatment such as primer treatment, and the resulting structure is composed of a substrate and a cured product. There may be no surface processing layer such as primer treatment between them.
- Example 1 Each component was mixed according to the prescription described in Table 1 (unit is part by weight) to obtain an ink.
- the viscosity of the obtained ink at 25 ° C. and a shear rate of 100 (1 / s) was measured using an E-type viscometer (trade name “VISCOMETER TV-25”, manufactured by Toki Sangyo Co., Ltd.). ⁇ It was s.
- Example 2 to 19 and Comparative Examples 1 and 2 An ink was obtained in the same manner as in Example 1 except that the formulation was changed as described in the following table (unit: parts by weight).
- the ink obtained in the examples and comparative examples was placed on a glass plate (trade name “S9112” manufactured by Matsunami Glass Industry Co., Ltd.) or an aluminum plate (trade name “A1050P” manufactured by ASONE Co., Ltd.) with a bar coater (# 4) (Coating thickness: 5 ⁇ m), 24-25 ° C, air atmosphere, humidity 50% RH or 70% RH, light irradiation (LED irradiator as light source (trade name “UV-LED Processed LSS-05 "(manufactured by CCR) was used to irradiate 365 nm light until tackiness disappeared to obtain a cured product / substrate laminate (1).
- the cured product / substrate laminate (1) obtained by the same method was subjected to post-baking (heat treatment at 120 ° C. for 10 minutes using an oven) to obtain a cured product / substrate laminate ( 2) was obtained.
- the adhesion of the obtained cured product / substrate laminates (1) and (2) was evaluated by a method based on the “cross cut method” of JIS K 5600-5-6. Specifically, using a cutter knife, six crosscuts (cut pieces) were formed by cutting the cured product / substrate laminate from the cured product surface side in the vertical and horizontal directions to reach the substrate. Then, an adhesive tape (trade name “Nichiban Tape No.
- the coating film is partially or completely peeled along the edge of the cut, and / or various portions of the lattice are partially or completely peeled off.
- the cross-cut portion is clearly affected by more than 15% but not more than 35%.
- 4 The coating film has been partially or completely peeled along the edge of the cut, and / or some lattices have been partially or completely peeled off. It is clearly not more than 35% that the cross-cut is affected. 5: Any of the degree of peeling that cannot be classified even with classification 4.
- ISBDVE isosorbide divinyl ether
- trade name “ISB-DVE” manufactured by Daicel Corporation
- CHDMDVE cyclohexanedimethanol divinyl ether
- TEGDVE triethylene glycol divinyl ether
- HEVE ethylene glycol monovinyl ether 2021P: 3,4-epoxycyclohexylmethyl (3 , 4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, Daicel Corporation OXT101: 3-ethyl-3-hydroxymethyloxetane, trade name “Aron Oxetane OXT-101”, manufactured by Toagosei Co., Ltd.
- OXT221 Bis [1-ethyl (3-oxetanyl)] methyl ether, trade name “Aron Oxetane OXT-221”, manufactured by Toagosei Co., Ltd. ⁇ Curing Catalyst>
- CPI110P Mixture of diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) (99.5 / 0.5), trade name “CPI -110P ", Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by San Apro Co., Ltd., trade name” Irgacure-184 ", manufactured by BASF ⁇ Sensitizer> UVS581: 9,10-di (capryloyloxy) anthracene, trade name “Anthracure UV
- UVS1331 9,10-dibutoxyanthracene, trade name “Anthracure UVS-1331” Manufactured by Kawasaki Chemical Industries Co., Ltd.
- Pigment Black 7 Carbon black
- Pigment White 6 Titanium dioxide ⁇ dispersant>
- Product name "Azisper polymer pigment dispersant, manufactured by Ajinomoto Fine Techno Co., Ltd.
- the compound (C) represented by the formula (c) the total content of the compound (A), the compound (B) and the compound (C) is 50% by weight or more of the total amount of the monomer mixture, and A monomer mixture in which the content [A] of the compound (A) and the content [B] of the compound (B) satisfy the following formula (1).
- the content of the compound (C) is 15 to 45% by weight of the total amount of the monomer mixture (or the total amount of cationically polymerizable monomers contained in the monomer mixture).
- [8] The monomer mixture according to any one of [1] to [7], wherein the compound (C) is a compound represented by the formula (c), wherein X is a group containing an ester bond. .
- a compound (D) in which two or more vinyl ether groups are bonded to an alicyclic skeleton or a non-aromatic heterocyclic skeleton (excluding a compound having a hydroxyl group) is added to the total amount of the monomer mixture.
- the compound represented by the formula (d-1) and / or the compound represented by the formula (d-2) is contained as a cationic polymerizable monomer in an amount of 1 to 10% by weight based on the total amount of the monomer mixture.
- To [8] The monomer mixture according to any one of [8].
- the cationic polymerizable monomer further contains a compound (E) having two or more oxetanyl groups (excluding a compound having a hydroxyl group) in an amount of 15 to 40% by weight based on the total amount of the monomer mixture.
- the monomer mixture as described in any one of.
- a curable composition comprising the monomer mixture according to any one of [1] to [11] and a curing catalyst.
- the curable composition according to [12] containing a sensitizer or a sensitizer and a sensitization aid.
- the curable composition according to [12] or [13] which contains a color material.
- [20] A cured product of a curable composition containing a cationically polymerizable monomer, which adheres to paper substrate, plastic substrate, metal substrate, and glass substrate in accordance with JIS K 5600-5-6 Cured product with a classification of 0 to 2 in the 6-step classification test by the cross-cut method.
- [22] A molded article comprising the cured product according to any one of [19] to [21].
- a curable composition according to [16] is ejected by an ink jet method, and then a cured product of the curable composition is obtained through a step of curing the ejected curable composition.
- a method for producing a molded product. [24] A structure comprising the cured product according to any one of [19] to [21] on the surface of a base material.
- the monomer mixture of the present invention is useful as a raw material for a curable composition useful as an ultraviolet curable ink jet ink, a coating agent, an adhesive and the like.
- a curable composition obtained by blending a curing catalyst with the monomer mixture of the present invention is used as an ultraviolet curable ink jet ink, it has a low viscosity and excellent ejection properties, and even on high-humidity surfaces of metals and glass. By directly applying and then curing, an ink film with very high accuracy and excellent adhesion can be formed.
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- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Polyethers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明の他の目的は、前記モノマー混合物と硬化触媒を含む硬化性組成物を提供することにある。
本発明の他の目的は、紫外線硬化型インクジェット用インク、コーティング剤、又は接着剤として有用な硬化性組成物を提供することにある。
本発明の他の目的は、紙やプラスチックはもちろん、金属やガラスに対しても優れた密着性を有する硬化物を提供することにある。
本発明の他の目的は、前記硬化性組成物の硬化物若しくは成形物を提供することにある。
本発明の他の目的は、基材上に前記硬化性組成物の硬化物を備えた構造物を提供することにある。
で表される化合物(C)を含有し、前記化合物(A)と化合物(B)と化合物(C)の合計含有量がモノマー混合物全量の50重量%以上であり、且つ前記化合物(A)の含有量[A]と化合物(B)の含有量[B]が下記式(1)を満たす、モノマー混合物を提供する。
A/(A+B)≧0.3 (1)
本発明のモノマー混合物は、2種以上のカチオン重合性モノマーからなるモノマー混合物であって、前記カチオン重合性モノマーとして、ビニルエーテル基と水酸基とを有する化合物(A)と、オキセタニル基と水酸基とを有する化合物(B)と、式(c)で表される化合物(C)を含有する。
化合物(A)は、ビニルエーテル基と水酸基とをそれぞれ少なくとも1個有する化合物であり、カチオン重合性モノマーである。化合物(A)を含む硬化性組成物を硬化して得られる硬化物は、化合物(A)のビニルエーテル基と水酸基とが重合して高度な架橋構造体を形成するため高硬度と強靱性とを有する。
HO-Ra-CH=CH2 (a-1)
(式中、Raは2価の炭化水素基、2価の複素環式基、又はこれらが単結合若しくは連結基を介して結合した2価の基を示す)
化合物(B)はオキセタニル基と水酸基とをそれぞれ少なくとも1個有する化合物であり、カチオン重合性モノマーである。尚、化合物(B)にはビニルエーテル基を含有する化合物は含まれない。化合物(B)を含む硬化性組成物は硬化性に優れ、当該硬化性組成物を硬化して得られる硬化物は、金属やガラスに対して優れた密着性を有する。
HO-Rb-Y (b-1)
(式中、Rbは2価の炭化水素基、2価の複素環式基、又はこれらが単結合若しくは連結基を介して結合した2価の基を示し、Yはオキセタニル基を示す)
化合物(C)は下記式(c)で表される化合物であり、カチオン重合性モノマーである。尚、化合物(C)にはビニルエーテル基やオキセタニル基を含有する化合物は含まれない。化合物(C)を含む硬化性組成物は速硬化性を有し、当該硬化性組成物を硬化して得られる硬化物は、高硬度を有する。
化合物(D)は、脂環骨格又は非芳香族性複素環骨格に2個以上のビニルエーテル基が結合した化合物(D)であり、カチオン重合性モノマーである。尚、化合物(D)には水酸基を含有する化合物や、エポキシ基を含有する化合物は含まれない。化合物(D)を含む硬化性組成物は速硬化性を有し、当該硬化性組成物を硬化して得られる硬化物は、高硬度を有する。
Rd-(O-CH=CH2)s (d)
(式中、Rdはs価の脂環式炭化水素基、s価の非芳香族性複素環式基、又はこれらが単結合若しくは連結基を介して結合したs価の基を示し、sは2以上の整数を示す)
化合物(E)は、オキセタニル基を2個以上有する化合物である。尚、化合物(E)には水酸基を含有する化合物や、エポキシ基を含有する化合物、ビニルエーテル基を含有する化合物は含まれない。化合物(E)を含む硬化性組成物は硬化性に優れ、当該硬化性組成物を硬化して得られる硬化物は、金属やガラスに対して優れた密着性を有する。
Re-(Y)t (e)
(式中、Reはt価の有機基を示し、Yはオキセタニル基を示す。tは2以上の整数を示す)
本発明のモノマー混合物は、上記化合物(A)~(E)以外にも他のカチオン重合性モノマーを1種又は2種以上含有していてもよい。
(1)脂環式エポキシ基を3個以上有する化合物
(2)脂環式エポキシ基とグリシジルエーテル基を有する化合物
(3)グリシジルエーテル基を2個以上有する化合物
(4)エチレンオキシド基を2個以上有する化合物
(5)脂肪族炭化水素基又は脂環式炭化水素基に2個以上のビニルエーテル基が結合した化合物
本発明のモノマー混合物は、2種以上のカチオン重合性モノマーからなるモノマー混合物であって、前記カチオン重合性モノマーとして、化合物(A)、化合物(B)、及び化合物(C)を少なくとも含有する。
A/(A+B)≧0.3 (1)
すなわち、化合物(A)と化合物(B)の合計含有量[A+B]における、化合物(A)の含有量[A]の占める割合は0.3以上である。
本発明の硬化性組成物は、上記モノマー混合物と硬化触媒を含有する。
顔料としては、一般に顔料として知られている色材であって、硬化性組成物中に分散可能なものであれば、特に制限なく使用することができる。顔料の平均粒子径は、例えば300nm以下であることが吐出性、インク飛翔性、及び印字再現性に優れる点で好ましい。
前記染料としては、例えば、ニトロアニリン系、フェニルモノアゾ系、ピリドンアゾ系、キノフタロン系、スチリル系、アントラキノン系、ナフタルイミドアゾ系、ベンゾチアゾリルアゾ系、フェニルジスアゾ系、チアゾリルアゾ系染料等が挙げられる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の硬化物は、カチオン重合性モノマーを含む硬化性組成物の硬化物である。本発明の硬化物は基材に対する密着性に優れ、紙やプラスチック基材に対して優れた密着性を示すのはもちろん、密着性向上のための表面加工処理(例えば、プライマー処理等)が施されていない金属やガラス基材に対しても優れた密着性を示す。
本発明の成形物は、上記硬化性組成物の硬化物から成る。本発明の成形物は、上記硬化性組成物を、インクジェット方式で吐出し、その後、吐出された硬化性組成物を硬化させる工程を経て、製造することができる。
本発明の構造物は、基材表面に上記硬化性組成物の硬化物を備えた構成を有する。当該構造物は、例えば、上記硬化性組成物を、基材表面にインクジェット方式で吐出し、その後、吐出された硬化性組成物を硬化させる工程を経て、製造することができる。
表1(単位は重量部)に記載の処方通りに各成分を混合して、インクを得た。得られたインクの25℃、せん断速度100(1/s)における粘度を、E型粘度計(商品名「VISCOMETER TV-25」、東機産業(株)製)を用いて測定したところ、12mPa・sであった。
下記表(単位は重量部)に記載の通りに処方を変更した以外は実施例1と同様にしてインクを得た。
実施例及び比較例で得られたインクをガラス板(商品名「S9112」、松浪硝子工業(株)製)又はアルミニウム板(商品名「A1050P」、アズワン(株)製)上にバーコーター(♯4)を用いて塗布し(塗膜厚み:5μm)、24~25℃、空気雰囲気、湿度50~80%条件下で、光源としてLED照射器(商品名「UV-LED PROCESSOR LSS-05」、CCR社製)を使用して365nmの光(照度:1.5W/cm2)を照射[1回の照射量(露光量)を1J/cm2とし、タック性がなくなるまで繰り返し照射]し、照射回数により硬化性を評価した。
実施例及び比較例で得られたインクをガラス板(商品名「S9112」、松浪硝子工業(株)製)又はアルミニウム板(商品名「A1050P」、アズワン(株)製)上にバーコーター(♯4)を用いて塗布し(塗膜厚み:5μm)、24~25℃、空気雰囲気、湿度50%RH又は70%RH条件下で、光照射(光源としてLED照射器(商品名「UV-LED PROCESSOR LSS-05」、CCR社製)を使用して365nmの光をタック性がなくなるまで照射)を施して硬化物/基材積層体(1)を得た。
また、同様の方法で得られた硬化物/基材積層体(1)にポストベーク(オーブンを使用して、120℃の温度で10分間加熱処理)を施して硬化物/基材積層体(2)を得た。
JIS K 5600-5-6の「クロスカット法」に準拠した方法で、得られた硬化物/基材積層体(1)、(2)の密着性を評価した。
具体的には、カッターナイフを使用して、硬化物/基材積層体を硬化物面側から縦横方向に切断して基材に達するような6個のクロスカット(切断片)を形成した。
そして、粘着テープ(商品名「ニチバンテープ1号」、ニチバン(株)製)をクロスカット上に貼り付けて引き剥がし、下記基準に従って6段階に分類して密着性を評価した。
<6段階分類>
0:カットの縁が完全に滑らかで、どの格子の目にもはがれがない。
1:カットの交差点における塗膜の小さなはがれあり。クロスカット部分で影響を受けるのは、明確に5%を上回ることはない。
2:塗膜がカットの縁に沿って、及び/又は交差点においてはがれている。クロスカット部分で影響を受けるのは明確に5%を超えるが15%を上回ることはない。
3:塗膜がカットの縁に沿って、部分的又は全面的に大はがれを生じており、及び/又は、格子の目のいろいろな部分が、部分的又は全面的にはがれている。クロスカット部分で影響を受けるのは、明確に15%を超えるが35%を上回ることはない。
4:塗膜がカットの縁に沿って、部分的又は全面的に大はがれを生じており、及び/又は数か所の格子の目が部分的又は全面的にはがれている。クロスカット部分で影響を受けるのは、明確に35%を上回ることはない。
5:分類4でも分類できないはがれ程度のいずれか。
<モノマー>
ISBDVE:イソソルビドジビニルエーテル、商品名「ISB-DVE」、(株)ダイセル製
CHDMDVE:シクロヘキサンジメタノールジビニルエーテル
TEGDVE:トリエチレングリコールジビニルエーテル
HEVE:エチレングリコールモノビニルエーテル
2021P:3,4-エポキシシクロヘキシルメチル(3,4-エポキシ)シクロヘキサンカルボキシレート、商品名「セロキサイド2021P」、(株)ダイセル製
OXT101:3-エチル-3-ヒドロキシメチルオキセタン、商品名「アロンオキセタン OXT-101」、東亞合成(株)製
OXT221:ビス[1-エチル(3-オキセタニル)]メチルエーテル、商品名「アロンオキセタン OXT-221」、東亞合成(株)製
<硬化触媒>
CPI110P:ジフェニル[4-(フェニルチオ)フェニル]スルホニウム ヘキサフルオロホスファートおよびチオジ-p-フェニレンビス(ジフェニルスルホニウム) ビス(ヘキサフルオロホスファート)の混合物(99.5/0.5)、商品名「CPI-110P」、サンアプロ(株)製
Irg184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、商品名「イルガキュア-184」、BASF社製
<増感剤>
UVS581:9,10-ジ(カプリロイルオキシ)アントラセン、商品名「アントラキュアー UVS-581」、川崎化成工業(株)製
UVS1331:9,10-ジブトキシアントラセン、商品名「アントラキュアー UVS-1331」、川崎化成工業(株)製
<色材>
Pigment Blue 15:4:銅フタロシアニン
Pigment Red 122:3,10-ジメチルキナクリドン
Pigment Yellow 155:2,2’-(1,4-フェニレン-ビス[イミノ(1-アセチル-2-オキソエタン-2,1-ジイル)アゾ])ビス(テレフタル酸ジメチル)
Pigment Black 7:カーボンブラック
Pigment White 6:二酸化チタン
<分散剤>
商品名「アジスパー」、高分子系顔料分散剤、味の素ファインテクノ(株)製
[1] 2種以上のカチオン重合性モノマーからなるモノマー混合物であって、前記カチオン重合性モノマーとして、ビニルエーテル基と水酸基とを有する化合物(A)と、オキセタニル基と水酸基とを有する化合物(B)と、式(c)で表される化合物(C)を含有し、前記化合物(A)と化合物(B)と化合物(C)の合計含有量がモノマー混合物全量の50重量%以上であり、且つ前記化合物(A)の含有量[A]と化合物(B)の含有量[B]が下記式(1)を満たす、モノマー混合物。
A/(A+B)≧0.3 (1)
[2] 化合物(A)の含有量[A]が、モノマー混合物全量(又はモノマー混合物に含まれるカチオン重合性モノマー全量)の10~45重量%である、[1]に記載のモノマー混合物。
[3] 化合物(a-1-1)の含有量が、モノマー混合物全量(又はモノマー混合物に含まれるカチオン重合性モノマー全量)の10~45重量%である、[1]に記載のモノマー混合物。
[4] 化合物(B)が式(b-1-1)で表される化合物である、[1]~[3]の何れか1つに記載のモノマー混合物。
[5] 化合物(B)の含有量[B]が、モノマー混合物全量(又はモノマー混合物に含まれるカチオン重合性モノマー全量)の1~15重量%である、[1]~[4]の何れか1つに記載のモノマー混合物。
[6] 式(b-1-1)で表される化合物の含有量[B]が、モノマー混合物全量(又はモノマー混合物に含まれるカチオン重合性モノマー全量)の1~15重量%である、[1]~[4]の何れか1つに記載のモノマー混合物。
[7] 化合物(C)の含有量が、モノマー混合物全量(又はモノマー混合物に含まれるカチオン重合性モノマー全量)の15~45重量%である、[1]~[6]の何れか1つに記載のモノマー混合物。
[8] 化合物(C)が、式(c)で表され、式中のXがエステル結合を含む基である化合物である、[1]~[7]の何れか1つに記載のモノマー混合物。
[9] カチオン重合性モノマーとして、更に、脂環骨格又は非芳香族性複素環骨格に2個以上のビニルエーテル基が結合した化合物(D)(水酸基を有する化合物は除く)を、モノマー混合物全量の1~10重量%含有する、[1]~[8]の何れか1つに記載のモノマー混合物。
[10] カチオン重合性モノマーとして、式(d-1)で表される化合物及び/又は式(d-2)で表される化合物を、モノマー混合物全量の1~10重量%含有する、[1]~[8]の何れか1つに記載のモノマー混合物。
[11] カチオン重合性モノマーとして、更に、オキセタニル基を2個以上有する化合物(E)(水酸基を有する化合物は除く)を、モノマー混合物全量の15~40重量%含有する、[1]~[10]の何れか1つに記載のモノマー混合物。
[12] [1]~[11]の何れか1つに記載のモノマー混合物と硬化触媒とを含有する硬化性組成物。
[13] 増感剤、又は増感剤と増感助剤とを含有する[12]に記載の硬化性組成物。
[14] 色材を含有する、[12]又は[13]に記載の硬化性組成物。
[15] 分散剤を含有する、[12]~[14]の何れか1つに記載の硬化性組成物。
[16] 紫外線硬化型インクジェット用インクである、[12]~[15]の何れか1つに記載の硬化性組成物。
[17] コーティング剤である、[12]~[15]の何れか1つに記載の硬化性組成物。
[18] 接着剤である、[12]~[15]の何れか1つに記載の硬化性組成物。
[19] [12]~[18]の何れか1つに記載の硬化性組成物の硬化物。
[20] カチオン重合性モノマーを含む硬化性組成物の硬化物であって、紙基材、プラスチック基材、金属基材、及びガラス基材に対する密着性が、JIS K 5600-5-6に準拠したクロスカット法による6段階分類試験において分類0~2である硬化物。
[21] カチオン重合性モノマーを含む硬化性組成物が、[12]~[15]の何れか1つに記載の硬化性組成物である、[20]に記載の硬化物。
[22] [19]~[21]の何れか1つに記載の硬化物から成る成形物。
[23] [16]に記載の硬化性組成物を、インクジェット方式で吐出し、その後、吐出された硬化性組成物を硬化させる工程を経て、前記硬化性組成物の硬化物から成る成形物を得る、成形物の製造方法。
[24] 基材表面に[19]~[21]の何れか1つに記載の硬化物を備えた構造物。
本発明のモノマー混合物に硬化触媒を配合して得られる硬化性組成物を、紫外線硬化型インクジェット用インクとして使用すれば、低粘度で吐出性に優れ、高湿度下でも、金属やガラスの表面に直接塗布し、その後硬化させることにより、非常に高精度で、密着性に優れるインク被膜を形成することができる。
Claims (15)
- カチオン重合性モノマーとして、更に、脂環骨格又は非芳香族性複素環骨格に2個以上のビニルエーテル基が結合した化合物(D)(水酸基を有する化合物は除く)を、モノマー混合物全量の1~10重量%含有する、請求項1に記載のモノマー混合物。
- カチオン重合性モノマーとして、更に、オキセタニル基を2個以上有する化合物(E)(水酸基を有する化合物は除く)を、モノマー混合物全量の15~40重量%含有する、請求項1又は2に記載のモノマー混合物。
- 請求項1~3の何れか1項に記載のモノマー混合物と硬化触媒とを含有する硬化性組成物。
- 増感剤、又は増感剤と増感助剤とを含有する請求項4に記載の硬化性組成物。
- 色材を含有する、請求項4又は5に記載の硬化性組成物。
- 分散剤を含有する、請求項4~6の何れか1項に記載の硬化性組成物。
- 紫外線硬化型インクジェット用インクである、請求項4~7の何れか1項に記載の硬化性組成物。
- コーティング剤である、請求項4~7の何れか1項に記載の硬化性組成物。
- 接着剤である、請求項4又は5に記載の硬化性組成物。
- 請求項4~10の何れか1項に記載の硬化性組成物の硬化物。
- カチオン重合性モノマーを含む硬化性組成物の硬化物であって、紙基材、プラスチック基材、金属基材、及びガラス基材に対する密着性が、JIS K 5600-5-6に準拠したクロスカット法による6段階分類試験において分類0~2である硬化物。
- 請求項11又は12に記載の硬化物から成る成形物。
- 請求項8に記載の硬化性組成物を、インクジェット方式で吐出し、その後、吐出された硬化性組成物を硬化させる工程を経て、前記硬化性組成物の硬化物から成る成形物を得る、成形物の製造方法。
- 基材表面に請求項11又は12に記載の硬化物を備えた構造物。
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