JP2019203052A - Radically polymerizable composition - Google Patents

Abstract

To provide a radically polymerizable composition that gives a polymer having a high radical polymerizing property (conversion rate) without using a photopolymerization initiator and a thermal polymerization initiator having a high potential toxicity, by using a dye having a fluorescein skeleton, an α,β-unsaturated double bond group-containing compound having an ethylene oxide chain, and a redox catalyst.SOLUTION: The radically polymerizable composition comprises a dye (A) having a fluorescein skeleton, an α,β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, and a redox catalyst (C).SELECTED DRAWING: None

Description

  The present invention is a radical comprising a dye (A) having a specific fluorescein skeleton, an α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, and a redox catalyst (C). The present invention relates to a polymerizable composition.

  It is known that a composition containing a reactive compound such as a (meth) acrylate compound easily undergoes radical polymerization by an active species generated from an initiator to form a cured product. These compositions are used in various fields, and examples thereof include printing inks, overcoat varnishes, paints, adhesives, photoresists, and 3D shaped articles.

  In recent years, compositions containing reactive compounds have been used for dental applications, medical and food packaging applications, and the like, and it is desirable to use materials with low toxicity. Since the photopolymerization initiator that generates active species causing radical polymerization in the composition is a low-molecular compound, those not involved in radical polymerization are left behind in the cured product. The photopolymerization initiator remaining in the cured product may cause odor due to oozing on the surface of the cured product, contamination of the content due to penetration into the content, or quality deterioration. Therefore, among materials contained in the composition, it is required to reduce the amount of the photopolymerization initiator as much as possible or to use a material with low potential toxicity.

  On the other hand, in radical polymerization, inhibition of curing by oxygen is a long-standing issue. When a radical polymerization reaction is performed in an environment where oxygen is present, the active species that causes radical polymerization generated from the photopolymerization initiator and oxygen react first, and a low activity radical is generated, resulting in poor curing. Cause problems. In order to improve this oxygen inhibition, it corresponds to whether the polymerization reaction is carried out under an inert atmosphere such as nitrogen or the amount of photopolymerization initiator used is increased, and there are significant problems in terms of cost and safety.

  In recent years, research on polymerization or curing reaction using oxygen, which is the greatest cause of curing inhibition, has been performed. For example, a photocurable adhesive using a reaction between singlet oxygen generated by irradiating Rose Bengal with light and a specific conjugated diene structure has been proposed. (Patent Document 1)

  However, other than those having a specific conjugated diene structure such as a furan ring, the curing reaction does not proceed, and the application is very limited.

  Furthermore, singlet oxygen generated by irradiating Rose Bengal with light is converted to hydrogen peroxide using ascorbic acid, which is an organic reducing agent, and further, active species capable of initiating radical polymerization from hydrogen peroxide with ascorbic acid. There is a report of radical polymerization of an acrylate compound which is a reactive compound by producing a hydroxy radical. (Non-Patent Document 1)

  However, the time required for polymerization is very long, and there are significant problems in working time and cost.

  Therefore, without using conventional photopolymerization initiators that are toxic or remain in the cured product and cause odor due to oozing to the surface of the cured product, contamination of the content due to penetration into the content, or quality deterioration. At present, there is no radical polymerizable composition that causes radical polymerization with high radical polymerization (conversion rate).

WO2009 / 099253

Macromolecules 2017, 50.1832-1846

  The present invention provides a photopolymerization initiator having high potential toxicity by using a dye having a fluorescein skeleton, an α, β-unsaturated double bond group-containing compound having an ethylene oxide chain, and a redox catalyst. Another object of the present invention is to provide a radically polymerizable composition that gives a polymer having high radical polymerizability (conversion rate), that is, good curability without using a thermal polymerization initiator initiator.

That is, the present invention provides the following general formula (1) and / or general formula (2) a dye (A) having a fluorescein skeleton, an α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, And a radically polymerizable composition comprising a redox catalyst (C).
^(Wherein, R 1 to R ⁴ represent independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group.)

(In the formula, R ^{5 to} R ⁸ each independently represents a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro group. In the formula, L ⁺ represents an arbitrary cation.)

  Furthermore, the present invention relates to the radically polymerizable composition as described above, wherein the α, β-unsaturated double bond group of the compound (B) is an acryloyl group and / or a methacryloyl group.

  Furthermore, the present invention relates to the radically polymerizable composition as described above, wherein the dye (A) having a fluorescein skeleton is an eosin skeleton.

  Furthermore, the present invention relates to the radically polymerizable composition as described above, wherein the dye (A) having a fluorescein skeleton is eosin Y.

  Furthermore, the present invention relates to the radically polymerizable composition as described above, which comprises an α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide in the molecule.

  Furthermore, the present invention relates to a polymer of the radical polymerizable composition described above.

  Furthermore, the present invention relates to the singlet oxygen generated by irradiating the dye (A) having a fluorescein skeleton with visible light by the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain. By converting the hydrogen peroxide into hydrogen peroxide and generating an active radical through a redox reaction with the redox catalyst (C), an α, β-unsaturated double bond group-containing compound having an ethylene oxide chain (B ) Or an α, β-unsaturated double bond group-containing compound (B) and an α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide chain are polymerized / crosslinked. It relates to the manufacturing method.

  According to the present invention, a conventional photopolymerization initiator that is toxic or remains in the cured product and has a odor due to oozing to the surface of the cured product, contamination of the content due to penetration into the content, or quality deterioration may be used. Thus, it was possible to provide a radically polymerizable composition that causes radical polymerization having high radical polymerizability (conversion rate).

Hereinafter, embodiments of the present invention will be described in detail.
In this specification, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” are “acryloyl” unless otherwise specified. And / or “methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”. The “radical polymerizable composition” may be abbreviated as “polymerizable composition”.

<Dye (A) having fluorescein skeleton>
In the present invention, the dye (A) having a fluorescein skeleton is a compound represented by the following general formula (1) and / or general formula (2), and having the ability to generate singlet oxygen by irradiation with visible light. Here, visible light in this specification is light having a wavelength of 400 nm to 750 nm.
^(Wherein, R 1 to R ⁴ represent independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group.)

(In the formula, R ^{5 to} R ⁸ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro group. In the formula, L ⁺ represents an arbitrary cation.)

R ^{1 to} R ⁸ in the general formula (1) and the general formula (2) each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro group. From the generation amount, a hydrogen atom, a bromine atom or a nitro group is preferable. In particular, the case where R ¹ , R ⁴ , R ⁵ and R ⁸ are bromine atoms or nitro groups and R ² , R ³ , R ⁶ and R ⁷ are bromine atoms is an eosin skeleton, and is most preferable.

L ^<+> in General formula (2) represents arbitrary cations, and a sodium cation, a potassium cation, and 1-hexadecyl pyridinium cation are preferable from availability.

In terms of easy availability, the amount of singlet oxygen generated, and compatibility with the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, R ⁵ in the general formula (2) Eosin Y in which R ⁶ , R ⁷ and R ⁸ are bromine atoms and L ⁺ is a sodium cation is most preferable.

  Although the specific example of the pigment | dye (A) of this invention is shown below, the pigment | dye (A) used for this invention is not limited to these.

  2 ′, 4 ′, 5 ′, 7′-tetrabromo-fluorescein (Solvent Red 43), 2 ′, 4 ′, 5 ′, 7′-tetrabromo-fluorescein-sodium salt (eosin Y, Acid Red 87), 4 ′ , 5'-Dibromo-2 ', 7'-dinitro-fluorescein-sodium salt (eosin B, Acid Red 91), 2', 7'-dichloro-fluorescein, 2 ', 7'-dichloro-fluorescein-sodium Salt, 4 ', 5'-dibromo-fluorescein (Solvent Red 72), 4', 5'-dibromo-fluorescein-sodium salt, 2 ', 7'-dibromo-fluorescein, 2', 7'-dibromo- Fluorescein-sodium salt, 4 ', 5'-dichloro-fluorescein, 4', 5'-dichloro-fluorose -Sodium salt, 4 ', 5'-diiodo-fluorescein (Solvent Red 73), 4', 5'-diiodo-fluorescein-sodium salt, 2 ', 7'-diiodo-fluorescein, 2', 7 ' -Diiodo-fluorescein-sodium salt, tribromo-fluorescein, tribromo-fluorescein-sodium salt, 2 ', 4', 5 ', 7'-tetrachloro-fluorescein, 2', 4 ', 5', 7 '-Tetrachloro-fluorescein-sodium salt, 2', 4 ', 5', 7'-tetraiodo-fluorescein, 2 ', 4', 5 ', 7'-tetraiodo-fluorescein-sodium salt (erythrosine B Acid Red 51), fluorescein, fluorescein-sodium salt, eosin-1-hexadecylpyridinium .

  In this invention, said compound can be used individually or in combination of 2 or more types as a pigment | dye (A).

  In this invention, a pigment | dye (A) is 0.001-20 mass parts with respect to 100 mass parts of compounds (B) mentioned later, and it is preferable that it is 0.01-10 mass parts. If the amount is less than 0.001 part by mass, the amount of singlet oxygen generated upon irradiation with visible light is not sufficient, the desired radical polymerizability (conversion rate) cannot be obtained, and the hardness of the polymer becomes insufficient. Unreacted monomers remain in the polymer, which causes problems in terms of odor and migration. On the contrary, if it exceeds 20 parts by mass, it causes light not to penetrate into the coating film, which also causes insufficient polymer hardness, unreacted monomers remain in the polymer, and causes odor and migration. It becomes a problem.

<Α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain>
In the present invention, the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain has ethylene oxide having an addition mole number of 1 or more in the molecule, and at least one α, β -A monomer of a compound having an unsaturated double bond group. The compound (B) was not only polymerized and crosslinked by the active species generated when the polymerizable composition of the present invention was irradiated with visible light, but also generated by irradiating the dye (A) with visible light. It plays the role of converting singlet oxygen into hydrogen peroxide. Although the cause is currently being elucidated, it is assumed that hydrogen peroxide was generated by supplying hydrogen to singlet oxygen from the ethylene oxide chain.

  The α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain of the present invention is obtained by adding ethylene oxide to a hydroxyl group possessed by an alcohol, a phenol derivative or the like, and (meth) acryloyl at the terminal hydroxyl group. A compound to which a group is added.

  Examples of monohydric alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, 1-octanol, 1-nonanol, and benzyl alcohol. It is not limited to.

  Examples of the divalent alcohol include ethylene glycol, propylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8- Octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol , Cyclopentadienedimethanol, dimer Although diol etc. are mentioned, it is not limited to these.

  Examples of the trihydric or higher polyhydric alcohol include, but are not limited to, trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, quadrolol, dipentaerythritol, and the like.

  Examples of phenol derivatives include phenol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4, 4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4′-isopropylidenephenol, 4, Examples include 4′-sulfonyldiphenol, bisphenol A, bisphenol F, and the like, but are not limited thereto.

  Further, for example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 1 -Hydroxybutyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) acrylic acid 8 -Hydroxyoctyl, cyclohexanedimethanol mono (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), simple Functional glycerol acrylate, or Fatty acid ester-based (meth) acrylic acid esters such as (meth) acrylic acid glycidyl laurate, (meth) acrylic acid glycidyl oleate, (meth) acrylic acid glycidyl stearate, or 2- (acryloyloxy) ethyl 6 -Hydroxyl content such as (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone to the hydroxyl-containing α, β-ethylenically unsaturated double bond group-containing compound such as hydroxyhexanonate hydroxyl-containing aliphatic (meth) acrylic acid esters such as ethylene oxide-added (meth) acrylic acid esters in which ethylene oxide is repeatedly added to an α, β-ethylenically unsaturated double bond group-containing compound;

  For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether Vinyl phenyl ether monomers having an ethylene oxide moiety such as n-pentyltetra (ethylene oxide) vinyl phenyl ether;

  For example, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene Oxide) Ethenyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, etc. Monomers;

  For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl Isopropenyl monomers having a polyethylene oxide moiety such as ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Vinyl benzoate or isopropenyl benzoate monomers having a polyethylene oxide moiety such as methyl 4-vinylbenzoate poly (ethylene oxide) and ethyl 4-vinylbenzoate poly (ethylene oxide);

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) Tetraethylene oxide adduct of propane, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, Di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane tetra Ethylene oxide adduct, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meta) ) Tetraethyleneoxy of acrylic acid-2,2-bis (hydroxyphenyl) propane Bifunctional (meth) acrylic acid cyclic esters, such as id adducts-dicaprolactonate, tetraethylene oxide adducts of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate, etc. However, it is not limited to these. These may use only 1 type or may use multiple types together.

  Examples of the commercially available product of the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain of the present invention include the following, but are not limited thereto.

  Blemmer ADE-200, Blemmer ADE-300, Blemmer ADE-400A, Blemmer ADE-600, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PE-200, Blemmer PE-350, Blemmer 50POEP-800B, Blemmer PLE-200, Blemmer PSE-1300, Blemmer PDE-100, Blemmer PDE-150, Blemmer PDE-200, Blemmer PDE-400, Blemmer PDE-600, Blemmer PDBE-200A, Blemmer PDBE-450A, Blemmer ALE-200, Blemmer AE-200, Blemmer AE-400, Blemmer AME-400, Blemmer AAE-300 New Frontier PE-200, New Frontier PE-300, New Frontier PE-400, New Frontier PE-600, New Frontier BPE-4, New Frontier BPE-10, New Frontier BPE-20, New Frontier TMP-3, New Frontier TMP-15, New Frontier GE3A, New Frontier NP-4, New Frontier N-177E, New Frontier ME-3, New Frontier ME-4S, New Frontier MPE-600, New Frontier HBPE- 4, New Frontier TMP-3, New Frontier PETA-4, New Frontier MPEM-400, New Frontier MPEM-1000, New Fronte A PEM-1000, New Frontier BPEM-4, New Frontier BPEM-10, New Frontier HBPEM-10 (Daiichi Kogyo Seiyaku Co., Ltd.), SR-101, SR-150, SR-210, SR-230, SR-252 SR-256, SR-259, SR-272, SR-415, SR-480, SR-494, SR-504, SR-540, SR-550, SR-602, SR-610, SR-9035, SR -344, SR-349, SR-454, SR-499, SR-502, SR-601, SR-9038 (Sartomer), Aronix M-260, Aronix M-102, Aronix M-111, Aronix M- 113, Aronix M-114, Aronix M-210, Aronix M-240 Aronix M-313, Aronix M-315, Aronix M-350, Aronix M-360, Aronix M-370 (manufactured by Toagosei Co., Ltd.), DM-811, DM-832, DM-851 (Nagase Chemtex), NK ester AM-30G, NK ester AM-90G, NK ester AM-130G, NK ester AM-230G, NK ester AMP-10G, NK ester AMP-20GY, NK ester A-LEN-10, NK ester A-200, NK Ester A-400, NK Ester A-600, NK Ester A-1000, NK Ester A-1206PE, NK Ester A-0612PE, NK Ester A-0412PE, NK Ester A-1000PER, NK Ester A-3000PER, NK Ester A -BPE-4, NK ester A-BPE-10, NK ester A-BPE-20, NK ester A-BPE-30, NK ester ABE-300, NK ester A-B1206PE, NK ester A-TMPT-3EO, NK Ester A-TMPT-9EO, NK ester AT-20E, NK ester AT-30E, NK ester A-GLY-3E, NK ester A-GLY-6E, NK ester A-GLY-9E, NK ester A-GLY-20E NK ester ATM-4EL, NK ester ATM-8EL, NK ester ATM-4E, NK ester ATM-35E, NK ester AD-TMP-4E, NK ester A-DPH-12E, NK economy A-PG5027E, NK economy A -PG5054E, NK ester M-4 0G, NK ester M-90G, NK ester M-130G, NK ester M-230G, NK ester S-20E, NK ester S-12E, NK ester EH-4E, NK ester B-20G, NK ester 9G, NK ester 14G, NK ester 23G, NK economy 1000PER, NK ester BPE-200, NK ester BPE-300, NK ester BPE-500, NK ester BPE-900, NK ester BPE-1300N, NK ester GLY-3E, NK ester GLY- 6E, NK ester GLY-9E, NK ester GLY-20E, NK ester TMPT-3EO, NK ester TMPT-9EO, NK ester TM-4EL, NK ester TM-4E, NK ester TM-35E, NK ester D TMP-4E, NK Ester M-DPH-6E, NK Ester M-DPH-12E, NK Economer M-PG5027E, NK Economer M-PG5054E, NK Ester ATM-120E, NK Ester A-DPH-48E, NK Ester A- DPH-96E (Shin Nakamura Chemical Co., Ltd.), Miramer M142, Miramer M144, Miramer M164, Miramer M166, Miramer M170, Miramer M232, Mirar M2100, Mirar M2200, Mirar M2200, Mirar M2200, Mirar M2200, Mirar M2200, Mirar M2200, Mirar M2200 M286, Miramer M290, Miramer M2040, Miramer M3160 , Miramer M3190, Miramer M3150, Miramer M4004, Miramer M193, Miramer M241, Miramer M2101, Miramer M2301 (manufactured by MIWON), Light acrylate EC-A, Light acrylate MTG-A, Light acrylate E130 Acrylate P2H-A, Light acrylate P-200A, Light acrylate BP-4EAL, Light acrylate 3EG-A, Light acrylate 4EG-A, Light acrylate 9EG-A, Light acrylate 14EG-A, Light acrylate TMP-6EO-3A (above Manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 190, Biscoat 360, Biscoat 700HV, Bisma -MPE400A, Bismer MPE550A (manufactured by Osaka Organic Chemical Co., Ltd.), Neomer PM201 (manufactured by Sanyo Chemical Industries), EBECRYL114, PEG400DA-D, EBECRYL11, TMPEOTA (manufactured by Daicel Ornex Co., Ltd.).

  In the present invention, the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain of the present invention is not particularly limited thereto. Moreover, these may use only 1 type or may use multiple types together.

<Redox catalyst (C)>
In the present invention, the redox catalyst (C) is a metal salt or complex that can exist in a state where the valence state is 2 or more. The redox catalyst (C) plays a role of generating active radicals by decomposing hydrogen peroxide converted by the compound (B) by a redox reaction.

  Specific examples of the redox catalyst (C) of the present invention are shown below, but the redox catalyst (C) used in the present invention is not limited thereto.

  Oxyvanadium salts or complexes such as oxyacetylacetone vanadium, vanadium oxysulfate, vanadium oxynaphthenate, oxytetraphenylporphyrinatovanadyl, oxyoctaethylporphyrinatovanadyl, oxytetra-t-butylphthalocyanine vanadyl, primary cobalt acetylacetonate, 2nd cobalt acetylacetonate, 1st cobalt naphthenate, 2nd cobalt naphthenate, 1st cobalt stearate, 2nd cobalt stearate, cobalt acetate, tetraphenylporphyrinatocobalt, octaethylporphyrinatocobalt, oxytetra-t -Cobalt salts or complexes such as butyl phthalocyanine cobalt, manganous stearate, manganous stearate, manganous acetylacetonate, Manganese salt or complex such as manganese acetylacetonate, manganese acetate, manganese naphthenate, tetraphenylporphyrinatomanganese, octaethylporphyrinatomanganese, tetra-t-butylphthalocyanine manganese, iron (III) acetylacetonate, iron (III) Benzoylacetonato, tetraphenylporphyrinatoiron (III) chloride, tetraphenylporphyrinatoiron (III) chloride, octaethylporphyrinatoiron (III) chloride, tetra-t-butylphthalocyanine iron <III> chloride, iron naphthenate ( III) Ferrocene, cyclopentadienyl-cumene iron hexafluorophosphate, iron (II) -o-phenanthroline, iron (II) sulfate, iron (II) chloride, iron (II) nitrate, iron hydroxide (II Hexacyanoiron (II) acid salt (ferrocyanide), iron (II) acetylacetonate, iron (II) benzoylacetonate, tetraphenylporphyrinatoiron (II), tetraphenylporphyrinatoiron (II), octaethylporphy Iron salts or complexes such as linato iron (II), tetra-t-butylphthalocyanine iron <II> chloride, titanium such as titanyl acetylacetonate, titanocene, dicyclopentadienyl titanium (II) dichloride, oxytitanium acetylacetonate Salt or complex. Copper salts or complexes such as copper sulfate (I), copper chloride copper sulfate (I), copper nitrate copper sulfate (I), and copper hydroxide copper sulfate (I).

  In this invention, said compound can be used individually or in combination of 2 or more types as a redox catalyst (C).

  The oxidation-reduction catalyst (C) of the present invention is preferably copper (I), iron (II), or cobalt (II) from the viewpoint of catalytic function, and iron (II) sulfate is easy to obtain. Particularly preferred.

  In this invention, a redox catalyst (C) is 0.001-5 mass parts with respect to 100 mass parts of compounds (B), and it is preferable that it is 0.005-1 mass parts. If the amount is less than 0.001 part by mass, the amount of active radicals generated by decomposing hydrogen peroxide is not sufficient, the desired radical polymerizability (conversion rate) cannot be obtained, and the hardness of the polymer becomes insufficient. In this respect, unreacted monomers remain in the polymer, which causes problems in terms of odor and migration. On the contrary, when the amount is more than 5 parts by mass, coloring of the polymer derived from the redox catalyst (C) becomes remarkable, and the use of the polymer of the present invention is limited.

<Α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide in the molecule>
In the present invention, in addition to the above essential components, an α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide in the molecule may be included. By using an α, β-unsaturated double bond group-containing compound (D) that does not have ethylene oxide in the molecule, the glass transition point (Tg) of the polymer is improved and high cohesive force is expressed, It becomes possible to form a polymer having good resistance such as heat resistance and water resistance.

  In particular, any compound containing one or more α, β-unsaturated double bond groups can be used without any limitation, but α, β-ethylene containing one or more hydroxyl groups in the structure thereof can be used. It is preferable to contain the polymerizable unsaturated double bond group-containing compound (d1) from the viewpoint of improving the reaction rate and suppressing polymerization curing shrinkage. The compound (d1) is divided into a compound (d1-1) having a hydroxyl group and not having a cyclic structure and a compound (d1-2) having a hydroxyl group and having a cyclic structure, both having a hydroxyl group Thus, a great effect is exhibited in reducing curing shrinkage accompanying the polymerization reaction.

Furthermore, an α, β-ethylenically unsaturated double bond group-containing compound which does not have a hydroxyl group in the molecule and has one or more cyclic structures from the viewpoint of improving durability such as heat resistance or heat and humidity resistance It is preferable to contain (d2).
Further, an α, β-ethylenically unsaturated double bond group-containing compound (d3) other than (d1) and (d2) can also be contained.

  Although it does not specifically limit, The following is mentioned as a compound which can be used as a compound (D).

  Of the α, β-ethylenically unsaturated double bond group-containing compound (d1) containing one or more hydroxyl groups, the compound (d1-1) having a hydroxyl group and not having a cyclic structure includes Is not particularly limited as long as it has a hydroxyl group but does not have a cyclic structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-methacrylic acid 2- Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4- (meth) acrylic acid 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol Mono (meth) acrylic acid ester, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic acid ethyl-α- (hydroxymethyl), monofunctional (meth) acrylic glycerol Or (meth) acrylic acid glycidyl lauric acid ester, (meth) acrylic acid glycidyl oleic acid ester, (meth) acrylic acid glycidyl stearic acid ester-based (meth) acrylic acid ester, or 2- (acryloyloxy) ) (Meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as ethyl 6-hydroxyhexanonate , Pentaerythritol tri (meta Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) aliphatic hydroxyl group-containing acrylates such as (meth) acrylic acid esters;

  For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, tetraethylene glycol monovinyl ether, trimethylolpropane monovinyl ether, penta Hydroxyl-containing aliphatic vinyl ethers such as erythritol monovinyl ether;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether Hydroxyl-containing aliphatic (meth) allyl such as hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether Alcohols or (meth) allyl ethers;

  For example, α, β-ethylenically unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

Examples thereof include monomers having a hydroxyl group and an ethenyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.
As the compound (d1-1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε -Especially preferred are α, β-ethylenically unsaturated double bond group-containing compounds such as caprolactone 1-2 mol added (meth) acrylic acid 2-hydroxyethyl, pentaerythritol tri (meth) acrylate and the like.

Among the compounds (d1), the compound (d1-2) having a hydroxyl group and having a cyclic structure can be used without particular limitation as long as it has both a hydroxyl group and a cyclic structure. Since the compound (d1-2) has one or more ring structures in the molecule, it is preferable from the viewpoint of water resistance in addition to durability such as heat resistance and moist heat resistance even if it has a hydroxyl group. .
The compound (d1-2) is not particularly limited as long as it has both a hydroxyl group and a cyclic structure in its structure. For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, ( 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy- (meth) acrylate 3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth ) Having a cyclic structure other than a hydroxyl group and a hetero ring such as acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (meth) acrylate;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Triazines and hydroxyl group-containing triazines such as 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

  As the compound (d1-2), acrylic acid 1,2-cyclohexanedimethanol, acrylic acid 1,3-cyclohexanedimethanol, acrylic acid 1,4-cyclohexanedi is preferable in terms of durability such as heat resistance and water resistance. Methanol, 2-hydroxy-3-phenoxypropyl acrylate and the like are particularly preferable.

  The α, β-ethylenically unsaturated double bond group-containing compound (d2) having no hydroxyl group in the molecule and having one or more cyclic structures has a ring structure containing no heteroatoms in the molecule. α, β-ethylenically unsaturated double bond group-containing compound (d2-1) and α, β-ethylenically unsaturated double bond group-containing compound having a ring structure containing a hetero atom in the molecule (d2-2) ) And is not particularly limited, but (d2-1) is preferred in terms of heat-resistant yellowing.

The compound (d2-1) is not particularly limited as long as it has a ring structure other than a heterocyclic ring in its structure. For example, cyclohexyl (meth) acrylate, 1-methyl-1- (meth) acrylate Cyclopentyl, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1-cyclohexyl (meth) acrylate, 1-ethyl (meth) acrylate 1-cyclohexyl, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, iso-bornyl (meth) acrylate, (meth) Phenyl acrylate, 2-methoxyethyl (meth) acrylate, 2-oxo-1, (meth) acrylate, -Phenylethyl, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, (meth ) 1-anthryl acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (Meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid 2-ethyladamantyl-2-yl, (meth) acrylic acid 2 -N-propyladamantyl-2-yl, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) -1-methylethyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-(meth) acrylic acid Yl) -1-methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1. 0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid dihydro -Α-Turpinyl, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3 3.1] Octa- 2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyl Oxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid-o-2 -(Meth) acrylic acid cyclic esters such as propenyl phenyl, (meth) acrylic acid cyclohexyl glycidyl ether, (meth) acrylic acid phenyl glycidyl ether;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, sulfonyl group-containing (meth) acrylic acid cyclic esters such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

  For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

  For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinyl Cyclic compounds containing alkenyl groups such as benzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid, cyclohexyl vinyl ether, cyclohexylmaleimide, vinylcyclohexene monooxirane ;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

  For example, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2- Cyclic vinyl ethers such as naphthyl vinyl ether;

  For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as E methylpropenylmethyl docosyl ether;

  For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long vinylbenzoic acid ester having a chain alkyl group or isopropenyl benzoic acid ester monomers;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

  For example, mono-long-chain alkyl ester cyclic monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

  For example, alkenyl group-containing cyclic sulfonic acids such as styrene sulfonic acid, 2-propenyloxybenzene sulfonic acid, 2-methyl-2-propenyloxybenzene sulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, triethyl styrene sulfonate Styrenesulfonic acid such as ammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, iron styrene sulfonate;
Metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate, etc .;
2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Examples include acid metal salts and ammonium salts.

  In addition, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like have an α, β-unsaturated double bond group, the compound (d2-1) included. These may use only 1 type or may use multiple types together.

  As the compound (d2-1), in view of durability such as heat resistance and water resistance, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, diacrylate acrylate Particularly preferred are cyclopentanyl, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate.

  The compound (d2-2) is not particularly limited as long as it has a heterocyclic structure in its structure. For example, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidin-2-yl) piperazine Heterocyclic (meth) acrylic acid esters containing nitrogen atom such as -1-yl (meth) acrylate;

  For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1 -Vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2'-bi (1H-imidazole) N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one 1-vinyl -2 (IH) - vinyl group-containing compounds having a heterocyclic nitrogen-containing, such as pyridinethione;

  For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1-benzyl 2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinyl-4,6-diamino-1,3,5-triazine, 6-vinyl 1,3,5-dimethyl-2,4-diamine, 3-vinyl-1,2,4,5-vinyl group-containing compounds having a six-membered ring nitrogen-containing, such as tetrazine;

  For example, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6-dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinyliso Xaline, 1-vinylquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen atoms such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Containing heteropolycyclic ethenyl group-containing compounds;

  For example, compounds having a nitrogen atom-containing heterocyclic structure and two or more vinyl groups such as 1-methyl-4,5-divinyl-1H-imidazole;

  For example, 1- (meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- (Meth) allylpyridine-containing compounds having a nitrogen atom-containing heterocyclic structure such as 1- (meth) allylpyridine, 3,6-dihydro-1- (meth) allylpyridine;

  For example, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl (Meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom such as -9H-carbazole;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

  For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

  For example, maleimide derivatives having both nitrogen and oxygen atoms, such as methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, 2-vinyloxazole, 2-phenyl-4-vinyloxazole, 2-phenyl-5-vinyloxazole, 5-ethoxy-2-vinyloxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, and 2-vinylbenzoxazole. Vinyl group-containing compounds;

  For example, (meth) acrylic acid glycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, ( (Meth) acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran -4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2- Dimethyl-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxoteto Hydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 , 3-Dimethyl-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl, and the like. ;

  For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, 1,3-butadiene monooxirane;

  For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, and these may be used alone or in combination of two or more.

  As the compound (d2-2), from the viewpoint of durability such as heat resistance and water resistance, glycidyl acrylate, glycidyl methacrylate, (3,4-epoxycyclohexyl) methyl methacrylate, 4-acryloylmorpholine, 1-vinyl Particularly preferred are imidazole, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, di (meth) acrylic acid ethoxylated isocyanuric acid, and tri (meth) acrylic acid ethoxylated isocyanuric acid.

  The compound (d3) other than (d1) or (d2) is not particularly limited as long as it has an α, β-ethylenically unsaturated double bond group in its structure.

  For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid sec- Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acryl iso-nonyl, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Of (meth) acrylic acid alkyl esters;

  For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, 2-chloro-2-propenyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters containing further unsaturated groups such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

  For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Me ) 2- (ethoxycarbonyloxy) butyl acrylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyl) (meth) acrylate Oxy) ethyl, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, (meth) Aliphatic (meth) acrylic acid esters having one carbonyl group such as 2- (octyloxycarbonyloxy) butyl acrylate;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 2.1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ( (Meth) acrylic acid cyclic esters;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acetate, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, butyryl valerate, isobutyryl valerate, palmitoyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

  For example, vinyl benzoyl formate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Vinyl naphthoyl butyrate, vinyl 1-naphthoyl valerate, vinyl 1-naphthoyl hexanoate, 2-naphthoyl vinyl acetate, 2-naphthoyl vinyl propionate, 2-naphthoyl vinyl butyrate, 2-naphthoyl vinyl valerate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoyl propionate, 2-furoyl vinyl butyrate, 2-furoyl vinyl valerate, 2-furoyl hexanoate, 2-furoyl decanoate, 2-furoyl dodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group, such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoyl propionate (meth) allyl, benzoyl butyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl α containing carbonyl groups of compounds, and the like, beta-unsaturated double bond-containing compounds;

  For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid esters containing phosphonic acid groups such as (meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, metal salts and ammonium of sulfonyl group-containing (meth) acrylic esters such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

  For example, di (meth) acrylic acid propylene oxide, di (meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (Meth) acrylic acid pentene oxide, di (meth) acrylic acid 2,2-dimethylpropyl, di (meth) acrylic acid hydroxypivalyl hydroxypivalate, di (meth) acrylic acid hydroxypivalyl hydroxypivalate dicaprolactonate Di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5- Hexanediol, di (meth) acrylic acid 1,7-hept Diol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1,2 -Decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1 , 2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) acrylic 1,2-hexadecanediol acid, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl di (meth) acrylate 1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di 2,2-diethyl-1,3-propanediol (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (Meth) acrylic acid 2-ethyl-1,3-hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-methyl-1,8-octane Diol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) acrylate Acid 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3 di (meth) acrylate -Propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexane di (meth) acrylate Diol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2, di (meth) acrylic acid Bifunctional (meth) acrylic acid esters such as 4-diethyl-1,5-pentanediol and 1,1,1-trishydroxymethylethane di (meth) acrylate;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

  For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- Ol, tetra (meth) acrylate ditrimethylol butane, tetra (meth) polyfunctional (meth) acrylic esters of acrylic acid ditrimethylol hexane, tetra (meth) ditrimethylol octanoic acrylate;

  For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Aliphatic vinyl ethers such as butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether;

  For example, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1 , 4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether (CHDVE), trimethylolpropane trivinyl ether, dipentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Sensuality vinyl a Le acids;

  For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing α, β-unsaturated double bond group-containing compounds such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

  For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
Metal salts and ammonium salts of 2-methyl-2-propenylsulfonic acid such as ammonium 2-methyl-2-propenylsulfonate, sodium 2-methyl-2-propenylsulfonate, and potassium 2-methyl-2-propenylsulfonate;

  For example, mono- or di-alkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleami , Fumaramide, mesaconamide, citraconic amide, itaconic amide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N Aliphatic (meth) acrylamides such as' -dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;
For example, nitrile group-containing α, such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itacononitrile, 2-propenenitrile, 2-methacrylic acid (meth) acrylate, etc. β-unsaturated double bond group-containing compounds;

  For example, saturated carboxylic acids such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate, (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of acids;

  For example, vinyl halides such as vinyl chloride, vinylidene chloride, allyl chloride;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-unsaturated double bond group-containing compounds containing a polyfunctional unsaturated bond such as vinyl 12,15-trienoate;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetracontene And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, etc .;

  For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, Angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine And alkylene oxides such as mono (meth) acrylic acid ω-carboxypolycaprolactone esters, such as polylactone-based (meth) acrylic acid esters, propylene oxide excluding ethylene oxide, having a carboxyl group at the terminal by ring-opening addition of a lactone ring Carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acids such as esters of alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid, which are repeatedly added And acid anhydrides thereof;

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and other carboxyl group-containing alicyclic and aromatic ring-containing α, β-unsaturated double bond group-containing carboxylic acids and acid anhydrides thereof Kind;

  For example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, (meth) acryl (Meth) acrylic acid esters having primary and / or secondary amino groups such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate, etc .;

  For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N2, N2 -Bis (2-chloroethyl) hydrazide, p-vinylbenzhydrazide, N- (m-vinylphenyl) acrylohydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) vinyl ] -4- (Meth) acrylic acid esters having a hydrazino group such as quinolinecarbohydrazide;

  For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (2-yl) piperazin-1-yl (meth) acrylates having a tertiary amino group such as (meth) acrylic acid esters;

  For example, it has primary and / or secondary amino groups such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, etc. (Meth) acrylamides;

  For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquino Phosphorus, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6- Vinyl compounds having primary and / or secondary amino groups such as divinylpyridine;

  For example, (meth) allylamine, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5- (Meth) having primary and / or secondary amino groups such as isopropylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-4- (meth) allylpyridine, etc. Allyl compounds;

  For example, vinyl compounds containing tertiary amino groups such as N-ethyl-N-nitrosovinylamine;

  For example, maleic derivatives of maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, Examples include β-unsaturated double bond group-containing compounds, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

  As said other (alpha), (beta) -ethylenically unsaturated double bond group containing compound (d3), the compound which has a (meth) acryloyl group from a reactive viewpoint is preferable, and the resin composition of this invention is optical stereolithography material. When used as, it is preferable that bifunctional or higher (meth) acrylic acid esters are included from the viewpoint of the active energy ray polymerization rate.

  In the α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide in the molecule of the present invention, polymerization curability, cure shrinkage of the polymer, heat resistance, moist heat resistance, water resistance, etc. The superiority of the compound (D) in terms of durability is (d1) containing a hydroxyl group, but a good polymerizable composition can be blended in a timely manner so as to contain both a hydroxyl group and a cyclic structure. It can be.

  Said compound (D) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., “Nakamura Chemical Co., Ltd.” "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by KK, "(Meth) acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd. "NICHIGO-UV Purple Light Urethane Acrylate Rigomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd., "Function" manufactured by Kojin Co., Ltd. Monomer "series and the like.

  Moreover, radically polymerizable cyclic compounds such as the following three-membered cyclic compounds of vinylcyclopropanes and vinyloxiranes and cyclic ketene acetals are also exemplified as the compound (D).

  Examples of the three-membered ring compounds include those described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 17, page 3169 (1979). Vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes described in Macromolecular Chem. Rapid Commun., Vol. 5, p. 63 (1984), Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition ( (Polym.Sci.Polym.Lett.Ed.), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 ( (1985) 2,3-divinyloxiranes.

  Examples of cyclic ketene acetals include, for example, Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 20, p. 3021 (1982) and Journal. 2-Methylene-1,3-dioxepane described in of Polymer Science Letter Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 21, p. 373 (1983). Dioxolanes, Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.) Described in Preprints, Vol. 34, 152 (1985). , Volume 20, 3 1 (1982), Macromolecular Chem., 183, 1913 (1982) and Macromolecular. Chem., 186, 1543 (1985). 2,7-Dimethyl-2-methylene-1,3- described in 2-methylene-4-phenyl-1,3-dioxepane, described in Macromolecules, Vol. 15, page 1711 (1982). Dioxepane, 5,6-benzo-2-methylene-1,3-dioxepane described in Polymer Preprints, Vol. 34, 154 (1985).

  Furthermore, the compound (D) can also mention the thing as described in the literature shown below. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  In this invention, a compound (D) is 1-900 mass parts with respect to 100 mass parts of compounds (B), and it is preferable that it is 10-500 mass parts. If the amount is less than 1 part by mass, the expression of high cohesion, which is the effect of the compound (D), and the improvement in resistance such as heat resistance and water resistance cannot be obtained. Since the ratio of the compound (B) in the composition decreases and hydrogen peroxide is not sufficiently generated, the desired radical polymerizability (conversion rate) cannot be obtained, and the hardness of the polymer becomes insufficient. In addition, unreacted monomers remain in the polymer, which causes problems in terms of odor and migration.

<Oligomer (E)>
In the present invention, in addition to the above components, the α, β-unsaturated double bond group-containing compound (B) having ethylene oxide in the molecule and α, β-unsaturated not having ethylene oxide in the molecule of the present invention. The oligomer (E) which does not correspond to a double bond group containing compound (D) may be included. By using the oligomer (E), the curing shrinkage suppressing effect of the polymer can be further improved. Furthermore, it becomes easy to improve heat resistance or heat-and-moisture resistance.

  The oligomer (E) is a compound obtained by adding an α, β-unsaturated double bond group to a polymer of monomers having at least an α, β-unsaturated double bond group and / or various compounds. , One or more α, β-unsaturated double bond groups in the molecule. The oligomer may have various functional groups in addition to the α, β-unsaturated double bond group. In one embodiment of the present invention, the oligomer (E) is selected from the group consisting of a polyester oligomer (e1), a polyurethane oligomer (e2), a polyepoxy oligomer (e3), and a polyacrylic oligomer (e4). Including at least one kind, these can be used without any particular limitation.

(E1) Polyester oligomer As the polyester oligomer (e1), the terminal of the polyester obtained by polycondensation of a polybasic acid and a polyhydric alcohol to the main chain skeleton or a hydroxyl group in the polyester chain and (meth) acrylic acid, maleic A compound obtained by esterification with an α, β-ethylenically unsaturated double bond group-containing compound having one or more carboxyl groups in the molecule such as an acid, or a carboxyl group in the terminal or polyester chain of the polyester ( It is a compound obtained by esterification with the aforementioned compound (d1) such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. In addition, a polyester oligomer obtained from an acid anhydride, glycidyl (meth) acrylate, and a compound having at least one hydroxyl group can also be used as the polyester oligomer (e1).

  Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each can be used without any particular limitation. More specifically, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, and dodecanedioic acid. Examples thereof include acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of succinic anhydride (methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl anhydride Succinic acid, etc.), glutaric anhydride derivatives (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, etc. ), Maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecyl Maleic anhydride, 2,3-dichloromaleic anhydride, phenyl maleic anhydride Phosphate, also anhydride derivative of 2,3-diphenyl maleic anhydride, etc.) and the like can be used.

  More specifically, as the alicyclic polybasic acid, for example, as the alicyclic dicarboxylic acid, for example, dimer acid, cyclopropane-1α, 2α-dicarboxylic acid, cyclopropane-1α, 2β-dicarboxylic acid , Cyclopropane-1β, 2α-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid, cyclobutane-1α, 2β-dicarboxylic acid, cyclobutane-1α, 3β-dicarboxylic acid, cyclobutane-1α, 3α-dicarboxylic acid, (1R) -Cyclopentane-1β, 2α-dicarboxylic acid, trans-cyclopentane-1,3-dicarboxylic acid, (1β, 2β) -cyclopentane-1,3-dicarboxylic acid, (1β, 3β) -cyclopentane-1, 3-dicarboxylic acid, (1S, 2S) -1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Saturated cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid, 1-cyclobutene-1,2-dicarboxylic acid, 3-cyclobutene-1,2-dicarboxylic acid, 1-cyclopentene-1,2-dicarboxylic acid Acid, 4-cyclopentene-1,3-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 2-cyclohexene-1,2-dicarboxylic acid, 3-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene- 1,3-dicarboxylic acid, 2,5-hexadiene-1α, 4α-dicar Unsaturated double bond in such phosphate rings include one or two unsaturated alicyclic dicarboxylic acid having, like these alicyclic dicarboxylic acids and anhydrides thereof can be used.

  In addition, derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride), derivatives of tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride, 3- Methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, etc.) Hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic acid anhydrides.

  More specifically, examples of the aromatic polybasic acid include, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, 2,5-dimethylterephthalic acid, 2 , 2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulene dicarboxylic acid, 1,3-azulene dicarboxylic acid, 4,5-azulene dicarboxylic acid, (−)-1,3-acenaphthene dicarboxylic acid, 1,4-anthracene dicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracenedica Aromatic dicarboxylic acids such as boronic acid, 1,2-phenanthenedicarboxylic acid, 4,5-phenanthenedicarboxylic acid, 3,9-perylenedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, These aromatic dicarboxylic acid and its anhydride etc. can be utilized.

  Furthermore, chlorendic anhydride, het anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endomethylene-1,2,3 , 6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic acid anhydride can also be used as the polybasic acid.

  Polyhydric alcohols include relatively low molecular weight polyols having a number average molecular weight (Mn) of about 50 to 500 and relatively high molecular weight polyols having a number average molecular weight (Mn) of 500 to 30,000. Each can be used without any particular limitation.

  More specific examples of relatively low molecular weight polyols include propylene glycol, dipropylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentane. Diol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxypropylene glycol, propanediol, 1,3-butane Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3- Hexanediol, cyclohexanediol, cyclohexanedimethanol, Li tricyclodecane, cyclopentadiene engine methanol, aliphatic or alicyclic diols and dimer diol;

  For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, addition of bisphenol with alkylene oxide And aromatic diols such as type bisphenol.

Examples of the raw material bisphenol of addition-type bisphenol include bisphenol A and bisphenol F, and the raw material alkylene oxide includes propylene oxide.
More specific examples of the relatively high molecular weight polyols include high molecular weight polyester polyols, high molecular weight polyamide polyols, high molecular weight polycarbonate polyols, and high molecular weight polyurethane polyols. The high molecular weight polycarbonate polyol is obtained by reacting the above-mentioned relatively low molecular weight diol with a carbonate or phosgene.

As a commercial item of the said high molecular weight polyester polyol, the Byron series by Toyobo Co., Ltd., the Kuraray polyol P series by Kuraray, and the Kyowapol series by Kyowa Hakko Chemical Co., Ltd. are mentioned, for example.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. can be used.
Examples of commercially available high molecular weight polycarbonate polyols include Oxymer N112 manufactured by Perstorp, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series, and Kuraray polyol C series manufactured by Kuraray.

Examples of commercially available high molecular weight polyurethane polyols include Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20 mgKOH / g, acid value <3 mgKOH / g), Takelac E551T (hydroxyl group) manufactured by Mitsui Chemicals Polyurethanes, Inc. Value = 30 mgKOH / g, acid value <3 mgKOH / g) and Takelac Y2789 (hydroxyl value = 10 mgKOH / g, acid value <2 mgKOH / g).
In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone diol, poly (β-methyl-γ-valerolactone) diol, and polyvalerolactone diol can also be used as the high molecular weight polyol. Included in polyols.

(E2) Polyurethane-based oligomer The polyurethane-based oligomer (e2) is a compound having at least one isocyanate group and an aliphatic α, β-unsaturated double bond group-containing carboxylic acid in the compound (d3) An acid anhydride, a compound obtained by reacting an alicyclic or aromatic ring-containing α, β-unsaturated double bond group-containing carboxylic acid or an acid anhydride thereof, or at least one isocyanate group; A compound obtained by reacting the compound (d1) with a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having the above-described polyhydric alcohol with the compound, or a compound having at least one isocyanate group and the polyhydric alcohol And a urethane prepolymer having a terminal isocyanate group obtained by reacting with It is a urethane prepolymer with the compound of the terminal isocyanate group obtained by reacting a compound having an amino group (d1) a compound obtained by reacting. Moreover, what contains the urea bond group obtained by making an isocyanate group and an amino group react is also contained in a polyurethane-type oligomer (e2).

  Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates and polyfunctional isocyanates, and aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, etc., respectively. Can be mentioned. More specifically, as monofunctional polyisocyanate, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p-chlorophenyl Isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α-methyl Benzyl isocyanate, (S)-(−)-α-methylbenzyl isocyan Nate, (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- And toluenesulfonyl isocyanate.

  Among polyfunctional isocyanates, the aromatic polyisocyanate is more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Alias: 4,4'-MDI), 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-tri Examples include isocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, and the like.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  Moreover, as a part of (e2) component, the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring, and the like can be used in combination. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, modified polyisocyanate thereof, and the like can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups.

  Examples of amines having an amino group include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, Isoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane (laurylamine), 1-aminotridecane, 1-aminohexadecane 1-aminotetradecane (myristylamine), 1-aminopentadecane, cetylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured beef tallow alkylamine, allylamine, stearylamine, aminocyclopropane, aminocyclobutane, Minocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-aminomethyl Heptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropyl Amine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonanaphthalene, 1-aminoanthraquinone, 2-aminoanthraquinone 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-aminobenzophenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, Primary amines such as benzylamine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine;

  For example, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2 -Dimethylpropylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidine Ethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkylamine, di-cured tallow alkyl Min, secondary amines such as di-stearylamine;

  For example, ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias : 1,4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], diethylenetriamine, Triaminopropane, 2,2-dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, dimer diamine, dicyclohexylmethane-4,4′-diamine, diethylene glycol bis (3-amino Propyl) , Phenylenediamine, xylylenediamine, dicyclohexylmethane-4,4'-diamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4 Diamines having two primary amino groups such as' -diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane, glutamine, asparagine, lysine, diaminopropionic acid, ornithine, diaminobenzoic acid and diaminobenzenesulfonic acid;

  For example, diamines having two secondary amino groups such as N, N-dimethylethylenediamine, N, N-diethylethylenediamine, and N, N'-di-tert-butylethylenediamine, piperazine;

  For example, N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or Methylaminopropylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1, 3-propanediamine or isopropylaminopropylamine], and N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine], triethyltetramine, diethylenetriamine, 2- Droxyethylethylenediamine, hexamethylenediamine 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2- Polyamines having primary and secondary amino groups, such as hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine;

  For example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanediohydrazide, eicosanedioic acid dihydrazide, maleic acid dihydrazide acid, maleic acid dihydrazide acid, Hydrazides such as dihydrazide, phthalic acid dihydrazide, carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyl dihydrazide, polyacrylic acid hydrazide;

  For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU) , Tertiary amines such as 1,5-diazabicyclo- [4.3.0] -5-nonene;

  For example, pyridine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, dimethyloxazoline, imidazole, N-methylimidazole, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be used.

(E3) Polyepoxy oligomer The polyepoxy oligomer (e3) is a compound having a glycidyl group and one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, and maleic acid. A compound obtained by a reaction with an α, β-unsaturated double bond group-containing compound having a compound, substantially having no glycidyl group and having an α, β-unsaturated double bond group-containing compound It is. Representative examples include bisphenol type, epoxidized oil type, phenol novolac type, and alicyclic type. As the bisphenol type polyepoxy oligomer, α, β-unsaturation having one or more carboxyl groups in the molecule such as bisphenol type diglycidyl ether obtained by reacting bisphenols and epichlorohydrin and (meth) acrylic acid It is obtained by reacting with a double bond group-containing compound.

  The epoxidized oil polyepoxy oligomer has at least one hydroxyl group or carboxyl group in the molecule such as epoxidized oil such as soybean oil and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with an α, β-unsaturated double bond group-containing compound can be used. As the novolak type polyepoxy oligomer, α, β-unsaturation having novolak type epoxy resin and one or more hydroxyl groups or carboxyl groups in the molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. What is obtained by reaction with a double bond group containing compound can be used. Examples of the alicyclic polyepoxy oligomer include α, β- having one or more hydroxyl groups or carboxyl groups in the molecule such as alicyclic epoxy resin and hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid and the like. What was synthesize | combined by reaction with an unsaturated double bond group containing compound can be used.

(E4) Polyacrylic oligomer In the present invention, an acrylic oligomer (e4) can also be used as the oligomer (E). Specific examples of usable compounds include modified polyethers having α, β-unsaturated double bond groups, amine-modified α, β-unsaturated double bond group-containing compounds, alkyd resins, and spiroacetal resins. Selected from the group consisting of a modified α, β-unsaturated double bond group-containing compound obtained by adding an α, β-unsaturated double bond group to various compounds such as polybutadiene resin, polythiol polyene resin and polyhydric alcohol. Oligomers or prepolymers of one or more compounds can be used.

In addition to the aggregation density, the weight average molecular weight (hereinafter referred to as Mw) of the oligomer (E) is from the viewpoint of obtaining excellent properties such as compatibility with other components and durability such as heat resistance and moist heat resistance. In terms of compatibility with other components, good durability (heat resistance, heat and humidity resistance), and agglomeration density, the range is preferably 300 to 50,000, and more preferably 400 to 30,000. . By using an oligomer having an Mw of 50,000 or less, it is possible to easily provide a polymerizable composition having excellent fluidity and excellent compatibility with the essential components of the present invention described above. Along with this, it is possible to easily suppress a decrease in durability such as curing shrinkage of the polymer. On the other hand, when the oligomer has an Mw of less than 300, it is difficult to further improve the durability of the polymer of the present invention.
In addition, the measuring method of a number average molecular weight (Mn), a weight average molecular weight (Mw), an acid value (AV), and a hydroxyl value (OHV) is mentioned later.

Although not particularly limited, in the present invention, the oligomer (E) preferably includes at least a polyurethane oligomer (e2). When using the said polymeric composition for uses, such as modeling material, there exists a tendency for the elasticity and softness | flexibility of hardened | cured material to change depending on the coupling group in the said oligomer (E). When the bonding group is an ester or ether group, it is easy to obtain excellent flexibility. However, it tends to have low elasticity and low hydrolysis resistance. On the other hand, when the component (e2) is used, it is easy to balance elasticity and flexibility based on the urethane bond. Moreover, since the said component (e2) is also excellent in hydrolysis resistance, it can improve water resistance and heat-and-moisture resistance easily.
However, in the present invention, even when an oligomer component other than the component (e2) is used, desired characteristics can be easily obtained by appropriately blending other constituent components.

<Coloring material (F)>
In the present invention, a color material (F) may be included in addition to the essential components. By using the color material (F), it is possible to impart not only design properties but also various functionalities such as thermal characteristics, electrical characteristics, and optical characteristics depending on the dyes and pigments contained therein.

The coloring material (F) is used by dispersing a dye or pigment (f1) at a high concentration with a dispersant. As such a dye or pigment (f1), for example, an achromatic pigment such as carbon black, titanium oxide, calcium carbonate, or a chromatic organic pigment or dye can be used.
Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red,
Soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indanthrone, thioindigo maroon,
Phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta;
Perylene organic pigments such as perylene red and perylene scarlet,
Isoindolinone organic pigments such as isoindolinone yellow and isoindolinone orange;
Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments,
Quinophthalone organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Other pigments include, but are not limited to, organic pigments such as Flavanthrone Yellow, Acylamide Yellow, Nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, Dioxazine Violet. Is not to be done.

Examples of the dye include, but are not limited to, azo dyes, rhodamine dyes, quinoline dyes, thiazine dyes, thiazole dyes, xanthene dyes, and nigrosine dyes.
These dye derivatives can be used without any particular problem.

  In the present invention, it is preferable to add a dispersant to the colorant (F) in order to improve the dispersibility of the pigment and the storage stability of the polymerizable composition. Among the colorant (F), as the dispersant, a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, High molecular weight unsaturated acid ester, high molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl Phosphate ester, polyoxyethylene nonylphenyl ether, stearylamine acetate and the like can be used.

  Specific examples of the dispersant include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101” (polyamino) manufactured by BYK Chemie. Amide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high Molecular copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Acid polycarboxylic acid and silicon) "," Lactimon (long-chain amine and unsaturated acid polycarbonate) Rubonic acid and silicon) ", but is not limited thereto.

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) ", Kyoeisha Chemical Co., Ltd." Floren TG-710 (urethane oligomer), "Flownon “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That, without being limited thereto.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxy) manufactured by Nikko Chemical Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., etc. It is not limited to.

  In this invention, it is preferable to use a dispersing agent in 10-60 mass parts in conversion of solid content with respect to 100 mass parts of dye and pigment (f1). When the dispersant is less than 10 parts by mass with respect to 100 parts by mass of the pigment, the dispersion stability may decrease, and the dispersion stability and storage stability of the polymerizable composition may deteriorate. On the other hand, when the dispersant exceeds 60 parts by mass with respect to 100 parts by mass of the dye or pigment (f1), the viscosity of the polymerizable composition is remarkably increased, which may adversely affect the storage stability of the polymerizable composition. In addition, when the polymerizable composition is irradiated with visible light and polymerized and cured to obtain a polymer, radical polymerizability (conversion rate) is lowered.

  In this invention, a coloring material (F) is 0.1-30 mass parts with respect to 100 mass parts of radically polymerizable compositions, and it is preferable that it is 1-10 mass parts. When the amount is less than 0.1 parts by mass, a sufficient coloring effect cannot be obtained. Conversely, when the amount is more than 30 parts by mass, visible light transmission is inhibited, and the desired radical polymerizability (conversion rate) cannot be obtained. There is a problem in that the hardness of the product becomes insufficient, and unreacted monomers remain in the polymer, which causes odor and migration.

<Other components (G)>
The polymerizable composition of the present invention can be appropriately mixed with other components (G) such as various additives as long as the effects of the present invention are not impaired. For example, radical polymerization (conversion rate) improvement, polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. From the viewpoint, an organic or inorganic filler can be blended. Such fillers may be composed of materials of polymers, ceramics, metals, metal oxides, and metal salts. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. In addition, when blending the above polymer-based materials, ascorbic acid and derivatives thereof, barbituric acid and derivatives thereof, dithionite or sulfite anion salts, sulfinic acid, organic reducing agents such as sulfinates, phenol -Based, hindered amine-based antioxidants, silane coupling agents, photosensitizers, flexibility imparting agents, plasticizers, flame retardants, storage stabilizers, UV absorbers, thixotropy imparting agents, dispersion stabilizers, flow As independent fillers such as property-imparting agents, foaming agents, antifungal agents, antistatic agents, magnetic materials, surface tension adjusting agents, slipping agents, antiblocking agents, leveling agents, infrared absorbers, and antifoaming agents In addition, it can be dissolved, semi-dissolved, or microdispersed in the polymerizable composition as a polymer blend or polymer alloy.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by applying energy with visible light having a wavelength of 400 to 750 nm to obtain a target polymer, but as a light source for applying energy, 400 nm Irradiation with visible light by a light source having a dominant wavelength of light emission in a wavelength region of ˜750 nm is preferable. Examples of a light source having a dominant wavelength of light emission in a wavelength region of 400 nm to 750 nm include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, and a pulsed emission xenon. Lamp, deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor-excited solid laser, emission wavelength in the wavelength range of 400 nm to 750 nm Various light sources such as an LED lamp light source having

  The polymerizable composition of the present invention can be printed or coated on various substrates, and the substrate on which the polymerizable composition of the present invention is printed or coated is made of glass, plastic, metal and paper. It can select suitably from a group. Furthermore, a composite substrate composed of a plurality of substrates can also be selected. These substrates may have a flat shape such as a plate, film, or paper, or may have a three-dimensional shape. The plastic film is preferably transparent.

  Examples of printing and coating methods include inkjet methods, blade coating methods, gravure coating methods, gravure offset coating methods, bar coating methods, roll coating methods, knife coating methods, air knife coating methods, comma coating methods, U comma coating methods, Examples thereof include an AKKU coating method, a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a four to five roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

  Examples of the plastic substrate include transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and polyacrylic polymers. Examples of the polyester polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulose polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the polyacrylic polymer include polymethyl methacrylate.

  Further, examples of the plastic substrate include transparent polymers such as polystyrene polymers, polyolefin polymers, polyvinyl chloride polymers, and polyamide polymers. Examples of the polystyrene-based polymer include polystyrene, acrylonitrile / styrene copolymer polymer, and the like. Examples of the polyolefin-based polymer include polyethylene, polypropylene, a polyolefin polymer having a cyclic or norbornene structure, and an ethylene / propylene copolymer polymer. Examples of the polyamide polymer include nylon and aromatic polyamide polymer.

  Polyimide polymer, polysulfone polymer, polyethersulfone polymer, polyether ketone polymer, polyphenyl sulfide polymer, polyvinyl alcohol polymer, polyvinylidene chloride polymer, polyvinyl butyral polymer, polyarylate polymer, poly Examples thereof also include transparent polymers such as oxymethylene polymers, polyepoxy polymers, and blends of the above polymers. In particular, those having a small birefringence are preferably used.

  In order to lower the viscosity of the polymerizable composition of the present invention and improve the wettability of the polymerizable composition, water or an organic solvent may be contained in the polymerizable composition.

  Organic solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl Ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, diethyl diglycol, diethylene glycol dialkyl ether, tetraethylene glycol dialkyl Ether, diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol Monoethyl ether butyrate, ethylene glycol monobutyl ether butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate, dipropylene glycol monomethyl ether Glycol monoacetates such as tyrate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propionate butyrate, ethylene Glycol dipropionate, ethylene glycol acetate dibutyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol acetate dibutyrate, propylene glycol acetate propionate, propylene glycol 1 Cetate butyrate, propylene glycol propionate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, dipropylene glycol propionate butyrate, di Glycol diacetates such as propylene glycol dipropionate and dipropylene glycol acetate dibutyrate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene Glycol monobutyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Examples include glycol ethers such as monobutyl ether and tripropylene glycol monomethyl ether, and lactic acid esters such as methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

<Production of radical polymerizable composition>
The polymerizable composition used in the present invention may contain, as necessary, the dye (A), the compound (B), the redox catalyst (C), the compound (D), the oligomer (E), the colorant (F), And other components (G) can be mixed and then mixed uniformly.

  When the polymerizable composition is stirred and mixed, it may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder, kneader, or dissolver equipped with a decompression device. Good. Usually, the temperature at the time of stirring and mixing is preferably set to 10 to 60 ° C.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples represent “parts by mass” and “% by mass”, respectively.

<Manufacture of colorant (F) dispersion>
[Production Examples 1 and 2]
After stirring the active energy ray polymerizable composition and the dispersion resin, and confirming that the dispersion resin is completely dissolved, the pigment is added, and the resulting mill base is stirred until it becomes uniform with a high speed mixer or the like. It was produced by dispersing for about 2 hours in a horizontal sand mill. Table 1 shows the composition of the dispersion (pigment dispersion) of the produced colorant (F) (the numerical value represents parts by mass). In Table 1, a blank means no blending.

The method for measuring the number average molecular weight (Mn), the weight average molecular weight (Mw), the acid value (AV) and the hydroxyl value (OHV) is described below.
《Molecular weight》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and weight average molecular weight (Mn) is determined in terms of polystyrene.

<< Hydroxyl value (OHV) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

《Acid value (AV)》
About 1 g of a sample was precisely weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

[Examples 1-35] [Comparative Examples 1-3]
<Production of polymerizable composition>
[Formulation Examples 1 to 38]
Charge the active energy ray-polymerizable composition into a light-shielded 300 ml or 500 ml glass bottle substituted with an oxygen concentration of 10% or less in the ratio shown in Table 2, and thoroughly stir with a stirrer to sufficiently degas. After performing, the polymeric composition shown to the compounding example was obtained. In Table 2, the blank represents no blending. Table 3 shows the abbreviations used in Table 2.

<Curability evaluation test>
The prepared radical polymerizable composition was applied onto a polyethylene terephthalate (PET) substrate so as to have a wet film thickness of 10 μm using a micrometer-adjustable applicator to prepare a coating film. Using PEN Bright (Matsukaze 430-490 nm), which is an LED lamp light source, as a visible light source, a polymer was prepared by irradiating visible light with an irradiation intensity of 1,200 mW / cm ² for 20 seconds. The surface of the polymer after irradiation was rubbed with a cotton cloth, and irradiation with visible light was repeated until the film was not damaged, and the curability was judged from the total irradiation time. It was judged that the shorter the visible light irradiation time, the better the curability, that is, the higher the radical polymerizability (conversion rate). Judgment criteria are as follows.

Judgment criteria A: 20.0 to less than 181.0 seconds. Especially good.
○: 181.0 seconds or more and less than 401.0 seconds. Good.
Δ: 401.0 seconds or more. Somewhat bad.
X: Uncured. Especially bad.

<Hardness evaluation test of polymer>
The prepared radical polymerization composition was applied onto a polyethylene terephthalate (PET) substrate so as to have a wet film thickness of 10 μm using a micrometer-adjustable applicator to prepare a coating film. Using PEN Bright (Matsukaze 430 to 490 nm) as a visible light source, a polymer was prepared by irradiating visible light with an irradiation intensity of 1,200 mW / cm ² for 10 minutes. When the surface of the polymer was pushed in with a load of 0.1 kgf (0.98 N) per cm ² for 5 seconds using a cotton swab, the state of the polymer after being pushed in was observed to determine the hardness of the polymer. Carried out. Judgment criteria are as follows.

Judgment criteria ◎: Not depressed when pressed, both after pressing. Especially good.
○: A dent is generated when pushed in, and no dent is found after pushing. Somewhat good.
X: Cracking occurred during indentation, or the cured product was disintegrated or uncured. Bad.

  When the polymerizable composition of the present invention was used, a polymer excellent in both curability and hardness could be produced (Examples 1 to 35). On the other hand, any of the essential components of the radical polymerizable composition of the present invention, the dye (A), the α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, and the redox catalyst (C) When a composition not contained is used, only a polymer having problems in both curability and hardness can be obtained (Comparative Examples 1 to 3).

Use of the radically polymerizable composition of the present invention is not limited in various applications. Examples of applications where high sensitivity, cured product characteristics, and safety can be expected to be improved by the present invention include molding resins, casting resins, stereolithography resins, and sealants utilizing polymerization or crosslinking reactions. , Dental polymerization resin, printing ink, printing varnish, paint, printing plate photosensitive resin, printing color proof, color filter resist, black matrix resist, liquid crystal photo spacer, rear projection screen material, optical fiber, plasma Display rib materials, dry film resists, printed circuit board resists, solder resists, semiconductor photoresists, microelectronics resists, micromachine component resists, etching resists, microlens arrays, insulating materials, hologram materials, optical switches , Waveguide materials , Overcoat agents, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesives, release coating agents, compositions for image recording materials using microcapsules, various devices, etc. It is done.

Claims (7)

A dye (A) having a fluorescein skeleton represented by the following general formula (1) and / or general formula (2), an α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, and oxidation A radically polymerizable composition comprising a reduction catalyst (C).
^(Wherein, R 1 to R ⁴ represent independently a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group.)

(In the formula, R ^{5 to} R ⁸ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a nitro group. In the formula, L ⁺ represents an arbitrary cation.)
  The radically polymerizable composition according to claim 1, wherein the α, β-unsaturated double bond group of the compound (B) is an acryloyl group and / or a methacryloyl group.   3. The radically polymerizable composition according to claim 1, wherein the dye (A) having a fluorescein skeleton is an eosin skeleton.   4. The radically polymerizable composition according to claim 3, wherein the dye (A) having a fluorescein skeleton is eosin Y.   The radically polymerizable composition according to any one of claims 1 to 4, further comprising an α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide in the molecule.   The polymer of the radically polymerizable composition in any one of Claims 1-5. Singlet oxygen generated by irradiating a dye (A) having a fluorescein skeleton with visible light is converted to hydrogen peroxide by an α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain. , By generating an active radical by oxidation-reduction reaction of the hydrogen peroxide with the oxidation-reduction catalyst (C), an α, β-unsaturated double bond group-containing compound (B) having an ethylene oxide chain, or α, β The method for producing a polymer according to claim 6, wherein the unsaturated double bond group-containing compound (B) and the α, β-unsaturated double bond group-containing compound (D) having no ethylene oxide chain are polymerized and crosslinked.