JP2019135277A - Monomer mixture, and curable composition containing the same - Google Patents

Abstract

To provide a monomer mixture rapidly curing even under highly humid environment, and for forming a cured product having excellent adhesion to not only plastic but also metal and glass.SOLUTION: A monomer mixture of the present invention is a monomer mixture composed of 2 or more cationically polymerizable monomers, and containing a compound (A) having 1 oxetanyl group and 1 hydroxy group, a compound (B) having 2 or more oxetanyl groups, and a compound (C) having 2 or more alicyclic epoxy groups, where the content of the compound (A) is 10-40 wt.% to a total amount of the monomer mixture, the content of the compound (C) is 40 wt.% or more to a total amount of the monomer mixture, and the total content of the compound (A), the compound (B), and the compound (C) is 80 wt.% or more to a total amount of the monomer mixture.SELECTED DRAWING: None

Description

  The present invention relates to a monomer mixture and a curable composition containing the same. The curable composition can be suitably used as an ultraviolet curable inkjet ink, a coating agent, an adhesive, and the like.

  The ink jet recording method in which printing is performed 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. As inkjet inks used in this inkjet recording method, cationic curable inks and radical curable inks are known.

  The radical curable ink has been used frequently because it has a fast curing property and has many types of monomers. However, in the ink jet recording method, low-viscosity ink is used from the viewpoint of dischargeability, and oxygen easily diffuses and enters the ink from the atmosphere. In addition, since 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.

  On the other hand, the cationic curable ink does not receive curing inhibition due to oxygen. In addition, the substrate adhesion is superior to radical curable inks. In Patent Document 1, a cation-curable composition containing alicyclic epoxy compound, di- or trivinyl ether compound, and 3-alkyl-3-hydroxyalkyloxetane as monomers has a 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.

Japanese Patent No. 3893833

  However, 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.

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 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 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 by the present inventors to solve the above problems, 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 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.

  That is, the present invention is a monomer mixture composed of two or more kinds of cationically polymerizable monomers, which is a compound (A) having one oxetanyl group and one hydroxyl group, and a compound (B) having two or more oxetanyl groups. And a compound (C) having two or more alicyclic epoxy groups, the content of the compound (A) is 10 to 40% by weight of the total amount of the monomer mixture, and the content of the compound (C) is a monomer. Provided is a monomer mixture in which the total content of the compound (A), the compound (B) and the compound (C) is 80% by weight or more of the total amount of the monomer mixture.

（式中、Ｘは単結合又は連結基を示す）
で表される化合物である、前記のモノマー混合物を提供する。 In the present invention, the compound (C) is represented by the following formula (c):

(Wherein X represents a single bond or a linking group)
A monomer mixture as described above is provided.

In the present invention, the compound (B) is represented by the following formula (b-1):
Y-R ^b1 -Y (b-1)
(Wherein R ^b1 represents a divalent aliphatic hydrocarbon group or a divalent group in which two or more of the aliphatic hydrocarbon groups are bonded via a linking group, and Y represents an oxetanyl group)
A monomer mixture as described above is provided.

  The present invention also provides the monomer mixture, wherein the content ratio of the compound (A) to the compound (C) (the former / the latter; the weight ratio) is 20/80 to 45/55.

  The present invention also provides a curable composition containing the monomer mixture and a curing catalyst.

  The present invention also provides the above-mentioned curable composition containing a sensitizer or a sensitizer and a sensitization aid.

  The present invention also provides the above curable composition containing a colorant.

  The present invention also provides the above curable composition containing a dispersant.

  The present invention also provides the curable composition, which is an ultraviolet curable ink jet ink.

  The present invention also provides the above curable composition which is a coating agent.

  The present invention also provides the curable composition as described above, which is an adhesive.

  The present invention also provides a cured product of the curable composition.

  The present invention also provides a molded article comprising 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 having the cured product on the surface of a substrate.

  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. Therefore, the said curable composition can be used conveniently as an ultraviolet curable inkjet ink, a coating agent, an adhesive agent, etc.

  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 is a monomer mixture composed of two or more kinds of cationically polymerizable monomers, and includes a compound (A) having one oxetanyl group and one hydroxyl group, and a compound having two or more oxetanyl groups (B And a compound (C) having two or more alicyclic epoxy groups.

(Compound (A))
Compound (A) is a compound having one oxetanyl group and one hydroxyl group, and is a cationically polymerizable monomer. The curable composition containing the compound (A) is excellent in curability, and the cured product obtained by curing the curable composition has excellent adhesion to metal and glass. Moreover, it has high hardness and low curing shrinkage.

The compound (A) is represented by the following formula (a), for example.
HO-R ^a -Y (a)
(In the formula, 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, and Y represents an oxetanyl group)

  The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

  Examples of the divalent aliphatic hydrocarbon group 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-butadinylene 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.

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, and perhydrophenalene. 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 (eg, cycloalkadiene dimers such as cyclopentadiene, cyclohexadiene, cycloheptadiene), hydrogenated products thereof, and the like.

  As a bivalent aromatic hydrocarbon group, C6-C18 arylene groups, such as a phenylene group, a biphenylene group, a naphthylene group, are mentioned, for example.

  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. In addition, an aromatic or non-aromatic heterocyclic ring may be condensed with a ring of an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The heterocyclic ring constituting the divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. For example, 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, γ-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-oxatri cyclo [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, Isochiazo Ring, 5-membered ring such as thiadiazole ring; 6-membered ring such as 4-oxo-4H-thiopyran ring; condensed ring such as benzothiophene ring, etc., heterocycle containing nitrogen atom as a hetero atom (eg, pyrrole ring, pyrrolidine) 5-membered rings such as rings, pyrazole rings, imidazole rings and triazole rings; 6-membered rings such as pyridine rings, pyridazine rings, pyrimidine rings, pyrazine rings, piperidine rings, piperazine rings; indole rings, indoline rings, quinoline rings, acridine rings , A naphthyridine ring, a quinazoline ring, a condensed ring such as a purine ring, etc.). In addition to the substituents that the hydrocarbon group may have, 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. Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the structural formula of the heterocyclic ring.

  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-) 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 of aliphatic hydrocarbon groups are bonded via a linking group, most preferably a linear or branched alkylene group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. 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 a compound represented by the following formula (a-1) (= compound (a-1)).

  As said compound (A), commercial items, such as "Aron oxetane OXT-101" (made by Toagosei Co., Ltd.), can be used, for example.

(Compound (B))
Compound (B) is a compound having two or more oxetanyl groups. 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.

Examples of the compound (B) include compounds represented by the following formula (b).
R ^b − (Y) _t (b)
(In the formula, R ^b represents a t-valent organic group, Y represents an oxetanyl group, and t represents an integer of 2 or more)

The t-valent organic group in R ^b 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.

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

Examples of the t-valent hydrocarbon group and the heterocyclic group include ^a divalent hydrocarbon group and a heterocyclic group in ^Ra above, and a t-valent group (t ≧ 3) corresponding thereto. Examples of the linking group include the same examples as the linking group for ^Ra .

The t-valent organic group is preferably a t-valent hydrocarbon group or a t-valent group in which two or more hydrocarbon groups are bonded via a linking group (particularly preferably, an ether bond). 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.

The compound (B) preferably contains at least a compound having two oxetanyl groups (for example, a compound in which t in the above formula (b) is 2). For example, in the following formula (bI) And a compound represented by the following formula (b-II). As the compound (B), for example, commercially available products such as “Aron oxetane OXT-221”, “Aron oxetane OXT-121” (manufactured by Toagosei Co., Ltd.) can be used.

As the compound (B), in particular, the following formula (b-1)
Y-R ^b1 -Y (b-1)
(Wherein R ^b1 represents a divalent aliphatic hydrocarbon group or a divalent group in which two or more of the aliphatic hydrocarbon groups are bonded via a linking group, and Y represents an oxetanyl group)
It is preferable to contain at least a compound represented by the formula (= compound (b-1)), and it is particularly preferable to contain at least a compound represented by the formula (bI) (= compound (bI)).

(Compound (C))
Compound (C) is a compound having two or more alicyclic epoxy groups and is a cationically polymerizable monomer. The compound (C) does not include a compound having one oxetanyl group and one hydroxyl group or a compound having two or more oxetanyl groups. The curable composition containing the compound (C) has fast curability, and the cured product obtained by curing the curable composition has high hardness. The “alicyclic epoxy group” in the present specification is an epoxy group composed of two adjacent carbon atoms constituting the alicyclic ring and an oxygen atom, and includes, for example, a cyclohexene oxide group. .

As said compound (C), the compound represented by a following formula (c) is mentioned, for example.

  In said formula (c), X shows a single bond or a coupling 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 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, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. 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 may be bonded to the cyclohexene oxide group in the above formula (c). Examples of the substituent include a halogen atom, a C _1-10 alkyl group, a C _1-10 alkoxy group, C _{2 -10} alkenyloxy 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 Examples thereof include an aralkyloxycarbonyl group, an epoxy group-containing group, an oxetanyl group-containing group, a C _1-10 acyl group, an isocyanate group, a sulfo group, a carbamoyl group, and an oxo group.

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). In addition, L in the following formula (c-5) is 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). Moreover, n < ¹ >, n < ² > in following formula (c-5) (c-7) shows the integer of 1-30, respectively.

Examples of the compound (C) include compounds having three or more alicyclic epoxy groups such as compounds represented by the following formulas (c-9) and (c-10). N < ³ > -n < ⁸ > in a following formula shows the integer of 1-30, respectively.

  The compound (C) preferably contains at least a compound represented by the above formula (c) (= compound (c)), particularly represented by the above formula (c), It contains at least a compound in which X is a group containing an ester bond (= compound (c-1)), which cures rapidly even in a high humidity environment, and has excellent adhesion to metal and glass and high hardness. It is preferable at the point which can form the hardened | cured material which has.

(Other cationic polymerizable monomers)
The monomer mixture of the present invention may contain one or more other cationic polymerizable monomers in addition to the compound (A), the compound (B), and the compound (C).

  Examples of the other cationic polymerizable monomers include monomers having at least one cationic polymerizable group (for example, vinyl ether group, oxetanyl group, epoxy group).

Examples of other cationic polymerizable monomers include the following compounds.
(1) Compound having one or more vinyl ether groups (2) Compound having alicyclic epoxy group and glycidyl ether group (3) Compound having two or more glycidyl ether groups (4) Compound having two or more ethylene oxide groups

(Compound (1) having at least one vinyl ether group)
Compound (1) is a compound having one or more vinyl ether groups and is a cationically polymerizable monomer. The compound (1) does not include a compound corresponding to the above compound (A), compound (B), or compound (C).

Compound (1) is represented by the following formula (1), for example.
R ¹ — (O—CH═CH ₂ ) _s (1)
(Wherein R ¹ represents an optionally substituted s-valent hydrocarbon group, s-valent heterocyclic group, or an s-valent group in which these are bonded via a single bond or a linking group. S represents an integer of 1 or more)

Examples of the s-valent hydrocarbon group, the s-valent heterocyclic group, and the s-valent group in which they are bonded via a single bond or a linking group include the divalent hydrocarbon group in R ^b described above, divalent And a divalent group in which these are bonded via a single bond or a linking group, and an s-valent group corresponding thereto.

  Examples of the substituent that the s-valent hydrocarbon group, the s-valent heterocyclic group, and the s-valent group in which they are bonded through a single bond or a linking group may have include a halogen atom, Hydroxyl group, oxo group, substituted oxy group (for example, alkoxy group, aryloxy group, aralkyloxy 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, sulfo group, heterocyclic group and the like.

Examples of the compound (1) include compounds containing a hydroxyl group and a vinyl ether group represented by the following formulas (1-1) to (1-3).

  As the compound (1), two or more vinyl ether groups are bonded to an aliphatic hydrocarbon group such as 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether or the like. Compounds.

The compound (1) further includes two or more vinyl ethers in a non-aromatic heterocyclic skeleton such as a compound represented by the following formula (1-4) and a compound represented by the following formula (1-5). A compound having a group bonded thereto may also be mentioned.

(Compound having alicyclic epoxy group and glycidyl ether group (2))
Compound (2) is a compound having an alicyclic epoxy group and a glycidyl ether group, and is a cationically polymerizable monomer. The compound (2) does not include a compound corresponding to the above compound (A), compound (B), compound (C), or compound (1).

Examples of the compound (2) include a compound represented by the following formula (2-1).

(Compound (2) having two or more glycidyl ether groups)
Compound (3) is a compound having two or more glycidyl ether groups and is a cationically polymerizable monomer. The compound (3) does not include a compound corresponding to the above compound (A), compound (B), compound (C), compound (1), or compound (2).

Examples of the compound (3) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenol type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type epoxy compounds, and the like; hydrogenated bisphenol A type epoxy Compounds, alicyclic epoxy compounds such as hydrogenated bisphenol F type epoxy compounds, hydrogenated biphenol type epoxy compounds, hydrogenated phenol novolac type epoxy compounds, hydrogenated cresol novolac type epoxy compounds; the following formulas (3-1) to (3 -5), trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, dipentaerythritol hexaglycidyl ether, etc. It includes aliphatic epoxy compounds.

(Compound (2) having two or more ethylene oxide groups)
Compound (4) is a compound having two or more ethylene oxide groups and is a cationically polymerizable monomer. The compound (4) does not include a compound corresponding to the above compound (A), compound (B), compound (C), compound (1), compound (2), or compound (3).

Examples of the compound (4) include a compound represented by the following formula (4-1).

In 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. Examples of 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, and n ⁹ is preferably 1 to 30. When p is 2 or more, n ⁹ in each [] (inside square brackets) may be the same or different. Specifically, the compound represented by the above formula (4-1) is a 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. [For example, trade name “EHPE3150” (manufactured by Daicel Corporation), etc.] and the like.

(Monomer mixture and production method thereof)
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 content of the compound (A) is 10 to 40% by weight of the total amount of the monomer mixture, and the lower limit is preferably 15% by weight, particularly preferably 18% by weight, and most preferably 20% by weight. The upper limit is preferably 35% by weight, particularly preferably 28% by weight, most preferably 25% by weight.

  The content of the compound (a-1) is preferably, for example, 10 to 40% by weight of the total amount of the monomer mixture, and the lower limit is more preferably 15% by weight, particularly preferably 18% by weight, and most preferably 20% by weight. The upper limit is more preferably 35% by weight, particularly preferably 28% by weight, and most preferably 25% by weight.

  The content of the cationically polymerizable monomer having a hydroxyl group in the monomer mixture of the present invention is, for example, 10% by weight or more, preferably 15% by weight or more, particularly preferably 18% by weight or more, most preferably the total amount of the monomer mixture. 20% by weight or more. The upper limit is, for example, 45% by weight, preferably 40% by weight, particularly preferably 35% by weight. When the content of the cationically polymerizable monomer having a hydroxyl group is lower than the above range, a cured product having excellent adhesion to metal or glass tends to be difficult to obtain. On the other hand, when the content of the cationically polymerizable monomer having a hydroxyl group becomes excessive, the curability in a high humidity environment tends to be lowered.

  The proportion of the compound (A) in the total amount of the cationically polymerizable monomer having a hydroxyl group contained in the monomer mixture of the present invention is, for example, 60% by weight or more, preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably. Is 90% by weight or more, particularly preferably 95% by weight or more. When the proportion of the compound (A) is less than the above range, the curability in a high humidity environment tends to decrease.

  The content of the compound (B) is preferably 5 to 45% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight, based on the total amount of the monomer mixture.

  The content of the compound (b-1) is, for example, preferably 5 to 45% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight, based on the total amount of the monomer mixture.

  The content of the compound (b-I) is preferably, for example, 5 to 45% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 35% by weight, based on the total amount of the monomer mixture.

  The content of the compound (C) is 40% by weight or more, preferably 45% by weight or more, particularly preferably 50% by weight or more of the total amount of the monomer mixture. Moreover, the upper limit of content of the said compound (C) is 60 weight%, for example, Preferably it is 55 weight%.

  The content of the compound (c) is 40% by weight or more, preferably 45% by weight or more, particularly preferably 50% by weight or more of the total amount of the monomer mixture. Moreover, the upper limit of content of the said compound (C) is 60 weight%, for example, Preferably it is 55 weight%.

  The content of the compound (c-1) is, for example, preferably 40% by weight or more, more preferably 45% by weight or more, and particularly preferably 50% by weight or more of the total amount of the monomer mixture. Moreover, the upper limit of content of the said compound (C) is 60 weight%, for example, Preferably it is 55 weight%.

  The total content of the compound (A), the compound (B) and the compound (C) is 80% by weight or more of the total amount of the monomer mixture, preferably 85% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more.

  The ratio of the content of the compound (A) to the compound (C) (the former / the latter; the weight ratio) is, for example, 20/80 to 45/55, preferably 25/75 to 40/60, particularly preferably 25/75. ~ 35/65.

  The ratio of the content of the compound (A) to the compound (B) (the former / the latter; the weight ratio) is, for example, 20/80 to 80/20, preferably 30/70 to 70/30, particularly preferably 40/60. -60/40, most preferably 45 / 55-55 / 45.

  The ratio of the content of the compound (B) to the compound (C) (the former / the latter; the weight ratio) is, for example, 20/80 to 45/55, preferably 25/75 to 40/60, particularly preferably 25/75. ~ 35/65.

  The ratio of the content of the compound (C) and the content of the compound (A) and the compound (B) [compound (C) / (compound (A) + compound (B); weight ratio) is, for example, 30/70 70/30, preferably 40/60 to 60/40, particularly preferably 45/55 to 55/45.

  The monomer mixture of the present invention has a low content of a compound containing a hydroxyl group and a vinyl ether group (for example, a compound represented by the above formulas (1-1) to (1-3)) in a high humidity environment. The content of the compound is preferably 15% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the monomer mixture. Most preferably, it is 5 weight% or less.

  The monomer mixture of the present invention also contains a compound in which two or more vinyl ether groups are bonded to a non-aromatic heterocyclic skeleton (for example, a compound represented by the above formula (1-4) or the above formula (1-5) It is preferable that the content of the compound is low in terms of excellent curability in a high-humidity environment, and the content of the compound (the total amount when two or more are included) is the total amount of the monomer mixture It is preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 3% by weight or less.

  The monomer mixture of the present invention further has a low content of the compound (3) having two or more glycidyl ether groups (for example, compounds represented by the above formulas (3-1) to (3-5)). In view of excellent curability in a high-humidity environment, the content of the compound (when 2 or more types are contained, the total amount thereof) is preferably less than 10% by weight, particularly preferably. 5% by weight or less, most preferably 3% 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.

  When a curing catalyst is mixed with the monomer mixture having the above structure, a curable composition is obtained. The curable composition thus obtained has excellent curability even in a high humidity environment, and can form a cured product having excellent adhesion to glass or metal. Therefore, the monomer mixture of the present invention is useful as a raw material for a cured composition having the above-described characteristics.

[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-6922”. (Above, manufactured by Dow Chemical Co., Ltd.), trade name “UVACURE 1590” (produced by Daicel Ornex Co., Ltd.), trade names “CD-1010”, “CD-1011”, “CD-1012” (above, US Sartomer) Commercially available products such as “Irgacure-264” (manufactured by BASF), “CIT-1682” (manufactured by Nippon Soda Co., Ltd.), and “PHOTOINITIATOR 2074” (manufactured by Rhodia Japan) It 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, benzyldimethylketa Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone Son, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphor A 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 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the monomer mixture. is there.

  Moreover, when using radical photopolymerization initiator with a photocationic polymerization initiator as a curing catalyst, the usage-amount of radical photopolymerization initiator has preferable 0.1-5 weight part with respect to 100 weight part of monomer mixtures, 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 necessary 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 a UV-LED, it may contain a sensitizer and, if necessary, a sensitization aid. It is preferable at the point which can improve a light absorptivity and can improve sclerosis | hardenability, and these content (The total amount when it contains 2 or more types) is 0.05-100 with respect to 100 weight part of monomer mixtures, for example. 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 (d-1) and a compound represented by the following formula (d-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 (d-1) / compound represented by formula (d-2); weight ratio] is: For example, it is 0.01 to 1.0, preferably 0.1 to 0.5, and particularly preferably 0.2 to 0.5. In addition, as a compound represented by a following formula (d-1), the brand name "Anthracure UVS-1331" (made by Kawasaki Kasei Kogyo Co., Ltd.) can be used, for example. Moreover, as a compound represented by a following formula (d-2), the brand name "Anthracure UVS-581" (made by Kawasaki Kasei Kogyo Co., Ltd.) can be used, for example.

  When the curable composition of the present invention is used as a color ink of an ultraviolet curable inkjet 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, or the like 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, Suazo orange, pyrazolone pigments, etc.), soluble azo pigments (eg, azo yellow lake, azo lake red, etc.), benzimidazolone pigments, β-naphthol pigments, naphthol AS pigments, condensed azo pigments, quinacridone pigments (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 pigments (Eg, isoindoline yellow), dioxazine pigment (eg, dioxazine violet), thioindigo pigment, anthraquinone pigment, quinophthalone pigment (eg, quinophthalone yellow), metal complex pigment, diketo Examples include pyrrolopyrrole pigments, phthalocyanine pigments (for example, phthalocyanine blue, phthalocyanine green, etc.), organic pigments such as 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 with respect to 100 parts by weight of the monomeric composition.

  When using the curable composition of this invention as an ultraviolet curable inkjet ink, it is preferable to contain a dispersing agent with the said color material from the viewpoint of improving the dispersibility of the dispersing agent. 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 dispersant 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. under 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 1 to 50 mPa · s, particularly preferably 1 to 45 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, a humidity of 50 to 90% RH, preferably a humidity of 65 to 90% RH, particularly preferably a humidity of 70 to 90% RH, and most preferably a humidity of 75 to 90% RH. In particular, 80-90% RH) or in the air 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 UV-LED, 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. When performing heat processing, heating temperature is about 40-200 degreeC, and heating time is about 1 minute-15 hours. In addition, the degree of curing can 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.

  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. A high hardness ink film can be formed.

[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 said curable composition has quick-curing property, when it uses for formation of a molded object (for example, three-dimensional molded object), the molded object of a desired shape can be manufactured easily and efficiently.

  The molded product of the present invention comprises a cured product of the above curable composition, and is particularly excellent in adhesion to metals 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 a base material, the above-mentioned base material can be used without 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 nature is, for example, classification 0 to 2 in a 6-stage classification test according to the cross-cut method (based on JIS K 5600-5-6).

  In addition, since the curable composition has a fast curing property, a structure (for example, a structure having a printed material or a coating film formed of a cured product of the curable composition on the substrate surface) is efficiently produced. Can do.

  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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by 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 2-9, Comparative Examples 1-3
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).

(Curability evaluation under high humidity environment)
Using the bar coater (# 4) on the glass plate (trade name “S9112”, manufactured by Matsunami Glass Co., Ltd.) or the aluminum plate (trade name “A1050P”, manufactured by ASONE) with the inks obtained in the examples and comparative examples. Apply (applied film thickness: 5 μm), LED irradiator (trade name “UV-LED PROCESSOR LSS-05”, manufactured by CCR) as a light source under conditions of 24 to 25 ° C., air atmosphere and humidity of 50 to 80%. Used to irradiate 365 nm light (illuminance: 1.5 W / cm ² ) [one dose (exposure amount) is 1 J / cm ² and repeatedly irradiate until tackiness disappears] Evaluated.

(Evaluation of adhesion to glass and metal)
Using the bar coater (# 4) on the glass plate (trade name “S9112”, manufactured by Matsunami Glass Co., Ltd.) or the aluminum plate (trade name “A1050P”, manufactured by ASONE) with the inks obtained in the examples and comparative examples. Apply (coating thickness: 5 μm), 24-25 ° C, air atmosphere, humidity 50% or 70%, light irradiation (LED irradiator as light source (trade name “UV-LED PROCESSOR LSS-05”, CCR The cured product / substrate laminate (1) was obtained by irradiation with 365 nm light until the tackiness disappeared.
Further, 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, 100 crosscuts (cut pieces) were formed by cutting the cured product / substrate laminate in the vertical and horizontal directions from the cured product surface side to reach the substrate.
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 is counted, and this is used as an index of adhesion. It was. In addition, it is excellent in adhesiveness, so that there are many crosscuts which remain | survived without peeling.

The results are summarized in the following table.

In addition, each component in a table | surface is demonstrated below.
<Monomer>
ISBDVE: isosorbide divinyl ether, trade name “ISB-DVE”, manufactured by Daicel Corporation HEVE: ethylene glycol monovinyl ether 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, trade name “Celoxide 2021P” "OXT101 manufactured by Daicel Corporation: 3-ethyl-3-hydroxymethyloxetane, trade name" Aron oxetane OXT-101 ", OXT221 manufactured by Toagosei Co., Ltd. Bis [1-ethyl (3-oxetanyl)] methyl ether , Trade name "Aron Oxetane OXT-221", manufactured by Toagosei Co., Ltd. <Curing Catalyst>
CPI110P: 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>
UVS581: 9,10-di (capryloyloxy) anthracene, trade name “anthracure UVS-581”, manufactured by Kawasaki Chemical Industries, Ltd. UVS1331: 9,10-dibutoxyanthracene, trade name “anthracure UVS-1331” 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.

Claims (15)

  A monomer mixture composed of two or more kinds of cationically polymerizable monomers, a compound (A) having one oxetanyl group and one hydroxyl group, a compound (B) having two or more oxetanyl groups, and an alicyclic epoxy A compound (C) having two or more groups, the content of the compound (A) is 10 to 40% by weight of the total amount of the monomer mixture, and the content of the compound (C) is 40% by weight of the total amount of the monomer mixture As mentioned above, the monomer mixture whose total content of the said compound (A), a compound (B), and a compound (C) is 80 weight% or more of a monomer mixture whole quantity. Compound (C) is represented by the following formula (c)

(Wherein X represents a single bond or a linking group)
The monomer mixture of Claim 1 which is a compound represented by these. Compound (B) is represented by the following formula (b-1)
Y-R ^b1 -Y (b-1)
(Wherein R ^b1 represents a divalent aliphatic hydrocarbon group or a divalent group in which two or more of the aliphatic hydrocarbon groups are bonded via a linking group, and Y represents an oxetanyl group)
The monomer mixture of Claim 1 or 2 which is a compound represented by these.   The monomer mixture according to any one of claims 1 to 3, wherein the content ratio of the compound (A) to the compound (C) (the former / the latter; the weight ratio) is 20/80 to 45/55.   A curable composition containing the monomer mixture according to any one of claims 1 to 4 and a curing catalyst.   The curable composition of Claim 5 containing a sensitizer or a sensitizer and a sensitization aid.   The curable composition of Claim 5 or 6 containing a coloring material.   The curable composition of any one of Claims 5-7 containing a dispersing agent.   The curable composition according to any one of claims 5 to 8, which is an ultraviolet curable inkjet ink.   The curable composition according to any one of claims 5 to 8, which is a coating agent.   The curable composition according to claim 5 or 6, which is an adhesive.   Hardened | cured material of the curable composition of any one of Claims 5-11.   A molded article comprising the cured product according to claim 12.   Molding, wherein the curable composition according to claim 9 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. Manufacturing method.   The structure provided with the hardened | cured material of Claim 12 on the base-material surface.