JP2020055960A - Polymerizable composition - Google Patents

Abstract

To provide a polymerizable composition that has a high radical-polymerizability (conversion rate) without using a photopolymerization initiator or a thermal polymerization initiator, which can cause an odor and migration, and has excellent curability.SOLUTION: A polymerizable composition contains a photosensitizer (A), a compound (B) having a double bond, and oxidation-reduction catalyst (C), and an organic reductant (D). Preferably, the photosensitizer (A) has light absorbency in a 200-900 nm region, and the compound (B) having a double bond has a compound having an acryloyl group and/or methacryloyl group.SELECTED DRAWING: None

Description

  The present invention relates to a polymerizable composition and a polymerized product thereof.

  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 include, for example, printing inks, overcoat varnishes, paints, adhesives, photoresists, and 3D shaped articles.

  In recent years, compositions containing a reactive compound have been used for dental applications, packaging of medical and food products, and the like. Since the photopolymerization initiator that generates an active species that causes radical polymerization in the composition is a low molecular weight compound, those not involved in radical polymerization are left in the cured product. The photopolymerization initiator remaining in the cured product may cause odor due to seepage onto the surface of the cured product, contamination of the content due to penetration into the content, and deterioration in quality. Therefore, among the materials contained in the composition, it is required to reduce the use amount of the photopolymerization initiator as much as possible, or to use a material which does not cause problems such as odor, contamination of contents, and quality deterioration.

  On the other hand, in radical polymerization, curing inhibition by oxygen has been an issue for many years. When performing a radical polymerization reaction in an environment where oxygen is present, an active species that causes radical polymerization generated from the photopolymerization initiator and oxygen react with each other first, low-active radicals are generated, and curing failure and the like occur. This can cause problems. In order to improve the oxygen inhibition, it is necessary to carry out the polymerization reaction in an inert atmosphere such as nitrogen or to increase the amount of the photopolymerization initiator, and there is a large problem in cost and safety.

  In recent years, studies on polymerization or curing reactions utilizing oxygen, which is the greatest factor in curing inhibition, have been conducted. 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, except for those having a specific conjugated diene structure such as a furan ring, the curing reaction does not proceed, and its use is very limited.

  Furthermore, singlet oxygen generated by irradiating Rose Bengal with light is converted to hydrogen peroxide using ascorbic acid, an organic reducing agent, and active species capable of initiating radical polymerization from hydrogen peroxide with ascorbic acid. There is a report that a hydroxy radical is generated and an acrylate compound as a reactive compound is radically polymerized (Non-Patent Document 1). However, the time required for the polymerization is very long, and there are significant problems in working time and cost.

  Therefore, without using a conventional photopolymerization initiator, which remains in the cured product and has an odor due to seepage to the surface of the cured product, contamination of the content due to penetration into the content, and quality deterioration, there is a concern. At present, there is no radical polymerizable composition that causes radical polymerization with high polymerizability (conversion rate).

WO 2009/092253

Macromolecules 2017, 50.1832-1846

  The problem to be solved by the present invention is to provide a polymerizable composition having a high radical polymerizability (conversion rate) without using a photopolymerization initiator or a thermal polymerization initiator which may cause odor or migration, and having a good curability. It is to provide things.

  The present inventor has conducted intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention relates to a polymerizable composition comprising a photosensitizer (A), a compound having a double bond (B), a redox catalyst (C), and an organic reducing agent (D).

  The present invention also relates to the above polymerizable composition, wherein the photosensitizer (A) has a light absorbency in a range of 200 to 900 nm.

  The present invention also relates to the above polymerizable composition, wherein the compound (B) having a double bond includes a compound having an acryloyl group and / or a methacryloyl group.

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

  According to the present invention, radical polymerization can be carried out without using a polymerization initiator which remains in the polymer, odors due to seepage to the polymer surface, contamination of the contents by permeation into the contents, and quality deterioration. It was possible to provide a polymerizable composition having high properties (conversion rate).

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” each refer to “acryloyl” unless otherwise specified. And / or methacryloyl "," acrylic acid and / or methacrylic acid "," acrylate and / or methacrylate ", and" acryloyloxy and / or methacryloyloxy ".

<Photosensitizer (A)>
In the present invention, the photosensitizer (A) refers to a substance that can absorb and excite an active energy ray to give excitation energy to oxygen. Specifically, it refers to a material capable of generating singlet oxygen by being excited by absorbing an active energy ray and transferring the excited triplet energy to oxygen molecules. The photosensitizer (A) preferably has light absorption in the ultraviolet (200 nm) to near-infrared (900 nm) region, and preferably has a triplet energy level of 100 kJ / mol or more. Those having an intersystem crossing efficiency to a triplet of 0.01 or more are preferable.

  Examples of the photosensitizer (A) include condensed polycyclic aromatic derivatives such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, naphthacene derivatives, perylene derivatives, pentacene derivatives, acridone derivatives, chalcone derivatives, dibenzalacetone, etc. Unsaturated ketones represented by 1,2-diketone derivatives represented by benzyl and camphorquinone, benzophenone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, Polymethine dyes such as fluorescein derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, benzothiazole derivatives, acridine Conductor, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, tetraaza Porphyrazine derivative, tetraquinoxalylloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, phthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, phenothiazine derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, Azo compounds, metal arene complexes, organic ruthenium complexes, C60 fullerenes and the like And more specifically, the dyes described in "Functional Dye Chemistry" (CMC, 1981) and "Special Functional Materials" (1986, CMC), edited by Chusaburo Ikemori et al. And sensitizers, but are not limited thereto, and include dyes and sensitizers that absorb light from ultraviolet to near infrared. Two or more of these may be used at any ratio as needed.

  The photosensitizer (A) preferably used includes, for example, naphthacene derivatives such as rubrene, anthraquinone derivatives such as purpurin, acridine derivatives such as acridine, Examples include porphyrin derivatives such as porphyrin IX, xanthene derivatives such as eosin Y and rose bengal, tetraphenylporphyrin derivatives such as tetraphenylporphyrin, phenothiazine derivatives such as methylene blue, ketocoumarin derivatives such as 3-ketocoumarin, and C60 fullerene.

  The photosensitizer (A) particularly preferably used in the present invention includes a xanthene derivative, which is easily available, has an ability to generate singlet oxygen, and has compatibility with the compound (B). In view of the above, a compound having a fluorescein skeleton represented by the following general formula (1) and / or general formula (2) can be given.

(In the formula, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or an amino group.)

(In the formula, R ^{11 to} R ²⁰ each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or an amino group. In the formula, L ⁺ represents an arbitrary cation.)

R ^{1 to} R ²⁰ in the general formulas (1) and (2) each independently represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, or an amino group. From the generation amount of the term oxygen, R ^{1 to} R ⁴ , R ^{11 to} R ¹⁴ are chlorine atoms, bromine atoms, iodine atoms or nitro groups, and R ^{7 to} R ¹⁰ and R ^{17 to} R ²⁰ are hydrogen atoms or chlorine atoms. Atoms are preferred.

L ⁺ in the general formula (2) represents an arbitrary cation, and is preferably a sodium cation, a potassium cation, an ammonium salt such as a triethylammonium salt, or a 1-hexadecylpyridinium cation from the viewpoint of availability.

Specific examples of the photosensitizer (A) are shown below, but are not limited thereto.
2 ′, 4 ′, 5 ′, 7′-Tetrabromo-fluorescein (Solvent Red 43), 2 ′, 4 ′, 5 ′, 7′-Tetrabromo-fluorescein-sodium salt (Eosin Y, Acid Red87), 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-fluorescein-sodium salt, 4 ', 5'-diiodo-off Fluorosein (Solvent Red 73), 4 ', 5'-diiodo-fluorescein-sodium salt, 2', 7'-diiodo-fluorescein, 2 ', 7'-diiodo-fluorescein-sodium salt, tribromo-fluorescein, Tribromo-fluorocein-sodium salt, 2 ′, 4 ′, 5 ′, 7′-tetrachloro-fluorocein, 2 ′, 4 ′, 5 ′, 7′-tetrachloro-fluorocein-sodium salt, 2 ′, 4 ′, 5 ′, 7′-Tetraiodo-fluorescein, 2 ′, 4 ′, 5 ′, 7′-Tetraiodo-fluorescein-sodium salt (erythrosin B, Acid Red 51), fluorescein (Solvent Yellow 94), fluorescein Sodium salt, 4-aminofluoroscein, 5-aminofluoroscein, 3,4,5,6-tetrachloro Ro-fluorocein, 3,4,5,6-tetrachloro-fluorocein-sodium salt, eosin-1-hexadecylpyridinium salt, 2 ', 4', 5 ', 7'-tetrabromo-3,4,5 , 6-Tetrachloro-fluorescein-sodium salt (Phloxin B, Acid Red 92), 2 ', 4', 5 ', 7'-tetraiodo-3,4,5,6-tetrachloro-fluorocein-sodium salt ( Rose Bengal, Acid Red 94), 2 ', 4', 5 ', 7'-tetraiodo-3,4,5,6-tetrachloro-fluorocein-bis (triethylammonium) salt.

  In the present invention, the photosensitizers described above can be used alone or in combination of two or more as the photosensitizer (A). The compounding amount of the photosensitizer (A) is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, based on 100 parts by mass of the compound (B) described later. preferable. When the amount is 0.001 parts by mass or more, the amount of singlet oxygen generated upon irradiation with active energy rays is sufficient, a desired radical polymerizability (conversion rate) can be obtained, and a polymer having sufficient hardness can be obtained. In addition, by controlling the residual amount in the polymer of the unreacted monomer, the problem of odor and migration can be improved. When the amount is 20 parts by mass or less, the active energy ray penetrates sufficiently into the inside of the coating film, so that the residual amount of the unreacted monomer in the polymer is suppressed, which leads to improvement of odor and migration problems.

<Compound (B) having double bond>
In the present invention, the compound (B) having a double bond (hereinafter sometimes abbreviated as “compound (B)”) is a compound having at least one carbon-carbon double bond in a molecule. The compound (B) itself is polymerized and cross-linked by active species generated when the polymerizable composition of the present invention is irradiated with active energy rays.

Compound (B) has no hydroxyl group _{- [O (CH 2) 2} ] 2 - and ( "sometimes abbreviated as compound (b1)" hereinafter) a compound having a (b1), a compound having a hydroxyl group or _{- [O (CH 2) 2} ] 2 - ( "sometimes to be abbreviated as compound (b2)" hereinafter) to have no compound (b2) and the double bond other than the compound (b1) and the compound (b2) (B2-3). The compound (b2) includes a compound (b2-1) having a hydroxyl group (hereinafter sometimes abbreviated as “compound (b2-1)”) and a compound (b2-2) having no cyclic group and having a cyclic structure. ) (Hereinafter sometimes abbreviated as “compound (b2-2)”). Further, the compound (b2-1) includes a compound (b2-1-1) having no hydroxyl structure and having a hydroxyl group (hereinafter, may be abbreviated as a compound (b2-1-1)) and a cyclic structure. And a compound having a hydroxyl group (b2-1-2) (hereinafter sometimes abbreviated as “compound (b2-1-2)”). Further, the compound (b2-2) is a compound (b2-2-1) having a cyclic structure having no hydroxyl group and not having a hetero atom as a ring member atom (hereinafter, abbreviated as “compound (b2-2-1)”). ") And a compound (b2-2-2) having a cyclic structure having no hydroxyl group and having a hetero atom as a ring member atom (hereinafter may be abbreviated as" compound (b2-2-2) "). ). The compound (B) preferably contains a compound having an acryloyl group and / or a methacryloyl group.

The compound (B) can be used without any particular limitation as long as it has at least one carbon-carbon double bond in the molecule. However, the use of the compound (b1) makes it possible to use the compound (B) In order to suppress the cross-linking density from becoming too high when the polymer is compatible with the polymer and to reduce the rigidity of the polymer having the cross-linking density of-[O (CH ₂ ) ₂ ] _2- , When a polymer is formed, flexibility can be imparted while maintaining hardness.

Further, when an attempt is made to obtain a cured product by polymerizing and curing with the active energy ray using the compound (b1), the curing speed is improved. Its cause is the in _{elucidated, - [O (CH 2)} 2] 2 - by the interaction between the group, the compound (b1) improvement of the curing speed by that distance are close to each other, or a photosensitizer ( against singlet oxygen generated by irradiation with active energy ray in a), - [O (CH 2) 2] 2 - generation of hydrogen peroxide by supplying hydrogen from the base, the generation of active species It is presumed that this leads to an improvement in the curing speed.

  Further, the compound (b2) may be used as the compound (B). By using the compound (b2), it is possible to improve the glass transition point (Tg) of the polymer to exhibit a high cohesive force and to form a polymer having good heat resistance and water resistance. Becomes

  In particular, it is preferable to use the compound (b2-1) from the viewpoint of improving the curing speed and suppressing the polymerization curing shrinkage. It is presumed that the presence of a hydroxyl group shows a great effect in reducing curing shrinkage due to the polymerization reaction.

  Furthermore, it is preferable to use the compound (b2-2) from the viewpoint of improving durability such as heat resistance or wet heat resistance. Further, compound (b2-3) can also be used.

  Although not particularly limited, the compounds that can be used as the compound (B) include the following.

The compound (b1) is not particularly limited as long as it has no hydroxyl group and has [[O (CH ₂ ) ₂ ] ₂ — and a double bond. For example, a compound having a hydroxyl group of alcohol or phenol may be used. And a carboxylic acid having a double bond such as (meth) acrylic acid or the like, which is obtained by subjecting ethylene oxide to ring-opening polymerization of ethylene oxide.
For example, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acryl Aliphatic (meth) acrylates such as tetraethylene glycol acid and polyethylene glycol di (meth) acrylate;

  For example, aromatic (meth) acrylates such as phenoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and diacrylate of ethylene oxide (EO) of bisphenol A;

  For example, tetra (oxyethylene) vinyl butyl ether, tetra (oxyethylene) vinylphenyl ether, poly (oxyethylene) vinylphenyl ether, vinyl ether monomers;

  For example, vinyl benzoate-based or isopropenyl benzoate-based monomers having a polyoxyethylene group site, such as vinylphenyl succinate poly (oxyethylene) and vinylphenylmethyl methyl hexahydrophthalate (oxyethylene);

Examples of the commercially available compound (b1) include, but are not limited to, the following.
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 50 POEP-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 AME-400, Blemmer AAE-300 (all manufactured by NOF Chemical Co., Ltd.), New Frontier PE-20 0, 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 Frontier PEM-1000, New Frontier BPEM 4, New Frontier BPEM-10, New Frontier HBPEM-10 (manufactured by 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 (manufactured by Sartomer), Aronix M-260, Aronix M-102, Aronix M-113, Aronix M-114, Aronix M-210, Aronix M -240, Aronix M-350, Aronix M-360, Aronix M-37 NK Ester AM-30G, NK Ester AM-90G, NK Ester AM-130G, NK Ester AM-230G, NK Ester AMP-20GY, 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 S 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 economer A-PG5027E, NK economer A-PG5054E, NK ester M-40G 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 Conomer 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 ( Miramer M142, Miramer M164, Miramer M166, Miramer M170, Miramer M232, Miramer M2100, Miramer M2200, Miramer M2200, Miramer M2200, Miramer M2200, Miramer M2200, Miramer M2300 Miramer M2040, Miramer M3160, Miramer M3190, Miramer M3150, Miramer M4004, Miramer M193, Miramer M241, Miramer M2101, Miramer M2301, Wright Acrylic M230A (MIWON-A) Rate MTG-A, Light acrylate EHDG-AT, Light acrylate 130A, Light 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 (manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 190, Biscoat 360, Biscoat 700HV, Bismer MPE400A, Bismer MPE550A (both manufactured by Osaka Organic Chemicals), Neomer PM201 (Sanyo Chemical Co., Ltd.) EBECRYL110, PEG400DA-D, and EBECRYL11 (all manufactured by Daicel Ornex).

  Compound (b1) is not limited to the above specific examples. These may be used alone or in combination of two or more.

  Hereinafter, the compound (b2) will be described. Among the compounds (b2), the compound (b2-1-1) is not particularly limited as long as it has a hydroxyl group and a double bond but does not have a cyclic structure.

  For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxy (meth) acrylate Butyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Octyl, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), glycerol monofunctional (meth) acrylate, or (meth) acrylic Glycidyl laurate, (meth) acrylic acid Fatty acid ester (meth) acrylates such as glycidyl oleate and glycidyl stearate (meth) acrylate, or the above-mentioned hydroxyl-containing double bond group such as 2- (acryloyloxy) ethyl 6-hydroxyhexanonate (Meth) acrylic acid ester having a hydroxyl group at a terminal by ring-opening addition of ε-caprolactone to a compound to be contained, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Hydroxyl-containing aliphatic (meth) acrylates such as

For example, hydroxyl-containing aliphatic vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether;
For example, aliphatic (meth) allyl alcohols or (meth) allyl ethers containing a hydroxyl group such as (meth) allyl alcohol and isopropenyl alcohol;
For example, double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol;

  For example, containing a hydroxyl group such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. (Meth) acrylamides;

  As the compound (b2-1-1), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate are preferred from the viewpoint of adhesion to a substrate. And 1 to 2 mol of ε-caprolactone, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate, are preferred.

Among the compounds (b2), the compound (b2-1-2) can be used without any particular limitation as long as it has a double bond, a hydroxyl group and a cyclic structure. Since the compound (b2-1-2) has one or more ring structures in the molecule, even if it has a hydroxyl group, it has not only durability such as heat resistance and wet heat resistance but also water resistance and the like. Is preferred.
For example, 1,2-cyclohexane dimethanol (meth) acrylate, 1,3-cyclohexane dimethanol (meth) acrylate, 1,4-cyclohexane dimethanol (meth) acrylate, 2-hydroxy (meth) acrylate 3-phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxybutyl (meth) acrylate, (meth) acrylate 2-hydroxy-3-phenoxydecyl acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2- (4-benzoyl-3-hydroxy) (meth) acrylate Hydroxyl groups such as phenoxy) ethyl and rings other than heterocycles Having concrete (meth) acrylic acid esters;

For example, hydroxyl group-containing benzophenone (meth) acryl such as 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2,2'-dihydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone Acid esters;
For example, hydroxyl group-containing benzotriazole (meth) acrylates such as 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole;

  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 and the like, and hydroxyl group-containing triazine (meth) acrylates and the like, and these may be used alone or Alternatively, a plurality of types may be used in combination.

  As the compound (b2-1-2), from the viewpoints of durability such as heat resistance and water resistance, 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanedimethanol acrylate, 1,4-acrylic acid 1,4 (Meth) acrylic esters having a cyclic structure other than a hydroxyl group and a hetero ring, such as cyclohexanedimethanol and 2-hydroxy-3-phenoxypropyl acrylate, are preferred.

  Among the compounds (b2), compounds (b2-2-1) and compounds (b2-2-2) can be roughly classified, but (b2-2-1) is preferable in terms of heat-resistant yellowing.

The compound (b2-2-1) is not particularly limited as long as it has no cyclic group and does not have a hetero atom as a ring atom and has a double bond, and for example, cyclohexyl (meth) acrylate 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, 1-methyl-1 (meth) acrylate -Cyclohexyl, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate, benzyl (meth) acrylate, Iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxy (meth) acrylate Ethyl, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2- (meth) acrylate Naphthyl, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl diacrylate , Dicyclopentenyl diacrylate, 2-ethyladamantyl-2-yl (meth) acrylate, (meth) 2-n-propyladamantyl-2-yl acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) -1-methylethyl (meth) acrylate, (meth) 1- (adamantan-1-yl) -1-ethylethyl acrylate, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-yl) (meth) acrylate -1-ethylpropyl, (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, dihydro-α-terpinyl (meth) acrylate, 6-oxo-7-oxa-bicyclo [ ³ ] (meth) acrylate . 2.1] Oct-2-yl, 7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl (meth) acrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (Meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (Meth) acryloyloxyethyl hexahydrophthalate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, -o-2-propenylphenyl (meth) acrylate, cyclohexyl glycidyl ether (meth) acrylate, (meth) Phenyl glycidyl acrylate (Meth) acrylic acid cyclic esters and the like;

For example, cyclic structure-containing (meth) acrylamides such as N- (4-carbamoylphenyl) (meth) acrylamide; for example, sulfonyl group-containing (meth) acrylic acid cyclic esters such as sulfophenoxyethyl (meth) acrylate;
For example, metal salts and ammonium salts of sulfonyl group-containing (meth) acrylic acid cyclic esters such as (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate;
For example, alkenyl group-containing cyclic compounds such as 5-vinylbicyclo [2.2.1] hepta-2-ene and 2,5-bis (allyloxy) norbornane;
For example, aromatic vinyl monomers such as styrene and 2-methylstyrene;
For example, cyclic vinyl ethers such as cyclohexyl vinyl ether and cycloxylmethyl vinyl ether;
For example, aromatic vinyl ether monomers having a long-chain alkyl group such as vinylphenylpentyl ether and vinylphenylhexyl ether;

For example, vinyl benzoate-based or isopropenyl benzoate-based monomers having a long-chain alkyl group such as hexyl 4-vinyl benzoate and octyl 4-vinyl benzoate;
For example, isopropenyl phenyl monomers having a long-chain alkyl group such as isopropenyl phenyl methyl butyl ether and isopropenyl phenyl methyl pentyl ether;
For example, mono-long chain alkyl ester-based cyclic monomers of dicarboxylic acids such as vinylphenyl nonyl succinate and vinyl phenyl methyl decyl hexahydrophthalate;
For example, alkenyl group-containing cyclic sulfonic acids such as styrenesulfonic acid and 2-propenyloxybenzenesulfonic acid;
For example, ammonium salts of styrenesulfonic acid such as ammonium styrenesulfonate and monomethylammonium styrenesulfonate;
Metal salts of styrene sulfonic acid such as sodium styrene sulfonate, and the like.

  As the compound (b2-2-1), from the viewpoint of durability such as heat resistance and water resistance, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, acrylic (Meth) acrylic acid cyclic esters such as dicyclopentanyl acrylate, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate are preferred.

  The compound (b2-2-2) is not particularly limited as long as it has no hydroxyl group and has a ring structure containing a hetero atom as a ring atom and a double bond. For example, pentamethylpiperidinyl ( Heterocyclic (meth) acrylates containing a nitrogen atom, such as meth) acrylate, 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

For example, vinyl group-containing compounds having a nitrogen-containing heterocycle such as 1-vinylpyrrole and 1-vinyl-2-imidazoline;
For example, vinyl group-containing compounds having a nitrogen atom-containing six-membered ring such as 1- (meth) allyl-1H-imidazole and 1- (meth) allyl-2-methyl-1H-imidazole;
For example, nitrogen-containing heteropolycyclic ethenyl group-containing compounds such as 1-vinyl-1H-benzimidazole and 1-vinyl-5,6-dimethyl-1H-benzimidazole;
For example, compounds having a nitrogen-containing heterocyclic structure and two or more vinyl groups, such as 1-methyl-4,5-divinyl-1H-imidazole;
For example, (meth) allyl having a heterocyclic structure containing a nitrogen atom, such as 1- (meth) allyl-3,5-dimethyl-1H-pyrazole and 1- (1-methylpropyl) -5- (meth) allylpyrimidine. Group-containing compounds;
For example, (meth) allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as 2- (meth) allyl-1H-indole and 3- (meth) allyl-1H-indole;

  For example, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylate isocyanuric acid oxyethylene (Meth) acrylates having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom, such as group-modified or tri (meth) acrylate isocyanurate oxyethylene group-modified;

For example, heterocyclic acrylamides such as 4-acryloylmorpholine and β- (2-furyl) (meth) acrylamide;
For example, maleimide derivatives having both a nitrogen atom and an oxygen atom, such as methylmaleimide and ethylmaleimide;
For example, vinyl group-containing compounds having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom, such as 2-vinyloxazole and 2-phenyl-4-vinyloxazole;
For example, heterocyclic-containing (meth) acrylates having an oxygen atom such as glycidyl (meth) acrylate and (3,4-epoxycyclohexyl) methyl (meth) acrylate;
For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate and allyl glycidyl ether;
For example, vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom, such as 2-vinylthiazole and 4-methyl-5-vinylthiazole, may be mentioned. Or a plurality of them may be used in combination.

  As the compound (b2-2-2), from the viewpoint of durability such as heat resistance and water resistance, hetero compounds having an oxygen atom such as glycidyl acrylate, glycidyl methacrylate, and (3,4-epoxycyclohexyl) methyl methacrylate are preferred. Heterocyclic acrylamides such as ring-containing (meth) acrylates, 4-acryloylmorpholine, etc., di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, etc. (Meth) acrylic esters having a heterocyclic structure containing

Examples of the compound (b2-3) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Acid alkyl esters;
For example, (meth) acrylates further containing a double bond group, such as (meth) allyl (meth) allyl and vinyl (meth) acrylate;
For example, perfluoroalkyl (meth) acrylates such as perfluoromethyl (meth) acrylate and perfluoroethyl (meth) acrylate;
For example, alkoxy group-containing (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate;
For example, alkylene oxide-containing (meth) acrylic acid derivatives such as alkylene oxide adducts of (meth) acrylic acid;
For example, aliphatic (meth) acrylates having one carbonyl group such as (methoxycarbonyl) methyl (meth) acrylate and (methoxycarbonyl) ethyl (meth) acrylate;
For example, aliphatic (meth) acrylates having two carbonyl groups such as 2-oxobutanoylethyl (meth) acrylate and 2-oxobutanoylpropyl (meth) acrylate;

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, 4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 (meth) acrylate] 2.1.2.1] octa-2-yl and a carbonyl group such as 4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl (meth) acrylate ( (Meth) acrylic acid cyclic esters;

For example, (meth) acrylamides having a carbonyl group such as N- (2-oxobutanoylethyl) (meth) acrylamide;
For example, aliphatic vinyl compounds having an acyl group such as vinyl acetoacetate;
For example, aromatic vinyl compounds having an acyl group such as vinyl benzoyl acetate and vinyl benzoyl propionate;
For example, aliphatic (meth) allyl compounds having an acyl group such as (meth) allyl acetoacetate and (meth) allyl acetopropionate;
For example, alkoxysilyl group-containing (meth) acrylates such as 3- (meth) acryloyloxypropylmethyldimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane;

  For example, bifunctional (such as di (meth) acrylic acid propylene oxide, di (meth) acrylic acid polypropylene oxide, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, etc. (Meth) acrylates;

  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, trimethylol hexane tri (meth) acrylate, trimethylol octane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate;

  For example, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetra (meth) acrylate 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylate di1,2 2,3-propanetriol, di-2-methylpentane-2,4-diol tetra (meth) acrylate, di-2-methylpentane-2,4-diol tetra (meth) acrylatetetracaprolactonate, tetra (meth) acrylate (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 acetate and vinyl propionate;
For example, aliphatic vinyl ethers such as methyl vinyl ether and ethyl vinyl ether;
For example, polyfunctional vinyl ethers such as propylene glycol divinyl ether 1,4-cyclohexanediol divinyl ether (CHODVE), trimethylolpropane trivinyl ether, dipentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, and dipentaerythritol hexavinyl ether;

For example, mono- or di-alkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide and diethylaminoethyl (meth) acrylamide;
For example, aliphatic (meth) acrylamides such as (meth) acrylamide and N-methyl (meth) acrylamide;
For example, N-alkoxy group-containing (meth) acrylamides such as N-methoxymethyl (meth) acrylamide and N-methoxyethyl (meth) acrylamide;
For example, nitrile group-containing double bond group-containing compounds such as (meth) acrylonitrile, maleene nitrile, and fumaronitrile;
For example, (meth) allyl esters of saturated carboxylic acids such as (meth) allyl acetate, coconut oil fatty acid, and vinyl pivalate;

  For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth) acrylate ) 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, senecioic acid, crotonic acid, isocrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicylic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine Alkylene oxides such as poly (lactone) (meth) acrylic acid esters having a carboxyl group at the terminal by ring-opening addition of a lactone ring, such as mono (meth) acrylic acid ω-carboxypolycaprolactone ester, and propylene oxide excluding oxyethylene group Is a carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxyl group such as an ester of an alkylene oxide addition system succinic acid having a carboxyl group at the terminal and (meth) acrylic acid, etc. Acids and their anhydrides;

For example, (meth) acryloyl group-containing carboxylic acids having carboxyl group-containing alicyclic or aromatic rings such as 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, and acid anhydrides thereof ;
For example, (meth) acrylates having primary and / or secondary amino groups such as N-methylaminoethyl (meth) acrylate and N-ethylaminoethyl (meth) acrylate;
For example, (meth) acrylates having a hydrazino group such as (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide;
For example, (meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
For example, (meth) acrylamides having a primary and / or secondary amino group such as monomethylaminoethyl (meth) acrylamide and monoethylaminoethyl (meth) acrylamide;
For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide and diethylaminoethyl (meth) acrylamide;
For example, vinyl compounds having a primary and / or secondary amino group such as vinylamine and methylvinylamine;

For example, (meth) allylamine, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5- (Meth) having a primary and / or secondary amino group such as isopropylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, and 3,6-dihydro-4- (meth) allylpyridine Allyl compounds;
For example, vinyl compounds containing a tertiary amino group such as N-ethyl-N-nitrosovinylamine;
Examples thereof include, but are not particularly limited to, heteroimide-containing double bond group-containing compounds of maleimide derivatives having both a nitrogen atom and an oxygen atom such as maleimide and methylmaleimide. One of these may be used alone, or a plurality of them may be used in combination.

  As the other compound having a double bond (b2-3), a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and in order to obtain a polymer having good curability, bifunctional or more ( It is preferable to include (meth) acrylates.

  In the compound (b2), the superiority of the compound (b2) in terms of polymerization curability, curing shrinkage of the polymer, and durability such as heat resistance, moist heat resistance, and water resistance includes a hydroxyl group (b2- Although it is 1), a good polymerizable composition can be obtained by appropriately mixing such that both the hydroxyl group and the cyclic structure are contained.

  Compound (b2) can be easily obtained as a commercial product of the following manufacturer. For example, “Light Acrylate”, “Light Ester”, “Epoxy Ester”, “Urethane Acrylate” and “Highly Functional Oligomer” series manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., “Shin Nakamura Chemical Co., Ltd.” "NK Ester" and "NK Oligo" series, "Fancryl" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Chemical 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 "Kayamer" series manufactured by Nippon Shokubai Co., Ltd., "(meth) acrylic acid / methacrylic acid ester monomer" series "NICHIGO-UV purple light urethane acrylate ligomer" 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. Series "and the like.

  Further, as the compound (b2), those described in the following documents can also be mentioned. For example, Shinzo Yamashita et al., “Handbook of Crosslinking Agents” (1981, Taiseisha) and Kiyomi Kato, “UV / EB Curing Handbook (Raw Materials)”, (1985, Polymer Publishing Association), Radtech Research Ed., Edited by Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resins", (1987, CMC), edited by Tsuyoshi Endo, "Refined Thermosetting Polymer", (1986, CMC), Takiyama Eiichiro, "Polyester Resin Handbook", (1988, Nikkan Kogyo Shimbun), edited by Radtech Research Group, "Applications and Markets of UV / EB Curing Technology", (CMC, 2002).

<Redox catalyst (C)>
In the present invention, the redox catalyst (C) is a metal salt or complex that can exist in two or more valence states. The oxidation-reduction catalyst (C) plays a role of decomposing hydrogen peroxide converted by an organic reducing agent (D) described later by an oxidation-reduction reaction to generate active radicals.

  Specific examples of the oxidation-reduction catalyst (C) are shown below, but the oxidation-reduction catalyst (C) used in the present invention is not limited to these.

  Oxyacetylacetone vanadium, vanadium oxysulfate, vanadium oxynaphthenate, oxytetraphenylporphyrinatovanadyl, oxyoctaethylporphyrinatovanadyl, oxyvanadium salts or complexes such as oxytetra-t-butylphthalocyanine vanadyl, 1st cobalt acetylacetonate, Cobalt acetylacetonato, cobaltous naphthenate, cobaltous naphthenate, cobaltous stearate, cobaltous stearate, cobalt acetate, cobalt acetate, tetraphenylporphyrinatocobalt, octaethylporphyrinatocobalt, oxytetra-t -Cobalt salt or complex such as butyl phthalocyanine cobalt, dimanganese stearate, dimanganese stearate, manganese acetylacetonate, Manganese salts or complexes such as manganese acetylacetonate, manganese acetate, manganese naphthenate, manganese tetraphenylporphyrinato, manganese octaethylporphyrinato, manganese tetra-t-butylphthalocyanine, 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 (II) hydroxide Hexiano ferrate (II) (ferrocyanide), iron (II) acetylacetonate, iron (II) benzoylacetonate, tetraphenylporphyrinato iron (II), tetraphenylporphyrinato iron (II), octaethylporphy Iron salts or complexes such as linatoiron (II), tetra-t-butylphthalocyanine iron <II> chloride, titanium such as titanylacetylacetonato, titanocene, dicyclopentadienyltitanium (II) dichloride, oxytitanium acetylacetonato Salt or complex. Copper salts or complexes such as copper sulfate (I), copper chloride copper sulfate (I), copper nitrate copper sulfate (I), copper hydroxide copper sulfate (I) and copper gluconate.

  In the present invention, the above compounds can be used alone or in combination of two or more as the oxidation-reduction catalyst (C).

  The oxidation-reduction catalyst (C) is preferably copper (I), iron (II), or cobalt (II) from the viewpoint of catalytic function, and particularly preferably iron (II) sulfate from the viewpoint of availability.

  The amount of the oxidation-reduction catalyst (C) is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 1 part by mass, based on 100 parts by mass of the compound (B). When the amount is 0.001 part by mass or more, the amount of active radicals generated by decomposing hydrogen peroxide is sufficient to obtain a desired radical polymerizability (conversion rate), and thus has sufficient hardness. A polymer can be obtained, and the amount of unreacted monomer remaining in the polymer can be reduced, leading to improvement of odor and migration problems. Further, when the amount is 5 parts by mass or less, coloring of the polymer derived from the oxidation-reduction catalyst (C) is suppressed, which leads to an expanded use of the polymer.

<Organic reducing agent (D)>
In the present invention, the organic reducing agent (D) can be reduced by hydride transfer, that is, can be a hydrogen donor. The organic reducing agent (D) plays a role of generating hydrogen peroxide by donating hydrogen to singlet oxygen generated by irradiating the photosensitizer (A) with active energy rays.

  Specific examples of the organic reducing agent (D) are shown below, but the organic reducing agent (D) used in the present invention is not limited to these.

  Ascorbic acid and its derivatives, barbituric acid and its derivatives, riboflavin and its derivatives, catechol and its derivatives, resorcin and its derivatives, hydroquinone and its derivatives, salts of dithionite or sulfite anions, sulfinic acid, and sulfinates.

  The organic reducing agent (D) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the compound (B). When the amount is 0.01 part by mass or more, the amount of hydrogen peroxide generated by reducing singlet oxygen becomes a sufficient amount, so that radical polymerizability (conversion rate) can be obtained, and sufficient hardness is obtained. A polymer can be obtained, and the amount of unreacted monomer remaining in the polymer can be reduced, leading to improvement of odor and migration problems.

<Oligomer (E)>
In the present invention, an oligomer (E) which does not correspond to the compound (B) having a double bond may be contained in addition to the above components. By using the oligomer (E), the effect of suppressing the shrinkage in curing of the polymer can be further improved. Further, it is easy to improve heat resistance or wet heat resistance.

  The oligomer (E) is a compound obtained by adding a substituent having a (meth) acryloyl group to at least a polymer of a monomer having a (meth) acryloyl group and / or various compounds. It has one or more (meth) acryloyl groups. The oligomer may have various functional groups in addition to the (meth) acryloyl group. The oligomer (E) includes a polyester oligomer (e1) having a (meth) acryloyl group whose main chain is a polyester, a polyurethane oligomer (e2) having a (meth) acryloyl group whose main chain is a polyurethane, and a main chain having a (meth) acryloyl group. At least one selected from the group consisting of a polyepoxy oligomer (e3) and a polyacryl oligomer (e4) having a structure formed by a reaction of a compound having a glycidyl group and a compound having a hydroxyl group, and having a (meth) acryloyl group; Including one or more, these can be used without any particular limitation.

(E1) Polyester-based oligomer having a (meth) acryloyl group whose main chain is a polyester As the polyester-based oligomer (e1), the terminal of a polyester obtained by polycondensing a polybasic acid and a polyhydric alcohol on the main chain skeleton or A compound obtained by esterification of a hydroxyl group in a polyester chain with an α, β-ethylenically unsaturated double bond-containing compound having at least one carboxyl group in a molecule such as (meth) acrylic acid or maleic acid; Alternatively, it is obtained by esterification of the above-mentioned compound (b2-1-1) such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate with a carboxyl group at the terminal of the polyester or in the polyester chain. Compound. In addition, polyester oligomers and the like 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 compounds, each of which can be used without any particular limitation. As the aliphatic polybasic acid, more specifically, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecane Examples include acids, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, and maleic anhydride, and aliphatic dicarboxylic acids and anhydrides thereof can be used. Also, 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.), derivatives of glutaric anhydride (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-methyl maleic anhydride, 2,3-dimethyl maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic 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, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,1-cycloheptanedicarboxylic acid, cubane-1,4-dicarboxylic acid, 2,3-norbornanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid , Saturated alicyclic 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-dical 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.

  Derivatives of hexahydrophthalic anhydride (3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride) and 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) and the like. Hydrogenated phthalic anhydride derivatives can also be used as alicyclic dicarboxylic anhydrides.

  As the aromatic polybasic acid, more specifically, for example, as the aromatic dicarboxylic acid, for example, o-phthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, 2,5-dimethylterephthalic acid, 2,2'-biphenyldicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, phenylindanedicarboxylic acid 1,2-azulenedicarboxylic acid, 1,3-azenedicarboxylic acid, 4,5-azenedicarboxylic acid, (-)-1,3-acenaphthenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,5- Anthracene dicarboxylic acid, 1,8-anthracene dicarboxylic acid, 2,3-anthracene dical Acid, 1,2-phenanthylenedicarboxylic acid, 4,5-phenanthylenedicarboxylic acid, aromatic dicarboxylic acids such as 3,9-perylenedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic anhydride and 4-methylphthalic anhydride An anhydride is mentioned, and these aromatic dicarboxylic acids and their anhydrides can be used.

  Further, chlorendic anhydride, heptic anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endmethylene-1,2,3,6-tetrahydrophthalic anhydride, methyl-3,6-endmethylene-1,2,3 6,6-tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, octahydro- Acid anhydrides such as 1,3-dioxo-4,5-isobenzofurandicarboxylic anhydride can also be used as polybasic acids.

  Examples of the polyhydric alcohol 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. And each can be used without particular limitation.

  As the relatively low molecular weight polyols, more specifically, for example, propylene glycol, dipropylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 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, Aliphatic or alicyclic diols such as licyclodecane dimethanol, cyclopentadiene dimethanol 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, Addition of alkylene oxide to 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidenephenol, bisphenol And aromatic diols such as bisphenols.

Examples of the raw material bisphenol of the addition type bisphenol include bisphenol A and bisphenol F, and examples of the raw material alkylene oxide include propylene oxide.
More specific examples of 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.

Commercial products of the high molecular weight polyester polyol include, for example, the Byron series manufactured by Toyobo Co., Ltd., the Kuraray polyol P series manufactured by Kuraray Co., Ltd., and the Kyowa Pole series manufactured by Kyowa Hakko Chemical Co., Ltd.
As a commercial product of the high molecular weight polyamide polyol, TPAE617 manufactured by Fuji Kasei Kogyo Co., Ltd. or the like can be used.
Commercially available high molecular weight polycarbonate polyols include, for example, Oximer N112 manufactured by Perstop, PCDL series manufactured by Asahi Kasei Chemicals, Kuraray polyol PMHC series manufactured by Kuraray, Kuraray polyol C series, and the like.

Commercially available high molecular weight polyurethane polyols include, for example, Byron UR series manufactured by Toyobo Co., Ltd., Takelac E158 (hydroxyl value = 20 mgKOH / g, acid value <3 mgKOH / g), Takeraq E551T (hydroxyl group) manufactured by Mitsui Chemicals Polyurethanes, Inc. Value = 30 mg KOH / g, acid value <3 mg KOH / g), and Takeluck Y2789 (hydroxyl value = 10 mg KOH / g, acid value <2 mg KOH / 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 are also usable as the high molecular weight polyols. Included in polyols.

(E2) Polyurethane-based oligomer having a (meth) acryloyl group whose main chain is polyurethane The polyurethane-based oligomer (e2) is a compound having at least one isocyanate group and (meth) acrylic acid, (meth) acrylic acid 2 Aliphatic carboxylic acids having an α, β-unsaturated double bond group represented by carboxyethyl and acid anhydrides thereof, or carboxylic acids having an alicyclic or aromatic ring having an α, β-unsaturated double bond group A compound obtained by reacting an acid or an acid anhydride thereof, or a urethane prepolymer having a terminal isocyanate group obtained by reacting a compound having at least one isocyanate group with the above-mentioned polyhydric alcohol, and the compound ( b2-1-1) reaction or a compound having at least one isocyanate group Urethane prepolymer having a terminal isocyanate group obtained by reacting a product with a polyhydric alcohol, and a urethane prepolymer having a terminal isocyanate group obtained by further reacting a compound having at least one or more amino groups with the compound ( b2-1-1). Further, those containing a urea bonding group obtained by reacting an isocyanate group and an amino group are also included in the polyurethane-based oligomer (e2).

  Examples of the compound having at least one isocyanate group include monofunctional polyisocyanates, and polyfunctional isocyanates, and include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates, respectively. No. As the monofunctional polyisocyanate, more specifically, 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 isocyanate , (R)-(-)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(-)-1-phenylethyl isocyanate, p- Toluenesulfonyl isocyanate and the like can be mentioned.

  Among the polyfunctional isocyanates, as the aromatic polyisocyanate, more specifically, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( Synonyms: 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, and 4,4 ′, 4 ″ -triphenylmethane triisocyanate.

  As the aliphatic polyisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also called 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-tetramethyl xylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (alias: IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

  Further, as a part of the component (e2), the above-mentioned 2-methylpentane-2,4-diol adduct of polyisocyanate, trimer having an isocyanurate ring, and the like can also be used in combination. Polyphenylmethane polyisocyanate (alias: PAPI), naphthylene diisocyanate, and their modified polyisocyanates can be used. As the modified polyisocyanate, a carbodiimide group, a uretdione group, a uretonimine group, a buret group reacted with water, or an isocyanurate group, or a modified compound 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 the amine having an amino group include, for example, 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, tallowalkylamine, hardened tallowalkylamine, 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-myristyloxypropyl Amine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 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-pipecholine, 3-pipecholine, 4-pipecholine, 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-hardened tallow alkyla Emissions, 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, dimerdiamine, dicyclohexylmethane-4,4′-diamine, diethyleneglycolbis (3-amino Propyl) ate 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, 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, hexamethylenediamine2-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, dodecane diacid dihydrazide, hexadecane dihydrazide, eicosan diacid dihydrazide, maleic acid dihydrazide, maleic acid dihydrazide dihydrazide Hydrazides such as dihydrazide, phthalic dihydrazide, carbonic acid dihydrazide, carbodihydrazide, thiocarbodihydrazide, oxalyldihydrazide, polyacrylic hydrazide;

  For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU) And 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 N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be used.

(E3) Polyepoxy oligomer having a structure formed by the reaction of a compound having a glycidyl group in the main chain with a compound having a hydroxyl group and having a (meth) acryloyl group The polyepoxy oligomer (e3) has a glycidyl group. A compound having a (meth) acryloyl group-containing compound having at least one hydroxyl group or a carboxyl group in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, or maleic acid; It is a compound having substantially no glycidyl group and having a (meth) acryloyl group-containing compound. Representative examples include a bisphenol type, an epoxidized oil type, a phenol novolak type, and an alicyclic type. Examples of the bisphenol-type polyepoxy oligomer include bisphenol-type diglycidyl ether obtained by reacting bisphenols with epichlorohydrin and (meth) acryloyl group having one or more carboxyl groups in a molecule such as (meth) acrylic acid. It is obtained by reacting with a compound.

  Epoxidized oils Polyepoxy oligomers include epoxidized oils such as soybean oil and one or more hydroxyl or carboxyl groups in the molecule of hydroxyethyl (meth) acrylate, (meth) acrylic acid, maleic acid, etc. Those obtained by reaction with a (meth) acryloyl group-containing compound can be used. The novolak-type polyepoxy oligomer includes a novolak-type epoxy resin and a (meth) acryloyl group having one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, or maleic acid. Those obtained by reaction with a compound can be used. Examples of the alicyclic polyepoxy oligomer include an alicyclic epoxy resin and (meth) acryloyl having one or more hydroxyl groups or carboxyl groups in a molecule such as hydroxyethyl (meth) acrylate, (meth) acrylic acid, or maleic acid. Those synthesized by reaction with a group-containing compound can be used.

(E4) Polyacrylic oligomer In the present invention, an acrylic oligomer (e4) can be used as the oligomer (E). Specific examples of usable compounds include a modified polyether having a (meth) acryloyl group, a compound containing an amine-modified (meth) acryloyl group, and an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiolpolyene resin, and a polyvalent resin. An oligomer or prepolymer of one or more compounds selected from the group consisting of a modified (meth) acryloyl group-containing compound obtained by adding a (meth) acryloyl group to various compounds such as alcohols 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 in terms of compatibility with other components and durability such as heat resistance and wet heat resistance. In terms of compatibility with other components, good durability (heat resistance, heat and moisture resistance), and cohesion density, it is preferably in the range of 300 to 50,000, and more preferably in the range of 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 above-mentioned essential components in the present invention. In addition, a decrease in durability such as curing shrinkage of the polymer can be easily suppressed.

  The methods for measuring the number average molecular weight (Mn), weight average molecular weight (Mw), acid value (AV) and hydroxyl value (OHV) will be described later.

Although not particularly limited, in the present invention, the oligomer (E) preferably includes a polyurethane-based oligomer (e2). When the polymerizable composition is used for a molding material or the like, the elasticity and flexibility of the cured product tend to change depending on the bonding group in the oligomer (E). When the bonding group is an ester or ether group, it is easy to obtain excellent flexibility. However, they tend 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 urethane bonds. In addition, since the component (e2) has good hydrolysis resistance, water resistance and moist heat resistance can be easily improved.
However, in the present invention, even when an oligomer component other than the component (e2) is used, desired properties can be easily obtained by appropriately blending other components.

<Color material (F)>
In the present invention, a coloring material (F) may be contained in addition to the above essential components. By using the coloring material (F), it becomes possible to impart not only design properties but also various functionalities such as thermal properties, electrical properties, and optical properties by the contained dyes and pigments.

  The coloring material (F) includes those in which a dye or a pigment (f1) is dispersed at a high concentration with a dispersant. As the dye or pigment (f1), for example, an achromatic pigment such as carbon black, titanium oxide, and calcium carbonate, or a chromatic organic pigment or dye can be used.

For example, as organic pigments, insoluble azo pigments such as toluidine red, toluidine maroon, hansa yellow, benzidine yellow, pyrazolone red,
Soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indanthrone, thioindigo maroon,
Phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green;
Quinacridone-based organic pigments such as quinacridone red and quinacridone magenta,
Perylene organic pigments such as perylene red and perylene scarlet,
Isoindolinone-based 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 organic pigments such as flavanthrone yellow, acylamide yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, diansuraquinonyl red, dioxazine violet, but are not limited thereto. It is not something to be done.

For example, 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.
Any of these dye derivatives can be used without any particular problem.

  In the present invention, it is preferable to add a dispersant to the coloring material (F) in order to improve the dispersibility of the pigment and the storage stability of the polymerizable composition. Among the coloring materials (F), examples of the dispersing agent include 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, polyetherester type anionic activator, naphthalene sulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl Phosphoric acid esters, 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)”, and “Disperbyk-101 (polyaminoamide)” manufactured by BYK Chemie. Amide phosphate and acid ester), 107 (hydroxyl-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) But not limited thereto.

  Also, “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, manufactured by Efka Chemicals, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) , 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine), Kyoeisha Chemical Co., Ltd., "Floren TG-710 (urethane oligomer)", "Flonon" SH-290, SP-1000 "," Polyflow No. 50E, No. 300 (acrylic copolymer) "," Dispalon KS-860, 873SN, 874 (polymer dispersant) manufactured by Kusumoto Kasei Co., # 2150 ( Aliphatic polycarboxylic acid), # 7004 (polyetherester 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 (Polymer)" (Carboxylic acid type polymer), "Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 24 (coconut amine acetate), 86 (stearylamine acetate)", manufactured by Abisia Solspers 5000 (phthalocyanine ammonium salt-based), 13940 (polyesteramine-based), 17000 (fatty acid amine-based), 24000 GR, 32,000, 33000, 39000, 41000, 53000 ”,“ Nikkor T106 (Polyoxy) Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), "Ajispar PB821, 822, 824" manufactured by Ajinomoto Fine Techno Co., and the like. However, the present invention is not limited to this.

  The dispersant is preferably used in an amount of 10 to 60 parts by mass in terms of solid content based on 100 parts by mass of the dye or pigment (f1). When the dispersant is 10 to 60 parts by mass with respect to 100 parts by mass of the pigment, the dispersion stability is improved without increasing the viscosity of the polymerizable composition more than necessary, and the dispersion stability of the polymerizable composition is improved. And storage stability is improved.

  The colorant (F) is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the polymerizable composition. When the amount is 0.1 to 30 parts by mass, a sufficient coloring effect can be obtained.

<Other components (G)>
In the polymerizable composition of the present invention, other components (G) such as various additives can be appropriately blended 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 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, metal salts. The shape is not particularly limited, and may be, for example, a particle shape or a fibrous shape. When the above-mentioned polymer-based material is blended, a phenol-based or hindered amine-based antioxidant, a silane coupling agent, a photosensitizer, a flexibility-imparting agent, a plasticizer, a flame retardant, storage stability, Agent, ultraviolet absorber, thixotropy-imparting agent, dispersion stabilizer, fluidity-imparting agent, foaming agent, antifungal agent, antistatic agent, magnetic substance, surface tension regulator, slipping agent, antiblocking agent, leveling agent, red It can be dissolved, semi-dissolved or microdispersed in the polymerizable composition as a polymer blend or polymer alloy, as well as as an independent filler such as an external absorbent and an antifoaming agent.

  The polymerizable composition of the present invention can be polymerized by applying heat or an energy by an active energy ray such as an ultraviolet ray, a visible ray, a near infrared ray, and an electron beam during a polymerization reaction to obtain a target polymer. However, irradiation of visible light by a light source having a main emission wavelength in a wavelength region of 250 nm to 750 nm is preferable as a light source for applying energy. Examples of the light source having a main wavelength of light emission in a wavelength region of 250 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 xenon. Lamps, deuterium lamps, fluorescent lamps, Nd-YAG third harmonic lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-excited solid-state lasers, emission wavelengths in the wavelength region of 250 nm to 750 nm And various light sources such as an LED lamp light source. In this specification, the definition of active energy rays such as ultraviolet rays, visible light, and near infrared rays is based on Ryogo Kubo et al., "Iwanami Physical and Chemical Dictionary, 4th Edition" (Iwanami, 1987).

  The polymerizable composition of the present invention can be printed or applied on various substrates, and the substrate on which the polymerizable composition is printed or applied is appropriately selected from the group consisting of glass, plastic, metal and paper. You can choose. Further, a composite substrate composed of a plurality of substrates can be selected. These substrates may have a flat shape such as a plate, a film, or paper, or may have a three-dimensional shape. A transparent plastic film is preferable.

  Examples of printing and coating methods include, for example, an inkjet method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma coating method, Examples include an AKKU coating method, a smoothing coating method, a microgravure 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-based polymers, cellulose-based polymers, polycarbonate-based polymers, and polyacryl-based polymers. Examples of the polyester-based polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulosic 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-based polymers, polyolefin-based polymers, polyvinyl chloride-based polymers, and polyamide-based polymers. Examples of the polystyrene-based polymer include polystyrene and acrylonitrile-styrene copolymer polymer. 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-based polymer include nylon and aromatic polyamide polymers.

  In addition, polyimide-based polymers, polysulfone-based polymers, polyethersulfone-based polymers, polyetherketone-based polymers, polyphenylsulfide-based polymers, polyvinyl alcohol-based polymers, polyvinylidene chloride-based polymers, polyvinylbutyral-based polymers, polyarylate-based polymers, and polyarylate-based polymers Transparent polymers such as oxymethylene-based polymers, polyepoxy-based polymers, and blends of the above polymers are also included. In particular, those having a small birefringence are preferably used.

  A solvent such as water or an organic solvent may be contained in the polymerizable composition in order to lower the viscosity of the polymerizable composition and improve the wettability and spreadability on a substrate.

  Examples of the organic solvent 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, and 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 , 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 citrate, 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 Acetate butyrate, propylene glycol propionate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, dipropylene glycol propionate butyrate, dipropylene Glycol diacetates such as propylene glycol dipropionate and dipropylene glycol acetate dibutylate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 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 polymerizable composition>
The polymerizable composition used in the present invention may contain, if necessary, the above-mentioned sensitizer (A) for active oxygen generation, compound (B), redox catalyst (C), organic reducing agent (D), oligomer (E) ), Coloring material (F), and other components (G), and then uniformly mixed.

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

  Hereinafter, specific examples of the present invention will be described 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.

<Production of colorant (F) dispersion>
[Production Examples 1 and 2]
The compound (B) having a double bond and the dispersing resin were stirred, and after confirming that the dispersing resin was completely dissolved, the pigment was added, and the mixture was stirred with a high-speed mixer or the like until the mixture became uniform. The mill base was manufactured by dispersing with a horizontal sand mill for about 2 hours. Table 1 shows the composition (the numerical values represent parts by mass) of the dispersion (pigment dispersion) of the produced coloring material (F). In Table 1, numerical values indicate parts, and blank columns indicate that no compounding is performed.

The methods for measuring the number average molecular weight (Mn), weight average molecular weight (Mw), acid value (AV) and hydroxyl value (OHV) are described below.
《Molecular weight》
For measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), GPC (gel permeation chromatography) “HLC-8320GPC” manufactured by Tosoh Corporation was used. The column was selected from “TSKgel SuperHZ1000”, “TSKgel SuperHZ2000”, “TSKgel SuperHZM-N”, and “TSKgel MultiporeHXL-M”, and the solvent was tetrohydrofuran and the measurement temperature was 40 ° C. The molecular weight was determined in terms of polystyrene.

<< Hydroxy group value (OHV) >>
About 1 g of the sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make the volume 100 ml) was added, and the mixture was stirred for about 1 hour. To this, phenolphthalein TS was added as an indicator and maintained for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned red.
The hydroxyl value was determined by the following equation. The hydroxyl value was a value in a dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (non-volatile concentration / 100) + D
Here, S: sampled amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: consumption of 0.1N alcoholic potassium hydroxide solution in blank experiment (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<< acid value (AV) >>
About 1 g of a sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and dissolved by adding 100 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). To this, phenolphthalein TS was added as an indicator, and after holding for 30 seconds, titration was performed with a 0.1N alcoholic potassium hydroxide solution until the solution turned 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 concentration / 100)
Here, S: sampled amount (g)
a: consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution

[Examples 1 to 16] [Comparative Examples 1 to 3]
<Production of polymerizable composition>
[Formulation Examples 1 to 20]
Into a light-shielded glass bottle in which the oxygen concentration was replaced to 10% or less, the materials were charged at the compounding amounts shown in Table 2, thoroughly stirred with a stirrer, and sufficiently defoamed. Each of the acidic compositions was obtained. In Table 2, numerical values indicate parts, and blank columns indicate that no compounding is performed. In Table 2, Formulation Examples 1 to 17 are the polymerizable compositions of the present invention, and Formulation Examples 18 to 20 are not the polymerizable compositions of the present invention. Table 3 shows the abbreviations of the materials used in Examples and Comparative Examples.

<Curability evaluation test>
The prepared polymerizable composition was applied to a polyethylene terephthalate (PET) base material using a micrometer-adjustable applicator so that the wet film thickness became 10 μm, to prepare a coating film. Using PEN Bright (430-490 nm, Matsukaze Co., Ltd.), which is an LED lamp light source, as an active energy ray source, an active energy ray was irradiated at an irradiation intensity of 1,200 mW / cm ² for 20 seconds to produce a polymer. The surface of the polymer after irradiation was rubbed with a cotton cloth, and irradiation was repeated until the film was not damaged, and the curability was determined from the total irradiation time. It can be said that the shorter the irradiation time, the better the curability. Table 4 shows the results. The criteria are as follows.

Judgment criteria A: 20.0 to less than 181.0 seconds. Especially good.
: 181.0 seconds or more to 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 polymerizable composition was applied to a polyethylene terephthalate (PET) base material using a micrometer-adjustable applicator so that the film thickness after application was 10 μm, to prepare a coating film. Using PEN Bright (Matsukaze Co., Ltd., irradiation wavelength: 430-490 nm) as an active energy ray source, an active energy ray was irradiated for 10 minutes at an irradiation intensity of 1,200 mW / cm ² to produce a polymer. Observing the state of the polymer when the surface of the polymer was continuously pushed in with a load of 0.1 kgf (0.98 N) per 1 cm ² for 5 seconds using a cotton swab, and after releasing the cotton swab after continuing to push in, The hardness of the polymer was determined. Table 4 shows the results. The criteria are as follows.

Judgment criteria ◎: When continuing to press, release the cotton swab and do not depress both. Especially good.
: Depression occurs when pushing is continued, and is not depressed after releasing the swab. Somewhat good.
X: Cracks are generated when pushing is continued, or the polymer is collapsed 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 16). On the other hand, when a composition not containing any of the essential components of the polymerizable composition of the present invention, the photosensitizer (A), the oxidation-reduction catalyst (C), and the organic reducing agent (D) is used, Only polymers having problems in both curability and hardness were obtained (Comparative Examples 1 to 3).

[Example 17]
The polymerizable composition of Formulation Example 5 shown in Table 2 was applied to a polyethylene terephthalate (PET) substrate using a micrometer-adjustable applicator so that the film thickness after application was 10 μm, and a coating film was obtained. Was prepared. When an argon laser (488 nm or 514 nm light) with a beam system of 2 mm was irradiated at 30 J / cm ² as an active energy ray source, the film was not damaged even if the surface was rubbed with a cotton cloth. When the surface is continuously pressed for 5 seconds with a load of 0.1 kgf (0.98 N) per cm ² , dents are generated when the surface is continuously pressed for 5 seconds, and there is no dent after releasing the swab after continuing to press the polymer. was gotten.

[Examples 18 to 33] [Comparative Examples 4 to 6]
<Curability evaluation test>
Each of the polymerizable compositions shown in Table 2 was applied to a polyethylene terephthalate (PET) substrate so as to have a film thickness of 10 μm using a micrometer-adjustable applicator to prepare a coating film. Using a xenon lamp as an active energy ray source, an active energy ray was irradiated for 20 seconds at an irradiation intensity of 50 mW / cm ² (365 nm) and 70 mW / cm ² (405 nm) to produce a polymer. The surface of the polymer after irradiation was rubbed with a cotton cloth, and irradiation was repeated until the film was not damaged, and the curability was determined from the total irradiation time. It was judged that the shorter the active energy ray irradiation time, the better the curability, that is, the higher the radical polymerizability (conversion rate). Table 5 shows the results. The criteria are as follows.

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

<Hardness evaluation test of polymer>
Each of the polymerizable compositions shown in Table 2 was applied to a polyethylene terephthalate (PET) substrate so as to have a film thickness of 10 μm using a micrometer-adjustable applicator to prepare a coating film. Using a xenon lamp as an active energy ray source, an active energy ray was irradiated for 20 seconds at an irradiation intensity of 50 mW / cm ² (365 nm) and 70 mW / cm ² (405 nm) to produce a polymer. Observing the state of the polymer when the surface of the polymer was continuously pushed in with a load of 0.1 kgf (0.98 N) per 1 cm ² for 5 seconds using a cotton swab, and after releasing the cotton swab after continuing to push in, The hardness of the polymer was determined. Table 5 shows the results. The criteria are as follows.

Judgment criteria ◎: When continuing to press, release the cotton swab and do not depress both. Especially good.
: Depression occurs when pushing is continued, and is not depressed after releasing the swab. Somewhat good.
X: Cracks are generated when pushing is continued, or the polymer is collapsed or uncured. Bad.

  When the polymerizable composition of the present invention was used, a polymer excellent in both curability and hardness could be produced even when the active energy ray source was changed (Examples 18 to 33). On the other hand, when a composition not containing any of the essential components of the polymerizable composition of the present invention, the photosensitizer (A), the oxidation-reduction catalyst (C), and the organic reducing agent (D) is used, Only polymers having problems in both curability and hardness were obtained (Comparative Examples 4 to 6).

[Examples 34 to 65]
<Production of polymerizable composition>
[Formulation Examples 21 to 52]
Into a light-shielded glass bottle in which the oxygen concentration was replaced to 10% or less, the materials were charged at the compounding amounts shown in Table 6, sufficiently stirred with a stirrer, and sufficiently defoamed. Each of the acidic compositions was obtained. In Table 6, numerical values indicate parts, and blank columns indicate that no compounding is performed. Table 3 shows the abbreviations of the materials used in the examples.

<Curability evaluation test>
The prepared polymerizable composition was applied on a polyethylene terephthalate (PET) base material using a micrometer-adjustable applicator so that the film thickness became 10 μm, to prepare a coating film. Using PEN Bright (Matsukaze Co., Ltd., wavelength 430 to 490 nm) as an active energy ray source, an active energy ray was irradiated at an irradiation intensity of 1,200 mW / cm ² for 20 seconds to produce a polymer. The surface of the polymer after irradiation was rubbed with a cotton cloth, and irradiation was repeated until the film was not damaged, and the curability was determined from the total irradiation time. It was judged that the shorter the active energy ray irradiation time, the better the curability, that is, the higher the radical polymerizability (conversion rate). Table 7 shows the results. The criteria are as follows.

Judgment criteria A: 20.0 to less than 181.0 seconds. Especially good.
: 181.0 seconds or more to 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 polymerizable composition was applied to a polyethylene terephthalate (PET) base material using a micrometer-adjustable applicator so that the wet film thickness became 10 μm, to prepare a coating film. Using PEN Bright (Matsukaze 430-490 nm) as an active energy ray source, an active energy ray was irradiated for 10 minutes at an irradiation intensity of 1,200 mW / cm ² to produce a polymer. Using a cotton swab, the surface of the polymer was pushed in for 5 seconds with a load of 0.1 kgf (0.98 N) per cm ² and the state of the polymer after pushing was observed to determine the hardness of the polymer. Carried out. Table 7 shows the results. The criteria are as follows.

Judgment criteria ◎: No depressed during and after pressing. Especially good.
: Depression occurs at the time of pressing, and no depression is assumed after pressing. Somewhat good.
×: Cracking occurred at the time of pushing, or the cured product collapsed or was uncured. Bad.

  When the polymerizable composition of the present invention was used, a polymer having excellent curability and hardness could be produced with any composition (Examples 34 to 65).

  Use of the polymerizable composition of the present invention is not limited in various uses. Examples of applications in which the present invention can be expected to improve sensitivity and properties of cured products, and further improve safety include molding resins, casting resins, resins for stereolithography, and encapsulants utilizing polymerization or crosslinking reactions. , Dental polymerization resin, printing ink, printing varnish, paint, photosensitive resin for printing plate, printing color proof, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, plasma Display rib material, dry film resist, printed board resist, solder resist, photoresist for semiconductor, resist for microelectronics, resist for manufacturing micromachine parts, resist for etching, microlens array, insulating material, hologram material, optical switch , Waveguide material , Overcoat agents, powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, compositions for image recording materials using microcapsules, various devices, etc. Can be

Claims (4)

  A polymerizable composition comprising a photosensitizer (A), a compound having a double bond (B), a redox catalyst (C), and an organic reducing agent (D).   The polymerizable composition according to claim 1, wherein the photosensitizer (A) has a light absorbency in a range of 200 to 900 nm.   The polymerizable composition according to claim 1 or 2, wherein the compound (B) having a double bond includes a compound having an acryloyl group and / or a methacryloyl group.   A polymer of the polymerizable composition according to claim 1.