JP5977063B2 - Polymerizable compound - Google Patents

Description

The present invention relates to a polymerizable compound that can be used as a curable material or the like in various industrial applications, and a polymerization or curable composition containing the same. More specifically, a polymerizable compound that can be polymerized under various polymerization conditions according to various uses, a polymerized or curable composition comprising the same as an essential component, the polymerizable compound, and a composition containing the same The present invention relates to a method for polymerizing or curing a polymer, and a polymer or a cured product obtained thereby.

As a representative example of the polymerizable compound, a polymerizable compound having a (meth) acryloyl group as a polymerizable group (hereinafter sometimes simply referred to as a (meth) acrylic compound) can be given. These have a (meth) acryloyl group which is a double bond activated by conjugation with an adjacent carbonyl group, and polymerize by a radical addition polymerization mechanism (hereinafter simply referred to as radical polymerization or radical polymerization). Sometimes.). Excellent in terms of polymerization rate, internal curability, durability of chemical bonds formed, economy, etc., wide application range, coating materials, adhesives, sealants, adhesives, paints, inks, resists, It is used in various applications such as dental materials, lenses and molding materials.

Recently, a polymerizable compound having an α-allyloxymethylacryloyl group (hereinafter sometimes simply referred to as an AMA group) is disclosed as a radical addition polymerizable compound having a polymerizability equal to or higher than that of a (meth) acryloyl group. (For example, refer to Patent Document 1, Patent Document 2, and Patent Document 3.)

International Publication No. 2011/148903 JP 2011-137123 A JP 2011-074068 A

This polymerizable compound having an AMA group (hereinafter sometimes simply referred to as an AMA compound) is a main chain skeleton having a repeating unit of a 5-membered ether structure in which a methylene group is arranged on both sides by polymerization while cyclizing. Form. Because of this unique main chain skeleton, the polymer or cured product obtained from the composition containing the AMA compound exhibits excellent properties such as heat decomposability, adhesion, and tough mechanical properties. It is an excellent polymerizable compound that can surpass conventional (meth) acrylic compounds.

However, the above-mentioned AMA-based compounds still have room for improvement, and there are cases where the heat-resistant coloring property and hardness are not sufficient.
The present invention has been made in view of the above problems, and includes a novel polymerizable compound capable of solving the problems of AMA compounds, including heat resistant colorability and hardness, and polymerization or polymerization comprising the polymerizable compound. It aims at providing the curable composition, its polymerization, or the hardening method. Another object of the present invention is to provide a polymer or a cured product obtained by the polymerization or curing method.

The present inventor has the following formula (1);

In particular, a compound having one or more functional groups in the same molecule (hereinafter referred to as MAMA compounds) is focused on a functional group represented by the formula (α-methallyloxymethylacryloyl group, hereinafter sometimes referred to as MAMA group). However, the present inventors have found that the problems of AMA compounds can be solved, including heat resistant colorability and hardness.
Then, the inventors have conceived that the compound can be suitably used for various applications such as a coating material, an adhesive, a sealing material, an adhesive, a paint, an ink, a resist, a dental material, a lens, and a molding material, and arrived at the present invention. It is a thing.

That is, the present invention provides the following formula (1);

It is a polymerizable compound characterized by having one or more functional groups represented by the following formula in the same molecule.
The present invention also provides the following formula (2);

(In the formula, Z represents an n-valent linking group. N is an integer of 1 or more.)

Furthermore, this invention is a superposition | polymerization or curable composition which comprises the said polymeric compound.
The present invention is the above polymerized or curable composition further comprising a radical initiator and / or a dryer.
Further, the present invention is a method for polymerizing or curing the polymerizable compound or the polymerization or curable composition, and the polymerization or curing method includes heating, irradiation with active energy rays, and oxygen. A polymerization or curing method comprising a step of applying at least one method selected from the group consisting of exposure to an atmosphere.
Furthermore, the present invention is a polymer or cured product obtained by the above polymerization or curing method.

The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The polymerizable compound of the present invention and the polymerization or curable composition comprising the same have excellent heat-resistant coloring and hardness as described above, and this is a repeating unit formed by polymerization of MAMA groups. It is presumed to be derived from the structure of That is, as shown in the following formula, the AMA group forms a 5-membered ring ether structure in which methylene groups are arranged on both sides, whereas the MAMA group forms a 6-membered ring ether structure in which a methylene group is arranged on one side. The 6-membered ring ether structure in which a methylene group is arranged on one side is less susceptible to oxidative degradation than the 5-membered ring ether structure in which a methylene group is arranged on both sides, and has a moderate flexibility while being rigid. For this reason, it is considered that the heat resistant colorability and hardness are superior.
In the following formula, X represents an initiator or a growth terminal, Z represents an n-valent linking group, and * represents that repeating units are bonded.

Therefore, since the polymerizable compound of the present invention has one or more MAMA groups in the same molecule, the structure of other parts of the polymerizable compound of the present invention is not limited as long as it has such a structure. It is not particularly limited. Moreover, what is necessary is just to select suitably according to a synthesis method, the availability of a raw material, the required characteristic of each use, etc., and it does not specifically limit. In addition, if the atom or atomic group to which the functional group represented by the formula (1) is bonded is an atom or atomic group that can be considered normally, there is no problem such as greatly impairing the curing characteristics of the functional group. It is considered that the effect is exerted.

The polymerizable compound has the following formula (2);

(Wherein Z represents an n-valent linking group, n is an integer of 1 or more).
In the above formula (2), n is not particularly limited as long as it is an integer of 1 or more, but is preferably an integer of 1 to 100, more preferably 1 to 50 in terms of synthesis ease and storage stability. It is an integer. When the polymerizable compound is used for an application requiring a low viscosity such as a reactive diluent, it is more preferably an integer of 1 to 10, and most preferably an integer of 1 to 6. Moreover, when using for the use which requires coating-film formation property like the binder resin of a coating material or an ink, More preferably, it is an integer of 5-50, Most preferably, it is an integer of 10-50.

In the general formula (2), the case where n is 1 and the case where n is an integer of 2 or more will be described separately.
First, in the general formula (2), when n is 1, Z represents a monovalent linking group.
Specific examples of the monovalent linking group for Z include a monovalent atom or atomic group capable of forming a covalent bond with the carbonyl group of the MAMA group. Examples of the element directly bonded to the carbonyl group of the MAMA group include non-metallic elements. Specifically, hydrogen, boron, group 14 elements (except tin and lead) of the periodic table, group 15 elements (excluding bismuth) ), Elements belonging to Group 16 to Group 18 and the like. From the viewpoint of ease of synthesis and chemical stability, the element directly bonded to the carbonyl group of the MAMA group is preferably hydrogen, carbon, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine, etc. Carbon, nitrogen, oxygen, and sulfur are more preferable in terms of ease of polymerization and polymerization activity.
That is, as the monovalent linking group of Z, —OR ¹ (R ¹ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms), —C≡N, —SR ² (R ² represents a hydrogen atom) Or an organic group having 1 to 30 carbon atoms), -NR ³ R ⁴ (R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms). More preferred. More preferred are —OR ¹ , —C≡N, and —NR ³ R ⁴ , and particularly preferred is —OR ¹ .
When Z is the monovalent linking group, the structure of the general formula (2) is preferably represented as follows.

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as described above.)
As shown in the above formula, when Z is —OR ¹ , it becomes a group constituting a carboxyl group or an ester group, when Z is —C≡N, it is a nitrile group, and when Z is —SR ² , A thiocarboxyl group or a group constituting a thioester group, and when Z is —NR ³ R ⁴ , a group constituting an amide group.

The organic group having 1 to 30 carbon atoms in R ^{1 to} R ⁴ may be linear, branched, or cyclic. The organic group preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and still more preferably 1 to 8. As said organic group, the organic group which consists of a hydrocarbon frame | skeleton or the hydrocarbon frame | skeleton containing an ether bond is preferable, for example. Moreover, what substituted the carbon atom directly couple | bonded with the oxygen atom, sulfur atom, or nitrogen atom in Z in these hydrocarbon frame | skeleton is mentioned as said organic group.

The organic group comprising the hydrocarbon skeleton is more preferably a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. These groups may have a substituent, that is, a substituted chain saturated hydrocarbon group or a substituted chain in which at least a part of the hydrogen atoms bonded to the carbon atoms constituting these groups are replaced with a substituent. It may be an unsaturated hydrocarbon group, a substituted alicyclic hydrocarbon group, or a substituted aromatic hydrocarbon group. Among them, a chain saturated hydrocarbon group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and an aromatic hydrocarbon group which may have a substituent are further included. preferable.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, alkoxy group, cyano group and trimethylsilyl group.

Examples of the chain saturated hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, neopentyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, Preferred examples include groups such as nonadecyl, eicosyl, seryl, melylyl and the like.

Further, at least part of the hydrogen atoms bonded to the carbon atoms constituting the chain saturated hydrocarbon group may be substituted with a hydroxy group, a halogen atom, etc., for example, a hydroxy-substituted chain saturated hydrocarbon Group, a halogen-substituted chain saturated hydrocarbon group and the like are preferable.
Suitable examples of the hydroxy-substituted chain saturated hydrocarbon group include groups such as hydroxyethyl, hydroxypropyl, and hydroxybutyl.
As the halogen-substituted chain saturated hydrocarbon group, the halogen atom is preferably a fluorine atom, a chlorine atom, or a bromine atom. For example, a group such as fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl, and the like It is mentioned as a suitable thing.

Examples of the chain unsaturated hydrocarbon group include crotyl, 1,1-dimethyl-2-propenyl, 2-methylbutenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, and 2-methyl-3. -Groups such as butenyl, oleyl, linole, linolene are preferred. Also about this, the substituted chain unsaturated hydrocarbon group which substituted at least one part of the hydrogen atom couple | bonded with the carbon atom which comprises with a hydroxyl group, a halogen atom, etc. may be sufficient.

Examples of the alicyclic hydrocarbon group include cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodecanyl, isobornyl, adamantyl, dicyclopentanyl, dicyclohexane. Groups such as pentenyl are preferred. Also about this, the substituted alicyclic hydrocarbon group which substituted at least one part of the hydrogen atom couple | bonded with the carbon atom which comprises with a hydroxyl group, a halogen atom, etc. may be sufficient.

Examples of the aromatic hydrocarbon group include groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, and anthranyl. It is mentioned as a suitable thing. Also about this, the substituted aromatic hydrocarbon group which substituted at least one part of the hydrogen atom couple | bonded with the carbon atom which comprises with an alkoxy group, a hydroxy group, a halogen atom, etc. may be sufficient.

The organic group comprising a hydrocarbon skeleton containing an ether bond includes at least one carbon constituting the chain saturated hydrocarbon group, chain unsaturated hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. -The thing of the structure where the oxygen atom was inserted in the carbon bond, etc. are mentioned. The organic group comprising a hydrocarbon skeleton containing an ether bond is not particularly limited as long as it has the above structure. For example, methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxy Chain ether groups such as ethoxyethyl, phenoxyethyl, phenoxyethoxyethyl; alicyclic hydrocarbon groups such as cyclopentoxyethyl, cyclohexyloxyethyl, cyclopentoxyethoxyethyl, cyclohexyloxyethoxyethyl, dicyclopentenyloxyethyl; A group having a chain ether group; a group having an aromatic hydrocarbon group such as phenoxyethyl and phenoxyethoxyethyl and a chain ether group; glycidyl, β-methylglycidyl, β-ethylglycidyl, 3,4-epoxy Cyclohexylmethyl, 2-oxetanemethyl, 3-methyl-3-oxetanemethyl, 3-ethyl-3-oxetanemethyl, tetrahydrofuranyl, tetrahydrofurfuryl, tetrahydropyranyl, dioxazolanyl, dioxanyl and the like are preferable. It is mentioned as a thing.

Preferred examples of the polymerizable compounds are illustrated by specific compound names: α-methallyloxymethylacrylic acid, α-methallyloxymethylmethyl acrylate, α-methallyloxymethylethyl acrylate, α- N-propyl methallyloxymethyl acrylate, n-butyl α-methallyloxymethyl acrylate, n-amyl α-methallyloxymethyl acrylate, s-amyl α-methallyloxymethyl acrylate, α-methallyl T-amyl oxymethyl acrylate, neopentyl α-methallyloxymethyl acrylate, n-hexyl α-methallyloxymethyl acrylate, s-hexyl α-methallyloxymethyl acrylate, α-methallyloxymethyl acrylic acid n-heptyl, α-methallyloxymethyl acrylate, n-octyl, α-methallyloxy S-octyl methyl acrylate, t-octyl α-methallyloxymethyl acrylate, 2-ethylhexyl α-methallyloxymethyl acrylate, capryl of α-methallyloxymethyl acrylate, nonyl α-methallyloxymethyl acrylate , Decyl α-methallyloxymethyl acrylate, Undecyl α-methallyloxymethyl acrylate, Lauryl α-methallyloxymethyl acrylate, Tridecyl α-methallyloxymethyl acrylate, Myristyl α-methallyloxymethyl acrylate , Pentadecyl α-methallyloxymethyl acrylate, cetyl α-methallyloxymethyl acrylate, heptadecyl α-methallyloxymethyl acrylate, stearyl α-methallyloxymethyl acrylate, nonadecyl α-methallyloxymethyl acrylate , Α- Eicosyl taryloxymethyl acrylate, ceryl α-methallyloxymethyl acrylate, melyl α-methallyloxymethyl acrylate; crotyl α-methallyloxymethyl acrylate, 1,1-dimethyl α-methallyloxymethyl acrylate 2-propenyl, α-methallyloxymethyl acrylate 2-methylbutenyl, α-methallyloxymethyl acrylate 3-methyl-2-butenyl, α-methallyloxymethyl acrylate 3-methyl-3-butenyl, α -2-methyl-3-butenyl methallyloxymethyl acrylate, oleyl α-methallyloxymethyl acrylate, linole α-methallyloxymethyl acrylate, linolene α-methallyloxymethyl acrylate; α-methallyloxy Cyclopentyl methyl acrylate, α-methallyloxime Cyclopentylmethyl acetyl acrylate, cyclohexyl α-methallyloxymethyl acrylate, cyclohexyl methyl α-methallyloxymethyl acrylate, 4-methylcyclohexyl α-methallyloxymethyl acrylate, 4-methallyloxymethyl acrylic acid 4- t-butylcyclohexyl, α-methallyloxymethyl acrylate tricyclodecanyl, α-methallyloxymethyl acrylate isobornyl, α-methallyloxymethyl acrylate adamantyl, α-methallyloxymethyl acrylate dicyclopentanyl Α-methallyloxymethyl acrylate dicyclopentenyl; α-methallyloxymethyl acrylate phenyl, α-methallyloxymethyl acrylate methylphenyl, α-methallyloxymethyl acrylate dimethylphenyl, α- Tallyloxymethyl acrylate trimethylphenyl, α-methallyloxymethyl acrylate 4-t-butylphenyl, α-methallyloxymethyl acrylate benzyl, α-methallyloxymethyl acrylate diphenylmethyl, α-methallyloxymethyl Diphenylethyl acrylate, α-methallyloxymethyl acrylate triphenylmethyl, α-methallyloxymethyl cinnamil acrylate, α-methallyloxymethyl naphthyl acrylate, α-methallyloxymethyl acrylate anthranil; α-meta Methoxyethyl ryloxymethyl acrylate, methoxyethoxyethyl α-methallyloxymethyl acrylate, methoxyethoxyethoxyethyl α-methallyloxymethyl acrylate, 3-methoxybutyl α-methallyloxymethyl acrylate, ethoxyethyl α-methallyloxymethyl acrylate, ethoxyethoxyethyl α-methallyloxymethyl acrylate, phenoxyethyl α-methallyloxymethyl acrylate, phenoxyethoxyethyl α-methallyloxymethyl acrylate, α-methallyl Cyclopentoxyethyl oxymethyl acrylate, cyclohexyloxyethyl α-methallyloxymethyl acrylate, cyclopentoxyethoxyethyl α-methallyloxymethyl acrylate, cyclohexyloxyethoxyethyl α-methallyloxymethyl acrylate, α- Dicyclopentenyloxyethyl methallyloxymethyl acrylate, phenoxyethyl α-methallyloxymethyl acrylate, phenoxyethoxyethyl α-methallyloxymethyl acrylate, α-methallyloxime Glycidyl acrylate, β-methylglycidyl α-methallyloxymethyl acrylate, α-methallyloxymethyl acrylate β-ethylglycidyl, α-methallyloxymethyl acrylate 3,4-epoxycyclohexylmethyl, α-methallyl 2-Oxetanemethyl oxymethylacrylate, 3-methyl-3-oxetanemethyl α-methallyloxymethylacrylate, 3-ethyl-3-oxetanemethyl α-methallyloxymethylacrylate, α-methallyloxymethylacrylic Acid tetrahydrofuranyl, α-methallyloxymethyl acrylate tetrahydrofurfuryl, α-methallyloxymethyl acrylate tetrahydropyranyl, α-methallyloxymethyl acrylate dioxazolanyl, α-methallyloxymethyl acrylate dioxanyl, etc. I can get lost.

In the general formula (2), when n is an integer of 2 or more, Z represents an n-valent linking group. Such a form in which Z in the general formula (1) represents an n-valent linking group and n is an integer of 2 or more is also one preferred embodiment of the present invention. In the above formula (2), Z is not particularly limited as long as it is a linking group capable of forming two or more covalent bonds with the carbonyl group of the MAMA group, that is, a linking group having two or more covalent bonds. It may be a divalent or higher valent linking group bonded via a divalent or a divalent or higher valent linking group bonded via two or more atoms. However, two or more linking groups may be used in terms of ease of synthesis and chemical stability. It is preferable that it is a bivalent or more valent coupling group couple | bonded through these atoms.

When Z is a divalent or higher-valent linking group bonded through only one atom, Z is not particularly limited, but includes atoms of Group 16 of the periodic table such as oxygen atom and sulfur atom; nitrogen atom, phosphorus Examples include a linking group containing a group 15 atom of the periodic table such as an atom; a group 14 atom of the periodic table such as a carbon atom, a silicon atom, and a germanium atom. ) And the like.

In the formula, R and R ′ represent a hydrogen atom or an organic group, and R and R ′ may be the same or different. The organic group may be a monovalent organic group that can be bonded to the above atom, and is preferably a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

When Z is a divalent or higher linking group bonded through two or more atoms, Z may have a low molecular structure or a high molecular structure. The terms “low molecular structure” and “low molecular skeleton” to be described later generally mean structures and skeletons that do not have repeating units of monomer units, and vice versa. In general, it means a structure or skeleton having repeating units of monomer units. The high molecular compound means a compound or a polymer having a molecular weight of 1000 or more as a general technical term. In the present invention, the terms “low molecule” and “polymer” are distinguished by such molecular weight. It is not limited.

Z includes at least a skeleton part Q, and further includes a divalent linking group X that binds the MAMA group and Q, a divalent or more valent linking group Y that binds two or more skeleton parts Q, and a skeleton part Q directly. It may contain a monovalent substituent W to be bonded. In the n-valent linking group Z, n hydrogen atoms in the skeleton Q may be substituted with MAMA groups or X, and the remaining hydrogen atoms may be substituted with Y and / or W.

Taking a polymerizable compound having two MAMA groups as an example, the polymerizable compound of the present invention can be represented, for example, by the following structural formula group (4).
For convenience, the MAMA group is represented by A in the formula, and the structural examples are some examples and are not limited thereto.

In the formula, Q ^m , X ^m , Y ^m , and W ^m (m represents an integer of 1 or more) are the m-th Q, X, and W when m is Q, X, Y, and W, respectively. Y and W, which may be the same or different.

Further, in the polymerizable compound having two MAMA groups, when Q is a cyclohexane skeleton, X is an oxygen atom, Y is a urethane bond, and W is a fluorine atom, the following structural formula group (5) Specific examples thereof include the following compounds.
In addition, the compounds shown in the structural formula group (5) are some examples of such compound groups, and not all examples. As shown in Structural Formula Group (5), two hydrogen atoms in the cyclohexane skeleton may be substituted with MAMA groups or X, and the remaining hydrogen atoms may be substituted with Y and / or W.

As described above, Z is composed of a skeleton part Q, and further, a divalent linking group X that binds to the MAMA group, a divalent or higher linking group Y that bonds two or more skeleton parts Q, and a skeleton part Q directly. It may contain a monovalent substituent W to be bonded. When Z consists of two or more skeleton parts Q, Qs may be directly bonded to each other without the linking group Y being interposed. Z may consist of only Q, that is, the MAMA group may be directly bonded to Q. However, from the viewpoint of ease of synthesis, availability of raw materials, chemical stability, etc., Z is at least Q and X. That is, the MAMA group is preferably bonded to Q via X, and the carbonyl group of Q in the MAMA group and Q are preferably bonded by a heteroatom. That is, Z is preferably an n-valent linking group bonded to the MAMA group via a hetero atom. Y and W may be appropriately selected according to the synthesis method, required performance in the application, and the like. Moreover, Z may be comprised from 2 or more types of Q, X, Y, and W, respectively.

Specific examples of Q, X, Y, and W are given below, but are not limited thereto. In the following Q, the structure is exemplified as a compound rather than a group, but when these are constituent elements of Z, two or more hydrogen atoms in the form showing the structure of Q as a compound are It is in the form of being substituted by an atom or atomic group bonded to Q (that is, MAMA group, Q, X, Y, W). Q, X, Y, and W are constituent elements of Z, but it is not limited to the fact that Z is composed of compounds that can form Q, X, Y, and W, respectively. When Z is structurally decomposed into each of Q, X, Y, and W, those structures and forms showing these structures as compounds are exemplified below.

The skeleton portion Q may be any as long as it has two or more atoms forming the skeleton and a MAMA group and / or X can be bonded to the skeleton. If the structure of Q is shown as a compound, the number of atoms forming the skeleton is two or more, and the atoms forming the skeleton are two or more hydrogen atoms (that is, hydrogen atoms that can be substituted for MAMA groups and / or X). The compound is not particularly limited as long as it is shown as a bonded compound and can form a Z skeleton in a form in which the hydrogen atom is substituted with a MAMA group and / or X. If the structure of the skeleton part Q is shown as a compound, for example, the structure is as follows.

Saturated hydrocarbon structures such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, etc .; ethylene, propene, Hydrocarbon monoene structures such as butene, pentene, hexene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene; allene, butadiene, pentadiene, hexadiene, nonadiene, decadien, undecadiene , Dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, Hydrocarbon diene structures such as decadiene and eicosadiene; hydrocarbon polyene structures such as heptadecatriene, heptadecatetraene, octadecatriene and octadecatetraene; acetylene structures such as acetylene, methylacetylene and hexadiyne; cyclopentane , Cyclopentene, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, norbornane, norbornene, norbornadiene, cyclodecane, dicyclopentadiene, adamantane, cyclopentanone, cyclohexanone, cyclooctanone, various compounds represented by the following chemical formula group (6), etc. Alicyclic structure;

Aromatic hydrocarbon structures such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, triphenylene, pyrene, perylene, biphenyl, various compounds represented by the following chemical formula group (7);

Ethylene oxide, ethyleneimine, oxetane, tetrahydrofuran, tetrahydropyran, dihydrofuran, dihydropyran, pyran, dioxane, pyrrolidine, piperidine, piperazine, morpholine, γ-lactone, δ-lactone, ε-caprolactone, γ-lactam, δ-laclam, heterocyclic structures such as ε-caprolactam, oxazoline, succinic anhydride, maleic anhydride, succinimide, maleimide, glutaric anhydride, glutarimide, and various compounds represented by the following chemical formula group (8);

Pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, pyridine, pyridazine, pyrazine, benzofuran, indole, benzimidazole, benzoxazole, benzothiazole, quinoline, quinoxaline, acridine, pyrimidine, triazine, carbazole , Heteroaromatic structures such as phenothiazine, quinacridone, xanthene, cyanuric acid, phthalic anhydride, phthalimide, and various compounds represented by the following chemical formula group (9);

And low molecular skeletons.
And a polyethylene skeleton represented by the following formula (10) obtained by (co) polymerization of an acyclic ethylenic compound such as ethylene, propylene, styrene, methyl acrylate, methyl methacrylate, and vinyl acetate;

Various compounds represented by the following structural formula group (11) obtained by (co) polymerization of unsaturated cyclic compounds typified by cycloalkenes such as norbornene, unsaturated acid anhydrides such as maleic anhydride, and maleimides such as phenylmaleimide Main chain ring structure skeleton;

Polyethylene-main chain ring structure copolymer skeleton obtained by copolymerization of the above acyclic ethylenic compound and unsaturated cyclic compound; dehydration condensation (co) polymerization of diols and the opening of alkylene oxides such as ethylene oxide, propylene oxide and tetrahydrofuran. A polyether skeleton obtained by ring (co) polymerization, etc., having an ether bond in the main chain; a main chain obtained by dehydration condensation (co) polymerization of dicarboxylic acid and diol, ring-opening (co) polymerization of cyclic lactone, etc. A polyester skeleton having an ester bond; a polyamide skeleton having an amide bond in the main chain obtained by dehydration condensation (co) polymerization of a dicarboxylic acid and a diamine or ring-opening (co) polymerization of a cyclic lactam; The main chain obtained by dealcoholization condensation (co) polymerization, ring-opening (co) polymerization of cyclic siloxane, etc. Obtained by reaction of a diisocyanate with a diol, a polyurethane backbone having a urethane structure in the main chain; polysiloxane backbone having a polymer backbone such as is also mentioned.
A part or all of the carbon atoms constituting Q may be replaced with silicon atoms.

The skeleton portion Q can be appropriately set depending on the use in which the polymerizable compound is used, but a low molecular skeleton is preferable in a use requiring a low viscosity such as a reactive diluent. A polymer skeleton is preferable in applications that require film-forming properties such as a binder resin in the material, and may be properly used depending on the application.
Among low molecular skeletons, it is at least one structure selected from the group consisting of a saturated hydrocarbon structure, an alicyclic structure, and an aromatic hydrocarbon structure in view of the availability of raw materials, chemical stability, etc. It is preferable.
Among the polymer skeletons, at least one skeleton selected from the group consisting of a polyethylene skeleton, a polyethylene-main chain ring structure copolymer skeleton, and a polyether skeleton in view of ease of synthesis, chemical stability, and the like. It is preferable that

The X is not particularly limited as long as it is a divalent linking group, and examples thereof include a bond shown in the following structural formula group (12) (for example, represented as AXQ, Show the atomic group as follows)

In the formula, R and R ′ are the same or different and are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 1 carbon which may have a substituent. 30 aryl groups are represented.
Among these, X is preferably an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom, or a disubstituted carbon atom from the viewpoint of ease of synthesis, chemical stability, and the like. preferable. That is, it is more preferable that the AX bond is an ester bond or an amide bond. In addition, when two or more X exists in Z, they may be the same or different.

The Y is not particularly limited as long as it is a divalent or higher valent linking group, and examples thereof include bonds shown in the following structural formula group (13).

In the formula, R and R ′ are the same or different and are a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or an alkyl group having 1 to 1 carbon which may have a substituent. 30 aryl groups are represented.
Among these, for ease of synthesis and chemical stability, ether bonds, thioether bonds, bonds with 2 to 4 carbon atoms, ketonic bonds, ester bonds, amide bonds, urethane bonds, or silica bonds. An acid ester bond is preferable, and an ether bond, a bond having 2 to 4 carbon atoms, an ester bond, an amide bond, or a urethane bond is more preferable. In addition, when two or more Y exists in Z, they may be the same or different.

The W is not particularly limited as long as it is a monovalent substituent that can be bonded to the skeleton Q. For example, W is a halogen atom belonging to Group 17 of the periodic table such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t- Butyl, n-amyl, s-amyl, t-amyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, Saturated hydrocarbon groups such as lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, ceryl, melylyl; unsaturated hydrocarbon groups such as vinyl, allyl, methallyl, crotyl, propargyl; cyclopentyl, cyclohexyl, 4 -Methylcyclohexyl, 4-t-butylcyclohexyl, tricyclodeca Alicyclic hydrocarbon groups such as ru, isobornyl, adamantyl and dicyclopentadienyl; aromatic hydrocarbon groups such as phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, naphthyl and anthranyl; hydroxy Group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group and other alkoxy groups; amino group, methylamino group, dimethylamino group, methylethylamino group, methylphenylamino group and other amino groups; (Meth) acryloyl group, mercapto group, thioalkoxy group, cyano group, nitro group, isocyanato group, thiocyanato group, quaternary ammonium base of amino group, carboxyl group or its salt, sulfonic acid group or its salt, sulfinic acid group or its Salt, phosphate group or salt thereof, etc. . What is necessary is just to use these suitably according to a use.

In the present invention, a particularly preferable form of the polymerizable compound in which n in formula (2) is 2 or more is a reaction of a polyvalent reactive compound with a compound having two or more reactive groups (polyvalent reactive compound). Examples thereof include a polymerizable compound in a form obtained by reacting a compound having one reactive group capable of reacting with a functional group and one MAMA group (monofunctional MAMA compound).

A preferred method for producing the polymerizable compound of the present invention is shown below.
First, a preferable production method when n = 1 in the general formula (2) includes a method of converting an acryloyl group of a compound having one acryloyl group into a MAMA group. As the compound having one acryloyl group, an ester of acrylic acid, acrylonitrile, a thioester of acrylic acid, and an amide of acrylic acid are preferable. When the acryloyl group of these compounds is converted into a MAMA group, Z in the general formula (2) is —OR ¹ (except when R ¹ is a hydrogen atom), —C≡N, —SR ² , —NR ³ R ⁴ compounds, that is, α-methallyloxymethylacrylic acid ester, α-methallyloxymethylacrylic acid nitrile, α-methallyloxymethylacrylic acid thioester, α-methallyloxymethylacrylic acid amide are obtained. become. The compound having one acryloyl group is more preferably an ester of acrylic acid or acrylonitrile, and more preferably an ester of acrylic acid.

As a method for converting the acryloyl group into a MAMA group, for example, a method using a reaction such as the following reaction formula group (14) is preferably exemplified.

The upper method of the above reaction formula group (14) is a method of allyl etherifying α-bromomethyl acrylate ester (for example, Michio Urushizaki, four others, “Macromolecules”). 1999, Vol. 32, pp. 322-327), and the lower method is the same method as the method of allyl etherifying α-hydroxymethyl acrylate (for example, Patent Document 1). It is.

In the general formula (2) obtained as described above, a compound in which Z is —OR ¹ (except when R ¹ is a hydrogen atom), —C≡N, —SR ² , —NR ³ R ⁴ ( That is, α-methallyloxymethylacrylic acid ester, α-methallyloxymethylacrylic acid nitrile, α-methallyloxymethylacrylic acid thioester, α-methallyloxymethylacrylic acid amide) are used as starting materials, and Can also obtain other R ¹ , R ² , R ³ , R ⁴ compounds. This is the same as a known method of converting a (meth) acrylic acid compound into another (meth) acrylic compound. Some such methods are illustrated, but not limited thereto.

For example, a polymerizable compound in which R ¹ is a hydrogen atom in the general formula (2) (that is, α-methallyloxymethylacrylic acid) is obtained by hydrolyzing the above α-methallyloxymethylacrylic ester. It is done. Hydrolysis is carried out in the presence of a basic catalyst to form a carboxylate salt and then treated with an acid to form α-methallyloxymethylacrylic acid, or in the presence of a strong acid catalyst. And a method of directly forming α-methallyloxymethylacrylic acid. As these basic catalyst and strong acid catalyst, the catalyst used when hydrolyzing (meth) acrylic acid ester can be used.

Another α-methallyloxymethyl acrylate can be obtained by transesterification using α-methallyloxymethyl acrylate as a starting material. The α-methallyloxymethyl acrylate ester as a starting material is preferably a lower ester. As the transesterification catalyst, a catalyst used for transesterification of (meth) acrylic acid ester can be used.

If α-methallyloxymethylacrylic acid is used as a starting material and α-methallyloxymethylacrylic acid chloride is formed and then reacted with thiol, α-methallyloxymethylacrylic acid thioester can be obtained. As a method of changing α-methallyloxymethylacrylic acid to α-methallyloxymethylacrylic acid chloride, the same method as the method of using (meth) acrylic acid as (meth) acrylic acid chloride can be used. As a method for obtaining α-methallyloxymethylacrylic acid thioester from α-methallyloxymethylacrylic acid chloride and thiol, the same method as for obtaining (meth) acrylic acid thioester from (meth) acrylic acid chloride and thiol is used. Can be used.

If α-methallyloxymethylacrylic nitrile is hydrolyzed as a starting material, α-methallyloxymethylacrylic amide can be obtained. As a catalyst for hydrolysis, a catalyst used for hydrolyzing (meth) acrylonitrile can be used.

Next, in the general formula (2), when n is an integer of 2 or more, the method for producing the polymerizable compound of the present invention includes (1) a compound having two or more acryloyl groups (polyfunctional acrylic compound and 2) a method for converting an acryloyl group into a MAMA group, and (2) a method for polyfunctionalizing a compound having one MAMA group in the same molecule (sometimes referred to as a monofunctional MAMA compound). It can be roughly divided into two. Among these, from the viewpoint of ease of synthesis, availability of raw materials, economy, and the like, the method (2) of polyfunctionalizing the monofunctional MAMA compound is preferable. That is, the production method of the polymerizable compound of the present invention including the step of polyfunctionalizing the monofunctional MAMA compound, and the polymerizable compound of the present invention produced by the production method are preferred embodiments of the present invention.

The method for converting the acryloyl group of the compound having two or more acryloyl groups into a MAMA group is not particularly limited, and examples thereof include a method using a reaction such as the above reaction formula group (14).

As a method for polyfunctionalizing the monofunctional MAMA compound, a reactive group capable of reacting with a reactive group of a polyvalent reactive compound is added to a compound having two or more reactive groups (polyvalent reactive compound). Examples thereof include a method of reacting a compound having one or more and one MAMA group (a monovalent reactive monofunctional MAMA compound or a polyvalent reactive monofunctional MAMA compound). This is because a compound having two or more reactive groups (polyvalent reactive compound) has one or more reactive groups capable of reacting with the reactive group of the polyvalent reactive compound, and (meta It is the same as the known method for obtaining a compound having two or more (meth) acryloyl groups by reacting a compound having one acryloyl group. Particularly preferably, a compound having a reactive group capable of reacting with a reactive group of the polyvalent reactive compound and a MAMA group (monovalent reactive monofunctional MAMA compound) is reacted with the polyvalent reactive compound. Is the method.
In the present specification, the polyvalent reactive monofunctional MAMA compound and the monovalent reactive monofunctional MAMA compound are both simply referred to as “monofunctional MAMA compound”.

As a preferable combination of the reactive group of the polyvalent reactive compound and the monofunctional MAMA compound, any combination capable of forming a covalent bond may be used. However, in terms of reactivity, availability, economy, and the like, the active hydrogen group and A combination with a functional group capable of reacting with an active hydrogen group is preferred. Examples of the active hydrogen group include a hydroxyl group (including a phenolic hydroxyl group, hereinafter, the expression “hydroxyl group” includes a phenolic hydroxyl group), a carboxylic acid group, a thiol group, and an amino group, preferably a hydroxyl group and a carboxylic acid group. And more preferably a hydroxyl group. Examples of functional groups capable of reacting with active hydrogen groups include ester groups, carboxylic acid groups, carboxylic anhydride groups, carboxylic acid chloride groups, epoxy groups, oxetane groups, isocyanate groups, oxazoline groups, and the like. Is an ester group, a carboxylic acid group, a carboxylic acid anhydride group, an epoxy group or an isocyanate group, more preferably an ester group, a carboxylic acid group or an epoxy group.
A plurality of reactive groups of the polyvalent reactive compound exist in the same polyvalent reactive compound, but any group capable of reacting with a reactive group that is not a MAMA group of the monofunctional MAMA compound. , They may be the same or different.

As a combination of the active hydrogen group and a functional group capable of reacting with the active hydrogen group, for example, the above specific examples can be arbitrarily combined, and are not particularly limited. And carboxylic acid group, hydroxyl group and carboxylic anhydride group, hydroxyl group and epoxy group, hydroxyl group and isocyanate group, carboxylic acid group and epoxy group, carboxylic acid group and oxetane group, carboxylic acid group and oxazoline group, and carboxylic acid group It is preferably a combination of at least one selected from the group consisting of isocyanate groups. More preferably, at least one selected from the group consisting of hydroxyl group and ester group, hydroxyl group and carboxylic acid group, hydroxyl group and epoxy group, hydroxyl group and isocyanate group, carboxylic acid group and epoxy group, and carboxylic acid group and isocyanate group It is a combination, and more preferably a combination of a hydroxyl group and an ester group and / or a hydroxyl group and a carboxylic acid group.

By the way, an ester bond is formed by a transesterification reaction in the case of a combination of the hydroxyl group and an ester group, and an ester bond is formed by a dehydration esterification reaction in the case of a combination of the hydroxyl group and a carboxylic acid group. Therefore, the structures of the polyvalent reactive compound and the monofunctional MAMA compound are restricted. The transesterification reaction or dehydration esterification reaction is a reversible reaction and is a method for obtaining a target product by biasing chemical equilibrium by dealcoholization or dehydration. Therefore, when the polyvalent reactive compound or the monofunctional MAMA compound contains an ester bond in addition to the reactive group that binds them, the ester bond also reacts to form a crosslinked product due to the ester bond as the reaction proceeds. It will be.

Thus, in the combination of a hydroxyl group and an ester group, and a hydroxyl group and a carboxylic acid group, it is preferable that the polyvalent reactive compound or the monofunctional MAMA compound does not contain an ester bond other than the reactive group that binds them. . In this case, the compound which has an ester bond in Z in the said Formula (2) among the polymeric compounds synthesize | combined will be remove | excluded. Examples of the polymerizable compound having an ester bond in Z include a high molecular compound having an ester bond in Z as the skeleton portion and a molecular weight of 1000 or more, and a low molecular compound having a molecular weight of less than 1000.
In the above Z, when the bonding site with the MAMA group has an -O- bond, an ester bond is constituted by this bond and the -CO- bond at the bonding site with Z in the MAMA group. However, this ester bond is not an ester bond in the skeleton part that gives rise to the above-mentioned crosslinked product, that is, it is not an ester bond that Z has.

As described above, the monofunctional MAMA compound can be polyfunctionalized by appropriately selecting the combination of reactive groups of the polyvalent reactive compound and the monofunctional MAMA compound and the structure of the skeleton portion. More specifically, the polyfunctionalization method is not particularly limited. For example, a polyhydric hydroxyl group-containing compound may be an α-methallyloxymethyl acrylate alkyl such as methyl α-methallyloxymethyl acrylate. A method of transesterifying with an ester, a method of dehydrating a polyhydric hydroxyl group-containing compound with α-methallyloxymethylacrylic acid, an α having an epoxy group such as glycidyl α-methallyloxymethyl acrylate on the polyhydric hydroxyl group-containing compound -A method of using a polyvalent hydroxyl group-containing compound as a polyvalent reactive compound, such as a method of adding a methallyloxymethylacrylic acid compound; an epoxy such as glycidyl α-methallyloxymethyl acrylate to a polyvalent carboxylic acid group-containing compound Multivalent reactivity, such as a method of adding an α-methallyloxymethylacrylic acid compound having a group A method using a polyvalent carboxylic acid group-containing compound as a compound; a method using a polyvalent epoxy group-containing compound as a polyvalent reactive compound, such as a method of adding α-methallyloxymethylacrylic acid to a polyvalent epoxy group-containing compound Method: Method of adding α-methallyloxymethylacrylic acid to a polyvalent isocyanate group-containing compound, α-methallyl having a hydroxyl group such as 2-hydroxyethyl α-methallyloxymethylacrylate on a polyvalent isocyanate group-containing compound A method of using a polyvalent isocyanate group-containing compound as a polyvalent reactive compound, such as a method of adding an oxymethylacrylic acid compound; 2-hydroxyethyl α-methallyloxymethyl acrylate to a polyvalent carboxylic anhydride group-containing compound Such as a method of adding an α-methallyloxymethylacrylic acid compound having a hydroxyl group such as Preferred examples include a method using a polyvalent carboxylic anhydride group-containing compound as the valence reactive compound.

That is, a compound having a reactive group capable of reacting with a reactive group of a polyvalent reactive compound (monofunctional MAMA) and a compound having two or more reactive groups (polyfunctional reactive compound). A polymerizable compound obtained by reacting a compound), wherein the polyvalent reactive compound is selected from the group consisting of a hydroxyl group, a carboxylic acid group, an epoxy group, an isocyanate group, and a carboxylic anhydride group. Having a plurality of at least one functional group is also one preferred embodiment of the present invention.

In addition, when reacting a polyfunctional compound with a monofunctional MAMA compound, it is not necessary to react the monofunctional MAMA compound with all reactive groups of the polyfunctional compound, and there are two or more MAMA groups in the same molecule. It is sufficient that a part of the reactive group of the polyvalent reactive compound reacts with the monofunctional MAMA compound, and of course all may react. Among the reactive groups of the polyvalent reactive compound, the reactive group that has not reacted with the monofunctional MAMA compound may be used as it is or may be used for further reaction.
For example, a polyhydric hydroxyl group-containing compound and an α-methallyloxymethylacrylic acid alkyl ester are reacted, and a polybasic acid anhydride is reacted with an unreacted hydroxyl group to convert it into a carboxylic acid group, or a polyvalent epoxy group is contained. The compound and α-methallyloxymethylacrylic acid are reacted to add acrylic acid to the unreacted epoxy group, or the polyisocyanate group-containing compound and α-methallyloxymethylacrylic acid are reacted to react. The isocyanate group may be inactivated by treatment with water. These are merely examples of using unreacted reactive groups for further reactions, and are not limited thereto.

The polyvalent hydroxyl group-containing compound is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1 , 4-dimethylolcyclohexane, (o, m, p-) xylylene glycol, bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene and other low molecular dihydric alcohols; glycerol, trimethylol propane, isocyanuric acid ethylene oxide adduct Low molecular trihydric alcohols such as pentaerythritol and ditrimethylolpropane; low molecular hexahydric alcohols such as dipentaerythritol; polyhydric phenols such as phenol novolac resins Compound: Compound obtained by ring-opening addition of one or more molecules of alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide to the low molecular weight polyhydric alcohol; One or more molecules of cyclic ester compound such as ε-caprolactone to the low molecular weight polyhydric alcohol Compounds that have undergone ring-opening addition; and the like can be mentioned, and may be properly used depending on the application.

The polyvalent carboxylic acid group-containing compound is not particularly limited. For example, a (co) polymer of succinic acid, maleic acid, fumaric acid, phthalic acid, trimellitic acid, naphthalenetetracarboxylic acid, and (meth) acrylic acid. Etc., and may be properly used depending on the application.

Although it does not specifically limit as said polyhydric epoxy group containing compound, For example, the compound obtained by making epichlorohydrin react with the said polyhydric alcohol; Celoxide 2021P, Celoxide 3000, Epolide GT401, EHPE3150, EHPE3150CE (all are brand names, Daicel) (Chemical Industry Co., Ltd.) alicyclic epoxy compounds; epoxidized products of conjugated diene polymers such as epoxidized polybutadiene; glycidyl (meth) acrylate (co) polymer, 3,4-epoxycyclohexylmethyl (meth) acrylate A polymer having an epoxy group in a side chain such as a (co) polymer; and the like may be mentioned, and may be appropriately used depending on the application.

Although it does not specifically limit as said polyvalent isocyanate group containing compound, For example, low molecular diisocyanates, such as hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate; A polymer having an isocyanate group in a side chain such as a (co) polymer of 2-isocyanatoethyl (meth) acrylate; and the like. What is necessary is just to use properly.
Examples of the polyvalent carboxylic anhydride group-containing compound include naphthalene carboxylic anhydride, maleic anhydride (co) polymer, and the like.

Examples of a method for obtaining an α-methallyloxymethylacrylic acid compound having an epoxy group such as glycidyl α-methallyloxymethylacrylate include α-methallyloxymethyl such as methyl α-methallyloxymethylacrylate. After the alkyl acrylate is hydrolyzed to a carboxylate in the presence of a basic catalyst, α-methallyloxymethyl acrylate and epichlorohydrin are preferably used with a quaternary ammonium salt as a catalyst. Examples thereof include a method of dehydrochlorination, a method of transesterifying an α-methallyloxymethyl acrylate alkyl ester such as methyl α-methallyloxymethyl acrylate and glycidol in the presence of a transesterification catalyst.
Examples of a method for obtaining an α-methallyloxymethylacrylic acid compound having a hydroxyl group such as 2-hydroxyethyl α-methallyloxymethylacrylate include α-methallyloxymethylacrylic acid and alkylene oxide such as ethylene oxide. And the like.

In producing the polymerizable compound (polyfunctional ester), in order to prevent polymerization of the MAMA group, it is preferably 0 to 150 ° C, more preferably 10 to 140 ° C, and further preferably 20 to 130 ° C. It is preferable to handle.
Moreover, it is preferable to handle by adding a polymerization inhibitor, and it is more desirable to allow a molecular oxygen-containing gas to coexist with the polymerization inhibitor.
As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the handling equipment. The concentration of the oxygen gas may be appropriately set according to the raw material (solvent etc.) used so that the inside of the facility does not become an explosion range, but it is usually preferably 1 to 20% by volume. More preferably, it is 2-15 volume%, More preferably, it is 3-10 volume%.

As the polymerization inhibitor, there can be used a polymerization inhibitor for a radically polymerizable monomer which is usually used as a polymerization inhibitor. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol. 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2′-methylenebis (4-methyl-6) -T-butylphenol) and the like, organic acid copper salts, and phenothiazine. Among these, phenol-based inhibitors are preferable from the viewpoint of low coloration and ability to prevent polymerization. Among them, p-methoxyphenol, 6-t-butyl-2,4-xylenol, 2,6- Di-t-butylphenol is preferred. In addition, it is more preferable to use these phenolic compounds in combination with stabilizers classified as so-called secondary antioxidants typified by phosphites and thioethers because the polymerization prevention property and the coloration prevention property are further enhanced.
These polymerization inhibitors may be used alone or in combination of two or more.

The amount of the polymerization inhibitor used may be appropriately adjusted according to handling conditions such as the temperature in the production process, but is 0.001 to 5.0% by mass with respect to 100% by mass of the polymerizable compound of the present invention. It is preferable to use so that it becomes. More preferably, it is used so that it may become 0.005-4.0 mass%. When a large amount of the polymerization inhibitor is used, a small amount of the inhibitor may be added again after passing through the step of removing the inhibitor such as distillation or separation with alkaline water.

The method for producing the polymerizable compound of the present invention can be appropriately set depending on the raw materials used, including the handling temperature and the use of the polymerization inhibitor described above, but the acryloyl group of the above-mentioned (1) polyfunctional acrylic compound. It is preferable to use a catalyst both in the method for converting to a MAMA group and in the method (2) for polyfunctionalizing the monofunctional MAMA compound.
In the case of (1) above, it is preferable to use a basic catalyst as described above. In the case of (2) above, a commonly used catalyst can be used according to each reaction such as transesterification reaction, dehydration esterification reaction, addition reaction of acid to polyvalent epoxy compound.
In these reactions, the amount of the catalyst used can be a commonly used amount.

The present invention is also a polymerization or curable composition comprising the polymerizable compound of the present invention having at least one MAMA group in the same molecule. The polymerization or curable composition of the present invention may contain various additives depending on the use in addition to the compound having one or more MAMA groups.
Although it does not specifically limit as such an additive, A hardening accelerator, a solvent, another polymerizable monomer, a reactive diluent, a curable oligomer / polymer, a stabilizer, a binder resin, a filler, a coloring material, a dispersing agent Etc. Among them, a curing accelerator such as a radical initiator and a dryer is a component that is preferably added because it can further bring out the performance of the polymerizable compound of the present invention. A preferable form of the polymerized or curable composition of the present invention further includes a form containing a radical initiator and / or a dryer.
The following description will be divided into (A) radical initiator, (B) dryer, (C) and other additives.

(A) Radical initiator The polymerizable compound of the present invention forms a main chain skeleton having a repeating unit of a 6-membered ring ether structure in which a methylene group is arranged on one side based on the radical addition polymerization mechanism as described above. Although radical polymerization can be initiated and cured by heating and / or irradiation with active energy rays such as electromagnetic waves and electron beams, it can be cured more effectively by using a radical initiator in combination.
Examples of the radical initiator include a thermal radical initiator that generates radicals by heating and a photo radical initiator that generates radicals by irradiation of active energy rays, and one or two of those usually used as radical initiators. More than seeds can be used.
Moreover, it is also preferable to add 1 type (s) or 2 or more types of the radical polymerization accelerator, photosensitizer, etc. which are used normally as needed.

As the thermal radical initiator, organic peroxide initiators and azo initiators are suitable, and specific examples include the following.
Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4 , 4-Di-t-butylperoxycyclohexyl) propane p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide , Stearoylpa Oxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di 2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di (3-methyl-3- Methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate 1- Rohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy Isobutyrate, t-butyl peroxymalate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl Peroxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylper Oxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone, 2 Organic peroxide initiators such as 1,3-dimethyl-2,3-diphenylbutane.

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2 '-Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-H Rophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6, 7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- 3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane ] Dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazoline- 2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2 -Azo initiators such as azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile].

The radical polymerization accelerator that can be used together with the thermal radical initiator is not particularly limited as long as it promotes the decomposition (generation of initiation radicals) of the thermal radical initiator, and those that are usually used can be used. is not. For example, organic salts, inorganic salts, oxides or metal complexes of metals such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, cerium, samarium; Quaternary ammonium compounds; thiourea compounds; ketone compounds and the like. Specifically, for example, cobalt octylate, cobalt naphthenate, zinc octylate, zinc naphthenate, zirconium octylate, zirconium naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, Examples include triethanolamine, triethylbenzylammonium chloride, di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, and methyl acetoacetate.

Examples of the photo radical initiator include alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, and titanocene. A compound, a benzoic acid ester compound, an acridine compound and the like are preferable, and specific examples thereof include the following.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; 2- (4-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) Vinyl)]-1,3,4-oxadiazole, halomethylated oxadiazole compounds such as 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5 ' Biphenyl such as raphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. Imidazole compounds; 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]-1,2-octanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime) ethanone and other oxime ester compounds; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) -phenyl) titanium compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; 9-phenyl Acridine-based compounds such as Kurijin.

Sensitivity and curability can be improved by using a photosensitizer and a radical polymerization accelerator together with the photo radical initiator. As such a photosensitizer and a radical polymerization accelerator, those usually used can be used and are not particularly limited. Dye-based compounds, dialkylaminobenzene-based compounds, mercaptan-based hydrogen donors, and the like are suitable. For example, xanthene dyes, coumarin dyes, 3-ketocoumarin-based compounds, pyromethene dyes and other dye-based compounds; ethyl 4-dimethylaminobenzoate And dialkylaminobenzene compounds such as 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

When the above radical initiator is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the viewpoint of the balance between polymerizability, adverse effects of decomposition products, and economy. It is preferable to set it as 0.01-30 mass% with respect to 100 mass% of polymeric compounds of invention. More preferably, it is 0.05-20 mass%, More preferably, it is 0.1-15 mass%.
In the case of adding the radical polymerization accelerator and the photosensitizer, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited. It is preferable to set it as 0.001-20 mass% with respect to 100 mass% of polymeric compounds of invention. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-10 mass%.

(B) Dryer The polymerizable compound of the present invention can be oxygen-cured (oxidative polymerization) in the same manner as the AMA compound. Oxygen curing is a curing mechanism in which various radicals generated by the reaction with active oxygen are coupled and crosslinked as disclosed in Patent Document 3 above. This is due to the fact that the methallyl ether structure is easy to extract the hydrogen of the etheric methylene group to oxygen like the allyl ether structure.
A dryer is a compound that promotes oxygen curing through the action of promoting the decomposition of peroxides, that is, a compound that decomposes peroxides by redox action to generate oxide radicals or peroxide radicals, and is usually used as a dryer. One or more can be used.

Examples of such a dryer include, but are not limited to, for example, cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, cerium, samarium, and other metal organic salts, inorganic salts, and oxidation. And primary or secondary amine compounds; quaternary ammonium salts; thiourea compounds; ketone compounds, and the like. Specifically, for example, cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, vanadium octylate, vanadium naphthenate, dimethylaniline, triethanolamine, triethylbenzylammonium chloride , Di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate and the like.

When the dryer is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited, but is 100% by mass of the polymerizable compound of the present invention from the balance of curability and economy. It is preferable to set it as 0.001-20 mass% with respect to. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-10 mass%.

(C) Other additives The additives other than the above (A) radical initiator and (B) dryer are not particularly limited. For example, curing accelerators other than radical initiators and dryers, solvents, and other polymerizable monomers. Mer, reactive diluent, curable oligomer / polymer, stabilizer, binder resin, filler, colorant (pigment, dye), dispersant, adhesion improver, release agent, plasticizer, UV absorber, gloss Examples include detergents, antifoaming agents, leveling agents, antistatic agents, slip agents, surface modifiers, coupling agents (silane-based, aluminum-based, titanium-based, etc.), acid generators, and the like. The main items are explained below.

<Hardening accelerator other than radical initiator and dryer>
Examples of the curing accelerator other than the radical initiator and the dryer include polyfunctional thiols. Since the polyfunctional thiol can act as a polyfunctional chain transfer agent in radical curing, and can also act as a crosslinking agent based on an ene-thiol reaction mechanism with a methallyl ether group, the polymerization or curable composition of the present invention can be used. Curability can be improved. Such a polyfunctional thiol is not particularly limited as long as it is a compound having two or more mercapto groups in the same molecule. For example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3 , 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like. These may be used alone or in combination of two or more.

The total amount of the curing accelerator other than the radical initiator and the dryer may be appropriately set depending on the purpose and application, and is not particularly limited, but is 0 to 150 with respect to 100% by mass of the polymerizable compound of the present invention. It is preferable to set it as the mass%. More preferably, it is 0-100 mass%, More preferably, it is 0-80 mass%.
The curing accelerator other than the radical initiator and the dryer is not an essential component of the polymerization or curable composition, and may not be added depending on the application or curing conditions. Good.

<Solvent>
The solvent is used for the reaction medium for obtaining the soluble polymer and the crosslinked fine particles, the viscosity reduction by dilution, the adjustment of the coating film thickness, the polymerization or the uniform mixing / dispersing of each component in the curable composition, etc. . Such a solvent may be a low-viscosity organic solvent or water that can dissolve or disperse each component in the polymerization or curable composition, and is usually used in radical polymerization reactions or polymerization or curable compositions. Can be used and is not particularly limited. Examples of the solvent include the following.

Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Esters of glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; methyl acetate, ethyl acetate, propyl acetate , Isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Alkyl esters such as ethyl ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketones such as ruketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone ;water.
These may be used alone or in combination of two or more, and may be appropriately selected depending on the purpose and application.

The total amount of the solvent added may be appropriately set in consideration of the molecular weight of the polymer, the viscosity of the polymerized or curable composition, the coating property, etc. depending on the purpose and application, and is not particularly limited. It is preferable to set it as 0-2000 mass% with respect to 100 mass% of polymeric compounds of invention. More preferably, it is 0-1500 mass%, More preferably, it is 0-1000 mass%.
The solvent is not an essential component of the polymerization or curable composition, and may not be added depending on the application, curing conditions, and the like, and may be 0% by mass.

<Other polymerizable monomers other than the polymerizable compound of the present invention>
The polymerized or curable composition of the present invention may contain other polymerizable monomers other than the polymerizable compound of the present invention within a range not losing its excellent characteristics in consideration of performance balance and economy. Good. In particular, those that are liquid and low-viscosity at room temperature can also be used in place of solvents because they have a viscosity adjusting function, and are sometimes classified as reactive diluents.
Examples of such other polymerizable monomers include a compound having a radical polymerizable group such as a carbon-carbon unsaturated bond; a compound having a cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group; Examples thereof include a hybrid compound having both a polymerizable group and a cationic polymerizable group. These may be used alone or in combination of two or more depending on the purpose and application, and are not particularly limited, but the polymerization of the present invention can be performed by the same mechanism as the polymerizable compound of the present invention described above. It is preferable that it is other radically polymerizable monomers other than a reactive compound.
The other radical polymerizable monomer includes a monofunctional radical polymerizable monomer having only one radical polymerizable unsaturated group in the same molecule and a polyfunctional radical polymerizable monomer having two or more. Can be classified as a mer.

Specific examples of the monofunctional radically polymerizable monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid i. -Propyl, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, (meta ) T-amyl acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Cyclohexylmethyl acid, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Benzyl, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacrylic acid 2- Methoxyethyl, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) Β-ethylglycidyl acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 3,4-epoxycyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate; N, N -(Meth) acrylamides such as dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, acryloylmorpholine; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, vinylbenzoic acid; Unsaturated polycarboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl Unsaturated monocarboxylic acids chain-extended between groups; anhydrous Unsaturated acid anhydrides such as oleic acid and itaconic anhydride; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzyl N-substituted maleimides such as maleimide and naphthylmaleimide; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether and ethyl vinyl ether Propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether Ter, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinyl N-vinyl compounds such as morpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate; α-allyloxymethylacrylic acid, methyl α-allyloxymethylacrylate, α-allyloxymethyl acrylate such as ethyl α-allyloxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, etc. Acrylic acid-based compounds.

Specific examples of the polyfunctional radical polymerizable monomer include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) Acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide Additive dipentaerythritol hexa (meth) acrelan , Ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol hexa (meth) Polyfunctional (meth) acrylates such as acrylates; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene Oxide divinyl ether, trimethylolpropane Livinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol Polyfunctional vinyl ethers such as tetravinyl ether and ethylene oxide-added dipentaerythritol hexavinyl ether; (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (Meth) acrylic acid 2-vinyli Xylpropyl, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic acid 4 -Vinyloxymethylcyclohexylmethyl, p-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, etc. Vinyl ether group-containing (meth) acrylic acid esters; ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexa Diol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether Polyfunctional allyl ethers such as dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; (Meta Allyl group-containing (meth) acrylic acid esters such as allyl acrylate; tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri Polyfunctional (meth) acryloyl group-containing isocyanurates such as (methacryloyloxyethyl) isocyanurate; Multifunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Multifunctional such as tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate Isocyanate and hydroxyl-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Multifunctional urethane (meth) acrylates obtained by the response; polyfunctional aromatic vinyl compounds such as divinylbenzene, and the like.

The total amount of the above other polymerizable monomers is appropriately determined in consideration of the viscosity, coating properties, curing characteristics, polymer or cured product properties of the polymerization or curable composition, depending on the purpose and application. Although it should just set and it is not specifically limited, It is preferable to set it as 0-1500 mass% with respect to 100 mass% of polymeric compounds of this invention. More preferably, it is 0-1000 mass%, More preferably, it is 0-800 mass%.
The other polymerizable monomer is not an essential component of the polymerization or curable composition, and may not be added depending on the application or curing conditions, and may be 0% by mass.

<Other polymerizable oligomer / polymer>
The other polymerizable monomer is a concept indicating that the skeleton portion other than the polymerizable group is a structure having no repeating unit due to the monomer unit, whereas the polymerizable oligomer or polymer Is a concept indicating that the skeleton other than the polymerizable group has a structure having repeating units of monomer units. In general, a compound having a molecular weight of less than 1000 is often classified as an oligomer, and a compound having a molecular weight of 1000 or more is often classified as a polymer. The aspect in which the polymerized or curable composition of the present invention contains a polymerizable oligomer or polymer is one of the preferred embodiments of the present invention.

Examples of the polymerizable group of the polymerizable oligomer or polymer include a radical polymerizable group such as a carbon-carbon unsaturated bond; and a cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group. These may be used alone or in combination of two or more depending on the purpose and application, and are not particularly limited, but are radically polymerizable groups that can be cured by the same polymerization mechanism as the polymerizable compound of the present invention described above. It is preferable that
Examples of the skeleton portion of the polymerizable oligomer or polymer include a polyester skeleton, a polyether skeleton, a conjugated diene polymer skeleton such as polybutadiene and polyisoprene, a cycloolefin polymer skeleton, and a polysiloxane skeleton. It is done.
Therefore, as a specific structure of the polymerizable oligomer or polymer, for example, urethane (meth) acrylates in which a polymerizable group is bonded to the skeleton portion by a urethane bond, epoxy resin (an oligomer or polymer having an epoxy group) Examples include epoxy (meth) acrylates having a structure to which (meth) acrylic acid is added.

The total amount of the above-mentioned polymerizable oligomer / polymer added may be appropriately set in consideration of the viscosity, coating properties, curing characteristics, polymer or cured product properties of the polymerization or curable composition, depending on the purpose and application. Although it does not specifically limit and it is preferable to set it as 0-1500 mass% with respect to 100 mass% of polymeric compounds of this invention. More preferably, it is 0-1000 mass%, More preferably, it is 0-800 mass%.
The polymerizable oligomer / polymer is not an essential component of the polymerization or curable composition, and may not be added depending on the application, curing conditions, or the like.

<Stabilizer>
Stabilizers are compounds that have the function of preventing radical polymerization and oxidative polymerization in order to improve handling and storage stability. One or more polymerization inhibitors and antioxidants that are usually used can be used. There is no particular limitation.
Examples of such compounds include phenolic compounds, organic acid copper salts, phenothiazines, phosphites, thioethers, hindered amine compounds, ascorbic acids, thiocyanates, thiourea derivatives, nitrites, sulfites, thiols, and the like. Examples thereof include sulfates and hydroxylamine derivatives. Among these, phenolic compounds are preferable in terms of coloring and compatibility. Specifically, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol, 6-t-butyl-2, 4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), and the like. . In addition, it is more preferable to use these phenolic compounds in combination with stabilizers classified as so-called secondary antioxidants typified by phosphites and thioethers because the polymerization prevention property and coloring prevention property are further enhanced.

When the stabilizer is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the viewpoint of the balance between polymerizability and economy, the polymerizable compound of the present invention is 100 masses. It is preferable to set it as 0.001-20 mass% with respect to%. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-5 mass%.

<Binder resin>
The binder resin is an oligomer or polymer that acts as a filler for imparting / improving coating film formability, preventing deformation, etc., and further, depending on the purpose and application, alkali developability, colorant dispersibility, heat resistance. Various functions such as sex are given. As such a binder resin, various oligomers or polymers usually used as a binder resin can be used singly or in combination of two or more, and are not particularly limited.
As the binder resin, for example, when an alkali-soluble oligomer or polymer such as a carboxyl group-modified vinyl ester resin or a (meth) acrylic acid copolymer is used for the binder resin, the polymerization or curable composition of the present invention is used. It can be applied to alkali developing permanent resist applications such as solder resist, color filter resist, protective film resist and the like. In addition, when a polymer having an appropriate glass transition temperature and compatibility with a coloring material and a dispersant, such as a (meth) acrylic acid ester polymer, is used as a binder resin, the polymerization or curable composition of the present invention is used. It can be applied to paint and ink applications.

The total addition amount of the binder resin may be appropriately set in consideration of the functionality according to the purpose and application, and is not particularly limited, but is 0 to 1000 with respect to 100% by mass of the polymerizable compound of the present invention. It is preferable to set it as the mass%. More preferably, it is 0-800 mass%, More preferably, it is 0-500 mass%.
The binder resin is not an essential component of the polymerization or curable composition, and may not be added depending on the application, curing conditions, or the like.

The present invention is also a method of polymerizing or curing a polymerizable compound having one or more MAMA groups, or a polymerization or curable composition containing the compound. As described above, the polymerizable compound of the present invention and the polymerized or curable composition comprising the compound are capable of a radical polymerization mechanism and / or an oxidative polymerization mechanism, so that heating, irradiation with active energy rays, oxygen The polymerization can be carried out by three methods, ie, exposure to an atmosphere containing benzene, and only one of these methods may be used, or two or more may be used in combination.
That is, the present invention is a method of polymerizing or curing the polymerizable compound having one or more MAMA groups in the same molecule, or the polymerization or curable composition comprising the compound, The curing method is also a polymerization or curing method including a step of applying at least one method selected from the group consisting of heating, irradiation with active energy rays, and exposure to an atmosphere containing oxygen.

The heating condition in the polymerization / curing method by heating, that is, the polymerization / curing temperature may be appropriately selected according to the combination of the compositions, etc., but when not using a curing accelerator, 30 to 400 ° C. is preferable, More preferably, it is 70-350 degreeC, More preferably, it is 100-350 degreeC. By setting it as such temperature, it can superpose | polymerize and harden | cure easily without a hardening accelerator, and can reduce thermal decomposition by excessive heating.
When using together a hardening accelerator, it can be made to harden | cure at lower temperature than the case where it does not use together, 0-400 degreeC is preferable, More preferably, it is 10-350 degreeC, More preferably, it is 20-350 degreeC.

Polymerization / curing by heating may be performed in one step or in two or more steps, and before polymerization / curing by irradiation with active energy rays and / or exposure to an atmosphere containing oxygen. You may go to or later. For example, after carrying out processing such as development after being crosslinked to some extent by heating at a low temperature or short-term active energy ray irradiation, preferably 100 ° C. or more, more preferably 130 ° C., and even more preferably 150 ° C. The step of curing at the above high temperature is also referred to as post-bake or post-cure, and is preferable because it can further promote the crosslinking reaction.

As the active energy ray in the polymerization / curing method by irradiation with the active energy ray, those usually used can be used, such as electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays, infrared rays, electron rays, neutron rays. And particle beams such as proton beams. Among these, gamma rays, X-rays, ultraviolet rays, visible rays, and electron beams are preferable, ultraviolet rays, visible rays, and electron beams are more preferable, and ultraviolet rays are most preferable from the viewpoints of energy intensity, energy beam generator, and the like. . When a curing accelerator is not used in combination, it is preferable to use an active energy ray having strong energy such as gamma rays, X-rays, and electron beams. When a curing accelerator is used in combination, energy such as ultraviolet light and visible light is Active energy rays that are relatively weak but easy to generate and economical can be preferably used.

The above-mentioned polymerization / curing method by exposure to an atmosphere containing oxygen is a method of polymerizing / curing by exposing the polymerizable compound of the present invention or a polymerization or curable composition comprising the same to an atmosphere containing oxygen. Is the method. The oxygen concentration in the atmosphere is preferably 5% by volume or more, more preferably 10% by volume or more, and most preferably 18% by volume or more. That is, the concentration is most preferably equal to or higher than the oxygen concentration in the air.
The polymerization / curing method by exposure to an atmosphere containing oxygen may be used in combination with the polymerization / curing method by heating and / or the polymerization / curing method by irradiation with active energy rays. In particular, a polymerization / curing method in which heating and / or irradiation with active energy rays is performed in the air is preferable as a polymerization / curing method that can be easily used together.

Furthermore, the present invention is obtained by polymerizing and curing a polymerizable compound having one or more MAMA groups in the same molecule and a polymerization or curable composition comprising the compound by the polymerization / curing method. It is also a polymer or cured product.
The polymer and cured product of the present invention are particularly excellent in heat-resistant colorability and hardness, which is considered to be contributed by the chemical structure formed by polymerization of the MAMA group. First, since the MAMA group has high radical curability and oxygen curing is possible, a cured product having a high crosslinking density can be formed. The main chain skeleton formed by the radical polymerization mechanism (6-membered ring ether structure with a methylene group next to it) is resistant to oxidative degradation, so it has excellent heat resistance, weather resistance, and light resistance. However, it is considered that it has an elastic recovery property and is excellent in hardness, particularly scratch hardness, since it has moderate flexibility.

The chemical structure formed by polymerization of AMA groups is somewhat hydrophilic and may cause inconveniences when high water / moisture resistance is required, but the chemical structure formed by polymerization of MAMA groups It can also be improved in terms. Further, the polymer and cured product of the present invention can raise the glass transition temperature more than the polymer and cured product obtained by polymerization and curing of AMA compounds, and various heat stability (heat resistance deformation, heat adhesion, etc.) Can also be improved.

According to the present invention, a novel polymerizable compound having a polymerizable group capable of forming a repeating unit structure excellent in heat-resistant colorability and hardness, a polymerization or curable composition comprising the polymerizable compound, and polymerization thereof Alternatively, a curing method is provided. Moreover, the polymer or hardened | cured material excellent in heat-resistant coloring property and hardness obtained by this superposition | polymerization or hardening method is provided. Accordingly, the polymerizable compound, the polymerized or curable composition, and the polymer or cured product of the present invention include a coating material, an adhesive, a sealing material, an adhesive, a paint, an ink, a resist, a molding material, a gas barrier material, It can be widely applied in various fields such as information technology (IT) fields, automobiles, architecture, medical care, daily necessities, such as water vapor barrier materials, oxygen absorbing materials, lenses, dental materials, rubber, tires, optical fibers, and optical waveguides.

It is a graph which shows ¹ H-NMR spectrum and attribution of Me-MAMA. It is a graph which shows IR spectrum and attribution of Me-MAMA. It is a graph which shows ¹ H-NMR spectrum and assignment of H-MAMA. It is a graph which shows IR spectrum and assignment of H-MAMA. It is a graph which shows the result of the transmittance | permeability retention rate [%].

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

<Synthesis of polymerizable compound>
[Synthesis Example 1]
Synthesis of methyl α-allyloxymethylacrylate: Me-AMA The compound was synthesized in the same manner as in Example 28 of International Publication No. 2011/148903. That is, to a round bottom flask (capacity 5 L) equipped with a distillation column, a phase separator, a reflux pump, etc., 1625.7 g of methyl α-hydroxymethyl acrylate, 1219.7 g of allyl alcohol (1.5 equivalents), 78.5 g (0.05 equivalent) of ethylenediamine (DABCO), 84.9 g (0.1 equivalent) of acetic acid as acid, 30.7 g (0.01 equivalent) of zinc acetate dihydrate, diisopropyl as an azeotropic agent of water 429.1 g (0.3 equivalent) of ether, 0.8 g of hydroquinone monomethyl ether and 0.8 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a polymerization inhibitor were charged. While blowing 5 ml of nitrogen gas containing 7% oxygen per minute, the reaction solution was heated to 90 ° C. at normal pressure and reacted for 16 hours. The liquid at the top of the column was separated into an oil phase and an aqueous phase by a phase separator, the oil phase was returned to the column top as a reflux liquid, and the aqueous phase was extracted and reacted while dehydrating. The resulting reaction solution was washed with water and distilled to obtain methyl α-allyloxymethyl acrylate.

[Example 1]
α-methallyloxymethyl acrylate: Synthesis of Me-MAMA A colorless transparent liquid was synthesized in the same manner as in Synthesis Example 1 except that 1514.3 g of methallyl alcohol was used instead of 1219.7 g of allyl alcohol. Obtained.
The obtained Me-MAMA was dissolved in deuterated dimethyl sulfoxide, and a ¹ H-NMR spectrum was measured with a nuclear magnetic resonance apparatus (400 MHz / manufactured by Varian). The spectrum and attribution are shown in Fig. 1-1. Further, an IR spectrum was measured by a liquid film method using an infrared spectrometer (device name: NEXUS-670 / manufactured by Thermo Nicolet). The spectrum and assignment are shown in Fig. 1-2.

[Example 2]
Synthesis of α-methallyloxymethylacrylic acid: H-MAMA A reactor equipped with a stirring bar was charged with 10.0 parts of 10% NaOH aqueous solution and 4.1 parts of Me-MAMA, and stirred with a magnetic stirrer while cooling in a water bath. Started. Transparency of the heterogeneous reaction solution gradually increased, and after 90 minutes, Me-MAMA disappeared and the solution became completely transparent and uniform, resulting in an aqueous solution of sodium α-methallyloxymethyl acrylate.
Next, 11.7 parts of a 15% aqueous sulfuric acid solution was added dropwise while cooling and stirring the α-methallyloxymethyl acrylate aqueous solution in a water bath. Stirring was continued for 30 minutes after completion of the dropping, and then the contents were transferred to a dropping funnel and extracted with dichloromethane and separated. Most of the dichloromethane was distilled off using an evaporator, and anhydrous magnesium sulfate was added to the resulting low-viscosity liquid, followed by stirring for 1 hour for dehydration. After the anhydrous magnesium sulfate was removed by filtration, it was further dried using a vacuum pump to obtain 3.2 parts of H-MAMA as a colorless transparent liquid.
The obtained H-MAMA was subjected to ¹ H-NMR measurement and IR measurement in the same manner as in Example 1. The obtained ¹ H-NMR spectrum and assignment are shown in FIG. 2-1, and the IR spectrum and assignment are shown in FIG. 2-2.

<Evaluation of polymerizable compound>
[Example 3]
10.0 parts of Me-MAMA of Example 1 as a polymerizable compound, 0.5 part of 1-hydroxycyclohexyl phenyl ketone as a photo radical initiator, and 0.01 part of Footent 710FM (manufactured by Neos) as a leveling agent The mixture was weighed into a screw tube and stirred well to obtain a curable composition of a uniform transparent solution.
The curable composition was applied to a glass plate using a bar coater (No. 8) so that the coating thickness was 10 μm. The film thickness calculated according to the following formula was defined as the coating film thickness.
Coating film thickness [μm] = 1.3 × Bar coater No. × Polymerizable compound concentration (% by mass) ÷ 100
Using a belt conveyor type UV irradiator, the glass plate on which this coating film was formed was cured by UV irradiation in the atmosphere so that the integrated light amount was 6 J / cm ² to obtain a colorless and transparent cured coating film.

The belt conveyor type UV irradiator used is as follows.
UV irradiation device: Light hammer 6
Belt conveyor device: Model LC-6B
As described above, the UV irradiation conditions manufactured by Fusion UV Systems are as follows.
Light source: H bulb Illuminance at a wavelength of 365 nm: 200 mW / cm ²

About the glass plate in which this cured coating film was formed, using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), the glass plate used as a base material was set as a reference, and the transmittance at a wavelength of 300 to 800 nm was measured. did. After measuring the transmittance, when heated at 230 ° C. for 1 hour in the air using a hot plate, it was colored pale yellow. The transmittance of the sample after heating was measured, and the transmittance retention [%] at a wavelength of 300 to 800 nm was calculated according to the following formula. The results are shown in FIG.
Transmittance retention [%] = transmittance after heating ÷ transmittance before heating × 100
Moreover, it was 4H when the scratch hardness (pencil method) in 1 kg of loads was measured about the sample after a heating based on JISK5600-4.

[Comparative Example 1]
Tests regarding heat resistant colorability and scratch hardness were conducted in the same manner as in Example 3 except that Me-AMA (Synthesis Example 1) was used instead of Me-MAMA (Example 1) as the polymerizable compound. After heating, the sample was colored deep yellow. The result of the transmittance retention [%] is shown in FIG. The scratch hardness of the sample after heating was 2H.

As a result of the above test, it was found that when the MAMA compound of Example 1 was used, a cured product excellent in heat-resistant colorability and hardness was obtained as compared with the case where the AMA compound of Synthesis Example 1 was used. As described above, this is presumed to be derived from the structure of the repeating unit formed by polymerizing the MAMA group, and such an action mechanism is based on the polymerizable compound, polymerized or curable composition of the present invention, and It is considered that all are expressed in the same manner in the polymer or cured product.
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in the present specification, and can exhibit advantageous effects.

Claims (6)

Following formula (1);

A polymerizable compound having at least one functional group represented by the formula: The polymerizable compound has the following formula (2):

The polymerizable compound according to claim 1, wherein Z is an n-valent linking group. N is an integer of 1 or more. A polymerizable or curable composition comprising the polymerizable compound according to claim 1. The polymerized or curable composition according to claim 3, further comprising a radical initiator and / or a dryer. A method for polymerizing or curing the polymerizable compound according to claim 1 or 2, or the polymerization or curable composition according to claim 3 or 4,
The polymerization or curing method includes a step of applying at least one method selected from the group consisting of heating, irradiation with active energy rays, and exposure to an atmosphere containing oxygen. Method. The polymerizable compound according to claim 1 or 2, or the polymer or cured product of the polymerization or curable composition according to claim 3 or 4 .

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