JP2005139405A - Curing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curing composition having adhesiveness to plastic materials and the like such as untreated PET and PC, flexibility, solvent resistance, and tack-free property. <P>SOLUTION: The curing composition has, as essential components, a copolymer composed of monomeric components wherein a (meth)acrylamide-based monomer and/or a polymeric monomer having (meth)acryloyl and amide groups within the same molecule is essential, and a multifunctional monomer. <P>COPYRIGHT: (C)2005,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 as a coating material or printing ink for a plastic material such as polyethylene terephthalate (PET) or 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 can be applied as an ink composition for printing on a plastic material or the like when it has good curing characteristics and the like, and can be used as an untreated polyethylene terephthalate (PET) or polycarbonate (PC ), And a material having thermosetting property and ultraviolet (UV) curable property.

At present, for example, PET 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.

Examples of conventional curing compositions include those described in the following prior art documents.
With regard to a binder for ink or paint, a binder mainly containing an acrylic copolymer obtained by copolymerizing a monomer mixture containing a specific amount of a nitrogen-containing monomer having radical polymerizability is disclosed. (For example, refer to Patent Document 1). About such a binder, it has a pigment dispersibility and compatibility with urethane resin, and if there is little compounding quantity of the nitrogen-containing monomer which has radical polymerizability, compatibility with urethane resin etc. will fall. It is disclosed. In the examples, it is described that a copolymer was obtained using N-methylolacrylamide, methyl methacrylate, butyl acrylate, hydroxypropyl acrylate and the like as monomer components. However, it is not described that the binder itself has curability.

Concerning the method of forming the coating film, the main component is a carboxylic acid amide copolymer which is a copolymer of α, β monoethylenically unsaturated carboxylic acid amide such as (meth) acrylamide and α, β unsaturated carboxylic acid hydroxyalkyl. It is disclosed that a solvent-based paint is used as a base paint (see, for example, Patent Document 2). About this solvent-based paint, it is possible to form a coating film by reacting a crosslinking agent such as carboxylic acid amide or melamine resin in a copolymer with a hydroxyalkyl carboxylate in the copolymer. It is disclosed that it is effective for painting. Furthermore, in the Examples, it is described that a carboxylic acid amide copolymer was obtained using acrylamide, methacrylic acid, 2-hydroxyethyl methacrylate, ethyl acrylate and methyl methacrylate as monomer components.

Concerning a composition for treating a metal ion-containing substrate surface, a polymer containing a highly polar, hydrophilic surface active group and a polymer composition containing a low-polarity, reactive group at the terminal position in a polymer composition in a solution. The use of a solvent is disclosed (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

There is disclosed a dry transfer product comprising a graphic pattern comprising an actinic radiation permeable carrier film and at least one layer of ink compatible with the carrier film and a continuous adhesive layer sensitive to actinic radiation (eg, (See Patent Document 4). In addition, an ethyl acetate solution of a mixed monomer of isooctyl acrylate, glycidyl methacrylate (GMA), and N-vinyl pyrrolidone (NVP) is applied onto a carrier film and pre-dried to form an adhesive layer. It is disclosed that after UV irradiation, the adhesive layer side is pressure-bonded to a steel plate and then the carrier film is peeled off, so that the UV-cured portion is stuck to the carrier film and peeled off. This means that the UV-cured portion (the portion of the NVP-containing polymer) is not attracted to the steel sheet but is attracted to the carrier film and peeled off. An example of the carrier film is PET. However, there is no description of specific results such as a cross-cut test for adhesion to the carrier film.

These conventional curing compositions are not suitable for untreated plastic materials such as polyethylene terephthalate (PET) and polycarbonate (PC), and improve basic performance such as adhesion and curability to these. There was room for ingenuity. Therefore, what can be used suitably as a coating agent, ink, etc. was calculated | required with respect to the use for which such a raw material is used, especially uses, such as a credit card and a prepaid card.
JP 2000-44861 A (page 2-3) JP 56-139183 A (page 1-4) JP-A-49-98878 (pages 1-3, 6, 7) JP 58-212981 (pages 1, 4, 8-11)

The present invention has been made in view of the above-described present situation, and has an adhesiveness to untreated PET, PC, and other plastic materials, and has a flexibility, a solvent resistance, and a tack-free property. The object is to provide a composition.

The inventors of the present invention have studied various curing compositions suitable for untreated plastic materials such as PET, and found that a curing composition formed using a copolymer and a polyfunctional monomer as essential components. It is possible to improve the curing characteristics and the like, and as the copolymer, a copolymer having no pendant double bond (hereinafter, also simply referred to as “polymer”) or a copolymer having a pendant double bond ( (Hereinafter also referred to as “modified polymer”), but it is found that the structural unit having a pendant double bond further imparts curability, and (meth) acrylamide monomers and (meth) When a polymerizable monomer having an acryloyl group and an amide group in the same molecule is an essential component, adhesion to a plastic material such as PET can be expressed. And has a formed product excellent curability, flexibility, solvent resistance, found that it is possible to improve the physical properties of the cured product of the tack-free property and the like, and conceived that can be admirably solved the above problems. In the prior art, there is no prior art that uses a curing composition formed of a polymer or modified polymer and a polyfunctional monomer as essential components for coating plastic materials such as PET and PC. In the invention, it is possible to satisfy performance requirements for coating (coating film) such as adhesion, flexibility, solvent resistance and tack-free property to plastic materials such as untreated PET. It has also been found that there is an advantageous effect over the prior art, and the present invention has been achieved.

That is, the present invention relates to a copolymer formed from a monomer component essentially comprising a (meth) acrylamide monomer and / or a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule. It is the composition for hardening which uses a coalescence and a polyfunctional monomer as an essential component.
The present invention is described in detail below.

The copolymer in the present invention includes at least one of a structural unit of a (meth) acrylamide monomer and a structural unit of a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule. Any structural unit may be used as long as it is essential, and the method for forming these structural units (monomer units) is not particularly limited. Usually, it is formed by polymerizing a monomer component essentially comprising a (meth) acrylamide monomer and / or a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule. become.
In the above copolymer, (A) a (meth) acrylamide monomer and / or a monomer component essentially comprising a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule. It has a structure to be formed, but in addition, (B) an epoxy group-containing radical polymerizable monomer and / or a carboxyl group-containing radical polymerizable monomer, and (C) other copolymerizable monomer You may have the structure formed by a body.

It is preferable that the copolymer has a 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 is a (A) (meth) acrylamide monomer and / or a monomer formed by a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule. A monomer unit and a polymerizable monomer unit having a radical polymerizable double bond in the side chain are included as essential constituent units.

In the double bond, the introduction method is not particularly limited. For example, (B) a monomer component containing an epoxy group-containing radical polymerizable monomer and / or a carboxyl group-containing radical polymerizable monomer is polymerized. After obtaining a polymer having an epoxy group and / or carboxyl functional group in the side chain, (D) by reacting a compound having a group that reacts with the functional group and a double bond, etc. It is preferable to introduce it, 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 compound (D) is preferably the same as the monomer (B). In this case, the epoxy group contained in the monomer unit formed by the (B1) epoxy group-containing radical polymerizable monomer is esterified by the carboxyl group of the (D1) carboxyl group-containing radical polymerizable monomer. (B2) The carboxyl group of the monomer unit formed by the carboxyl group-containing radical polymerizable monomer is esterified by (D2) the epoxy group-containing radical polymerizable monomer. .

In the copolymer, for example, when it is formed from a monomer component containing the monomer (A) and the monomer (C), the blending ratio of (A) and (C) is (A ) + (C) = 100 mol%, (A) is preferably 5 to 60 mol%. More preferably, it is 8-55 mol%, More preferably, it is 10-50 mol%. Moreover, (C) is preferably 40 to 95 mol%. More preferably, it is 45-92 mol%, More preferably, it is 50-90 mol%.
When the copolymer is formed from a monomer component containing, for example, the monomer (A), the monomer (B), and the monomer (C), (A) to ( As a blending ratio of C), when (A) + (B) + (C) = 100 mol%, (A) is preferably 5 to 60 mol%. More preferably, it is 8-55 mol%, More preferably, it is 10-50 mol%. (B) is preferably 5 to 50 mol%. More preferably, it is 8-45 mol%, More preferably, it is 10-40 mol%. (C) is preferably 5 to 80 mol%. More preferably, it is 8-75 mol%, More preferably, it is 10-70 mol%.
Further, in the modified polymer, for example, when a double bond is introduced by the method as described above, 10 to 100 mol% of the epoxy group and carboxyl group in the polymer is (D) containing a carboxyl group. It is preferably esterified with a radical polymerizable monomer and / or an epoxy group-containing radical polymerizable monomer.

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.

Examples of the (meth) acrylamide monomer in the monomer (A) include (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) N-alkyl (meth) acrylamides such as acrylamide; N, N-dialkyls such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide N-alkoxymethyl (meth) acrylamide such as (meth) acrylamide; N-methylol (meth) acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. Is preferred.
Examples of the polymerizable monomer having the (meth) acryloyl group and the amide group in the monomer (A) in the same molecule include N- (2- (meth) acryloyloxy) ethylpyrrolidone, N- A (meth) acrylate having an amide group such as (2- (meth) acryloyloxy) ethyl oxazolidone is suitable.

The epoxy group-containing radical polymerizable monomer in the monomer (B) may be any monomer having an epoxy group and a radical polymerizable group in the molecule. For example, glycidyl methacrylate, glycidyl acrylate, Allyl glycidyl ether, methallyl glycidyl ether, and the like are preferable. Of these, glycidyl methacrylate is preferred. In addition, 3,4-epoxycyclohexylmethyl methacrylate and its caprolactone modified product, which is an epoxy group-containing unsaturated compound having at least one alicyclic skeleton in the molecule, 3,4-epoxycyclohexylmethyl acrylate and its caprolactone modified product Compounds represented by the general formulas (1) to (13) are also preferable. In the following formulae, R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent aliphatic saturated hydrocarbon having 1 to 6 carbon atoms.

The carboxyl group-containing radical polymerizable monomer in the monomer (B) may be any monomer having a group capable of forming a carbanion and a radical polymerizable group in the molecule. Carboxylic acid and unsaturated dicarboxylic acid are preferred. As the unsaturated monocarboxylic acid, for example, (meth) acrylic acid, crotonic acid and the like are suitable, and as the unsaturated dicarboxylic acid, maleic acid, itaconic acid, citraconic acid, fumaric acid and the like are suitable. Among these, (meth) acrylic acid is preferable.

Examples of the other copolymerizable monomer (C) include α, β-unsaturated carboxylic acid esters; styrenes such as styrene, α-methylstyrene, and monochlorostyrene; α such as (meth) acrylonitrile; β-unsaturated nitrile monomers; vinyl acetate monomers such as vinyl acetate and vinyl butyrate are suitable.
The α, β-unsaturated carboxylic acid ester is a carboxyl group-containing radical polymerizable monomer as described above, which is an alkyl ester of a carboxylic acid in which a double bond is formed at the α-position and the β-position carbon atom. It is preferable that a copolymer that can impart sufficient flexibility and solvent resistance to the coating film can be obtained by containing such a monomer in the monomer component. . More preferably, the alkyl moiety is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group. An aliphatic alkyl group having 1 to 18 carbon atoms such as n-nonyl group, dodecyl group, stearyl group; phenyl group, benzyl group, 2-phenylethyl group, 4-ethylphenyl group, 4-nonylphenyl group, 4 An aromatic alkyl group having 6 to 24 carbon atoms such as dodecylphenyl group; methoxyethyl group, ethoxyethyl group, butoxyethyl group, 2- (2-methoxy) ethoxyethyl group, 2- (2-ethoxy) ethoxyethyl Group, 2- (2-butoxy) ethoxyethyl group, 2- (2-methoxy) propoxypropyl group, 2- (2-butoxy) propoxy group Are those wherein alkoxyalkyl group having 3 to 10 carbon atoms such as propyl group. Among these, an alkyl part is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group. (Meth) acrylic acid alkyl ester is more preferred. A part of hydrogen bonded to carbon forming these alkyl groups may be substituted with halogen such as chlorine, bromine and fluorine.

Preferred forms of the polymer include (i) (A) (meth) acrylamide monomer and / or polymerizable monomer having (meth) acryloyl group and amide group in the same molecule, (B1) A form formed from an epoxy group-containing radical polymerizable monomer and a monomer component essentially comprising (C) (meth) acrylic acid alkyl ester, (ii) (A) (meth) acrylamide monomer and / or Alternatively, a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule, (B2) a carboxyl group-containing radical polymerizable monomer and (C) a (meth) acrylic acid alkyl ester are essential. Examples thereof include a copolymer formed from a monomer component. Further, as a preferred form of the modified polymer, (iii) a part or all of the epoxy groups in the copolymer of (i) are esterified by reaction with (D1) a carboxyl group-containing radical polymerizable monomer. (Iv) a copolymer in which some or all of the carboxyl groups of the copolymer of (ii) are esterified by reaction with an epoxy group-containing radical polymerizable monomer (D2), etc. Is mentioned. By setting the polymer or modified polymer, which is a copolymer in the present invention, in such a form, the effects of the present invention can be sufficiently exhibited.

In the polymer or modified polymer, examples of the monomer unit obtained from the monomer (A) include monomer units represented by the following general formula (14) and general formula (15). be able to. Moreover, as a monomer unit which has a radically polymerizable double bond in the side chain in a modified polymer, the monomer unit represented by following General formula (16) can be mentioned, for example. In the following formula, R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxyl group, or the like. R ^{5 to} R ⁸ represent a hydrogen atom or a methyl group.

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 weight part, More preferably, it is 30 weight part. 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.

The modified polymer in the present invention can be obtained, for example, by introducing a pendant double bond after obtaining a polymer having an epoxy group and / or carboxyl group functional group in the side chain as described above. 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 of the compound (D) used for the introduction of the double bond may be an amount necessary for expressing the desired physical properties. For example, for the epoxy group or carboxyl group in the polymer, It is preferable to use 10 to 100 mol% of (D1) carboxyl group-containing radical polymerizable monomer and (D2) epoxy group-containing radical polymerizable monomer.

A catalyst is preferably used for the double bond introduction reaction. For example, as a catalyst used in the reaction of 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; tetra-n-butyl Phosphonium salts such as phosphonium bromide, tetraphenylphosphonium bromide, tri-n-butylbenzylphosphonium chloride; ammonium salts such as tetra-n-butylammonium bromide and triethylbenzylammonium chloride; triethylamine, tributylamine, N, N-dimethylaniline, Amines such as pyridine and N-methylimidazole can be used.

In the double bond introduction reaction, a polymerization inhibitor can be used so that the compound (D) used for introduction of the pendant double bond is not polymerized. 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. When 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. When the reaction temperature is higher than 150 ° C., it is used for introducing a double bond (D). Since side reactions such as the polymerization of the compound proceed may occur, this is not preferred. 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 with cationically polymerizable compounds (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 viscosity of such an active energy ray-curable ink composition is preferably 10 mPa · s or more and 600 mPa · s or less at 25 ° C. when used as a gravure ink. More preferably, it is 20 mPa · s or more and 400 mPa · s or less. More preferably, they are 30 mPa * s or more and 300 mPa * s or less.

When used as a screen ink, it is preferably 500 mPa · s or more and 40000 mPa · s or less at 25 ° C. More preferably, it is 1000 mPa · s or more and 20000 mPa · s or less. More preferably, it is 2000 mPa · s or more and 10000 mPa · s or less.
When used as an offset ink, it is preferably 5000 mPa · s or more and 500000 mPa · s or less at 25 ° C. More preferably, it is 8000 mPa · s or more and 300000 mPa · s or less. More preferably, it is 10000 mPa · s or more and 200000 mPa · s or less.

When used as a relief printing ink, it is preferably 10 mPa · s or more and 300000 mPa · s or less at 25 ° C. More preferably, it is 20 mPa · s or more and 150,000 mPa · s or less. More preferably, they are 30 mPa * s or more and 80000 mPa * s or less.
When used as inkjet ink, it is preferably 0.1 mPa · s or more and 200 mPa · s or less at 25 ° C. More preferably, it is 0.5 mPa · s or more and 100 mPa · s or less. More preferably, they are 1 mPa * s or more and 50 mPa * s or less.

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 good adhesion to plastic materials such as PET and PC, has excellent curability, and is excellent in flexibility, solvent resistance and tack-free property. 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).
The weight average molecular weight (Mw) of the obtained polymer (I) is measured by gel permeation chromatography (GPC), and the conversion rate of each monomer component after polymerization is determined by an internal standard method by liquid chromatography (LC). It calculated using.
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.

<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, 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) obtained, and about 30 mg of N, N-dimethylformamide used as an internal standard (Weighed accurately) was added and 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

Synthesis example 1
<Synthesis of polymer (I-1)>
A container equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel is charged with 80 parts of isopropyl alcohol (hereinafter abbreviated as IPA) as a solvent, and the temperature at which IPA is refluxed with stirring (80 ° C.) Until heated. Thereafter, the inside of the flask was replaced with nitrogen gas for 10 minutes.
On the other hand, two dropping funnels were prepared, and after charging 25 parts of methacrylamide, 60.2 parts of n-butyl acrylate, and 58.5 parts of glycidyl methacrylate in one dropping funnel (referred to as mixed solution a), the dropping was performed. The inside of the funnel was replaced with nitrogen gas for 3 minutes. In another dropping funnel, 2.87 parts of dimethyl-2,2′-azobis (2-methylpropionate) [V-601] as a polymerization initiator and 30 parts of IPA as a solvent were added (mixed solution). b)), and the inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.
After completion of replacement of nitrogen gas in the container and the dropping funnel, the temperature in the container was maintained at a temperature at which IPA was refluxed, and the mixed liquids a and b were added dropwise over 3 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued at a temperature at which IPA refluxed (inner temperature 85 to 88 ° C.), and the reaction was further aged at this temperature for 4 hours to obtain a colorless and transparent uniform solution.

When the conversion of each monomer was calculated after completion of aging, the conversion of methacrylamide was 97.7%, the conversion of n-butyl acrylate was 96.9%, and the conversion of glycidyl methacrylate was 100%. From this result, the composition of the obtained polymer (I-1) was methacrylamide / n-butyl acrylate / glycidyl methacrylate = 24.9 / 39.5 / 35.6 (molar ratio). Moreover, the weight average molecular weight of the obtained polymer (I-1) was 18100.
Finally, 100 parts of the obtained polymer (I-1) solution was poured into a large amount of water for precipitation, and the precipitate was sufficiently dried to obtain a solid polymer (I-1).

Synthesis example 2
<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, 7.0 parts of methacrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.021 part of hydroxypiperidine-1-oxyl and 0.32 part of tetra-n-butylammonium bromide as a catalyst were added and reacted for 10 hours at a temperature (86 to 88 ° C) at which IPA refluxed while stirring. A yellow transparent homogeneous solution was obtained.
After completion of the reaction, the conversion rate of methacrylic acid was calculated to be 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 methacrylic acid was an epoxy in the polymer (I-1). It was found to have reacted with the group. The modified polymer (II-1) had a double bond equivalent (g / eq) of 614 and a weight average molecular weight (Mw) of 20,800.
Finally, the obtained modified polymer (II-1) solution was poured into a large amount of water to precipitate, and the precipitate was sufficiently dried to obtain a solid modified polymer (II-1).

Synthesis example 3
<Synthesis of polymer (I-2)>
A container equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel is charged with 100 parts of isopropyl alcohol (hereinafter abbreviated as IPA) as a solvent, and the temperature at which IPA is refluxed with stirring (80 ° C.) Until heated. Thereafter, the inside of the flask was replaced with nitrogen gas for 10 minutes.
On the other hand, after preparing two dropping funnels and charging one dropping funnel with 49.5 parts of N- (2- (acryloyloxy) ethyl) pyrrolidone, 45 parts of n-butyl acrylate and 45 parts of glycidyl methacrylate ( The mixture funnel was replaced with nitrogen gas for 3 minutes. In another dropping funnel, 1.4 parts of 2,2′-azobisisobutyronitrile [V-60] as a polymerization initiator and 100 parts of IPA as a solvent (mixed solution d) were added. The inside of the dropping funnel was replaced with nitrogen gas for 3 minutes.
After completion of the nitrogen gas replacement in the container and the dropping funnel, the temperature in the container was maintained at a temperature at which IPA was refluxed, and the mixed liquids c and d were added dropwise over 3 hours while continuing stirring. After completion of the dropwise addition, heating and stirring were continued at a temperature at which IPA refluxed (inner temperature 85 to 88 ° C.), and the reaction was further aged at this temperature for 4 hours to obtain a colorless and transparent uniform solution.

After completion of the aging, the conversion rate of each monomer was calculated. The conversion rate of N- (2- (acryloyloxy) ethyl) pyrrolidone was 95.3%, the conversion rate of n-butyl acrylate was 100%, and the conversion of glycidyl methacrylate. The rate was 100%. From this result, the composition of the obtained polymer (I-2) was N- (2- (acryloyloxy) ethyl) pyrrolidone / n-butyl acrylate / glycidyl methacrylate = 27.8 / 38.0 / 34.2. (Molar ratio). Moreover, the weight average molecular weight of the obtained polymer (I-2) was 12600.
Finally, 100 parts of the obtained polymer (I-2) solution was poured into a large amount of water for precipitation, and the precipitate was sufficiently dried to obtain a solid polymer (I-2).

Synthesis example 4
<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, 5.2 parts of methacrylic acid, and 2,2,6,6-tetramethyl-4 as a polymerization inhibitor. -0.016 part of hydroxypiperidine-1-oxyl and 0.32 part of tetra-n-butylammonium bromide as a catalyst were added and reacted for 10 hours at a temperature (86 to 88 ° C) at which IPA refluxed while stirring. A yellow transparent homogeneous solution was obtained.
After completion of the reaction, the conversion rate of methacrylic acid was calculated to be 100%. The acid value (mgKOH / g) of the obtained modified polymer (II-2) was measured by potentiometric titration, but no inflection point was observed, and methacrylic 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 753, and the weight average molecular weight (Mw) was 15800.
Finally, the obtained modified polymer (II-2) solution was poured into a large amount of water for precipitation, and the precipitate was sufficiently dried to obtain a solid modified polymer (II-2).

Examples 1-12
Using the polymers and modified polymers obtained in Synthesis Examples 1 to 4, a curing composition was prepared according to the composition shown in Table 1, and the film thickness was formed on a polyethylene terephthalate film substrate using a bar coater. It was applied so as to be 20 microns. Next, UV irradiation of 300 mJ / cm ² is performed using an UV exposure apparatus, the coating film is cured, and tack-free properties, adhesion, toughness (flexibility) and solvent resistance are evaluated by the following methods. It was. The results are shown in Table 2.
“Irgacure 907” in Table 1 is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals).

[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]
An adhesive tape (manufactured by Nichiban Co., Ltd., cello tape (R) CT-15S) was affixed to the coating surface, and the tape was peeled off at a 90 ° angle with respect to the film surface, and the change in the coating surface was visually evaluated. The evaluation method was as follows: ○ = no peeling, Δ = partial peeling, and x = most peeling.
[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 methanol 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.

Claims (2)

(Meth) acrylamide monomers and / or copolymers formed from monomer components essentially comprising a polymerizable monomer having a (meth) acryloyl group and an amide group in the same molecule, and many A curing composition comprising a functional monomer as an essential component. The curable composition according to claim 1, wherein the copolymer has a double bond.