JP7815679B2 - Polymerizable composition and cured product - Google Patents

Description

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

Reactive compounds containing ethylenically unsaturated sites readily undergo polymerization reactions due to active species generated from polymerization initiators when heated or irradiated with active energy rays, forming reactive cured products. These reactive compounds are used in a wide variety of applications, and further improvements in reaction speed are required to improve work efficiency and shorten work times.

Patent Document 1 discloses that the presence of a polymerizable ionic liquid enables efficient curing even in the presence of oxygen, thereby improving the curing rate of a polymerizable composition, and describes that a composition containing a polyfunctional polymerizable ionic liquid and another ethylenically unsaturated monomer, oligomer, or polymer is suitable for use in coating agents and dental composite materials.
Furthermore, Patent Document 2 discloses that an ion-conductive curable composition containing an ionic liquid having a polymerizable group and a cross-linking agent having a multifunctional group that undergoes a cross-linking reaction with the polymerizable group has excellent ion conductivity, heat resistance, and mechanical strength.

Special Publication No. 2013-506718 JP 2011-213862 A

However, the polymerizable composition described in Patent Document 1 improves the reaction rate, but does not reach a sufficient level. Also, the composition described in Patent Document 2 has a problem with solvent resistance.
In addition, polymerizable compositions generally use a combination of various monomers depending on the required performance, and when film strength such as pencil hardness is required, a polyfunctional monomer having two or more functionalities is often used. However, the use of a polyfunctional monomer causes a problem of curling during curing.
Therefore, an object of the present invention is to provide a polymerizable composition that has an excellent reaction rate and solvent resistance and is suppressed in curling, and a cured product that has excellent solvent resistance and is suppressed in curling.

After extensive research, the inventors discovered that a polymerizable composition having a "ratio of acid value to amine value" and "absorption peak in infrared absorption spectrum" within specified ranges can solve the above-mentioned problems.

That is, the present invention relates to a polymerizable composition comprising a carboxyl group-containing ethylenically unsaturated monomer (A) (excluding those having a basic group), a basic group-containing ethylenically unsaturated monomer (B), and a photopolymerization initiator (D), wherein the polymerizable composition has a ratio of acid value to amine value of more than 1 and less than 10, and has an absorption peak in the range of 1550 to 1650 ^cm in an infrared absorption spectrum measured by FT-IR spectroscopy.

The present invention relates to the above polymerizable composition, which has an acid value of 25 to 480 mg KOH/g and an amine value of 10 to 180 mg KOH/g.

The present invention relates to the above polymerizable composition, wherein the basic group-containing ethylenically unsaturated monomer (B) includes an ethylenically unsaturated monomer (B1) having a basic group with a pKa of 6 or more.

The present invention relates to the above polymerizable composition, in which at least one of the carboxy group-containing ethylenically unsaturated monomer (A) and the basic group-containing ethylenically unsaturated monomer (B) is a (meth)acrylic monomer.

The present invention relates to a cured product of the above polymerizable composition.

The present invention makes it possible to provide a polymerizable composition that exhibits excellent reaction rate and solvent resistance while suppressing curling, as well as a cured product that exhibits excellent solvent resistance and suppresses curling.

The polymerizable composition of the present invention comprises a carboxy group-containing ethylenically unsaturated monomer (A), a basic group-containing ethylenically unsaturated monomer (B), and a photopolymerization initiator (D), and is characterized in that the polymerizable composition has a ratio of acid value to amine value that is greater than 1 and less than 10, and has an absorption peak in the range of 1550 to 1650 ^cm in an infrared absorption spectrum measured by FT-IR spectroscopy.
By controlling the compounding ratio of the carboxy group-containing ethylenically unsaturated monomer (A), the basic group-containing ethylenically unsaturated monomer (B), and the photopolymerization initiator (D) and setting the above-mentioned "ratio of acid value to amine value" and "absorption peak in infrared absorption spectrum" within predetermined ranges, it is possible to obtain a polymerizable composition that exhibits excellent reaction rate and solvent resistance and further has excellent curl suppression.

<Polymerizable composition>
As described above, the polymerizable composition of the present invention contains a carboxy group-containing ethylenically unsaturated monomer (A), a basic group-containing ethylenically unsaturated monomer (B), and a photopolymerization initiator (D), and it is important that the ratio of the acid value to the amine value is greater than 1 and less than 10, and that the polymerizable composition has an absorption peak in the range of 1550 to 1650 cm ⁻¹ in an infrared absorption spectrum measured by FT-IR spectroscopy.
When the ratio of the acid value to the amine value is more than 1 but less than 10 and has an absorption peak in the range of 1550 to 1650 ^cm , the reaction rate of the polymerizable composition increases and the solvent resistance improves. The ratio of the acid value to the amine value is preferably 2 or more and 5 or less.

The details of why the reaction rate and solvent resistance improve when the ratio of acid value to amine value is within a specific range are not known, but analysis using computational chemistry, IR testing, and viscosity evaluation has led to the following speculation.

When the ratio of the acid value to the amine value is in the range of more than 1 and less than 10, it is thought that after the carboxyl group and a basic group such as an amino group form a salt in the polymerizable composition, an aggregate-like structure is formed in which multiple carboxy groups are coordinated around the ionized carboxy group. This is also suggested by the fact that such a structure is calculated to be the most stable structure by molecular dynamics simulation using J-OCTA. Furthermore, polymerizable compositions in which the ratio of the acid value to the amine value is in the range of more than 1 and less than 10 exhibit a higher viscosity than that of the monomer contained alone, which also suggests the formation of an aggregate.
The absorption peak in the range of 1550 to 1650 cm ⁻¹ is believed to be a peak that arises from the above structure.
That is, when there is an absorption peak in the range of 1550 to 1650 cm ^-1 and the ratio of the acid value to the amine value is in the range of more than 1 but less than 10, the monomers in the polymerizable composition are appropriately arranged, the distance between the double bonds of the multiple carboxy group-containing ethylenically unsaturated monomers (A) and the single basic group-containing ethylenically unsaturated monomer (B) becomes shorter, and it is thought that the reaction rate is improved. Furthermore, it is thought that by adopting such a structure, the acid-base interaction becomes stronger and solvent resistance is improved.

Furthermore, by using a carboxy group-containing ethylenically unsaturated monomer (A) and a basic group-containing ethylenically unsaturated monomer (B) in combination, and further by using a composition in which the ratio of the acid value to the amine value is greater than 1 and less than 10, and which has an absorption peak in the range of 1550 to 1650 cm ⁻¹ in an infrared absorption spectrum measured by FT-IR spectroscopy, it is possible to achieve suppression of curling while maintaining film strength. This is presumably due to a relaxation phenomenon accompanying dynamic crosslinking by an acid and a base.
Each component constituting the present invention will be described in detail below.

<Carboxy Group-Containing Ethylenically Unsaturated Monomer (A)>
The carboxyl group-containing ethylenically unsaturated monomer (A) used in the present invention is not particularly limited as long as it is a monomer having a carboxyl group and an ethylenically unsaturated double bond (excluding those having a basic group), and can be appropriately selected from known materials.
Examples of the carboxy group-containing ethylenically unsaturated monomer (A) include (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, β-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-( Unsaturated monocarboxylic acids such as 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, and 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, citraconic acid, alkenyl succinic acid, alkadienyl succinic acid, and endic acid; and half ester compounds obtained from these unsaturated dicarboxylic acids and monoalcohols;
Examples of the alcohol having an ethylenically unsaturated double bond include a reaction product of an alcohol having an ethylenically unsaturated double bond with an acid anhydride such as tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, or maleic anhydride. Examples of the alcohol having an ethylenically unsaturated double bond include monofunctional acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate. Examples of the polyfunctional acrylate include trimethylolpropane di(meth)acrylate, pentaerythritol acrylate, and the like. tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxy group-containing polyol polyacrylate.
Furthermore, examples of commercially available carboxyl group-containing ethylenically unsaturated monomers include Aronix (registered trademark) M510 and M520 (manufactured by Toagosei Co., Ltd.).

<Basic Group-Containing Ethylenically Unsaturated Monomer (B)>
The basic group-containing ethylenically unsaturated monomer (B) used in the present invention is not particularly limited as long as it is a monomer having a basic group and an ethylenically unsaturated double bond, and can be appropriately selected from known materials.
Examples of the ethylenically unsaturated monomer having a basic group include N,N-dialkylamino group-containing (meth)acrylic acid esters such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; piperidyl skeleton-containing (meth)acrylic acid esters such as 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate; morpholine skeleton-containing (meth)acrylic esters such as morpholinoethyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylamide; N,N-diethylaminoethyl (meth)acrylate; Examples of suitable N,N-dialkylamino group-containing (meth)acrylamides include N,N-dialkylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide; amino group-containing styrenes such as dimethylaminostyrene and diethylaminostyrene; amino group-containing vinyl compounds such as 4-vinylpyridine, 2-vinylpyridine, and 1-vinylimidazole; amino group- and acid-containing (meth)acrylic acid esters such as 2-[[2-((meth)acryloyloxy)ethyl]dimethylammonio]acetate and 3-[[2-((meth)acryloyloxy)ethyl]dimethylammonio]propionate; and salts thereof. Examples of commercially available N,N-dialkylamino groups include EBECRYL 80 and EBECRYL 7100 (manufactured by Daicel Allnex).

The basic group-containing ethylenically unsaturated monomer (B) may be a Michael adduct of a difunctional or higher ethylenically unsaturated monomer and a primary or secondary amine compound. Examples of the difunctional or higher ethylenically unsaturated monomer include bifunctional (meth)acrylates such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; vinyl ether group-containing ethylenically unsaturated monomers such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, and 1-methyl-2-vinyloxyethyl (meth)acrylate; trifunctional (meth)acrylates such as glycerin PO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane EO-modified tri(meth)acrylate; and tetrafunctional or higher (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate monopropionate, and dipentaerythritol hexa(meth)acrylate.
Examples of the amine compound include secondary amine compounds such as dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-octylamine, 2-(propylamino)ethanol, 2-hydroxymethylaminoethanol, diethanolamine, diisopropanolamine, and N-ethyl-D-glucamine; and primary amine compounds such as methylamine, ethylamine, n-propylamine, n-butylamine, n-octylamine, ethanolamine, and isopropanolamine.

The basic group-containing ethylenically unsaturated monomer (B) preferably contains an ethylenically unsaturated monomer (B1) having an amino group with a pKa of at least 6. The inclusion of such a monomer (B1) is preferred because it allows the carboxylic acid to be more strongly coordinated to the amino group, leading to improved solvent resistance.
Examples of the unsaturated monomer (B1) having an amino group and a pKa of 6 or more include N,N-dialkylamino group-containing (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl tacrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide.

At least one of the carboxy group-containing ethylenically unsaturated monomer (A) and the amino group-containing ethylenically unsaturated monomer (B) is preferably a (meth)acrylic monomer having a (meth)acrylate group. Having either one of them be a (meth)acrylic monomer can increase the reaction rate. This is also preferable because improved curability also improves solvent resistance.

<Other Monomers (C)>
The polymerizable composition of the present invention may contain another monomer (C) other than (A) and (B) within the range that does not impair the effects of the present invention. The other monomer (C) is a compound that does not contain a carboxy group or a basic group and has at least one radically polymerizable skeleton in the molecule, and is preferably an ethylenically unsaturated monomer.
The other monomer (C) may be used alone or in combination of two or more.

Other monomers (C) include, for example, monofunctional alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate; monofunctional halogen-containing (meth)acrylates such as 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and 1H-hexafluoroisopropyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 1,3-butylene glycol methyl ether (meth)acrylate, and butoxyethyl (meth)acrylate; Monofunctional ether group-containing (meth)acrylates such as diethyl (meth)acrylate; bifunctional (meth)acrylates such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, and 1-methyl-2-vinyloxyethyl (meth)acrylate Trifunctional (meth)acrylates such as glycerin PO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane EO-modified tri(meth)acrylate; tetrafunctional or higher (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate monopropionate, and dipentaerythritol hexa(meth)acrylate; allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, and triallyl isocyanurate; arylates such as acrylate; acid amides such as (meth)acrylamide, N-methylol(meth)acrylamide, diacetoneacryl(meth)amide, and (meth)acryloylmorpholine; styrenes such as styrene, p-hydroxystyrene, and p-chlorostyrene; other vinyl compounds such as vinyl acetate, vinyl monochloroacetate, and vinyl benzoate; three-membered ring compounds such as vinylcyclopropane and vinyloxirane; and radically polymerizable cyclic compounds such as cyclic ketene acetals; and oligomers or prepolymers may also be used.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) used in the present invention is a compound that generates radicals, which are active species, when irradiated with various types of energy, particularly with active energy rays such as ultraviolet rays. The generated radicals can quickly initiate a polymerization reaction of the carboxy group-containing ethylenically unsaturated monomer (A), the basic group-containing ethylenically unsaturated monomer (B), and other monomers (C), thereby curing the resulting composition.

The photopolymerization initiator is not particularly limited, and examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl methyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1 benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); and other phenylglyoxylic methyl esters. Commercially available oxime ester compounds include BASF's 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02), N-1919 (manufactured by ADEKA Corporation), TRONLY TR-PBG-304, TRONLY TR-PBG-305, and TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.). Among these, acetophenones, such as aminoketones, phosphines, and oxime ester compounds are preferred.

The photopolymerization initiator (D) may be used singly or in combination of two or more. The amount of the photopolymerization initiator (D) to be blended is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the carboxy group-containing ethylenically unsaturated monomer (A), the basic group-containing ethylenically unsaturated monomer (B), and the other monomer (C).
When the amount of the photopolymerization initiator (D) is 0.01% by mass or more, the amount of active species generated by light irradiation is sufficient to obtain a desired curing rate, and when the amount is 20% by mass or less, the amount of low-molecular-weight components in the polymerizable composition is not too large, and the properties of the cured product are fully exhibited, which is preferable.

<Other ingredients>
The polymerizable composition of the present invention may contain other components such as a resin, a sensitizer, a polymerization inhibitor, a surface conditioner, a coloring component, and other additives, as long as the effects of the present invention are not impaired.

[resin]
Examples of the resin include alkyd resins, polyester resins, polyvinyl chloride, poly(meth)acrylic acid ester resins, polyepoxy resins, polyurethane resins, cellulose derivatives, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyvinyl acetal resins, diallyl phthalate resins, silicone resins, butadiene-acrylonitrile copolymers, polyamide resins, polyformaldehyde resins, polycarbonate resins, polystyrene resins, polyvinyl ether resins, polyvinyl ester resins, polyvinyl amide resins, novolac resins, and phenolic resins. These resins may be used alone or in combination of two or more.

[Sensitizer]
The polymerizable composition of the present invention may contain a sensitizer for the purpose of further improving the sensitivity and improving the film properties after curing.
The sensitizer is not particularly limited, and examples thereof include unsaturated ketone derivatives such as benzophenone derivatives, chalcone derivatives, and dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, Examples of such compounds include squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organic ruthenium complexes. One compound may be used alone, or two or more compounds may be used in combination.

The amount of sensitizer added is preferably 0.01 to 100% by mass, and more preferably 0.1 to 50% by mass, relative to the mass of the photopolymerization initiator.

[Polymerization inhibitor]
A polymerization inhibitor may be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.
The polymerization inhibitor is not particularly limited, and examples thereof include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, and phenothiazine. The amount of the polymerization inhibitor to be added is preferably 0.001 to 5% by mass relative to the mass of the photopolymerization initiator.

[Surface conditioner]
The polymerizable composition of the present invention may contain a surface conditioner for the purpose of improving adhesion to a substrate. Commercially available surface conditioners include, for example, BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, 375, 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, and UV3570 manufactured by BYK Chemie, and Tegorad-2100, 2200, 2250, 2500, and 2700 manufactured by Tego Chemie. These surface conditioners may be used alone or in combination of two or more.
The amount of the surface conditioner to be added is preferably 5% by mass or less based on the mass of the polymerizable composition.

[Coloring component]
The polymerizable composition of the present invention may contain a coloring component. The coloring component is not particularly limited, and examples thereof include conventionally known colorants such as dyes, organic pigments, inorganic pigments, and carbon black. These coloring components may be used alone or in combination of two or more to obtain the desired color density and hue.

Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, and metal complex pigments.

Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

Examples of carbon black include acetylene black, channel black, and furnace black.

When a pigment is used as the coloring component, a pigment derivative or pigment dispersant can be used to improve the dispersibility of the pigment and the storage stability of the polymerizable composition. The amount of pigment blended is preferably 0.01 to 100% by mass, and more preferably 1 to 60% by mass, based on the total mass of the carboxy group-containing ethylenically unsaturated monomer (A), the basic group-containing ethylenically unsaturated monomer (B), and the other monomer (C).

From the perspective of the absorption coefficient of visible light and transparency, the particle size of the pigment is preferably sufficiently small relative to the wavelength of visible light, with the average primary particle size preferably being 0.01 to 0.3 μm, and more preferably 0.01 to 0.1 μm. The average primary particle size is the average value of the diameter of the smallest unit pigment particle measured using an electron microscope.

The polymerizable composition of the present invention preferably contains substantially no organic solvent, but may contain an organic solvent to the extent that the effects of the present invention are not impaired. Examples of organic solvents include methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents.

Depending on the intended purpose, the polymerizable composition of the present invention may further contain oxygen scavengers such as phosphines, phosphonates, and phosphites, reducing agents, antifoggants, anti-fading agents, antihalation agents, fluorescent brighteners, surfactants, extenders, plasticizers, flame retardants, antioxidants, dye precursors, UV absorbers, foaming agents, anti-mold agents, antistatic agents, magnetic materials, storage stabilizers such as silane coupling agents and quaternary ammonium chlorides, plasticizers, slipping agents, anti-blocking agents, light stabilizers, defoamers, infrared absorbers, thixotropic agents, antibacterial agents, fine particles such as silica, and additives that impart various other properties, as well as dilution solvents.

The polymerizable composition of the present invention preferably has an acid value of 25 to 480 mgKOH/g and an amine value of 10 to 180 mgKOH/g, because the reaction rate and solvent resistance are improved within these ranges.
The pH of the polymer composition is preferably in the range of 4.8 to 6.5, which is preferable because the reaction rate and solvent resistance are further improved within this range.

<Cured product>
The cured product of the present invention is obtained by curing the polymerizable composition, and can be obtained by applying the polymerizable composition to a substrate, optionally removing the organic solvent and the like through a drying step, and then irradiating the composition with active energy rays.
The method for applying the polymerizable composition onto the substrate is not particularly limited, and for example, a Mayer bar, an applicator, a brush, a spray, a roller, a gravure coater, a die coater, a microgravure coater, a lip coater, a comma coater, a curtain coater, a knife coater, a reverse coater, a spin coater, or the like can be used.

The substrate to which the polymerizable composition is applied (hereinafter referred to as the first substrate) is not particularly limited and can be appropriately selected from the group consisting of glass, plastic, metal, and paper, depending on the application. The substrate may be a composite substrate composed of multiple materials. The shape of the substrate is not particularly limited and examples thereof include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape. A second substrate may be further attached to the surface to which the polymerizable composition is applied. The second substrate may be the same as or different from the first substrate.
The substrate is preferably a glass substrate or a plastic substrate, and is preferably transparent.

Examples of plastic substrates include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate; cellulose resins such as diacetyl cellulose and triacetyl cellulose (TAC); polycarbonate resins; polyacrylic resins; polystyrene resins such as polystyrene and acrylonitrile-styrene copolymers; polyolefin resins such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; polyvinyl chloride resins; polyamide resins such as nylon and aromatic polyamides; polyimide resins; polysulfone resins; polypolyethersulfone resins; polyetherketone resins; polyphenylsulfide resins; polyvinyl alcohol resins; polyvinylidene chloride resins; polyvinyl butyral resins; polyarylate resins; polyoxymethylene resins; and polyepoxy resins; as well as mixtures of the above resins. Resins with low birefringence are preferably used.

Activin energy rays used to cure the polymerizable composition of the present invention include heat, ultraviolet light, visible light, near-infrared light, and electron beams. A method of irradiating with active energy rays using a light source having a dominant wavelength in the 250 to 450 nm wavelength range is preferred. Examples of light sources having a dominant wavelength in the 250 to 450 nm wavelength range include ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high-power metal halide lamps, xenon lamps, pulsed xenon lamps, deuterium lamps, fluorescent lamps, Nd-YAG triple harmonic lasers, He-Cd lasers, nitrogen lasers, Xe-Cl excimer lasers, Xe-F excimer lasers, semiconductor-pumped solid-state lasers, and LED lamp light sources having emission wavelengths of 365 nm, 375 nm, and 385 nm.

As used herein, active energy rays such as ultraviolet light, visible light, and near-infrared light are defined in the Iwanami Dictionary of Physics and Chemistry, 4th Edition, edited by Kubo Ryogo et al. (Iwanami, 1987). A thermionic emission gun, an electrolytic emission gun, or the like can be used as the electron beam source. These active energy ray irradiations may also be combined with heat treatments such as infrared, far-infrared, hot air, and high-frequency heating. Furthermore, to further improve reaction speed and solvent resistance, it is preferable to cure in a nitrogen atmosphere.

As described above, the polymerizable composition of the present invention has excellent reaction speed and solvent resistance, and exhibits suppressed curling. Therefore, it can be applied to a variety of substrates and is suitable for use in various inks, overcoat varnishes, various printing plate materials, photosensitive materials such as photoresists, color resists, electrophotography, optical fibers, and hologram materials, various recording media such as microcapsules, as well as adhesives, pressure-sensitive adhesives, release coating agents, sealants, and various paints.

Specific examples of the present invention will be described below along with comparative examples, but the present invention is not limited to the following examples. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples represent "parts by mass" and "% by mass," respectively.

<Amine value>
The amine value was measured as follows: First, 1 g of sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and 100 ml of a toluene/ethanol mixture (volume ratio: toluene/ethanol = 1/1) was added and dissolved, followed by titration with a 0.1 N alcoholic hydrochloric acid solution. The amine value (unit: mg KOH/g) was calculated using the following formula:
Amine value = (5.61 x a x F) / S
In the formula, each symbol represents the following parameter:
S: Amount of sample collected (g)
a: Amount of 0.1N alcoholic hydrochloric acid solution consumed (ml)
F: Factor of 0.1N alcoholic hydrochloric acid solution

<Acid value>
The acid value was measured as follows. First, 1 g of sample was precisely weighed and placed in a stoppered Erlenmeyer flask, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol = 2/1) mixture was added and dissolved, followed by titration with a 0.1 N alcoholic potassium hydroxide solution. The acid value (unit: mgKOH/g) was calculated using the following formula:
Acid value = (5.61 x a x F) / S
In the formula, each symbol represents the following parameter:
S: Amount of sample collected (g)
a: Amount of 0.1N alcoholic potassium hydroxide solution consumed (ml)
F: Factor of 0.1N alcoholic potassium hydroxide solution

<pKa>
In this specification, pKa is a value estimated based on the chemical structure under the conditions of temperature: 273 K, pH: 7 using software MarvinSketch manufactured by ChemAxon.

Abbreviations used in the examples are shown in Table 1.

<Synthesis of reaction product>
(Production Example 1)
In a reaction vessel equipped with a stirrer and a thermometer, 0.030 mol of dipentaerythritol hexaacrylate (hexafunctional), a (meth)acrylate compound, was heated to 50°C. After the temperature stabilized, 0.060 mol of dipropylamine, a secondary amine compound, was added dropwise over 30 minutes, and the mixture was allowed to react for 5 hours to obtain a mixture (A-1) containing a Michael addition reaction product. The pKa of (A-1) was calculated using the pKa of a compound in which 2 moles of dipropylamine were added to dipentaerythritol hexaacrylate, the main component in the Michael addition reaction product, as a representative value.
(Production Example 2)
In a reaction vessel equipped with a stirrer and a thermometer, 0.060 mol of 1,6-hexanediol diacrylate (bifunctional), a (meth)acrylate compound, was heated to 50°C. After the temperature stabilized, 0.030 mol of butylamine, a primary amine compound, was added dropwise over 30 minutes, and the mixture was allowed to react for 5 hours to obtain a mixture (A-2) containing a Michael addition reaction product. The pKa of (A-2) was calculated using the pKa of a compound in which 1 mol of butylamine was added to 2 mol of 1,6-hexanediol diacrylate, the main component in the Michael addition reaction product, as a representative value.
<Production of polymerizable composition>
[Example 1]
45.1 parts of MAA, 54.9 parts of DM, and 5.0 parts of TPO were added to a light-shielding glass bottle whose air had been purged with nitrogen so that the oxygen concentration was 10% or less, and the mixture was thoroughly stirred with a stirrer and then degassed to obtain a polymerizable composition.

[Examples 2 to 34, Comparative Examples 1 to 7]
Polymerizable compositions were obtained in the same manner as in Example 1, except that the compositions and blending amounts were changed as shown in Table 2. In Table 2, the numerical values represent parts, and blank spaces represent that no blending was performed.

<Evaluation of Polymerizable Composition>
The polymerizable compositions thus obtained were evaluated as follows, and the results are shown in Tables 2 and 3.

[Measurement of absorption peaks]
The prepared polymerizable composition was applied to an aluminum plate using a No. 5 bar coater to a wet thickness of 10 μm, and an OPP film ("Pylen P2161" manufactured by Toyobo Co., Ltd., thickness 20 μm) was placed on the coated surface to prepare a laminate for evaluation. FT-IR reflection measurement was performed on the evaluation laminate from the OPP film side to confirm whether or not it had an absorption peak in the range of 1550 to 1650 ^cm .

[Response rate evaluation]
The OPP film side of the laminate used in the absorption peak measurement was irradiated with ultraviolet light at an irradiation intensity of 70 mW/ ^cm2 (365 nm equivalent) using a mercury xenon lamp Hypercure-200 (Yamashita Denso), and the consumption rate of ethylenically unsaturated bonds over time of ultraviolet irradiation was observed by time-resolved infrared spectroscopy. The consumption rate of ethylenically unsaturated bonds was calculated using the following formula from the characteristic absorption peak intensity at 810 cm ^-1 in the IR spectrum.
Formula: Consumption rate of ethylenically unsaturated bonds = (peak area before light irradiation - peak area after 1 second of light irradiation) / peak area before light irradiation
Evaluation criteria ○: Consumption rate of ethylenically unsaturated bonds is 20% or more (good)
×: Consumption rate of ethylenically unsaturated bonds is less than 20% (bad)

[Preparation of cured product (under nitrogen purging)]
The prepared polymerizable composition was coated onto the adhesive surface of an adhesive PET film (A4100, manufactured by Toyobo Co., Ltd.) using a bar coater, and the film was cut into a size of 10 cm x 10 cm to obtain a coated film. The coated film was then placed in a nitrogen purge box, and nitrogen was blown in so that the oxygen concentration in the system was 1% or less. Then, using a conveyor irradiator, the coated surface was irradiated with a metal halide lamp at 2.7 m/min and 1205 (mJ/cm ² ) (UVA equivalent) to cure the polymerizable composition and produce a cured product. The thickness of the cured product (cured film) was adjusted to 20 μm.

[Curl test]
The film having the cured film was placed on a flat and smooth table with the cured film facing up and left to stand for 1 hour in an environment of 23°C and 50% relative humidity. The degree of lift from the table was measured at each of the four corners of the film having the cured film, and the average value was used as the curl test value. Based on the obtained values, the curling property was evaluated according to the following criteria.
Criteria: Curl test value is less than 10 mm (good)
○: Curl test value is 10 mm or more and less than 20 mm (usable)
×: Curl test value is 20 mm or more (bad)

[Pencil hardness test]
The pencil hardness of the cured film was measured at a load of 750 gf (7.35 N) in accordance with JIS K 5600-5-4 using a Clemens scratch hardness tester (model: HA-301, manufactured by Tester Sangyo Co., Ltd.) in a constant temperature and humidity room at 23°C and 50% relative humidity. The obtained results were evaluated according to the following criteria.
Criterion 3: Pencil hardness is H or higher (very good)
2: Pencil hardness is 3B or more and less than H (good)
1: Pencil hardness is 9B or more and less than 3B (usable)
0: The pencil hardness is not measurable or is less than 9B, or the cured film is tacky (poor)

[Solvent resistance test]
The surface of the cured film was rubbed continuously in one direction with a cotton swab soaked in methyl ethyl ketone at a constant force, and the number of times it was rubbed until abnormalities in the coating (whitening, dissolution, disintegration) were observed was counted. Based on the number of times, the film was evaluated according to the following criteria.
Criteria ◎: The number of times until abnormalities in the coating were observed was 400 or more (good)
○: The number of times until abnormalities in the coating film were observed was 200 or more but less than 400 (usable)
×: The number of times until abnormalities in the coating film were observed was less than 200 (bad)

[Preparation of cured product (in air)]
The prepared polymerizable compositions (Examples 26, 31, 32, and 34) were applied to the adhesive surface of an adhesive PET film (A4100, manufactured by Toyobo Co., Ltd.) using a bar coater to obtain a coated film. Next, using a conveyor irradiator, the coated surface was irradiated with a metal halide lamp at 2.7 m/min and 1,205 (mJ/cm ² ) (UVA equivalent) in an atmospheric environment to cure the polymerizable composition and produce a cured product. The thickness of the cured product (cured film) was adjusted to 20 μm.

[Curl test and solvent resistance test of cured film in air]
The obtained film cured under atmospheric conditions was used to evaluate the curling property and solvent resistance of the film cured under atmospheric conditions in the same manner as in the above-mentioned [Curling Test] and [Solvent Resistance Test]. The results are shown in Table 3.

According to the evaluation results in Table 2, all of the polymerizable compositions of the present invention, which have an acid value to amine value ratio of more than 1 but less than 10 and an absorption peak in the range of 1550 to 1650 cm ^-1 , have excellent reactivity, and the cured products of these polymerizable compositions exhibit suppressed curling and excellent pencil hardness and solvent resistance. On the other hand, none of the comparative examples achieved a balance between reactivity, suppression of curling, and solvent resistance.
Furthermore, according to the evaluation results in Table 3, the polymerizable composition of the present invention was able to form a cured product that was suppressed from curling and had excellent solvent resistance, even when cured in an atmospheric atmosphere.

Claims (4)

A polymerizable composition comprising a carboxy group-containing ethylenically unsaturated monomer (A) (excluding those having a basic group), a basic group-containing ethylenically unsaturated monomer (B), and a photopolymerization initiator (D),
the basic group-containing ethylenically unsaturated monomer (B) is at least one selected from the group consisting of an amino group-containing ethylenically unsaturated monomer, 4-vinylpyridine, 2-vinylpyridine, and 1-vinylimidazole;
the polymerizable composition has a ratio of acid value to amine value of 2 or more and less than 10, and has an absorption peak in the range of 1550 to 1650 cm ⁻¹ in an infrared absorption spectrum measured by FT-IR spectroscopy;
A polymerizable composition having an acid value of 25 to 480 mgKOH/g and an amine value of 10 to 180 mgKOH/g . The polymerizable composition according to claim 1, wherein the basic group-containing ethylenically unsaturated monomer (B) comprises an ethylenically unsaturated monomer (B1) having a basic group and a pKa of 6 or more. The polymerizable composition according to claim 1 or 2 , wherein at least one of the carboxy group-containing ethylenically unsaturated monomer (A) and the basic group-containing ethylenically unsaturated monomer (B) is a (meth)acrylic monomer. A cured product of the polymerizable composition according to any one of claims 1 to 3 .