WO2019181862A1 - Monomer mixture and curable composition containing same - Google Patents

Abstract

Provided is a monomer mixture which is rapidly cured even in a high humidity environment, and which is used for the purpose of forming a cured product that exhibits excellent adhesion not only to plastics but also to metals and glass. A monomer mixture according to the present invention contains (I) a cationically polymerizable monomer which contains at least (A) a polyvalent vinyl ether compound that has a structure wherein two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton or to a heterocyclic skeleton, and (II) a hydroxyl group-containing monomer which has two or more hydroxyl groups but does not have a cationically polymerizable group; and the component (II) is contained in an amount of 0.01-20 parts by weight relative to 100 parts by weight of the component (I).

Description

Monomer mixture and curable composition containing the same

The present invention relates to a monomer mixture and a curable composition containing the monomer mixture. The curable composition is preferably used for an ultraviolet curable ink-jet ink. This application claims the priority of Japanese Patent Application No. 2018-053809 for which it applied to Japan on March 22, 2018, and uses the content here.

The ink jet system that performs printing by flying ink droplets onto a recording medium to form recording dots is suitable for use in printing many types of products little by little because an original plate is unnecessary. Cationic curable inks and radical curable inks are known as inks used for printing by this ink jet method, that is, ink jet inks.

The radical curable ink has been frequently used because it has a fast curing property and has many types of monomers. However, the problem is that the curing reaction is inhibited by oxygen. In particular, in the ink jet method, since ink is ejected as small droplets, it is easily exposed to oxygen, and oxygen easily diffuses and enters the ink from the atmosphere. Therefore, the inhibition of curing due to oxygen is remarkable, and a large amount of unreacted monomer that causes bleeding or causes 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.

On the other hand, although the cationic curable ink is not inhibited by oxygen, for example, since a vinyl ether compound having a cyclic ether skeleton easily absorbs moisture, a cationic curable ink containing a large amount thereof is cured by moisture. It is known that curing is likely to occur when it is easily disturbed and used when the humidity is high, or when moisture in the air is taken in during storage.

As a method for solving the above problem, Patent Document 1 discloses that a content of a vinyl ether compound having a cyclic ether skeleton is limited, and a cationically polymerizable compound instead of the vinyl ether compound is blended in combination, so that even in the presence of oxygen or moisture can be quickly obtained. In US Pat. No. 5,849,831 that a monomer mixture that cures is obtained.

JP 2016-27127 A

However, it has been found that the monomer mixture described in Patent Document 1 is still markedly inhibited by curing in a high humidity environment with a humidity of 50% RH or higher. In addition, the cured product has excellent adhesion to plastic, but it has low adhesion to metal and glass, and in order to improve adhesion, surface treatment such as primer treatment may be applied to metal or glass. It was necessary. Furthermore, the cured product was inferior in alkali resistance, and it was found that the print of the ultraviolet curable ink containing the monomer mixture described in Patent Document 1 was easily removed when wiped with an alkaline chemical or the like.

Therefore, an object of the present invention is to provide a monomer mixture for rapidly curing even in a high humidity environment to form a cured product having excellent adhesion to not only plastic but also metal and glass. is there.
Another object of the present invention is a monomer mixture for rapidly curing even in a high humidity environment, having excellent alkali resistance, and forming a cured product having excellent adhesion to metal and glass as well as plastic. Is to provide.
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 that can be used as an ultraviolet curable inkjet ink.
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 having a cured product of the curable composition on a substrate.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a specific proportion of the cationic polymerizable monomer (I) containing at least the specific polyvalent vinyl ether compound (A) and the specific hydroxyl group-containing monomer (II) When a curing catalyst is added to the monomer mixture, the monomer mixture has excellent curing sensitivity, and when it is irradiated with ultraviolet rays, it cures quickly even in a high-humidity environment. However, it is possible to form a cured product having excellent adhesion, and when a specific epoxy compound is used in combination as the cationic polymerizable monomer (I), a cured product having further excellent alkali resistance can be formed. I found. The present invention has been completed based on these findings.

That is, the present invention provides a cationically polymerizable monomer (I) comprising at least a polyvalent vinyl ether compound (A) having a structure in which two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton or a heterocyclic skeleton; The hydroxyl group-containing monomer (II) having two or more hydroxyl groups and having no cationic polymerizable group is a ratio of 0.01 to 20 parts by weight of (II) with respect to 100 parts by weight of (I). A monomer mixture is provided.

The present invention also provides the monomer mixture, wherein the polyvalent vinyl ether compound (A) is a compound represented by the following formula (a-1) and / or (a-2).

In the present invention, the hydroxyl group-containing monomer (II) has a structure in which three or more hydroxyl groups are bonded to the branched hydrocarbon skeleton and / or a structure in which two hydroxyl groups are bonded to the alicyclic skeleton. A monomer mixture as described above is provided.

In the present invention, the cationic polymerizable monomer (I) further contains a polyvalent epoxy compound (B) and a polyvalent oxetane compound (C), and the content of the (A) is the cationic polymerizable monomer (I). And 5) to 20% by weight of the total amount, and the total monomer content of (A), (B) and (C) is 65% by weight or more of the total amount of the cationic polymerizable monomer (I).

（式中、Ｌは単結合又は連結基を示す）
で表される化合物を含有する前記のモノマー混合物を提供する。 In the present invention, the polyvalent epoxy compound (B) is represented by the following formula (b-1):

(Wherein L represents a single bond or a linking group)
The monomer mixture containing a compound represented by the formula:

The present invention further contains, as the cationic polymerizable monomer (I), a compound (D) having one cationic polymerizable group and a hydroxyl group in an amount of 5 to 30% by weight based on the total amount of the cationic polymerizable monomer (I). A monomer mixture as described above is provided.

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 also provides a molded article made of the cured product.

The present invention also provides a molding obtained by ejecting the curable composition by an ink jet method and then curing the ejected curable composition to obtain a molded product composed of a cured product of the curable composition. A method for manufacturing a product is provided.

The present invention also provides a structure provided with the above cured product on the surface of a substrate.

In this specification, an epoxy group is a group containing a 3-membered cyclic ether skeleton, and an epoxy compound is a compound having a group containing a 3-membered cyclic ether skeleton. The oxetanyl group is a group containing a 4-membered cyclic ether skeleton, and the oxetane compound is a compound having a group containing a 4-membered cyclic ether skeleton.

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 quickly to form a cured product having excellent adhesion to metal and glass as well as plastic.
In addition, if the combination of the monomer mixture of the present invention is further selected, it cures rapidly by irradiating ultraviolet rays even in a high humidity environment, and has excellent adhesion to not only plastic but also metal and glass. At the same time, a cured product having excellent alkali resistance can be formed.
Therefore, the curable composition containing the monomer mixture of the present invention can be suitably used as an ultraviolet curable inkjet ink, a coating agent, an adhesive, and the like.

For example, if 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.

[Monomer mixture]
The monomer mixture of the present invention comprises a cationically polymerizable monomer (I) containing at least a polyvalent vinyl ether compound (A) having a structure in which two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton, or a heterocyclic skeleton. A hydroxyl group-containing monomer (II) having two or more hydroxyl groups and having no cationically polymerizable group is used in an amount of 0.01 to 20 parts by weight of (II) with respect to 100 parts by weight of (I). Contains in proportions.

The monomer mixture of the present invention includes a polyvalent epoxy compound (B), a polyvalent oxetane compound (C), and a single cationic polymerization as the cationic polymerizable monomer (I) (that is, a compound having a cationic polymerizable group). May contain a compound (D) having a functional group (vinyl ether group, epoxy group, or oxetanyl group) and a hydroxyl group, and may further contain other cationically polymerizable compounds other than those described above.

(Polyvalent vinyl ether compound (A))
The compound (A) in the present invention is a compound having a structure in which two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton or a heterocyclic skeleton. The curable composition containing the compound (A) is excellent in curability under a high humidity environment.

The compound (A) is represented by the following formula (a), for example.
R ^a — (O—CH═CH ₂ ) _t (a)
(Wherein R ^a represents a t-valent hydrocarbon group, a t-valent heterocyclic group, or a t-valent group in which two or more of these groups are bonded via a single bond or a linking group; Represents an integer of 2 or more)

The t-valent hydrocarbon group is a group obtained by removing t hydrogen atoms from the structural formula of hydrocarbon. The hydrocarbon includes aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. The aliphatic hydrocarbon includes saturated aliphatic hydrocarbon and unsaturated aliphatic hydrocarbon. The carbon number of the aliphatic hydrocarbon is, for example, 1 to 20, preferably 1 to 10. The carbon number of the alicyclic hydrocarbon is, for example, 3 to 20, preferably 3 to 10. The carbon number of the aromatic hydrocarbon is, for example, 6 to 10.

The alicyclic hydrocarbon includes a monocyclic hydrocarbon ring and a polycyclic hydrocarbon ring, and the polycyclic hydrocarbon ring includes a spiro hydrocarbon ring, a ring assembly hydrocarbon ring, a bridged cyclic ring. A hydrocarbon ring, a condensed cyclic hydrocarbon ring, and a bridged condensed cyclic hydrocarbon ring are included.

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.

Examples of the spiro hydrocarbon ring include C _5-16 spiro hydrocarbon rings such as spiro [4.4] nonane, spiro [4.5] decane, and spirobicyclohexane.

Examples of the ring assembly hydrocarbon ring include a ring assembly hydrocarbon ring including two or more C _5-12 cycloalkane rings such as _{bicyclohexane} .

Examples of the bridged cyclic hydrocarbon ring 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.

Examples of the bridged condensed cyclic hydrocarbon ring include diene dimers (for example, dimers of cycloalkadiene such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like.

Examples of the aromatic hydrocarbon include benzene and naphthalene.

The t-valent heterocyclic group is a group obtained by removing t hydrogen atoms from the heterocyclic structural formula. The heterocycle includes an aromatic heterocycle and a non-aromatic heterocycle, for example, a heterocycle containing an oxygen atom as a hetero atom (for example, a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole Ring, isoxazole ring, 5-membered ring such as γ-butyrolactone ring; 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H- Fused rings such as a chromene ring, a chroman ring, and an isochroman ring; 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8] bridged ring nonane-2-one ring), a heterocyclic ring containing a sulfur atom as a hetero atom (e.g., thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, 5-membered ring; 6-membered ring such as 4-oxo-4H-thiopyran ring; condensed ring such as benzothiophene ring, etc.], heterocycle containing a nitrogen atom as a hetero atom (eg, pyrrole ring, pyrrolidine ring, pyrazole ring, imidazole) 5-membered ring such as ring, triazole ring; 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring And a condensed ring such as a purine ring).

The above hydrocarbons and heterocycles may have various substituents [for example, C _1-4 alkyl group, cycloalkyl group, halogen atom, oxo group, hydroxyl group, substituted oxy group (for example, alkoxy group, aryloxy group, aralkyloxy group). Group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group , A sulfo group, a heterocyclic group, etc.]. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic ring may be condensed with the heterocyclic ring.

T is an integer of 2 or more, for example, 2 to 5, preferably 2 to 3.

Examples of the linking group 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—), silyl bond (—Si—), a group in which a plurality of these are linked, and the like.

Examples of the compound (A) include compounds represented by the following formula (a-1), compounds represented by the following formula (a-2), ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. , Tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, Nonanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimeta Divinyl ether, trimethylolpropane divinyl ether, ethylene oxide-added trimethylolpropane divinyl ether, pentaerythritol divinyl ether, ethylene oxide-added pentaerythritol divinyl ether, hydroquinone divinyl ether, trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether , Pentaerythritol trivinyl ether, ethylene oxide-added pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. It is.

As the compound (A), among them, a structure in which two or more vinyl ether groups are bonded to an alicyclic hydrocarbon skeleton or a heterocyclic skeleton (particularly preferably a heterocyclic skeleton, particularly preferably a non-aromatic heterocyclic skeleton). A polyvalent vinyl ether having a high curing property is preferable, and a compound represented by the above formula (a-1) and / or (a-2) is particularly preferable.

The compounds represented by the above formulas (a-1) and (a-2) can be produced using known methods. For example, the compound represented by the above formula (a-1) includes 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane and a vinyl ester compound (in the presence of a transition metal compound). For example, it can be produced by reacting with vinyl propionate). Further, the compound represented by the formula (a-2) (= isosorbide divinyl ether) is used except that isosorbide is used instead of 2-hydroxy-6-hydroxymethyl-7-oxabicyclo [2.2.1] heptane. Can be produced by the same method as described above.

(Polyvalent epoxy compound (B))
The compound (B) in the present invention is a compound having two or more epoxy groups as a cationic polymerizable group in one molecule. The compound (B) may have another cationic polymerizable group (for example, vinyl ether group, oxetanyl group) as the cationic polymerizable group in addition to the epoxy group, but the compound (B) has a vinyl ether group. A compound having 2 or more is not included. The curable composition containing the compound (B) is excellent in curability under a high humidity environment.

The epoxy group includes two adjacent carbon atoms constituting an alicyclic ring (for example, a 3- to 8-membered alicyclic ring) such as a cyclohexene oxide group represented by the following formula (e-1), and an oxygen atom. (Hereinafter sometimes referred to as “alicyclic epoxy group”) and ethylene oxide groups represented by the following formula (e-2). In the following formula, R ¹ represents a hydrogen atom or a C _1-3 alkyl group.

As the compound (B), a compound having two or more alicyclic epoxy groups in one molecule is preferable because it can form a cured product having high hardness and excellent substrate adhesion, In particular, a compound represented by the following formula (b-1) is preferable.

In the above formula (b-1), L represents a single bond or a linking group. Examples of 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 group (—O—CO—O—), an amide group (—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.

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) 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. In particular, 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 such as a C _1-10 alkyl group may be bonded to the cyclohexene oxide group in the above formula (b-1).

Representative examples of the compound represented by the formula (b-1) 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-epoxycyclohexane-1-yl) ethane and compounds represented by the following formulas (b-1-1) to (b-1-8). In the following formula (b-1-5), R represents an alkylene group having 1 to 8 carbon atoms (preferably a straight chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, or an isopropylene group). Or a branched alkylene group). In the following formulas (b-1-5) and (b-1-7), n ¹ and n ² each represent an integer of 1 to 30.

Among the compounds represented by the above formula (b-1), in particular, a compound in which L in the formula is a group containing an ester bond may form a cured product having high hardness and excellent substrate adhesion. It is preferable in that it can be performed.

The compound (B) is represented by the above formula (e-2) together with a compound having two or more alicyclic epoxy groups in one molecule (for example, a compound represented by the above formula (b-1)). That a compound having 3 or more ethylene oxide groups per molecule can produce an effect of further improving the curing rate in a high humidity environment, and can form a cured product having excellent alkali resistance. It is preferable in that it can be performed.

In the present specification, the alkali resistance is selected from alkaline substances (for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium hypochlorite, 2-aminoethanol, Lewis bases such as pyridine, etc.) It shows resistance (for example, resistance to dissolution) under conditions where at least one kind is present (pH is, for example, 8 to 14).

（式中、Ｒ^bは、ｓ価の炭化水素基、又は２個以上の炭化水素基がエーテル結合を介して結合したｓ価の基を示し、ｓは３以上の整数を示す） The compound having three or more ethylene oxide groups represented by the above formula (e-2) in one molecule is represented by the following formula (b-2), for example.

(In the formula, R ^b represents an s-valent hydrocarbon group or an s-valent group in which two or more hydrocarbon groups are bonded via an ether bond, and s represents an integer of 3 or more)

Examples of the hydrocarbon group for R ^b include the same examples as R ^a in the above formula (a). s represents an integer of 3 or more, and is preferably an integer of 3 to 6, for example. The hydrocarbon group in R ^b may have various substituents, and examples of the substituent include substituents that the hydrocarbon group in the above formula (a) may have.

Examples of the compound represented by the formula (b-2) include trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, dipentayl. And erythritol hexaglycidyl ether.

(Polyvalent Oxetane Compound (C))
The compound (C) in the present invention is a compound having two or more oxetanyl groups in one molecule as a cationic polymerizable group. The compound (C) may have another cationic polymerizable group (for example, vinyl ether group, epoxy group) in addition to the oxetanyl group as the cationic polymerizable group, but the compound (C) has a vinyl ether group. And / or a compound having two or more epoxy groups is not included. The curable composition containing the compound (C) is excellent in curability under a high humidity environment.

Examples of the compound (C) include a compound represented by the following formula (c).
R ^c- (X) _u (c)
(In the formula, R ^c represents a u-valent hydrocarbon group, heterocyclic group, or a u-valent group in which two or more of these groups are bonded via a single bond or a linking group, and X represents an oxetanyl group. (U represents an integer of 2 or more)

Examples of the u-valent hydrocarbon group and heterocyclic group include groups in which u hydrogen atoms have been removed from the hydrocarbon or heterocyclic structural formula in ^Ra above. 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 that the group in ^Ra may have.

U represents an integer of 2 or more, and is, for example, 2 to 5, preferably 2.

As the compound represented by the above formula (c), R ^c in the formula (c) is a u-valent hydrocarbon group, or two or more hydrocarbon groups are bonded through a single bond or a linking group. A compound in which R ^c in formula (c) is a divalent hydrocarbon group, or a divalent group in which two or more of the hydrocarbon groups are bonded via a single bond or a linking group is particularly preferable. A compound which is a group, most preferably a compound represented by the following formulas (c-1) to (c-2).

As the compound (C), 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.

(Compound (D) having one cationic polymerizable group and a hydroxyl group)
The compound (D) in the present invention is a compound having one cationic polymerizable group (vinyl ether group, epoxy group, or oxetanyl group) and one or more hydroxyl groups in one molecule. The curable composition containing the compound (D) is excellent in fast curability.

Examples of the compound (D) include compounds represented by the following formula (d).
(HO) _m -R ^d -Y (d)
(Wherein R ^d represents an m + 1 valent hydrocarbon group, a heterocyclic group, or an m + 1 valent group in which two or more of these groups are bonded via a single bond or a linking group, and Y represents cationic polymerization. (M represents an integer of 1 or more)

Examples of the m + 1 valent hydrocarbon group and the heterocyclic group include groups obtained by removing m + 1 hydrogen atoms from the structural formula of the hydrocarbon or heterocyclic ring in the ^Ra . 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 that the group in ^Ra may have.

M is an integer of 1 or more, for example, an integer of 1 to 3, preferably 1.

Examples of the compound represented by the formula (d), among others, R ^d is (m + 1) -valent hydrocarbon group or two or more hydrocarbon groups linking group m + 1 valent group bonded through a in the formula (preferably Is an m + 1 valent aliphatic hydrocarbon group or an m + 1 valent group in which two or more aliphatic hydrocarbon groups are bonded via a linking group, particularly preferably a divalent aliphatic hydrocarbon group or two or more A divalent group in which an aliphatic hydrocarbon group is bonded via a linking group), particularly at least one selected from compounds represented by the following formulas (d-1) to (d-4) In particular, at least one selected from the compounds represented by the following formulas (d-2) to (d-4) is preferable from the viewpoint of particularly excellent curing rate in a high humidity environment.

(Other cationic polymerizable monomers)
The monomer composition of the present invention comprises the above-mentioned polyvalent vinyl ether compound (A), polyvalent epoxy compound (B), polyvalent oxetane compound (C), and one cationic polymerizable monomer as the cationic polymerizable monomer (I). In addition to the compound (D) having a group and a hydroxyl group, it may contain other compounds, for example, one cationic polymerizable group (vinyl ether group, epoxy group, or oxetanyl group) per molecule. One or two or more monofunctional cationically polymerizable compounds having no hydroxyl group can be contained.

The monofunctional cationically polymerizable compound has a low viscosity (viscosity is, for example, 10 mPa · s or less), and can reduce the viscosity of the monomer mixture without impairing the curing sensitivity, and can impart good coatability. This is preferable. Among the monofunctional cation polymerizable compounds, the boiling point under normal pressure is, for example, 80 ° C. or higher [particularly preferably 100 ° C. or higher, most preferably 120 ° C. or higher. It is to be noted that the upper limit of the boiling point is, for example, 200 ° C., preferably 180 ° C., particularly preferably 150 ° C.], which suppresses the volatilization from room temperature to the temperature environment during coating, thereby reducing the viscosity of the monomer mixture. It is preferable in that it can be kept constant, and thereby generation of voids can be suppressed.

Examples of the monofunctional cationically polymerizable compound include 3-ethyl-3 [(2-ethylhexyloxy) methyl] oxetane.

(Hydroxyl group-containing monomer (II))
The hydroxyl group-containing monomer (II) has two or more hydroxyl groups and does not have a cationically polymerizable group (vinyl ether group, epoxy group, and oxetanyl group) (hereinafter sometimes referred to as “polyhydric alcohol”). Yes). A curable composition containing a polyhydric alcohol is excellent in curability, and a cured product obtained by curing the curable composition has excellent adhesion to metal and glass.

Examples of the polyhydric alcohol include compounds represented by the following formula (ii).
R ^e- (OH) _v (ii)
(Wherein R ^e represents a v-valent hydrocarbon group, a v-valent heterocyclic group, or a v-valent group in which two or more of these groups are bonded via a single bond or a linking group; Represents an integer of 2 or more)
Examples of the v-valent hydrocarbon group and the heterocyclic group include groups obtained by removing v hydrogen atoms from the hydrocarbon group and the structural formula of the heterocyclic ring in ^Ra . Examples of the linking group include the same examples as the linking group for ^Ra . These groups may have a substituent, and examples of the substituent include the same examples as the substituent that the group in ^Ra may have.

V is an integer of 2 or more, for example, an integer of 2 to 5.

R ^e is preferably a v-valent hydrocarbon group, a v-valent heterocyclic group, or a v-valent group in which two or more hydrocarbon groups are bonded via a single bond or a linking group, In particular, a v-valent aliphatic hydrocarbon group, a v-valent alicyclic hydrocarbon group, or a v-valent group in which two or more of these groups are bonded via a single bond or a linking group is preferable.

Therefore, the following compounds are preferred as the compound represented by the formula (ii).
1. Compound (ii-1) wherein R ^e in formula (ii) is a v-valent aliphatic hydrocarbon group or a v-valent group in which two or more aliphatic hydrocarbon groups are bonded via a linking group
2. Compound (ii) wherein R ^e in formula (ii) is a v-valent alicyclic hydrocarbon group, or a v-valent group in which two or more alicyclic hydrocarbon groups are bonded via a single bond or a linking group. -2)
3. Compound (ii-3) wherein R ^e in formula (ii) is a v-valent group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded via a single bond or a linking group

Examples of the compound (ii-1) include divalent aliphatic alcohols such as tetramethylene glycol and hexamethylene glycol; trivalent or higher aliphatic alcohols such as glycerin, sorbitol, pentaerythritol, and trimethylolpropane. .

The compound (ii-1) is preferably a compound having a structure in which three or more hydroxyl groups are bonded to an aliphatic hydrocarbon skeleton, and particularly three or more hydroxyl groups are bonded to a branched aliphatic hydrocarbon skeleton. A compound having the above structure is preferred.

The alicyclic hydrocarbon constituting the alicyclic hydrocarbon group in the compound (ii-2) and the compound (ii-3) is a 3- to 6-membered (preferably 5- to 6-membered) monocycle, A polycyclic ring in which two or more are condensed or bonded, or a structure in which two or more selected from the monocyclic or polycyclic are bonded through a single bond or a linking group is preferable. The alicyclic ring represented by (2-6) is preferred. In the following formula, L ′ represents a single bond or a linking group (for example, a divalent hydrocarbon group (for example, a linear or branched C _1-3 alkylene group, a C _3-10 cycloalkylene group, C _{6 -10} arylene group, a group in which two or more of these are bonded by a single bond, etc.), a sulfonyl group (—S (═O) ₂ —), a carbonyl group (—CO—), an ether bond (—O—), An ester bond (—COO—) and the like.

The compound (ii-2) has a structure in which v (preferably two) hydroxyl groups are bonded to the alicyclic skeleton represented by the above formulas (2-1) to (2-6). [In detail, v (preferably 2) of the alicyclic structural formulas represented by the above formulas (2-1) to (2-6) in a group obtained by removing v hydrogen atoms A compound having a structure in which a hydroxyl group is bonded] is preferred.

As the compound (ii-3), an alkylene group (particularly a methylene group) having 1 to 3 carbon atoms is added to the alicyclic skeleton represented by the above formulas (2-1) to (2-6). Therefore, a compound having a structure in which v (preferably two) hydroxyl groups are bonded is preferable.

The compound represented by the formula (ii) is a compound (ii-1) in which R ^e in the formula (ii) is a v-valent aliphatic hydrocarbon group in that it is particularly excellent in adhesion to a metal or glass. And most preferably a compound in which R ^e in formula (ii) is a trivalent or higher aliphatic hydrocarbon group, particularly preferably a branched aliphatic carbon in which R ^e in formula (ii) is trivalent or higher. It is a compound that is a hydrogen group.

[Monomer mixture]
The monomer mixture of the present invention contains at least the compound (A) as the cationic polymerizable monomer and a polyhydric alcohol.

The compound (A) [preferably having a structure in which two or more vinyl ether groups are bonded to an alicyclic hydrocarbon skeleton or a heterocyclic skeleton (particularly preferably a heterocyclic skeleton, particularly preferably a non-aromatic heterocyclic skeleton). The content of the polyvalent vinyl ether, particularly preferably the compound represented by the formula (a-1) and the formula (a-2)] (the total content when two or more are contained) is a cationic polymerization contained in the monomer mixture. The lower limit is preferably 3% by weight, particularly preferably 5% by weight, most preferably 7% by weight, based on the total amount of the monomer. The upper limit is preferably 18% by weight, particularly preferably 15% by weight. When content of the said compound exceeds the said range, there exists a tendency for the cure rate in a high humidity environment to fall. On the other hand, when the content of the compound is below the above range, the curing rate tends to decrease.

A compound having a structure in which two or more vinyl ether groups are bonded to an alicyclic hydrocarbon skeleton or a heterocyclic skeleton (particularly preferably a heterocyclic skeleton, particularly preferably a non-aromatic heterocyclic skeleton) in the total amount of the compound (A). The proportion of the monovalent vinyl ether compound (particularly preferably, the compounds represented by the formulas (a-1) and (a-2)) (the total content when containing two or more) is, for example, 60% by weight It is preferably at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight, particularly preferably at least 95% by weight.

The content of the polyhydric alcohol is 0.01 to 20 parts by weight with respect to 100 parts by weight of the cationic polymerizable monomer contained in the monomer mixture, and the effect of further improving the adhesion to metal or glass can be obtained. Preferably, 0.3 to 10 parts by weight, particularly preferably 0.8 to 7 parts by weight, and the effect of further improving the adhesion to metal and glass can be obtained while maintaining a high curing rate in a high humidity environment. Most preferred is 0.8 to 3 parts by weight.

Content of the compound (B) (particularly the total content of the compound having 2 or more alicyclic epoxy groups in one molecule and the compound having 3 or more ethylene oxide groups in one molecule, in particular, the formula (b- The total content of the compound represented by 1) and the compound represented by formula (b-2)) (the total content when two or more compounds are contained) is the total amount of cationically polymerizable monomers contained in the monomer mixture. For example, it is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, particularly preferably 20 to 45% by weight, and most preferably 30 to 45% by weight. When content of the said compound exceeds the said range, there exists a tendency for the cure rate in a high humidity environment to fall. On the other hand, when the content of the compound is below the above range, the curing rate tends to decrease.

Among the compounds (B), the content (especially a compound represented by the formula (b-1)) having two or more alicyclic epoxy groups in one molecule (in the case of containing two or more types) The total content) is preferably, for example, 10 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of the cationically polymerizable monomer contained in the monomer mixture, from the viewpoint of particularly excellent curing speed in a high humidity environment. % By weight, particularly preferably 10-30% by weight, most preferably 10-20% by weight.

Among the compounds (B), the content of a compound having 3 or more ethylene oxide groups in one molecule (especially the compound represented by the formula (b-2)) (when two or more are contained, the total content) ) Is preferably, for example, 10 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of the cationically polymerizable monomer contained in the monomer mixture, in view of particularly excellent curing speed in a high humidity environment. Particularly preferred is 15 to 30% by weight, and most preferred is 15 to 25% by weight.

As the compound (B), a compound (2B) having 2 or more alicyclic epoxy groups in one molecule (particularly, a compound represented by the formula (b-1)) and one molecule of ethylene oxide group are used. Containing 3 or more compounds (3B) (especially the compound represented by formula (b-2)) can improve the curing rate in a high humidity environment, and It is preferable in that a cured product excellent in alkalinity can be formed, and it is preferable that the weight ratio of (2B) / (3B) is 0.1 to 3.0. The lower limit of the weight ratio is preferably 0.3, particularly preferably 0.5. The upper limit of the weight ratio is preferably 1.8, particularly preferably 1.4, most preferably 1.2, and particularly preferably 0.8.

The total content of the compound (B) in the total amount of the compound having two or more alicyclic epoxy groups in one molecule and the compound having three or more ethylene oxide groups in one molecule (particularly represented by the formula (b-1) The proportion of the total amount of the compound represented by formula (b-2) and the compound represented by formula (b-2) is preferably, for example, 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight. Above, most preferably 90% by weight or more, particularly preferably 95% by weight or more.

Compound (C) [preferably a compound in which R ^c in formula (c) is a divalent hydrocarbon group, or a divalent group in which two or more of the hydrocarbon groups are bonded via a single bond or a linking group. , Most preferably the compound represented by formula (c-1) and formula (c-2)] is the total amount of cationically polymerizable monomers contained in the monomer mixture. The lower limit is preferably 15% by weight, particularly preferably 20% by weight, and most preferably 25% by weight. The upper limit is preferably 45% by weight, particularly preferably 40% by weight. When content of the said compound exceeds the said range, there exists a tendency for the cure rate in a high humidity environment to fall. On the other hand, when the content of the compound is below the above range, the curing rate tends to decrease.

Compound in which R ^c in formula (c) is a divalent hydrocarbon group or a divalent group in which two or more of the hydrocarbon groups are bonded via a single bond or a linking group in the total amount of compound (C) ( Preferably, the proportion of the compound (compounds represented by formula (c-1) and formula (c-2)) (the total content when two or more are contained) is, for example, 60% by weight or more. More preferably, it is 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more.

Compound (D) [wherein R ^d in formula (d) is an m + 1 valent hydrocarbon group or an m + 1 valent group in which two or more hydrocarbon groups are bonded via a linking group (preferably an m + 1 valent aliphatic group). M + 1 valent group in which a hydrocarbon group or two or more aliphatic hydrocarbon groups are bonded via a linking group, particularly preferably a divalent aliphatic hydrocarbon group or two or more aliphatic hydrocarbon groups are linked A divalent group bonded via a group, particularly preferably at least one selected from the compounds represented by formulas (d-1) to (d-4), particularly preferably formula (d -2) to at least one selected from the compounds represented by (d-4)] (the total content when two or more are included) is the total amount of cationically polymerizable monomers contained in the monomer mixture. For example, it is 30% by weight or less, odor generation due to volatilization, curing sensitivity Reduction, preferably in that it is possible to suppress a decrease in adhesion to substrates of the cured product obtained, 25 wt% and more preferably less, particularly preferably 15 wt% or less. Moreover, it is preferable that it is 1 weight% or more at the point which can reduce a viscosity and can improve applicability | paintability, Especially preferably, it is 5 weight% or more.

In the total amount of compound (D), R ^d in formula (d) is an m + 1 valent hydrocarbon group or an m + 1 valent group in which two or more hydrocarbon groups are bonded via a linking group (preferably an m + 1 valent fat An m + 1 valent group in which an aromatic hydrocarbon group or two or more aliphatic hydrocarbon groups are bonded via a linking group, particularly preferably a divalent aliphatic hydrocarbon group or two or more aliphatic hydrocarbon groups. A divalent group bonded via a linking group [particularly preferably, at least one selected from the compounds represented by formulas (d-1) to (d-4), and particularly preferably The proportion of the content (at least one selected from the compounds represented by d-2) to (d-4)] (the total content when two or more are included) is, for example, 60% by weight or more. Is preferable, more preferably 70% by weight or more, particularly preferably 80% by weight or more, Preferably 90 wt% or more, particularly preferably 95 wt% or more.

Containing other cationic polymerizable monomers (for example, a monofunctional cationic polymerizable compound having one cationic polymerizable group (vinyl ether group, epoxy group, or oxetanyl group) in one molecule and no hydroxyl group) The amount (the total content when two or more types are contained) is, for example, 30% by weight or less of the total amount of the cationic polymerizable monomer contained in the monomer mixture. This is preferable in that printing by an inkjet method may be difficult), a decrease in curing sensitivity, and a decrease in adhesion of the obtained cured product to the substrate, more preferably 25% by weight or less, particularly preferably. Is 20% by weight or less, most preferably 15% by weight or less.

In the present invention, the total content of compounds having two cationically polymerizable groups selected from a vinyl ether group, an epoxy group, and an oxetanyl group in one molecule is, for example, 30% of the total amount of cationically polymerizable monomers contained in the monomer mixture. % Or more, more preferably 40% by weight or more, particularly preferably 50% by weight or more, and most preferably 55% by weight or more. The upper limit is, for example, 95% by weight, preferably 90% by weight, particularly preferably 85% by weight, and most preferably 80% by weight.

In the present invention, the total content of compounds having 3 or more cationically polymerizable groups selected from vinyl ether groups, epoxy groups, and oxetanyl groups in one molecule is, for example, 5 of the total amount of cationically polymerizable monomers contained in the monomer mixture. It is preferable that the content is not less than wt% because it is particularly excellent in the curing rate in a high humidity environment, more preferably not less than 10 wt%, and particularly preferably not less than 15 wt%. The upper limit is, for example, 30% by weight.

The monomer mixture of the present invention comprises a compound (A) as the above-mentioned cationic polymerizable monomer, a polyhydric alcohol, and, if necessary, other cationic polymerizable monomers (for example, compounds (B), (C), (D) Etc.) can be produced by uniform mixing using generally known mixing equipment such as a revolving and stirring agitation apparatus, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. Each component may be mixed simultaneously or sequentially.

The monomer mixture having the above-described configuration can form a curable composition by adding a curing catalyst. The curable composition obtained by using the monomer mixture having the above structure is cured rapidly even under a high humidity environment by irradiating with ultraviolet rays, and has high hardness and excellent adhesion to metal or glass. A cured product can be formed.

Among the above monomer mixtures, particularly as compound (B), a compound (2B) having two or more alicyclic epoxy groups in one molecule and a compound (3B) having three or more ethylene oxide groups in one molecule are specified. In the case of a monomer mixture containing at a ratio of, the curable composition containing this is cured rapidly under high humidity environment by irradiating with ultraviolet rays, and has high hardness and excellent adhesion to metal and glass. And a cured product having excellent alkali resistance.

[Curable composition]
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 | cured material obtained may be sufficient. May improve.

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. In the present invention, for example, trade names “CPI-101A”, “CPI-100P”, “CPI-110P” (manufactured by San Apro Co., Ltd.), trade names “CYRACURE UVI-6990”, “CYRACURE UVI-692”. (Above, manufactured by Dow Chemical Co., Ltd.), trade name “UVACURE 1590” (manufactured by Daicel Ornex Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, US Sartomer) Product name: “Irgacure-264” (manufactured by BASF), product name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), product name “PHOTOINITITORＡＴ 2074” (manufactured by Rhodia Japan) Can be preferably used. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the photo radical polymerization initiator 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-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthio Xanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, A camphor quinone etc. are mentioned. In the present invention, for example, trade names “Irgacure-184”, “Irgacure-127”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-651”. "Irgacure-754", "Irgacure-784", "Irgacure-819", "Irgacure-907", "Irgacure-1116", "Irgacure-1173", "Irgacure-1664", "Irgacure-1700", " Commercially available products such as “Irgacure-1800”, “Irgacure-1850”, “Irgacure-2959”, “Irgacure-4043”, “Darocur-1173”, “Darocur-MBF” (manufactured by BASF) can be preferably used. . These can be used individually by 1 type or in combination of 2 or more types.

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.

Further, when the photo radical polymerization initiator is used together with the photo cationic polymerization initiator as a curing catalyst, 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.

Although 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. Examples of other components include well-known and conventional sensitizers (eg, acridine compounds, benzoflavins, perylenes, anthracenes, thioxanthone compounds, laser dyes, etc.), sensitizers, surface conditioners, oxidation Examples thereof include stabilizers and stabilizers such as amines. In particular, when the curable composition of the present invention is 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. The content thereof (the total amount when two or more are included) is, for example, 0.05 to 100 parts by weight with respect to 100 parts by weight of the monomer mixture. The amount is 10 parts by weight, preferably 0.1 to 5 parts by weight.

In addition, as 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. However, it is preferable in that 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. As 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. In addition, as the compound represented by the following formula (f-2), for example, trade name “Anthracure UVS-581” (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) can be used.

In the case where 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. In addition, when it does not contain a color material, it can be used as a clear ink.

(Pigment)
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 yellow lake, azo lake red, etc.), benzimidazolone pigment, β-naphthol pigment, naphthol AS pigment, condensed azo pigment, quinacridone pigment (eg, quinacridone red, Quinacridone magenta, etc.), perylene pigments (eg, perylene red, perylene scarlet, etc.), perinone pigments (eg, perinone orange, etc.), isoindolinone pigments (eg, isoindolinone yellow, isoindolinone orange, etc.), isoindoline. 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 of the dye 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.

In the case of using the curable composition of the present invention as an ultraviolet curable ink-jet ink, it is preferable to contain a dispersing agent together with the above-mentioned color material in order to improve the dispersibility of the color material. Examples of 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 | liquidity, for example, when discharging (or ejecting) using an inkjet printer, it is excellent in dischargeability.

The curable composition of the present invention can be used in a high humidity environment (for example, humidity 50 to 90% RH, preferably humidity 50 to 80% RH, particularly preferably humidity 50 to 70% RH) or in the air. By irradiating with ultraviolet rays, it can be quickly cured 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. Use mercury lamps, mercury xenon lamps, metal halide lamps, tungsten lamps, arc lamps, excimer lamps, excimer lasers, semiconductor lasers, YAG lasers, laser systems combining lasers and nonlinear optical crystals, high-frequency induced ultraviolet light generators, etc. Can do. The ultraviolet irradiation amount (integrated light 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. By performing the heat treatment, the degree of curing can be further improved, and the adhesion to metal and glass can be further improved. When heat treatment is performed, 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 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 cloth, non-woven cloth, cloth, paper (for example, high-quality paper, glassine paper, craft paper, Japanese paper, etc.), silicon wafers, ceramics, and composites thereof, as well as glass, metal Excellent adhesion to (eg, aluminum foil, copper foil, SUS plate, etc.). Therefore, conventionally, in order to adhere a cured product to glass or metal, it has been necessary to perform pretreatment (for example, primer treatment) on the surface of glass or metal, but the curable composition of the present invention is used. In this case, it is not necessary to perform a pretreatment, and a cured product having excellent adhesion can be formed by directly applying to glass or metal and curing, so that the workability is extremely excellent.

Accordingly, 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.

Further, among the curable composition of the present invention, the curable composition containing a specific monomer mixture is not only excellent in acid resistance and neutral resistance, but also in a cured product excellent in alkali resistance, and its A molded product and a structure including the cured product can be formed.

If 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. Ink films having high hardness can be formed.
In the case of a curable composition containing a specific monomer mixture, it further has excellent alkali resistance, and forms an ink film that does not dissolve or become cloudy even when wiped with an alkaline chemical. be able to.

[Molded product and manufacturing method thereof]
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.

Since 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.

[Structure and manufacturing method thereof]
The structure of this invention has the structure provided with the hardened | cured material of the said curable composition on the base-material surface. 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.

As the substrate, 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 plastic but also to metal or glass) and adheres to the substrate. The property is, for example, classification 0 to 2 in a 6-step classification test by the cross-cut method (conforming to JIS K 5600-5-6).

Moreover, since 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 | cured material of the said curable composition on the base-material surface) is manufactured efficiently. be able to.

Furthermore, since 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.
Furthermore, in the case of a cured product of a curable composition containing a specific monomer mixture, since the alkali resistance is also excellent, for example, the structure of the present invention comprises a cured product of the curable composition on the substrate surface. In the case of a structure having printing, the printing has a characteristic that it is difficult to disappear even if wiped with an alkaline chemical or the like.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

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.

Examples 2 to 23, Comparative Examples 1 to 4
Inks were obtained in the same manner as in Example 1 except that the formulation was changed as described in Tables 1 and 2 (units are parts by weight). In Examples 19 to 23, each component was mixed and then filtered using a 1 μm PTFE filter.

(Curability evaluation under high humidity environment)
The ink obtained in Examples and Comparative Examples was applied on a glass plate (trade name “S9112”, manufactured by Matsunami Glass Co., Ltd.) using a bar coater (# 4) (coating thickness: 5 μm), and 24 to 25 ° C. , 365nm light (illuminance: 1.5W / cm) using an LED irradiator (trade name “UV-LED PROCESSOR LSS-05”, manufactured by CCR) as a light source under the conditions of air atmosphere and humidity 50-80% ² ) was irradiated [one irradiation amount (exposure amount was 1 J / cm ² and repeatedly irradiated until tackiness disappeared)], and the curability was evaluated by the number of irradiations.

(Alkali resistance evaluation)
The ink obtained in Example or Comparative Example was applied to an ABS base material (trade name “Hishiplate 296”, manufactured by Mitsubishi Plastics Co., Ltd.) to a thickness of about 10 μm using a bar coater, and an LED irradiator was used. Then, it was cured by irradiating 365 nm light until tackiness disappeared, and a cured product / ABS base material laminate was obtained. The obtained laminate was further subjected to heat treatment at 80 ° C. for 30 minutes using an oven. This was used as a sample.
The obtained sample was immersed in the following alkaline chemicals at room temperature for 24 hours. After immersion, the change in appearance was visually observed and evaluated according to the following criteria.
Alkaline chemicals: 4% sodium hypochlorite + 1% NaOH-containing aqueous solution (pH = 13) + N, N-dimethyldodecylamine N-oxide 1% by weight

<Evaluation criteria for alkali resistance>
There is no cloudiness in the cured product and there is no dissolution: very good alkali resistance (◎)
Cloudy but no dissolution: good alkali resistance (○)
Part of the cured product of the sample is dissolved: Alkaline resistance is slightly poor (△)
Completely melts the cured product of the sample: poor alkali resistance (x)

(Evaluation of adhesion to metal)
The inks obtained in the examples and comparative examples were applied onto an aluminum plate (trade name “A1050P”, manufactured by ASONE) using a bar coater (# 4) (coating thickness: 5 μm), 24 to 25 ° C., Light irradiation under the conditions of air atmosphere and humidity 50% or 70% (using LED irradiator (trade name “UV-LED PROCESSOR LSS-05”, manufactured by CCR) as a light source) eliminates tackiness of 365 nm light To obtain a cured product / aluminum plate laminate (1), and post-bake the resulting cured product / aluminum plate laminate (1) at a temperature of 120 ° C. for 10 minutes using an oven. The cured product / aluminum plate laminate (2) was obtained.

The adhesion of the obtained cured product / aluminum plate laminate (2) was evaluated by a method based on the “cross-cut method” of JIS K 5600-5-6.
Specifically, using a cutter knife, 100 crosscuts (cut pieces) that reach the aluminum plate by cutting the cured product / aluminum plate laminate (2) vertically and horizontally from the cured product surface side are performed. Formed.
Adhesive tape (trade name “Nichiban Tape No. 1”, manufactured by Nichiban Co., Ltd.) is attached to the crosscut and peeled off. The remaining crosscut without peeling from the aluminum plate is counted, and this is adhered. It was used as an index of sex. In addition, it is excellent in adhesiveness, so that there are many crosscuts which remain | survived without peeling.

(Adhesion evaluation to glass)
A cured product / glass plate laminate was obtained and obtained in the same manner as described above (evaluation of adhesion to metal) except that a glass plate (trade name “S9112” manufactured by Matsunami Glass Co., Ltd.) was used instead of the aluminum plate. The adhesion of the cured product / glass plate laminate to the glass plate was evaluated.

The results are summarized in the following table.

The abbreviations in the table are described below.
<Vinyl ether compound>
ISBDVE: isosorbide divinyl ether, trade name “ISB-DVE”, manufactured by Daicel Corporation HEVE: ethylene glycol monovinyl ether <epoxy compound>
2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P”, manufactured by Daicel Corporation YH300: trimethylolpropane triglycidyl ether <oxetane compound>
OXT101: 3-ethyl-3-hydroxymethyloxetane, boiling point 105 ° C./0.93 kPa, viscosity at 25 ° C .: 17 to 22 mPa · s, trade name “Aron Oxetane OXT-101”, manufactured by Toagosei Co., Ltd. OXT212: 3 -Ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, boiling point 133 ° C./1.33 kPa, viscosity at 25 ° C .: 3 to 6 mPa · s, trade name “Aron Oxetane OXT-212”, Toagosei Co., Ltd. OXT221: bis [1-ethyl (3-oxetanyl)] methyl ether, trade name “Aronoxetane OXT-221”, boiling point 119 ° C./0.67 kPa, viscosity at 25 ° C .: 9-14 mPa · s, Toagosei Co., Ltd. OXT121: 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl ] Benzene, solid at 25 ° C., trade name "ARON OXT-121", manufactured by Toagosei Co., Ltd. ALOX: 3- allyloxy oxetane, viscosity at boiling point 146 ℃ / 760mmHg, 25 ℃: 9mPa · s
<Polyhydric alcohol>
TMP: trimethylolpropane TCDDM: tricyclo [5.2.1.0 ^2,6 ] decanedimethanol HBPA: hydrogenated bisphenol A (= 2,2′-bis (4-hydroxycyclohexyl) propane)
<Curing catalyst>
CPI-110P: Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate and thiodi-p-phenylenebis (diphenylsulfonium) bis (hexafluorophosphate) mixture (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>
UVS1331: 9,10-dibutoxyanthracene, trade name “anthracure UVS-1331”, manufactured by Kawasaki Kasei Kogyo Co., Ltd. UVS581: 9,10-di (capryloyloxy) anthracene, tradename “anthracure UVS-581” Manufactured by Kawasaki Chemical Industries Co., Ltd.
Pigment Blue 15: 4: Copper phthalocyanine Pigment Red 122: 3,10-dimethylquinacridone Pigment Yellow 155: 2,2 ′-(1,4-phenylene-bis [imino (1-acetyl-2-oxoethane-2,1- Diyl) azo]) bis (dimethyl terephthalate)
Pigment Black 7: Carbon black Pigment White 6: Titanium dioxide <dispersant>
Product name "Azisper", polymer pigment dispersant, manufactured by Ajinomoto Fine Techno Co., Ltd.

As a summary of the above, the configuration of the present invention and its variations are appended below.
[1] Cationic polymerizable monomer (I) containing at least a polyvalent vinyl ether compound (A) having a structure in which two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton or heterocyclic skeleton, and two or more The hydroxyl group-containing monomer (II) having a hydroxyl group and having no cationically polymerizable group is contained in an amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of (I). Monomer mixture.
[2] The monomer mixture according to [1], wherein the polyvalent vinyl ether compound (A) is a compound represented by the formula (a-1) and / or (a-2).
[3] The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 1 to 20% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. , [1] or the monomer mixture according to [2].
[4] The total content of the compound represented by the formula (a-1) and the compound represented by the formula (a-2) is 60% by weight or more of the total amount of the polyvalent vinyl ether compound (A), [1 ] The monomer mixture according to any one of [3] to [3].
[5] A compound in which the hydroxyl group-containing monomer (II) has a structure in which three or more hydroxyl groups are bonded to a branched aliphatic hydrocarbon skeleton and / or a compound in which two hydroxyl groups are bonded to an alicyclic skeleton. The monomer mixture according to any one of [1] to [4].
[6] The hydroxyl group-containing monomer (II) is at least one compound selected from glycerin, sorbitol, pentaerythritol, tetramethylene glycol, hexamethylene glycol, and trimethylolpropane, [1] to [4] The monomer mixture as described in any one.
[7] The hydroxyl group-containing monomer (II) is an alicyclic skeleton selected from formulas (2-1) to (2-6), wherein two or more hydroxyl groups are directly or an alkylene group having 1 to 3 carbon atoms (preferably Is a compound bonded via a methylene group). The monomer mixture according to any one of [1] to [4].
[8] The cation polymerizable monomer (I) further contains a polyvalent epoxy compound (B) and a polyvalent oxetane compound (C), and the content of (A) is the total amount of the cation polymerizable monomer (I). Any one of [1] to [7], wherein 5 to 20% by weight, and the total content of (A), (B) and (C) is 65% by weight or more of the total amount of the cationic polymerizable monomer (I) The monomer mixture described in 1.
[9] The monomer mixture according to [8], wherein the polyvalent epoxy compound (B) contains a compound represented by the formula (b-1).
[10] The monomer mixture according to [9], wherein L in the formula (b-1) is a group containing an ester bond.
[11] The compound represented by the formula (b-1) is at least one compound selected from compounds represented by the formulas (b-1-1) to (b-1-8). 9] The monomer mixture described in [9].
[12] Any one of [8] to [11], wherein the polyvalent epoxy compound (B) contains a compound represented by the formula (b-1) and a compound represented by the formula (b-2) The monomer mixture described in 1.
[13] The compound represented by the formula (b-2) is trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, and dipenta The monomer mixture according to [12], which is at least one compound selected from erythritol hexaglycidyl ether.
[14] The monomer mixture according to any one of [8] to [13], wherein the content of the polyvalent epoxy compound (B) is 10 to 50% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. .
[15] The total content of the compound represented by the formula (b-1) and the compound represented by the formula (b-2) is 10 to 50% by weight of the total amount of the cationic polymerizable monomers contained in the monomer mixture. , [12] to [14] The monomer mixture according to any one of [14].
[16] Any one of [9] to [15], wherein the content of the compound represented by the formula (b-1) is 10 to 50% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. The monomer mixture described in 1.
[17] Any one of [12] to [16], wherein the content of the compound represented by the formula (b-2) is 10 to 50% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. The monomer mixture described in 1.
[18] The weight ratio of the compound represented by formula (b-1) to the compound represented by formula (b-2) (the former / the latter) is 0.1 to 3.0, [12] to [ [17] The monomer mixture according to any one of [17].
[19] The total content of the compound represented by the formula (b-1) and the compound represented by the formula (b-2) is 60% by weight or more of the total amount of the polyvalent epoxy compound (B), [12 ] To [18] The monomer mixture according to any one of [18].
[20] Any of [8] to [19], wherein the polyvalent oxetane compound (C) is at least one compound selected from compounds represented by formulas (c-1) to (c-2) A monomer mixture according to any one of the above.
[21] The monomer according to any one of [8] to [20], wherein the content of the polyvalent oxetane compound (C) is 10 to 50% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. blend.
[22] The total content of the compound represented by the formula (c-1) and the compound represented by the formula (c-2) is 10 to 50% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture. , [20] or the monomer mixture according to [21].
[23] The total content of the compound represented by the formula (c-1) and the compound represented by the formula (c-2) is 60% by weight or more of the total amount of the polyvalent oxetane compound (C), [20 ] To [22] The monomer mixture according to any one of [22].
[24] The cation polymerizable monomer (I) further contains a compound (D) having one cation polymerizable group and a hydroxyl group in an amount of 5 to 30% by weight based on the total amount of the cation polymerizable monomer (I). ] To [23] the monomer mixture according to any one of [23].
[25] The monomer mixture according to [24], wherein the compound (D) is at least one compound selected from compounds represented by formulas (d-1) to (d-4).
[26] The monomer mixture according to [24], wherein the compound (D) is at least one compound selected from compounds represented by formulas (d-2) to (d-4).
[27] The monomer mixture according to any one of [24] to [26], wherein the content of the compound (D) is 1 to 30% by weight of the total amount of the cationically polymerizable monomers contained in the monomer mixture.
[28] The content of the compounds represented by formulas (d-1) to (d-4) (the total amount when two or more are contained) is 60% by weight or more of the total amount of the compound (D). The monomer mixture according to any one of 24] to [27].
[29] The content of the compounds represented by the formulas (d-2) to (d-4) (when two or more compounds are contained, the total amount thereof) is 60% by weight or more of the total amount of the compound (D). The monomer mixture according to any one of 24] to [28].
[30] The content of monofunctional cation polymerizable monomers (excluding monomers containing a hydroxyl group) (when two or more types are included, the total amount thereof) is 30% by weight or less of the total amount of the cation polymerizable monomers contained in the monomer mixture. The monomer mixture according to any one of [1] to [29].
[31] The monomer mixture according to any one of [1] to [30], wherein the bifunctional cation polymerizable monomer is 30% by weight or more of the total amount of the cation polymerizable monomer contained in the monomer mixture.
[32] The monomer mixture according to any one of [1] to [31], wherein the trifunctional or higher functional cationic polymerizable monomer is 5 to 30% by weight of the total amount of the cationic polymerizable monomer contained in the monomer mixture.
[33] A curable composition containing the monomer mixture according to any one of [1] to [32] and a curing catalyst.
[34] The curable composition according to [33], containing a sensitizer or a sensitizer and a sensitization aid.
[35] The curable composition according to [33] or [34], which contains a coloring material.
[36] The curable composition according to any one of [33] to [35], which contains a dispersant.
[37] The curable composition according to any one of [33] to [36], which is an ultraviolet curable inkjet ink.
[38] The curable composition according to any one of [33] to [36], which is a coating agent.
[39] The curable composition according to any one of [33] to [36], which is an adhesive.
[40] The curable composition according to any one of [33] to [39], which has a viscosity of 1 to 1000 mPa · s at 25 ° C. and a shear rate of 100 (1 / s).
[41] The curable composition according to any one of [33] to [40], having the following curability.
Curability:
Irradiate 365 nm light (exposure amount: 1 J / cm ² ) to the coating film (thickness: 5 μm) of the curable composition under an air atmosphere and humidity of 50 to 90% RH until tackiness disappears The number of times of irradiation is 5 or less.
[42] A cured product of the curable composition according to any one of [33] to [41].
[43] The cured product according to [42], which has the following alkali resistance.
Alkali resistance:
Even if the cured product is immersed for 24 hours in an alkaline chemical in which 1% by weight of N, N-dimethyldodecylamine N-oxide is added to an aqueous solution of pH 13 containing 4% sodium hypochlorite and 1% NaOH. Does not dissolve.
[44] Described in [42] or [43], wherein the adhesion to a metal substrate and a glass substrate is a classification 0 to 3 in a 6-step classification test by a cross-cut method in accordance with JIS K 5600-5-6. Cured product.
[45] A molded article comprising the cured product according to any one of [42] to [44].
[46] The curable composition according to any one of [33] to [41] is ejected by an ink jet method, and then the ejected curable composition is cured. A method for producing a molded product, which obtains a molded product comprising a cured product.
[47] A structure provided with the cured product according to any one of [42] to [44] on a substrate surface.

The monomer mixture of the present invention has low viscosity and excellent coatability before being irradiated with ultraviolet rays, and is cured rapidly by irradiating with ultraviolet rays even in a high humidity environment. It is suitable as a raw material for a curable composition capable of forming a cured product having excellent adhesion.
And the curable composition containing the monomer mixture of this invention is suitable as an ultraviolet curable inkjet ink, a coating agent, an adhesive agent, etc.

Claims (17)

A cationically polymerizable monomer (I) containing at least a polyvalent vinyl ether compound (A) having a structure in which two or more vinyl ether groups are bonded to a chain or cyclic hydrocarbon skeleton, or a heterocyclic skeleton; and two or more hydroxyl groups. A monomer mixture containing a hydroxyl group-containing monomer (II) having no cationic polymerizable group and 0.01 to 20 parts by weight of (II) with respect to 100 parts by weight of (I). The monomer mixture according to claim 1, wherein the polyvalent vinyl ether compound (A) is a compound represented by the following formula (a-1) and / or (a-2).

The hydroxyl group-containing monomer (II) is a compound having a structure in which three or more hydroxyl groups are bonded to a branched hydrocarbon skeleton and / or a compound having a structure in which two hydroxyl groups are bonded to an alicyclic skeleton. The monomer mixture according to 1 or 2. The cation polymerizable monomer (I) further contains a polyvalent epoxy compound (B) and a polyvalent oxetane compound (C), and the content of (A) is 5 to 20 of the total amount of the cation polymerizable monomer (I). The monomer according to any one of claims 1 to 3, wherein the total content of (A), (B), and (C) is 65% by weight or more of the total amount of the cationic polymerizable monomer (I). blend. The polyvalent epoxy compound (B) is represented by the following formula (b-1)

(Wherein L represents a single bond or a linking group)
The monomer mixture of Claim 4 containing the compound represented by these. The cation polymerizable monomer (I) further contains a compound (D) having one cation polymerizable group and a hydroxyl group in an amount of 5 to 30% by weight based on the total amount of the cation polymerizable monomer (I). The monomer mixture according to any one of the above. A curable composition comprising the monomer mixture according to any one of claims 1 to 6 and a curing catalyst. The curable composition according to claim 7 containing a sensitizer or a sensitizer and a sensitization aid. The curable composition according to claim 7 or 8, comprising a coloring material. The curable composition according to any one of claims 7 to 9, comprising a dispersant. The curable composition according to any one of claims 7 to 10, which is an ultraviolet curable inkjet ink. The curable composition according to any one of claims 7 to 10, which is a coating agent. The curable composition according to claim 7 or 8, which is an adhesive. A cured product of the curable composition according to any one of claims 7 to 13. A molded product comprising the cured product according to claim 14. A molded product obtained by discharging the curable composition according to claim 11 by an inkjet method and then curing the discharged curable composition to obtain a molded product made of a cured product of the curable composition. Manufacturing method. A structure provided with the cured product according to claim 15 on a substrate surface.