JP2023087353A - Polymerizable composition and its polymer - Google Patents

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

The present invention relates to polymerizable compositions and polymers thereof.

A composition containing a reactive compound such as a (meth)acrylate compound is known to readily undergo radical polymerization by active species generated from an initiator to form a cured product. These compositions are used in various fields, and their uses include, for example, printing inks, overcoat varnishes, paints, adhesives, photoresists, and 3D objects.

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

Thermal polymerization initiators and photopolymerization initiators are generally known as types of initiators. A thermal polymerization initiator or a photopolymerization initiator functions by heating or irradiation with active energy rays, respectively. The initiator is selected according to the application and purpose, but it is not suitable for applications requiring high safety because it has high potential toxicity and causes odor and migration. Further, in general, if a thermal polymerization initiator or a photopolymerization initiator is not used, the reaction will not proceed sufficiently, and sufficient coating film resistance will not be obtained.

Patent Document 1 discloses an inorganic powder-containing resin composition characterized by containing an inorganic powder, a binder resin containing a polymer having a pyrrolidone skeleton, a polyfunctional (meth)acrylate, and a photopolymerization initiator. things are proposed. However, since a low-molecular-weight photopolymerization initiator is used, there are problems of odor and migration. Further, Patent Document 2 proposes an active energy ray-curable resin composition for a three-dimensional modeling support material containing a water-soluble polymer obtained by polymerizing an unsaturated compound. However, a system using a homopolymer of N-vinylpyrrolidone uses a photopolymerization initiator as in Patent Document 1, and has problems of odor and migration.

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, in order to allow the reaction to proceed sufficiently, a certain amount or more of the polymerization initiator must be used, which poses problems of odor and migration.

JP-A-2005-232366 Japanese Patent Application Laid-Open No. 2020-12052 JP 2018-35310 A

The problem to be solved by the present invention is that even if the photopolymerization initiator or thermal polymerization initiator that can cause odor or migration is reduced or removed, the radical polymerizability (conversion rate) is high, and the polymerizability with good curability An object of the present invention is to provide a composition and a polymer having high hardness and water resistance.

The present inventor has completed the present invention as a result of earnest studies to solve the above problems.

That is, the present invention is 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 with respect to the total 100% by mass 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.

（一般式（１）中、Ｒ_１は水素原子、Ｃ１～Ｃ２０の直鎖もしくは分岐のアルキル基、またはＣ１～Ｃ２０のシクロアルキル基を表し、Ｒ_２、Ｒ_３は、それぞれ独立に、水素原子またはメチル基を表す。） The present invention also relates to the polymerizable composition, wherein the polymer (A) has a skeleton represented by the following general formula (1).
General formula (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 and R ₃ each independently represent a hydrogen atom; or represents a methyl group.)

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

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

The present invention also relates to a polymer of the above polymerizable composition.

According to the present invention, it is possible to reduce or remove the polymerization initiator, which remains in the polymer and causes odor due to exudation to the surface of the polymer, contamination of the content due to penetration into the content, and deterioration of quality, even if it is reduced or removed. It is possible to provide a polymerizable composition with high polymerizability (conversion rate) and good curability, and a polymer with high hardness and water resistance.

The polymerizable composition and polymer of the present invention are described in detail below.

The polymerizable composition of the present invention will be explained. 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. . Furthermore, a polymerization initiator may be included, and may be 2.0% by mass or less with respect to the total 100% by mass of the polymer (A) and the compound (B) having a double bond.

The polymer (A) used in the present invention will be explained. The polymer (A) may be a polymer having an α,β-unsaturated lactam structure, and the α,β-unsaturated lactam structure is located at the α-position and β-position with respect to the carbonyl group in the lactam structure. Carbons are linked by unsaturated bonds (double bonds). In order to obtain a polymer having an α,β-unsaturated lactam structure, for example, a lactam-containing polymer may be converted to an α,β-unsaturated lactam structure. A lactam structure can be converted to an α,β-unsaturated lactam structure by, for example, the action of an oxidizing agent. Examples of oxidizing agents include gases containing oxygen, hydrogen peroxide, inorganic peroxides such as sodium peroxide, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid, monoperoxyphthalic acid. and organic peroxides such as magnesium acid, peroxymaleic acid, peroxytrifluoroacetic acid, peroxyphthalic acid, peroxylauric acid, tert-butyl hydroperoxide, cumene hydroperoxide, menthyl hydroperoxide and 1-methylhexane hydroperoxide.

Examples of the polymer having a lactam for obtaining the polymer (A) used in the present invention include ethylenically unsaturated polymers having a lactam structure such as N-vinylpyrrolidone, N-vinylpiperidone, and N-vinyl-ε-caprolactam. Examples thereof include polymers having structural units derived from monomers. It may be a homopolymer or a copolymer with other copolymerizable monomers. Copolymers include alternating copolymers, random copolymers and block polymers. A graft polymer grafted with an ethylenically unsaturated monomer having a lactam structure can also be used. By using a polymer having a structural unit derived from an ethylenically unsaturated monomer having a lactam structure, it remains in the polymer, causing odor due to seepage to the surface of the polymer, and content due to permeation into the content. A polymerizable composition with high radical polymerizability (conversion rate) can be obtained without using a polymerization initiator that may cause contamination of the product and deterioration of quality.

（一般式（１）中、Ｒ_１は水素原子、Ｃ１～Ｃ２０の直鎖もしくは分岐のアルキル基、またはＣ１～Ｃ２０のシクロアルキル基を表し、Ｒ_２、Ｒ_３は、それぞれ独立に、水素原子またはメチル基を表す。） The lactam structure of the polymer (A) used in the present invention is preferably represented by the following general formula (1). By having a skeleton represented by the following general formula (1), the polymer can be obtained at a lower temperature when the polymer is obtained by heating as described below.
General formula (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 and R ₃ each independently represent a hydrogen atom; or represents a methyl group.)

The polymer (A) used in the present invention preferably further has a pyrrolidone skeleton, and more preferably has structural units 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%. in mol %. When the content is within the above range, the effect of the present invention, namely water resistance, is fully exhibited.

In the polymer having a lactam for obtaining the polymer (A) used in the present invention, other constituent monomers other than ethylenically unsaturated monomers having a lactam structure include, for example,
Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl phenyl acetate;
Vinyl ethers such as vinyl isobutyl ether, vinyl isopropyl ether, vinyl ethyl ether, vinyl n-butyl ether, 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.

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

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, particularly 10,000 to 300. ,000. When Mw is within the above range, sufficient curability and water resistance of the polymer can be obtained.

The polymer (A) used in the polymerizable composition of the present invention is preferably contained 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.

The compound (B) having a double bond used in the present invention is explained.
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.

The compound (B) comprises a compound (b1) having —[O(CH ₂ ) ₂ ] ₂ — without a hydroxyl group (hereinafter sometimes abbreviated as “compound (b1)”), and a compound having a hydroxyl group or Compound (b2) not having —[O(CH ₂ ) ₂ ] ₂ — (hereinafter sometimes abbreviated as “compound (b2)”) and a double bond other than compound (b1) and compound (b2) (hereinafter sometimes abbreviated as compound (b2-3)). The above compound (b2) includes a compound (b2-1) having a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1)") and a compound having a cyclic structure without a hydroxyl group (b2-2 ) (hereinafter sometimes abbreviated as compound (b2-2)). Further, the compound (b2-1) is a compound (b2-1-1) having no cyclic structure and having a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1-1)"), and a cyclic structure and a compound (b2-1-2) having a hydroxyl group (hereinafter sometimes abbreviated as "compound (b2-1-2)"). Further, the compound (b2-2) is a compound (b2-2-1) having a cyclic structure that does not have a hydroxyl group and does not contain a heteroatom as a ring member atom (hereinafter abbreviated as "compound (b2-2-1) and a compound (b2-2-2) having a cyclic structure containing a heteroatom as a ring member atom without a hydroxyl group (hereinafter sometimes abbreviated as “compound (b2-2-2)”). ). Compound (B) preferably contains a compound having an acryloyl group and/or a methacryloyl group.

Compound (B) preferably contains a compound having an aromatic ring or an isocyanurate ring. Including a compound having an aromatic ring or an isocyanurate ring may improve the curability of the polymerizable composition and the hardness of the polymer.

In addition, when the compound (b1) is polymerized and cured with an active energy ray to obtain a cured product, the curing rate is improved. Although the cause is still being clarified, it is presumed that the interaction between the -[O(CH ₂ ) ₂ ] ₂ - groups brings the compounds (b1) closer together, leading to an improvement in the curing speed.

Moreover, you may use a compound (b2) as a compound (B). By using the compound (b2), it is possible to improve the glass transition point (Tg) of the polymer to express high cohesive strength, and to form a polymer having good resistance such as 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 polymerization curing shrinkage. It is presumed that having a hydroxyl group exhibits a great effect in reducing curing shrinkage associated with a polymerization reaction.

Further, the compound (b2-2) is preferably used from the viewpoint of improving durability such as heat resistance and wet heat resistance. Furthermore, compound (b2-3) can also be used.

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

The compound (b1) is not particularly limited as long as it is a compound having —[O(CH ₂ ) ₂ ] ₂ — without a hydroxyl group and a double bond. It can be produced by esterifying a hydroxyl group of a reaction product obtained by ring-opening polymerization of ethylene oxide with a carboxylic acid having a double bond such as (meth)acrylic acid.
Specifically, for example, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Aliphatic (meth)acrylic acid esters such as tetraethylene glycol di(meth)acrylate and polyethylene glycol di(meth)acrylate;

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;

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

For example, vinyl benzoic acid ester or isopropenyl benzoic acid ester monomers having a polyoxyethylene group moiety such as vinylphenylpoly(oxyethylene) succinate and vinylphenylmethylpoly(oxyethylene) hexahydrophthalate; are mentioned.

Among them, aromatic (meth)acrylic acid esters are preferable from the viewpoint of water resistance.

Examples of commercially available products of 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, Blenmer 50POEP-800B, Blenmer PLE-200, Blenmer PSE-1300, Blenmer PDE-100, Blenmer PDE-150, Blenmer PDE-200, Blenmer PDE-400, Blenmer PDE-600, Blenmer PDBE-200A, Blenmer PDBE-450A, Blenmer ALE-200, Blenmer AME-400, Blenmer AAE-300 (manufactured by NOF Chemical Co., Ltd.), 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 (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-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, 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 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Miramer M142, Miramer M144, Miramer M164, Miramer M166, Miramer M170, Miramer M232, Miramer M2100, Mira mer M2200, Miramer M2300 , MiramerM280, MiramerM282, MiramerM284, MiramerM286, MiramerM290, MiramerM2040, MiramerM3160, MiramerM3190, MiramerM3150, MiramerM4004, MiramerM193, Miramer M241, Miramer M2101, Miramer M2301 (manufactured by MIWON), light acrylate EC-A, light acrylate 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.), Viscoat 190, Viscoat 360, Viscoat 700HV, Bismer MPE400A, Bismer MPE550A (manufactured by Osaka Organic Chemical Co., Ltd.), Neomer PM201 (manufactured by Sanyo Chemical Industries), EBECRYL110, PEG400DA- D, EBECRYL11 (manufactured by Daicel Ornex).

Compound (b1) may be used alone or in combination of multiple types.

The compound (b2) is described below. Among 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.

Specifically, for example, 2-hydroxyethyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate 1-hydroxybutyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylate 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl-α-(hydroxymethyl) (meth)acrylate, monofunctional glycerol (meth)acrylate, Alternatively, fatty acid ester-based (meth)acrylic acid esters such as glycidyl laurate (meth)acrylate, glycidyl oleate (meth)acrylate, glycidyl acrylate (meth)acrylic acid ester, or 2-(acryloyloxy) (Meth)acrylic acid esters having hydroxyl groups at the ends, pentaerythritol tri(meth)acrylate, di hydroxyl group-containing aliphatic (meth)acrylic acid esters such as pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate;

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;
double bond group-containing compounds having multiple hydroxyl groups such as propenediol;

For example, hydroxyl group-containing compounds such as N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, N-hydroxybutyl (meth)acrylamide, N-hydroxyhexyl (meth)acrylamide, and N-hydroxyoctyl (meth)acrylamide of (meth) acrylamides; These may be used alone, or may be used in combination of multiple types.

As the compound (b2-1-1), 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are used in terms of adhesion to the substrate. .

Among compounds (b2), 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, in addition to durability such as heat resistance and moist heat resistance, it also has aspects such as water resistance. preferred from
Specifically, for example, 1,2-cyclohexanedimethanol (meth)acrylate, 1,3-cyclohexanedimethanol (meth)acrylate, 1,4-cyclohexanedimethanol (meth)acrylate, (meth)acryl Acid 2-hydroxy-3-phenoxymethyl, 2-hydroxy-3-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Butyl, 2-hydroxy-3-phenoxydecyl (meth)acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth)acrylate, monohydroxyethyl phthalate (meth)acrylate, 2-(4-(meth)acrylate) (Meth)acrylic acid esters having a cyclic structure other than a hydroxyl group and a heterocyclic ring such as benzoyl-3-hydroxyphenoxy)ethyl;

For example, 2-hydroxy-4-{2-(meth)acryloyloxy}ethoxybenzophenone, 2,2′-dihydroxy-4-{2-(meth)acryloyloxy}ethoxybenzophenone, and other hydroxyl group-containing benzophenone-based (meth)acryl Acid esters;
For example, hydroxyl group-containing benzotriazole-based (meth)acrylic acid esters 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 other hydroxyl group-containing triazine-based (meth)acrylic acid esters, which may be used alone, or , may be used in combination.

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

The compound (b2) can be roughly classified into the compound (b2-2-1) and the compound (b2-2-2), and among them, the compound (b2-2-1) is preferable from the viewpoint of heat resistance to yellowing.

The compound (b2-2-1) is not particularly limited as long as it is a compound having a double bond and a cyclic structure containing no heteroatom as a ring member atom and having no hydroxyl group. 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-phenoxyethyl (meth)acrylate, 2-oxo-1,2-phenylethyl (meth)acrylate, 2-oxo (meth)acrylate -1,2-diphenylethyl, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 1-naphthylmethyl (meth)acrylate, 1-anthryl (meth)acrylate, (meth)acrylic acid 2-anthryl, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) ) dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl diacrylate, dicyclopentenyl diacrylate, 2-ethyladamantyl-2-yl (meth)acrylate, (meth)acrylic acid 2-n-propyladamantyl-2-yl, 2-isopropyladamantyl-2-yl (meth)acrylate, 1-(adamantan-1-yl)-1-methylethyl (meth)acrylate, (meth)acrylic acid 1-(adamantan-1-yl)-1-ethylethyl, 1-(adamantan-1-yl)-1-methylpropyl (meth)acrylate, 1-(adamantan-1-yl)-1 (meth)acrylate -ethylpropyl, 5-oxo-4-oxa-tricyclo[4.2.1.0 ^3,7 ]non-2-yl (meth)acrylate, 5-oxo-4-oxa (meth)acrylate -tricyclo[5.2.1.0 ^3,8 ]dec-2-yl, dihydro-α-terpinyl (meth)acrylate, 6-oxo-7-oxa-bicyclo(meth)acrylate [3.2 .1] octa-2-yl, (meth)acrylic acid-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 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)acrylic (meth)acrylic acid cyclic esters such as acid phenyl glycidyl ether;

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 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]hept-2-ene and 2,5-bis(allyloxy)norbornane;
aromatic vinyl monomers such as styrene and 2-methylstyrene;
Cyclic vinyl ethers such as cyclohexyl vinyl ether and cycloxyl methyl vinyl ether;
aromatic vinyl ether-based monomers having long-chain alkyl groups such as vinyl phenyl pentyl ether and vinyl phenyl hexyl ether;

For example, vinyl benzoate or isopropenyl benzoate monomers having a long-chain alkyl group such as hexyl 4-vinyl benzoate and octyl 4-vinyl benzoate;
For example, isopropenylphenyl-based monomers having a long-chain alkyl group such as isopropenylphenylmethylbutyl ether and isopropenylphenylmethylpentyl ether;
For example, mono-long-chain alkyl ester-based cyclic monomers of dicarboxylic acids such as vinylphenyl nonyl 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;
metal salts of styrenesulfonic acid such as sodium styrenesulfonate; These may be used alone, or may be used in combination of multiple types.

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

The compound (b2-2-2) is not particularly limited as long as it is a compound having a cyclic structure containing a heteroatom as a ring member atom and a double bond without having a hydroxyl group. Examples include pentamethylpiperidinyl ( Nitrogen atom-containing heterocyclic (meth)acrylic acid esters such as meth)acrylate, 4-(pyrimidin-2-yl)piperazin-1-yl (meth)acrylate;

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, 1-(meth)allyl-2-methyl-1H-imidazole;
nitrogen atom-containing heteropolycyclic ethenyl group-containing compounds such as 1-vinyl-1H-benzimidazole and 1-vinyl-5,6-dimethyl-1H-benzimidazole;
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 having a nitrogen atom-containing heterocyclic structure such as 1-(meth)allyl-3,5-dimethyl-1H-pyrazole, 1-(1-methylpropyl)-5-(meth)allylpyrimidine, etc. Group-containing compounds;
For example, (meth)allyl group-containing compounds having a nitrogen atom-containing heteropolycyclic structure 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, oxyethylene di(meth)acrylic acid isocyanurate (meth)acrylic acid esters having a heterocyclic structure containing oxygen atoms other than nitrogen atoms, such as group-modified, tri(meth)acrylic acid isocyanuric acid oxyethylene group-modified;

Heterocyclic acrylamides such as, for example, 4-acryloylmorpholine, β-(2-furyl)(meth)acrylamide;
For example, maleimide derivatives having both a nitrogen atom and an oxygen atom such as methylmaleimide and ethylmaleimide;
Vinyl group-containing compounds having a heterocyclic structure containing an oxygen atom other than a nitrogen atom, such as 2-vinyloxazole and 2-phenyl-4-vinyloxazole;
For example, heterocyclic (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;
Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing sulfur atoms in addition to nitrogen atoms, such as 2-vinylthiazole and 4-methyl-5-vinylthiazole. Alternatively, a plurality of types may be used together.

As the compound (b2-2-2), from the viewpoint of durability such as heat resistance and water resistance, hetero Ring-containing (meth)acrylic acid esters, heterocyclic acrylamides such as 4-acryloylmorpholine, di(meth)acrylic acid ethoxylated isocyanuric acid, tri(meth)acrylic acid ethoxylated isocyanuric acid, etc. Oxygen atoms other than nitrogen atoms (Meth)acrylic acid esters having a heterocyclic structure containing are preferred, and among them, (meth)acrylic acid esters having a heterocyclic structure containing an isocyanurate ring and containing an oxygen atom in addition to a nitrogen atom are preferred.

Further, the compound (b2-3) includes, for example, (meth)acrylic compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. acid alkyl esters;
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)acrylates having two carbonyl groups such as 2-oxobutanoylethyl (meth)acrylate and 2-oxobutanoylpropyl (meth)acrylate;

For example, (meth)acrylate-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.0 ^3,7 ]non-2-yl, (meth)acrylate-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)acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo[3.3.1]oct-2-yl having a carbonyl group ( 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)acrylic acid esters such as 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropyltrimethoxysilane;

For example, di(meth)acrylate propylene oxide, di(meth)acrylate polypropylene oxide, di(meth)acrylate 1,6-hexanediol, di(meth)acrylate 1,9-nonanediol and other bifunctional ( meth) acrylic acid esters;

For example, 1,2,3-propanetriol tri(meth)acrylate, 2-methylpentane-2,4-diol tri(meth)acrylate, 2-methylpentane-2,4-diol tri(meth)acrylate tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri(meth)acrylate, trimethylolhexane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, tri(meth)acrylic acid 2,2-bis(hydroxymethyl)1,3-propanediol, 1,1,1-trishydroxymethylethane tri(meth)acrylate, 1,1,1-trishydroxymethylpropane tri(meth)acrylate, Trifunctional (meth)acrylic acid esters 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)acrylic acid 2, 2-bis(hydroxymethyl)1,3-propanediol, tetra(meth)acrylic acid 2,2-bis(hydroxymethyl)1,3-propanediol tetracaprolactonate, tetra(meth)acrylic acid di-1, 2,3-propanetriol, di-2-methylpentane-2,4-diol tetra(meth)acrylate, di-2-methylpentane-2,4-diol tetra(meth)acrylate, tetracaprolactonate, tetra( Di-2,2-dimethylpropane-1,3-diol meth)acrylate, ditrimethylolbutane tetra(meth)acrylate, ditrimethylolhexane tetra(meth)acrylate, ditrimethyloloctane tetra(meth)acrylate, etc. functional (meth) acrylic acid esters;

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;
Polyfunctional vinyl ethers such as, for example, propylene glycol divinyl ether 1,4-cyclohexanediol divinyl ether (CHODVE), trimethylolpropane trivinyl ether, dipentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, 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, maleinitrile, 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) ) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric 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, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, geranic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth)acryloyloxyethyl succinate, mono(meth)acrylic acid ω-carboxy polycaprolactone ester, polylactone-based (meth)acrylic acid esters, oxyethylene groups having carboxyl groups at the end due to ring-opening addition of the lactone ring An alkylene oxide addition system having a carboxyl group at the end, in which an alkylene oxide such as propylene oxide is repeatedly added, excluding succinic acid and a carboxyl group-containing aliphatic α, β-, such as an ester of (meth) acrylic acid Carboxylic acids containing unsaturated double bond groups and acid anhydrides thereof;

For example, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate, and (meth)acryloyl group-containing carboxylic acids having carboxyl group-containing alicyclic or aromatic rings and acid anhydrides thereof ;
For example, (meth)acrylic acid esters having primary and/or secondary amino groups 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, 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 primary and/or secondary amino groups 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;
vinyl compounds having primary and/or secondary amino groups, 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- Isopropylpyrimidine, 2-(meth)allylpyridine, 4-(meth)allylpyridine, 3,6-dihydro-4-(meth)allylpyridine, etc. having a primary and/or secondary amino group (meth) allyl compounds;
For example, tertiary amino group-containing vinyl compounds such as N-ethyl-N-nitrosovinylamine;
Examples thereof include, but are not limited to, heterocyclic double bond group-containing compounds of maleimide derivatives having both a nitrogen atom and an oxygen atom, such as maleimide and methylmaleimide. These may be used alone, or may be used in combination of multiple types.

As the compound (b2-3) having another double bond, a compound having a (meth)acryloyl group is preferable from the viewpoint of reactivity. (Meth)acrylic acid esters are preferably included.

In the compound (b2), the advantage of the compound (b2) in terms of polymerization curability, cure shrinkage of the polymer, and durability such as heat resistance, moist heat resistance and water resistance is that it contains a hydroxyl group (b2- As described in 1), a good polymerizable composition can be obtained by appropriately blending so as to contain both hydroxyl groups and cyclic structures.

Compound (b2) can be easily obtained as a commercial item from the manufacturers shown below. For example, "light acrylate", "light ester", "epoxy ester", "urethane acrylate" and "high-performance oligomer" series manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd. " NK Ester" and "NK Oligo" series, Hitachi Chemical Co., Ltd.'s "Funkryl" series, Toagosei Chemical Co., Ltd.'s "Aronix M" series, Daihachi Chemical Co., Ltd.'s "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam Oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by Nippon Shokubai Co., Ltd. "(Meth)acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "NICHIGO-UV Shiko Urethane" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Acrylate Ligomer" series, Shin-Etsu Vinyl Acetate Co., Ltd. "Carboxylate Vinyl Ester Monomer" series, Kojin Co., Ltd. "Functional Monomer" series.

Furthermore, as the compound (b2), those described in the literature shown below can also be mentioned. For example, edited by Shinzo Yamashita et al., "Crosslinking Agent Handbook" (1981, Taiseisha) and Kiyomi Kato, edited by "UV/EB Curing Handbook (Raw Materials)" (1985, Kobunshi Publishing Association), Radtech Research Edited by Kai, Kiyoshi Akamatsu, "Practical Technology of New Photosensitive Resins", (1987, CMC), Tsuyoshi Endo, edited, "Precision of Thermosetting Polymers", (1986, CMC), Takiyama Eiichiro, "Polyester Resin Handbook" (1988, Nikkan Kogyo Shimbun), Radtech Research Group, "Application and Market of UV/EB Curing Technology" (2002, CMC).

As a result of remaining in the polymer, the polymerizable composition of the present invention may cause odor due to seepage to the surface of the polymer, contamination of the contents due to permeation into the contents, and deterioration of quality due to conventional photopolymerization. It may not contain an initiator or a thermal polymerization initiator. However, it may be added as long as the above characteristics are not a problem, and the content is 2.0% by mass or less with respect to the total 100% by mass of the polymer (A) and the compound (B) having a double bond. is. It 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.

Examples of photopolymerization initiators include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, m-chloroacetophenone, p-tert-butyltrichloroacetophenone, and 4-dialkylacetophenone;
Benzophenones such as benzophenone;
Michler ketones such as Michler ketone;
benzyls such as benzyl, benzyl methyl ether, benzyl dimethyl ketal;
Benzoins such as benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether;
Thioxanthones such as thioxanthones;
carbonyl compounds such as propiophenone, anthraquinone, acetoin, butyroin, toluoin, benzoyl benzoate, α-acyloxime ester;
can be mentioned.
As the photopolymerization initiator, in addition to the above carbonyl compounds, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, thioxanthone, sulfur compounds such as 2-chlorothioxanthone; azobisisobutyronitrile, azobis- azo compounds such as 2,4-dimethylvaleronitrile; peroxides such as benzoyl peroxide and di-tert-butyl peroxide;

Examples of thermal polymerization initiators include
Persulfates such as potassium persulfate and ammonium persulfate;
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 -Azo polymerization initiators such as 1-carbonitrile;
Hydroperoxides such as tert-alkyl hydroperoxide; di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxide Oxy-2-ethylhexanoate, tert-butylperoxypivalate, di-isopropylperoxydicarbonate, di-tert-butylperoxyisophthalate, 1,1',3,3'-tetramethylbutylperoxy -Peroxides such as 2-ethylhexanoate and tert-butyl peroxybutyrate;
etc.

In the present invention, a coloring material may be included in addition to the above essential components. Depending on the dyes and pigments contained in the colorant, it is possible to impart not only design properties but also various functionalities such as thermal properties, electrical properties, or optical properties. Examples of coloring materials 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.

The polymerizable composition of the present invention can be appropriately blended with other components (G) such as various additives within a range that does not impair the effects of the present invention. For example, from the viewpoint of improving radical polymerizability (conversion rate), reducing polymerization curing shrinkage rate, reducing coefficient of thermal expansion, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, and improving coloring. can be blended with organic or inorganic fillers. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, and metal salts. Moreover, the shape is not particularly limited, and may be, for example, particulate or fibrous. In addition, when blending the above polymer-based materials, antioxidants such as phenolic and hindered amine-based antioxidants, silane coupling agents, photosensitizers, softening agents, plasticizers, flame retardants, storage stabilizers, etc. agent, UV absorber, thixotropy imparting agent, dispersion stabilizer, fluidity imparting agent, foaming agent, anti-mold agent, antistatic agent, magnetic material, surface tension modifier, slipping agent, anti-blocking agent, leveling agent, red They can be dissolved, semi-dissolved, or microdispersed in the polymerizable composition as polymer blends or alloys, as well as independent fillers such as external absorbents and defoamers.

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. can be selected. Furthermore, composite substrates composed of a plurality of substrates can also be selected. These substrates may be of flat shape such as plate, film or paper, or may be of three-dimensional shape. As the plastic film, a transparent one is preferable.

Examples of printing and coating methods include ink jet method, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, and U comma coating method. , AKKU coating method, smoothing coating method, micro gravure coating method, reverse roll coating method, four or five roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, and spray coating method.

A solvent such as water or an organic solvent may be contained in the polymerizable composition for the purpose of lowering the viscosity of the polymerizable composition and improving the wet spreadability on the substrate.

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 polymerization and cross-linking reaction with heat or active energy rays.

In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by applying energy by heat or active energy rays such as ultraviolet rays, visible rays, near-infrared rays, electron beams, etc., to obtain the desired polymer. be. As a method for imparting energy, it is preferable to irradiate visible light from a light source having a dominant emission wavelength in the wavelength range of 250 nm to 750 nm. Examples of light sources having a dominant wavelength of light emission in the wavelength range of 250 nm to 750 nm 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, and pulse emission xenon. Lamps, deuterium lamps, fluorescent lamps, Nd-YAG triple wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor excitation solid-state lasers, emission wavelengths in the wavelength range of 250 nm to 750 nm Various light sources such as an LED lamp light source having However, electron beams are excluded. In the present specification, active energy rays such as ultraviolet rays, visible light, and near-infrared rays are defined by Ryogo Kubo et al.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is in no way limited only to the following examples.

<Production Example 1>
13.6 parts by mass of a 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 reacted for 8 hours. After cooling, the polymer (A1) was obtained by concentrating with an evaporator. The polymer (A1) contains 1.0 mol% of a unit having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ , R ₂ , R It was confirmed by NMR that both ₃ are hydrogen atoms.

<Production Example 2>
13.6 parts by mass of a 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 reacted for 8 hours. After cooling, the polymer (A2) was obtained by concentrating with an evaporator. The polymer (A2) contains 4.5 mol% of units having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ , R ₂ , R It was confirmed by NMR that both ₃ are hydrogen atoms.

<Production Example 3>
13.6 parts by mass of a 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 reacted for 8 hours. After cooling, the polymer (A3) was obtained by concentrating with an evaporator. The polymer (A3) contains 1.1 mol% of units having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ , R ₂ , R It was confirmed by NMR that both ₃ are hydrogen atoms.

<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 reacted for 8 hours. After cooling, the polymer (A4) was obtained by concentrating with an evaporator. The polymer (A4) contains 0.9 mol% of a unit having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ , R ₂ , R It was confirmed by NMR that both ₃ are hydrogen atoms.

<Production Example 5>
13.6 parts by mass of polyvinylpyrrolidone (P-904LC, manufactured by DSP Gokyo Food & Chemical Co., Ltd.) in which the pyrrolidone ring is alkylated at the 3- or 5-position was dissolved in 16 mL of pyridine and heated to 90°C. 36 mL of 10% aqueous hydrogen peroxide solution was added and reacted for 8 hours. After cooling, the polymer (A5) was obtained by concentrating with an evaporator. The polymer (A5) contains 0.8 mol% of a unit having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ and R ₃ are n -butyl group, and R ₂ was confirmed to be a hydrogen atom by NMR.

<Production Example 6>
19.4 parts by mass of poly(vinylpyrrolidone/vinyl acetate) (vinylpyrrolidone/vinyl acetate = 70/30, Mw 51,000, manufactured by 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 reacted for 8 hours. After cooling, the polymer (A6) was obtained by concentrating with an evaporator. The polymer (A6) contains 0.6 mol% of units having an α,β-unsaturated lactam structure, the α,β-unsaturated lactam structure is represented by general formula (1), and R ₁ , R ₂ , R It was confirmed by NMR that both ₃ are hydrogen atoms.

<Production Example 7>
24 parts by mass of ion-exchanged water was charged into a reaction vessel equipped with a reflux tube, a thermometer, a nitrogen inlet, a monomer dropping port, and an initiator dropping port. The temperature was raised while blowing nitrogen through the nitrogen blowing port, and after confirming reflux, 12 parts by mass of N-vinylpiperidone was added from the monomer dropping port, and V-50 (azo initiator, FUJIFILM Wako Pure Chemical Industries, Ltd. from the initiator dropping port. An aqueous solution obtained by dissolving 0.28 parts by mass of the same product manufactured by Kogyo Co., Ltd. in 4 parts by mass of ion-exchanged water was dropped simultaneously over 3 hours and 30 minutes to polymerize. After completion of dropping, the mixture was aged for 30 minutes and cooled to obtain an aqueous poly(N-vinylpiperidone) 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 reacted for 8 hours. After cooling, the polymer (A7) was obtained by concentrating with an evaporator. It was confirmed by NMR that the polymer (A7) contained 1.2 mol % of units having an α,β-unsaturated lactam structure.

<Production Example 8>
24 parts by mass of ion-exchanged water was charged into a reaction vessel equipped with a reflux tube, a thermometer, a nitrogen inlet, a monomer dropping port, and an initiator dropping port. The temperature was raised while blowing nitrogen through the nitrogen blowing port, and after confirming reflux, 12 parts by mass of N-vinyl-2-caprolactam was added from the monomer dropping port, and V-50 (azo initiator, Fuji An aqueous solution prepared by dissolving 0.28 parts by mass of Film Wako Pure Chemical Industries, Ltd. in 4 parts by mass of ion-exchanged water was dropped simultaneously over 3 hours and 30 minutes for polymerization. After completion of dropping, the mixture was aged for 30 minutes and 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 reacted for 8 hours. After cooling, the polymer (A8) was obtained by concentrating with an evaporator. It was confirmed by NMR that the polymer (A8) contained 1.1 mol % of units having an α,β-unsaturated lactam structure.

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

<Curability 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 a high-pressure UV lamp USH-500SC (Ushio Inc.) was used as an active energy ray to irradiate ultraviolet rays for 1 second at an irradiation intensity of 30 mW/cm ² (converted to 254 nm). After the irradiation, the surface of the polymerized product was rubbed with a cotton cloth, and the UV irradiation was repeated until the film was no longer scratched, and the curability was determined. It was judged that the shorter the UV irradiation time, the better the curability. Judgment criteria are as follows.

Judgment criteria ◎: 1 to 15 seconds. Especially good.
○: 16 seconds to 60 seconds. Good.
△: 61 seconds or more. Somewhat poor.
x: Unsuitable for practical use because it hardens before UV irradiation. Especially bad.

<Hardness of Polymer, Residual Percentage of Low Molecular Compounds, and Water Resistance Evaluation Test>
The prepared active energy ray-curable composition was applied onto 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 is placed on the coating film, and a high-pressure UV lamp USH-500SC (Ushio Inc.) is used as an active energy ray to irradiate ultraviolet rays at an irradiation intensity of 50 mW/cm ² (converted to 365 nm) for 30 seconds to form a polymer. got
The hardness of the polymer was measured by observing the state of the polymer when it was pushed in with a load of 0.1 kgf (0.98 N) for 5 seconds and after it was pushed in, and the hardness of the polymer was determined. Judgment criteria are as follows.

Judgment criteria ⊚: No dent during and after pushing. Especially good.
◯: Depression occurred during pressing, no dent after pressing. Fairly good.
x: Cracks occurred during pressing, or the cured product collapsed. Defective.

The residual rate of low-molecular-weight compounds was measured by cutting the obtained polymer (10 cm x 10 cm) together with the substrate into 1 cm square pieces and immersing them in 100 ml of methyl ethyl ketone in a sealed container at 60°C for 3 days. The residual ratio of low-molecular-weight residual components in the cured film was extracted. Two days later, the stirred and homogenized methyl ethyl ketone was taken out from the container, and the peak area ratio of the extracted component measured by GPC was evaluated as the residual ratio of low-molecular-weight compounds. In addition, a low-molecular-weight compound means a compound having a molecular weight of less than 1,000. It was judged that the lower the residual ratio of low-molecular-weight compounds, the better. Judgment criteria are as follows.

Judgment criteria ◯: Low-molecular-weight compound residual rate is less than 0.5%. Especially good.
Δ: Low-molecular-weight compound residual rate is 0.5% or more and less than 1%. Fairly good.
x: Low-molecular-weight compound residual rate is 1% or more, not suitable for practical use. Defective.

For evaluation of water resistance, the obtained polymer (5 cm×5 cm) was immersed in water at 25° C. and allowed to stand 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 as follows from the weight change before and after immersion, and the water resistance was evaluated.
Elution rate: (weight before water immersion - weight after water immersion) / weight before water immersion x 100 (% by weight)
◎: Less than 1% by weight ○: 1% by weight or more and less than 3% by weight ×: 3% by weight or more

A9: Polyvinylpyrrolidone K30 (Mw40,000, manufactured by Tokyo Chemical Industry Co., Ltd.)
HEA: 2-hydroxyacrylate ACMO: acryloylmorpholine AM90G: methoxypolyethylene glycol #400 acrylate (manufactured by 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-methylpripiophenone PI2: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide

Next, polymerizable compositions were obtained with the formulations shown in Table 2 (Examples 15 to 22 and Comparative Examples 6 to 7). Using the resulting polymerizable composition, 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. Table 2 shows the results.

<Hardness of Polymer, Residual Percentage of Low Molecular Compounds, and Water Resistance Evaluation Test>
The prepared active energy ray-curable composition was applied onto 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 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 it was pushed in with a load of 0.1 kgf (0.98 N) for 5 seconds and after it was pushed in, and the hardness of the polymer was determined. Judgment criteria are as follows.

Judgment criteria ⊚: No dent during and after pushing. Especially good.
◯: Depression occurred during pressing, no dent after pressing. Fairly good.
x: Cracks occurred during pressing, or the cured product collapsed. Defective.

The residual rate of low-molecular-weight compounds was measured by cutting the resulting cured product (10 cm x 10 cm) into 1 cm squares together with the base material, and immersing it in 100 ml of methyl ethyl ketone in a sealed container at 60°C for 3 days. The residual ratio of low-molecular-weight residual components in the cured film was extracted. Two days later, the stirred and homogenized methyl ethyl ketone was taken out from the container, and the peak area ratio of the extracted component measured by GPC was evaluated as the residual ratio of low-molecular-weight compounds. In addition, a low-molecular-weight compound means a compound having a molecular weight of less than 1,000. It was judged that the lower the residual ratio of low-molecular-weight compounds, the better. Judgment criteria are as follows.

Judgment criteria ◯: Low-molecular-weight compound residual rate is less than 0.5%. Especially good.
Δ: Low-molecular-weight compound residual rate is 0.5% or more and less than 1%. Fairly good.
x: Low-molecular-weight compound residual rate is 1% or more, not suitable for practical use. Defective.

For evaluation of water resistance, the obtained polymer (5 cm×5 cm) was immersed in water at 25° C. and allowed to stand 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 as follows from the weight change before and after immersion, and the water resistance was evaluated.
Elution rate: (weight before water immersion - weight after water immersion) / weight before water immersion x 100 (% by weight)
◎: Less than 1% by weight ○: 1% by weight or more and less than 3% by weight ×: 3% by weight or more

According to the present invention, a polymerizable composition with high radical polymerizability (conversion rate) and good curability even when photopolymerization initiators and thermal polymerization initiators that can cause odor and migration are reduced or removed, and , a polymer having high hardness and water resistance can be provided. Examples of applications in which the present invention can be expected to increase sensitivity and improve properties include molding resins utilizing polymerization or cross-linking reactions, casting resins, stereolithography resins, sealants, dental polymerization resins, printing inks, Printing varnishes, paints, photosensitive resins for printing plates, color proofing for printing, resists for color filters, resists for black matrixes, photospacers for liquid crystals, screen materials for rear projection, optical fibers, rib materials for plasma displays, dry film resists, Printed circuit board resists, solder resists, semiconductor photoresists, microelectronics resists, micromachine component manufacturing resists, etching resists, microlens arrays, insulating materials, hologram materials, optical switches, waveguide materials, overcoating agents , powder coatings, adhesives, adhesives, release agents, optical recording media, adhesives, release coating agents, compositions for image recording materials using microcapsules, and various devices.

Claims (5)

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 with respect to the total 100% by mass of the polymer (A) and the compound (B) having a double bond,
A polymerizable composition, wherein the polymer (A) has an α,β-unsaturated lactam structure. 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)

(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 and R ₃ each independently represent a hydrogen atom; or represents a methyl group.) 3. The polymerizable composition according to claim 1, wherein the polymer (A) further has a pyrrolidone skeleton. 4. The polymerizable composition according to any one of claims 1 to 3, wherein the compound (B) having a double bond contains a compound having an aromatic ring or an isocyanurate ring. A polymer of the polymerizable composition according to any one of claims 1 to 4.