Polymerizable composition and polymer thereof

Abstract

To provide a polymerizable composition having a high radical polymerization property (conversion rate) and good curability even if a photopolymerization initiator or a thermal polymerization initiator, which may cause odor or migration, is reduced or removed and to provide a polymer having high hardness and water resistance.SOLUTION: There is provided a polymerizable composition comprising a polymer (A) and a compound (B) having a double bond, wherein the content ratio of a polymerization initiator is 2.0 mass% or less based on 100 mass% of the total of the polymer (A) and the compound (B) having a double bond and the polymer (A) has an α,β-unsaturated lactam structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition and a polymer thereof. [Background technology]

[0002] Compositions containing reactive compounds such as (meth)acrylate compounds are known to readily undergo radical polymerization in the presence of active species generated from initiators to form cured products. These compositions are used in a variety of fields, including printing inks, overcoat varnishes, paints, adhesives, photoresists, and 3D models.

[0003] In recent years, compositions containing reactive compounds have been increasingly used in dental applications and for packaging medical and food products, making it desirable to use low-toxicity materials in these compositions. Because the initiators in these compositions that generate the active species that cause radical polymerization are low-molecular-weight compounds, any that do not participate in the radical polymerization are left behind in the cured product. Residual initiators in the cured product can lead to odors due to seepage onto the surface of the cured product, contamination of the contents due to penetration into the contents, and quality degradation. Therefore, there is a demand to minimize the amount of initiators used as much as possible, or to use materials with low potential toxicity.

[0004] Thermal polymerization initiators and photopolymerization initiators are commonly known as types of initiators. Thermal polymerization initiators and photopolymerization initiators function by heating or irradiation with active energy rays, respectively. Initiators are selected based on the application and purpose, but they are not suitable for applications requiring high safety because they are potentially highly toxic and cause odors and migration. In addition, generally, if a thermal polymerization initiator or photopolymerization initiator is not used, the reaction will not proceed sufficiently and sufficient coating film resistance will not be obtained.

[0005] Patent Document 1 proposes an inorganic powder-containing resin composition characterized by containing inorganic powder, a binder resin containing a polymer having a pyrrolidone skeleton, a polyfunctional (meth)acrylate, and a photopolymerization initiator. However, the use of a low-molecular-weight photopolymerization initiator causes problems of odor and migration. Patent Document 2 also proposes an active energy ray-curable resin composition for a three-dimensional modeling support material, which contains a water-soluble polymer obtained by polymerizing an unsaturated compound. However, in a system using an N-vinylpyrrolidone homopolymer, a photopolymerization initiator is used as in Patent Document 1, causing problems of odor and migration.

[0006] Patent Document 3 proposes a composition containing a metal salt of an unsaturated carboxylic acid compound and a polymer obtained by polymerizing a monomer component containing N-vinylpyrrolidone. However, to ensure that the reaction proceeds sufficiently, a certain amount or more of a polymerization initiator must be used, which causes problems such as odor and migration. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-232366 [Patent Document 2] Japanese Patent Publication No. 2020-12052 [Patent Document 3] Japanese Patent Application Laid-Open No. 2018-35310 Summary of the Invention [Problem to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a polymerizable composition that has high radical polymerizability (conversion rate) and good curability even when the amount of a photopolymerization initiator or a thermal polymerization initiator, which can cause odor or migration, is reduced or removed, and to provide a polymer that has high hardness and water resistance. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above problems and have completed the present invention.

[0010] That is, the present invention provides a polymerizable composition comprising a polymer (A) and a compound (B) having a double bond, the content of the polymerization initiator is 2.0% by mass or less relative to 100% by mass of the total of the polymer (A) and the compound (B) having a double bond, The polymerizable composition is characterized in that the polymer (A) has an α,β-unsaturated lactam structure.

[0011] The present invention also relates to the above polymerizable composition, wherein the polymer (A) has a skeleton represented by the following general formula (1): General formula (1) [ka] (In general formula (1), R1 represents a hydrogen atom, a C1 to C20 linear or branched alkyl group, or a C1 to C20 cycloalkyl group, and R2 and R3 each independently represent a hydrogen atom or a methyl group.)

[0012] The present invention also relates to the above polymerizable composition, wherein the polymer (A) further has a pyrrolidone skeleton.

[0013] The present invention also relates to the above polymerizable composition, wherein the compound (B) having a double bond includes a compound having an aromatic ring or an isocyanurate ring.

[0014] The present invention also relates to a polymer of the above polymerizable composition. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a polymerizable composition that has high radical polymerizability (conversion rate) and good curability, and a polymer that has high hardness and water resistance, even when the amount of a polymerization initiator that remains in a polymer and is likely to cause odor due to seepage onto the surface of the polymer, contamination of the contents due to penetration into the contents, and quality deterioration, is reduced or removed. DETAILED DESCRIPTION OF THE INVENTION

[0016] The polymerizable composition and polymer of the present invention will be described in detail below.

[0017] The polymerizable composition of the present invention will now be described. The polymerizable composition of the present invention contains a polymer (A) and a compound (B) having a double bond, and the polymer (A) may have an α,β-unsaturated lactam structure. The polymerizable composition may further contain a polymerization initiator, and the amount of the polymerization initiator may be 2.0% by mass or less relative to 100% by mass of the total of the polymer (A) and the compound (B) having a double bond.

[0018] The polymer (A) used in the present invention will now be described. The polymer (A) may be any polymer having an α,β-unsaturated lactam structure, and an α,β-unsaturated lactam structure is one in which the carbons located at the α- and β-positions relative to the carbonyl group in the lactam structure are connected by an unsaturated bond (double bond). To obtain a polymer having an α,β-unsaturated lactam structure, for example, a polymer having a lactam may be converted into an α,β-unsaturated lactam structure. A lactam structure can be converted into an α,β-unsaturated lactam structure, for example, by the action of an oxidizing agent. Examples of the oxidizing agent include inorganic peroxides such as oxygen-containing gas, hydrogen peroxide, and sodium peroxide, and organic peroxides such as peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid, magnesium monoperoxyphthalate, peroxymaleic acid, peroxytrifluoroacetic acid, peroxyphthalic acid, peroxylauric acid, tert-butyl hydroperoxide, cumene hydroperoxide, menthyl hydroperoxide, and 1-methylhexane hydroperoxide.

[0019] Examples of lactam-containing polymers for obtaining the polymer (A) used in the present invention include polymers having structural units derived from ethylenically unsaturated monomers having a lactam structure, such as N-vinylpyrrolidone, N-vinylpiperidone, and N-vinyl-ε-caprolactam. These may be homopolymers or copolymers with other copolymerizable monomers. Examples of copolymers include alternating copolymers, random copolymers, and block polymers. Graft polymers in which ethylenically unsaturated monomers having a lactam structure are grafted can also be used. By using a polymer having structural units derived from an ethylenically unsaturated monomer having a lactam structure, a polymerizable composition with high radical polymerizability (conversion rate) can be obtained without using a polymerization initiator that remains in the polymer and can cause odor due to leaching to the surface of the polymer, contamination of the contents due to penetration into the contents, and quality degradation.

[0020] The lactam structure of the polymer (A) used in the present invention is preferably represented by the following general formula (1): By having the skeleton represented by the following general formula (1), the polymer can be obtained at a lower temperature when being heated as described below to obtain a polymer. General formula (1) [ka] (In general formula (1), R1 represents a hydrogen atom, a C1 to C20 linear or branched alkyl group, or a C1 to C20 cycloalkyl group, and R2 and R3 each independently represent a hydrogen atom or a methyl group.)

[0021] The polymer (A) used in the present invention preferably further has a pyrrolidone skeleton, and more preferably has a structural unit derived from N-vinylpyrrolidone. When the polymer (A) has a structural unit derived from N-vinylpyrrolidone, the content of the structural unit derived from N-vinylpyrrolidone is preferably 20 to 99 mol %, more preferably 50 to 95 mol %. When the content is within the above range, water resistance, which is the effect of the present invention, is fully exhibited.

[0022] In the lactam-containing polymer for obtaining the polymer (A) used in the present invention, examples of constituent monomers other than the ethylenically unsaturated monomer having a lactam structure include: vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, and vinyl phenyl acetate; vinyl ethers such as vinyl isobutyl ether, vinyl isopropyl ether, vinyl ethyl ether, vinyl n-butyl ether, and vinyl methyl ether; hydroxyl group-containing (meth)acrylic acid monomers such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; phenolic hydroxyl group-containing monomers such as o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene; etc.

[0023] Among these, vinyl acetate and vinyl propionate are particularly preferred from the viewpoint of copolymerizability.

[0024] The weight-average molecular weight (Mw) of the polymer having a pyrrolidone skeleton for obtaining the polymer (A) used in the present invention is preferably 5,000 to 5,000,000, and particularly preferably 10,000 to 300,000. When Mw is within the above range, sufficient curability and water resistance of the polymer can be obtained.

[0025] The polymer (A) used in the polymerizable composition of the present invention is preferably contained in the polymerizable composition in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight. When the content of the polymer is within the above range, a polymer having sufficient hardness can be obtained.

[0026] The compound (B) having a double bond used in the present invention will now be described. 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 the molecule. The compound (B) itself polymerizes and crosslinks when the polymerizable composition of the present invention is irradiated with active energy rays or heated.

[0027] Compound (B) can be broadly divided into compounds (b1) that have no hydroxyl group and have -[O(CH2)2]2- (hereinafter sometimes abbreviated as "compound (b1)"), compounds (b2) that have a hydroxyl group or do not have -[O(CH2)2]2- (hereinafter sometimes abbreviated as "compound (b2)"), and compounds (b2-3) that have a double bond other than compounds (b1) and (b2) (hereinafter sometimes abbreviated as "compound (b2-3)"). The above-mentioned compound (b2) can be broadly divided into compounds (b2-1) that have a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1)") and compounds (b2-2) that have a cyclic structure and do not have a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-2)"). Compound (b2-1) can be broadly divided into compounds (b2-1-1) that have no cyclic structure but have a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1-1)") and compounds (b2-1-2) that have a cyclic structure and a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1-2)"). Compound (b2-2) can be broadly divided into compounds (b2-2-1) that have a cyclic structure but do not have a hydroxyl group and do not contain a heteroatom as a ring member (hereinafter sometimes abbreviated as "compound (b2-2-1)") and compounds (b2-2-2) that have a cyclic structure but do not have a hydroxyl group and contain a heteroatom as a ring member (hereinafter sometimes abbreviated as "compound (b2-2-2)"). Compound (B) preferably includes a compound having an acryloyl group and / or a methacryloyl group.

[0028] Furthermore, compound (B) preferably contains a compound having an aromatic ring or an isocyanurate ring, which may improve the curability of the polymerizable composition and the hardness of the polymerized product.

[0029] Furthermore, when compound (b1) is used to obtain a cured product by polymerization and curing with active energy rays, the curing speed increases. Although the reason for this is still being elucidated, it is presumed that the interaction between -[O(CH2)2]2- groups brings compounds (b1) closer to each other, leading to an increase in the curing speed.

[0030] Compound (b2) may also be used as compound (B). Use of compound (b2) can improve the glass transition temperature (Tg) of the polymer, thereby enabling the polymer to exhibit high cohesive strength and to form a polymer having good resistance properties such as heat resistance and water resistance.

[0031] In particular, the use of compound (b2-1) is preferred in terms of improving the curing rate and suppressing polymerization cure shrinkage. It is presumed that the presence of a hydroxyl group is highly effective in reducing cure shrinkage associated with the polymerization reaction.

[0032] Furthermore, it is preferable to use the compound (b2-2) in terms of improving durability such as heat resistance, moist heat resistance, etc. Furthermore, the compound (b2-3) can also be used.

[0033] Although not particularly limited, compounds that can be used as compound (B) include the following.

[0034] Compound (b1) is not particularly limited as long as it is a compound that does not have a hydroxyl group but has -[O(CH)]- and a double bond. For example, compound (b1) can be produced by esterifying the hydroxyl group of the reaction product obtained by ring-opening polymerization of ethylene oxide using a compound having a hydroxyl group of an alcohol or phenol with a carboxylic acid having a double bond, such as (meth)acrylic acid. Specific examples include aliphatic (meth)acrylic acid esters such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate;

[0035] For example, aromatic (meth)acrylic acid esters such as phenoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and ethylene oxide (EO) adduct diacrylate of bisphenol A;

[0036] For example, tetra(oxyethylene)vinylbutyl ether, tetra(oxyethylene)vinylphenyl ether, poly(oxyethylene)vinylphenyl ether, vinyl ether monomers;

[0037] For example, vinylbenzoate or isopropenylbenzoate monomers having a polyoxyethylene group moiety such as vinylphenyl poly(oxyethylene) succinate and vinylphenyl methyl poly(oxyethylene) hexahydrophthalate may be mentioned.

[0038] Among these, aromatic (meth)acrylic acid esters are preferred from the viewpoint of water resistance.

[0039] Examples of commercially available products of compound (b1) include, but are not limited to, the following: Blenmar ADE-200, Blenmar ADE-300, Blenmar ADE-400A, Blenmar ADE-600, Blenmar PME-100, Blenmar PME-200, Blenmar PME-400, Blenmar PME-1000, Blenmar PE-200, Blenmar PE-350, Blenmar 50POEP-800B, Blenmar PLE-200, Blenmar PSE-1300, Blenmar PDE-100, Blenmar PDE-150, Blenmar PDE-200, Blenmar PDE-400, Blenmar PDE-600, Blenmar PDBE-2 00A, Blenmar PDBE-450A, Blenmar ALE-200, Blenmar AME-400, Blenmar AAE-300 (all manufactured by NOF Chemical Corporation), New Frontier PE-200, New Frontier PE-300, New Frontier PE-400, New Frontier PE-600, New Frontier BPE-4, New Frontier BPE-10, New Frontier BPE-20, New Frontier TMP-3, New Frontier TMP-15, New Frontier GE3A, New Frontier NP-4, New Frontier N- 177E, New Frontier ME-3, New Frontier ME-4S, New Frontier MPE-600, New Frontier HBPE-4, New Frontier TMP-3, New Frontier PETA-4, New Frontier MPEM-400, New Frontier MPEM-1000, New 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, S R-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-370,(Manufactured by Toagosei Co., Ltd.), 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 Ester AT-20E, NK Ester AT-30E, NK Ester A-GLY-3E, NK Ester A-GLY-6E, NK Ester A-GLY-9E, NK Ester A-GLY-20E, NK Ester ATM-4EL, NK Ester ATM-8EL, NK Ester ATM-4E, NK Ester ATM-35E, NK Ester AD-TMP-4E, NK Ester A-DPH-12E , NK 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 Economer 1000PER, NK Ester BPE-200, NK Ester BPE-300, NK Ester BPE-500, NK Ester BPE-900, NK Ester BPE-1300N, N K 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 (above,Shin-Nakamura Chemical Co., Ltd.), Miramer M142, Miramer M144, Miramer M164, Miramer M166, Miramer M170, Miramer M232, Miramer M2100, Miramer M2200, Miramer M2300, Miramer M280, Miramer M282, Miramer M284, Miramer M286, Miramer M290, Miramer M2040, Miramer M3160, Miramer M3190, Miramer M3150, Miramer M4004, Miramer M193, Miramer M241, Miramer M2101, Miramer M2301 (manufactured by MIWON), Light Acrylate EC-A, Light Acrylate MTG-A, Light Acrylate EH DG-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 (all manufactured by Kyoeisha Chemical Co., Ltd.), Viscoat 190, Viscoat 360, Viscoat 700HV, Vismer MPE400A, Vismer MPE550A (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Neomer PM201 (manufactured by Sanyo Chemical Industries, Ltd.), EBECRYL110, PEG400DA-D, EBECRYL11 (all manufactured by Daicel Allnex Co., Ltd.).

[0040] The compound (b1) may be used alone or in combination of two or more kinds.

[0041] Compound (b2) will be described below: Of compounds (b2), compound (b2-1-1) has a hydroxyl group and a double bond, but is not particularly limited as long as it does not have a cyclic structure.

[0042] Specific examples include 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl-α-(hydroxymethyl) (meth)acrylate, monofunctional glycerol (meth)acrylate, or fatty acid ester-based (meth)acrylic acid esters such as (meth)acrylic acid glycidyl laurate, (meth)acrylic acid glycidyl oleate, and (meth)acrylic acid glycidyl stearate, or (meth)acrylic acid esters having a terminal hydroxyl group obtained by ring-opening addition of ε-caprolactone to the above-mentioned hydroxyl group-containing double bond group-containing compounds such as 2-(acryloyloxy)ethyl 6-hydroxyhexanoate, hydroxyl group-containing aliphatic (meth)acrylic acid esters such as pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate;

[0043] For example, hydroxyl group-containing aliphatic vinyl ethers such as hydroxyethyl vinyl ether and hydroxypropyl vinyl ether; For example, hydroxyl group-containing aliphatic (meth)allyl alcohols or (meth)allyl ethers such as (meth)allyl alcohol and isopropenyl alcohol; For example, double bond group-containing compounds having multiple hydroxyl groups such as propenediol;

[0044] Examples include hydroxyl group-containing (meth)acrylamides such as N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, N-hydroxybutyl(meth)acrylamide, N-hydroxyhexyl(meth)acrylamide, and N-hydroxyoctyl(meth)acrylamide. These may be used alone or in combination of two or more.

[0045] As the compound (b2-1-1), from the viewpoint of adhesion to the substrate, hydroxyl group-containing aliphatic (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate adduct with 1 to 2 mol of ε-caprolactone, and pentaerythritol tri(meth)acrylate are preferred.

[0046] Of the compounds (b2), the compounds (b2-1-2) can be used without any particular limitation as long as they have a double bond, a hydroxyl group, and a cyclic structure. Because the compound (b2-1-2) has one or more cyclic structures in the molecule, it is preferable from the viewpoint of durability such as heat resistance and moist heat resistance, as well as water resistance, even if it has a hydroxyl group. Specific examples thereof include (meth)acrylic acid esters having a hydroxyl group and a cyclic structure other than a heterocycle, such as 1,2-cyclohexanedimethanol (meth)acrylate, 1,3-cyclohexanedimethanol (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, 2-hydroxy-3-phenoxymethyl (meth)acrylate, 2-hydroxy-3-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxybutyl (meth)acrylate, 2-hydroxy-3-phenoxydecyl (meth)acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth)acrylate, monohydroxyethyl (meth)acrylate phthalate, and 2-(4-benzoyl-3-hydroxyphenoxy)ethyl (meth)acrylate;

[0047] For example, hydroxyl group-containing benzophenone-based (meth)acrylic acid esters such as 2-hydroxy-4-{2-(meth)acryloyloxy}ethoxybenzophenone and 2,2'-dihydroxy-4-{2-(meth)acryloyloxy}ethoxybenzophenone; For example, hydroxyl group-containing benzotriazole-based (meth)acrylic acid esters such as 2-(2'-hydroxy-5'-(meth)acryloyloxyethylphenyl)-2H-benzotriazole;

[0048] For example, 2,4-diphenyl-6-[2-hydroxy-4-{2-(meth)acryloyloxyethoxy}]-S-triazine, 2,4-bis(2-methylphenyl)-6-[2- Examples thereof include hydroxyl group-containing triazine-based (meth)acrylic acid esters such as hydroxy-4-{2-(meth)acryloyloxyethoxy}]-S-triazine, and these may be used alone or in combination of two or more kinds.

[0049] As the compound (b2-1-2), from the viewpoint of durability such as heat resistance and water resistance, preferred are (meth)acrylic acid esters having a hydroxyl group and a cyclic structure other than a heterocycle, such as 1,2-cyclohexanedimethanol acrylate, 1,3-cyclohexanedimethanol acrylate, 1,4-cyclohexanedimethanol acrylate, and 2-hydroxy-3-phenoxypropyl acrylate.

[0050] The compound (b2) can be roughly divided into the compound (b2-2-1) and the compound (b2-2-2), of which (b2-2-1) is preferred in terms of heat yellowing resistance.

[0051] The compound (b2-2-1) is not particularly limited as long as it is a compound having a cyclic structure and a double bond that does not have a hydroxyl group or a heteroatom as a ring member atom, and examples thereof include cyclohexyl (meth)acrylate, 1-methyl-1-cyclopentyl (meth)acrylate, 1-ethyl-1-cyclopentyl (meth)acrylate, 1-isopropyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, 1-ethyl-1-cyclohexyl (meth)acrylate, and (meth) 1-Isopropyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclooctyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-oxo-1,2-phenylethyl (meth)acrylate, 2-oxo-1,2-diphenylethyl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, (meth)acrylate p) 1-anthryl 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)acrylate 2-n-Propyladamantyl-2-yl (meth)acrylate, 2-isopropyladamantyl-2-yl (meth)acrylate, 1-(adamantan-1-yl)-1-methylethyl (meth)acrylate, 1-(adamantan-1-yl)-1-ethylethyl (meth)acrylate, 1-(adamantan-1-yl)-1-methylpropyl (meth)acrylate, 1-(adamantan-1-yl)-1-ethylpropyl (meth)acrylate, 5-oxo-4-oxa-tricyclo[4.2.1.0](meth)acrylate 3,7 ]non-2-yl, (meth)acrylic acid-5-oxo-4-oxa-tricyclo[5.2.1.0 3,8]dec-2-yl, (meth)acrylate dihydro-α-terpinyl, (meth)acrylate-6-oxo-7-oxa-bicyclo[3.2.1]oct-2-yl, (meth)acrylate-7-oxo-8-oxa-bicyclo[3.3.1]oct-2-yl, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxybutyl phthalate, 2-(meth)acryloyloxyhexyl (meth)acrylic acid cyclic esters such as methyl 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 (meth)acrylate glycidyl ether, and phenyl (meth)acrylate glycidyl ether;

[0052] For example, (meth)acrylamides containing a cyclic structure 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 or ammonium salts of sulfonyl group-containing (meth)acrylic acid cyclic esters such as (meth)acryloyloxyethyl dimethylbenzylammonium-p-toluenesulfonate; For example, alkenyl group-containing cyclic compounds such as 5-vinylbicyclo[2.2.1]hept-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 vinyl phenyl pentyl ether and vinyl phenyl hexyl ether;

[0053] For example, vinylbenzoate or isopropenylbenzoate monomers having a long chain alkyl group such as hexyl 4-vinylbenzoate and octyl 4-vinylbenzoate; For example, isopropenylphenyl-based monomers having a long-chain alkyl group such as isopropenylphenyl methyl butyl ether and isopropenylphenyl methyl pentyl ether; For example, mono-long chain alkyl ester cyclic monomers of dicarboxylic acids such as vinylphenylnonyl succinate and vinylphenylmethyldecyl 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; Examples include metal salts of styrenesulfonic acid such as sodium styrenesulfonate. These may be used alone or in combination of two or more.

[0054] As the compound (b2-2-1), from the viewpoint of durability such as heat resistance and water resistance, (meth)acrylic acid cyclic esters such as cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-phenoxyethyl acrylate, iso-bornyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl diacrylate, dicyclopentenyl acrylate, dicyclopentenyl diacrylate, and 2-ethyladamantyl-2-yl acrylate are preferred.

[0055] The compound (b2-2-2) is not particularly limited as long as it is a compound that does not have a hydroxyl group, has a cyclic structure containing a heteroatom as a ring member, and has a double bond, and examples thereof include nitrogen atom-containing heterocyclic (meth)acrylic acid esters such as pentamethylpiperidinyl (meth)acrylate and 4-(pyrimidin-2-yl)piperazin-1-yl (meth)acrylate;

[0056] For example, vinyl group-containing compounds having a nitrogen atom-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 atom-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 atom-containing heterocyclic structure and two or more vinyl groups, such as 1-methyl-4,5-divinyl-1H-imidazole; For example, (meth)allyl group-containing compounds having a nitrogen atom-containing heterocyclic structure such as 1-(meth)allyl-3,5-dimethyl-1H-pyrazole and 1-(1-methylpropyl)-5-(meth)allylpyrimidine; For example, 2-(meth)allyl-1H-indole, 3-(meth)allyl-1H-indole (Meth)allyl group-containing compounds having a heteropolycyclic structure containing a nitrogen atom, such as aryl;

[0057] For example, (meth)acrylic acid esters having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom, such as di(meth)acrylic acid ethoxylated isocyanuric acid, tri(meth)acrylic acid ethoxylated isocyanuric acid, ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate, di(meth)acrylic acid isocyanuric acid oxyethylene group-modified, and tri(meth)acrylic acid isocyanuric acid oxyethylene group-modified;

[0058] 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, heterocycle-containing (meth)acrylic acid esters 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 used alone or in combination.

[0059] As the compound (b2-2-2), from the viewpoint of durability such as heat resistance and water resistance, preferred are heterocycle-containing (meth)acrylic acid esters having an oxygen atom, such as glycidyl acrylate, glycidyl methacrylate, and (3,4-epoxycyclohexyl)methyl methacrylate; heterocyclic acrylamides such as 4-acryloylmorpholine; and (meth)acrylic acid esters having a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom, such as di(meth)acrylic acid ethoxylated isocyanuric acid and tri(meth)acrylic acid ethoxylated isocyanuric acid. Among these, preferred are (meth)acrylic acid esters having an isocyanurate ring and a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom.

[0060] Examples of the compound (b2-3) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; For example, (meth)acrylic acid esters further containing a double bond group, such as (meth)allyl (meth)acrylate and vinyl (meth)acrylate; For example, perfluoroalkyl (meth)acrylates such as perfluoromethyl (meth)acrylate and perfluoroethyl (meth)acrylate; For example, alkoxy group-containing (meth)acrylic acid esters 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)acrylic acid esters having one carbonyl group, such as (methoxycarbonyl)methyl (meth)acrylate and (methoxycarbonyl)ethyl (meth)acrylate; For example, aliphatic (meth)acrylic acid esters having two carbonyl groups such as 2-oxobutanoylethyl (meth)acrylate and 2-oxobutanoylpropyl (meth)acrylate;

[0061] For example, (meth)acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0 3,7 ]non-2-yl, (meth)acrylic acid-10-methoxycarbonyl-5-oxo-4-oxa-tricyclo[5.2.1.0 3,8 ]non-2-yl (meth)acrylate, 4-methoxycarbonyl-6-oxo-7-oxa-bicyclo[3.2.1]oct-2-yl (meth)acrylate, 4-methoxycarbonyl-7-oxo-8-oxa-bicyclo[3.3.1]oct-2-yl (meth)acrylate, and other (meth)acrylic acid cyclic esters having a carbonyl group;

[0062] 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 benzoylpropionate; 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)acrylic acid esters such as 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane;

[0063] For example, bifunctional (meth)acrylic acid esters such as propylene oxide di(meth)acrylate, polypropylene oxide di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate;

[0064] For example, trifunctional (meth)acrylic acid esters such as 1,2,3-propanetriol tri(meth)acrylate, 2-methylpentane-2,4-diol tri(meth)acrylate, 2-methylpentane-2,4-diol tricaprolactonate tri(meth)acrylate, 2,2-dimethylpropane-1,3-diol tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, 2,2-bis(hydroxymethyl)1,3-propanediol tri(meth)acrylate, 1,1,1-trishydroxymethylethane tri(meth)acrylate, 1,1,1-trishydroxymethylpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate;

[0065] For example, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(hydroxymethyl)1,3-propanediol tetra(meth)acrylate, 2,2-bis(hydroxymethyl)1,3-propanediol tetra(meth)acrylate, di-1,2, polyfunctional (meth)acrylic acid esters such as 3-propanetriol, tetra(meth)acrylate di2-methylpentane-2,4-diol, tetra(meth)acrylate di2-methylpentane-2,4-diol tetracaprolactonate, tetra(meth)acrylate di2,2-dimethylpropane-1,3-diol, tetra(meth)acrylate ditrimethylolbutane, tetra(meth)acrylate ditrimethylolhexane, and tetra(meth)acrylate ditrimethyloloctane;

[0066] 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;

[0067] For example, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide ) mono- or di-alkylaminoalkyl (meth)acrylamides such as 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, maleic nitrile, and fumaronitrile; For example, (meth)allyl esters of saturated carboxylic acids such as (meth)allyl acetate, coconut oil fatty acid, and vinyl pivalate;

[0068] For example, (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 4-carboxybutyl (meth)acrylate, (meth)acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senecioic acid, crotonic acid, isocrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, geranic acid, citronellol, aliphatic α,β-unsaturated double bond group-containing carboxylic acids and their acid anhydrides, such as polylactone-based (meth)acrylic acid esters having a carboxyl group at the terminal by ring-opening addition of a lactone ring, such as 2-(meth)acryloyloxyethyl succinate, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2-(meth)acryloyloxyethyl succinate, and mono(meth)acrylic acid ω-carboxypolycaprolactone ester, and alkylene oxide-added succinic acids having a carboxyl group at the terminal to which alkylene oxides such as propylene oxide excluding oxyethylene groups are repeatedly added, and (meth)acrylic acid;

[0069] For example, (meth)acryloyl group-containing carboxylic acids having a carboxyl group-containing alicyclic or aromatic ring, such as 2-(meth)acryloyloxyethyl hexahydrophthalate and 2-(meth)acryloyloxyethyl phthalate, and acid anhydrides thereof; For example, (meth)acrylic acid esters having a primary and / or secondary amino group such as N-methylaminoethyl (meth)acrylate and N-ethylaminoethyl (meth)acrylate; For example, (meth)acrylic acid esters having a hydrazino group such as (meth)acrylic acid hydrazide and 2-(2-furyl)-3-(5-nitro-2-furyl)(meth)acrylic acid hydrazide; For example, (meth)acrylic acid esters 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 primary and / or secondary amino groups such as vinylamine and methylvinylamine;

[0070] For example, (meth)allyl compounds having a primary and / or secondary amino group such as (meth)allylamine, 4-(meth)allyl-3,5-dimethyl-1H-pyrazole, 5-(1-methylpropyl)-5-(meth)allylpyrimidine, 5-(meth)allyl-5-isopropylpyrimidine, 2-(meth)allylpyridine, 4-(meth)allylpyridine, and 3,6-dihydro-4-(meth)allylpyridine; For example, vinyl compounds containing a tertiary amino group such as N-ethyl-N-nitrosovinylamine; Examples of the heterocyclic double bond group-containing compounds include, but are not limited to, maleimide derivatives having both a nitrogen atom and an oxygen atom, such as maleimide and methylmaleimide, which may be used alone or in combination.

[0071] As the compound (b2-3) having another double bond, a compound having a (meth)acryloyl group is preferred from the viewpoint of reactivity, and in order to obtain a polymer with good curability, it is preferred that the compound contains a (meth)acrylic acid ester having two or more functionalities.

[0072] The advantage of compound (b2) in terms of polymerization curability, cure shrinkage of the polymer, and durability such as heat resistance, moist heat resistance, and water resistance lies in (b2-1) containing a hydroxyl group. However, by appropriately blending (b2-1) so that both a hydroxyl group and a cyclic structure are contained, a good polymerizable composition can be obtained.

[0073] Compound (b2) can be easily obtained as a commercial product from the following manufacturers. For example, "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate" and "High Functional Oligomer" series manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., "NK Ester" and "NK Oligo" series manufactured by Shin-Nakamura Chemical Co., Ltd., "Fancryl" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Chemical Industry Co., Ltd., "Functional Monomer" series manufactured by Daihachi Chemical Industry Co., Ltd., "Special Acrylic Monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., Examples include the "Acryester" and "Diabeam Oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., the "Kayarad" and "Kayamer" series manufactured by Nippon Kayaku Co., Ltd., the "(meth)acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd., the "NICHIGO-UV Purple Light Urethane Acrylate Ligomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., the "Carboxylic Acid Vinyl Ester Monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd., and the "Functional Monomer" series manufactured by Kohjinsha Co., Ltd.

[0074] Further examples of compound (b2) include those described in the following documents: "Crosslinking Agent Handbook" edited by Yamashita Shinzo et al. (1981, Taiseisha); "UV / EB Curing Handbook (Raw Materials)" edited by Kato Kiyomi (1985, Polymer Publishing Association); "New Practical Technology of Photosensitive Resins" edited by RadTech Research Group and Akamatsu Kiyoshi (1987, CMC); "Refinition of Thermosetting Polymers" edited by Endo Tsuyoshi (1986, CMC); "Polyester Resin Handbook" written by Takiyama Eiichiro (1988, Nikkan Kogyo Shimbun); and "Applications and Markets of UV / EB Curing Technology" edited by RadTech Research Group (2002, CMC).

[0075] The polymerizable composition of the present invention does not need to contain conventional photopolymerization initiators or thermal polymerization initiators, which remain in the polymer and can cause odor due to seepage onto the polymer surface, contamination of the contents due to penetration into the contents, and quality deterioration. However, they may be added to the extent that the above-mentioned properties do not become a problem. The content is 2.0% by mass or less, based on 100% by mass of the total of the polymer (A) and the compound (B) having a double bond. The content is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.

[0076] Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, m-chloroacetophenone, p-tert-butyltrichloroacetophenone, and 4-dialkylacetophenone; benzophenones such as benzophenone; Michler's ketones such as Michler's ketone; benzyls such as benzyl, benzyl methyl ether, and benzyl dimethyl ketal; benzoins such as benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether; Thioxanthones such as thioxanthone; Carbonyl compounds such as propiophenone, anthraquinone, acetoin, butyroin, toluoin, benzoyl benzoate, α-acyloxime esters; Examples include: In addition to the above carbonyl compounds, examples of the photopolymerization initiator include sulfur compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, thioxanthone, and 2-chlorothioxanthone; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvaleronitrile; and peroxides such as benzoyl peroxide and di-tert-butyl peroxide.

[0077] Examples of the thermal polymerization initiator include: Persulfates such as potassium persulfate and ammonium persulfate; azo polymerization initiators such as 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide], 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(methyl isobutyrate), 1,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, 1,1'-azobis(cyclohexane-1-carbonitrile); Hydroperoxides such as tert-alkyl hydroperoxides; peroxides such as di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, di-isopropyl peroxydicarbonate, di-tert-butyl peroxyisophthalate, 1,1',3,3'-tetramethylbutylperoxy-2-ethylhexanoate, and tert-butyl peroxybutyrate; etc.

[0078] In the present invention, in addition to the above essential components, a colorant may be contained. The dye or pigment contained in the colorant can impart not only design properties but also various functionalities such as thermal properties, electrical properties, or optical properties. Examples of colorants include organic pigments, inorganic pigments, dyes, and carbon. If necessary, a dispersant may be added to improve the dispersibility of the pigment and the storage stability of the polymerizable composition.

[0079] The polymerizable composition of the present invention can also contain other components (G), such as various additives, as long as they do not impair the effects of the present invention. For example, organic or inorganic fillers can be added to improve radical polymerizability (conversion rate), reduce polymerization cure shrinkage, reduce thermal expansion, improve dimensional stability, improve elastic modulus, adjust viscosity, improve thermal conductivity, improve strength, improve toughness, and improve colorability. Such fillers may be composed of polymers, ceramics, metals, metal oxides, or metal salts. Furthermore, their shape is not particularly limited and may be, for example, particulate or fibrous. When the above polymer-based materials are blended, they can be used not only as independent fillers such as phenol-based and hindered amine-based antioxidants, silane coupling agents, photosensitizers, flexibility-imparting agents, plasticizers, flame retardants, storage stabilizers, ultraviolet absorbers, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, foaming agents, mildew-proofing agents, antistatic agents, magnetic materials, surface tension modifiers, slipping agents, antiblocking agents, leveling agents, infrared absorbers, and antifoaming agents, but also as polymer blends or polymer alloys, which can be dissolved, semi-dissolved, or micro-dispersed in the polymerizable composition.

[0080] The polymerizable composition of the present invention can be printed or coated on various substrates, and the substrate on which the polymerizable composition is printed or coated can be appropriately selected from the group consisting of glass, plastic, metal, and paper. Furthermore, a composite substrate composed of multiple substrates can also be selected. These substrates may be flat, such as plates, films, or paper, or may have a three-dimensional shape. Transparent plastic films are preferred.

[0081] Examples of printing and coating methods include inkjet coating, blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U comma coating, AKKU coating, smoothing coating, microgravure coating, reverse roll coating, four- to five-roll coating, dip coating, curtain coating, slide coating, die coating, and spray coating.

[0082] For the purpose of lowering the viscosity of the polymerizable composition and improving the wetting and spreading properties of the composition on a substrate, the polymerizable composition may contain a solvent such as water or an organic solvent.

[0083] Next, the polymer of the polymerizable composition of the present invention will be described. The polymer can be obtained by subjecting the polymerizable composition of the present invention to a polymerization / crosslinking reaction using heat or active energy rays.

[0084] The polymerizable composition of the present invention can be polymerized by applying energy to the composition during the polymerization reaction using heat or active energy rays such as ultraviolet light, visible light, near-infrared light, or electron beams to obtain the desired polymer. A preferred method of applying energy is irradiation with visible light from a light source having a dominant wavelength in the 250-750 nm wavelength range. Examples of light sources having a dominant wavelength in the 250-750 nm wavelength range include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, mercury xenon lamps, metal halide lamps, high-power metal halide lamps, xenon lamps, pulsed xenon lamps, deuterium lamps, fluorescent lamps, Nd-YAG triple harmonic lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-pumped solid-state lasers, and LED lamps having a wavelength in the 250-750 nm range, excluding electron beams. In this specification, definitions of active energy rays such as ultraviolet light, visible light, and near-infrared light are based on "Iwanami Dictionary of Physics and Chemistry, 4th Edition" edited by Kubo Ryogo et al. (Iwanami, 1987). [Example]

[0085] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples in any way.

[0086] <Production Example 1> 13.6 parts by mass of polyvinylpyrrolidone homopolymer (Mw 40,000) was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A1). NMR confirmed that polymer (A1) contained 1.0 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), and that R1, R2, and R3 were all hydrogen atoms.

[0087] <Production Example 2> 13.6 parts by mass of polyvinylpyrrolidone homopolymer (Mw 40,000) was dissolved in 16 mL of pyridine and heated to 90°C. 108 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A2). NMR confirmed that polymer (A2) contained 4.5 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), and that R1, R2, and R3 were all hydrogen atoms.

[0088] <Production Example 3> 13.6 parts by mass of polyvinylpyrrolidone homopolymer (Mw 10,000) was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A3). NMR confirmed that polymer (A3) contained 1.1 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), and that R1, R2, and R3 were all hydrogen atoms.

[0089] <Production Example 4> 13.6 parts of polyvinylpyrrolidone homopolymer (MW 360,000) was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A4). NMR confirmed that polymer (A4) contained 0.9 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), and that R1, R2, and R3 were all hydrogen atoms.

[0090] <Production Example 5> 13.6 parts by mass of polyvinylpyrrolidone (P-904LC, DSP Gokyo Food & Chemical Co., Ltd.) alkylated at the 3rd or 5th position of the pyrrolidone ring was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A5). NMR confirmed that polymer (A5) contained 0.8 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), that R1 and R3 were n-butyl groups, and that R2 was a hydrogen atom.

[0091] <Production Example 6> 19.4 parts by mass of poly(vinylpyrrolidone / vinyl acetate) (vinylpyrrolidone / vinyl acetate = 70 / 30, Mw 51,000, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and the mixture was allowed to react for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A6). NMR confirmed that polymer (A6) contained 0.6 mol% of units having an α,β-unsaturated lactam structure, that the α,β-unsaturated lactam structure was represented by general formula (1), and that R1, R2, and R3 were all hydrogen atoms.

[0092] <Production Example 7> A reaction vessel equipped with a reflux tube, thermometer, nitrogen inlet, monomer drop inlet, and initiator drop inlet was charged with 24 parts by mass of ion-exchanged water. The temperature was raised while blowing nitrogen through the nitrogen inlet. After reflux was confirmed, 12 parts by mass of N-vinylpiperidone was added dropwise through the monomer drop inlet, and 0.28 parts by mass of V-50 (an azo-based initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 4 parts by mass of ion-exchanged water through the initiator drop inlet. Polymerization was carried out by simultaneously adding dropwise additions over 3 hours and 30 minutes. After the dropwise additions were completed, the mixture was aged for 30 minutes and cooled to obtain an aqueous solution of poly(N-vinylpiperidone). An additional 16 mL of pyridine was added, and the temperature was raised to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added, and the reaction was allowed to proceed for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A7). NMR confirmed that polymer (A7) contained 1.2 mol% of units having an α,β-unsaturated lactam structure.

[0093] <Production Example 8> A reaction vessel equipped with a reflux tube, thermometer, nitrogen inlet, monomer drop inlet, and initiator drop inlet was charged with 24 parts by mass of ion-exchanged water. The temperature was raised while blowing nitrogen through the nitrogen inlet. After reflux was confirmed, 12 parts by mass of N-vinyl-2-caprolactam was added dropwise through the monomer drop inlet, and an aqueous solution of 0.28 parts by mass of V-50 (an azo-based initiator, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in 4 parts by mass of ion-exchanged water was added dropwise through the initiator drop inlet over 3 hours and 30 minutes, respectively, to polymerize the mixture. After the addition was completed, the mixture was aged for 30 minutes and then cooled to obtain an aqueous poly(N-vinyl-2-caprolactam) solution. Further, 16 mL of pyridine was added, and the temperature was raised to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added, and the reaction was carried out for 8 hours. After cooling, the mixture was concentrated using an evaporator to obtain polymer (A8). It was confirmed by NMR that polymer (A8) contained 1.1 mol% of units having an α,β-unsaturated lactam structure.

[0094] <Polymerizable composition> Polymerizable compositions were obtained according to the formulations shown in Table 1 (Examples 1 to 14 and Comparative Examples 1 to 5). Using the obtained polymerizable compositions, the curability, hardness of the polymerized product, residual rate of low-molecular-weight compounds, and water resistance of the coating film were evaluated by the following methods. The results are shown in Table 1.

[0095] <Curing evaluation test> The prepared polymerizable composition was applied to a polyethylene terephthalate (PET) substrate using a micrometer-adjustable applicator so that the wet film thickness was 1000 μm to prepare a coating film. A polyethylene film was placed on the coating film, and the active energy rays were applied using a high-pressure UV lamp USH-500SC (Ushio Inc.) at 30 mW / cm. 2 The polymer was irradiated with ultraviolet light for 1 second at an irradiation intensity of 1000 kJ / cm (254 nm equivalent). After irradiation, the surface of the polymer was rubbed with a cotton cloth, and ultraviolet light irradiation was repeated until the film was no longer scratched, and then the curing property was judged. The shorter the ultraviolet light irradiation time, the better the curing property was judged. The criteria for judgment are as follows:

[0096] Judgment criteria ◎: 1 to 15 seconds. Particularly good. ○: 16 seconds to 60 seconds. Good. △: Over 61 seconds. Slightly poor. ×: Not suitable for practical use because it hardens before UV irradiation. Particularly poor.

[0097] <Evaluation tests for polymer hardness, residual rate of low molecular weight compounds, and water resistance> The prepared active energy ray-curable composition was applied to a polyethylene terephthalate (PET) substrate using a micrometer-adjustable applicator so that the wet film thickness was 1000 μm, to produce a coating film. A polyethylene film was placed on the coating film, and active energy rays were applied using a high-pressure UV lamp USH-500SC (Ushio Inc.) at 50 mW / cm. 2 (365 nm equivalent) for 30 seconds to obtain a polymer. The hardness of the polymer was measured by observing the state of the polymer when and after it was pressed with a load of 0.1 kgf (0.98 N) for 5 seconds, and the hardness of the polymer was judged based on the following criteria.

[0098] Judgment criteria ◎: No dents when or after pressing. Particularly good. ○: Dent occurs when pressed, but no dent occurs after pressing. Fairly good. ×: Cracks occurred when pressed or the hardened product collapsed.

[0099] To measure the residual percentage of low-molecular-weight compounds, the resulting polymer (10 cm x 10 cm) was cut into 1 cm squares along with the substrate and immersed in 100 ml of methyl ethyl ketone in a sealed container at 60°C for three days to extract the residual percentage of low-molecular-weight components in the cured film. After two days, the methyl ethyl ketone was stirred to homogenize it, removed from the container, and the peak area percentage of the extracted components measured by GPC was evaluated as the residual percentage of low-molecular-weight compounds. Note that low-molecular-weight compounds are compounds with a molecular weight of less than 1,000. The lower the residual percentage of low-molecular-weight compounds, the better the product was considered to be. The evaluation criteria are as follows:

[0100] Judgment criteria ○: Residual rate of low molecular weight compounds is less than 0.5%. Particularly good. △: The residual rate of low molecular weight compounds is 0.5% or more and less than 1%. Fairly good. ×: The residual rate of low molecular weight compounds is 1% or more, and it is not suitable for practical use.

[0101] Water resistance was evaluated by immersing the obtained polymer (5 cm × 5 cm) in water at 25°C and leaving it for 24 hours. After immersion, the surface of the test piece was lightly wiped with Kimwipe (registered trademark) [S-200, manufactured by Nippon Paper Crecia Co., Ltd.] and dried at 25°C for 12 hours. The elution rate was calculated from the change in weight before and after immersion as follows, and water resistance was evaluated. Dissolution rate: (weight before immersion in water - weight after immersion in water) / weight before immersion in water x 100 (weight%) ◎: Less than 1% by weight ○: 1% by weight or more and less than 3% by weight ×: 3% by weight or more

[0102] [Table 1]

[0103] A9: Polyvinylpyrrolidone K30 (Mw 40,000, manufactured by Tokyo Chemical Industry Co., Ltd.) HEA: 2-hydroxyacrylate ACMO: acryloylmorpholine AM90G: Methoxypolyethylene glycol #400 acrylate (Shin-Nakamura Chemical Co., Ltd.) BP-4WAL: EO adduct diacrylate of bisphenol A (Light Acrylate BP-4WAL, manufactured by Kyoeisha Chemical Co., Ltd.) TMPA: Trimethylolpropane triacrylate M315: Isocyanuric acid EO-modified di- and triacrylate (manufactured by Toagosei Co., Ltd.) PI1: 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone PI2: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide

[0104] Next, polymerizable compositions were obtained according to the formulations shown in Table 2 (Examples 15 to 22 and Comparative Examples 6 and 7). Using the obtained polymerizable compositions, the hardness of the polymer, the residual rate of low-molecular-weight compounds, and the water resistance of the coating film were evaluated by the following methods. The results are shown in Table 2.

[0105] <Evaluation tests for polymer hardness, residual rate of low molecular weight compounds, and water resistance> The prepared active energy ray-curable composition was applied to a polyethylene terephthalate (PET) substrate using a micrometer-adjustable applicator to a wet film thickness of 1000 μm to produce a coating film. A polyethylene film was placed on the coating film, and the film was stored in an oven at 60°C or 120°C for 1 hour to obtain a polymer. The hardness of the polymer was measured by observing the state of the polymer when and after it was pressed with a load of 0.1 kgf (0.98 N) for 5 seconds, and the hardness of the polymer was judged based on the following criteria.

[0106] Judgment criteria ◎: No dents when or after pressing. Particularly good. ○: Dent occurs when pressed, but no dent occurs after pressing. Fairly good. ×: Cracks occurred when pressed or the hardened product collapsed.

[0107] To measure the residual percentage of low-molecular-weight compounds, the resulting cured product (10 cm x 10 cm) was cut into 1 cm squares along with the substrate and immersed in 100 ml of methyl ethyl ketone in a sealed container at 60°C for three days to extract the residual percentage of low-molecular-weight components in the cured film. After two days, the methyl ethyl ketone was stirred to homogenize it, removed from the container, and the peak area percentage of the extracted components measured by GPC was evaluated as the residual percentage of low-molecular-weight compounds. Note that low-molecular-weight compounds are compounds with a molecular weight of less than 1,000. The lower the residual percentage of low-molecular-weight compounds, the better the product was considered to be. The evaluation criteria are as follows:

[0108] Judgment criteria ○: Residual rate of low molecular weight compounds is less than 0.5%. Particularly good. △: The residual rate of low molecular weight compounds is 0.5% or more and less than 1%. Fairly good. ×: The residual rate of low molecular weight compounds is 1% or more, and it is not suitable for practical use.

[0109] Water resistance was evaluated by immersing the obtained polymer (5 cm × 5 cm) in water at 25°C and leaving it for 24 hours. After immersion, the surface of the test piece was lightly wiped with Kimwipe (registered trademark) [S-200, manufactured by Nippon Paper Crecia Co., Ltd.] and dried at 25°C for 12 hours. The elution rate was calculated from the change in weight before and after immersion as follows, and water resistance was evaluated. Dissolution rate: (weight before immersion in water - weight after immersion in water) / weight before immersion in water x 100 (weight%) ◎: Less than 1% by weight ○: 1% by weight or more and less than 3% by weight ×: 3% by weight or more

[0110] [Table 2]

[0111] According to the present invention, it is possible to provide a polymerizable composition that has high radical polymerizability (conversion rate) and good curability even when the amount of a photopolymerization initiator or a thermal polymerization initiator, which can cause odor or migration, is reduced or removed, and a polymer that has high hardness and water resistance. Examples of applications in which the present invention can be expected to provide increased sensitivity and improved properties include molding resins that utilize polymerization or crosslinking reactions, casting resins, resins for stereolithography, sealants, dental polymerized resins, printing inks, printing varnishes, paints, photosensitive resins for printing plates, color proofs for printing, resists for color filters, resists for black matrices, photospacers for liquid crystal displays, screen materials for rear projection, optical fibers, rib materials for plasma displays, dry film resists, resists for printed circuit boards, solder resists, photoresists for semiconductors, resists for microelectronics, resists for manufacturing micromachine parts, etching resists, microlens arrays, insulating materials, hologram materials, optical switches, waveguide materials, overcoating agents, powder coatings, adhesives, pressure-sensitive adhesives, release agents, optical recording media, pressure-sensitive adhesives, release coating agents, compositions for image recording materials using microcapsules, and various devices.

Claims

1. A polymerizable composition for use in polymerization by active energy rays, comprising a polymer (A) and a compound (B) having a double bond, the content of the polymerization initiator is 2.0% by mass or less, relative to 100% by mass of the total of the polymer (A) and the compound (B) having a double bond, the polymer (A) is a polymer having an α,β-unsaturated lactam structure derived from a polymer having structural units derived from an ethylenically unsaturated monomer having one or more structural units selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, and N-vinyl-ε-caprolactam; the content of the polymer (A) is 1 to 50% by mass relative to 100% by mass of the polymerizable composition; A polymerizable composition, wherein the compound (B) having a double bond includes a compound having an acryloyl group and / or a methacryloyl group.

2. 2. The polymerizable composition according to claim 1, wherein the polymer (A) has a skeleton represented by the following general formula (1): General formula (1) 【Chemistry 1】 (In general formula (1), R １ represents a hydrogen atom, a C1-C20 linear or branched alkyl group, or a C1-C20 cycloalkyl group; R ２ , R ３ each independently represents a hydrogen atom or a methyl group.

3. 3. The polymerizable composition according to claim 1, wherein the polymer (A) further has a pyrrolidone skeleton.

4. 4. The polymerizable composition according to claim 1, wherein the compound (B) having a double bond includes a compound having an aromatic ring or an isocyanurate ring.

5. A polymer of the polymerizable composition according to any one of claims 1 to 4.

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