Curable composition and cured product thereof

Abstract

To provide: a curable composition which has high curability and high transparency, while exhibiting good adhesion to various base materials, and which is used in both an aqueous system and an organic system and is applied to UV curing and / or thermal curing; a coating agent composition, a bonding agent composition, an adhesive composition, an ink composition, an aqueous ink composition, an ink composition for three-dimensional modeling, an aqueous coating material composition, a sealing agent composition, a nail cosmetic composition, a dental material and a decorative coating agent, each of which contains this curable composition; and cured products and molded articles of these materials.SOLUTION: A curable composition contains: (A) a water-insoluble multifunctional (meth)acrylamide; and (B) a polymerizable compound other than the component (A).SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a non-water-soluble polyfunctional (meth)acrylamide-containing curable composition.

Background Art

[0002] N-substituted or N,N-disubstituted (meth)acrylamides having two or more (meth)acrylamide groups in the molecule are referred to as polyfunctional (meth)acrylamides and are widely used as components of ultraviolet (UV) and thermosetting resins. Polyfunctional (meth)acrylamides have a wide variety of structures depending on the type and number of their substituents, and can cover a wide range of physical properties and functions, such as from liquid to solid, hydrophilic (high polarity) to hydrophobic (low polarity), low viscosity to high viscosity, etc. They are used in extremely diverse fields such as inks, adhesives, binders, various coating agents and paints, nail cosmetics and dental materials, cosmetics and medical materials such as contact lenses, reactive diluents for ultraviolet (UV) curable resins, crosslinking agents for thermal polymerization or photopolymerization, etc.

[0003] In recent years, volatile organic chemicals (VOCs) have been regarded as a cause of air pollution, and suppression of VOC emissions in various fields has been demanded. Therefore, water-based (aqueous) curable compositions that do not contain organic solvents or the like and use water as a solvent, and active energy ray curable compositions such as UV and EB (electron beam) that do not contain organic solvents or water have attracted attention. In particular, aqueous curable compositions using water as a solvent require extremely large amounts of energy for water drying, whereas active energy ray curable compositions are highly expected because of energy saving and low environmental impact. Furthermore, water-soluble or water-dispersible aqueous UV curable resins can rapidly obtain a cured film with a small amount of energy by the simultaneous progress of UV curing and drying as the polymerization reaction (curing) proceeds by active energy ray irradiation and water is evaporated by the generated heat, and can suppress viscosity adjustment of the composition and shrinkage during curing (curing shrinkage) by adjusting the water content, and thus the research thereof has been actively conducted.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present disclosure provides a curable composition that has high curability and transparency, good wettability and adhesion to various substrates, excellent handling properties as a normal-temperature liquid, is used in both aqueous and organic systems, and is applicable to UV curing and / or thermal curing. Also provided are a coating agent composition, an adhesive composition, an adhesive composition, an ink composition, an aqueous ink composition, an ink composition for three-dimensional printing, an aqueous paint composition, a sealing agent composition, a nail cosmetic composition, a dental material composition, a decorative coating agent composition, and cured products and molded articles thereof containing the curable composition.

Means for Solving the Problems

[0005] It has been found that the above problems can be solved by using a curable composition containing a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B) other than (A).

Effects of the Invention

[0006] The curable composition of the present disclosure contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and has high curability. Due to the interaction between A and B, potentially the curable composition has high wettability and adhesion to various substrates from low-polarity resin-based materials to high-polarity glass and metal materials, good compatibility with water, organic solvents from low polarity to high polarity, and various general-purpose monomers, etc., and has high transparency. The curable composition is a normal-temperature liquid, has good handling properties, and its viscosity can be adjusted without limitation from low viscosity to high viscosity according to the application. The curable composition of the present disclosure is used in both aqueous and organic systems, and also in UV curing and / or thermal curing, and is suitable for various applications such as inkjet printing, screen printing, offset printing, flexographic printing, gravure printing, etc., ink compositions for printing, ink compositions for three-dimensional printing, coating agent compositions, adhesive compositions, adhesive compositions, paint compositions, sealing agent compositions, nail cosmetics, decorative coating agents used for decorative films and decorative sheets, etc., and dental materials.

Modes for Carrying Out the Invention

[0007] Hereinafter, embodiments of the present disclosure will be described in detail. However, the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention. Also, when a plurality of upper limit values and lower limit values are described for a specific parameter, any upper limit value and lower limit value can be combined to form a suitable numerical range.

[0008] One embodiment of the present disclosure is a curable composition (D) containing a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B). The polyfunctional (meth)acrylamide (A) is a compound having two or more (meth)acrylamide groups in the molecule. The number of (meth)acrylamide groups in A is preferably 6 or less. When the number of (meth)acrylamide groups exceeds 6, the acrylic equivalent becomes small, the shrinkage during curing of the curable composition increases, and deformation and cracking of the resulting cured film are likely to occur. Also, due to the formation of hydrogen bonds between (meth)acrylamide groups, the viscosity and polarity of A increase, which may deteriorate the handling of A and the compatibility between A and the above-mentioned B. From the same viewpoint, the number of (meth)acrylamide groups in A is more preferably 4 or less.

[0009] The polyfunctional (meth)acrylamide (A) is amphiphilic although it is water-insoluble by itself. By coexisting with the water-soluble polymerizable compound (B), A becomes soluble in water, and by coexisting with the water-insoluble polymerizable compound (B), A becomes soluble in a low-polarity organic solvent. Therefore, the curable composition (D) containing A and B can be used in both aqueous and organic systems. By adjusting the types, contents, etc. of A and B, the curable composition has good compatibility with water, organic solvents ranging from low polarity to high polarity, and various general-purpose monomers, and has high transparency. Also, when used as an aqueous curable composition such as an aqueous ink or an aqueous paint, it has good drying and curability, and in the ink film (image) or paint film that has dried by evaporating water, it has the effect of maintaining transparency, smoothness, and gloss without causing unevenness or cloudiness in the image. Furthermore, since the polyfunctional (meth)acrylamide (A) has one or more (meth)acrylamide groups in the molecule and the polymerizable compound (B) has one or more polymerizable groups in the molecule, the curable composition (D) containing A and B has high curability by active energy rays such as ultraviolet rays (UV) and electron beams (EB) and / or heat, and the strength, hardness, heat resistance, etc. of the resulting cured product are also excellent.

[0010] One embodiment of the present disclosure is a curable composition (D) containing a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B) (excluding (A)), wherein the solubility parameter (SP value) of the polyfunctional (meth)acrylamide (A) is 8.8 to 11.0 (cal / cm 3 ) 1 / 2 . The solubility SP value in the present disclosure is calculated by the Fedors method described in Polymer Engineer Science, Vol.14, P.147, Y.1974, and the unit is (cal / cm 3 ) 1 / 2That is, the higher the SP value, the higher the hydrophilicity of the compound, and the lower the SP value, the higher the hydrophobicity of the compound. The SP value of the polyfunctional (meth)acrylamide (A) is in the range of 8.8 to 11.0 (hereinafter, the unit is omitted), and A has amphiphilicity showing both hydrophilicity and hydrophobicity. Due to the amphiphilicity of the (meth)acrylamide (A) and the high aggregability derived from the (meth)acrylamide group and the high adhesiveness to the base material, the curable composition (D) has high wettability, adhesiveness, adhesive strength, etc. to various base materials from low-polarity resin-based materials to high-polarity glass and metal materials. Coating agent compositions, adhesive compositions, ink compositions, etc. containing the curable composition (D) have high wettability, adhesiveness, and tackiness, and the adhesive composition containing D has high adhesive strength.

[0011] One embodiment of the present disclosure is the curable composition (D) in which the SP value of the polymerizable compound (B) (excluding the polyfunctional (meth)acrylamide (A)) is 8.5 to 14.5. The SP value of the polymerizable compound (B) is within this range, and B has hydrophilicity, hydrophobicity, or amphiphilicity of hydrophilic and hydrophobic depending on the type. Therefore, the compatibility between the polymerizable compound (B) and the polyfunctional (meth)acrylamide (A) is good, the transparency of the curable composition (D) containing A and B is high, and the transparency of the cured product obtained by curing D is also high. In addition, the curable composition (D) has good solubility in water and various organic solvents, and is suitably used for both aqueous systems and organic systems. In the present disclosure, the aqueous system and water-based in the aqueous curable composition, aqueous ink composition, or aqueous paint composition mean that water occupies 60% by mass or more of the total mass of the volatile components in various compositions. Similarly, the organic system and organic in the organic curable composition, organic ink composition, or organic paint composition mean that the organic components occupy 60% by mass or more of the total mass of the volatile components in various compositions. In addition, when not described as an aqueous system or water-based below, it means an organic system or organic. Such various compositions containing the curable composition (D) can be obtained in both organic systems and aqueous systems. Particularly in the aqueous ink composition and aqueous paint composition, the pigment dispersibility of the curable composition (D) is good, and the printing characteristics of the ink composition such as ejection stability and printing sharpness, and the surface characteristics of the coating film obtained by curing the paint composition such as surface smoothness and surface glossiness are excellent.

[0012] One embodiment of the present disclosure is the various curable compositions (D) in which the absolute value of the difference in the SP values between the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B) is 3.0 or less. The closer the SP values of A and B are, the closer their hydrophilicity and hydrophobicity are, so the compatibility between A and B is higher, and the transparency of the curable composition (D) and the cured product of D is excellent. From this viewpoint, the absolute value of the difference in the SP values between A and B is preferably 2.5 or less, more preferably 1.5 or less. A colorless and transparent clear-type coating agent composition, adhesive composition, adhesive composition, ink composition, three-dimensional modeling ink composition, paint composition, sealing material composition, nail cosmetic, dental material, decorative coating agent, and their colorless and transparent cured products and molded products containing the curable composition (D) can be obtained and can be suitably used as materials for optical members, electronic devices, etc. When two or more polyfunctional (meth)acrylamides (A) and / or polymerizable compounds (B) are used in the curable composition, the SP value of A is a weighted average value based on the weight ratio of all A, and the SP value of B is a weighted average value based on the weight ratio of all B. When A or B has a repeating unit in its structure, their SP values are weighted average values.

[0013] One embodiment of the present disclosure is the various curable compositions (D) in which the acrylic equivalent of the polyfunctional (meth)acrylamide (A) is 180 or more. The acrylic equivalent in the present disclosure is the molecular weight per (meth)acrylamide group, that is, the value obtained by dividing the molecular weight by the number of acrylic groups. When the acrylic equivalent is low, the density of the (meth)acrylamide groups is high and the curability is high, but the resistance to curing shrinkage is low. If the acrylic equivalent of the polyfunctional (meth)acrylamide (A) is less than 180, the density of the (meth)acrylamide groups, which are hydrophilic functional groups in the A molecule, is too high, and A may become solid at normal temperature or may become water-soluble, resulting in problems such as difficult handling, cloudiness and unevenness in the resulting curable composition and cured product. Note that the normal temperature in the present disclosure is the temperature range of 5°C to 35°C. The higher the acrylic equivalent of the polyfunctional (meth)acrylamide (A), the more favorable it is because it is easier to balance hydrophilicity and hydrophobicity. However, if it exceeds 3000, the molecular weight and viscosity of A will increase, and there is a risk that the handleability and curability will deteriorate. From these viewpoints, the acrylic equivalent of A is preferably 190 to 2500, and more preferably 200 to 2000.

[0014] One embodiment of the present disclosure is the various curable compositions (D) in which the polyfunctional (meth)acrylamide (A) is a compound represented by general formulas [1] to [4].

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0015] In general formulas [1] to [4], R 1 represents a hydrogen atom or a methyl group. R 2 and R 3each represents a divalent chain hydrocarbon group having 3 carbon atoms, which may be linear or branched, and may be the same or different. R 4 represents a hydrogen atom or a chain hydrocarbon group having 1 to 2 carbon atoms. n is an integer of 1 to 70, m is 0 or 1. x1 and z1 are each independently an integer of 1 to 10, y1 is an integer of 1 to 40, x2, y2 and z2 are each independently an integer of 1 to 30, and s3, x3, y3 and z3 are each independently an integer of 1 to 20.

[0016] Specific examples of the polyfunctional (meth)acrylamide (A) represented by the general formulas [1] to [4] include polypropyleneoxydi(meth)acrylamide, polypropyleneoxypolyethyleneoxydi(meth)acrylamide, trimethylolpropane polypropyleneoxytri(meth)acrylamide, pentaerythritol polypropyleneoxytetra(meth)acrylamide, and the like. When the number of repeating units of the propyleneoxy group and ethyleneoxy group contained in these compounds is 1 to 30, it is easy to adjust the balance between the acrylic equivalent and viscosity of A. That is, it is preferable because it has an appropriate acrylic equivalent, is liquid or wax-like at room temperature, and has good handleability. From these viewpoints, the number of repeating units is more preferably 1 to 20, and particularly preferably 2 to 10.

[0017] When the polyfunctional (meth)acrylamide (A) is a compound having the structures represented by General Formulas [1] to [4], it preferably has a large number of ether groups in the molecule and has an effect of preventing inhibition of photoradical polymerization due to oxygen. Further, by having repeating units of isopropyleneoxy, A is hydrophilic, and a cured product of a curable composition containing the same can obtain sufficiently satisfactory water resistance. Further, although the polyfunctional (meth)acrylamide (A) represented by General Formulas [1] to [4] is water-insoluble, it is possible to prepare a water-soluble or water-dispersible aqueous curable composition by combining (A) with a water-soluble curable compound (B). This is because (A) contains a large number of hydrophilic (meth)acrylamide groups and is thus easily compatibilized with water-soluble B at the molecular level. Furthermore, although the polyfunctional (meth)acrylamide (A) of General Formulas [3] and [4] has trifunctionality and tetrafunctionality, it has a branched structure, and thus, like the bifunctional (A) of General Formulas [1] and [2], it has the characteristic of low shrinkage during curing.

[0018] One embodiment of the present disclosure is a curable composition (D) in which the content of the polyfunctional (meth)acrylamide (A) is 1 to 95% by mass and the content of the polymerizable compound (B) is 5 to 99% by mass with respect to the total mass of the curable composition. If the contents of A and B are within these ranges, the resulting curable composition can satisfy all physical properties and characteristics such as low viscosity, low curing shrinkage, high transparency, high curability, high wettability, and adhesiveness, and can be dissolved or dispersed in both organic solvents and water, and curable compositions (D) in various forms such as organic systems, aqueous systems, and emulsions can be obtained. Although the polyfunctional (meth)acrylamide (A) is water-insoluble, by coexisting with the water-soluble polymerizable compound (B), it becomes soluble in water, and an aqueous curable composition can be easily obtained. In the present disclosure, "soluble in water" (water-soluble) means that 1 g or more can be dissolved in 100 g of water at 25°C to obtain a stable aqueous solution. Further, from the viewpoint that the strength, hardness, heat resistance, etc. of the cured product obtained by curing the curable composition (D) can be easily adjusted according to various applications, the contents of A and B in D are preferably 2 to 90% by mass and 10 to 98% by mass, respectively, and more preferably 5 to 80% by mass and 20 to 95% by mass, respectively.

[0019] One embodiment of the present disclosure is that the polymerizable compound (B) has, in the molecule, one or more polymerizable groups selected from the group consisting of (meth) acrylate group, (meth) acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth) allyl ether group, maleimide group, α-substituted maleimide group, and α,β-substituted maleimide group, in the various curable compositions (D). Note that B is a compound other than the polyfunctional (meth) acrylamide (A). The polymerizable group of the polymerizable compound (B) has an ethylenically unsaturated bond and can be polymerized by the application of energy such as light or heat, and a crosslinkable polymer (cured product) can be obtained by a polymerization reaction with the polyfunctional (meth) acrylamide (A). From the viewpoint of high polymerizability, the polymerizable group of B is preferably a (meth) acrylate group, a (meth) acrylamide group, or a vinyl group. From the viewpoint of having a self-photopolymerization initiation effect by irradiation with active energy rays such as light, it is preferably a vinyl ether group, a methyl vinyl ether group, a (meth) allyl ether group, a maleimide group, an α-substituted maleimide group, or an α,β-substituted maleimide group. The selection of the polymerizable group of the polymerizable compound (B) can be adjusted and designed according to the preferable physical properties and characteristics of the curable composition (D) and the cured product obtained by curing D.

[0020] One embodiment of the present disclosure is the various curable compositions (D) in which the polymerizable compound (B) contains a monofunctional polymerizable compound (b1) and / or a polyfunctional polymerizable compound (b2). The content of (b1) is 0 to 80% by mass, and the content of (b2) is 0 to 40% by mass with respect to the total mass of the curable composition. By containing b1 or b2, a curable composition can be obtained that contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), has high curability and transparency, and also has good wettability and adhesion to various substrates. Further, by containing b1 and b2, a curable composition can be obtained that is a room-temperature liquid, has excellent handleability, and can be used in both aqueous and organic systems. From the viewpoint that the monofunctional polymerizable compound (b1) can lower the viscosity of the curable composition (D) and improve handleability, the content of b1 is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. On the other hand, when the content of b1 exceeds 80% by mass, the total of the polyfunctional (meth)acrylamide (A) and the polyfunctional polymerizable compound (b2) in the curable composition (D) becomes less than 20% by mass, and depending on the use of D, the surface hardness and strength of the obtained cured product may not be sufficiently satisfactory. From the viewpoint that the polyfunctional polymerizable compound (b2) can improve the curability of the curable composition (D), the content of b2 is preferably 2% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. On the other hand, when the content of b2 exceeds 40% by mass, the total of the polyfunctional (meth)acrylamide (A) and the polyfunctional polymerizable compound (b2) in the curable composition (D) exceeds 41% by mass, the curing shrinkage of D increases, and deformation and cracking of the obtained cured product may occur.

[0021] The monofunctional polymerizable compound (b1) and the polyfunctional polymerizable compound (b2) have one or more polymerizable groups arbitrarily selected from the group of the various polymerizable groups described above. Further, from the viewpoints of high polymerizability, curability, and hydrophilicity, the polymerizable groups of b1 and b2 are preferably (meth)acrylate groups and (meth)acrylamide groups. Furthermore, in an aqueous curable composition, it is particularly preferable to use water-soluble b1 and / or b2.

[0022] The monofunctional polymerizable compound (b1) is a monofunctional (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hydroxyethyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate, etc.

[0023] The monofunctional polymerizable compound (b1) is a monofunctional (meth)acrylamide, such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-isobutyl(meth)acrylamide, N-hexyl(meth)acrylamide and other N-alkyl (saturated or unsaturated linear or branched chain with 1 to 18 carbon atoms) (meth)acrylamides, N-alkoxy (linear or branched chain with 1 to 6 carbon atoms) alkyl (linear or branched chain with 1 to 6 carbon atoms) (meth)acrylamides, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide and other N-alkoxy (linear or branched chain with 1 to 6 carbon atoms) alkyl (linear or branched chain with 1 to 6 carbon atoms) (meth)acrylamides, N-isobutoxymethyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide and other hydroxyalkyl (linear or branched chain with 1 to 6 carbon atoms) (meth)acrylamides, N-[3-(dimethylamino)]propyl acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide, N,N-diisobutyl(meth)acrylamide, N-(meth)acryloylmorpholine, allyl(meth)acrylamide, 2-ethylhexyl(meth)acrylamide, diacetone acrylamide and the like. These monofunctional polymerizable compounds (b1) may be used alone or in combination of two or more.

[0024] The polyfunctional polymerizable compound (b2) is a polyfunctional (meth)acrylate, including monomers and oligomers such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ditetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified diphosphate di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexane dimethanol di(meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, etc.

[0025] Examples of the polyfunctional polymerizable compound (b2) as a polyfunctional (meth)acrylamide include methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, N,N'-(2-methylpropane-1,1-diyl)di(meth)acrylamide, N,N'-cyclohexylmethylenedi(meth)acrylamide, N,N'-(pentane-1,1-diyl)di(meth)acrylamide, N,N'-(3-methylbutane-1,1-diyl)di(meth)acrylamide, 2-(meth)acrylamido-2-methylpropanesulfonic acid, 1,4-bis(acryloyl)piperazine, ditrimethylolpropane tetraacrylamide, dipentaerythritol hexamethacrylamide, and the like. These polyfunctional polymerizable compounds (b2) may be used individually or in combination of two or more.

[0026] One embodiment of the present disclosure further contains a polymerizable polymerization initiator (C), and is the above-described various curable compositions (D) containing 0.1 to 20% by mass of C based on the total mass of the curable composition. The polymerizable polymerization initiator (C) is a compound other than the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B) having one or more polymerizable groups and one or more polymerization-initiating functional groups (initiating groups) in the molecule. The polymerizable group of C is one or more groups selected from the group consisting of (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, α-substituted maleimide group, and α,β-substituted maleimide group. The initiating group of C is not particularly limited as long as it generates radicals, cations, anions, etc. as growth active species by light irradiation or heating. For example, in the case of an active energy ray curing reaction such as UV or EB, after absorbing light such as UV, an intramolecular cleavage type that generates radicals by intramolecular cleavage, a hydrogen abstraction type and an electron donation type of initiating group that generate radicals by the exchange of hydrogen and electrons can be mentioned. More specifically, the initiating groups of the intramolecular cleavage type include benzoin derivatives, benzyl ketals, α-hydroxyacetophenone, α-aminoacetophenone, acylphosphine oxides, titanocenes, and o-acyl oxime types. The initiating groups of the hydrogen abstraction type include benzophenone derivatives having a diaryl ketone skeleton such as benzophenone, alkyldiaminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and thioxanthone derivatives having a thioxanthone skeleton such as 2-hydroxy thioxanthone. A compound selected from one or more of these initiating groups and combined with the above-described one or more polymerizable groups can be used. Among them, the initiating group of the hydrogen abstraction type is preferable because there is no by-production of low molecular compounds after the radical generation reaction and no residue in the cured product. Further, it is more preferable to have a structure in which the initiating group of the hydrogen abstraction type is combined with a (meth)acrylate group or a (meth)acrylamide group, which is a highly polymerizable group. Furthermore, in an aqueous curable composition, it is particularly preferable to use a water-soluble or hydrophilic polymerizable polymerization initiator (C).

[0027] The content of the coincidence polymerization initiator (C) varies depending on the structure of the starting group, the type of polymerizable group, the composition of the curable composition, etc. However, when it contains 0.1% by mass or more based on the total mass of the curable composition, thermal polymerization, photopolymerization, active energy ray curing, etc. can be immediately started, and the curable composition can be sufficiently cured. Also, since (C) has a polymerizable group, if its content is 20% by mass or less, the curable composition cures rapidly and at the same time the physical properties of the cured product do not deteriorate. In order to suitably adjust the physical properties of the cured product according to various applications, the content of the polymerizable polymerization initiator (C) with respect to the whole curable composition is preferably 0.5 to 15% by mass, and more preferably 1 to 10% by mass.

[0028] One embodiment of the present disclosure is the above-mentioned various curable compositions (D) further containing a quaternary salt monomer. The quaternary salt monomer is a compound other than the polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), and is a compound having both a polymerizable group and a quaternary salt structure in the molecule, and may be monofunctional or polyfunctional. The polymerizable group of the quaternary salt monomer is one or more groups selected from the group consisting of (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, α-substituted maleimide group, and α,β-substituted maleimide group. The quaternary salt structure may be cationic, anionic, or amphoteric with both cation and anion. As the quaternary salt monomer, a compound combined with one or more cationic groups and / or anionic groups selected from the group consisting of ammonium salts, imidazolium salts, choline salts, sulfonium salts, pyrazolium salts, oxazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, carboxylates, sulfonates, and phosphates, and one or more groups selected from the above-mentioned various polymerizable groups can be used. Among them, the quaternary ammonium salt monomer is particularly preferable because it has antistatic properties and antibacterial properties and has the effect of promoting the dissolution and dispersion of pigments in the ink composition. These quaternary salt monomers may be used alone or in combination of two or more.

[0029] The quaternary salt monomer is 0.1 to 30% by mass based on the total mass of the curable composition (D). The quaternary salt monomer includes water-soluble and water-insoluble ones, but since both have high hydrophilicity, it is preferable when contained in an organic-based curable composition at 30% by mass or less because the water resistance of the resulting cured product does not deteriorate. In an aqueous curable composition, it is preferable to contain 0.1% by mass or more because the water solubility and water dispersibility of the curable composition are significantly improved. Also, from these viewpoints, the quaternary salt monomer content in the curable composition is preferably 0.5 to 25% by mass, and more preferably 1 to 20% by mass.

[0030] One embodiment of the present disclosure is a coating agent composition (hereinafter also referred to as a coating agent) containing the various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the coating agent composition, can be brought in from the curable composition (D) according to each of the above embodiments, or can be additionally added as necessary when preparing the coating agent composition. With respect to the total mass of the coating agent composition, the content of A is preferably 1 to 60% by mass, and the content of B is preferably 20 to 99% by mass. By combining the amphiphilic A with the hydrophilic or hydrophobic or amphiphilic B, a hydrophilic or hydrophobic or amphiphilic coating agent composition can be obtained. Further, although A is water-insoluble, by combining it with the water-soluble B, a water-soluble coating agent composition or an emulsion-like coating agent composition that can be stably and uniformly dispersed in water can be obtained. Such a coating agent composition can easily adjust the types and contents of A and B, and thus has excellent compatibility with a wide range of compounds from hydrophobic to water-soluble other than A and B, high wettability with various materials from organic to inorganic, and the cured film (coating film) obtained by curing the coating agent composition is uniform without unevenness and has high transparency and surface smoothness. Further, since A has a large number of isopropyleneoxy groups, water resistance can be imparted to the obtained cured film, and the appearance and surface hardness of the cured film can also be adjusted according to the application. For example, when A is used in combination with the monofunctional polymerizable compound (b1) as B, no unevenness occurs on the surface of the cured film, and the appearance such as surface smoothness is improved. When A is used in combination with the polyfunctional polymerizable compound (b2) as the polymerizable compound (B), the surface hardness of the cured film is remarkably improved. Such a coating agent composition can be suitably used for various coating applications such as hard coat, vehicle, indoor or outdoor building materials, etc.

[0031] One embodiment of the present disclosure is an adhesive composition (hereinafter also referred to as an adhesive) containing the above various curable compositions. The essential components (A) and polymerizable compound (B) of the adhesive composition can be brought in from the curable composition (D) according to the above embodiments, or can be additionally added as necessary when preparing the adhesive composition. With respect to the total mass of the adhesive composition, the content of A is preferably 2 to 50% by mass, and the content of B is preferably 10 to 90% by mass. A is amphiphilic and has a plurality of (meth)acrylamide groups. Due to the interaction between the wettability derived from amphiphilicity and the cohesiveness of the (meth)acrylamide groups, the adhesive composition has excellent adhesion to various substrates (from organic materials to inorganic materials) and stain resistance (reworkability of being re-peelable). Also, A is amphiphilic, has a large number of (meth)acrylamide groups with high hydrolysis resistance, and isopropylenoxy groups with high water resistance and resistance to curing shrinkage. In the adhesive layer, adhesive sheet, and laminate formed by laminating through the adhesive layer obtained by curing the adhesive composition by the combination of A and B, it has good yellowing resistance (including transparency) and durability (moisture and heat resistance). Also, the adhesive composition of this embodiment can further contain polymerization initiators such as polymerizable polymerization initiators, non-polymerizable polymerization initiators, photoinitiators, and thermal polymerization initiators, various solvents from low polarity to high polarity, general-purpose monomers, and various additives, and can be adjusted from low viscosity to high viscosity according to the application. Such an adhesive composition can also be suitably used in the optical field such as adhesives for optical members, adhesive layers, and adhesive sheets. Also, the obtained adhesive layer and the laminate composed of the adhesive layer and various substrates can be applied as an adhesive film or adhesive sheet for electronic materials, optical members, and automotive members.

[0032] The pressure-sensitive adhesive composition of this embodiment can form a pressure-sensitive adhesive layer by being cured by irradiation with active energy rays after being applied or molded onto a separator or a substrate. Further, when the pressure-sensitive adhesive composition contains an organic solvent, it may be applied or molded onto a separator or a substrate, irradiated with active energy, and cured while evaporating (drying) the organic solvent. However, it is preferable to perform drying by heating at a temperature of 60 to 120°C for 1 to 30 minutes and then perform active energy curing because a pressure-sensitive adhesive layer with higher transparency can be obtained. For the application of the pressure-sensitive adhesive composition, ordinary coating film forming methods such as spin coating method, spray coating method, knife coating method, dipping method, gravure roll, reverse roll method, screen printing method, bar coater method, etc. are used.

[0033] In addition, a laminate can be obtained by laminating various substrates using a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition. Examples of the lamination method include a transfer method and a roll-to-roll method. The thickness of the pressure-sensitive adhesive layer in the laminate varies depending on various applications and is not particularly limited, but it is usually 4 to 150 μm. When used for automobile members, it is about 20 to 120 μm, and when used for electronic materials or optical members, it is about 30 to 100 μm.

[0034] Since the pressure-sensitive adhesive composition of this embodiment or the pressure-sensitive adhesive layer obtained therefrom exhibits high adhesion to various materials, as the substrate to be adhered or the substrate to be laminated, a wide variety of materials can be used, including low-polarity materials to high-polarity materials, organic-based substrates, inorganic-based substrates, and materials composed of organic-inorganic composite materials. For example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polycarbonate, ABS resin which is an acrylonitrile-butadiene-styrene copolymer, polyimide resin, polyamide resin, and acrylic resins such as polymethyl methacrylate, metals such as steel, stainless steel, copper, and aluminum, glasses, and hybrid materials in which silica fine particles as an inorganic material are dispersed in polyimide as an organic material, etc. can be mentioned. The uses of the various obtained laminates are not particularly limited, but examples include those for electronic materials, optical members, and automobile members.

[0035] One embodiment of the present disclosure is an adhesive composition (hereinafter also referred to as an adhesive) containing the above-described various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the adhesive composition, can be brought in from the curable composition (D) according to the above embodiments, or can be additionally added as necessary when preparing the adhesive composition. With respect to the total mass of the adhesive composition, the content of A is preferably 2 to 70% by mass, and the content of B is preferably 20 to 90% by mass. A is amphiphilic and has a plurality of (meth)acrylamide groups. Due to the interaction between the wettability derived from amphiphilicity and the aggregability of the (meth)acrylamide groups, the adhesive composition can adhere uniformly and without unevenness to various base materials (from organic materials to inorganic materials), has a high adhesive strength after curing, and is preferably used for both adhesion of the same kind of materials and adhesion of different kinds of materials. Further, A has a large number of isopropyleneoxy groups and (meth)acrylamide groups, and the cured product (adhesive layer, adhesive laminate, etc.) of the adhesive composition containing A has good hydrolysis resistance and water resistance. A can easily adjust the viscosity of the adhesive composition by being used in combination with a monofunctional polymerizable compound (b1), and a thin to thick adhesive layer can be produced according to the application. By being used in combination with a polyfunctional polymerizable compound (b2), the heat resistance and cold and heat shock resistance of the cured product can be significantly improved. Furthermore, the adhesive composition containing the amphiphilic A, various Bs, and a polymerizable or non-polymerizable polymerization initiator, etc., has high transparency, and the adhesive layer obtained by curing it also maintains high transparency. Therefore, such an adhesive composition can also be preferably used in the optical field such as an adhesive for optical members.

[0036] One embodiment of the present disclosure is an ink composition (hereinafter also referred to as ink) containing the various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the ink composition, can be brought in from the curable composition (D) according to the respective embodiments, or can be additionally added as necessary when preparing the ink composition. With respect to the total mass of the ink composition, the content of A is preferably 3 to 50% by mass, and the content of B is preferably 20 to 85% by mass. A is amphiphilic, and by mixing with Bs having various polarities from hydrophilic to hydrophobic, it has excellent dispersibility for various inorganic pigments and organic pigments, and excellent coatability for various printed circuit boards, and the print clarity of the obtained printed matter is excellent. The ink composition has high curability by containing A, and the surface drying property of the obtained printed surface is good. Further, by using A and the polyfunctional polymerizable compound (b2) in combination, the surface drying property of the printed surface obtained from the ink composition is further improved. By using A and the monofunctional polymerizable compound (b1) in combination, an ink composition with a viscosity ranging from low to high can be obtained. The ink composition of the present embodiment can be suitably adjusted in viscosity according to various applications and printing methods, and has high discharge stability and printing accuracy (including print clarity) during printing. The viscosity of the ink composition is preferably 1000 mPa·s or less at 25°C, more preferably 500 mPa·s or less, and particularly preferably 100 mPa·s or less from the viewpoint of being suitably used for the inkjet method. After being printed on a substrate, the ink composition is cured by irradiation with active energy rays or heat to form a printed surface (ink layer or printed layer). Further, since the quaternary salt monomer has excellent compatibility with the pigment, the dissolution and dispersion of the pigment are promoted by containing the quaternary salt monomer in the ink composition. From the viewpoint of balancing the printing characteristics such as the viscosity, pigment dispersibility, curability, discharge stability, and surface drying property and clarity of the obtained printed surface of the ink composition, the ink composition preferably contains 3 to 50% by mass of A, 30 to 80% by mass of b1, and 5 to 40% by mass of b2. Such an ink composition can be suitably used for various printing methods such as inkjet printing, offset printing, screen printing, and flexographic printing.For example, offset printing is a printing method that utilizes the property that an offset printing ink composition, which is oil-based, repels water. By containing A and hydrophobic B, the ink composition exhibits high hydrophobicity and curability, enabling high-speed and high-precision printing. Also, in an ink composition containing A having a large number of isopropyleneoxy groups and hydrophilic B, the water resistance of the resulting printed matter is sufficiently satisfactory.

[0037] One embodiment of the present disclosure is an aqueous ink composition (hereinafter also referred to as aqueous ink) containing the various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the ink composition, can be brought in from the curable composition (D) according to the above embodiments, or can be additionally added as necessary when preparing the aqueous ink composition. With respect to the total mass of the aqueous ink composition, the content of A is preferably 1 to 60% by mass, the content of B is preferably 5 to 89% by mass, and the content of water is preferably 10 to 50% by mass. Since A is amphiphilic while being water-insoluble, it has good compatibility with water-soluble B, and the curable composition obtained by mixing with water-soluble B is used as an aqueous ink composition. Such an ink composition exhibits excellent solubility in water or excellent compatibility with water, and also exhibits good solubility or dispersibility with respect to water-soluble pigments and the like. As a clear ink containing no pigment, it has high storage stability, and as a pigment-containing ink, it has high pigment dispersibility and storage stability. Further, since the aqueous ink composition contains A, it has high curability, and the obtained printed surface is excellent in water resistance. Depending on the purpose, a wide variety of inks can be prepared, such as an ink composition having high compatibility between A and B and high compatibility between D containing A and B with additives such as water and water-soluble pigments, and having a viscosity range suitable for inkjet printing. Also, the ejection stability of the ink composition during inkjet printing is good, and high printing characteristics can be exhibited. Furthermore, when containing 0.1% by mass or more of a quaternary salt monomer, the solubility of A in water is remarkably improved, and the above various characteristics of the aqueous ink composition and the printed matter which is a cured product thereof are further improved, which is preferable. The aqueous ink composition of the present embodiment may be in a state of an aqueous solution dissolved in water, or may be in a state of a water dispersion such as an emulsion dispersed in water. Also, the water content is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more with respect to the total mass of the aqueous ink composition. As the water, water containing no ionic impurities such as ion-exchanged water and distilled water is preferable.

[0038] One embodiment of the present disclosure is an ink composition for three-dimensional modeling (hereinafter also referred to as a modeling ink composition or a modeling ink) containing the above-described various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the modeling ink composition, can be brought in from the curable composition (D) according to the above-described embodiments, and can be additionally added as necessary when preparing the modeling ink composition. With respect to the total mass of the modeling ink composition, the content of A is preferably 1 to 60% by mass, and the content of B is preferably 20 to 99% by mass. A has a plurality of (meth)acrylamide groups and isopropyleneoxy groups, and the curability of the modeling ink composition is high, and the strength, toughness (impact resistance), and water resistance of the obtained molded article (cured product) are good. By containing the monofunctional polymerizable compound (b1) as B, the viscosity of the modeling ink composition can be suitably adjusted according to the specifications of the apparatus used for modeling, and the handleability is also improved. By containing the polyfunctional polymerizable compound (b2) as B, the curability of the modeling ink composition, the strength, hardness, etc. of the obtained molded article can be further enhanced. When the absolute value of the difference in the SP values of A and B is 3.0 or less, the compatibility of A and B is high, and the transparency of the modeling ink composition and the ink ejection stability during modeling are high. Also, when the acrylic equivalent of A is 180 or more, the resistance to curing shrinkage of the modeling ink composition is higher, and a molded article with excellent molding accuracy can be obtained.

[0039] When the modeling ink composition is formed into a predetermined shape pattern, it is cured by irradiation with active energy rays or heat simultaneously or immediately after formation to form a thin film, and a three-dimensional molded article can be obtained by laminating the thin films. The modeling method is not particularly limited, and examples thereof include a photopolymerization method in which the ink is ejected by an inkjet method and cured by irradiation with active energy rays. In this case, from the viewpoint of ejection stability, the viscosity of the modeling ink composition at 25°C is preferably 1 to 200 mPa·s, and the ejection temperature is preferably in the range of 20 to 100°C. From the viewpoint that the obtained three-dimensional molded article can exhibit strength, molding accuracy, and impact resistance in a well-balanced manner, the modeling ink composition more preferably contains 5 to 60% by mass of A, 10 to 70% by mass of b1, and 5 to 50% by mass of b2.

[0040] One embodiment of the present disclosure is an aqueous paint composition (hereinafter also referred to as aqueous paint) containing the various curable compositions. The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the aqueous paint composition, can be brought in from the curable composition (D) according to the respective embodiments, and can be additionally added as necessary when preparing the aqueous paint composition. With respect to the total mass of the aqueous paint composition, the content of A is preferably 1 to 50% by mass, the content of B is preferably 5 to 79% by mass, and the content of water is preferably 20 to 80% by mass. Since A is amphiphilic while being water-insoluble, it has good compatibility with water-soluble B, and the curable composition obtained by mixing with water-soluble B is used as an aqueous paint composition. Such a paint composition exhibits excellent solubility in water or excellent compatibility with water, and also exhibits good solubility or dispersibility with respect to water-soluble pigments, etc. It has high storage stability as a clear ink without pigments, and high pigment dispersibility and storage stability as a pigment-containing ink. Further, since the aqueous paint composition contains A, it has high curability, and the obtained coating film is excellent in water resistance. Due to the high compatibility between A and B and the high compatibility of D containing A and B with additives such as water and water-soluble pigments, and since A has both a plurality of (meth)acrylamide groups and isopropyleneoxy groups, it has high wettability and adhesion to various substrates such as wood, metal, concrete, rubber, pottery, plastic, paper, fiber, non-woven fabric, etc., and is used for coating multi-materials. Furthermore, when the quaternary salt monomer is contained in an amount of 0.1% by mass or more, the solubility of A in water is remarkably improved, and in the aqueous paint composition and the coating film which is the cured product thereof, the above various properties are further improved, which is preferable. The aqueous paint composition of the present embodiment may be in a state of an aqueous solution dissolved in water, or may be in a state of a water dispersion such as an emulsion dispersed in water. Also, the water content is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more with respect to the total mass of the aqueous paint composition. Water is preferably water that does not contain ionic impurities such as ion-exchanged water and distilled water.

[0041] The aqueous coating composition of this embodiment can contain an organic solvent as needed, and the content thereof is 40% by mass or less, preferably 30% by mass or less, and more preferably 20% by mass or less based on the total mass of the volatile components (the total of the organic solvent and water). After the aqueous coating composition is applied to a separator or a substrate and formed into a coating or a film, it may be cured by irradiating active energy such as UV or EB while evaporating (drying) the organic solvent and water. However, it is preferable to perform active energy curing after drying by heating at a temperature of 60 to 120°C for 1 to 30 minutes because a coating film with higher transparency can be obtained. The application of the aqueous coating composition can be carried out by using ordinary coating film forming methods such as spin coating method, spray coating method, knife coating method, dipping method, dip method, gravure roll, reverse roll method, screen printing method, bar coater method, etc., and is also preferably used for manual painting with a roller brush, brush, spatula, etc.

[0042] One embodiment of the present disclosure is a sealant composition (hereinafter also referred to as a sealant). The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the sealant composition, can be brought in from the curable composition (D) according to each of the above embodiments, or can be additionally added as necessary when preparing the sealant composition. With respect to the total mass of the sealant composition, the content of A is preferably 1 to 60% by mass, and the content of B is preferably 10 to 99% by mass. The (meth)acrylamide group of A has high curability with respect to both active energy rays and heat, and the sealant composition obtained by using A and B in combination also exhibits high curability. Further, since A is polyfunctional, the amount of unreacted polymerizable compound (residual monomer) in the cured product such as the sealant layer or sealant obtained by curing the sealant composition is extremely small, and the outgas resistance, moisture and heat yellowing resistance, corrosion resistance, etc. of the cured product are high, and an excellent sealing effect as a sealant can be exhibited. A and B have high compatibility, and the cured product such as the sealant composition and the sealant layer obtained by curing it has good transparency and is also suitably used for optical applications. The numerous isopropyleneoxy groups of A have the effect of imparting water resistance and curing shrinkage resistance to the obtained cured product. Further, the handling property of the sealant composition is improved by using A in combination with a monofunctional polymerizable compound (b1), and the curability of the sealant composition, the strength of the obtained cured product, and the heat seal resistance are improved by using A in combination with a polyfunctional polymerizable compound (b2).

[0043] One embodiment of the present disclosure is a nail cosmetic composition (hereinafter also referred to as a nail cosmetic). The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the nail cosmetic composition, can be brought in from the curable composition (D) according to each of the above embodiments, or can be additionally added as necessary when preparing the nail cosmetic composition. With respect to the total mass of the nail cosmetic composition, the content of A is preferably 1 to 40% by mass, and the content of B is preferably 10 to 99% by mass. A has a plurality of (meth)acrylamide groups, and the resulting nail cosmetic composition has high curability and high adhesion to nails, and the strength of the resulting cured product (also referred to as a cured film or nail) is also high. Since the compatibility between A and B and the compatibility between A, B and other components such as pigments are also high, the nail cosmetic composition and its cured film that do not contain pigments have high transparency and surface gloss, and the nail cosmetic composition that contains pigments has high pigment dispersibility (uniformity), and the resulting cured film has high surface gloss, and there is almost no unevenness in the cured film due to overcoating or repair work. Further, when the acrylic equivalent of A is 180 or more, the nail cosmetic composition has more excellent resistance to curing shrinkage, no unevenness occurs on the surface of the cured film, and the appearance of the nail is good. By appropriately adjusting the types and contents of the monofunctional polymerizable compound (b1) and / or the polyfunctional polymerizable compound (b2) and A, a nail cosmetic composition that can be used for various substrates such as natural nails, artificial nails, nail films, and nail tips can be obtained.

[0044] One embodiment of the present disclosure is a dental material composition (hereinafter also referred to as a dental material). The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the dental material composition, can be brought in from the curable composition (D) according to each of the above embodiments, or can be additionally added when preparing the dental material composition as needed. With respect to the total mass of the dental material composition, the content of A is preferably 0.5 to 50% by mass, and the content of B is preferably 5 to 99% by mass. A has a plurality of (meth)acrylamide groups, has high curability and adhesiveness of the dental material composition, and can obtain a high adhesive force when used as an adhesive dental material. Further, when the acrylic equivalent of A is 180 or more, the dental material composition has high shrinkage resistance during curing, no deformation over time or surface irregularities are observed after curing, and the surface smoothness is also good. A and B have high compatibility and excellent dispersibility of white pigments and inorganic fillers, and are also suitable as dental materials used for artificial tooth production such as inlay teeth, bridges, and implants, as well as composite resins for treating and restoring natural teeth, fillings, and veneers. Furthermore, A can easily adjust the viscosity of the dental material composition by being used in combination with a monofunctional polymerizable compound (b1), and the handleability can be improved. A can be used in combination with a polyfunctional polymerizable compound (b2) to further increase the curability of the dental material composition and the hardness of the resulting cured product.

[0045] One embodiment of the present disclosure is a decorative coating agent composition (hereinafter also referred to as a decorative coating agent). The polyfunctional (meth)acrylamide (A) and the polymerizable compound (B), which are essential components of the decorative coating agent composition, can be brought in from the curable composition (D) according to each of the above embodiments, or can be additionally added as necessary when preparing the decorative coating agent composition. With respect to the total mass of the decorative coating agent composition, the content of A is preferably 1 to 50% by mass, and the content of B is preferably 20 to 99% by mass. A has a plurality of (meth)acrylamide groups, the resulting decorative coating agent composition has high curability, and the surface hardness and scratch resistance of cured products such as the resulting decorative coating, decorative film, and decorative film are good. Further, A has a large number of isopropyleneoxy groups, the resulting cured product exhibits flexibility, and the flexural resistance of the decorative coating, decorative film, and decorative film is excellent. A is amphiphilic, has high compatibility with B, and it is possible to dissolve oligomers, polymers, etc. in D containing A and B, and the elongation rate of the cured product obtained from such a composition is higher.

[0046] In each embodiment of the present disclosure, the curable composition (D) may contain, as optional components, components other than those described above as necessary. As optional components, organic solvents and various additives can be used as necessary. Examples of the organic solvent include alcohols such as ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alkylene glycols, polyalkylene glycols, glycol ethers, glycol esters; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane; esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; and acetonitrile and N,N-dimethylformamide. These organic solvents can be used alone or in combination of two or more. In particular, in the case of an organic curable composition, low-boiling ethyl acetate, methyl ethyl ketone, acetone, etc. are more preferable from the viewpoint of being easily removed by a method such as drying during or after coating, film formation, molding. In the case of an aqueous curable composition, low-boiling water-soluble ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc. are more preferable. When an organic solvent is contained, its content is preferably 1.0 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the curable composition. Within this range, there is no risk of adversely affecting the properties expected of the compositions of each embodiment of the present disclosure and the cured products obtained by curing them.

[0047] Examples of the additives used in the present disclosure include polymerization initiators (excluding the polymerizable polymerization initiator (C)), thermal polymerization inhibitors, anti-aging agents, antioxidants, ultraviolet sensitizers, preservatives, phosphate ester-based and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, colorants, plasticizers, surface lubricants, leveling agents, softeners, pigments, organic fillers, inorganic fillers, silica particles, etc. The addition amount of these additives is not particularly limited as long as it does not adversely affect the expected properties of the compositions of each embodiment of the present disclosure and the cured products obtained by curing them, and is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the curable composition.

[0048] In each embodiment of the present disclosure, a non-polymerizable component can be further contained as necessary. The non-polymerizable component is a compound that does not contain the above-mentioned polymerizable group in the molecule. When classified by molecular weight (weight average molecular weight (Mw)), the non-polymerizable component is a non-polymerizable oligomer when Mw is 1,000 or more and less than 10,000, and a non-polymerizable polymer when Mw is 10,000 or more. Examples of the non-polymerizable oligomer and the non-polymerizable polymer include thermoplastic resins, rosin-based resins, or mixtures thereof. Examples of the thermoplastic resin include (meth)acrylic resins, cyclic polyolefin resins, cellulose resins, polyester resins, polyurethane resins, polysulfonic acid resins, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resins, polyamide resins, and polyimide resins. Examples of the rosin-based resin include natural rosins such as gum rosin, and modified rosin resins such as hydrogenated rosin, disproportionated rosin, rosin-modified phenol resin, maleic acid-modified rosin resin, maleated rosin, and esterified gum obtained by modifying natural rosin. These non-polymerizable oligomers and non-polymerizable polymers may be used alone or in combination of two or more.

[0049] The content of the non-polymerizable component is preferably 0.1 to 20% by mass based on the total mass of the curable composition. The non-polymerizable component has the effects of adjusting the viscosity of the curable composition, improving the adhesion of the pressure-sensitive adhesive composition and the adhesive composition to the substrate, improving the adhesive strength of the pressure-sensitive adhesive layer and the adhesive strength of the adhesive, and imparting toughness to the cured products of the coating agent composition, the ink composition, and the three-dimensional shaping ink composition, the encapsulant composition, and the cured product of the decorative coating agent composition. From these viewpoints, the content of the non-polymerizable component is more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass.

[0050] The curable composition according to each embodiment of the present disclosure can be cured by active energy rays such as UV and EB and / or heat, and a cured product suitable for various applications can be obtained. For example, as an adhesive composition, after applying the curable composition to a separator or various substrates, an adhesive layer can be formed by curing with active energy rays. In the present disclosure, curing the curable composition by active energy rays and heat is also referred to as hybrid curing. In hybrid curing, curing may be performed in the order of active energy rays and heat, or in the order of heat and active energy rays, or heat curing using the amount of heat generated by active energy ray curing, that is, simultaneous curing of active energy rays and heat may be performed.

[0051] The above-mentioned active energy rays are defined as energy rays capable of decomposing a compound (photoinitiator) that generates active species to generate active species. Examples of such active energy rays include visible light, ultraviolet light, infrared light, α-rays, β-rays, γ-rays, X-rays, electron beams (EB), and the like. When using an electron beam as the active energy ray, it is not necessary to use a photoinitiator. On the other hand, when using ultraviolet light, visible light, or the like, it is preferable to use a photoinitiator. Irradiation of the active energy ray is preferably performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or in an atmosphere with a reduced oxygen concentration. However, since the curable composition according to each embodiment of the present disclosure has a polyfunctional (meth)acrylamide (A), it has good curability and can be sufficiently cured even in a normal air atmosphere. The irradiation temperature of the active energy ray is preferably 10°C to 200°C, and the irradiation time is preferably 1 second to 60 minutes.

[0052] As the non-polymerizable photoinitiator, any substance that generates radicals by irradiating ultraviolet light of an appropriate wavelength capable of causing its polymerization reaction according to the type of active energy ray-reactive component (i.e., a photo radical polymerization initiator) may be used. Such photoinitiators may be appropriately selected from ordinary ones such as acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based ones, etc. As commercially available products, those manufactured by IGM Resins B.V. under the trade names Omnirad 1116, Omnirad 1173, Omnirad 184, Omnirad 369, Omnirad 500, Omnirad 651, Omnirad 754, Omnirad 819, Omnirad 907, Omnirad 1300, Omnirad 1800, Omnirad 1870, Omnirad 2959, Omnirad 4265, Omnirad TPO, Omnipol 2702, Omnipol 910, Omnipol 9210, Omnipol 2702, Omnipol BP, Omnipol TP, Omnipol TX, etc., those manufactured by Arkema under the trade names Speed Cure 7005, Speed Cure 7010, etc., those manufactured by Fujifilm Wako Pure Chemical Corporation under the trade name FOM-03011, etc., and those manufactured by UCB under the trade name Ubecryl P36, etc. may be used. These non-polymerizable photoinitiators may be used alone or in combination of two or more.

[0053] The non-coincident photo radical polymerization initiator is not particularly limited. For example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, anisole methyl ether, etc., 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone and other acetophenones, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-2-methylpropiophenone and other propiophenones, benzophenones such as benzophenone, methylbenzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-t-butylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, (bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide, benzyl, dibenzosuberone, α-acyl oxime ester, etc. These non-coincident photo radical polymerization initiators may be used alone or in combination of two or more.

[0054] The content of the non-polymerizable photoinitiator is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 5% by weight, based on the total mass of the curable composition according to each embodiment of the present disclosure. If the content of the non-polymerizable photoinitiator is less than 0.1% by mass, sufficient curability cannot be obtained, and if it exceeds 20% by mass, the performance such as the strength of the cured product may deteriorate. Also, the polymerizable photoinitiator (C) and the non-polymerizable photoinitiator can be used in combination.

[0055] The thermal curing of the curable composition according to each embodiment of the present disclosure can be carried out by a known method in the presence of a thermal polymerization initiator. For example, methods such as emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method, etc. can be utilized to obtain a crosslinkable cured product. When adopting the solution polymerization method, the solvents that can be used include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, etc., aliphatic hydrocarbons such as hexane, heptane, octane, decane, cyclohexane, etc., esters such as ethyl acetate, butyl acetate, 2-hydroxyethyl acetate, etc., aliphatic alcohols such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., acetonitrile, N,N-dimethylformamide, etc. These solvents may be used alone or in combination of two or more. In particular, from the viewpoint of being easily removed from the cured product, it is preferable to use low-boiling ethyl acetate, methyl ethyl ketone, acetone, etc. The temperature and time of thermal polymerization vary depending on the thermal polymerization method adopted and the thermal polymerization initiator used, but are usually calculated from the half-life of the initiator. The temperature is preferably usually 60°C to 120°C, and the time is preferably usually 2 hours to 20 hours, and more preferably 5 hours to 10 hours.

[0056] Examples of the thermal polymerization initiator include thermal radical polymerization initiators, such as azo compound-based catalysts like azobisisobutyronitrile, azobisvaleronitrile, azobis(isobutyric acid)dimethyl, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, 2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-azobis[2-(2-imidazolin-2-yl)propane], peroxide-based catalysts like benzoyl peroxide and hydrogen peroxide, and persulfate-based catalysts like ammonium persulfate and sodium persulfate. The content of the thermal polymerization initiator is about 0.01 to 10% by mass based on the total mass of the curable composition. Furthermore, ordinary radical polymerization techniques, such as adjusting the molecular weight with a chain transfer agent, can be applied.

Examples

[0057] The present disclosure will be described in more detail below with reference to examples and comparative examples, but the present disclosure is not limited to the following examples. The abbreviations of the respective components described in the examples and comparative examples are as follows. Also, in the following, "parts" and "%" are all based on mass unless otherwise specified. Note that the unit of the SP value (cal / cm 3 ) 1 / 2 is omitted.

[0058] The various compounds and materials described in the examples and comparative examples are as follows. (1) Polyfunctional (meth)acrylamide (A) A-1: Polypropyleneoxydimethacrylamide (D400) (n is an integer from 1 to 2, SP value = 10.6, average molecular weight = 366, acrylic equivalent = 183) A-2: Polypropyleneoxydiacrylamide (D400) (n is an integer from 2 to 3, SP value = 10.4, average molecular weight = 400, acrylic equivalent = 200) A-3: Polypropyleneoxydiacrylamide (D2000) (n = 33, SP value = 9.0, average molecular weight = 2100, acrylic equivalent = 1050) A-4: Polypropylene Oxydiacrylamide (D4000) (n = 67, SP value = 8.8, average molecular weight = 4100, acrylic equivalent = 2050) A-5: Trimethylolpropane Polypropylene Oxytriacrylamide (D600) (x2 is an integer from 1 to 2, y2 is an integer from 1 to 2, z2 is an integer from 1 to 2, x2 + y2 + z2 = 5 to 6, m = 1, SP value = 10.5, average molecular weight = 600, acrylic equivalent = 200) A-6: Trimethylolpropane Polypropylene Oxytriacrylamide (D3000) (x2 is an integer from 1 to 20, y2 is an integer from 1 to 10, z2 is an integer from 1 to 20, x2 + y2 + z2 = 50, m = 0, SP value = 9.0, average molecular weight = 3200, acrylic equivalent = 1067) A-7: Trimethylolpropane Polypropylene Oxytriacrylamide (D5000) (x2 is an integer from 1 to 30, y2 is an integer from 1 to 25, z2 is an integer from 1 to 30, x2 + y2 + z2 = 84, m = 0, SP value = 8.9, average molecular weight = 5200, acrylic equivalent = 1733) A-8: Polypropylene Oxypolyethylene Oxydiacrylamide (D700) (x1 is an integer from 1 to 2, y1 is an integer from 1 to 9, z1 is an integer from 1 to 2, x1 + z1 = 2 to 4, SP value = 10.0, average molecular weight = 700, acrylic equivalent = 350) A-9: Polypropylene Oxypolyethylene Oxydiacrylamide (D1000) (x1 is an integer from 1 to 3, y1 is an integer from 1 to 13, z1 is an integer from 1 to 3, x1 + z1 = 2 to 6, SP value = 9.7, average molecular weight = 1000, acrylic equivalent = 500) A-10: Polypropylene Oxypolyethylene Oxydiacrylamide (D2000) (x1 is an integer from 1 to 3, y1 is an integer from 1 to 39, z1 is an integer from 1 to 3, x1 + z1 = 2 to 6, SP value = 9.5, average molecular weight = 2100, acrylic equivalent = 1050) A-11: Pentaerythritol Polypropylene Oxytetraacrylamide (D800) (x3 is an integer from 1 to 3, y3 is an integer from 1 to 3, z3 is from 1 to 3, s3 is an integer from 1 to 3, x3 + y3 + z3 + s3 = 8, SP value = 10.7, average molecular weight = 813, acrylic equivalent = 203) (2) Coincidence compound (B) (2-1) Monofunctional polymerizable compound (b1) b1-1: Acryloylmorpholine (registered trademarks "Kohshylmer" and "ACMO", SP value = 11.2, water-soluble) b1-2: N-Hydroxyethylacrylamide (registered trademarks "Kohshylmer" and "HEAA", SP value = 14.4, water-soluble) b1-3: Dimethylacrylamide (registered trademarks "Kohshylmer" and "DMAA", SP value = 10.6, water-soluble) b1-4: Diethylacrylamide (registered trademarks "Kohshylmer" and "DEAA", SP value = 10.1, water-soluble) b1-5: Isopropylacrylamide (registered trademarks "Kohshylmer" and "NIPAM", SP value = 10.6, water-soluble) b1-6: Diacetoneacrylamide (registered trademark "Kohshylmer", SP value = 10.7, water-soluble) b1-7: N,N-Dimethylaminopropylacrylamide (registered trademarks "Kohshylmer" and "DMAPAA", SP value = 10.3, water-soluble) b1-8: N-Hydroxyethylmethacrylamide (registered trademark "Kohshylmer", SP value = 13.8, water-soluble) b1-9: N-Methyl-N-hydroxyethylacrylamide (registered trademark "Kohshylmer", SP value = 13.3, water-soluble) b1-10: N-Octylacrylamide ((registered trademark "Kohshylmer", SP value = 9.9, water-insoluble) b1-11: Isobornyl acrylate (SP value = 8.7, water-insoluble) b1-12: 4-t-Butylcyclohexyl acrylate (registered trademark "Kohshylmer", SP value = 8.7, water-insoluble) b1-13: Butyl acrylate (SP value = 8.8, water-insoluble) b1-14: 2-Ethylhexyl acrylate (SP value = 8.6, water-insoluble) b1-15: Tetrahydrofurfuryl acrylate (SP value = 9.5, water-soluble) b1-16: Hydroxyethyl acrylate (SP value = 12.5, water-soluble) b1-17: 4-Hydroxybutyl acrylate (SP value = 11.7, water-soluble) b1-18: Phenoxyethyl acrylate (SP value = 10.1, water-insoluble) b1-19: Acrylic acid (SP value = 11.1, water-soluble) b1-20: Isobornyl methacrylate (SP value = 8.7, water-insoluble) b1-21: Acryloylaminoethyltrimethylammonium trifluoromethanesulfonate (SP value = 8.3, water-insoluble)) b1-22: Acryloylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl)imide (SP value = 11.1, water-insoluble)) (2-1) Polyfunctional polymerizable compound (b1) b2-1: 1,6-Hexanediol diacrylate (SP value = 9.6, water-insoluble) b2-2: Dipentaerythritol hexaacrylate (SP value = 10.4, water-insoluble) b2-3: Polyethylene glycol 400 diacrylate (SP value = 9.6, water-soluble) b2-4: Pentaerythritol triacrylate (SP value = 11.5, water-insoluble) b2-5: Bifunctional urethane acrylate UV-3000B (estimated SP value = 10.0 (refer to polyurethane SP value), water-insoluble) b2-6: Bifunctional urethane acrylate UV-6640B (estimated SP value = 10.0 (refer to polyurethane SP value), water-insoluble) b2-7: Methylene bisacrylamide (SP value = 13.4, water-soluble) (3) Polymerizable polymerization initiator (C) C-1: 2-[4-(2-Hydroxy-2-methylpropionyl)phenoxy]ethyl acrylate (water-insoluble) C-2: 2-Phenylphenacyl acrylate (water-insoluble) C-3: 4-Acryloyloxybenzophenone (water-insoluble) C-4: Kohshyex-I 3002 (Polymeric type, water-insoluble) (Registered trademark "Kohshyex", manufactured by KJ Chemicals Co., Ltd.) (4) Other components (E) (4-1) Additives (non-polymerizable polymerization initiators, sensitizers, pigments, etc.) E1-1: Omnirad 2595 (Water-soluble photoinitiator E1-2: Omnirad TPO (Water-insoluble photoinitiator) E1-3: Omnirad 1173 (Water-insoluble photoinitiator) E1-4: Tacky Fire KE-359 (Non-polymerizable hydrogenated rosin, manufactured by Arakawa Chemical Industries, Ltd.) E1-5: Carbon black (Pigment, C.I. Pigment Black 7) E1-6: Solsperse 6000 (Pigment dispersant, manufactured by Lubrizol Japan Co., Ltd.) E1-7: 2,4-Diethylthioxanthone (Sensitizer, manufactured by Lambson) E1-8: BYK-377 (Silicone-based surface conditioner, 100% solids content, manufactured by BYK-Chemie Japan) E1-9: Antox MS60 (Sulfonate-based emulsifier, manufactured by Nippon Emulsifier Co., Ltd.) E1-10: 2,2’-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (Water-soluble, thermal polymerization initiator) E1-11: Pigment Blue 15:4 (Water-soluble pigment, manufactured by Toyo Color Co., Ltd.) E1-12: BYKJET-9151 (Water-soluble pigment dispersant, manufactured by BYK) E1-13: Inorganic filler (Titanium oxide) (4-2) Organic solvents, quaternary salt monomers, etc. E2-1: Ethyl acetate E2-2: Methyl ethyl ketone E2-3: Toluene E2-4: Acryloylaminopropyltrimethylammonium p-toluenesulfonate E2-5: Acryloyloxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imide (5) Water-soluble polyfunctional (meth)acrylamide and water-insoluble polyfunctional (meth)acrylate F-1: Polyethylene glycol diacrylamide (n = 2) (molecular weight = 256, acrylic equivalent = 128, SP value = 11.8, water-soluble) F-2: N-[Tris(3-acrylamidopropoxymethyl)methyl]acrylamide (molecular weight = 508, acrylic equivalent = 127, SP value = 12.1, water-soluble) F-3: N,N’-[Oxydibis(2,1-ethanediyl-oxy-3,1-propanediyl)]bisacrylamide (molecular weight = 328, acrylic equivalent = 164, SP value = 11.1, water-soluble) F-4: Tripropylene glycol diacrylate (n = 3) (molecular weight = 300, acrylic equivalent = 150, SP value = 9.3, water-insoluble) (6) Abbreviations of substrates for evaluation PET: Adhesive polyethylene terephthalate plates and films PMMA: Polymethyl methacrylate plates and films PC: Polycarbonate plates and films PVC: Polyvinyl chloride plates and films ABS: Acrylonitrile-butadiene-styrene copolymer synthetic resin plates GL: Glass plates AL: Aluminum plates

[0059] Examples 1 to 15 and Comparative Examples 1 to 6 (Preparation and evaluation of curable compositions) Polyfunctional (meth)acrylamide (A), polymerizable compound (B) and other components were weighed at the mass ratios shown in Table 1, and mixed at 35°C for 1 hour to prepare curable compositions of Examples 1 to 15 and Comparative Examples 1 to 6. The transparency (compatibility) and active energy ray curability of the obtained curable compositions were evaluated by the following methods, and the results are shown in Table 1. Also, the SP values of A and B and the absolute value of the difference between the SP values of A and B are summarized in Table 1.

[0060] Evaluation of transparency (compatibility) of curable compositions Each of the obtained various curable compositions was allowed to stand at 23°C overnight, and the state of the composition was observed visually, and the transparency was evaluated in four grades as follows. ◎: High transparency, no cloudiness or separation observed at all. ○: High transparency, but slight cloudiness can be seen. △: No layer separation, but cloudy. ×: Cloudy and further layer-separated.

[0061] Evaluation of the active energy ray curability of the curable composition The easy-adhesion surface of a 100-μm-thick PET film (manufactured by Toyobo Co., Ltd., polyester film Cosmo Shine A4100) was closely adhered to the surface of a horizontally placed glass plate so that it became the surface, and using a bar coater (No. 12), the curable compositions of each example and comparative example were applied so that the thickness of the dried coating film became 20 μm. After heating at 60 °C for 2 minutes, ultraviolet rays were irradiated (device: manufactured by ITEC SYSTEM Co., Ltd., tabletop batch type UV-LED curing device MUVBA-0.3×0.3×0.5, wavelength 405 nm, illuminance (UV-V) 50 mW / cm 2 ) to cure the curable composition. Then, the presence or absence of tack on the surface of the cured film was confirmed, and ultraviolet irradiation was additionally performed until the tack disappeared, and the curability was evaluated according to the following criteria based on the required integrated light amount. ◎: The tack disappeared with an integrated light amount of less than 500 mJ / cm 2 . ○: The tack disappeared with an integrated light amount of 500 mJ / cm 2 or more and less than 1000 mJ / cm 2 . △: The tack disappeared with an integrated light amount of 1000 mJ / cm 2 or more and less than 2000 mJ / cm 2 . ×: The tack remained even with an integrated light amount of 2000 mJ / cm 2 or more.

[0062]

Table 1

[0063] As is clear from the results in Table 1, the curable composition (D) containing the water-insoluble polyfunctional (meth)acrylamide (A) and the polymerizable compound (B) other than A was excellent in both transparency and curability. Although A is water-insoluble, it exhibits amphiphilicity and can be compatibilized with the hydrophobic, hydrophilic, and water-soluble B. Also, when the SP value of A is 8.8 to 11.0, the SP value of B is 8.5 to 14.5, and the difference in the SP values of A and B is 3.0 or less, the transparency of the resulting D is higher. The content of A is 1 to 95% by mass and the content of B is 5 to 99% by mass based on the total mass of D. By containing the monofunctional polymerizable compound (b1) and / or the polyfunctional polymerizable compound (b2) as B, both the transparency and curability of D are good. In particular, it was found that when the total content of A and b2 exceeds 15% by mass, the curability of D becomes higher. On the other hand, when only A (Comparative Example 2) or only B (Comparative Example 4) is contained, the transparency of the curable composition is poor because the compatibility of A or B with the polymerization initiator is insufficient. Also, when not containing A (Comparative Example 4), containing water-soluble polyfunctional (meth)acrylamide (Comparative Examples 1, 3, and 5), or containing water-insoluble polyfunctional acrylate (Comparative Example 6), the transparency and curability of the curable composition were not satisfactory.

[0064] Examples 16 to 21 and Comparative Examples 7 and 8 (Preparation and Evaluation of Coating Agent Compositions) The curable composition, polyfunctional (meth)acrylamide (A), polymerizable compound (B), and other components obtained in Table 1 were weighed at the mass ratios shown in Table 2 and mixed at 35°C for 1 hour to prepare the coating agent compositions of Examples 16 to 21 and Comparative Examples 7 and 8. The wettability of the obtained coating agent compositions with respect to various substrates and the resistance to curing shrinkage during active energy ray curing were evaluated by the following methods. Also, using the coating agent composition, a coating film (also referred to as a cured film or a coating film) was formed on a PET film by the following method, and the tack resistance, appearance, and surface hardness of the obtained coating film were evaluated by the following methods. The various evaluation results are shown in Table 2.

[0065] Evaluation of Wettability of Coating Agent Composition Using the coating agent compositions of the examples and comparative examples, various substrates described in Table 2 were coated with a bar coater (No. 12), and the repellency of the coating liquid was visually observed. ◎: There is no repellency, and it is a uniform coating film. ○: There is extremely little repellency, and it is almost a uniform coating film. △: There is some repellency, but it is almost a uniform coating film as a whole. ×: There is a lot of repellency, and it is a non-uniform coating film.

[0066] Evaluation of the resistance to curing shrinkage (curl resistance) of the coating agent composition Using the coating agent compositions of the examples and comparative examples, they were applied to a PET film with a thickness of 100 μm using a bar coater (No. 12), and irradiated with ultraviolet rays (apparatus: Inverter type conveyor apparatus ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm 2 , integrated light quantity: 1000 mJ / cm 2 ) to produce a coating film with a thickness of 10 μm. When using a solvent, it was dried at 80 °C for 3 minutes after coating and then irradiated with ultraviolet rays. The obtained coating film was cut into a 10 cm square, and the average of the lifting at the four corners was measured to evaluate the resistance to curing shrinkage (curl resistance). The larger the lifting, the larger the curl and the lower the resistance to curing shrinkage. ◎: There is a lifting of 0.5 mm or less. ○: There is a lifting of 1 mm or less. △: There is a lifting of 3 mm or less. ×: It curls greatly.

[0067] Evaluation of the tack resistance of the coating film Using the coating agent compositions of the examples and comparative examples, a coating film was produced in the same manner as the evaluation of the resistance to curing shrinkage (curl resistance) so that the film thickness after drying was 5 μm using a bar coater (No. 6). The surface of the obtained coating film was tapped with a silicon rubber stopper, and the stickiness (surface tackiness) was evaluated according to the following criteria, and the results are shown in Table 2. The worse the stickiness, the lower the tack resistance. ◎: No stickiness at all. 〇: There is some stickiness, but no trace remains on the surface. △: There is stickiness and a trace remains on the surface. ×: The stickiness is severe and a rubber stopper adheres to the surface.

[0068] Appearance evaluation of the coating film Using the coating agent compositions of each example and comparative example, a coating film with a thickness of 10 μm was prepared in the same manner as the above-mentioned evaluation of resistance to curing shrinkage (curl resistance). The surface smoothness and transparency of the obtained coating film were visually observed, and the appearance of the coating film was evaluated according to the following criteria. The higher the surface smoothness and the higher the transparency of the coating, the better the appearance. ◎: The surface was smooth and the coating film was transparent. ○: The surface was smooth and the coating film was generally transparent with a slight cloudy part. △: The surface was uneven or the coating film had a cloudy part. ×: The surface had unevenness and the coating film had cloudiness.

[0069] Surface hardness evaluation of the coating agent composition Using the curable compositions of each example and comparative example, a coating film with a thickness of 10 μm was prepared in the same manner as the above-mentioned evaluation of resistance to curing shrinkage (curl resistance). Using the obtained coating film, in accordance with JIS K 5600, after scratching with a pencil at an angle of 45° for about 10 mm, the hardest pencil that did not damage the surface of the film was taken as the pencil hardness, and the surface hardness was evaluated as follows. ◎: The pencil hardness is 2H or higher. ○: The pencil hardness is HB - H. △: The pencil hardness is 3B - B. ×: The pencil hardness is 4B or lower.

[0070]

Table 2

[0071] As is clear from the results in Table 2, the coating agent composition of the examples contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), has high curability and resistance to curing shrinkage, and shows good wettability to various substrates from plastic substrates (PET, PVC, ABS) to metals (aluminum). The appearance of the coating film obtained from the coating agent composition of the examples was good, and both the tack resistance and surface hardness of the coating film were high. These effects are due to the interaction between A and B. No similar properties were confirmed for the coating agent compositions of the comparative examples that did not contain A and B simultaneously.

[0072] Examples 22 to 27 and Comparative Examples 9 and 10 (Preparation and Evaluation of Adhesive Compositions) The curable compositions, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C), and other components obtained in Table 1 were weighed at the mass ratios shown in Table 3, mixed at 35 °C for 1 hour, and the adhesive compositions of Examples 22 to 27 and Comparative Examples 9 and 10 were prepared. Using the obtained adhesive compositions, an adhesive layer and an adhesive sheet were produced by the following method, and the curability of the adhesive composition, the adhesion to various substrates, and the adhesive strength, transparency, stain resistance (reworkability), yellowing resistance, and damp heat resistance of the obtained adhesive layer were evaluated, and the results are shown in Table 3.

[0073] Evaluation of Curability of Adhesive Composition A 75-μm-thick double-release PET film (manufactured by Toyobo Co., Ltd., polyester film E7001) was adhered to a horizontally placed glass plate, a spacer with a thickness of 1 mm and an internal size of 60 mm × 100 mm was installed, and after filling the curable adhesive composition of each example and comparative example prepared inside the spacer, a 50-μm-thick light-release PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) was further overlaid on it, and the integrated light amount was 3000 mJ / cm 2 by a UVLED lamp with a wavelength of 385 nm and an output of 100 mW / cm 2 and irradiated so as to be, and the adhesive composition was cured. Then, the cured product (adhesive layer) obtained by removing the release PET films on both sides was touched with a finger and evaluated in three stages of curability according to the following criteria. ○: A cured product that can maintain its shape is obtained. When touching the cured product, tack is observed, but there is no adhesion of the liquid uncured product. △: A cured product that can maintain its shape is obtained. When touching the cured product, tack is observed, but there is adhesion of the liquid uncured product. ×: Curing is insufficient, and a cured product that can maintain its shape cannot be obtained. A large amount of adhesion of liquid residue is observed.

[0074] Adhesive sheet production and adhesion evaluation The adhesive compositions of each example and comparative example were applied onto various plate-like substrates (substrates), and using a tabletop roll laminator (RSL-382S manufactured by Royal Sovereign) so that no bubbles would enter with a light release separator (silicone-coated PET film), they were laminated so that the thickness of the adhesive layer would be 5 μm, and irradiated with ultraviolet rays (apparatus: Inverter conveyor apparatus ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm 2 , integrated light quantity: 5000 mJ / cm 2 ). Then, the light release separator was peeled off to obtain an adhesive sheet composed of an adhesive layer and a substrate. Using the obtained adhesive sheet, in accordance with JIS K 5600, 100 squares of 1 mm square were created, cellophane tape was attached, and when peeled off all at once, the number of squares where the adhesive layer remained on the substrate side was counted, and the adhesion was evaluated according to the following criteria. The larger the number of remaining squares, the higher the adhesion. ◎: The number of remaining squares was 100. 〇: The number of remaining squares was 95 - 99. △: The number of remaining squares was 70 - 94. ×: The number of remaining squares was 0 - 69.

[0075] Adhesive force evaluation Under the conditions of a temperature of 23°C and a relative humidity of 50%, the above-mentioned adhesive layer was transferred onto various film-shaped or plate-shaped base materials, and pressure bonding was performed by reciprocating twice using a pressure roller with a weight of 2 kg, and then left in the same atmosphere for 30 minutes. Thereafter, using a tensile testing machine (device name: Tensilon RTA-100 manufactured by ORIENTEC Co., Ltd.), the 180° peel strength (N / 25 mm) was measured at a peel rate of 300 mm / min in accordance with JIS Z0237. The higher the peel strength, the higher the adhesive force. ◎: 30 (N / 25 mm) or more ○: 15 (N / 25 mm) or more and less than 30 (N / 25 mm) △: 8 (N / 25 mm) or more and less than 15 (N / 25 mm) ×: Less than 8 (N / 25 mm)

[0076] Evaluation of the transparency of the adhesive layer Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000), in accordance with JIS K 7105, the total light transmittance of the glass substrate was measured. Under the conditions of a temperature of 23°C and a relative humidity of 50%, the above-mentioned adhesive layer was transferred onto the glass substrate, and the total light transmittance of the glass substrate and the adhesive layer was measured. Thereafter, the transmittance of the glass plate was subtracted to calculate the transmittance of the adhesive layer itself, and the transparency was evaluated in four grades as follows. The higher the transmittance, the higher the transparency. ◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% △: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50%

[0077] Evaluation of the stain resistance (reworkability) of the adhesive layer An adhesive sheet was produced in the same manner as above and left at 80°C for 24 hours. Thereafter, the contamination (remaining state of the adhesive layer (paste)) on the surface of the base film after peeling off the adhesive layer was visually observed. The less the paste residue, the higher the stain resistance. ◎: No contamination (no paste residue). ○: Slightly contaminated. △: Slightly contaminated. ×: Contaminated (there is paste residue).

[0078] Evaluation of the yellowing resistance of the adhesive layer An adhesive sheet was prepared in the same manner as described above, set in a xenon fade meter (SC-700-WA, manufactured by Suga Test Instruments Co., Ltd.), and irradiated with ultraviolet rays at an intensity of 70 mW / cm 2 for 120 hours. Then, the discoloration of the adhesive layer on the adhesive sheet was visually observed. ◎: No yellowing can be visually confirmed at all. ○: Slight yellowing can be visually confirmed. △: Yellowing can be visually confirmed. ×: Obvious yellowing can be visually confirmed.

[0079] Evaluation of the heat and humidity resistance of the adhesive layer An adhesive sheet was prepared in the same manner as described above, held under the conditions of a temperature of 85°C and a relative humidity of 85% for 100 hours, and then the presence or absence of lifting, peeling, bubbles, and clouding of the adhesive layer was visually observed and evaluated. ◎: Transparent, with no lifting, peeling, or bubbles occurring. ○: Slightly cloudy, but no lifting, peeling, or bubbles occurring. △: Slightly cloudy or with lifting, peeling, or bubbles. ×: Extremely cloudy or with lifting, peeling, or bubbles.

[0080] [Table 3]

[0081] As is clear from the results in Table 3, the pressure-sensitive adhesive composition of the examples contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and due to their interaction, the pressure-sensitive adhesive composition exhibits high curability, and furthermore, the transparency of the pressure-sensitive adhesive layer obtained by curing it was high. Also, the pressure-sensitive adhesive composition of the examples had good adhesion and tack (adhesive strength) to various materials from general-purpose plastics to inorganic glass. The cured product (pressure-sensitive adhesive layer) obtained from the pressure-sensitive adhesive composition of the examples maintained high transparency, and the stain resistance when the cured product was peeled off from the substrate, as well as the yellowing resistance and moisture and heat resistance of the cured product were also good. On the other hand, in the compositions of the comparative examples, it was found that any of the curability, adhesion and tack to various materials were low, and any of the transparency, stain resistance, yellowing resistance and moisture and heat resistance of the cured product were low.

[0082] Examples 28 to 33 and Comparative Examples 11 and 12 (Preparation and Evaluation of Adhesive Compositions) The curable compositions, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C) and other components obtained in Table 1 were weighed at the mass ratios shown in Table 4, mixed at 35°C for 1 hour, and the adhesive compositions of Examples 28 to 33 and Comparative Examples 11 and 12 were prepared. The transparency of the obtained adhesive compositions was evaluated by the following method. Also, using the adhesive compositions of each example and comparative example, the same or different plate-shaped substrates were adhered by the following method to prepare adhesive test pieces, and the adhesive strength, water resistance and impact resistance were evaluated, and the results are shown in Table 4.

[0083] Transparency of Adhesive Composition) Evaluation The obtained adhesive composition was allowed to stand at 23°C overnight, and its state was observed visually, and the transparency was evaluated in four grades as follows. ◎: High transparency, and no clouding or separation is confirmed at all. ○: High transparency, but slight clouding is visible. △: No layer separation, but cloudy. ×: Cloudy and further layer separation.

[0084] Preparation of Adhesive Test Pieces Using two sheets of the same or different plate-shaped base materials with a length of 100 mm, a width of 25 mm, and a thickness of 1 mm, an adhesive composition was uniformly applied to any one of them. When the adhesive composition contains a solvent, the mixture was applied in an amount such that the thickness after drying is approximately the same as that without the solvent, and dried at 90 °C for 2 minutes. Then, in accordance with JIS K 6850, the other sheet of plate-shaped base material was placed on the applied adhesive composition, and bonded so that the overlapping area is 12.5 mm in length and 25 mm in width. By using a spacer, the thickness of the adhesive layer was adjusted to 100 μm, and a bonded test piece was prepared. Then, from the upper surface of the bonded transparent or translucent base material, ultraviolet rays (ultraviolet irradiation device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm 2 , integrated light quantity: 5000 mJ / cm 2 ) irradiation was performed. The test piece after irradiation was used as an adhesive test piece.

[0085] Adhesive strength evaluation Using the obtained adhesive test piece, in accordance with JIS K 6850, a tensilon RTA-100 (manufactured by ORIENTEC) was used as a testing machine, and the tensile shear strength was measured under the condition of a tensile speed of 10 mm / min. Note that the higher the tensile shear strength, the higher the adhesive strength. ◎: Tensile shear strength is 20 MPa or more. ○: Tensile shear strength is 15 MPa or more and less than 20 MPa. △: Tensile shear strength is 10 MPa or more and less than 15 MPa. ×: Tensile shear strength is less than 10 MPa.

[0086] Water resistance of the adhesive test piece Using the obtained adhesive test piece, after immersing it in warm water at 60 °C for 48 hours, the presence or absence of peeling at the interface of the same or different plate-shaped base materials was confirmed, and evaluation was performed according to the following criteria. ◎: No peeling at the interface (less than 1 mm) ○: Some peeling at the interface (1 mm or more and less than 3 mm) △: Some peeling at the interface (3 mm or more and less than 5 mm) ×: Peeling occurred at the interface (5 mm or more)

[0087] Evaluation of the impact resistance of the adhesive test piece Using the obtained adhesive test piece, in accordance with JIS K6855, an impact tester No. 511 (manufactured by Mize Testing Machine Co., Ltd.) was used to measure the impact peel adhesion strength. Note that the higher the impact peel adhesion strength, the higher the impact resistance. ◎: Impact peel adhesion strength is 20 KJ / m 2 or more. ○: Impact peel adhesion strength is 15 KJ / m 2 or more and less than 20 KJ / m2. △: Impact peel adhesion strength is 10 KJ / m 2 or more and less than 15 KJ / m2. ×: Impact peel adhesion strength is less than 10 KJ / m 2

[0088]

Table 4

[0089] As is clear from the results in Table 4, the adhesive compositions of the examples contained polyfunctional (meth)acrylamide (A) and polymerizable compound (B) and exhibited high transparency. Also, the adhesive compositions of the examples were used for bonding various homogeneous or heterogeneous materials from plastic substrates (PET, PMMA, PC, PVC, ABS) to metal (aluminum), and sufficient and satisfactory adhesive strength was obtained. This is because the adhesive composition was excellent in wettability to various materials and at the same time the adhesive strength of the adhesive obtained after curing was high. Also, by having a large number of A containing isopropyleneoxy groups, the water resistance and impact resistance of the adhesives obtained in the examples were good. In particular, in Examples 29 to 31 in which a branched structure isopropyleneoxy group was introduced, further improvement in water resistance and impact resistance was confirmed. On the other hand, the adhesive compositions of the comparative examples that did not contain A and B simultaneously and the adhesives obtained therefrom did not show the same characteristics.

[0090] Examples 34 to 39 and Comparative Examples 13 and 14 (Preparation and evaluation of curable ink compositions)​ The curable composition obtained in Table 1, the polyfunctional (meth)acrylamide (A), the polymerizable compound (B), the photopolymerization initiator (C), and other components were weighed at the mass ratios shown in Table 5 and mixed at 35°C for 1 hour to prepare the ink compositions of Examples 34 to 39 and Comparative Examples 13 and 14. Using the obtained ink compositions, viscosity measurement was performed by the following method, and the transparency when the pigment was not contained (clear ink) and the pigment dispersibility when the pigment was contained were evaluated respectively. Also, the curability of the ink composition and the ejection stability during inkjet printing were evaluated, and the sharpness of the obtained printed matter was evaluated. The results of these evaluations are summarized in Table 5.

[0091] Viscosity Measurement and Evaluation of Ink Composition The viscosity of the obtained ink composition at 25°C was measured using a cone plate viscometer (RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K5600-2-3. As an ink composition for inkjet printing, the viscosity was evaluated in four grades as follows. ◎: 5 or more and less than 100 mPa·s ○: 100 or more and less than 500 mPa·s △: 500 or more and less than 2000 mPa·s ×: 2000 mPa·s or more

[0092] Pigment Dispersibility Evaluation Using the obtained ink composition, the aggregation and precipitation states of the pigment immediately after preparation and after standing at room temperature for 2 months were visually observed, and the pigment dispersibility was evaluated according to the following criteria. ◎: No aggregation or precipitation of the pigment was observed either immediately after preparation or after standing for 2 months. 〇: None was observed immediately after preparation, but slight pigment precipitation was observed after standing for 2 months. △: Slight aggregation or precipitation of the pigment was observed immediately after preparation, and clear aggregation and precipitation of the pigment were observed after standing for 2 months. ×: Clear aggregation and precipitation of the pigment were observed immediately after preparation.

[0093] Transparency Evaluation (Clear Ink) The obtained ink composition was placed in a transparent screw tube, and the initial state was visually observed and left standing at room temperature in the dark for 24 hours. Thereafter, the state of the ink composition after standing was visually observed, and the compatibility was evaluated according to the following criteria. ◎: No liquid layer separation or turbidity was observed either initially or after standing. 〇: No liquid layer separation or turbidity was observed initially, but slight layer separation or turbidity was observed after standing. △: Slight layer separation or turbidity was observed initially, and distinct layer separation or turbidity was observed after standing. ×: Distinct layer separation or turbidity was observed initially.

[0094] Production of Printed Matter by Active Energy Ray Irradiation The ink composition was applied to a 100-μm-thick PET film using a bar coater (No. 12) (film thickness after drying: 10 μm), and cured by ultraviolet irradiation (apparatus: Inverter type conveyor apparatus ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm 2 , integrated light quantity: 1000 mJ / cm 2 ) to produce a printed matter.

[0095] Evaluation of Curing Property of Ink Composition A printed matter was prepared by the above method, and the integrated light quantity until the ink composition was completely cured (non-sticky state) was measured to evaluate the curing property. The lower the required integrated light quantity, the higher the curing property. ◎: Completely cured with less than 1000 mJ / cm 2 ○: Completely cured with 1000 or more and less than 2000 mJ / cm 2 △: Completely cured with 2000 or more and less than 5000 mJ / cm 2 ×: 5000 mJ / cm or more is required to be completely cured 2

[0096] Inkjet Printing and Evaluation of Ink Discharge Stability ​​​​The ink composition was filled into a commercially available inkjet printer (LuxelJet U V350GTW manufactured by Fujifilm Corporation), and a solid image was printed using coated paper. The printing state of the obtained printed matter was visually observed, and the ejection stability was evaluated according to the following criteria. ◎: Printed well without nozzle clogging. 〇: Slight nozzle clogging. △: Nozzle clogging in a wide range. ×: No ejection.

[0097] Evaluation of vividness The image vividness of the inkjet printed matter obtained from the ink composition containing the pigment was visually observed. ◎: No ink bleeding was observed at all, and the image was clear. ○: Almost no ink bleeding, and the image was good. △: Slight ink bleeding was observed. ×: Considerable ink bleeding was observed.

[0098]

Table 5

[0099] As is clear from the results in Table 5, the ink compositions of the examples contained a highly compatible polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and had high transparency (clear ink) or pigment dispersibility. Also, the ink compositions containing A and B had high curability, and the viscosity could be adjusted low as an ink composition for inkjet printing, and the ejection stability was obtained, and the print vividness of the printed matter was also good. On the other hand, the ink compositions of the comparative examples all had low viscosity, transparency, pigment dispersibility, curability or ejection stability, and the print vividness of the obtained printed matter was not satisfactory.

[0100] Examples 40 to 45 and Comparative Examples 15 and 16 (Preparation and evaluation of aqueous ink compositions) The curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), water, and other components were weighed at the mass ratios shown in Table 6 and mixed at 35°C for 1 hour to prepare the aqueous ink compositions of Examples 40 to 45 and Comparative Examples 15 and 16. Using the obtained aqueous ink compositions, the compatibility with water (clear ink) and the dispersibility of the water-soluble pigment were evaluated by the following method. Also, the initial viscosity was measured to evaluate the viscosity suitability as an ink composition for inkjet printing. Further, the aqueous ink composition obtained at 40°C in the dark was stored for 1 month, the viscosity after storage was measured in the same manner, the rate of change in viscosity after storage with respect to the initial value was calculated by the following formula, and the storage stability of the ink was evaluated according to the following criteria. The curability of the aqueous ink composition and the ejection stability during inkjet printing were evaluated, and the surface dryness and vividness of the obtained printed matter were evaluated. The results of these evaluations are summarized in Table 6. Viscosity change rate (%) = (Viscosity after storage - Initial viscosity) / Initial viscosity × 100%

[0101] Compatibility evaluation (clear ink) The obtained aqueous ink composition was placed in a transparent screw tube, the initial state was visually observed, and it was allowed to stand at room temperature in the dark for 24 hours. Then, the state of the aqueous ink composition after standing was visually observed, and the compatibility evaluation was performed according to the following criteria. ◎: Neither liquid layer separation nor turbidity was observed either initially or after standing. 〇: Neither liquid layer separation nor turbidity was observed initially, but slight layer separation or turbidity was observed after standing. △: Slight layer separation or turbidity was observed initially, and distinct layer separation or turbidity was observed after standing. ×: Distinct layer separation or turbidity was observed both initially and after standing.

[0102] Evaluation of pigment dispersibility of aqueous ink composition The obtained aqueous pigment-containing aqueous ink composition was placed in a transparent screw tube, the initial state was visually observed, and it was allowed to stand at room temperature in the dark for 24 hours. Then, the state of the aqueous pigment-containing aqueous ink composition after standing was visually observed, and the pigment dispersibility evaluation was performed according to the following criteria. ◎: No pigment precipitation was observed either initially or after standing. 〇: No pigment precipitation was observed initially, but slight pigment precipitation was observed after standing. △: Slight pigment precipitation was observed initially, and distinct pigment precipitation was observed after standing. ×: Distinct pigment precipitation was also observed initially.

[0103] Viscosity Measurement and Evaluation of Aqueous Ink Composition The viscosity of the obtained aqueous ink composition was measured using a cone-plate viscometer (RE550 viscometer manufactured by Toki Sangyo Co., Ltd.) in accordance with JIS K5600-2-3. The viscosity suitability of the ink composition for inkjet printing was evaluated according to the following criteria. ◎: 5 mPa·s or more and less than 100 mPa·s ○: 100 mPa·s or more and less than 500 mPa·s △: 500 mPa·s or more and less than 2000 mPa·s ×: 2000 mPa·s or more

[0104] Evaluation of Storage Stability of Aqueous Ink Composition The viscosity of the aqueous ink composition after storage at 40 °C in the dark for 1 month was measured in the same manner, the rate of change in viscosity was calculated, and the evaluation was carried out according to the following criteria. ◎: Rate of change ± less than 10% 〇: Rate of change ± 10% or more and less than ± 20% △: Rate of change ± 20% or more and less than ± 30% ×: Rate of change ± 30% or more

[0105] Production and Evaluation of Printed Matter with Aqueous Ink Composition Using the obtained aqueous ink composition, printing was performed on OK top coat paper (manufactured by Oji Paper Co., Ltd.) with an inkjet evaluation apparatus (manufactured by K-SOLUTION), and ultraviolet light with an integrated light amount (200 mJ / cm 2 ) was irradiated to cure it, and a printed matter was obtained. The ejection stability of the aqueous ink composition, the surface dryness and water resistance of the obtained printed matter were evaluated according to the following criteria.

[0106] Evaluation of Ejection Stability of Aqueous Ink Composition The printed state of the obtained printed matter was visually evaluated. ◎: Printed well without nozzle clogging. 〇: Slight nozzle clogging was present. △: Nozzle clogging was present over a wide range. ×: There was non - ejection.

[0107] Evaluation of the curability of the aqueous ink composition The obtained printed matter was rubbed with a cotton swab, and the curability was evaluated according to the following criteria. ◎: No trace remained after rubbing with a cotton swab. ○: Slight trace remained after rubbing. △: The rubbed trace remained over a wide range. ×: The printed matter was picked up by the cotton swab.

[0108] Evaluation of the surface dryness of the printed matter The obtained printed matter was left standing in an environment of 23°C at room temperature and 50% relative humidity for 5 minutes, and high - quality paper was placed on the printed surface, and a load of 1 kg / cm 2 was applied for 1 minute, and the degree of ink transfer to the paper was evaluated. ◎: The ink was dry and there was no transfer to the paper at all. ○: The ink was dry and there was slight transfer to the paper. △: The ink was almost dry and there was transfer to the paper. ×: The ink was hardly dry and there was a lot of transfer to the paper.

[0109] Evaluation of the water resistance of the aqueous ink composition The obtained printed matter was rubbed with a cotton swab moistened with water, and the water resistance was evaluated according to the following criteria. ◎: Even after 40 reciprocations, no adhesion of ink components to the cotton swab or rubbing marks on the printed surface were observed. ○: When 40 reciprocations were made, there was slight adhesion of ink components to the cotton swab and rubbing marks on the printed surface. △: When 11 - 39 reciprocations were made, there was adhesion of ink components to the cotton swab and rubbing marks on the printed surface. ×: When 10 reciprocations or less were made, there was adhesion of ink components to the cotton swab and rubbing marks on the printed surface.

[0110]

Table 6

[0111] As is clear from the results in Table 6, the aqueous ink compositions of the examples had low viscosity, high compatibility or pigment dispersibility, and good ejection stability in inkjet printing. Also, the aqueous ink compositions of the examples had high curability while having good storage stability. The reason for such results is that the aqueous ink compositions of the examples contain a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and the compatibility between A and B is extremely high, and they are also excellent in pigment dispersibility and water solubility. It was confirmed that the printed matter obtained by curing the aqueous ink composition of the example has excellent surface drying property and printing clarity. On the other hand, in the aqueous ink compositions of the comparative examples and their printed matters, the property evaluations of many items were all unsatisfactory.

[0112] Examples 46 to 51 and Comparative Examples 17 and 18 (Preparation and Evaluation of Ink Compositions for Three-Dimensional Modeling) The curable compositions, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components obtained in Table 1 were weighed at the mass ratios shown in Table 7, and mixed at 35°C for 1 hour to prepare the three-dimensional modeling ink compositions of Examples 46 to 51 and Comparative Examples 17 and 18. Using the obtained three-dimensional modeling ink compositions, three-dimensional molded articles were produced by the following method, and the hardening shrinkage resistance of the three-dimensional modeling ink compositions, the strength, impact resistance, water resistance, and molding accuracy of the obtained hardened products were evaluated, and the evaluation results are shown in Table 7.

[0113] Production and Strength Evaluation of Three-Dimensional Molded Articles A 75-μm thick peelable PET film (E7001 polyester film, manufactured by Toyobo Co., Ltd.) was adhered to a horizontally placed glass plate. A spacer with a thickness of 1 mm and punched into a No. 2 dumbbell shape compliant with JIS K6251 was installed. After filling the inside of the spacer with the three-dimensional shaping ink compositions obtained in each of the examples and comparative examples, a 50-μm thick peelable PET film (E7002 polyester film, manufactured by Toyobo Co., Ltd.) was further placed on top, and ultraviolet rays were irradiated from both sides (equipment: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics Co., Ltd., metal halide lamp: M04-L41 manufactured by Eye Graphics Co., Ltd., ultraviolet illuminance 200 mW / cm 2 , integrated light quantity 1000 mJ / cm 2 ) to cure the three-dimensional shaping ink composition. Thereafter, the peelable PET films on both sides were removed to obtain test pieces of the cured product for strength evaluation. According to JIS K7161, using a desktop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation), the tensile strength was measured under the conditions of a temperature environment of 25°C, a tensile speed of 10 mm / min, and a chuck distance of 50 mm, and the strength was evaluated according to the following criteria. ◎: Tensile strength was 40 MPa or more. ○: Tensile strength was 30 MPa or more and less than 40 MPa. △: Tensile strength was 20 MPa or more and less than 30 MPa. ×: Tensile strength was less than 20 MPa.

[0114] Evaluation of the resistance to curing shrinkage of the three-dimensional shaping ink composition A cured product was prepared in the same manner as the test piece for the strength evaluation described above. Based on JIS K5600 2-4, the curing shrinkage rate was determined from the specific gravity (d0) of the curable composition before curing and the specific gravity (d1) of the sheet-like cured product obtained after curing using the following formula, and the resistance to curing shrinkage was evaluated based on the following criteria. The lower the curing shrinkage rate, the higher the resistance to curing shrinkage. Curing shrinkage rate (%) = (d1 - d0) / d1 × 100% ◎: Less than 2% 〇: 2% to less than 5% △: 5% to less than 10% ×: 10% or more

[0115] Evaluation of Impact Resistance (Toughness) of Three-Dimensional Shaped Objects Similar to the test pieces for the strength evaluation, prepare spacers with a thickness of 4 mm and an internal dimension of 10×80 mm. Fill each of the three-dimensional shaping ink compositions obtained in each example and comparative example with a thickness of 4 mm inside the spacers. Similarly, stack a lightly peelable PET film and irradiate with ultraviolet light from both sides to cure the ink composition. After that, remove the peelable PET films on both sides and further irradiate with ultraviolet light at a predetermined integrated light quantity (apparatus: manufactured by ITEC SYSTEMS CO., LTD., desktop batch type UV-LED curing apparatus MUVBA-0.3×0.3×0.5, wavelength 405 nm, illuminance (UV-V) 50 mW / cm 2 , integrated light quantity 5,000 mJ / cm 2 ), perform post-curing to completely cure it. After that, using the obtained cured product as a test piece, measure the Izod impact strength (with notch) according to JIS K-7110, and evaluate the impact resistance as follows. In addition, an Izod Charpy impact tester "Model No. 195-R" manufactured by Yasuda Seiki Seisakusho Co., Ltd. was used. The higher the impact strength, the higher the impact resistance. ◎: 40 J / m or more ○: 30 J / m or more and less than 40 J / m △: 20 J / m or more and less than 30 J / m ×: less than 20 J / m

[0116] Evaluation of Water Resistance of Three-Dimensional Shaped Objects Using a spacer with a thickness of 1 mm and an internal dimension of 10 cm×1 cm, in the same manner as the production of the test pieces for the strength evaluation, produce a cured product test piece for water resistance evaluation with a length of 10 cm×width of 1 cm×thickness of 1 mm. After measuring the weight of the obtained test piece immediately after shaping, immerse it in a beaker containing 100 ml of water and measure the weight after immersion after 1 day. Calculate the water absorption rate from the weight before immersion and the weight after immersion using the following formula, and evaluate the water resistance according to the following criteria. The lower the water absorption rate, the higher the water resistance. Water absorption rate (%) = (weight after immersion - weight before immersion) / weight before immersion × 100% ◎: water absorption rate less than 2% ○: water absorption rate 2% or more and less than 2.5% △: Water absorption rate is 2.5% or more and less than 3% ×: Water absorption rate is 3% or more

[0117] Evaluation of shaping accuracy Similar to the test piece for the above strength evaluation, prepare a test piece with a thickness of 10 mm and a 10 × 10 mm spacer inside. After filling the inside of the spacer with the three-dimensional shaping ink composition obtained in each example and comparative example with a thickness of 1 mm, keep it warm at 60 °C for 30 seconds to smooth the surface, and then irradiate it with ultraviolet light in the same way to cure the three-dimensional shaping ink composition. Then, fill the obtained cured product with the three-dimensional shaping ink composition with a thickness of 1 mm and repeat the curing 10 times in total to obtain a cured product of 10 × 10 × 10 mm. Measure the height of the obtained cured product and visually observe the side surface, and evaluate the shaping accuracy according to the following criteria. ◎: Height is less than 10 mm ± 0.1 mm, and there are no irregularities on the side surface. ○: Height is 10 mm ± 0.1 mm or more and less than ± 0.2 mm, or there are slight irregularities on the side surface. △: Height is 10 mm ± 0.2 mm or more and less than ± 0.3 mm, or there are some irregularities on the side surface. ×: Height is 10 mm ± 0.3 mm or more, or there are obvious irregularities on the side surface.

[0118]

Table 7

[0119] As is clear from the results in Table 7, the three-dimensional shaping ink composition of the examples contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), and the strength, impact resistance, water resistance, and shaping accuracy of the obtained shaped article were all good. In particular, in Examples 49 and 51 containing A having an isopropyleneoxy group with a branched structure, further improvement in the curing shrinkage resistance of the three-dimensional shaping ink composition and the water resistance and impact resistance of the obtained shaped article was confirmed. On the other hand, in the comparative examples that did not contain A and B at the same time, the curing shrinkage resistance of the three-dimensional shaping ink composition was low, and various physical properties of the obtained shaped article were also low.

[0120] Examples 52 to 57 and Comparative Examples 19 and 20 (Preparation and Evaluation of Aqueous Paint Compositions) The curable compositions obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components were weighed at the mass ratios shown in Table 8, mixed at 35 °C for 1 hour, and the aqueous paint compositions of Examples 52 to 57 and Comparative Examples 19 and 20 were prepared. The obtained aqueous paint composition was applied onto an ABS substrate with a bar coater (No. 12) (film thickness after drying: 10 μm), and dried with a hot air dryer at 80 °C for 10 minutes. Then, the dried paint films obtained in Examples 52 to 56 and Comparative Examples 19 and 20 were irradiated with ultraviolet rays (the same inverter type conveyor device manufactured by Eye Graphics as described above, the same metal halide lamp as described above, ultraviolet illuminance: 300 mW / cm 2 , integrated light quantity 2000 mJ / cm 2 ) to be cured, and a cured product (cured paint film) of UV curing was obtained. Also, the dried paint film obtained in Example 57 was heat-cured with a hot air dryer at 120 °C for 10 minutes to obtain a cured product (cured paint film) of heat curing. The appearance, adhesion, hot water resistance, and chemical resistance of the obtained cured products were evaluated by the following methods, and the results are shown in Table 8.

[0121] Appearance Evaluation of Aqueous Paint Cured Film The obtained cured paint film was visually observed, and the appearance was evaluated according to the following criteria based on the surface smoothness and transparency of the cured paint film. Paint film appearance: ◎: The surface was smooth and the paint film was transparent. ○: The surface was smooth and the paint film was generally transparent with slight cloudiness. △: The surface was uneven or the paint film had cloudy parts. ×: The surface had unevenness and the paint film had cloudiness.

[0122] Adhesion Evaluation of Aqueous Paint Cured Film In accordance with JIS K 5600, 100 squares of 1 mm square were made on the cured paint film, an adhesive tape was attached, and when peeled off at once, the number of squares of the cured film remaining on the substrate side was counted, and the adhesion was evaluated according to the following criteria. The higher the number of remaining squares, the higher the adhesion. ◎: Number of remaining squares 100 〇: Remaining number of squares is 90 or more and less than 100 △: Remaining number of squares is 50 or more and less than 90 ×: Remaining number of squares is less than 50

[0123] Evaluation of the hot water resistance of the cured film of the water-based paint The cured film on the obtained ABS substrate was immersed in hot water at 80 °C together with the ABS plate for 2 hours, then taken out and dried at 25 °C for 2 hours. Thereafter, the above adhesion evaluation was carried out, the number of remaining squares was counted, and the hot water resistance was evaluated according to the following criteria. The more the remaining number of squares, the higher the hot water resistance. ◎: Remaining number of squares is 100 〇: Remaining number of squares is 90 or more and less than 100 △: Remaining number of squares is 50 or more and less than 90 ×: Remaining number of squares is less than 50

[0124] Evaluation of the chemical resistance of the cured film of the water-based paint The cured film on the obtained ABS substrate was immersed in an aqueous NaOH solution with a pH of 9 at 60 °C together with the ABS plate for 1 hour, then taken out and dried at 25 °C for 2 hours. Thereafter, the above adhesion evaluation was carried out, the number of remaining squares was counted, and the chemical resistance was evaluated according to the following criteria. The more the remaining number of squares, the higher the chemical resistance. ◎: Remaining number of squares is 100 〇: Remaining number of squares is 90 or more and less than 100 △: Remaining number of squares is 50 or more and less than 90 ×: Remaining number of squares is less than 50

[0125]

Table 8

[0126] As is clear from the results in Table 8, the aqueous coating composition of the example had high adhesion and could be cured by either UV (active energy rays) or heat, and a cured coating film with high transparency, high surface smoothness, i.e., excellent appearance, was obtained. Also, the obtained cured coating film had good hot water resistance and chemical resistance. These are, as described above, the result of the aqueous coating composition of the example containing the non-aqueous polyfunctional (meth)acrylamide (A) and the polymerizable compound (B) simultaneously. On the other hand, since the aqueous coating composition of the comparative example contained only A and B simultaneously, the physical properties of the cured coating film were not satisfactory.

[0127] Examples 58 to 62 and Comparative Examples 21 and 22 (Preparation and Evaluation of Sealing Agent Compositions) The curable composition, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components obtained in Table 1 were weighed at the mass ratios shown in Table 9 and mixed at 35°C for 1 hour to prepare the sealing agent compositions of Examples 58 to 62 and Comparative Examples 21 and 22. Using the obtained sealing agent compositions, a cured product of the sealing agent (sealing layer) was prepared by the following method, and the physical property evaluation of the obtained sealing layer was carried out as follows.

[0128] Preparation of Cured Product of Sealing Agent (Sealing Layer) A silicone spacer (30 mm long × 15 mm wide × 3 mm thick) was set on a glass plate (50 mm long × 50 mm wide × 5 mm thick), a copper foil (5 mm long × 5 m wide × 80 μm thick) was placed inside the spacer, and the prepared curable sealing agent composition was injected. After sufficient degassing, ultraviolet rays were irradiated (the same Eye Graphics inverter-type conveyor device as described above, the same metal halide lamp as described above, ultraviolet illuminance: 700 mW / cm 2 , integrated light quantity: 1000 mJ / cm 2 ), and a cured product of the sealing agent was obtained. The properties of the obtained cured product were evaluated by the following method, and the results are shown in Table 9.

[0129] Transparency Evaluation of Cured Product of Sealing Agent A portion without copper foil was cut from the obtained cured sealing agent, left standing for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%, and then the transmittance of the cured product was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000), and the transparency was evaluated according to the following criteria. The higher the transmittance, the higher the transparency. ◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% △: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50%

[0130] Water resistance evaluation of the cured sealing agent 1 g was cut from the obtained cured product and set as a test piece in a thermo-hygrostat at a temperature of 85°C × relative humidity of 95%. After leaving it standing for 48 hours, the weight of the test piece was measured again, and the water absorption rate was calculated according to the following formula, and the water resistance was evaluated according to the following criteria. The lower the water absorption rate, the higher the water resistance. Water absorption rate (%) = (weight after water absorption - weight before water absorption) / weight before water absorption × 100% ◎: Water absorption rate is less than 1.0% ○: Water absorption rate is 1.0% or more and less than 2.0% △: Water absorption rate is 2.0% or more and less than 3.0% ×: Water absorption rate is 3.0% or more

[0131] Outgassing resistance evaluation 1 g was cut from the obtained cured product and set as a test piece in a constant temperature bath set at a temperature of 100°C. It was left standing, and a dry nitrogen stream was passed for 24 hours. Then, the weight of the test piece was measured again, and the outgassing generation rate was calculated according to the following formula, and the outgassing resistance was evaluated according to the following criteria. The lower the outgassing generation rate, the higher the outgassing resistance. Outgassing generation rate (%) = (weight after the test - weight before the test) / weight before the test × 100% ◎: Generation rate is less than 0.1% ○: Generation rate is 0.1% or more and less than 0.3% △: Generation rate is 0.3% or more and less than 1.0% ×: Generation rate is 1.0% or more

[0132] Evaluation of resistance to damp heat yellowing After the obtained cured encapsulant was left standing for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%, the transmission spectrum of the cured product was measured using a dedicated transmission color measuring instrument (TZ-6000, manufactured by Nippon Denshoku Industries Co., Ltd.) to obtain the initial b value. Subsequently, the cured product was left standing in a thermo-hygrostat set at 85°C and a relative humidity of 85% for 500 hours to conduct an accelerated test for resistance to damp heat yellowing. After the test, the cured product was similarly left standing for 24 hours in an atmosphere at a temperature of 23°C and a relative humidity of 50%, and the transmitted color was measured to obtain the b value after damp heat The difference between the b value after damp heat and the initial b value was defined as the change value Δb (Δb = b value after damp heat - initial b value). The resistance to damp heat yellowing of the cured product was evaluated according to the following criteria ◎: Both the initial b value and the b value after damp heat are 0.2 or less, and Δb is 0.1 or less ○: Either one or both of the initial b value and the b value after damp heat exceed 0.2, but both are 0.5 or less, and Δb is 0.2 or less △: Either one or both of the initial b value and the b value after damp heat exceed 0.5, but both are 1.0 or less, and Δb is 0.3 or less ×: Either one or both of the initial b value and the b value after damp heat exceed 1.0, or Δb exceeds 0.3

[0133] Evaluation of heat cycle resistance The obtained cured encapsulant was left standing at -40°C for 30 minutes and then at 100°C for 30 minutes, and this was repeated 100 times as one cycle. The state of the cured product was visually observed, and the heat cycle resistance was evaluated according to the following criteria ◎: No change is observed 〇: Slight generation of bubbles is observed, but no generation of cracks is observed. It is transparent △: Generation of some bubbles or cracks is observed, and there is slight cloudiness ×: Bubbles or cracks are generated throughout, and it is in a translucent state

[0134] Evaluation of corrosion resistance After the above-mentioned test for resistance to damp heat yellowing, the surface of the copper foil was visually observed, and the corrosion resistance of the cured product was evaluated in four grades ◎: No corrosion ○: Slightly corroded △: Somewhat corroded ×: Significantly corroded

[0135]

Table 9

[0136] As is clear from the results in Table 9, the sealant composition of the example contains a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B). Due to the numerous isopropyleneoxy groups and (meth)acrylamide groups of A, the resulting cured sealant has high water resistance, little outgassing, and good resistance to hygrothermal yellowing, heat cycle resistance, and corrosion resistance. Also, due to the high compatibility between A and B, the transparency of the cured sealant was also high. On the other hand, none of these physical properties were satisfactory for the cured products obtained from the curable compositions of the comparative examples. The sealant composition of the present disclosure can be suitably used as a sealant for optical members, electrical equipment, etc.

[0137] Examples 63 to 67 and Comparative Examples 23 and 24 (Preparation and Evaluation of Curable Nail Cosmetics) The active energy ray curable composition, (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components obtained in Table 1 were weighed at the mass ratios shown in Table 10 and mixed at 35°C for 1 hour to prepare the nail cosmetics of the examples and comparative examples. Using the obtained nail cosmetics, the curability and the physical property evaluation of the obtained cured film were carried out by the following method, and the results are shown in Table 10.

[0138] Evaluation of Curability of Nail Cosmetics The obtained curable nail cosmetics were applied onto a test piece of nylon 6 (“SHT-N6(NC)”, manufactured by Toray Plastics Seiko Co., Ltd.) using a bar coater (No. 12) so that the film thickness became 10 μm. Then, ultraviolet irradiation was performed using a UV-LED lamp dedicated to gel nails (manufactured by Beauty Nailer, wavelength 405 nm, 48 W), and the time until the tack disappeared when touching the surface of the cured film was measured, and the curability of the nail cosmetics was evaluated according to the following criteria. The shorter the time required until the tack disappears, the higher the curability. ◎: Tack disappears in less than 1 minute. ○: Tack disappears in 1 minute or more and less than 3 minutes. △: Tack disappears in 3 minutes or more and less than 10 minutes. ×: Tack does not disappear even after 10 minutes.

[0139] Evaluation of the adhesion of nail cosmetics Using the obtained curable nail cosmetics, it was applied onto a test piece of nylon 6 in the same manner as described above, and a cured film was prepared by light irradiation for 3 minutes. Using the obtained cured film, in accordance with JIS K 5600, 100 squares of 1 mm square were made on the cured film with a cutter knife, and after sticking an adhesive tape and then peeling it off all at once, the number of squares remaining on the test piece was counted, and the adhesion of the nail cosmetics was evaluated according to the following criteria. The more the number of remaining squares, the higher the adhesion. ◎: The number of remaining squares was 100. ○: The number of remaining squares was 90 - 99. △: The number of remaining squares was 60 - 89. ×: The number of remaining squares was less than 60.

[0140] Evaluation of the surface hardness of the cured film of nail cosmetics In the same manner as the adhesion evaluation, cured films of each example and comparative example were prepared. The surface of the obtained film was drawn with a pencil of hardness HB under a load of 750 g, and the presence or absence of peeling and the presence or absence of scratches were visually confirmed, and the surface hardness of the cured film of nail cosmetics was evaluated according to the following criteria. The less the occurrence of scratches and peeling, the higher the surface hardness. ○: Neither scratches nor peeling occurred. The surface hardness has a pencil hardness of HB or more. △: No peeling occurred, but scratches occurred. ×: Peeling occurred.

[0141] Evaluation of the surface glossiness of the cured film of nail cosmetics In the same manner as the adhesion evaluation, cured films of each example and comparative example were prepared, and the surface gloss of the cured film was visually observed and evaluated according to the following criteria. ○: It has gloss. △: Reflection of light can be confirmed, but cloudiness can be seen. ×: No light reflection can be confirmed, and there is no gloss.

[0142]

Table 10

[0143] As is clear from the results in Table 10, in the performance evaluation using a commercially available UV lamp for gel nails, the curable nail cosmetic of the example contained (meth)acrylamide (A) and polymerizable compound (B) simultaneously, and while having excellent curability, it had high adhesion to a nylon substrate (a material having a large number of amide groups similar to nails mainly composed of protein). From this result, it was found that the curable nail cosmetic of the present disclosure can be suitably used as a gel nail for a base gel directly applied to nails. Also, the surface hardness and surface glossiness of the obtained cured film were good, and it can also be suitably used as a gel nail for a top coat. On the other hand, the curable composition of the comparative example had low curability, and the surface hardness and surface glossiness of the cured film were low.

[0144] Examples 68 to 72 and Comparative Examples 25 and 26 (Preparation and evaluation of curable dental materials) The curable compositions, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photoinitiator (C) and other components obtained in Table 1 were weighed at the mass ratios shown in Table 11, and mixed at 35°C for 1 hour to prepare curable dental materials of the examples and comparative examples. The solubility or dispersibility (when blending an insoluble inorganic filler) of the obtained curable dental materials was observed visually. Also, using the curable dental materials, dental material cured products were produced by the following method, and the curability of the curable dental materials, the surface smoothness, hardness, and adhesive strength of the obtained dental material cured products were evaluated. These evaluation results are shown in Table 11.

[0145] Evaluation of solubility or dispersibility of curable dental materials ◎: The obtained composition was uniform and transparent. 〇: The obtained composition was uniform and translucent. △: The obtained composition was turbid and it was difficult to judge the uniformity. ×: The resulting composition did not mix completely.

[0146] Evaluation of the curability of curable dental materials Using the curable dental materials obtained in the examples and comparative examples, the composition was filled into a polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) having a 6-mm-diameter hole in the center, pressure-bonded with a polypropylene film, and irradiated with a dental light irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Corporation, light output density 700 mW / cm2, light intensity on the irradiation surface 640 - 650 mW / cm 2 , the light source was a halogen lamp, the irradiation aperture was 8 mm), which was brought into close contact with the polypropylene film and irradiated for 30 seconds. The polypropylene film was peeled off, and the cured product was touched by hand to check for stickiness and the presence of uncured components, and the curability was evaluated according to the following criteria. ◎: No stickiness at all (completely cured). ○: Slightly sticky, but no finger marks remain on the surface (almost completely cured, no wiping of uncured components is required). △: Sticky, and finger marks remain on the surface (incompletely cured, wiping of uncured components is necessary). ×: Very sticky, and the finger sticks to the surface (a large amount of uncured components remain and it cannot be used as a cured film).

[0147] Surface smoothness of the cured dental material Using the curable dental materials of the examples and comparative examples, the surface of the cured product obtained in the above curability evaluation was visually observed to check for smoothness and glossiness, and the surface smoothness was evaluated according to the following criteria. ◎: The surface is smooth and shiny. ○: The surface is almost smooth, with a slight haze or slight unevenness. △: The surface is overall hazy, and some unevenness or granularity is confirmed. ×: The surface is overall hazy and covered with granular substances.

[0148] Hardness evaluation of the cured dental material Using the surface of the cured product obtained in the evaluation of the curability of the above curable dental material after buff polishing, the Knoop hardness was measured with a microhardness tester manufactured by Matsuzawa Seiki Co., Ltd. (load: 10 g, 20 seconds, measurement temperature: 23°C). The higher the Knoop hardness, the higher the hardness of the cured dental material. ◎: Knoop hardness is 200 KHN or more (equivalent to permanent tooth enamel). ○: Knoop hardness is 70 KHN or more and less than 200 KHN (equivalent to dentin). △: Knoop hardness is less than 70 KHN. ×: Since it did not cure, measurement could not be performed.

[0149] Evaluation of the adhesive strength (dentin adhesion) of the cured dental material The anterior teeth of the bovine mandible were polished with #1000 waterproof abrasive paper under running water to cut out a flat dentin surface for adhesion, blown with compressed air for 10 seconds to dry, and a tape with a 3-mm diameter hole was attached to set the adherend surface. Then, adhesive test specimens were prepared by a known method (referring to the method described in JP-A-2010-208964). The adhesive test specimens were immersed in water at 37°C for 24 hours, and the tensile adhesive strength was measured with an Instron universal testing machine (crosshead speed: 2 mm / min), and the adhesion between the enamel and dentin of the curable dental materials obtained in the examples and comparative examples was used. The value of the tensile adhesive strength is the average value of 5 test specimens. ◎: The adhesive strength between both enamel and dentin is 20 Mpa or more. ○: The adhesive strength between enamel and dentin is 20 Mpa or more for only one of them. △: The adhesive strength between both enamel and dentin is 7 Mpa or more. ×: The adhesive strength between both enamel and dentin is less than 7 Mpa.

[0150]

Table 11

[0151] As is clear from the results in Table 11, the curable dental material of the examples contained (meth)acrylamide (A) and polymerizable compound (B) simultaneously, had excellent solubility or dispersibility, and high curability. Further, the cured dental material obtained in the examples had good hardness, surface smoothness, and adhesive strength. On the other hand, the curable dental material of the comparative examples did not contain A and B simultaneously, had low solubility or dispersibility, sufficient curing could not proceed, the hardness and surface smoothness of the obtained cured product were low, and the adhesive strength was insufficient.

[0152] Examples 73 to 77 and Comparative Examples 27 and 28 (Preparation and Evaluation of Curable Decorative Coating Agent) The curable composition obtained in Table 1, polyfunctional (meth)acrylamide (A), polymerizable compound (B), photopolymerization initiator (C), and other components were weighed at the mass ratios shown in Table 12, mixed at 35 ° C for 1 hour, and curable decorative coating agents of the examples and comparative examples were prepared. Using the obtained decorative coating agent, a laminate was produced by the following decorative processing, and the physical properties of the laminate were evaluated.

[0153] Production of Laminate The obtained decorative coating agent was applied onto a PC film (「Panlite PC-2151」 manufactured by Teijin Limited) with a thickness of 180 μm using a bar coater (No. 6) so that the film thickness after drying would be 5 μm, then heated at 80 ° C for 3 minutes, and irradiated with ultraviolet rays (the same inverter type conveyor device manufactured by Eye Graphics as described above, the same metal halide lamp as described above, ultraviolet illuminance: 700 mW / cm 2 , integrated light amount: 1000 mJ / cm 2 ) to cure the coating film, and a laminate having a hard coat layer was obtained. The obtained laminate was cut out, and the surface tack resistance, surface hardness, scratch resistance of the hard coat layer of the laminate, and the elongation and flexural resistance of the laminate were evaluated by the following methods, and the results are shown in Table 12.

[0154] Evaluation of Surface Tack Resistance of Hard Coat Layer of Laminate Using the obtained laminate, the surface of the hard coat layer was touched with a finger to evaluate the stickiness. ◎: No stickiness at all. 〇: There is some stickiness, but no finger marks remain on the surface. △: Sticky, with fingerprints remaining on the surface. ×: Extremely sticky, with fingers sticking to the surface.

[0155] Elongation Rate Evaluation of the Laminate The obtained laminate was cut into pieces with a length of 50 mm and a width of 15 mm, fixed in a tensile universal testing machine RTA - 100 (manufactured by Orientec Co., Ltd.) with a chuck - to - chuck distance of 25 mm, and pulled in one direction at a speed of 250 mm / min in an oven set at a temperature of 150°C while visually observing the appearance. The length (mm) of the test piece when cracks or whitening occurred in the coating layer was measured. The elongation rate was calculated by the following method and evaluated according to the following criteria. Elongation Rate (%) = (Length of the test piece after the test / 25) × 100% ◎: Elongation rate is 200% or more 〇: Elongation rate is 150 or more and less than 200% △: Elongation rate is 110% or more and less than 150% ×: Elongation rate is less than 110%

[0156] Surface Hardness Evaluation of the Hard - Coat Layer of the Laminate On the hard - coat layer of the laminate, in accordance with JIS K 5600, after scratching with a pencil at an angle of 45° for about 10 mm, the hardest pencil that did not damage the surface of the laminate was taken as the pencil hardness, and the surface hardness was evaluated according to the following criteria. ◎: Pencil hardness was 2H or higher. ○: Pencil hardness was HB - H. △: Pencil hardness was 3B - B. ×: Pencil hardness was 4B or lower.

[0157] Scratch Resistance Evaluation of the Hard - Coat Layer of the Laminate The hard - coat layer of the laminate was rubbed 10 times with #0000 steel wool with a weight of 200 g, and the surface of the hard - coat layer was visually observed, and the scratch resistance was evaluated according to the following criteria. ◎: No peeling or scratches of the film were observed. ○: Slight thin scratches were observed in a part of the film. △: Streaky scratches were observed throughout the film. ×: The film peels off.

[0158] Flexural resistance evaluation of the laminate The test piece of the laminate was bent at 180° with the hard coat surface facing outward, a 1 kg weight was placed on it, and it was left for 10 minutes. The presence or absence of cracks on the surface of the laminate was visually observed, and the flexural resistance was evaluated according to the following criteria. ◎: No cracks were observed at all. ○: The bent part was partially whitened. △: Some cracks were observed in the bent part. ×: Cracks were observed in the bent part.

[0159]

Table 12

[0160] As is clear from the results in Table 12, the curable decorative coating agent of the example contains polyfunctional (meth)acrylamide (A) and polymerizable compound (B), and by applying and curing it on the surface of a general-purpose plastic substrate, a laminate having a decorative coating layer (decorative coating film) can be easily obtained. The surface of the obtained laminate (coating surface such as hard coat) has tack resistance, high hardness and scratch resistance, and the obtained laminate has good flexural resistance. On the other hand, the curable decorative coating agent of the comparative example did not show similar decorative performance. The decorative coating agent of the present disclosure is suitably used for various decorative molding, decorative processing, and decorative printing such as decorative films, decorative sheets, and decorative coatings.

[0161] The present disclosure contains the following contents. (1) A curable composition containing a water-insoluble polyfunctional (meth)acrylamide (A) and a polymerizable compound (B) other than (A). (2) The solubility parameter (SP value) of the polyfunctional (meth)acrylamide (A) is 8.8 to 11.0 (cal / cm 3 ) 1 / 2 The curable composition according to (1) above. (3) The solubility parameter (SP value) of the polymerizable compound (B) is 8.5 to 14.5 (cal / cm3 ) 1 / 2 The curable composition according to the above (1) or (2). (4) The absolute value of the difference between the solubility parameter (SP value) of the polyfunctional (meth)acrylamide (A) and the solubility parameter (SP value) of the polymerizable compound (B) is 3.0 (cal / cm 3 ) 1 / 2 The curable composition according to any one of the above (1) to (3) below. (5) The acrylic equivalent of the polyfunctional (meth)acrylamide (A) is 180 or more, and the curable composition according to any one of the above (1) to (4). (6) The polyfunctional (meth)acrylamide (A) is a compound represented by general formulas [1] to [4], and the curable composition according to any one of the above (1) to (5). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In formulas [1] to [4], R 1 represents a hydrogen atom or a methyl group, and may be the same or different. R 2 and R 3 both represent a divalent chain hydrocarbon group having 3 carbon atoms, and may be linear or branched, and may be the same or different. R 4 represents a hydrogen atom or a chain hydrocarbon group having 1 to 2 carbon atoms. n is an integer from 1 to 70, x1 and z1 are each independently an integer from 1 to 10, y1 is an integer from 1 to 40, x2, y2 and z2 are each independently an integer from 1 to 30, s3, x3, y3 and z3 are each independently an integer from 1 to 20, and m is an integer of 0 or 1.) (7) Based on the total mass of the curable composition, the content of the polyfunctional (meth)acrylamide (A) is 1 to 95% by mass, and the content of the polymerizable compound (B) is 5 to 99% by mass, and the curable composition according to any one of the above (1) to (6). (8) The polymerizable compound (B) has, in its molecule, one or more polymerizable groups selected from the group consisting of (meth)acrylate group, (meth)acrylamide group, vinyl group, vinyl ether group, methyl vinyl ether group, allyl group, (meth)allyl ether group, maleimide group, α-substituted maleimide group, and α,β-substituted maleimide group, and is the curable composition according to any one of (1) to (7) above. (9) The polymerizable compound (B) contains a monofunctional polymerizable compound (b1) and / or a polyfunctional polymerizable compound (b2), and the content of (b1) is 5 to 80% by mass and the content of (b2) is 0 to 40% by mass based on the total mass of the curable composition, and is the curable composition according to any one of (1) to (8) above. (10) Further contains a polymerizable polymerization initiator (C) (excluding (A) and (B)), and the content of (C) is 0.1 to 20% by mass based on the total mass of the curable composition, and is the curable composition according to any one of (1) to (9) above. (11) Contains a quaternary salt monomer as the polymerizable compound (B), and its content is 0.1 to 30% by mass based on the total mass of the curable composition, and is the curable composition according to any one of (1) to (10) above. (12) A coating agent composition containing the curable composition according to any one of (1) to (11) above. (13) An adhesive composition containing the curable composition according to any one of (1) to (11) above. (14) An adhesive composition containing the curable composition according to any one of (1) to (11) above. (15) An ink composition containing the curable composition according to any one of (1) to (11) above. (16) An aqueous ink composition containing the curable composition according to any one of (1) to (11) above. (17) A three-dimensional shaping ink composition containing the curable composition according to any one of (1) to (11) above. (18) An aqueous paint composition containing the curable composition according to any one of (1) to (11) above. (19) A sealing agent composition containing the curable composition according to any one of (1) to (11) above. A nail cosmetic containing the curable composition according to any one of (1) to (11) above. A dental material containing the curable composition according to any one of (1) to (11) above. A decorative coating agent containing the curable composition according to any one of (1) to (11) above.

Industrial Applicability

[0162] As described above, the curable composition of the present disclosure contains a polyfunctional (meth)acrylamide (A) and a polymerizable compound (B), (A) is amphiphilic, and can be mixed with a wide variety of (B) in a wide range of proportions. Further, if necessary, it can contain a polymerizable polymerization initiator, a polymerizable compound, a non-polymerizable component, an additive, etc. other than (A) and (B), and the results can be various special coating agents, adhesives, adhesives, inks, aqueous inks, inks for three-dimensional modeling, water-based paints, sealants, nail cosmetics, dental materials, decorative coating agents, etc. from general-purpose products. It can be suitably used for applications.

Claims

1. A curable composition containing a water-insoluble (not soluble in 1 g or more in 100 g of water at 25°C) polyfunctional (meth)acrylamide (A), a polymerizable compound other than (A) (B), and a polymerizable polymerization initiator (C).

2. The solubility parameter (SP value) of polyfunctional (meth)acrylamide (A) is 8.8–11.0 (cal / cm³). ３ ) １／２ The solubility parameter (SP value) of polymerizable compound (B) is 8.5 to 14.5 (cal / cm³). ３ ) １／２ The curable composition according to claim 1, wherein the absolute value of the difference between the SP values ​​of A and B is 3.0 or less.

3. The curable composition according to claim 1, wherein the polyfunctional (meth)acrylamide (A) is a compound represented by general formulas [1] to [4]. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 (In formulas [1] to [4], R １ R represents a hydrogen atom or a methyl group, and may be the same or different. ２ and R ３ Both represent a divalent chain hydrocarbon group with 3 carbon atoms, and may be linear or branched in structure, and may be the same or different. ４ (where n represents a hydrogen atom or a chain-like hydrocarbon group having 1 to 2 carbon atoms. n is an integer from 1 to 70, x1 and z1 are independently integers from 1 to 10, y1 is an integer from 1 to 40, x2, y2 and z2 are independently integers from 1 to 30, s3, x3, y3 and z3 are independently integers from 1 to 20, and m is an integer of 0 or 1.)

4. The curable composition according to claim 1, further comprising a quaternary salt monomer and / or a filler.

5. The curable composition according to claim 1, wherein the content of polyfunctional (meth)acrylamide (A) is 1 to 95% by mass, the content of polymerizable compound (B) is 5 to 99% by mass, and the content of polymerizable polymerization initiator (C) is 0.1 to 20% by mass, based on the total mass of the curable composition.

6. A coating agent composition containing the curable composition according to any one of claims 1 to 5.

7. An adhesive composition containing the curable composition according to any one of claims 1 to 5.

8. An adhesive composition containing the curable composition according to any one of claims 1 to 5.

9. An ink composition containing the curable composition according to any one of claims 1 to 5.

10. An aqueous ink composition containing the curable composition according to any one of claims 1 to 5.

11. A three-dimensional modeling ink composition containing the curable composition according to any one of claims 1 to 5.

12. An aqueous coating composition containing the curable composition according to any one of claims 1 to 5.

13. A sealing agent composition containing the curable composition according to any one of claims 1 to 5.

14. A nail cosmetic containing the curable composition described in any one of claims 1 to 5.

15. A dental material containing the curable composition according to any one of claims 1 to 5.

16. A decorative coating agent containing the curable composition according to any one of claims 1 to 5.

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