JP2005290209A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition excellent in adhesivity to various substrates such as a metal substrate, a glass substrate, a plastic substrate, etc., and the cured coated surface is tack-free and exhibiting flexibility and solvent resistance, usable for various applications of ink, coating material, adhesive, etc., for example credit card or prepaid card, etc. <P>SOLUTION: A curable composition comprising a monomer unit having an amide group, a copolymer comprising a monomer unit having amide group as essential constituting unit and a polyfunctional monomer unit, as essential component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition that can be used for coating materials and printing inks on various substrates such as metals, glass, plastics such as polyethylene terephthalate (PET) and polycarbonate (PC).

The curable composition is a composition that is polymerized by heat treatment or active energy ray irradiation to form a cured film or the like, and is used in various applications such as inks, coating materials, paints, and adhesives. Such a curable composition as an ink composition for printing on various substrates such as metal, glass, plastics such as polyethylene terephthalate (PET) and polycarbonate (PC), etc., with good curing characteristics and the like. For example, it can be suitably used as a coating agent or ink for applications such as credit cards and prepaid cards, so that it has good adhesion to these various substrates and is thermally cured. There is a demand for a material having a property and ultraviolet (UV) curability.

At present, for example, PET or the like is surface-treated by plasma discharge treatment or the like, and then a coating of a composition that is cured by irradiation with active energy rays is applied, but (1) corrosion of the apparatus and (2) running There is a problem that the cost is high. The corrosion of the apparatus is probably caused by decomposition and generation of terephthalic acid and the like when PET or the like is processed. For this reason, the coating agent (liquid) is applied to an untreated plastic material such as PET, heat treated, and irradiated with active energy rays such as UV, etc., and various performances are excellent. What can form a hardened film etc. is calculated | required.

Regarding hair cosmetics, a cationic thickener obtained by polymerizing a composition containing an amine-containing (meth) acrylic monomer, a (meth) acryloyl group-containing monomer, a crosslinkable vinyl monomer, and an amide group-containing vinyl monomer; It is disclosed that it contains an oxyalkylene derivative (for example, refer to Patent Document 1). In such hair cosmetics, acrylamide or N-vinylpyrrolidone (NVP) or the like is used as an amide group-containing monomer, and dimethylaminoethyl acrylate (DAA) or the like is used as an amino group-containing monomer. Has been described. However, there is room for contrivance to be curable and applicable to coating materials and printing inks for various substrates such as metal, glass, and plastic.

With respect to conventional UV curable copolymers, at least different types selected from the group consisting of vinyl lactam (a) and hydrophobic vinyl monomers, hydrophilic vinyl monomers and functional vinyl monomers. A water-soluble cross-linkable copolymer containing a copolymer product of a monomer mixture substantially consisting of another vinyl monomer (b) is disclosed (for example, see Patent Document 2). In this copolymer, it is a water-soluble crosslinkable copolymer, and in the composition ratio range of the monomer mixture, 30 to 95 mol% vinyl lactam (a), and 5 to 70 mol% It is disclosed as vinyl monomer (b). However, it has adhesion to various base materials and the combination of monomers and co-polymers so that the characteristics such as solvent resistance such as methanol resistance required in ink applications etc. can be fully exhibited. There was room for improvement to optimize the characteristics of coalescence.

In addition, regarding a composition for treating the surface of a metal ion-containing substrate, a polymer containing a highly polar, hydrophilic surface active group and a polymer composition containing a low polarity of the sequence at the terminal position and a reactive group in the polymer composition is contained in the solution. It is disclosed that a solvent comprising a solvent to be used is used (for example, see Patent Document 3). It is described that such a polymer is used as a primer for improving adhesion between teeth and a polymer material, and is used for a dental restoration process and for fixing an orthodontic appliance to an external tooth surface. Is valid. It is considered that the copolymer used as such a primer requires a structural unit formed by a carboxyl group-containing monomer such as acrylic acid in order to improve adhesion to teeth (Ca). Moreover, although it is described in the Examples that a copolymer obtained by modifying a copolymer of acrylic acid and acrylamide with glycidyl methacrylate is used, there is no disclosure of UV curability and the like, and tooth restoration, etc. It is used for

Furthermore, it is disclosed that the curable resin composition contains, as essential components, a polymer having an N-vinylamide unit and a compound having two or more functional groups that react with active hydrogen (for example, see Patent Document 4). .) It is also disclosed that a thermoset of polyvinylpyrrolidone (PVP) and water-soluble melamine can form a cured film on PET. Since this curable resin composition is a thermosetting resin composition that can achieve both hydrophilicity and water resistance, a cured film excellent in various performances even by a process of irradiating active energy rays such as UV. There was room for ingenuity to be able to form etc.

On the other hand, with respect to inhibition of curing of an acrylate compound by oxygen, a method for avoiding oxygen inhibition by introduction of a hydroxyl group, introduction of a polyether, introduction of an amino group-containing monomer, addition of an amine compound, etc. is described (for example, non-patent literature). 1). However, simply applying such a method cannot sufficiently exhibit other basic characteristics such as adhesion to the substrate, flexibility, and solvent resistance, as well as tack-free properties of the cured coating film. Therefore, by improving these characteristics, it is desired to obtain a composition that can be used for coating materials and printing inks for various substrates. Regarding the addition of the amine compound, the amine compound may bleed out from the surface of the cured coating over time, and the amine compound is generally a corrosive compound. There was room.

Further, regarding the photosensitive recording element, the carboxyl group is composed of at least one N-vinylamide, acrylic acid and / or methacrylic acid, and at least one hydrophobic comonomer that itself forms a homopolymer insoluble in water and an aqueous alkaline solution. In particular, it is disclosed that a film-forming copolymer esterified by reaction with glycidyl (meth) acrylate is contained (for example, see Patent Document 5). In addition, this copolymer contains N-vinylpyrrolidone and / or N-vinylcaprolactam as an N-vinylamide comonomer, and is introduced with a polyfunctional photopolymerizable ethylenically unsaturated compound or photopolymerization start. It is disclosed that an agent may be contained and a resist pattern is produced by UV-laser. However, such a photosensitive recording element is suitable for producing a resist pattern, and has been devised so that it can be suitably used as a coating agent or ink for various substrates. There was room.
JP-A-10-265345 (page 2-4) JP-A-7-196744 (2nd page) JP-A-49-98878 (pages 1-3, 6, 7) JP 2003-113220 A (pages 2 and 7) Supervised by Kunihiro Ichimura, edited by Radtech Study Group, “Current Status and Prospects of UV / EB Curing Technology”, CM Publishing, 2003, p. 25 Japanese Patent No. 2592454 (pages 1-2, 5, 7, 9)

The present invention has been made in view of the above-described situation, and has excellent adhesion to various substrates such as metal, glass, plastic, and the like, and the surface of the cured coating film is tack-free and has flexibility and solvent resistance. It aims at providing the composition for hardening which can exhibit property.

The inventors of the present invention have studied various curing compositions suitable for plastic materials such as untreated PET, etc., and by using a copolymer and a polyfunctional monomer as essential components, the curing characteristics can be improved. By making the copolymer an amide group-containing monomer unit composed of acrylamide, N-vinylpyrrolidone (NVP), or the like, and an amino group-containing monomer unit, an amide can be obtained. Due to the group-containing monomer unit, the adhesiveness of the cured coating film to various substrates is expressed, the surface-curability of the cured coating film is improved due to the amino group-containing monomer unit, and can be tack-free. Furthermore, the inventors have found that these synergistic actions can also improve the physical properties of the cured product such as flexibility and solvent resistance, and have conceived that the above problems can be solved brilliantly. . Further, in the prior art, there is no prior art in which a curing composition formed using a copolymer and a polyfunctional monomer as essential components is used for coating a plastic material such as PET, PC, etc. With such a composition, there is a demand for coating (coating film) such as adhesion, flexibility, solvent resistance and tack-free property to various substrates such as metal, glass, plastics such as PET and PC, etc. It is possible to satisfy the performance, and in this respect, it has been found that the present invention has an advantageous effect over the prior art, and the present invention has been achieved.

In the curable composition, in order to express the adhesion of the cured coating film to the substrate, a monomer unit composed of an amide group-containing monomer such as N-vinylpyrrolidone (NVP) in the polymer. In addition to the need to contain, it is also important to have a structure that can relieve internal stress when cured by ultraviolet (UV), and in order to relieve this internal stress, It has also been found that the introduction of a component, for example, an alkyl (meth) acrylate having a certain chain length such as 2-ethylhexyl acrylate, alleviates internal stress and further improves the adhesion to the substrate. Moreover, when it has the form which has an amino-group-containing monomer unit and the monomer unit comprised from such an alkyl (meth) acrylate, tack-free property will improve further and coexistence with flexibility is sufficient. I also found what I can do. Further, when the copolymer contains a certain amount or more of monomer units composed of such alkyl (meth) acrylates, the compound blended with the monofunctional monomer or polyfunctional monomer is cured. In some cases, however, a phenomenon that tackiness is generated on the surface of the cured coating film may be observed. In addition, after the copolymer has a composition as described above, an alkyl group-containing monomer having 4 to 12 carbon atoms is further included. By having a unit, the composition for curing having both good adhesion to the substrate, flexibility resulting from a structure capable of relaxing internal stress due to curing, and tack-free property of the cured coating film surface; I also found what I can do.

That is, the present invention is a curable composition comprising a copolymer having an amide group-containing monomer unit and an amino group-containing monomer unit as essential constituent units and a polyfunctional monomer as essential components.
The present invention is described in detail below.

The copolymer in the present invention only needs to have an amide group-containing monomer unit and an amino group-containing monomer unit as essential constituent units, and the method for forming these structural units (monomer units) is particularly preferred. It is not limited. In the present invention, the amide group-containing monomer unit can exhibit adhesiveness to various substrates, and the amino group-containing monomer unit improves the surface curability of the cured coating film and is tack-free. Usually, the functional group of a monomer unit obtained by polymerizing a monomer component containing an amide group-containing monomer or amino group-containing monomer, or by polymerizing the monomer component, and the functional group By reacting with a compound having a group capable of reacting with a group, an amide group-containing monomer unit or an amino group-containing monomer unit is formed. In addition, in this invention, the monomer component which forms a copolymer, another component, etc. can use 1 type (s) or 2 or more types, respectively.

The amide group-containing monomer unit is preferably formed from an amide group-containing monomer. Examples of the amide group-containing monomer include (meth) acrylamide; N-methyl ( N-alkyl (meth) acrylamides such as meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide N, N-dialkyl (meth) acrylamide such as N-methyl-N-ethyl (meth) acrylamide; N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-alkoxymethyl (meth) such as N-butoxymethyl (meth) acrylamide (Meth) acrylate having an amide group such as N- (2- (meth) acryloyloxy) ethylpyrrolidone, N- (2- (meth) acryloyloxy) ethyloxazolidone; N-vinylformamide, N-vinylacetamide, N-vinyl amides such as N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-2-piperidone, N-vinyl-3-methyl-2-pyrrolidone, etc. Vinyl lactam and the like are preferred.

As the amino group-containing monomer unit, (1) a form composed of an amino group-containing monomer, (2) a monomer composed of an epoxy group-containing radical polymerizable monomer in the copolymer A form in which a tertiary amino group is introduced by a reaction between an epoxy group in a unit and a compound having a secondary amino group (for example, a secondary amine) is preferable. The form (2) is preferred. By adopting such a form, as a compound having a secondary amino group, for example, an amine having a hydroxyl group such as diethanolamine can be used, and the hydroxyl group and the amino group are allowed to coexist in the copolymer. Therefore, tack-free property on the surface of the cured coating film can be expressed more sufficiently. Thus, the hardening composition in which the site | part containing an amino group is formed by reaction of an epoxy group and a secondary amine is one of the preferable embodiment of this invention.

Examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like. N-dialkylaminoalkyl (meth) acrylate; N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide and the like are preferable.
Examples of the epoxy group-containing radical polymerizable monomer include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methallyl glycidyl ether, monomers represented by the following general formulas (1) to (13), and the like. Is preferred.

In the above formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents a C 1-6 divalent aliphatic saturated hydrocarbon group.
Suitable examples of the secondary amine include dialkylamines such as dimethylamine, diethylamine and diisopropylamine; diarylamines such as diphenylamine; and hydroxyl group-containing dialkylamines such as diethanolamine and diisopropanolamine.

The copolymer preferably has an alkyl group-containing monomer unit having 4 to 12 carbon atoms. In the present invention, such a monomer unit can impart flexibility to the cured coating film and relieve internal stress. Such a monomer unit is preferably a monomer unit different from the above-mentioned amide group-containing monomer unit or amino group-containing monomer unit. Moreover, it is suitable that it is formed from a C4-C12 alkyl group containing monomer, for example, an alkyl part is n-butyl group, isobutyl group, pentyl group, n-hexyl group, cyclohexyl. (Meth) acrylic acid alkyl esters and the like, which are aliphatic alkyl groups having 4 to 12 carbon atoms, such as a group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and dodecyl group, are preferred.
Among these, (meth) acrylic acid alkyl esters in which the alkyl moiety is an n-butyl group, isobutyl group, pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, or 2-ethylhexyl group are more preferable.

The copolymer may also have other monomer units. Examples of the monomer forming such a monomer unit include, for example, an alkyl moiety having a methyl group, an ethyl group, n -An aliphatic alkyl group having 1 to 13 or 13 to 18 carbon atoms such as propyl group, isopropyl group, stearyl group, phenyl group, benzyl group, 2-phenylethyl group, 4-ethylphenyl group, 4-nonylphenyl (Meth) acrylic acid alkyl ester having 6 to 24 carbon atoms such as 4-dodecylphenyl group; styrenes such as styrene, α-methylstyrene, monochlorostyrene; (meth) acrylonitrile, etc. α, β-unsaturated nitrile monomer; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; glycidyl (meth) acrylate, allyl glycidyl ether , Epoxy group-containing monomers such as methallyl glycidyl ether are preferred. The monomer unit formed from the epoxy group-containing monomer is a monomer unit formed from the above-described epoxy group-containing radical polymerizable monomer, and the epoxy group reacts with a secondary amine. It may be a monomer unit that was not.

The copolymer preferably further has a radically polymerizable double bond. Thereby, curability will be further imparted to the curable composition of the present invention. More preferably, the side chain has a pendant double bond. In such a case, the copolymer has an amide group-containing monomer unit, an amino group-containing monomer unit, and a polymerizable monomer unit having a radical polymerizable double bond in the side chain as an essential constituent unit. Will be included. In the present invention, the curing degree (crosslinking density) of the curable composition can be further increased by the polymerizable monomer unit having a radical polymerizable double bond in the side chain.

In the double bond, the introduction method is not particularly limited. For example, a polymer having an epoxy group in a side chain is obtained by polymerizing a monomer component containing an epoxy group-containing radical polymerizable monomer. Thereafter, it is preferably introduced by a method of reacting a compound having a group that reacts with the epoxy group and a double bond, and a modified polymer can be obtained by such a method. Here, the polymer and the modified polymer are both included in the copolymer in the present invention.
The epoxy group-containing radical polymerizable monomer is preferably the same as described above.
The compound having a group that reacts with the epoxy group and a double bond may be any monomer that has a group that reacts with the epoxy group and a radical polymerizable group in the molecule. For example, (meth) acrylic acid Suitable are unsaturated monocarboxylic acids such as crotonic acid, caprolactone adducts of (meth) acrylic acid, and those obtained by adding acid anhydrides to hydroxyalkyl (meth) acrylates.
As the acid anhydride, acid anhydrides such as succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid are preferable. Among these, acid anhydrides of succinic acid, maleic acid, and tetrahydrophthalic acid are preferable.

Preferred forms of the copolymer in the present invention include (i) (A) an amide group-containing monomer unit, (B) an amino group-containing monomer unit, and (C) an alkyl group having 4 to 12 carbon atoms. A form in which a contained monomer unit and other monomer units are essential, (ii) (A) an amide group-containing monomer unit, (B) an amino group-containing monomer unit, (C) 4 to 4 carbon atoms Examples include 12 alkyl group-containing monomer units, other monomer units, and (D) a polymerizable monomer unit having a radical polymerizable double bond in the side chain. . By setting the copolymer in the present invention in such a form, the effects of the present invention can be sufficiently exhibited.

In the copolymer, examples of the monomer unit (A) include a monomer unit represented by the following general formula (14). Examples of the monomer unit (B) include monomer units represented by the following general formulas (15) and (16). In the monomer unit (C), examples of the alkyl group-containing monomer unit having 4 to 12 carbon atoms include a monomer unit represented by the following general formula (17). As a monomer unit of (D), the monomer unit represented by following General formula (18) can be mentioned, for example. In the following formulae, R ³ , R ⁴ , R ⁷ , R ¹⁰ and R ¹¹ represent a hydrogen atom or a methyl group. R ⁵ , R ⁶ , R ⁸ and R ⁹ are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group, or the like.

When the copolymer is in the form (i) above, the composition of each monomer unit is (A) + (B) + (C) = 100 mol%. It is preferable that it is mol%. More preferably, it is 8-55 mol%, More preferably, it is 10-50 mol%. (B) is preferably 1 to 30 mol%. More preferably, it is 3-25 mol%, More preferably, it is 5-20 mol%. (C) is preferably 40 to 94 mol%. More preferably, it is 50-90 mol%, More preferably, it is 60-85 mol%.

When the copolymer is in the form (ii) above, the composition of each monomer unit is (A) + (B) + (C) + (D) = 100 mol%. 5 to 60 mol% is preferable. More preferably, it is 8-55 mol%, More preferably, it is 10-50 mol%. (B) is preferably 1 to 30 mol%. More preferably, it is 3-25 mol%, More preferably, it is 5-20 mol%. (C) is preferably 40 to 93 mol%. More preferably, it is 50-90 mol%, More preferably, it is 60-85 mol%. (D) is preferably 1 to 40 mol%. More preferably, it is 3-35 mol%, More preferably, it is 5-30 mol%.
In the form (ii) above, for example, when a double bond is introduced by the method as described above, 10 to 100 mol% of the epoxy group in the polymer reacts with the epoxy group. It is preferably esterified with a compound having a group and a double bond.

In the copolymer, the weight average molecular weight (Mw) in terms of polystyrene is preferably 1000 to 100,000. If the Mw is less than 1000, the properties of the cured product, such as the coating film becoming brittle, may deteriorate. If the Mw exceeds 100000, the viscosity of the curing composition that is a blend with the polyfunctional monomer is high. Thus, workability may be deteriorated and handling may be difficult. More preferably, it is 2000-80000, More preferably, it is 3000-50000.
The copolymer is preferably not water-soluble, and thereby has adhesiveness to untreated PET, PC and other plastic materials, and has flexibility, solvent resistance and tack-free properties. The effect of this invention of having it will fully be exhibited.

The curable composition of the present invention contains a polyfunctional monomer as an essential component. In the curable composition of the present invention, by containing a polyfunctional monomer, the physical properties of the cured product can be improved, and may be in the state of syrup containing such a polyfunctional monomer, Furthermore, it is good also as a state containing a solvent etc.

The content of the polyfunctional monomer may be set in accordance with the desired physical properties of the cured product, and the lower limit is preferably 10 parts by weight with respect to 100 parts by weight of the copolymer. . More preferably, it is 20 parts by weight, and still more preferably 30 parts by weight. The upper limit is preferably 1000 parts by weight. More preferably, it is 900 parts by weight, and still more preferably 800 parts by weight. Moreover, as a preferable range, it is 10-1000 weight part, More preferably, it is 20-900 weight part, More preferably, it is 30-800 weight part. If it is less than 10 parts by weight, curing may not be sufficient, and the solvent resistance of the cured product may be reduced. If it exceeds 1000 parts by weight, the tack-free property of the cured product may be lowered, or the physical properties such as the cured product may become brittle.

Examples of the polyfunctional monomer include polyethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol, and triethylene glycol, propylene glycol di (meth) acrylate, dipropylene glycol, and tripropylene glycol. Dihydric alcohols such as di (meth) acrylate of polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,4-dimethylolbenzene (Meth) acrylate, di (meth) acrylate of a dihydric alcohol obtained by reacting the above dihydric alcohol with ethylene oxide and / or propylene oxide, trimethylolpropane tri (meth) ) Divalent trivalent alcohol obtained by reacting acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane or glycerine with ethylene oxide and / or propylene oxide. A tetrahydric alcohol tri (meta) obtained by reacting (meth) acrylate and tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate or pentaerythritol with ethylene oxide and / or propylene oxide. ) Polyfunctional (meth) acrylates such as acrylate and tetra (meth) acrylate; Polyfunctional vinyl compounds such as divinylbenzene; (Meth) acrylic group in the same molecule And a vinyl ether group 2- vinyloxyethyl (meth) acrylate, 2- (2-vinyloxy) ethyl (meth) heterologous polymerizable compounds such acrylate are preferable. These can use 1 type (s) or 2 or more types.

In recent years, in the paint and ink industries, there is a tendency to use polyfunctional monomers with low primary skin irritation (PII) in consideration of workers and the environment, and polyfunctionality with high primary skin irritation. The use of monomers is discouraged. The polyfunctional monomer that can be used in the curable composition of the present invention can be used regardless of the level of primary skin irritation as long as it belongs to the above-described polyfunctional monomer. It is preferable to use a polyfunctional monomer having low irritation. As the polyfunctional monomer having low primary skin irritation, tripropylene glycol di (meth) acrylate, di (meth) acrylate of dihydric alcohol obtained by reacting neopentyl glycol with ethylene oxide and / or propylene oxide, Obtained by reacting trimethylolpropane or glycerin with ethylene oxide and / or propylene oxide and reacting di (meth) acrylate and tri (meth) acrylate of trihydric alcohol and pentaerythritol with ethylene oxide and / or propylene oxide. And polyfunctional (meth) acrylates such as tri (meth) acrylate and tetra (meth) acrylate of tetrahydric alcohol, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, etc. The deviation can be suitably used.

Below, the manufacturing method of the copolymer in this invention is demonstrated. In addition, about the raw material etc. which can be used in a manufacturing method, 1 type (s) or 2 or more types can each be used.
As a polymerization method for preparing the copolymer in the present invention, solution polymerization, precipitation polymerization, emulsion polymerization, and suspension polymerization can be used. When emulsion polymerization or suspension polymerization is performed, a dispersant is usually used. For example, alkyl sulfates, alkyl sulfonates, polyoxyethylene alkyl phenyl ethers and the like can be used as emulsifiers during emulsion polymerization, and stabilizers for suspension polymerization include polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, polyvinyl Pyrrolidone or the like can be used.

Solvents that can be used for the solution polymerization include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and 2-butanol; carboxylic acid esters such as methyl acetate, ethyl acetate, isopropyl acetate, and methyl propionate. Preferred are ketones such as acetone, methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as benzene and toluene.
As the solvent that can be used for the precipitation polymerization, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-pentane are preferable.

In the above polymerization method, a polymerization initiator is usually used. Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2- (2-imidazolin-2-yl ) Propane], 2,2'-azobis (2,4-dimethylvaleronitrile) and other azo polymerization initiators; organic compounds such as benzoyl peroxide, t-butyl hydroperoxide, diisopropyl peroxydicarbonate, dibutyl peroxide Peroxide polymerization initiators: persulfates such as ammonium persulfate and potassium persulfate can be used.
As content of the said polymerization initiator, it is preferable to set it as 0.01-20 mass% with respect to the total amount of the polymerizable monomer used in preparing the copolymer concerning this invention. More preferably, it is 0.05-10 mass%.
In the said polymerization conditions, it does not specifically limit as polymerization temperature, However, It is preferable to superpose | polymerize at 40-150 degreeC. The polymerization is usually carried out under normal pressure, but it may be under pressure or under reduced pressure. Although it does not specifically limit as superposition | polymerization time, Usually, 3 to 15 hours are preferable.

In the above copolymer, a compound having an amino group-containing monomer unit having an epoxy group and a secondary amino group in a monomer unit composed of an epoxy group-containing radical polymerizable monomer in the copolymer (two When a tertiary amino group is introduced by reaction with a tertiary amine), the amino group-containing monomer unit is formed before the double bond introduction reaction. If a compound having a secondary amino group is added to the system after the double bond has been introduced, the secondary amino group may be Michael-added to the double bond and the double bond may be crushed. As a solvent that can be used in such a tertiary amino group introduction reaction, when the polymer is obtained by solution polymerization, the solvent may be used as it is. When a polymer is obtained by precipitation polymerization, suspension polymerization, or emulsion polymerization, the copolymer may be taken out by filtration, washing, and drying by a conventional method, and the reaction may be performed by dissolving in a solvent in which the polymer is dissolved. . Usable solvents are the same as those usable for the solution polymerization.
What is necessary is just to use the quantity required in order for the usage-amount of the said secondary amine to express the desired physical property, and it is 10-100 mol% of secondary amines to be used with respect to the epoxy group in a polymer. preferable.

In the tertiary amino group introduction reaction, a reaction catalyst may not be used, and an added secondary amine or a tertiary amino group introduced into a polymer can act as a catalyst.
Although it does not specifically limit as said reaction temperature, Usually, it is the range of 20-80 degreeC, Preferably it is 30-70 degreeC. When the reaction temperature is lower than 20 ° C., the reaction time may be long, which is not preferable. When the reaction temperature is higher than 80 ° C., the secondary hydroxyl group generated by the reaction between the epoxy group and the secondary amine in the polymer remains. Since it may react with an epoxy group and gelatinize, it is not preferable. Although reaction time is not specifically limited, Usually, it is 1 to 10 hours.

When the copolymer has a radical polymerizable double bond, for example, after obtaining a polymer having an epoxy group in the side chain as described above, a modified polymer is introduced by introducing a pendant double bond. Can be obtained. As a solvent that can be used in the reaction for introducing such a pendant double bond, when the polymer is obtained by solution polymerization, the solvent may be used as it is. When a polymer is obtained by precipitation polymerization, suspension polymerization, or emulsion polymerization, the polymer may be taken out by filtration, washing, and drying by a usual method, and the reaction may be performed by dissolving in a solvent in which the polymer is dissolved. Usable solvents are the same as those usable for the solution polymerization. Moreover, the polyfunctional monomer which is an essential component of the hardening composition of this invention, and the monofunctional monomer which can be used as a structural component can also be used as a solvent.
The amount used of the compound having a double bond and a group that reacts with an epoxy group used for the introduction of the double bond may be an amount necessary for expressing the desired physical properties. For example, in the polymer It is preferable to use 10-100 mol% with respect to the epoxy group.

In the double bond introduction reaction, the catalyst may not be used because a tertiary amino group in the polymer can be a reaction catalyst for an epoxy group and a carboxyl group, but can also be used if necessary. For example, as a catalyst that can be used in the reaction between an epoxy group and a carboxyl group, a catalyst that can be used in esterification can be used, and phosphines such as triphenylphosphine and tris (perfluorophenyl) phosphine; Phosphonium salts such as butylphosphonium bromide, tetraphenylphosphonium bromide, tri-n-butylbenzylphosphonium chloride; ammonium salts such as tetra-n-butylammonium bromide, triethylbenzylammonium chloride; triethylamine, tributylamine, N, N-dimethyl Amines such as aniline, pyridine and N-methylimidazole can be used.

In the double bond introduction reaction, a polymerization inhibitor can be used so that the compound used for introducing the pendant double bond does not polymerize. Examples of the polymerization inhibitor include quinone polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, Alkylphenol polymerization inhibitors such as 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine; Amine polymerization inhibitors such as N, N'-diphenyl-p-phenylenediamine and phenothiazine; N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; dimethyldithiocarbamic acid Copper, copper diethyldithiocarbamate, di Copper dithiocarbamate-based polymerization inhibitors such as chill copper dithiocarbamate and the like. Among these, quinone-based and N-oxyl polymerization inhibitors are preferable, and benzoquinone, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and the like are preferably used.

The reaction temperature for the double bond introduction reaction is not particularly limited, but is usually 50 to 150 ° C, and preferably 70 to 120 ° C. If the reaction temperature is lower than 50 ° C, the reaction time becomes too long or the catalyst may be deactivated during the reaction, which is not preferable. If the reaction temperature is higher than 150 ° C, polymerization of the compound used for introducing the double bond is not preferable. Since side reactions such as the progress of the reaction may occur, it is not preferable. Although reaction time is not specifically limited, Usually, it is 3 to 20 hours.

The curable composition of the present invention can be used for various applications such as inks, coating materials, paints, and adhesives. In particular, it is a material that has good adhesion to untreated polyethylene terephthalate (PET), polycarbonate (PC), etc. and has heat and / or ultraviolet (UV) curability, such as credit cards and prepaid cards. It is useful for.
In the various uses described above, a colorant can be blended in the curable composition of the present invention. Thus, the hardening composition which mix | blended the coloring agent is one of preferable embodiment of this invention. As the colorant, dyes and pigments are suitable, and one or more of each can be used. Moreover, you may use together a dye and a pigment.

As the dye, various dyes such as a direct dye, an acid dye, a reactive dye, and an oil-soluble dye can be used, and among these, an oil-soluble dye is particularly preferable.
Examples of the pigment include inorganic pigments and organic pigments. Examples of the inorganic pigments include oxides such as zinc white, titanium dioxide, bengara, cobalt blue, and iron black; hydroxides such as alumina white and yellow iron oxide; Sulfides and selenides such as zinc and vermilion; Ferrocyanides such as bitumen; Chromates such as zinc chromate and molybdenum red; Sulfates such as precipitated barium sulfate; Carbonates such as precipitated calcium carbonate; Hydrous silicic acid Suitable examples include silicates such as salts and ultramarine blue; phosphates such as manganese violet; metal powders such as aluminum powder (paste), bronze powder and zinc powder; and carbon black.

Examples of the organic pigment include nitroso pigments such as naphthol green; nitro pigments such as naphthol yellow S; azo lake pigments such as risol red, lake red C, watching red, brilliant carmine 6B, and bordeaux 10B, fast yellow, disazo yellow, and pyrazolone orange. , Insoluble azo pigments such as Lake Red 4R and Naphthol Red, azo pigments such as condensed azo pigments such as chromophthale yellow and chromophthale red; acid dye lakes such as peacock blue lake and alkali blue lake, rhodamine lake, methyl violet Dye rake pigments such as lakes, malachite green lakes and other basic dye lakes; phthalocyanine pigments such as phthalocyanine blue, first sky blue, phthalocyanine green; anthrapyrimidine -Condensation of selenium pigments such as perinone orange, perylene red, thioindigo red and indanthrone blue, quinacridone pigments such as quinacridone red and quinacridone violet, dioxazine pigments such as dioxazine violet, and isoindolinones such as isoindolinone yellow Polycyclic pigments; dye resin solid solutions such as daylight fluorescent pigments are suitable.

As content of the said coloring agent, when a hardening composition is 100 mass%, it is preferable that they are 0.01 mass% or more and 40 mass% or less. More preferably, they are 0.05 mass% or more and 35 mass% or less, More preferably, they are 0.1 mass% or more and 30 mass% or less.

The curable composition of the present invention preferably comprises a polymerization initiator. As a polymerization initiator, a radical photopolymerization initiator, a thermal polymerization initiator, etc. are suitable, and these can use 1 type (s) or 2 or more types.
As the thermal polymerization initiator, it is preferable to use the same polymerization initiator as that preferably used when the above-mentioned copolymer is produced.

As the radical photopolymerization initiator, the following compounds are suitable.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1 Acetophenones such as [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl Methyl perfume, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Benzophenones such as 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl- 9H-thioxanthone-9 Thioxanthones such as Onmesokurorido. Among these, acetophenones, benzophenones, and acyl phosphine oxides are preferable. Particularly 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one.

As content of the said polymerization initiator, when a hardening composition is 100 mass%, it is preferable that it is 0.01 mass% or more, and it is preferable that it is 30 mass% or less. More preferably, it is 0.05 mass% or more, and is 20 mass% or less. More preferably, it is 0.1 mass% or more and 10 mass% or less.

When the curable composition of the present invention is cured by light irradiation, light (particularly, ultraviolet light) is absorbed or concealed by dyes, pigments, or the like when irradiated with light (particularly ultraviolet light). A sensitizer can also be used for the purpose of preventing a decrease in the curing rate due to.
Examples of the sensitizer include aliphatic amines, amines having aromatic groups, cyclic amine compounds such as piperidine, urea compounds such as O-tolylthiourea, soluble salts of sodium cythyl thiophosphate or aromatic sulfinic acid, etc. Sulfur compounds, nitrile compounds such as N, N'-disubstituted-p-aminobenzonitrile, phosphorus compounds such as tri-n-butylphosphine or sodium diethyldithiophosphate, Michler's ketone, N-nitrosohydroxylamine derivatives, oxazolidine compounds, A nitrogen compound such as a tetrahydro-1,3-oxazine compound, formaldehyde or a condensate of acetaldehyde and a diamine, and the like are preferable. These can use 1 type (s) or 2 or more types.

The curable composition of the present invention may also contain a curable resin. The curable resin refers to a macromonomer or prepolymer having a curable polymerizable group, which is cured by heat and / or active energy rays such as ultraviolet rays, electron beams, and gamma rays. As such a curable resin, a macromonomer or a prepolymer having a radical polymerizable group can be used.
The number average molecular weight of the curable resin is preferably 300 or more, more preferably 1000000 or less. If it is less than 300, the dispersion stabilizer such as a pigment may be lowered, and if it exceeds 1000000, the viscosity of the curable composition may be increased. More preferably, it is 500,000 or less, More preferably, it is 100,000 or less, Especially preferably, it is 50000 or less.

Examples of the macromonomer or prepolymer having a radical polymerizable group include saturated or unsaturated polybasic acids or anhydrides thereof (for example, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydro Phthalic acid and the like) and saturated or unsaturated polyhydric alcohols (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol) , Polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and (meth) acrylic acid to obtain polyester (meth) acrylate; saturated or unsaturated polyhydric alcohol ( For example, ethylene glycol , Neopentyl glycol, polytetramethylene glycol, polyester polyol, polycaprolactone polyol, etc.) and organic polyisocyanates (eg, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) and hydroxyl group-containing (meth) acrylates (eg, 2- Urethane poly (meth) acrylate obtained by reaction with hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc .; polysiloxane and (meth) acrylic acid Polysiloxane poly (meth) acrylate obtained by reaction with amide; Polyamide poly (meth) acrylate obtained by reaction of polyamide with (meth) acrylic acid; Vinyl ether (Meth) acryloyl group pendant polymer obtained by reaction of containing (meth) acrylic acid esters and the like with a cationic polymerizable compound (for example, vinyl ethers, alkylene oxides, glycidyl ethers, etc.); bisphenol A type epoxy resin, bisphenol Epoxy (meth) acrylate obtained by reaction of epoxy resin such as F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and (meth) acrylic acid, and , Hydroxyl groups of these epoxy (meth) acrylates and saturated or unsaturated polybasic acids or anhydrides thereof (eg, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid) An acid-modified epoxy (meth) acrylate obtained by reaction with (such as taric acid) is preferred.

As content of the said curable resin, when a hardening composition is 100 mass%, 0.1 mass% or more is preferable and 90 mass% or less is preferable. More preferably, it is 1 mass% or more and 80 mass% or less.

The curable composition of the present invention may further contain a monofunctional monomer. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol Monofunctional (meth) acrylates such as (meth) acrylate, methoxydipropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate Monofunctional (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide Monofunctional N-vinyl compounds such as the above can be used, and any of them can be suitably used. However, it is preferable to use a monofunctional monomer having a low primary skin irritation for the reasons described above. Monofunctional monomers with low primary skin irritation include phenoxy polyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethoxydipropylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene Monofunctional (meth) acrylates such as glycol (meth) acrylate and phenoxyethyl (meth) acrylate can be mentioned, and any of them can be suitably used.

As content of the said monofunctional monomer, when a hardening composition shall be 100 mass%, 0.1 mass% or more is preferable and 80 mass% or less is preferable. More preferably, it is 1% by mass or more and 70% by mass or less.

The curable composition of the present invention may further contain one or more additives other than the above-described constituent elements, for example, a diluent solvent, a binder, a filler, a pigment dispersant, a conductivity imparting agent, Ultraviolet absorbers, antioxidants, drying inhibitors, penetrants, pH adjusters, metal sequestering agents, antibacterial and fungicides, surfactants, plasticizers, waxes, leveling agents, surface conditioners, and the like are suitable.

Examples of the dilution solvent include mineral spirits, petroleum naphtha S-100, petroleum naphtha S-150, hydrocarbons such as toluene, xylene, tetralin, and turpentine oil; esters such as n-butyl acetate and methoxybutyl acetate; methyl isobutyl ketone ( MIBK), alcohols such as diacetone alcohol, cyclohexanone, isophorone; alcohols such as isopropyl alcohol (IPA) and n-butanol; polyhydric alcohol derivatives such as methyl cellosolve: ethyl cellosolve: butyl cellosolve: cellosolve acetate: butyl cellosolve acetate: butyl carbitol Etc. are suitable.
As the usage-amount of the said dilution solvent, 50 mass% or less is preferable with respect to 100 mass% of curable compositions. More preferably, it is 30 mass% or less.

As the binder, vinyl chloride / vinyl acetate copolymer resin, acrylic resin, polyester resin, polyurethane resin, epoxy resin, phenoxy resin, alkyd resin, cyclized rubber, chlorinated polyolefin resin, aqueous resin and the like are suitable.
As the usage-amount of the said binder, 30 mass% or less is preferable with respect to 100 mass% of curable compositions. More preferably, they are 0.5 mass% or more and 20 mass% or less, More preferably, they are 1 mass% or more and 10 mass% or less.

As the filler, glass frit, silica fine particles, organic fine particles, metal fine particles and the like are suitable.
As a usage-amount of the said filler, 30 mass% or less is preferable with respect to 100 mass% of curable compositions. More preferably, they are 2 mass% or more and 20 mass% or less, More preferably, they are 5 mass% or more and 10 mass% or less.

Examples of the pigment dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyacrylic acid, hydroxyl group-containing carboxylic acid ester, salt of long chain polyaminoamide and high molecular weight acid ester, salt of high molecular weight polycarboxylic acid, and long chain polyaminoamide. And polar acid ester salt, high molecular weight unsaturated acid ester, high molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensation Physical salts, polyoxyethylene alkyl phosphate esters, polyoxyethylene nonylphenyl ether, stearylamine acetate, pigment derivatives and the like are suitable.
The amount of the pigment dispersant used is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the pigment. More preferably, it is 20 parts by weight or more and 100 parts by weight or less.

The conductivity imparting agent may be any salt that is soluble in the curable composition, and alkali metal, alkaline earth metal halides, nitrates, and thiocyanates are used. Among these, lithium nitrate, lithium trioxide nitrate, ammonium thiocyanate, dimethylamine hydrochloride and the like are preferable.
As the usage-amount of the said electroconductivity imparting agent, 10 mass% or less is preferable with respect to 100 mass% of curable compositions. More preferably, it is 0.05 mass% or more and 5 mass% or less. More preferably, it is 0.5 mass% or more and 3 mass% or less.

As the ultraviolet absorber, for example, the following compounds are suitable.
2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5 ' -Methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl 5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di -T-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'hydroxy-4'-n-octoxy-phenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octyl-phenyl) Benzotriazole, 2- {2'-hydroxy-3,5-di (1,1-dimethylbenzyl) phenyl} -2H-benzotriazole, 2- ( ', 5'-di-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-5'-methyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-4'- Benzotriazole compounds such as dihydroxyphenyl) benzotriazole.

2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2- Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-xanthenecarboxy- Benzophenones such as 4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, 2-hydroxy-4-benzoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Salicylates such as phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate; N- (2-ethoxyphenyl) -N '-(4-isododecylphenyl) ethanediamide, N- (2-ethoxyphenyl) Oxalic anilide derivatives such as —N ′-(2-ethyl) ethanediamide; 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2, Triazine derivatives such as 4-dimethylphenyl) -1,3,5-triazine; 2-cyano-3,3′-diphenylacrylic acid Octyl, ethyl 2-cyano-3,3′-diphenylacrylate, 2-cyano-3-phenyl-3- (3,4-dimethylphenyl) acrylic acid- (2-ethylhexyl), 2-cyano-3- ( Contains an unsaturated nitrile group such as p-methoxyphenyl) -3- (3,4-dimethylphenyl) acrylic acid- (2-ethylhexyl), p-methoxy-α- (3,4-xylyl) benzylidenemalononitrile UV absorber.

Among these, as the ultraviolet absorber, triazine compounds, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-) are preferable because they are difficult to inhibit ultraviolet curing. Preference is given to using nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone.
The amount of the ultraviolet absorber used is 0.0001% by mass or more and preferably 10% by mass or less with respect to 100% by mass of the curable composition. More preferably, it is 0.001 mass% or more and 5 mass% or less.

As the antioxidant, for example, the following compounds are suitable.
4,4'-methylenebis (2,6-t-butylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) propane, 2,2'-ethylidenebis -(4,6, -di-t-butylphenol), triethylene glycol bis-3- (t-butyl-4-hydroxy-5-methylphenyl) propionate, 3- (3 ', 5'-di-t- Butyl-4'-hydroxyphenyl) octadecylpropionate, 2,2'-methylenebis- (4-ethyl-6-t-butylphenol, pentaerythrityl-tetrakis- {3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate}, 2,6-di-t-butyl-4-methylphenol, 6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenylacrylate-t-butyl, 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), tetrakis- {methylene-3- (3 ', 5'-di-t-butyl) -4'-hydroxyphenyl) propionate} methane, NN'-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 1,6-hexanediol bis-3- ( 3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 2,2'-thiodiethylbis- {3- (3', 5'-t-butyl-4-hydroxyphenyl) Le) propionate}, 4,4'-thiobis (3-methyl -6-t-butylphenol) hindered phenolic compounds such as.

Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1- [2- {3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6 6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspin [4,5] undecane-2,4-dione, 4-benzoyloxy- Hindered amine compounds such as 2,2,6,6-tetramethylpiperidine; dilauryl dithiopropionate, distearyl thiodipropionate, pentaerythritol-tetrakis- (3 Lauryl thiopropionate), di-myristyl thiodipropionate, organic sulfur compounds such as di-tridecyl thiopropionate; 3,5-di-t-butyl-4-hydroxybenzyl phosphate diethyl ester, 3 , 5-Di-t-butyl-4-hydroxybenzyl phosphate dioctadecyl ester and the like are preferable. Among these, hindered amine compounds and hindered phenol compounds are particularly preferred from the viewpoint of improving durability.
As the usage-amount of the said antioxidant, 0.0001 mass% or more and 10 mass% or less are preferable with respect to 100 mass% of curable compositions. More preferably, it is 0.001 mass% or more and 5 mass% or less.

As the anti-drying agent, glycerin, polyglycerin, glycol and the like are suitable. As the penetrant, alcohol, glycol ether and the like are preferable. The amount of the drying inhibitor and penetrant used is preferably 0.05% by mass or more and 20% by mass or less with respect to 100% by mass of the curable composition. More preferably, it is 0.5 mass% or more and 10 mass% or less.

The curing composition of the present invention can be used in the form of a mixture (syrup state) in which a copolymer and a polyfunctional monomer are blended, or in a solution state in which these are dissolved in an appropriate solvent. Can be used. When using in a syrup state, the copolymer is prepared in a solvent, and after adding a predetermined amount of a polyfunctional monomer to the resulting copolymer solution, the solvent is distilled off for curing. The composition may be prepared, or the copolymer is poured into a poor solvent to precipitate, filtered and dried by a usual method, the copolymer is taken out, and a predetermined amount of a polyfunctional monomer is added thereto. A curable composition may be prepared. When using in a solution state, after applying the curable composition to the article to be coated, it is dried and then the solvent is distilled off, followed by curing.
The curable composition of the present invention can be obtained by mixing or the like so as to include the above-described essential components and, if necessary, other components. As a mixing method, a normal disperser such as a three-roll or bead mill can be used.

The curable composition of the present invention has excellent pigment dispersibility and excellent properties after curing such as flexibility, adhesion, flexibility, solvent resistance, and high toughness. It is suitable for various uses such as paints and adhesives, especially for inks. In this case, it is used as an ink composition for curing active energy rays, and is used for letterpress printing, gravure printing, offset printing, screen printing, inkjet printing. It can be suitably applied to various printing methods such as printing.

The curable composition of the present invention is applied to a substrate as a coating film, printed as ink, and cured by heat treatment and / or light irradiation. Preferably, it is light irradiation.
As said base material, plastics, such as PET and PC, a plastic film, a metal, a ceramic, glass, paper, wood, etc. are suitable. As a plastic material, the present invention exerts a remarkable effect on polyester and polyamide.
In the case of curing by the heat treatment, the processing temperature is preferably 50 to 200 ° C. More preferably, it is 60-180 degreeC, More preferably, it is 70-160 degreeC.

In the case of curing by the light irradiation, it is preferable to irradiate active energy rays such as electromagnetic waves, ultraviolet rays (UV), visible rays, infrared rays, electron beams, gamma rays and the like. Among these, ultraviolet rays and electron beams are preferable.
In the case of curing by irradiation with ultraviolet rays, it is preferable to use a light source including light having a wavelength of 150 to 450 nm. As such a light source, a solar ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like is preferable. Together with these light sources, it is possible to use heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

In the curing by irradiation with the electron beam, the acceleration voltage of the electron beam is preferably 10 kV or more, and preferably 500 kV or less. More preferably, it is 20 kV or more and 300 kV or less. More preferably, it is 30 kV or more and 200 kV or less. Further, the irradiation amount is preferably 2 kGy or more, and preferably 500 kGy or less. More preferably, it is 3 kGy or more and 300 kGy or less. More preferably, it is 5 kGy or more and 200 kGy or less. In addition to the electron beam, it is possible to use heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

The curable composition of the present invention has the above-described configuration, has excellent adhesion to various substrates such as metal, glass and plastic, and has a cured coating film surface that is tack-free, flexible, and solvent resistant. Therefore, it is useful as an ink used in various applications such as inks, coating materials, paints, and adhesives, particularly in various printing systems.

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

Hereinafter, the radical-polymerized copolymer is referred to as polymer (I), and the copolymer into which pendant double bonds are introduced is referred to as modified polymer (II). In addition, a polymer obtained by reacting a secondary amine with an epoxy group-containing copolymer to introduce a tertiary amino group is referred to as a polymer (I).
The weight average molecular weight (Mw) of the obtained polymer (I) was measured by gel permeation chromatography (GPC), and the conversion rate of each monomer component after polymerization was determined by liquid chromatography (LC). Calculated using standard methods.
Moreover, the conversion rate of the component used in order to introduce | transduce a pendant double bond into polymer (I) was computed using the internal standard method by the liquid chromatography (LC).
The weight average molecular weight (Mw) of the obtained modified polymer (II) was measured by gel permeation chromatography (GPC), and the acid value (mgKOH / g) was measured using a usual potentiometric titration method.
Further, when the epoxy group in the polymer was modified with a secondary amine, the secondary amine was quantified by gas chromatography (GC).

<GPC measurement method and measurement conditions>
The obtained polymer (I) or the obtained modified polymer (II) was dissolved in an eluent so that the solid concentration was about 0.5% by mass, and then measured under the following measurement conditions.
(Measurement condition)
Column: TSKgel SuperH2000, TSKgel SuperHM-M, and TSKgel Super2000 each connected in series (all manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran eluent flow rate: 0.6 ml / min The weight average molecular weight was calculated from a calibration curve prepared with Tosoh standard polystyrene.

<LC measurement method and measurement conditions>
In a 100 ml volumetric flask, about 0.5 g (weigh accurately) of the obtained polymer (I) or modified polymer (II) solution and about 30 mg of N, N-dimethylformamide used as an internal standard ( The sample was diluted to 100 ml with an eluent and then measured under the following measurement conditions.
(Measurement condition)
Column: TSK-gel ODS-80Ts (25 cm)
Eluent: 0.05 mass% ammonium dihydrogen phosphate aqueous solution / acetonitrile = 50/50 (mass ratio)
Eluent flow rate: 0.5 ml / min Detection wavelength: 210 nm

<GC measurement method and measurement conditions>
After adding about 20 mg of methylcyclohexane (exactly weigh) used as an internal standard to about 0.5 g (exactly weigh) of the obtained reaction solution, add about 3 g of N, N-dimethylformamide used as a diluent. Then, a uniform solution was obtained and measured under the following measurement conditions.
(Measuring method)
Column: SPB-130m (supplico)
Temperature condition: 60 ° C. * 3 minutes hold → Temperature rise at 20 ° C./minute→240° C. * 8 minutes hold Carrier: Helium gas Carrier pressure: 0.5 kg / cm ²

Synthesis example 1
<Synthesis of polymer (I-1)>
(Copolymerization reaction)
A container equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube and a dropping funnel is charged with 30 parts of N-vinylpyrrolidone and 100 parts of 2-butanol as a solvent until the internal temperature reaches 95 ° C. while stirring. Heated. Thereafter, the inside of the container was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared, and 43.5 parts of 2-ethylhexyl acrylate and 24 parts of glycidyl methacrylate were charged into one dropping funnel (mixed liquid 1), and then the inside of the dropping funnel was filled with nitrogen gas for 3 minutes. Replaced. In another dropping funnel, 0.98 part of t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) as a polymerization initiator and 20 parts of 2-butanol as a solvent are charged. Thereafter (mixed solution 2), the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.
After the replacement of the nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at around 95 ° C., and the liquid mixtures 1 and 2 were added dropwise over 2.5 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued so that the internal temperature became 97 to 100 ° C., and the reaction was further aged at this temperature for 3 hours to obtain a colorless and transparent uniform solution.
After the ripening, the conversion rate of each monomer was calculated. The conversion rate of N-vinylpyrrolidone was 100%, the conversion rate of 2-ethylhexyl acrylate was 100%, and the conversion rate of glycidyl methacrylate was 100%. From this result, the composition of the obtained copolymer was N-vinylpyrrolidone / 2-ethylhexyl acrylate / glycidyl methacrylate = 40/35/25 (molar ratio).

(Reaction of epoxy group with secondary amine)
10.65 parts of diethanolamine was added to the reaction solution, and the reaction was performed for 2 hours while heating and stirring so that the internal temperature became 60 ° C. The conversion of diethanolamine was calculated to be 100%. From this result, the composition of the polymer (I-1) obtained was N-vinylpyrrolidone / 2-ethylhexyl acrylate / glycidyl methacrylate / diethanolamine adduct of glycidyl methacrylate = 40/35/10/15 (molar ratio). became. At this time, the polymer (I-1) had a weight average molecular weight of 5,800.
Finally, 50 parts of the obtained polymer (I-1) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid polymer (I-1). It was.

<Synthesis of Modified Polymer (II-1)>
In a container equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts of the polymer (I-1) solution, 1.5 parts of acrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.033 part of hydroxypiperidine-1-oxyl was added and reacted for 6 hours at a temperature (100 ° C) at which 2-butanol was refluxed with stirring to obtain a light brown transparent uniform solution.
After the reaction was completed, the conversion rate of acrylic acid was 100%. Moreover, although the acid value (mgKOH / g) of the obtained modified polymer (II-1) was measured by potentiometric titration, no inflection point was observed, and acrylic acid was an epoxy in the polymer (I-1). It was found to have reacted with the group. Moreover, the double bond equivalent (g / eq) of modified polymer (II-1) was 2450, and the weight average molecular weight (Mw) was 6200.
Finally, the obtained modified polymer (II-1) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid modified polymer (II-1). It was.

Synthesis example 2
<Synthesis of polymer (I-2)>
(Copolymerization reaction)
A container equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube and a dropping funnel is charged with 30 parts of N-vinylpyrrolidone and 100 parts of 2-butanol as a solvent until the internal temperature reaches 95 ° C. while stirring. Heated. Thereafter, the inside of the container was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared, and 43.5 parts of 2-ethylhexyl acrylate and 24 parts of glycidyl methacrylate were charged into one dropping funnel (mixed liquid 1), and then the inside of the dropping funnel was filled with nitrogen gas for 3 minutes. Replaced. In another dropping funnel, 0.98 part of t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) as a polymerization initiator and 20 parts of 2-butanol as a solvent are charged. Thereafter (mixed solution 2), the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.
After the replacement of the nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at around 95 ° C., and the liquid mixtures 1 and 2 were added dropwise over 2.5 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued so that the internal temperature became 97 to 100 ° C., and the reaction was further aged at this temperature for 3 hours to obtain a colorless and transparent uniform solution.
After the ripening, the conversion rate of each monomer was calculated. The conversion rate of N-vinylpyrrolidone was 100%, the conversion rate of 2-ethylhexyl acrylate was 100%, and the conversion rate of glycidyl methacrylate was 100%. From this result, the composition of the obtained copolymer was N-vinylpyrrolidone / 2-ethylhexyl acrylate / glycidyl methacrylate = 40/35/25 (molar ratio).

(Reaction of epoxy group with secondary amine)
7.4 parts of diethylamine was added to the reaction solution, and the reaction was performed for 3 hours while heating and stirring so that the internal temperature became 50 ° C. The conversion rate of diethylamine was calculated to be 100%. From this result, the composition of the obtained polymer (I-2) was N-vinylpyrrolidone / 2-ethylhexyl acrylate / glycidyl methacrylate / diethylamine adduct of glycidyl methacrylate = 40/35/10/15 (molar ratio). became. At this time, the polymer (I-2) had a weight average molecular weight of 5,400.
Finally, 50 parts of the obtained polymer (I-2) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid polymer (I-2). It was.

<Synthesis of Modified Polymer (II-2)>
In a container equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts of the polymer (I-2) solution, 1.5 parts of acrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.033 part of hydroxypiperidine-1-oxyl was added and reacted for 6 hours at a temperature (100 ° C) at which 2-butanol was refluxed with stirring to obtain a light brown transparent uniform solution.
After the reaction was completed, the conversion rate of acrylic acid was 100%. Further, the acid value (mgKOH / g) of the obtained modified polymer (II-2) was measured by potentiometric titration, but no inflection point was observed, and acrylic acid was an epoxy in the polymer (I-2). It was found to have reacted with the group. Moreover, the double bond equivalent (g / eq) of modified polymer (II-2) was 2390, and the weight average molecular weight (Mw) was 5900.
Finally, the obtained modified polymer (II-2) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid modified polymer (II-2). It was.

Synthesis example 3
<Synthesis of polymer (I-3)>
(Copolymerization reaction)
A container equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube and a dropping funnel is charged with 30 parts of N-vinylpyrrolidone and 100 parts of 2-butanol as a solvent until the internal temperature reaches 95 ° C. while stirring. Heated. Thereafter, the inside of the container was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared, and after charging 37.3 parts of 2-ethylhexyl acrylate, 8.7 parts of n-butyl acrylate, and 19.2 parts of glycidyl methacrylate in one dropping funnel (mixed liquid 1 and The inside of the dropping funnel was replaced with nitrogen gas for 3 minutes. In another dropping funnel, 0.95 part of t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, product name: Perbutyl O) as a polymerization initiator and 10 parts of 2-butanol as a solvent are charged. Thereafter (mixed solution 2), the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.
After the replacement of the nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at around 95 ° C., and the liquid mixtures 1 and 2 were added dropwise over 2.5 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued so that the internal temperature became 97 to 100 ° C., and the reaction was further aged at this temperature for 3 hours to obtain a colorless and transparent uniform solution.
After the ripening, the conversion rate of each monomer was calculated. The conversion rate of N-vinylpyrrolidone was 100%, the conversion rate of 2-ethylhexyl acrylate was 100%, the conversion rate of n-butyl acrylate was 100%, and the glycidyl methacrylate The conversion rate was 100%. From this result, the composition of the obtained copolymer was N-vinylpyrrolidone / 2-ethylhexyl acrylate / n-butyl acrylate / glycidyl methacrylate = 40/30/10/20 (molar ratio).

(Reaction of epoxy group with secondary amine)
7.1 parts of diethanolamine was added to the reaction solution, and the reaction was performed for 2 hours while heating and stirring so that the internal temperature became 60 ° C. The conversion of diethanolamine was calculated to be 100%. From this result, the composition of the obtained polymer (I-3) was N-vinylpyrrolidone / 2-ethylhexyl acrylate / n-butyl acrylate / glycidyl methacrylate / diethanolamine adduct of glycidyl methacrylate = 40/30/10/10. / 10 (molar ratio). The weight average molecular weight of the polymer (I-3) at this time was 5900.
Finally, 50 parts of the obtained polymer (I-3) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid polymer (I-3). It was.

<Synthesis of Modified Polymer (II-3)>
In a container equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts of the polymer (I-3) solution, 1.5 parts of acrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.033 part of hydroxypiperidine-1-oxyl was added and reacted for 6 hours at a temperature (100 ° C) at which 2-butanol was refluxed with stirring to obtain a light brown transparent uniform solution.
After the reaction was completed, the conversion rate of acrylic acid was 100%. Moreover, although the acid value (mgKOH / g) of the obtained modified polymer (II-3) was measured by potentiometric titration, no inflection point was observed, and acrylic acid was an epoxy in the polymer (I-3). It was found to have reacted with the group. Moreover, the double bond equivalent (g / eq) of modified polymer (II-3) was 2367, and the weight average molecular weight (Mw) was 6300.
Finally, the obtained modified polymer (II-3) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid modified polymer (II-3). It was.

Synthesis example 4
<Synthesis of polymer (I-4)>
A container equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel was charged with 30 parts of N-vinylpyrrolidone and 100 parts of toluene as a solvent, and heated while stirring until the internal temperature reached 95 ° C. . Thereafter, the inside of the container was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared. In one dropping funnel, 43.5 parts of 2-ethylhexyl acrylate, 4.3 parts of n-butyl acrylate, 9.6 parts of glycidyl methacrylate, N, N-dimethylaminoethyl acrylate After charging 9.7 parts (mixed liquid 1), the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes. Further, after charging 0.97 part of t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) as a polymerization initiator and 10 parts of toluene as a solvent in another dropping funnel. (The mixture is 2), and the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.

After the replacement of the nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at around 95 ° C., and the liquid mixtures 1 and 2 were added dropwise over 2.5 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued so that the internal temperature became 97 to 100 ° C., and the reaction was further aged at this temperature for 3 hours to obtain a colorless and transparent uniform solution.
After the ripening, the conversion rate of each monomer was calculated. The conversion rate of N-vinylpyrrolidone was 100%, the conversion rate of 2-ethylhexyl acrylate was 100%, the conversion rate of n-butyl acrylate was 100%, and the glycidyl methacrylate The conversion rate was 100%, and the conversion rate of N, N-dimethylaminoethyl acrylate was 100%. From this result, the composition of the obtained polymer (I-4) was N-vinylpyrrolidone / 2-ethylhexyl acrylate / n-butyl acrylate / glycidyl methacrylate / N, N-dimethylaminoethyl acrylate = 40/35/5. / 10/10 (molar ratio). Moreover, the weight average molecular weight of the polymer (I-4) was 5200.
Finally, 50 parts of the obtained polymer (I-4) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid polymer (I-4). It was.

<Synthesis of Modified Polymer (II-4)>
In a container equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts of the polymer (I-4) solution, 1.6 parts of acrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.033 part of hydroxypiperidine-1-oxyl was charged, and the mixture was reacted for 6 hours while stirring and stirring so that the internal temperature was 100 to 105 ° C, to obtain a light brown transparent uniform solution.
After the reaction was completed, the conversion rate of acrylic acid was 100%. Further, the acid value (mgKOH / g) of the obtained modified polymer (II-4) was measured by potentiometric titration, but no inflection point was observed, and acrylic acid was an epoxy in the polymer (I-4). It was found to have reacted with the group. Moreover, the double bond equivalent (g / eq) of modified polymer (II-4) was 2187, and the weight average molecular weight (Mw) was 5500.
Finally, the obtained modified polymer (II-4) solution is poured into a large amount of n-hexane to precipitate, and the precipitate is sufficiently dried to obtain a solid modified polymer (II-4). It was.

Comparative Synthesis Example 1
<Synthesis of Comparative Polymer (III-1)>
A container equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube and a dropping funnel is charged with 30 parts of N-vinylpyrrolidone and 100 parts of 2-butanol as a solvent until the internal temperature reaches 95 ° C. while stirring. Heated. Thereafter, the inside of the container was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared, and after charging 62.1 parts of 2-ethylhexyl acrylate and 9.6 parts of glycidyl methacrylate into one dropping funnel (referred to as mixed solution 1), the inside of the dropping funnel was kept for 3 minutes. Nitrogen gas replacement was performed. In another dropping funnel, 0.6 part of t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perbutyl O) as a polymerization initiator and 15 parts of 2-butanol as a solvent are charged. Thereafter (mixed solution 2), the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.

After the replacement of the nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at around 95 ° C., and the liquid mixtures 1 and 2 were added dropwise over 2.5 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued so that the internal temperature became 97 to 100 ° C., and the reaction was further aged at this temperature for 3 hours to obtain a colorless and transparent uniform solution.
After the ripening, the conversion rate of each monomer was calculated. The conversion rate of N-vinylpyrrolidone was 99.9%, the conversion rate of 2-ethylhexyl acrylate was 99.8%, and the conversion rate of glycidyl methacrylate was 100%. It was. From this result, the composition of the obtained comparative polymer (III-1) was N-vinylpyrrolidone / 2-ethylhexyl acrylate / glycidyl methacrylate = 40/50/10 (molar ratio). Further, the weight average molecular weight of the comparative polymer (III-1) was 6800.
Finally, 50 parts of the obtained comparative polymer (III-1) solution was poured into a large amount of n-hexane to precipitate, the precipitate was sufficiently dried, and the solid comparative polymer (III- 1) was obtained.

<Synthesis of Modified Polymer for Comparison (IV-1)>
In a container equipped with a stirrer, a thermometer and a reflux condenser, 100 parts of the above comparative polymer (III-1) solution, 1.24 parts of acrylic acid, 2,2,6,6-tetramethyl as a polymerization inhibitor 0.033 parts of -4-hydroxypiperidine-1-oxyl was added and reacted for 6 hours at a temperature (100 ° C.) at which 2-butanol was refluxed with stirring to obtain a light brown transparent uniform solution.
After the reaction was completed, the conversion rate of acrylic acid was 100%. Further, the acid value (mgKOH / g) of the obtained comparative modified polymer (IV-1) was measured by potentiometric titration, but no inflection point was observed, and acrylic acid was used for the comparative polymer (III-1). ) Was found to have reacted with the epoxy group in The modified polymer for comparison (IV-1) had a double bond equivalent (g / eq) of 2242 and a weight average molecular weight (Mw) of 7,300.
Finally, the obtained comparative modified polymer (IV-1) solution was poured into a large amount of n-hexane to precipitate, the precipitate was sufficiently dried, and a solid comparative modified polymer (IV- 1) was obtained.

Examples 1-40 and Comparative Examples 1-10
Using the polymers, modified polymers, comparative polymers and comparative modified polymers obtained in the synthesis examples and comparative synthesis examples, a curable composition was prepared according to the formulation shown in Tables 1 to 3, and untreated A polyethylene terephthalate (thickness: 125 microns) substrate was coated with a bar coater to a thickness of 20 microns. Next, the coating film is cured by irradiating with an ultraviolet ray of 500 mJ / cm ² using an ultraviolet exposure device (250 mW ultra-high pressure mercury lamp, manufactured by Ushio Tech Co., Ltd.). Property) and solvent resistance were evaluated. The results are shown in Table 4.

[Finger touch test]
The surface of the coating was touched with a finger to evaluate the presence or absence of tack. The evaluation methods were as follows: ○ = tack free, Δ = slightly tacky, and x = tacky.
[Adhesion test]
Evaluation was performed according to JIS K 5600-5-6 (cross-cut method).
100 squares of 1 mm square were prepared, adhesive tape (Nichiban Co., Cello Tape (R) CT-15S) was applied to the coating surface, and the end of the tape was grasped at an angle of 60 ° with respect to the film surface. The adhesive tape was peeled off in 5 seconds, and the change in the coating surface was visually evaluated. The evaluation method was as follows: ◯ = no peeling, Δ = about half peeled, and X = most peeled.
[Bending test]
The film was bent at an angle of 90 ° so that the coating film surface became a mountain, and it was visually evaluated whether the coating film was peeled off from the film. The evaluation method was as follows: ○ = no peeling, Δ = partial peeling, and x = most peeling.
[Solvent resistance test]
The cloth was impregnated with ethanol and rubbed 100 times back and forth on the film. Then, the change of the coating film was visually evaluated. The evaluation method was as follows: ◯ = no change, Δ = partially peeled or swollen, and x = most peeled or swollen.

Examples 41-50 and Comparative Examples 11-20
Using the polymers, modified polymers, comparative polymers and comparative modified polymers obtained in the synthesis examples and comparative synthesis examples, curable compositions were prepared according to the blending compositions shown in Tables 1 and 3. It apply | coated so that the film thickness might be set to 20 microns using the bar-coater on the process polycarbonate (thickness 300 micron) base material. Next, the coating film was cured by irradiating with an ultraviolet ray of 500 mJ / cm ² using an ultraviolet exposure device (250 mW ultra-high pressure mercury lamp, manufactured by Ushio Tech Co., Ltd.), and tack-free, adhesive and tough ( Flexibility) and solvent resistance were evaluated. The results are shown in Table 5.

Examples 51-60 and Comparative Examples 21-30
Using the polymers, modified polymers, comparative polymers and comparative modified polymers obtained in the synthesis examples and comparative synthesis examples, curable compositions were prepared according to the blending compositions shown in Tables 1 and 3, and corona It apply | coated so that a film thickness might be set to 20 micrometers using the bar-coater on the process polypropylene (thickness 100 micron) base material. Next, the coating film was cured by irradiating with an ultraviolet ray of 500 mJ / cm ² using an ultraviolet exposure device (250 mW ultra-high pressure mercury lamp, manufactured by Ushio Tech Co., Ltd.), and tack-free, adhesive and tough ( Flexibility) and solvent resistance were evaluated. The results are shown in Table 6.

In Tables 1 to 3, “Irgacure 907” and “Irgacure 819” are photopolymerization initiators manufactured by Ciba Specialty Chemicals.

Claims (3)

A curing composition comprising a copolymer having an amide group-containing monomer unit and an amino group-containing monomer unit as essential constituent units and a polyfunctional monomer as essential components. The composition for curing according to claim 1, wherein the amino group-containing monomer unit has a portion containing an amino group formed by a reaction between an epoxy group and a secondary amine. The curable composition according to claim 1 or 2, wherein the copolymer has an alkyl group-containing monomer unit having 4 to 12 carbon atoms.