Polymerizable compositions, their polymers, and molded articles obtained therefrom

Abstract

[Technical Problem] The technical problem to be solved by the present invention is to provide a polymeric composition and a polymer thereof, and various molded articles using the polymeric composition or its polymer, wherein the polymeric composition exhibits excellent wettability to various substrates, including organic substrates, inorganic substrates and substrates composed of organic-inorganic composite materials, which have a wide range of polarities from low to high polarity, and has high transparency and curability, and can provide a cured product with excellent water resistance by curing. [Solution] The polymeric composition contains N-substituted (meth)acrylamide (A) represented by general formula [1]. (wherein, R 1 R represents a hydrogen atom or a methyl group. 2 With R 3 One side represents a chain hydrocarbon group with 6 or more carbon atoms or a cyclic hydrocarbon group with 6 or more carbon atoms, and the other side represents a hydrogen atom, a chain hydrocarbon group with 1 or more carbon atoms, or a cyclic hydrocarbon group with 3 or more carbon atoms. R 2 and R 3 May include carrying R 2 and R 3 (The case where nitrogen atoms together form a saturated ring with 6 or more members).

Description

Technical Field

[0001] This invention relates to a polymeric composition, its polymer, and molded articles using the polymeric composition or polymer. Background Technology

[0002] In recent years, N-substituted (meth)acrylamide has been widely used as a raw material monomer in adhesives, adhesives for optical components, active energy-curable adhesives for polarizing plates, inkjet inks, resin compositions for photoforming, sealing materials for semiconductors or electronic materials, and coating agents for glass or resin molded articles (Patent Documents 1 to 4). In particular, the amide group has high cohesive strength, excellent adhesion to various substrates, and is non-corrosive to metals or metal oxides; therefore, there are numerous reports of using N-substituted (meth)acrylamide as a substitute for (meth)acrylic acid (Patent Documents 5 to 7). However, commonly used N-substituted (meth)acrylamides often contain many water-soluble hydrophilic monomers, and depending on the content of the N-substituted (meth)acrylamide or the intended use of the resulting molded article, its water resistance is often insufficient.

[0003] In addition, N-substituted (meth)acrylamide is often used as a component of active energy line curable resins, but no method has been proposed to improve its water resistance when it is formulated into long-life products such as electronic materials and optical materials.

[0004] [Existing technical documents]

[0005] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2008-287207.

[0007] [Patent Document 2] Japanese Patent Application Publication No. 2011-122013.

[0008] [Patent Document 3] Japanese Patent Application Publication No. 2001-310918.

[0009] [Patent Document 4] Japanese Patent Application Publication No. 2010-155889.

[0010] [Patent Document 5] Japanese Patent Application Publication No. 2011-137181.

[0011] [Patent Document 6] Japanese Patent Application Publication No. 2010-235646.

[0012] [Patent Document 7] Japanese Patent Application Publication No. 2013-256552. Summary of the Invention

[0013] [The technical problem the invention aims to solve]

[0014] The first technical problem to be solved by the present invention is to provide a polymerizable composition, a polymer thereof, etc., which exhibits excellent wettability to various substrates, including organic substrates, inorganic substrates, and substrates composed of organic-inorganic composite materials, having a wide range of polarities from low to high polarity. It also possesses high transparency and curability, and can provide a cured product with excellent water resistance upon curing. Furthermore, the second technical problem to be solved by the present invention is to provide an adhesive composition, and a laminate of an adhesive layer composed of the adhesive composition and various substrates. The adhesive composition contains the polymerizable composition and / or its polymer, exhibiting strong adhesion and bonding to various substrates, and possessing high transparency, water resistance, stain resistance, yellowing resistance, and durability. Furthermore, the third technical problem to be solved by the present invention is to provide a substance containing the polymeric composition and / or its polymer: an adhesive composition for bonding similar or dissimilar materials, having high adhesion, impact resistance, and water resistance to various substrates; a coating composition having high wettability and adhesion to various substrates, exhibiting high surface hardness and water resistance upon curing; a hair cosmetic and an oil-in-water emulsion cosmetic composition, wherein the hair cosmetic has moisture resistance, smoothness, non-stickiness, good hand feel, and long-term stability, and the oil-in-water emulsion cosmetic composition does not exhibit skin irritation and has excellent emulsion stability, user experience, and long-term stability; an ink having high adhesion to various substrates, excellent printing properties such as pigment dispersibility, surface drying, discharge stability, and clarity, and high curability, yellowing resistance, and water resistance; and a three-dimensional shaping ink composition capable of precisely shaping three-dimensional objects with high strength, heat resistance, and water resistance, and excellent resistance to curing shrinkage.

[0015] [Methods used to solve technical problems]

[0016] The inventors, through dedicated research in view of the above circumstances, discovered that a polymerizable composition containing an amphiphilic N-substituted (meth)acrylamide with a specific structure having at least one chain or cyclic hydrocarbon group having six or more carbon atoms as a hydrophobic group and a (meth)acrylamide group as a hydrophilic group can solve the above-mentioned technical problems, thereby completing the present invention.

[0017] That is, the present invention provides the following content.

[0018] (1) A polymerizable composition comprising N-substituted (meth)acrylamide (A) represented by general formula [1].

[0019] [Chemistry 1]

[0020]

[0021] (where R is in the formula)1 R represents a hydrogen atom or a methyl group. 2 With R 3 One of them represents a chain hydrocarbon group with 6 or more carbon atoms or a cyclic hydrocarbon group with 6 or more carbon atoms, and the other represents a hydrogen atom, a chain hydrocarbon group with 1 or more carbon atoms or a cyclic hydrocarbon group with 3 or more carbon atoms. R 2 and R 3 Including with carrying R 2 and R 3 (The case where nitrogen atoms together form a saturated ring with more than 6 members).

[0022] (2) The polymerizable composition as described in (1), wherein the N-substituted (meth)acrylamide (A) is an N-monosubstituted (meth)acrylamide or an N,N-disubstituted (meth)acrylamide, having one or more substituents selected from chain-like saturated and unsaturated structures and cyclic saturated and unsaturated structures having 6 or more to 36 carbon atoms.

[0023] (3) The polymeric composition as described in (1) or (2), wherein the saturated water absorption rate of the cured product is less than 10%.

[0024] (4) The polymerizable composition as described in any one of (1) to (3), wherein the surface tension of the N-substituted (meth)acrylamide (A) is 24.0 mN·m -1 Up to 46.0 mN·m -1 .

[0025] (5) The polymeric composition as described in any one of (1) to (4), wherein the content of N-substituted (meth)acrylamide (A) is 1% by weight or more relative to the total polymeric composition.

[0026] (6) A polymer formed by polymerizing a polymeric composition as described in any one of (1) to (5) by means of an active energy line and / or heat.

[0027] (7) A polymerizable composition, which is any one of the polymerizable compositions described in (1) to (5), and further comprises one or more selected from a polymerization initiator, a compound having unsaturated bonds (excluding N-substituted (meth)acrylamide (A) and polymers using the N-substituted (meth)acrylamide (A), a nonpolymerizable oligomer and a nonpolymerizable polymer (excluding polymers using the N-substituted (meth)acrylamide (A), and the polymer described in (6).

[0028] (8) An adhesive composition comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6), or the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6) and a crosslinking agent.

[0029] (9) A laminate comprising an adhesive layer comprising the adhesive composition of (8) and an organic and / or inorganic substrate, wherein the surface tension of the organic and / or inorganic substrate is 22.6 mN·m -1 Up to 59.0 mN·m -1 .

[0030] (10) An adhesive composition comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6) and a crosslinking agent.

[0031] (11) An adhesive composition comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6) and a crosslinking agent, wherein the absolute value of the difference in surface tension between the two dissimilar bonded materials is 37.0 mN·m -1 the following.

[0032] (12) A cosmetic composition comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6).

[0033] (13) A coating composition comprising a polymeric composition as described in any one of (1) to (5) and (7) or a polymer as described in (6), or a polymeric composition as described in any one of (1) to (5) and (7) or a polymer as described in (6) and a crosslinking agent.

[0034] (14) An ink composition comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6), or the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6) and a crosslinking agent.

[0035] (15) An ink composition for three-dimensional shaping, comprising the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6), or the polymeric composition of any one of (1) to (5) and (7) or the polymer of (6) and a crosslinking agent.

[0036] [Invention Effects]

[0037] According to the present invention, a polymerizable composition containing N-substituted (meth)acrylamide (A) with a specific structure can, through the well-balanced amphiphilicity of N-substituted (meth)acrylamide (A), obtain a polymerizable composition, polymer of the polymerizable composition, etc., that has high transparency and good curability, and excellent wettability on various substrates with a wide range of polarities from low to high polarity, composed of organic substrates, inorganic substrates, and organic-inorganic mixed substrates. By including the obtained polymerizable composition and / or its polymer, it is possible to provide an adhesive composition that exhibits good adhesion and bonding to various substrates, high transparency, stain resistance, yellowing resistance, and durability, and a laminate of an adhesive layer composed of the adhesive composition with various substrates. Furthermore, the present invention, by containing the aforementioned polymeric composition and / or its polymers, can provide: an adhesive composition for similar or dissimilar materials, exhibiting high adhesion, impact resistance, and water resistance to various substrates; a hair cosmetic and an oil-in-water emulsion cosmetic composition, wherein the hair cosmetic exhibits moisture resistance, smoothness, non-stickiness, good hand feel, and long-term stability, and the oil-in-water emulsion cosmetic composition does not exhibit skin irritation and has excellent emulsion stability, user experience, and long-term stability; a coating agent exhibiting high wettability and adhesion to various substrates, and exhibiting high surface hardness and water resistance upon curing; an ink exhibiting high adhesion to various substrates, excellent printing properties such as pigment dispersibility, surface drying, discharge stability, and clarity, and high curability and resistance to yellowing; and a three-dimensional shaping ink composition capable of precisely shaping three-dimensional objects with high strength, heat resistance, and water resistance, and exhibiting excellent resistance to curing shrinkage. Detailed Implementation

[0038] The first embodiment of the present invention is a polymerizable composition. The second embodiment is a polymer obtained by polymerizing the polymerizable composition of the first embodiment using an active energy line and / or heat. The third embodiment is a polymerizable composition further comprising one or more of the polymerizable composition of the first embodiment selected from polymerization initiators, compounds having unsaturated bonds (excluding N-substituted (meth)acrylamide (A) and polymers using N-substituted (meth)acrylamide (A), nonpolymerizable oligomers and nonpolymerizable polymers (excluding polymers using N-substituted (meth)acrylamide (A),) and polymers of the second embodiment. The fourth embodiment is a polymerizable composition, which is formed by further containing one or more of the polymer of the second embodiment, selected from polymerization initiators, compounds having unsaturated bonds (excluding N-substituted (meth)acrylamide (A) and polymers using N-substituted (meth)acrylamide (A), nonpolymerizable oligomers and nonpolymerizable polymers (excluding polymers using N-substituted (meth)acrylamide (A), and crosslinking agents having two or more reactive functional groups in their molecules (excluding compounds having two or more unsaturated bonds in their molecules). Hereinafter, the first to fourth embodiments of the present invention will be described in summary.

[0039] The polymerizable composition of the first embodiment of the present invention contains N-substituted (meth)acrylamide (A) represented by the following general formula [1].

[0040] [Chemistry 2]

[0041]

[0042] In general formula [1], R 1 R represents a hydrogen atom or a methyl group. 2 With R 3 One of them represents a chain hydrocarbon group with 6 or more carbon atoms or a cyclic hydrocarbon group with 6 or more carbon atoms, and the other represents a hydrogen atom, a chain hydrocarbon group with 1 or more carbon atoms or a cyclic hydrocarbon group with 3 or more carbon atoms, R 2 and R 3 Including the following situations: with R-carrying 2 and R 3 The nitrogen atoms together form a saturated ring with 6 or more members. This saturated ring with 6 or more members may or may not contain heteroatoms. Furthermore, R... 2 and R 3 It may contain or not contain substituents containing heteroatoms, and in the case where it contains substituents containing heteroatoms, the number of heteroatoms is 3 or less. The term heteroatoms refers to oxygen atoms, sulfur atoms, nitrogen atoms, or boron atoms. Furthermore, N-substituted (meth)acrylamides not included in the general formula [1] are also called N-substituted (meth)acrylamides (B).

[0043] The polymer of the second embodiment of the present invention is obtained by polymerizing the polymerizable composition of the first embodiment using an active energy line and / or heat. This polymer is a soluble polymer without a cross-linked structure and may be a homopolymer of any monomer selected from the N-substituted (meth)acrylamide (A), or a copolymer of A obtained by copolymerizing two or more monomers selected from A in any proportion, or a copolymer obtained by copolymerizing one or more monomers selected from A with copolymerizable monomers other than A in any proportion. Furthermore, in copolymers obtained from N-substituted (meth)acrylamide (A) and monomers other than A, the content of A in the copolymer is preferably 1% by weight or more relative to the total weight of the copolymer.

[0044] The N-substituted (meth)acrylamide (A) used in the first to fourth embodiments of the present invention (hereinafter also referred to collectively as "this embodiment") is amphiphilic and has the following in its molecule: a hydrophobic substituent, selected from a chain hydrocarbon group having 6 or more carbon atoms, a cyclic hydrocarbon group having 6 or more carbon atoms, and a substituent containing R. 2 and R 3The composition contains at least one substituent from the group consisting of saturated rings with six or more nitrogen atoms; and a hydrophilic (meth)acrylamide group capable of imparting wettability to highly polar substrates. The polymerizable composition of this embodiment, by containing N-substituted (meth)acrylamide (A), exhibits good compatibility among its components, high transparency, and good wettability to various substrates, including organic substrates, inorganic substrates, and organic-inorganic mixed substrates, which possess a wide range of polarities from low to high. Furthermore, N-substituted (meth)acrylamide (A) exhibits sufficient curability and polymerizability to active energy lines and / or heat; therefore, the polymerizable composition containing this N-substituted (meth)acrylamide (A) has high curability and polymerizability. Through the synergistic effect of excellent wettability on various substrates with broad polarity and the strong cohesive force between the amide groups, adhesive compositions and bonding agents formed from polymeric compositions containing N-substituted (meth)acrylamide (A) and / or polymers obtained by polymerizing such polymeric compositions (hereinafter also referred to as polymers of polymeric compositions or polymers) exhibit excellent adhesion to various substrates. Therefore, as molded products of polymeric compositions and / or their polymers, adhesive compositions with high adhesion and stain resistance (reworkability) and bonding agents with high adhesion, impact resistance, and water resistance can be obtained. The polymeric compositions and / or their polymers of this embodiment, by utilizing the properties of N-substituted (meth)acrylamide (A), can be applied not only to adhesive compositions or bonding agents, but also to coating compositions, cosmetic compositions, ink compositions, inkjet ink compositions, ink compositions for three-dimensional shaping, and various other applications.

[0045] Regarding R in the above general formula [1] 2 R 3 From the viewpoint of improving the wettability of the polymeric composition of this embodiment to a low-polarity substrate, the carbon number of the chain-like or cyclic hydrocarbon group is preferably 8 or more, more preferably 12 or more, and even more preferably 16 or more. On the other hand, the carbon number of the chain-like or cyclic hydrocarbon group is not particularly limited, but in order to also sufficiently maintain the wettability of the polymeric composition to a high-polarity substrate, that is, from the viewpoint of balancing the wettability of the low-polarity substrate and the high-polarity substrate, it is generally 36 or less, preferably 24 or less, and more preferably 22 or less. In addition, regarding the inclusion of R in the general formula [1] 2 and R 3 From the viewpoint of achieving a balance between the wettability of the polymeric composition on low-polarity and high-polarity substrates, the number of nitrogen atoms in the saturated ring is preferably 6 or more to 12 or less.

[0046] The N-substituted (meth)acrylamide (A) used in this embodiment is an N-monosubstituted (meth)acrylamide or an N,N-disubstituted (meth)acrylamide. As mentioned above, it is preferable to have one or more substituents selected from chain-like saturated and unsaturated structures and cyclic saturated and unsaturated structures with 6 to 36 carbon atoms. Furthermore, the N-substituted (meth)acrylamide (A) is more preferably having at least one substituent with an unsaturated structure. Generally, among aliphatic compounds with the same number of carbon atoms, compounds containing unsaturated bonds tend to have lower melting points compared to compounds without unsaturated bonds. As will be described later, since the N-substituted (meth)acrylamide (A) is liquid at room temperature, its content in the polymerizable composition of this embodiment can be adjusted to a certain extent. Therefore, it is more preferable that the N-substituted (meth)acrylamide (A) contains one or more substituents with unsaturated structures, which has the effect of lowering the melting point of the N-substituted (meth)acrylamide (A).

[0047] The polymeric composition of this embodiment preferably has a saturated water absorption rate of 10% or less in the cured form at room temperature. In this specification, room temperature refers to 5°C to 35°C at atmospheric pressure. The saturated water absorption rate of the cured form is the water absorption rate in the saturated water absorption state, which can be calculated by the method described later. Furthermore, as long as the saturated water absorption state is achieved, the method and conditions for reaching this state are not limited. If the saturated water absorption rate of the cured form is 10% or less, it has sufficient water resistance. The lower the saturated water absorption rate, the higher the water resistance of the cured form; therefore, a saturated water absorption rate of 7% or less is more preferred, and particularly preferably 5% or less.

[0048] The surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 In this specification, the surface tension of N-substituted (meth)acrylamide (A) is a calculated value at 23°C obtained by the Meissner method (Chemical Engineering Handbook, 7th Revision, page 66), with an average error of 3%.

[0049] When the surface tension of N-substituted (meth)acrylamide (A) is within the aforementioned numerical range, when the polymeric composition containing N-substituted (meth)acrylamide (A) is coated onto substrates of different polarities, the molecules can be arranged according to the polarity of the substrate. This results in good wettability on various substrates exhibiting a wide range of polarities, and also improves the adhesion of the polymeric composition and / or its polymer-formed adhesive composition or bonding agent composition. From these perspectives, the surface tension of N-substituted (meth)acrylamide (A) is more preferably 28.0 mN·m. -1 Up to 36.0 mN·m -1The preferred value is 30.0 mN·m -1 Up to 33.0 mN·m -1 .

[0050] N-substituted (meth)acrylamide (A) is preferably a liquid at room temperature. Because N-substituted (meth)acrylamide (A) is a liquid at room temperature, its content in the polymeric composition of this embodiment can be adjusted to a certain extent even without heating or other operations, making it easy to maintain the transparency of the resulting polymeric composition. N-substituted (meth)acrylamide (A) is more preferably a liquid at 30°C or below, and even more preferably a liquid at 25°C or below. In this specification, "liquid" includes both a fluid liquid state and a non-fluid wax state.

[0051] In the polymerizable composition of this embodiment, the content of N-substituted (meth)acrylamide (A) relative to the total weight of the polymerizable composition can be 1% by weight or more, or 100% by weight. The content of A can be appropriately adjusted according to the specific application of the polymerizable composition. If 1% by weight of N-substituted (meth)acrylamide (A) is contained, the polymerizable composition can exhibit improved curability or polymerizability of active energy lines and / or heat, transparency, and wettability on various substrates exhibiting a wide range of polarities. Furthermore, in order to better exhibit this balance of curability, polymerizability, transparency, and wettability, the content of N-substituted (meth)acrylamide (A) is more preferably 5% by weight to 90% by weight, more preferably 10% by weight to 80% by weight, and particularly preferably 20% by weight to 70% by weight.

[0052] N-substituted (meth)acrylamide (A) has an aliphatic hydrocarbon group with 6 or more carbon atoms that does not contain unsaturated bonds as a substituent. This aliphatic hydrocarbon group can be straight-chain, branched, or cyclic. Examples of N-substituted (methyl)acrylamides include: n-hexyl (methyl)acrylamides, sec-hexyl (methyl)acrylamides, tert-hexyl (methyl)acrylamides, n-heptyl (methyl)acrylamides, sec-heptyl (methyl)acrylamides, tert-heptyl (methyl)acrylamides, n-octyl (methyl)acrylamides, sec-octyl (methyl)acrylamides, tert-octyl (methyl)acrylamides, 2-ethylhexyl (methyl)acrylamides, N,N-di-(2-ethylhexyl)acrylamides, n-nonyl (methyl)acrylamides, n-decyl (methyl)acrylamides, n-undecyl (methyl)acrylamides, n-dodecyl (methyl)acrylamides, n-tridecyl (methyl)acrylamides, n-trimethyldecyl (methyl)acrylamides, n-tetradecyl (methyl)acrylamides, n-hexadecyl (methyl)acrylamides, stearyl (methyl)acrylamides, n-eicosyl (methyl)acrylamides, n-docodecyl (methyl)acrylamides, n-tetradecyl (methyl)acrylamides. N-Cyclohexyl (meth)acrylamide, N,N-dicyclohexyl (meth)acrylamide, N-cyclohexyl-N-methyl (meth)acrylamide, N-cyclohexyl-N-ethyl (meth)acrylamide, N-cyclohexyl-N-propyl (meth)acrylamide, N-cyclohexyl-N-butyl (meth)acrylamide, N-cyclohexyl-N-pentyl (meth)acrylamide, N-cyclohexyl-N-hexyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-(methyl)acrylamide N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-3-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-(meth)acryloyl-3,3-dimethylpiperidine, N-(meth)acryloyl-4,4-dimethylpiperidine, N-(meth)acryloyl-2,2,6,6-Tetramethylpiperidine, N-(meth)acryloyl-2-methyl-5-ethylpiperidine, N-(meth)acryloyl-4-methyl-4-ethylpiperidine, N-(meth)acryloyl-2-ethylpiperidine, N-(meth)acryloyl-3-ethylpiperidine, N-(meth)acryloyl-4-ethylpiperidine, N-(meth)acryloyl-2-propylpiperidine, N-(meth)acryloyl-3-propylpiperidine, N-(meth)acryloyl-4-propylpiperidine, N-(meth)acryloyl-3-isopropylpiperidine, N-(meth)acryloyl-4-isopropylpiperidine, N-(meth)acryloylhexamethyleneimine, N-(meth)acryloyl-2-methylhexamethyleneimine, N-(meth)acryloyl-3-methylhexamethyleneimine, N-(meth)acryloyl-4-methylhexamethyleneimine, N-(meth)acryloyl-2-ethylhexamethyleneimine, N-(meth)acryloyl-3-ethylhexamethyleneimine, N-(meth)acryloyl-4-ethylhexamethyleneimine, N-(meth)acryloyl-3-propylhexamethyleneimine, N-(meth)acryloyl-4-propylhexamethyleneimine, N-(meth)acryloyl-3-isopropylhexamethyleneimine, N-(meth)acryloyl-4-isopropylhexamethyleneimine, N-(meth)acryloyl-3,5-dimethylhexamethyleneimine, N-(meth)acryloyl-4,4-dimethylhexamethyleneimine, N-(meth)acryloyl-heptamethyleneimine, N-(meth)acryloyl-octamethyleneimine, N-(meth)acryloyl-decapethyleneimine, dopamine (meth)acrylamide, 3-(meth)acrylamide phenylboronic acid. From the perspective of easy access to industrial products, the preferred formulations are n-hexyl (meth)acrylamide, n-octyl (meth)acrylamide, tert-octyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, N,N-di-(2-ethylhexyl)acrylamide, n-nonyl (meth)acrylamide, n-decyl (meth)acrylamide, n-dodecyl (meth)acrylamide, n-tridecyl (meth)acrylamide, n-trimethyldecyl (meth)acrylamide, n-tetradecyl (meth)acrylamide, n-hexadecyl (meth)acrylamide, and stearin. N-Cyclohexylacrylamide, N,N-dicyclohexylacrylamide, N-cyclohexyl-N-methylacrylamide, N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-phenyl(meth)acrylamide, dopamine(meth)acrylamide, 3-(meth)acrylamide phenylboronic acid.

[0053] N-substituted (meth)acrylamide (A) has an aliphatic hydrocarbon group with 6 or more carbon atoms containing an unsaturated bond as a substituent. This aliphatic hydrocarbon group can be straight-chain, branched, or cyclic. Examples of N-substituted (meth)acrylamides include: hexenyl (meth)acrylamide, heptenyl (meth)acrylamide, octenyl (meth)acrylamide, nonenyl (meth)acrylamide, decenyl (meth)acrylamide, undecenyl (meth)acrylamide, dodecenyl (meth)acrylamide, tetradecenyl (meth)acrylamide, hexadecenyl (meth)acrylamide, oleyl (meth)acrylamide ("oleyl": oleyl; (9Z)-octadec-9-en-1-yl; (9Z)-octadec-9-en-1-yl), eicosene (meth)acrylamide, dodecenyl (meth)acrylamide, dodecenyl (meth)acrylamide, octadecadienyl (meth)acrylamide, eicosene (... Methacrylamide, docosadienyl (meth)acrylamide, docosadienyl (meth)acrylamide, octadecadienyl (meth)acrylamide, eicostrienyl (meth) ...

[0054] The polymerizable composition of this embodiment may also contain, in addition to N-substituted (meth)acrylamide (A), one or more of the following: polymerization initiators, compounds having unsaturated bonds (excluding N-substituted (meth)acrylamide (A) and polymers using N-substituted (meth)acrylamide (A), non-polymerizable oligomers and non-polymerizable polymers (excluding polymers using N-substituted (meth)acrylamide (A)), and polymers of the polymerizable composition. When the polymerizable composition further contains a polymerization initiator, its curability and polymerizability to active energy lines and / or heat are further improved. When it further contains compounds having unsaturated bonds, it can be more suitable as an adhesive composition, bonding agent composition, coating agent composition, and various ink compositions. Furthermore, when the polymerizable composition further contains non-polymerizable oligomers and / or non-polymerizable polymers, the viscosity of the polymerizable composition and the softness of its cured product can be easily adjusted. Especially when the polymeric composition further contains its polymer, the adhesion of the adhesive composition to various substrates, or the adhesion of the adhesive composition to various substrates, is improved. Hereinafter, the polymeric composition refers to both polymeric compositions without its polymer and polymeric compositions containing its polymer.

[0055] Examples of compounds with unsaturated bonds include: monofunctional monomers or monofunctional oligomers having one unsaturated bond, polyfunctional monomers or polyfunctional oligomers having two or more unsaturated bonds, and polymerizable polymers having unsaturated bonds. These compounds with unsaturated bonds are not limited to any particular application of the polymerizable composition. Monofunctional monomers are used to adjust the viscosity of the polymerizable composition towards lower viscosity, polymerizable polymers are used to adjust the viscosity of the polymerizable composition towards higher viscosity, and polyfunctional monomers, polyfunctional oligomers, and polymerizable polymers are used to adjust the curability of the polymerizable composition or the crosslinking rate of the resulting cured product. In the polymerizable composition of this embodiment, components other than N-substituted (meth)acrylamide (A) can be added individually or in combination of two or more. The content of each monomer can be adjusted appropriately according to the specific application. Relative to the total weight of the polymerizable composition, the preferred content is 1% to 99% by weight for monofunctional monomers, 0.05% to 50% by weight for polyfunctional monomers, 0.05% to 50% by weight for polyfunctional oligomers, 0.01% to 10% by weight for polymerizable or non-polymerizable polymers, and 0.01% to 10% by weight of the polymer in the polymerizable composition. In this specification, homopolymers or copolymers of various monomers with a weight-average molecular weight (Mw) of 1,000 or more but less than 10,000 are classified as oligomers, and those with a Mw of 10,000 or more are classified as polymers.

[0056] Multifunctional monomers are monomers whose molecules contain two or more unsaturated bonds selected from (meth)acrylate, (meth)acrylamide, vinyl, allyl, and maleimide groups. Examples include multifunctional (meth)acrylates and multifunctional (meth)acrylamides. Generally, multifunctional monomers with fewer than 10 unsaturated bonds in their molecules are suitable.

[0057] Examples of multifunctional (meth)acrylates include: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, di-tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol dimethacrylate, and butylene glycol dimethacrylate. 1,3-Butanediol di(meth)acrylate, 1,4-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-Hexanediol di(meth)acrylate, 1,6-Hexanediol ethylene oxide modified di(meth)acrylate, 1,7-Heptanediol di(meth)acrylate, 1,8-Octadiol di(meth)acrylate, 1,9-Nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate with hydroxypentanoic acid, dicyclopentyl di(meth)acrylate, caprolactone modified di(meth)acrylate Dicyclopentenyl (meth)acrylate, ethylene oxide modified di(meth)acrylate phosphate, glycerol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate Acrylic esters, diglycidyl phthalate di(meth)acrylate, glycerol polyglycidyl ether poly(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, ethylene oxide modified bisphenol A type di(meth)acrylate, propylene oxide modified bisphenol A type di(meth)acrylate, cyclohexanediethanol di(meth)acrylate, acrylate-ester (dioxanediol diacrylate) (acrylate) ester (dioxaneglycoldiacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanediethanol di(meth)acrylate, epoxy (meth)acrylate, (meth)acrylate carbamate, ethylene oxide-modified diacrylate of isocyanuric acid, ethylene oxide-modified tri(meth)acrylate of isocyanuric acid, tri(meth)acryloyloxyethoxytrimethylolpropane, ethylene oxide-modified pentaerythritol penta(meth)acrylate, ethylene oxide-modified pentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, etc.

[0058] Examples of multifunctional (meth)acrylamides include: methylene bis(meth)acrylamides, ethylene bis(meth)acrylamides, diallyl(meth)acrylamides, N-[tris(3-(meth)acrylamidespropoxymethyl)methyl](meth)acrylamides, N,N-bis(2-(meth)acrylamidesethyl)(meth)acrylamides, 4,7,10-trioxa-1,13-tetanebis(meth)acrylamides, and N,N'-1,2-ethanediylbis[N-(2-(meth)acrylamidesethyl)](meth)acrylamides. These multifunctional monomers can be used alone or in combination with two or more.

[0059] Monofunctional monomers include: monofunctional (meth)acrylates, monofunctional (meth)acrylamides, styrene, alkoxy-containing monomers, vinyl-containing monomers, allyl-containing monomers, and maleimide-containing monomers, which are free radical polymerizable compounds with reactive double bonds in their molecules.

[0060] Examples of monofunctional (meth)acrylates include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, stearyl methacrylate, isostearyl methacrylate, tridecyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, diethylene glycol (meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy) Ethyl acrylate, phenoxyethyl acrylate, diethylene glycol methacrylate, tetraethylene glycol methacrylate, hexaethylene glycol methacrylate, dipropylene glycol methacrylate, tripropylene glycol methacrylate, cyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, benzyl methacrylate, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, borneol acrylate, isoborneol acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantane acrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, hydroxyhexyl methacrylate, etc.

[0061] Examples of monofunctional (meth)acrylamides include: N-methyl (meth)acrylamides, N-ethyl (meth)acrylamides, N-isopropyl (meth)acrylamides, N-butyl (meth)acrylamides, N-methoxymethyl (meth)acrylamides, N-ethoxymethyl (meth)acrylamides, N-methoxyethyl (meth)acrylamides, N-ethoxyethyl (meth)acrylamides, N-n-butoxymethyl (meth)acrylamides, N-isobutoxymethyl (meth)acrylamides, N-(2-hydroxyethyl)acrylamides, N-[3-(dimethylamino)]propylacrylamides, N,N-dimethyl (meth)acrylamides, N,N-diethyl (meth)acrylamides, diacetone (meth)acrylamides, etc. These monofunctional (meth)acrylamides are included in the above-mentioned N-substituted (meth)acrylamides (B).

[0062] Examples of vinyl-containing monomers include: N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, vinyl acetate, styrene, and vinyloxazoline. These monofunctional monomers can be used alone or in combination with two or more.

[0063] As monofunctional oligomers, polyfunctional oligomers, and polymerizable polymers, examples include: straight-chain and / or branched oligomers and polymers with backbones such as acrylic acid, esters, ethers, carbamates, and amides, which are classified into carbamates, epoxy compounds, and acrylics according to their main chain structure. If these are classified by weight-average molecular weight (Mw), oligomers composed of the aforementioned polyfunctional (meth)acrylates and / or polyfunctional (meth)acrylamides can be exemplified as having a Mw of 1,000 or more but less than 10,000. Polymers with a Mw of 10,000 or more can be exemplified as follows: difunctional poly(meth)acrylate urethane, polyfunctional poly(meth)acrylate urethane, difunctional polyester (meth)acrylate, polyfunctional (meth)acrylate urethane, difunctional polyester (meth)acrylate, polyfunctional polyester (meth)acrylate, difunctional polyether (meth)acrylate, polyfunctional polyether (meth)acrylate, difunctional polyamide (meth)acrylate. Esters, polyamide (meth)acrylates, difunctional poly(meth)acrylates (meth)acrylates, polyfunctional poly(meth)acrylates (meth)acrylates, difunctional poly(meth)acrylates (meth)acrylamide, polyfunctional poly(meth)acrylates (meth)acrylamide, difunctional poly(meth)acrylamide (meth)acrylate, polyfunctional poly(meth)acrylamide (meth)acrylate, difunctional polystyrene (meth)acrylate, polyfunctional polystyrene (meth)acrylate, difunctional polyacrylonitrile (meth)acrylate, polyfunctional polyacrylonitrile (meth)acrylate, difunctional epoxy acrylate (bisphenol A type), polyfunctional epoxy acrylate (bisphenol A type), etc. These oligomers or polymers can be used alone or in combination of two or more.

[0064] Furthermore, considering that monofunctional or polyfunctional oligomers are readily available from commercially available products, as urethane acrylates, examples include: Mitsubishi Chemical's trade names UV-3200B, UV-3000B, UV-6640B, UV-3700B, UV-3310B, and UV-7000B; or Shin-Nakamura Chemical Industry's trade names U-4HA and U-200PA; and Daicel-Cyclad (Daicel) acrylates. Trade names such as EBECRYL245, EBECRYL1259, EBECRYL8210, EBECRYL284, and EBECRYL8402 manufactured by Cytec, CN944, CN969, CN9002, and CN9029 manufactured by SARTOMER, UN1255 and UN-5507 manufactured by Negami Kogyo, and AH-600 and UA-306I manufactured by Kyoei Co., Ltd., etc., can be used as UV (ultraviolet) curable urethane oligomers. KJ Chemicals' Quick Cure (registered trademark) 6100, Quick Cure (registered trademark) 7100, and Quick Cure (registered trademark) 8100, etc., can also be used.

[0065] The compounds having unsaturated bonds can be monomers or oligomers having unsaturated bonds, preferably the various monofunctional monomers, polyfunctional monomers, and oligomers described above. From the viewpoint of obtaining a thermoplastic polymer for adjusting physical properties such as viscosity, the compounds having unsaturated bonds contained in the polymeric composition of this embodiment are preferably monofunctional monomers having one unsaturated bond, and from the viewpoint of improving the cohesiveness of the obtained polymer, monomers capable of introducing crosslinking points are particularly preferred. The content of these compounds having unsaturated bonds can be adjusted arbitrarily according to the specific application, and is preferably from 1% to 99% by weight relative to the total weight of the polymeric composition of this embodiment.

[0066] The monomer capable of introducing crosslinking points is a monomer having one or more reactive functional groups in its molecule. Examples include: (meth)acrylic acid monomers containing hydroxyl groups, (meth)acrylic acid monomers containing carboxyl groups, (meth)acrylic acid monomers containing amino groups, (meth)acrylic acid monomers containing acetoacetyl groups, (meth)acrylic acid monomers containing isocyanate groups, (meth)acrylic acid monomers containing glycidyl groups, vinyl monomers containing oxazoline groups, and other (meth)acrylic acid monomers containing functional groups.

[0067] Examples of hydroxyl-containing (meth)acrylic acid monomers include, for example: 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and other hydroxyalkyl (meth)acrylate esters; N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, and other hydroxyalkyl (meth)acrylamides; in addition, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid monomers can be included. Dicarboxylic acid, N-hydroxymethyl (meth)acrylamide, and other (meth)acrylic acid monomers containing primary hydroxyl groups; (meth)acrylic acid monomers containing secondary hydroxyl groups such as 2-hydroxypropyl (meth)acrylic acid, 2-hydroxybutyl (meth)acrylic acid, 2-hydroxy-3-phenoxypropyl (meth)acrylic acid, 3-chloro-2-hydroxypropyl (meth)acrylic acid, and 2-hydroxy-3-phenoxypropyl (meth)acrylic acid; and (meth)acrylic acid monomers containing tertiary hydroxyl groups such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylic acid. Hydroxyalkyl (meth)acrylic acid esters are preferably used.

[0068] Examples of carboxyl-containing (meth)acrylic acid monomers include: monocarboxylic acids such as (meth)acrylic acid and butenoic acid; and dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. Among these, (meth)acrylic acid is preferred.

[0069] Examples of amino-containing (meth)acrylic monomers include: N,N-dimethylaminoethyl (meth)acrylic acid, N,N-dimethylaminopropyl (meth)acrylic acid, N,N-di-tert-butylaminoethyl (meth)acrylic acid, N,N-diethylaminoethyl (meth)acrylic acid, and other aminoalkyl (meth)acrylic acid esters; and N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and other aminoalkyl (meth)acrylamides.

[0070] Examples of (meth)acrylic acid monomers containing acetyl groups include (meth)acrylic acid-2-(acetylacetoxy)ethyl ester.

[0071] Examples of (meth)acrylic acid monomers containing glycidyl groups include: glycidyl methacrylate, glycidyl (meth)acrylamide glycidyl, N-hydroxyethyl (meth)acrylamide glycidyl ether, N-methyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-ethyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-propyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-butyl-N-hydroxyethyl (meth)acrylamide glycidyl ether, N-hydroxypropyl (meth)acrylamide glycidyl ether, N-hydroxybutyl (meth)acrylamide glycidyl ether, N-hydroxypentyl (meth)acrylamide glycidyl ether, N-hydroxyhexyl (meth)acrylamide glycidyl ether, N-hydroxyheptyl (meth)acrylamide glycidyl ether, N-hydroxyoctyl (meth)acrylamide glycidyl ether, etc.

[0072] Examples of vinyl monomers containing the oxazoline group include: 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl- 2-Oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl-2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline, etc. Furthermore, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, and 4,4-dimethyl-2-vinyl-2-oxazoline, which have high reactivity, are preferred, with 2-vinyl-2-oxazoline being the most preferred. These monomers capable of introducing crosslinking sites are not limited to one type and can be used in combination.

[0073] In this embodiment, the crosslinking agent is a compound capable of introducing a crosslinked structure into the cured polymeric composition. Examples include: monomers capable of introducing crosslinking points, oligomers and polymers capable of introducing multiple crosslinking points obtained by polymerizing such monomers, compounds having two or more reactive functional groups in their molecules, polyfunctional monomers having two or more unsaturated bonds in their molecules, polyfunctional oligomers, and polymeric polymers. Furthermore, in this embodiment, if the monomer capable of introducing crosslinking points is a monofunctional monomer having one or more reactive functionalities in its molecule, it is treated as a monofunctional monomer. The crosslinking methods using crosslinking agents in this embodiment include: (1) a method of crosslinking a polymeric composition or polymer by further containing a compound having a functional group (e.g., isocyanate group or carboxyl group) that reacts with the reactive functional group (e.g., hydroxyl or amino group) contained in the polymeric composition or polymer; (2) a method of crosslinking a polymeric composition or polymer by irradiation with an active energy line by containing a polyfunctional monomer, polyfunctional oligomer or polymeric polymer; (3) a method of crosslinking a polymeric composition or polymer by irradiation with an active energy line and / or reaction of the crosslinking agent by containing a polyfunctional monomer, polyfunctional oligomer or polymeric polymer, or a monomer capable of introducing crosslinking points. Furthermore, crosslinking method (3) is a method of appropriately combining crosslinking methods (1) and (2).

[0074] In the crosslinking method (1) described above, the crosslinking agent (i.e., a compound having a functional group that reacts with the reactive functional group contained in the polymerizable composition or its polymer) can be listed as: isocyanate compounds, epoxy compounds, aziridine compounds, compounds having carboxyl or oxazolinyl groups, etc.

[0075] Examples of isocyanate compounds include: aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate. More specifically, examples of isocyanate compounds include: lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl dimethyl diisocyanate; and isocyanate adducts such as trimethylolpropane / toluene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate L), trimethylolpropane / hexamethylene diisocyanate trimer adduct (manufactured by Tosoh Corporation, trade name: Coronate HL), and isocyanurate ester of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate HX). These isocyanate compounds can be used alone or in combination of two or more.

[0076] Examples of epoxy compounds include: polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, glycerol diglycidyl ether, diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N,N,N',N'-tetraglycidyl-m-xylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-X), or 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C), etc. These compounds can be used alone, or in combination of two or more.

[0077] Examples of aziridine compounds include commercially available products under the trade names HDU, TAZM, and TAZO (all manufactured by Mutual Pharmaceutical Co., Ltd.). These compounds can be used alone or in combination of two or more.

[0078] Examples of compounds containing a carboxyl group include: aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl etherdicarboxylic acid, and diphenyl sulfonedicarboxylic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; alicyclic dicarboxylic acids such as malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, azelaic acid, sebacic acid, and octanoic acid; hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxyvalerateic acid, hydroxypropionic acid, hydroxyhexanoic acid, and hydroxybenzoic acid, as well as their ester-forming derivatives or compounds containing a dicarboxyl group derived from their anhydrides. These compounds can be used alone, or in combination of two or more.

[0079] Examples of compounds containing an oxazoline group include: alkylene bisoxazolines such as tetramethylene bisoxazoline and hexamethylene bisoxazoline; aromatic bisoxazolines such as 1,3-phenylene bis(2-oxazoline) and 1,4-bis(4,5-dihydro-2-oxazolinyl)benzene; and homopolymers of the aforementioned oxazoline-containing vinyl monomers or copolymers with compounds having unsaturated bonds. These compounds can be used alone or in combination of two or more.

[0080] The content of the crosslinking agent (i.e., a compound having two or more functional groups in its molecule that react with the reactive functional groups contained in the polymerizable composition or its polymer) in the crosslinking method (1) can be appropriately selected according to the amount of reactive functional groups contained in the polymerizable composition or its polymer, or in balance with the molecular weight, and further according to the specific application. Generally, it is preferably 0.1% to 15% by weight, more preferably 0.5% to 10% by weight, and particularly preferably 1% to 5% by weight relative to the total weight of the polymerizable composition. When the content is less than 0.1% by weight, the crosslinking formation caused by the crosslinking agent becomes insufficient. In the case where the molded article after the crosslinking reaction is a cured product of the adhesive composition and the bonding agent composition, sufficient durability may not be obtained, and there is also a tendency to cause residue (contamination) in the adhesive composition. In addition, in the case where the molded article after the crosslinking reaction is a cured product of the coating agent, sufficient surface hardness may not be obtained, and in the case where the molded article after the crosslinking reaction is a cured product of the three-dimensional shaping ink (i.e., a three-dimensional shape), it may not be possible to obtain a shape with sufficient hardness and tensile strength. On the other hand, when the content exceeds 15% by weight, if the molded article after the crosslinking reaction is a cured product of the adhesive composition and the bonding agent composition, the softness decreases and the adhesion to the substrate also decreases, making it impossible to obtain sufficient adhesion and bonding strength. In addition, if the molded article after the crosslinking reaction is a cured product of three-dimensional molding ink (i.e., a three-dimensional molded product), it may be impossible to obtain a molded product with sufficient elongation at break. Furthermore, the crosslinking reaction in crosslinking method (1) can also be carried out at room temperature, but in order to promote the reaction, it is preferable to carry it out at a temperature of about 40°C to 120°C.

[0081] In the crosslinking method (2) described above, the crosslinking agent (i.e., a multifunctional monomer, a multifunctional oligomer, or a polymerizable polymer) can be one of the aforementioned crosslinking agents. Furthermore, in the crosslinking method (2), various active energy lines described later can be used for irradiation. When using ultraviolet light (UV, UV-LED, etc.) or visible light as the active energy line, it is preferable to use a photopolymerization initiator. When using an electron beam (EB) or an energy line with a wavelength shorter than that of an electron beam as the active energy line, high energy can be provided, and therefore a photopolymerization initiator may not be required. Additionally, when the unsaturated bonds in the molecules of the multifunctional monomer, multifunctional oligomer, or polymerizable polymer are functional groups that can initiate polymerization on their own, such as maleimide, allyl ether, or vinyl ether groups, a photopolymerization initiator may not be required.

[0082] Regarding the content of the crosslinking agent (i.e., multifunctional monomer, multifunctional oligomer, or polymeric polymer) in the crosslinking method (2), it is preferably 0.05% to 50% by weight relative to the total weight of the polymeric composition. Furthermore, from the viewpoint of achieving good adhesion of the cured crosslinked material to various substrates and a good balance with the hardness or strength of the resulting cured material, it is more preferably 0.1% to 30% by weight, and particularly preferably 0.5% to 20% by weight. When the content is less than 0.05% by weight, the crosslinking formation caused by the crosslinking agent becomes insufficient. In cases where the molded product after the crosslinking reaction is an adhesive composition or a bonding agent composition, sufficient durability may not be obtained, and there is a tendency for residue (contamination) to occur in the adhesive composition. Additionally, in cases where the molded product after the crosslinking reaction is a cured coating agent, sufficient surface hardness cannot be obtained; and in cases where the molded product after the crosslinking reaction is a cured ink for three-dimensional molding materials (i.e., a three-dimensional molded object), it may be impossible to obtain a molded object with sufficient hardness and tensile strength. On the other hand, when the content exceeds 50% by weight, and the molded article after the crosslinking reaction is a cured product of the adhesive composition and the bonding agent composition, the following trend occurs: shrinkage due to curing, characteristic of active energy line curing, easily occurs, leading to peeling or cracking. In this case, sufficient adhesion and bonding strength cannot be obtained. Furthermore, when the molded article after the crosslinking reaction is a cured product of the coating agent, peeling or cracking of the cured film as the molded article is easily caused by curing shrinkage. When the molded article after the crosslinking reaction is a three-dimensional object, sufficient elongation at break may not be obtained.

[0083] The content of the crosslinking agent (i.e., multifunctional monomer, multifunctional oligomer or polymeric polymer, and compound having two or more reactive functional groups in its molecule) in the crosslinking method (3) varies depending on the type of crosslinking agent used. The content of the multifunctional monomer, multifunctional oligomer or polymeric polymer is preferably 0.05% to 30% by weight relative to the total weight of the polymeric composition. In addition, the content of the compound having two or more reactive functional groups in its molecule is preferably 0.1% to 10% by weight relative to the total weight of the polymeric composition. Furthermore, since the multifunctional monomer, multifunctional oligomer and polymeric polymer are used in combination with the compound having two or more reactive functional groups in its molecule, the total content of these crosslinking agents is preferably 0.15% to 40% by weight relative to the total weight of the polymeric composition, more preferably 0.2% to 35% by weight, and particularly preferably 0.5% to 30% by weight. When the total content is less than 0.15% by weight, the crosslinking formation caused by the crosslinking agent becomes insufficient. If the molded article after the crosslinking reaction is a cured product of the adhesive and bonding agent compositions, sufficient durability may not be obtained, and there is a tendency for residue (contamination) to occur in the adhesive composition. Furthermore, if the molded article after the crosslinking reaction is a cured product of the coating agent, sufficient surface hardness may not be obtained. If the molded article after the crosslinking reaction is a cured product of 3D modeling ink (i.e., a 3D model), it may be impossible to obtain a model with sufficient hardness and tensile strength. When the total content exceeds 40% by weight, if the molded article after the crosslinking reaction is a cured product of the adhesive and bonding agent compositions, the softness decreases, and the adhesion to the substrate also decreases, resulting in insufficient adhesion and bonding strength. Furthermore, if the molded article after the crosslinking reaction is a cured product of 3D modeling ink (i.e., a 3D model), it may be impossible to obtain a model with sufficient elongation at break.

[0084] As described above, the polymerizable composition of this embodiment may further contain nonpolymerizable oligomers with a weight-average molecular weight (Mw) of 1,000 or more but less than 10,000 and / or nonpolymerizable polymers with a Mw of 10,000 or more. Examples of nonpolymerizable oligomers and nonpolymerizable polymers include thermoplastic resins, rosin-based resins, or mixtures thereof. Examples of the aforementioned thermoplastic resins include (meth)acrylic resins, cyclic polyolefin resins, cellulose resins, polyester resins, polyurethane resins, polysulfonic acid resins, ABS resins as copolymers of acrylonitrile, butadiene, and styrene, polycarbonate resins, polyamide resins, and polyimide resins. Examples of rosin-based resins include natural rosin such as rosin resin; and modified rosin resins such as hydrogenated rosin, disproportionated rosin, rosin-modified phenolic resins, maleic acid-modified rosin resins, maleic rosin, and esterified gum obtained by modifying natural rosin. These non-polymerizable oligomers and non-polymerizable polymers can be used alone or in combination with two or more.

[0085] As described above, the polymerizable composition of this embodiment may further contain a polymerization initiator and / or a compound having unsaturated bonds. In this case, the polymerizable composition further improves the curability and polymerizability obtained by the active energy line and / or heat, and is suitable for use as an adhesive composition, bonding agent composition, coating agent composition, and ink composition that is curable by the active energy line and / or heat. For example, as an adhesive composition, the polymerizable composition can be coated onto a separator or various substrates described later and then cured by the active energy line to form an adhesive layer. In this specification, the polymerization of the polymerizable composition by the active energy line and heat is also referred to as hybrid polymerization. In hybrid polymerization, polymerization can be carried out in the order of active energy line and heat, or in the order of heat and active energy line.

[0086] An active energy beam is defined as an energy beam capable of decomposing a compound (photopolymerization initiator) that generates active species to produce active species. Examples of such active energy beams include visible light, ultraviolet light, infrared light, alpha rays, beta rays, gamma rays, X-rays, and electron beams (EB). When using an electron beam as the active energy beam, a photopolymerization initiator may not be used. On the other hand, when using ultraviolet light or visible light, a photopolymerization initiator is preferred. Irradiation with the active energy beam is preferably carried out in an inert gas atmosphere such as nitrogen or carbon dioxide, or in an atmosphere with reduced oxygen concentration. However, the polymerizable composition of this embodiment contains N-substituted (meth)acrylamide (A), thus exhibiting good curability and sufficient curing even in a normal air atmosphere. The irradiation temperature of the active energy beam is preferably from 10°C to 200°C, and the irradiation time is preferably from 1 second to 60 minutes.

[0087] As a photopolymerization initiator, it is sufficient to irradiate a substance with a suitable wavelength of ultraviolet light that can induce a polymerization reaction by means of irradiating it with ultraviolet light of an appropriate wavelength according to the type of reactive component of the active energy line, thereby generating a free radical (i.e., a photoradical polymerization initiator). Photopolymerization initiators can be appropriately selected from commonly used photopolymerization initiators such as acetophenone, benzoin, benzophenone, and thioxanthone. Commercially available products include: IGM Resins BV's 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, and Omnirad TPO, etc., and UCB's Ubecryl P36, etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0088] There are no particular limitations on its use as a photoradical polymerization initiator. Examples include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, anisole methyl ether, and other benzoin derivatives; acetophenones such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, α-hydroxy-α,α'-dimethylacetophenone, methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-cyclohexylacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylone, 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, and other acetophenone derivatives; acetophenones such as 2-hydroxy-2-methylacetophenone and 2-hydroxy-4'-isopropyl-2-methylacetophenone; benzophenone, methyl... Benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, and other benzophenone derivatives; thioxanthone, 2-chlorothioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and other thioxanthone derivatives; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide, and other acylphosphine oxide derivatives; benzoyl, dibenzocycloheptanone, α-acyl oxime esters, etc. Photoradical polymerization initiators can be used alone or in combination with two or more.

[0089] The content of these photopolymerization initiators is typically 0.1% to 10% by weight relative to the total weight of the polymerizable composition of this embodiment, preferably 0.1% to 5% by weight, and more preferably 0.5% to 3% by weight. This is because if the content of the photopolymerization initiator is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 10% by weight, the properties such as the strength of the cured product may decrease.

[0090] The thermal polymerization of the polymerizable composition of this embodiment can be carried out in the presence of a thermal polymerization initiator by known methods, such as emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization. When using solution polymerization, there are no particular limitations on the solvent that can be used, as long as it dissolves the polymer obtained from the polymerization. Examples include: 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; aliphatic alcohols such as ethanol, n-propanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and acetonitrile and N,N-dimethylformamide. These solvents can be used alone or in combination. Especially from the viewpoint of easy removal during the formation of the molded article, it is preferable to use low-boiling-point solvents such as ethyl acetate, methyl ethyl ketone, and acetone. The temperature or time of thermal polymerization varies depending on the thermal polymerization method used and the thermal polymerization initiator used. It is usually calculated based on the half-life of the initiator. The temperature is usually preferred to be 60°C to 120°C, and the time is usually preferred to be 2 hours to 20 hours, more preferably 5 hours to 10 hours.

[0091] Examples of thermal polymerization initiators include thermal free radical polymerization initiators such as azo compounds like azobisisobutyronitrile, azobispentaronitrile, and dimethyl azobis(isobutyrate); peroxide catalysts like benzoyl peroxide and hydrogen peroxide; and persulfate catalysts like ammonium persulfate and sodium persulfate. The content of the thermal polymerization initiator is approximately 0.01% to 10% by weight relative to the total weight of the polymerizable composition. Furthermore, conventional free radical polymerization techniques, such as adjusting the molecular weight using chain transfer agents, can also be applied.

[0092] As described above, the polymer obtained by polymerizing the polymeric composition of this embodiment through the various methods described above may also be included as a component of the polymeric composition. The molecular weight of the polymer in the polymeric composition of this embodiment, expressed as weight-average molecular weight (Mw), is typically 1,000 to 2,000,000, preferably 5,000 to 1,000,000, and particularly preferably 10,000 to 500,000. If Mw is in the range of 1,000 to 2,000,000, the viscosity of the solution when the polymer is dissolved in a solvent or a commonly used low-viscosity monomer will not be too high or too low, thus allowing for suitable operation and high processing accuracy for adhesive sheets, coatings, three-dimensional shapes, etc. When diluted with ethyl acetate such that the polymer solids constitute 30%, the solution viscosity at 25°C is typically from 10 mPa·s to 100,000 mPa·s, preferably from 500 mPa·s to 10,000 mPa·s, and more preferably from 1,000 mPa·s to 5,000 mPa·s. Viscosity can be determined according to the cone-plate viscometer method of JIS (Japanese Industrial Standards) K5600-2-3.

[0093] The fifth embodiment of the present invention is an adhesive composition (hereinafter also referred to as an adhesive). The adhesive composition of the fifth embodiment contains the polymeric composition or polymer thereof of the first to fourth embodiments, or the polymeric composition or polymer thereof and a crosslinking agent. The polymeric composition or polymer thereof of the first to fourth embodiments contains N-substituted (meth)acrylamide (A), and therefore, as an adhesive composition, it has sufficient cohesive or adhesive strength, good adhesion to various substrates, and stain resistance, and also has durability and resistance to yellowing. Therefore, the above-mentioned polymeric composition or polymer thereof can also be used directly as an adhesive composition. On the other hand, by crosslinking the adhesive composition including the above-mentioned polymeric composition or polymer thereof through the crosslinking method (1) to crosslinking method (3) using the crosslinking agent, an adhesive composition with better stain resistance and durability can also be obtained.

[0094] The adhesive composition of the fifth embodiment can be used directly as an adhesive layer after being coated or formed onto a separator or substrate. Alternatively, it can be formed by curing with active energy lines and / or heat; that is, it can be used as an adhesive composition with active energy lines and / or thermosetting properties. Furthermore, when the adhesive composition contains an organic solvent, it is dried at a temperature of 60°C to 120°C for 1 to 30 minutes after being coated or formed onto the separator or substrate. The method of coating the adhesive composition onto the separator or substrate can use conventionally known methods, such as spin coating, spray coating, knife coating, dip coating, gravure roller coating, reverse roller coating, screen printing, bar coating, and other common film-forming methods.

[0095] A laminate can be obtained by laminating an adhesive layer composed of the adhesive composition of the fifth embodiment with various substrates. Methods for laminating the adhesive layer with various substrates include, for example, transfer printing or roll-to-roll printing. The thickness of the adhesive layer in the laminate varies depending on the application and is not particularly limited, typically ranging from 4 μm to 150 μm. For automotive parts, approximately 20 μm to 120 μm is suitable, while for electronic materials or optical components, approximately 30 μm to 100 μm is suitable.

[0096] As a substrate, various substrates can be listed depending on the application, such as organic substrates with a wide range of polarities from low to high, inorganic substrates, and substrates composed of organic-inorganic composite materials. Materials used as substrates include, for example, polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polycarbonate, ABS resin as an acrylonitrile-butadiene-styrene copolymer, acrylic resins such as polyimide, polyamide, and polymethyl methacrylate, metals such as steel, stainless steel, copper, and aluminum, and glass. Additionally, composite materials formed by dispersing silica particles (an inorganic material) in polyimide (an organic material) can be included. The applications of these various substrates are not particularly limited; for example, they can be used in electronic materials, optical components, or automotive parts.

[0097] The adhesive layer constituting the laminate of the fifth embodiment is formed from a polymeric composition or polymer containing N-substituted (meth)acrylamide (A). The N-substituted (meth)acrylamide (A) has hydrophobic substituents that exhibit wettability to low-polarity substrates and hydrophilic (meth)acrylamide groups that exhibit wettability to high-polarity substrates, thus imparting excellent adhesion to substrates ranging from low-polarity to high-polarity. Furthermore, by exhibiting strong cohesive forces through hydrogen bonds between the amide groups derived from A, high adhesion and stain resistance are provided. Moreover, the polymeric composition or polymer has high transparency and resistance to yellowing; therefore, the adhesive layer obtained from this polymeric composition or polymer also exhibits high transparency and resistance to yellowing, making it suitable for use in optical fields such as adhesives for optical components and adhesive sheets. Laminates composed of adhesive layers with these properties and various substrates can be used as adhesive films or adhesive sheets for electronic materials, optical components, and automotive components.

[0098] In the adhesive composition of the fifth embodiment, the N-substituted (meth)acrylamide (A) in the adhesive composition can be introduced from a polymerizable composition containing A, or A can be introduced in the form of structural units from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and structural units of A in the adhesive is preferably from 0.1% to 90% by weight, more preferably from 1% to 70% by weight, and particularly preferably from 5% to 60% by weight, relative to the total weight of the adhesive composition (excluding solvents (hereinafter also excluding solvents)). Furthermore, from the viewpoint of further improving wettability and adhesion to various substrates, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

[0099] In the adhesive composition of the fifth embodiment, from the viewpoint of improving the water resistance of the adhesive layer formed using the adhesive composition, the further contained polymerization initiator, compounds having unsaturated bonds, and non-polymerizable components (including non-polymerizable oligomers, non-polymerizable polymers, and the polymer of the second embodiment of the present invention) are preferably hydrophobic. Furthermore, in order to adjust the balance between the hydrophilicity and hydrophobicity of the adhesive composition, the content of monofunctional monomers (excluding N-substituted (meth)acrylamide (A)) is preferably 10% to 90% by weight relative to the total weight of the adhesive composition, more preferably 20% to 80% by weight, and particularly preferably 30% to 70% by weight. The total content of crosslinking agents containing polyfunctional monomers is preferably 1% to 30% by weight relative to the total weight of the adhesive composition, more preferably 2% to 20% by weight, and particularly preferably 5% to 15% by weight. The total content of the non-polymeric components relative to the total weight of the adhesive composition is preferably from 0.1% to 20% by weight, more preferably from 0.5% to 15% by weight, and particularly preferably from 1% to 10% by weight. This adhesive composition exhibits high adhesion to various substrates, and the adhesive layer formed by this adhesive composition has high adhesion. It is possible to obtain an adhesive composition with excellent transparency, water resistance, stain resistance, yellowing resistance, and durability, as well as laminates of the adhesive layer formed by this adhesive composition and various substrates.

[0100] The sixth embodiment of the present invention is an adhesive composition (hereinafter also referred to as an adhesive). The adhesive composition of the sixth embodiment contains the polymerizable composition or polymer thereof of the first to fourth embodiments and a crosslinking agent. The above-mentioned adhesive composition, by containing N-substituted (meth)acrylamide (A) and a crosslinking agent, exhibits high adhesion and impact resistance to various substrates, including organic substrates, inorganic substrates, and substrates composed of organic-inorganic composite materials, which have a wide range of polarities from low to high polarity. Therefore, it can be used as an adhesive composition for similar or dissimilar materials.

[0101] The term "similar materials" refers to materials of the same type among the aforementioned resins, metals, glasses, and composite materials. Preferably, the surface tension of each material at 23°C is 22.6 mN·m. -1 Up to 59.0 mN·m -1 If the surface tension of the materials is within the above-mentioned range, high adhesion can be obtained. The surface tension of the above materials at 23°C can be measured according to JIS K 6768, and the lowest surface tension that can be measured using this method is 22.6 mN·m. -1 In this specification, for the convenience of calculating the absolute value of the difference in surface tension between the dissimilar materials described later, the surface tension value measured by this method is lower than 22.6 mN·m. -1 The surface tension of the material is 22.6 mN·m. -1 .

[0102] The term "dissimilar materials" refers to different types of materials among the aforementioned resins, metals, glasses, and composite materials. Preferably, the dissimilar materials bonded together by the adhesive composition have an absolute value of 37.0 mN·m between their surface tensions at 23°C. -1 The following applies to dissimilar materials. Even when the materials are different, their surface tensions can sometimes be the same. Therefore, the absolute value of the difference in surface tension is 0.0 mN·m. -1 The above applies. If the absolute value of the difference in surface tension is within the above range for dissimilar materials, good adhesion can be obtained.

[0103] In the adhesive composition of the sixth embodiment, the N-substituted (meth)acrylamide (A) contained in the adhesive composition can be introduced from a polymerizable composition containing A, or A can be introduced in the form of structural units from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of the structural units of N-substituted (meth)acrylamide (A) and A in the adhesive is preferably 1% to 95% by weight, more preferably 10% to 85% by weight, and particularly preferably 2% to 80% by weight relative to the total weight of the adhesive (excluding solvent). Furthermore, from the viewpoint of further improving the adhesion between similar materials and between dissimilar materials, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 to 46.0 mN·m. -1 .

[0104] In the adhesive composition of the sixth embodiment, from the viewpoint of improving the water resistance of the cured product obtained by curing using the adhesive composition, the further contained polymerization initiator, compound having unsaturated bonds, and non-polymerizable components (including non-polymerizable oligomers, non-polymerizable polymers, and the polymer of the second embodiment of the present invention) are preferably hydrophobic. Furthermore, in order to adjust the balance between hydrophilicity and hydrophobicity of the adhesive composition and improve cohesiveness, the content of the monofunctional monomer (excluding N-substituted (meth)acrylamide (A)) relative to the total weight of the adhesive composition is preferably 1% to 85% by weight, more preferably 2% to 80% by weight, and particularly preferably 5% to 75% by weight. Furthermore, regarding the content of the (meth)acrylate monomer as the monofunctional monomer, in order to sufficiently maintain the cohesiveness derived from the (meth)acrylamide monomer, it is most preferably less than 50% by weight.

[0105] In the adhesive composition of the sixth embodiment, the total content of the crosslinking agent, including the multifunctional monomer, relative to the total weight of the adhesive composition is preferably 1% to 50% by weight, more preferably 5% to 30% by weight, and particularly preferably 10% to 25% by weight. When the content is less than 1% by weight, the crosslinking formation caused by the crosslinking agent becomes insufficient, and sometimes the cohesiveness of the adhesive is insufficient, so that sufficient impact resistance or heat resistance cannot be obtained. On the other hand, when the content is more than 50% by weight, the crosslinking density of the crosslinked adhesive is too high, so there is a tendency for the adhesion to the substrate to decrease due to shrinkage, resulting in a decrease in adhesion. The crosslinking reaction using the crosslinking agent can be carried out by the crosslinking method (1) to the crosslinking method (3) described above. Further, the total content of the nonpolymeric component relative to the total weight of the adhesive composition is preferably 0.01% to 15% by weight, more preferably 0.1% to 10% by weight, and particularly preferably 0.5% to 8% by weight. This adhesive composition has high adhesion, impact resistance and water resistance to various substrates, and is suitable for bonding similar or dissimilar materials. In addition, the N-substituted (meth)acrylamide (A) used in the invention has high resistance to yellowing, and the adhesive composition of the sixth embodiment can also be used as an adhesive for optical film laminates such as phase difference films or polarizing plates.

[0106] The seventh embodiment of the present invention is a cosmetic composition (hereinafter also referred to as a cosmetic). The cosmetic composition of the seventh embodiment contains the polymerizable composition or polymer thereof of the first to fourth embodiments. The above-mentioned cosmetic composition can be used as a cosmetic composition with moisture resistance by containing N-substituted (meth)acrylamide (A). Furthermore, it can also be used as a cosmetic composition with emulsion stability due to the well-balanced amphiphilicity of N-substituted (meth)acrylamide (A). From the viewpoint of improving moisture resistance and emulsion stability, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

[0107] The cosmetic composition of the seventh embodiment may further contain other ingredients depending on the application or dosage form, and there are no particular limitations on the other ingredients. For example, when the cosmetic composition is used as a skin cosmetic, other ingredients may include: various polymerization initiators, polyoxyethylene macromonomers such as polyoxyethylene macromonomers, oil phase components such as hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid oils, solid oils, waxes, and fragrances used in the manufacture of oil-in-water emulsion cosmetics, and aqueous phase components such as water, water-soluble alcohols, and thickeners. In addition, when the cosmetic composition is used as a hair cosmetic in the form of a hair spray, other ingredients may include polymerization initiators, polymeric surfactants, and alkaline compounds. In particular, by using tert-octylacrylamide, tert-butylacrylamide, etc., the cosmetic composition has good solubility in LPG (Liquefied Petroleum Gas), so it is appropriate to use (tert-octylacrylamide) or in combination with (tert-butylacrylamide) in aerosol products such as hair sprays that use LPG as hair cosmetics.

[0108] In the cosmetic composition of the seventh embodiment, the N-substituted (meth)acrylamide (A) contained in the cosmetic composition can be introduced from a polymeric composition containing A, or A can be introduced in the form of structural units from the polymer of the polymeric composition and the polymer of N-substituted (meth)acrylamide (A). The total content of the structural units of N-substituted (meth)acrylamide (A) and A in the cosmetic composition is preferably from 1% to 80% by weight, more preferably from 5% to 70% by weight, and particularly preferably from 10% to 60% by weight relative to the total weight of the cosmetic composition. This cosmetic composition does not exhibit skin irritation, has moisture resistance or emulsification stability and time stability, and has excellent user experience in terms of smoothness, non-stickiness, hand feel, moisturizing feel, and rapid skin affinity.

[0109] The eighth embodiment of the present invention is a coating composition (hereinafter also referred to as a coating agent). The coating composition of the eighth embodiment contains the polymeric composition or polymer thereof of the first to fourth embodiments. The coating composition, by containing N-substituted (meth)acrylamide (A), exhibits high wettability to various substrates, including organic substrates, inorganic substrates, and substrates composed of organic-inorganic composite materials, which have a wide range of polarities from low to high polarity. The method of applying the coating composition to the substrate can be any conventionally known method. After being applied to the substrate, the coating composition is cured by the aforementioned active energy line and / or heat. The thickness of the coating composition applied to the substrate is not particularly limited, but a thickness that is sufficiently cured by the active energy line and / or heat is preferred, typically from 1 μm to 100 μm. The resulting cured product (coating layer) exhibits excellent adhesion to the aforementioned various substrates, and displays high pencil hardness and water resistance.

[0110] In the coating composition of the eighth embodiment, the N-substituted (meth)acrylamide (A) contained in the coating composition can be introduced from a polymeric composition containing A, or A can be introduced in the form of structural units from the polymer of the polymeric composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and structural units of A in the coating agent is preferably from 1% to 80% by weight relative to the total weight of the coating agent (excluding solvent), more preferably from 5% to 70% by weight, and particularly preferably from 10% to 60% by weight. Furthermore, from the viewpoint of further improving adhesion to various substrates, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

[0111] The coating composition of the eighth embodiment preferably further contains the aforementioned crosslinking agent, in which case the pencil hardness and water resistance of the coating layer are improved. From this viewpoint, the content of the crosslinking agent in the total weight of the coating composition is preferably 5% to 70% by weight, more preferably 10% to 60% by weight, and particularly preferably 20% to 50% by weight. The coating composition may also contain the aforementioned photopolymerization initiator, monofunctional monomers and oligomers, non-polymerizable oligomers and polymers as other components. The content of other components is only required to be within the range that does not impair the aforementioned characteristics of the coating composition, and is typically 0.1 parts by weight to 20 parts by weight relative to 100 parts by weight of the polymerizable composition. This coating composition has high wettability and adhesion to various substrates, and by curing using this coating composition, coating films exhibiting high surface hardness and water resistance can be obtained.

[0112] The ninth embodiment of the present invention is an ink composition (hereinafter also referred to as ink). The ink composition of the ninth embodiment contains the polymerizable composition or polymer thereof of the first to fourth embodiments. The above-mentioned ink composition has high curability by containing N-substituted (meth)acrylamide (A). The method of applying the ink composition to the substrate can be a conventionally known method. From the viewpoint that the ink viscosity at 25°C is preferably less than 500 mPa·s, it is more preferably less than 100 mPa·s. After the ink composition is applied to the substrate, it is cured by the above-mentioned active energy line and / or heat to form an ink layer. From the viewpoint that the resulting ink layer has better adhesion to various substrates, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

[0113] In the ink composition of the ninth embodiment, the N-substituted (meth)acrylamide (A) contained in the ink composition may be introduced from a polymerizable composition containing A, or A may be introduced in the form of structural units from the polymer of the polymerizable composition and the polymer of N-substituted (meth)acrylamide (A). The total content of N-substituted (meth)acrylamide (A) and structural units of A in the ink is preferably 5% to 90% by weight relative to the total weight of the ink (excluding solvent), more preferably 10% to 85% by weight, and particularly preferably 15% to 80% by weight.

[0114] The ink composition of the ninth embodiment may further contain the aforementioned crosslinking agent, in which case the curability, surface drying properties, and water resistance of the ink layer are improved. From these views, the content of the crosslinking agent in the total weight of the ink composition is preferably 1% to 50% by weight, more preferably 5% to 45% by weight, and particularly preferably 10% to 40% by weight. The ink composition may further contain the aforementioned photopolymerization initiator, monofunctional monomers and oligomers, nonpolymerizable oligomers, and polymers as other components. The content of other components is only required to be within the range that does not impair the aforementioned characteristics of the ink composition, and is typically 0.1 parts by weight to 30 parts by weight relative to 100 parts by weight of the polymerizable composition. This ink composition exhibits high adhesion to various substrates, excellent printing properties such as pigment dispersion, surface drying, discharge stability, and clarity, and by using this ink composition, an ink with high curability, yellowing resistance, and water resistance can be obtained.

[0115] The tenth embodiment of the present invention is a three-dimensional shaping ink composition. The three-dimensional shaping ink composition of the tenth embodiment contains the polymeric composition or polymer thereof of the first to fourth embodiments, or the polymeric composition or polymer thereof and a crosslinking agent. Since the polymeric composition or polymer thereof of the first to fourth embodiments contains N-substituted (meth)acrylamide (A), the above-mentioned three-dimensional shaping ink composition has high curability and resistance to curing shrinkage. The cured product of the three-dimensional shaping ink composition has high strength and water resistance, and excellent shaping accuracy. The above-mentioned three-dimensional shaping ink composition is cured by irradiation and / or heat from an active energy line while or immediately after being formed into a predetermined shape pattern, thereby forming a thin film. A three-dimensional object is shaped by stacking these films. The shaping method is not particularly limited; for example, a photoforming method in which ink is ejected by inkjet and cured by irradiation from an active energy line can be cited. In this case, from the viewpoint of stable discharge, the viscosity of the three-dimensional shaping ink composition at 25°C is preferably from 1 mPa·s to 200 mPa·s, and the discharge temperature is preferably in the range of 20°C to 100°C. From the viewpoint that the resulting three-dimensional shape can exhibit good appearance such as gloss and density, the surface tension of N-substituted (meth)acrylamide (A) is preferably 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

[0116] In the three-dimensional shaping ink composition of the tenth embodiment, the N-substituted (meth)acrylamide (A) in the three-dimensional shaping ink composition can be introduced from a polymeric composition containing A, or A can be introduced in the form of structural units from the polymer of the polymeric composition and the polymer of N-substituted (meth)acrylamide (A). The total content of the structural units of N-substituted (meth)acrylamide (A) and A in the three-dimensional shaping ink composition is preferably 1% to 80% by weight relative to the total weight of the three-dimensional shaping ink, more preferably 2% to 70% by weight, and particularly preferably 5% to 60% by weight.

[0117] The three-dimensional shaping ink composition of the tenth embodiment preferably further contains the aforementioned crosslinking agent. In this case, three-dimensional shapes with superior strength, water resistance, and heat resistance can be formed. From this perspective, the content of the crosslinking agent in the total weight of the three-dimensional shaping ink composition is preferably 1% to 50% by weight, more preferably 5% to 40% by weight, and particularly preferably 10% to 30% by weight. Furthermore, the three-dimensional shaping ink composition may also further contain the aforementioned photopolymerization initiator, monofunctional monomers and oligomers, non-polymerizable oligomers, and polymers as other components. The content of other components is only required to be within the range that does not impair the aforementioned characteristics of the three-dimensional shaping ink composition, and is typically 0.1 to 20 parts by weight relative to 100 parts by weight of the polymerizable composition. With this three-dimensional shaping ink composition, three-dimensional shapes with high strength, heat resistance, and water resistance can be formed with high precision.

[0118] In the polymerizable compositions of the first to fourth embodiments, various additives other than those mentioned above may be incorporated as needed. Examples of additives include: thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, colorants such as pigments or dyes, fragrances, defoamers, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles, etc. These additives may be used alone or in combination of two or more. The content of these additives is not particularly limited as long as it does not adversely affect the properties exhibited by the polymerizable composition or various molded articles of its polymer, and is preferably 5% by weight or less relative to the total weight of the polymerizable composition.

[0119] In the various compositions of the fifth to tenth embodiments, various additives other than those mentioned above may be incorporated as needed. Examples of additives include: thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, colorants such as pigments or dyes, fragrances, defoamers, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers, silica particles, etc. These additives may be used individually or in combination of two or more. The content of these additives is not particularly limited as long as it does not adversely affect the properties exhibited by the various molded articles obtained from the various compositions; it is preferably 30% by weight or less relative to the total weight of the composition. Furthermore, water, organic solvents, and mixtures thereof may be used as solvents or diluents as needed. The content of such solvents is not particularly limited as long as it does not adversely affect the properties exhibited by the various molded articles obtained from the various compositions; it is preferably 95% by weight or less relative to the total weight of the composition.

[0120] [Example]

[0121] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The abbreviations of the components described in the examples and comparative examples are as follows. Furthermore, unless otherwise specified, "parts" and "%" in the following text are all based on weight.

[0122] (1) N-substituted (meth)acrylamide (A)

[0123] CHAA: N-cyclohexylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 32.3 mN·m) -1 )

[0124] CHMAA: N-cyclohexyl-N-methylacrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 32.5 mN·m) -1 )

[0125] ACP: N-Acryloylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 35.7 mN·m) -1 )

[0126] ACMP: N-Acryloyl-4-methylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 31.6 mN·m) -1 )

[0127] ACDMP: N-Acryloyl-3,5-Dimethylpiperidine (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 28.6 mN·m) -1 )

[0128] NOAA: n-Octylacrylamide (registered trademark "Kohshylmer") (in wax state at room temperature, surface tension value: 30.0 mN·m) -1 )

[0129] TOAA: Tert-octylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 29.1 mN·m) -1 )

[0130] EHAA: N-(2-ethylhexyl)acrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 29.7 mN·m) -1 )

[0131] DEHAA: N,N-Di-2-ethylhexylacrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 31.0 mN·m) -1 )

[0132] LMAA: N-Laurylmethacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 31.2 mN·m) -1 )

[0133] OLAA: N-Oil-based Acrylamide (registered trademark "Kohshylmer") (liquid at room temperature, surface tension: 32.3 mN·m) -1 )

[0134] STAA: N-Stearylacrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 31.9 mN·m) -1 )

[0135] AAPB: 3-Acrylamidophenylboronic acid (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 24.0 mN·m) -1 )

[0136] DPAA: Dopamine Acrylamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 36.5 mN·m) -1 )

[0137] PHAM: Phenylacetamide (registered trademark "Kohshylmer") (solid at room temperature, surface tension: 45.3 mN·m) -1 )

[0138] (2) Monofunctional monomers

[0139] TBAA: tert-butylacrylamide

[0140] BA: Butyl acrylate

[0141] 2EHA: 2-Ethylhexyl acrylate

[0142] STA: Stearyl Acrylate

[0143] OLA: Acrylate

[0144] EA: Ethyl acrylate

[0145] HEA: Hydroxyethyl acrylate

[0146] 4HBA: 4-Hydroxybutyl Acrylate

[0147] PEA: Phenoxyethyl acrylate

[0148] IBOA: Isoborneol Acrylate

[0149] THFA: Tetrahydrofurfuryl acrylate

[0150] AAc: Acrylic acid

[0151] VOZO: 2-Vinyl-2-oxazoline (registered trademark "Kohshylmer")

[0152] MHAGE: N-Methyl-N-hydroxyethylacrylamide glycidyl ether (registered trademark "Kohshylmer")

[0153] GA: Glycidyl acrylate (registered trademark "Kohshylmer")

[0154] HEAA: Hydroxyethyl Acrylamide (registered trademarks "Kohshylmer" and "HEAA")

[0155] DMAA: Dimethylacrylamide (registered trademarks "Kohshylmer" and "DMAA")

[0156] DEAA: Diethylacrylamide (registered trademarks "Kohshylmer" and "DEAA")

[0157] NIPAM: Isopropylacrylamide (registered trademarks "Kohshylmer" and "NIPAM")

[0158] DAAM: Diacetone Acrylamide (registered trademark "Kohshylmer")

[0159] (3) Multifunctional monomers, etc. (multifunctional monomers and oligomers)

[0160] PETA: Pentaerythritol Triacrylate

[0161] DPHA: Dipentaerythritol hexaacrylate

[0162] HDDA: 1,6-Hexanediol diacrylate

[0163] TPGDA: Tripropylene glycol diacrylate

[0164] UV-3000B: Difunctional carbamate acrylate (Ziguang, manufactured by Mitsubishi Chemical Corporation)

[0165] UV-6640B: Difunctional carbamate acrylate (Ziguang, manufactured by Mitsubishi Chemical Corporation)

[0166] Quick Cure 7100: UV-curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals).

[0167] Quick Cure 8100: UV-curable urethane oligomer (registered trademark "Quick Cure", manufactured by KJ Chemicals).

[0168] (4) Other

[0169] O-184: Omnirad 184 (photopolymerization initiator, manufactured by IGM Resins BV).

[0170] O-1173: Omnirad 1173 (photopolymerization initiator, manufactured by IGM Resins BV).

[0171] TPO: Omnirad TPO (photopolymerization initiator, manufactured by IGM Resins BV).

[0172] HDI: Hexamethylene diisocyanate (crosslinking agent)

[0173] HHPA: Hexahydrophthalic anhydride (crosslinking agent)

[0174] AIBN: Azobisisobutyronitrile (free radical polymerization initiator)

[0175] V-601: Dimethyl azobis(isobutyrate) (free radical polymerization initiator)

[0176] KE-359: Hydrogenated rosin (Tackifier, a non-polymerizable polymer, manufactured by Arakawa Chemical Industry).

[0177] VS-1063: Styrene-acrylic resin (non-polymerizable oligomer, manufactured by Starlight PMC).

[0178] VS-1057: Acrylic resin (non-polymeric polymer, manufactured by Starlight PMC).

[0179] 50HB-55: Polyoxyethylene (2)polyoxypropyl (2)butyl ether (m=2, n=2, molecular weight 240) (manufactured by Sanyo Chemical Industry Co., Ltd.)

[0180] 50HB-100: Polyoxyethylene (5) Polyoxypropyl (5) Butyl Ether (m=5, n=5, molecular weight 540) (manufactured by Sanyo Chemical Industries Co., Ltd.)

[0181] 50HB-260: Polyoxyethylene (10) Polyoxypropyl (7) Butyl Ether (m=10, n=7, molecular weight 880) (manufactured by Sanyo Chemical Industry Co., Ltd.)

[0182] AMP: 2-Amino-2-methyl-1-propanol

[0183] PME4000: Blemmer PME-4000 (manufactured by Nippon Oil Company)

[0184] (5) Substrate

[0185] PE: Polyethylene sheets and films (surface tension: 22.6 mN·m) -1 )

[0186] PP: Polypropylene sheets and films (surface tension: 22.6 mN·m) -1 )

[0187] PC: Polycarbonate sheets and films (surface tension: 34.0 mN·m) -1 )

[0188] ABS: Acrylonitrile-butadiene-styrene copolymer resin sheet (surface tension: 34.0 mN·m) -1 )

[0189] PI: Polyimide sheets and films (surface tension: 40.0 mN·m) -1 )

[0190] PMMA: Polymethyl methacrylate sheets and films (surface tension: 36.0 mN·m) -1 )

[0191] PET: Easily bonded polyethylene terephthalate sheets and films (surface tension: 59.0 mN·m) -1 )

[0192] SPCC: Cold-rolled steel sheet (surface tension: 45.0 mN·m) -1 )

[0193] SST: Stainless steel sheet (surface tension: 40.0 mN·m) -1 )

[0194] Cu: Copper plate (surface tension: 38.0 mN·m) -1 )

[0195] Al: Aluminum plate (surface tension: 36.0 mN·m) -1 )

[0196] GL: Transparent glass plate (surface tension: 40.0 mN·m) -1 )

[0197] PI-Silica: Silica microparticle-dispersed polyimide plates and films (surface tension: 40.0 mN·m) -1 )

[0198] Example 1 (Preparation and evaluation of polymers of N-substituted (meth)acrylamide (A))

[0199] In a 500 mL flask equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube, 30 g of CHAA (as N-substituted (meth)acrylamide (A), 44 g of 2EHA, 20 g of NIPAM, 5 g of HEA, 1 g of AIBN, and 100 g of ethyl acetate as solvent were added. After uniform mixing at room temperature, the mixture was purged with nitrogen for 30 minutes, and the reaction solution was heated to 70°C for 8 hours for polymerization. After the reaction was completed, ethyl acetate was added to the reaction solution to prepare a polymer solution with 30% solids. The viscosity of the polymer solution at 25°C was measured using a cone-plate viscometer (Toki Sangyo Co., Ltd., RE550 type) according to JIS K5600-2-3, and was found to be 4250 mPa·s. Additionally, 30 g of the polymer solution was taken out, and the volatile components in the solution were completely removed to obtain the polymer. The obtained polymer was then dissolved in tetrahydrofuran (THF) to prepare a 0.5 wt% THF solution of the polymer, which was left to stand overnight. The THF solution of the polymer was then filtered through a 0.45 μm membrane filter, and the filtrate was subjected to gel permeation chromatography (GPC) (Shimadzu Prominence GPC system, Shodex KF-806L column, THF solution). The weight-average molecular weight (Mw) of the polymer was calculated to be 960,000 using polystyrene conversion.

[0200] [Evaluation of the water resistance of polymers]

[0201] Similarly, 30g of polymer solution was taken out, and the volatile components in the solution were completely removed. The polymer was then dried under vacuum at 60°C for 24 hours to obtain dried polymer. Then, 5g of the dried polymer was accurately weighed using a plastic petri dish (weighed) as the weight of the polymer in its dry state. The petri dish containing the polymer was placed in a constant temperature and humidity chamber and kept at 30°C and 90% humidity for 24 and 48 hours. The weight immediately after removal from the chamber was then measured to confirm that the polymer had reached saturation water absorption, and this weight was taken as the polymer's saturation water absorption weight. The saturation water absorption rate was calculated according to the following formula, and the polymer's water resistance was evaluated in four grades as described below. The results are shown in Table 1.

[0202] Saturated water absorption rate (%) = (Weight in saturated water condition - Weight in dry condition) / Weight in dry condition × 100%

[0203] ◎: Saturated water absorption rate is 5% or higher.

[0204] ○: Saturated water absorption rate exceeds 5% but is below 7%.

[0205] △: Saturated water absorption rate exceeds 7% but is below 10%.

[0206] ×: Saturated water absorption rate exceeds 10%.

[0207] Examples 2 to 12 and Comparative Examples 1 to 3 (Preparation of polymers of N-substituted (meth)acrylamide (A) and other polymers)

[0208] As shown in Table 1, the types and contents of N-substituted (meth)acrylamide, monofunctional monomers, and polymerization initiators were varied, and the polymerization reactions of Examples 2 to 12 and Comparative Examples 1 to 3 were carried out in the same manner as in Example 1 to obtain polymer solutions with 30% solids. The viscosity of the obtained polymer solutions and the molecular weight of the polymers were determined in the same manner as in Example 1, and the results are shown in Table 1.

[0209] [Table 1]

[0210]

[0211] Examples 13 to 28 and Comparative Examples 4 to 7 (Preparation and evaluation of polymeric compositions)

[0212] The N-substituted (meth)acrylamide (A) and other components used in this embodiment were weighed according to the proportions shown in Table 2, and uniformly mixed at room temperature to prepare the polymeric compositions of the examples and comparative examples. The transparency and wettability of the obtained polymeric compositions to various substrates were evaluated by the following methods, and the results are shown in Table 2. In addition, the polymeric compositions of Examples 15, 16, 18 and 21 are polymeric resin compositions for thermal polymerization, namely Examples 4, 2, 8 and 3 shown in Table 1, respectively, and the properties of these polymers are shown in Table 1. The polymeric resin compositions other than those for thermal polymerization are polymeric resin compositions for active energy line curing. The curability and water resistance of the obtained cured products were evaluated by the following methods, and the results are shown in Table 2. Furthermore, Example 14 is a method of curing by irradiation with an electron beam (EB) instead of ultraviolet light. As the EB irradiation device, a Curetron EBC-200-AA3 (accelerating voltage: 200kV, irradiation line dose 20kGy) manufactured by Nissin High Voltage Co., Ltd. was used.

[0213] [Table 2]

[0214]

[0215] [Transparency Assessment]

[0216] The various polymeric compositions were left to stand overnight at 23°C, and their state was observed visually. The transparency was evaluated in four grades as described below.

[0217] ◎: High transparency, no cloudiness or separation was detected.

[0218] ○: High transparency, but slightly cloudy.

[0219] △: No layer separation occurred, but it is cloudy.

[0220] ×: White turbidity, further layer separation occurs.

[0221] [Wetness Evaluation]

[0222] The obtained polymeric compositions were applied to various substrates using a rod coater (RDS 3). The repulsion of the coating film was observed visually, and the wettability was evaluated in four grades as described below.

[0223] ◎: No rejection, forms a uniform coating film.

[0224] ○: Although there is very little rejection, it is a basically uniform coating film.

[0225] △: Although there is some rejection, the overall coating film is basically uniform.

[0226] ×: High rejection rate, indicating an uneven coating film.

[0227] [Cureability Evaluation]

[0228] The curing process involved bonding a 100 μm thick PET film (manufactured by Toyobo Co., Ltd., Cosmoshine A4100 polyester film) to a horizontally positioned glass plate using a rod coater No. 30. After coating the polymeric resin composition for curing active energy lines prepared in the various examples and comparative examples, a 50 μm thick light-release PET film (manufactured by Toyobo Co., Ltd., E7002 polyester film) was further superimposed on the polymeric resin composition. Ultraviolet light was then irradiated with a predetermined cumulative light intensity (applied to an ITEC System Co., Ltd. benchtop batch UV-LED curing apparatus MUVBA-0.3×0.3×0.5, wavelength 405 nm, illuminance (UV-V) 50 mW / cm²). 2 The resin composition was then cured. The PET film was then removed to obtain sample pieces of the cured products used for the examples and comparative examples for evaluating curability. The tack of the obtained cured product surface was evaluated using the cumulative light intensity after the tack disappeared.

[0229] ◎: The total light intensity is less than 200 mJ / cm² 2The viscosity disappears over time.

[0230] ○: The integrated light intensity is 200 mJ / cm². 2 Above but not exceeding 500mJ / cm 2 The viscosity disappears over time.

[0231] △: The integrated light intensity is 500 mJ / cm² 2 Above but not exceeding 1000mJ / cm 2 The viscosity disappears over time.

[0232] ×: Viscosity disappears when the total optical intensity is above 1000 mJ / cm (including cases where viscosity does not disappear).

[0233] [Evaluation of the water resistance of the cured product]

[0234] A spacer made of polysiloxane (30mm x 15mm x 1mm) is placed on a glass plate (50mm x 50mm x 5mm). The polymeric resin composition for curing active energy lines prepared in the various examples and comparative examples flows into the interior of the spacer. The mixture is then irradiated with ultraviolet light (700mW / cm²). 2 2000mJ / cm 2 The curing process is carried out to produce cured sheets. 3cm squares are cut from the resulting sheets and dried under vacuum at 60°C for 24 hours to form dried sheets. These dried sheets are then precisely weighed as the weight of the cured product in its dry state. The dried sheets are immersed in deionized water at 30°C for 24 hours and 48 hours, and their weight immediately after removal from the deionized water is measured to confirm that the sheets have reached saturated water absorption. This weight is taken as the weight of the cured product in its saturated water absorption state. The saturated water absorption rate is calculated using the following formula, and the water resistance of the cured product is evaluated in four grades as described below.

[0235] Saturated water absorption rate (%) = (Weight in saturated water condition - Weight in dry condition) / Weight in dry condition × 100%

[0236] ◎: Saturated water absorption rate is less than 5%.

[0237] ○: Saturated water absorption rate exceeds 5% but is below 7%.

[0238] △: Saturated water absorption rate exceeds 7% but is below 10%.

[0239] ×: Saturated water absorption rate exceeds 10%.

[0240] Examples 29 to 70 and Comparative Examples 8 to 20 (Preparation and evaluation of adhesive compositions)

[0241] (Examples 29 to 40 and Comparative Examples 8 to 10)

[0242] The polymer solutions obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were applied to a re-peeling separator (polysiloxane-coated PET film) to a thickness of 25 μm after drying, and dried at 90°C for 2 minutes to form an adhesive layer. Subsequently, the layer was placed in an environment of 23°C and 50% relative humidity for 1 day to obtain a test adhesive sheet (type a-1). Furthermore, the type a test adhesive sheets of Examples 30, 35, 38, and Comparative Example 10 (corresponding polymers containing unsaturated bonds derived from oil groups) were irradiated with ultraviolet light (applied to an inverter-type conveyor device ECS-4011GX manufactured by Eyegraphics, a metal halide lamp M04-L41 manufactured by Eyegraphics, and an ultraviolet irradiance of 700 mW / cm²). 2 Integrated light intensity: 1000 mJ / cm 2 ), and obtained the experimental adhesive sheet (type a-2).

[0243] [Examples 41 to 48 and Comparative Example 11]

[0244] The polymer solutions obtained in Examples 1, 4, 6, 8, 12, and Comparative Example 1, along with HDI as a crosslinking agent, were measured and uniformly mixed to achieve the solid content shown in Table 4. Similarly, the mixture was applied to a PET film with a dried thickness of 25 μm and dried at 90°C for 2 minutes to form an adhesive layer. Then, it was aged in a constant temperature bath at 40°C for 3 days and placed in an environment with a temperature of 23°C and a relative humidity of 50% for 1 day to obtain a test adhesive sheet (type b-1). Additionally, the polymer solutions obtained in Examples 7, 9, and 10, along with polyacrylic acid (PAAc, manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd., average molecular weight 5,000) as a crosslinking agent, were measured and uniformly mixed to achieve the solid content shown in Table 4. Similarly, the mixture was applied to a PET film with a dried thickness of 25 μm and dried at 90°C for 2 minutes to form an adhesive layer. Then, it was aged in a constant temperature bath at 40°C for 3 days and placed in an environment at 23°C and 50% relative humidity for 1 day to obtain the test adhesive sheet (type b-2).

[0245] [Examples 49 to 53 and Comparative Examples 12 and 13]

[0246] The polymer solutions obtained in Examples 2, 4, 5, 7, 8, 11, and Comparative Examples 2 and 3 were measured, and the monofunctional monomers, polyfunctional monomers and / or polyfunctional oligomers as crosslinking agents, photopolymerization initiators, and other components were measured in predetermined amounts as shown in Table 5 and mixed uniformly. Similarly, the mixture was coated onto a PET film to a thickness of 25 μm after drying and dried at 90°C for 2 minutes to form an adhesive layer. Then, the film was irradiated with ultraviolet light (applied by: Eyegraphics ECS-4011GX inverter-type conveyor device; metal halide lamp: Eyegraphics M04-L41; ultraviolet irradiance: 700 mW / cm²). 2 Integrated light intensity: 1000 mJ / cm 2 The adhesive sheet was cured and placed in an environment with a temperature of 23°C and a relative humidity of 50% for 1 day to obtain the test adhesive sheet (type C).

[0247] [Examples 54 to 65 and Comparative Examples 14 to 17]

[0248] The polymeric compositions obtained in Examples 13, 14, 17, 19, 20, 22 to 28 and Comparative Examples 4 to 7 were applied to a heavy-release separator (polysiloxane-coated PET film). Using a light-release separator (polysiloxane-coated PET film), the films were laminated without air bubbles using a benchtop roller laminator (Royal Sovereign RSL-382S) to achieve an adhesive layer thickness of 25 μm. The films were then irradiated with ultraviolet light (applied by an Eyegraphics ECS-4011GX inverter conveyor system, an Eyegraphics M04-L41 metal halide lamp, and an ultraviolet irradiance of 700 mW / cm²). 2 Integrated light intensity: 1000 mJ / cm 2 ), to manufacture optical transparent adhesive sheets (type d).

[0249] [Examples 66 to 72 and Comparative Examples 18 to 20]

[0250] The polymer solutions or polymeric compositions obtained in Examples 1, 6, 8, 12 to 14, 19, 24, and Comparative Examples 1, 4, and 5, along with HDI or multifunctional monomers and / or multifunctional oligomers as crosslinking agents, photopolymerization initiators, and other components, were measured in the predetermined amounts shown in Table 7 and mixed uniformly. Adhesive sheets were prepared in the same manner as in Type c (using polymers) or Type d (using polymeric compositions) described above and cured by ultraviolet light. Then, the sheets were aged in a constant temperature bath at 40°C for 3 days and placed in an environment at 23°C and 50% relative humidity for 1 day to obtain test adhesive sheets (Type e).

[0251] The properties of the various adhesive sheets produced were evaluated using the methods described below, and the results are shown in Tables 3 to 7.

[0252] [Evaluation of the transparency of the adhesive sheet]

[0253] The total light transmittance of the glass substrate was measured using a haze meter (NDH-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to JIS K 7105. The aforementioned adhesive layer was transferred onto the glass substrate at a temperature of 23°C and a relative humidity of 50%, and the total light transmittance of the glass substrate and the adhesive layer was measured. Then, the transmittance of the adhesive layer itself was calculated by subtracting the transmittance of the glass substrate, and the transparency was evaluated in four grades as follows.

[0254] ◎: Transmittance is over 90%.

[0255] ○: Transmittance is 85% or higher but less than 90%.

[0256] △: Transmittance is above 50% but below 85%.

[0257] ×: Transmittance not reaching 50%.

[0258] [Closeness Assessment]

[0259] The above-prepared active energy line curable adhesive composition was applied to various plate-shaped substrates (substrates). A partition (polysiloxane-coated PET film) was gently peeled off to prevent air bubbles from being incorporated. The layers were then laminated using a benchtop roller laminator (Royal Sovereign RSL-382S) to achieve an adhesive layer thickness of 5 μm. The laminators were then irradiated with ultraviolet light (device: Eyegraphics ECS-4011GX inverter-type conveyor system; metal halide lamp: Eyegraphics M04-L41; ultraviolet irradiance: 700 mW / cm²). 2 Integrated light intensity: 2000 mJ / cm² 2Then, the lightly peeling separator is removed to obtain an adhesive sheet consisting of an adhesive layer and a substrate. Using the obtained adhesive sheet, 100 1mm square grids are made according to JIS K 5600, and celluloid tape is attached. The number of grids remaining on the substrate side of the adhesive layer when peeled off in one go is counted, and the adhesion is evaluated according to the following criteria.

[0260] ◎: 100 without peeling.

[0261] 〇: 95 to 99 without stripping.

[0262] △: 70 to 94 without peeling.

[0263] ×: 0 to 69 without peeling.

[0264] [Adhesion Evaluation]

[0265] Under conditions of 23°C and 50% relative humidity, the above adhesive layer was transferred to various film or plate-like substrates. A 2kg pressing roller was used to apply pressure twice, and the substrates were left to stand for 30 minutes in the same atmosphere. Then, using a tensile testing machine (Tensilon RTA-100, manufactured by ORIENTEC), the 180° peel strength (N / 25mm) was measured according to JIS Z0237 at a peel speed of 300mm / min.

[0266] ◎: 30 (N / 25mm) or more.

[0267] ○: 15 (N / 25mm) or more to less than 30 (N / 25mm).

[0268] △: 8 (N / 25mm) or more to less than 15 (N / 25mm).

[0269] ×: Not up to 8 (N / 25mm).

[0270] [Evaluation of stain resistance (reworkability)]

[0271] In the same manner as the above adhesion determination, an adhesive sheet was prepared and placed at 80°C for 24 hours. After that, the contamination (residual state of the adhesive layer (paste)) on the surface of the substrate film after the adhesive sheet was peeled off was observed visually.

[0272] ◎: No contamination (no residue).

[0273] ○: Very little pollution.

[0274] △: Slight contamination.

[0275] ×: Contaminated (with residual paste).

[0276] [Evaluation of yellowing resistance]

[0277] Adhesive plates were prepared in the same manner as those used for the adhesion determination described above, and placed in a xenon fading tester (SC-700-WA: manufactured by Suga Test Instruments) with an irradiation intensity of 70 mW / cm². 2 After 120 hours of exposure to ultraviolet light, the color change of the adhesive layer on the adhesive sheet is observed visually.

[0278] ◎: Yellowing cannot be confirmed by visual inspection.

[0279] ○: Only a very small amount of yellowing can be confirmed by visual inspection.

[0280] △: Yellowing can be visually confirmed.

[0281] ×: Visual inspection confirms obvious yellowing.

[0282] [Durability Evaluation]

[0283] In the same manner as the above-mentioned adhesion determination, an adhesive sheet was prepared and kept at 85°C and 85% relative humidity for 100 hours. The adhesive layer was then visually observed and evaluated for any bulging or peeling, bubbles, or cloudiness.

[0284] ◎: Transparent, and no bulging, peeling, or bubbles are produced.

[0285] ○: There is very little fogging, but no bulging, peeling, or bubbles are produced.

[0286] △: Slight fogging, bulging, peeling, or bubbles.

[0287] ×: Extreme fogging, bulging, peeling, or bubbles.

[0288] [Table 3]

[0289]

[0290] [Table 4]

[0291]

[0292] [Table 5]

[0293]

[0294] [Table 6]

[0295]

[0296] [Table 7]

[0297]

[0298] Examples 73 to 82 and Comparative Examples 21 to 24 (Preparation and evaluation of adhesive compositions)

[0299] The polymers obtained in Examples 1 to 4, 6, 8, 9, 11 and Comparative Examples 1 and 2, along with / or the polymeric compositions, crosslinking agents, and other components obtained in Examples 13, 14, 19, 20, 25 to 27 and Comparative Examples 4 and 5, were measured in the manner shown in Table 8 and uniformly mixed at room temperature to obtain a homogeneous mixture. Two similar or dissimilar plate-shaped substrates, each 100 mm long × 25 mm wide × 1 mm thick, were uniformly coated onto either one of them. Furthermore, if the mixture contained solvent, the mixture was coated slightly more to the same extent as when solvent-free, and dried at 90°C for 2 minutes. Then, according to JIS K 6850, another plate-shaped substrate was placed on the coated mixture and bonded together with an overlap of 12.5 mm long × 25 mm wide. The thickness of the adhesive layer was adjusted to 100 μm using spacers to prepare a bonded sample sheet. Then, UV or EB irradiation is performed on the bonded transparent or translucent substrate in the same manner as the adhesive layer preparation. Furthermore, in the examples described in Table 8 where UV or EB is used as the curing method, the sample sheets irradiated with UV or EB rays, respectively, are used as adhesive sample sheets. In the examples where UV heat or EB heat is used as the curing method, the sample sheets irradiated with UV or EB rays, respectively, are further heated at 40°C for 72 hours, and the resulting sample sheets are used as adhesive sample sheets. In the examples where heat is used as the curing method, the prepared sample sheets are heated at 40°C for 72 hours without irradiation with UV or EB rays, and the resulting sample sheets are used as adhesive sample sheets. Additionally, the adhesion and impact resistance of the obtained adhesive sample sheets are evaluated using the following methods, and the results are shown in Table 8.

[0300] [Adhesion Evaluation]

[0301] Using the obtained adhesive specimens, the tensile shear strength was determined according to JIS K 6850 using a Tensilon RTA-100 (manufactured by ORIENTEC) as the testing machine at a tensile speed of 10 mm / min.

[0302] ◎: Tensile shear strength is above 20MPa.

[0303] ○: Tensile shear strength is above 15MPa but less than 20MPa.

[0304] △: Tensile shear strength is above 10MPa but less than 15MPa.

[0305] ×: Tensile shear strength did not reach 10MPa.

[0306] [Impact Resistance Evaluation]

[0307] Using the obtained adhesive sample, the impact peel bond strength was determined according to JIS K6855 using an impact testing machine No. 511 (manufactured by MYS Tester).

[0308] ◎: Impact peel bonding strength is 20KJ / m 2 above.

[0309] ○: Impact peel bonding strength is 15KJ / m 2 The above up to less than 20KJ / m 2 .

[0310] △: Impact peel bonding strength is 10KJ / m 2 The above up to less than 15KJ / m 2 .

[0311] ×: Impact peel adhesion strength did not reach 10KJ / m 2 .

[0312] [Table 8]

[0313]

[0314]

[0315] Examples 83 to 97 and Comparative Examples 25 to 28 (Preparation and evaluation of cosmetic compositions)

[0316] Examples 83 to 89 and Comparative Examples 25 and 26 (Preparation and evaluation of cosmetic compositions for hair use)

[0317] 100g of ethanol was added to a 1L four-necked flask equipped with a reflux condenser, thermometer, nitrogen purging tube, and stirrer. The polymer obtained in Table 1, the polymerizable composition obtained in Table 2, and other components were then added in the proportions shown in Table 9 (solids conversion). The polymerization reaction was carried out under reflux (approximately 80°C) for 8 hours under a nitrogen stream. After the polymerization reaction was completed, 2-amino-2-methyl-1-propanol (AMP) diluted with an equal volume of ethanol (solids conversion) was added at 50°C as a basic compound for neutralization in the proportions shown in Table 9. The mixture was further diluted with ethanol to a solids content of 40% to obtain a hair cosmetic base. The obtained hair cosmetic base, ethanol, and liquefied petroleum gas were mixed in a weight ratio of 7.5:42.5:50 and sealed into a spray can to obtain a hair spray-type hair cosmetic. The moisture resistance, smoothness, stickiness resistance, hand feel, and long-term stability of the obtained hair cosmetic were evaluated using the following methods, and the results are shown in Table 9. Furthermore, the polymerizable composition of Example 23 in Example 83 and the polymerizable composition of Example 28 in Example 84 were used with the polymerization initiator removed.

[0318] [Evaluation of hair retention (moisture resistance) obtained by the curl retention method]

[0319] Spray 0.4g of the test formulation onto a 22cm long, 2g hair bundle and spread it with a comb. Wrap the hair bundle around a 2.2cm diameter curling iron and dry at 20°C for 20 hours. Unwind the hair bundle into a spiral shape, mount it on a vertically oriented graduated glass plate, and place it in a constant temperature and humidity chamber conditioned to 30°C and 95% RH. Record the tip position of the hair after 10 hours. Calculate the curl retention force based on the following formula and evaluate according to the following criteria.

[0320] Curl retention (%) = {(L - Lt) / (L - L0)} × 100

[0321] L: The length of the hair when it is stretched during the test.

[0322] Lt: The tip of the test hair after being placed in a constant temperature and humidity chamber for 10 hours.

[0323] L0: The tip of the test hair before it is placed in the constant temperature and humidity chamber.

[0324] ◎: More than 80%.

[0325] ○: 65% or more but less than 80%.

[0326] △: 50% or more but less than 65%.

[0327] ×: Less than 50%.

[0328] [Smoothness Evaluation]

[0329] For a 22cm long and 2g dried hair bundle spray test formulation, the ease with which the hair bundle could be manually separated was determined by the company's observation group immediately after spraying and after drying (before drying) and after drying (after drying), and evaluated according to the following criteria.

[0330] ◎: It has a smooth feel without any stickiness or astringency before or after drying.

[0331] ○: It feels smooth before drying, but becomes slightly sticky or astringent after drying.

[0332] △: Slightly sticky or astringent before drying, and becomes more sticky or astringent after drying.

[0333] ×: It is too sticky or astringent to be practical before or after drying.

[0334] [Evaluation of stickiness resistance]

[0335] Prepare dried hair bundles, spray the test formula, and evaluate the stickiness when the dried hair bundles are held tightly in the palm of the hand.

[0336] ◎: It feels refreshing to the touch without any stickiness.

[0337] ○: It feels slightly sticky when touched with fingers.

[0338] △: It feels sticky when touched with fingers.

[0339] ×: It is sticky to the touch and difficult to remove from the fingers.

[0340] [Feel Evaluation]

[0341] Using sensory tests conducted by the company's in-house observation group, the tactile feel of hair prepared in the same manner as the moisture resistance evaluation was assessed, and the changes over time when the same test was performed after one day were also evaluated. The evaluation criteria are as follows.

[0342] ◎: Smooth and dry.

[0343] ○: Although it has a slightly firm feel, it is still satisfactory.

[0344] △: Hardened or sticky.

[0345] ×: Very hard or strongly adhesive.

[0346] [Time-bound stability evaluation]

[0347] After the above experimental formula was left to stand at room temperature for one month, the degree of separation of the formula components was observed visually and evaluated as follows.

[0348] ◎: No separation occurred at all.

[0349] ○: Slight separation, shake for 1 minute, and stand for 7 days without separation.

[0350] △: Slight separation, although it can be re-dispersed by oscillation for 1 minute, but separation occurs again after 1 hour.

[0351] ×: Separation has occurred, and even oscillation cannot disperse it again.

[0352] [Table 9]

[0353]

[0354] Examples 90 to 97 and Comparative Examples 27 and 28 (Preparation and evaluation of cosmetic compositions for skin use)

[0355] 100g of a water-ethanol mixture (75:25 by weight) was added to a 1L three-necked flask equipped with a reflux tube and a nitrogen inlet tube. The polymer obtained in Table 1, the polymerizable composition obtained in Table 2, and other components were added according to the proportions (solids conversion) listed in Table 10. After thorough dissolution or dispersion, nitrogen purging was performed for 20 minutes to remove dissolved oxygen. Then, the polymerization reaction was carried out in an oil bath at 65°C to 70°C for 8 hours with stirring. After polymerization, the polymer solution was allowed to return to room temperature, and the resulting dispersion was used as a cosmetic raw material. 1g of the carboxyvinyl polymer (aqueous phase) and 0.6g of potassium hydroxide were added to ion-exchanged water and mixed. 100g of the cosmetic raw material, separately dispersed in ion-exchanged water, was then added to this mixture and stirred. The total amount of ion-exchanged water used was 500g. After uniformly dispersing the cosmetic raw materials and aqueous components, 100 parts of liquid paraffin, 100g of glyceryl tri-2-ethylhexanoate, and dimethylpolysiloxane (6cs) as the oil phase components were added. The mixture was then sheared and mixed using a homogenizer until homogeneous, yielding an oil-in-water emulsion cosmetic. The emulsion stability, skin irritation, user experience, and long-term stability of the obtained oil-in-water emulsion cosmetic were evaluated using the following methods, and the results are shown in Table 10. Furthermore, the polymerizable compositions of Example 13 in Example 90, Example 17 in Example 91, Example 19 in Example 95, and Example 28 in Example 97 were used without the polymerization initiator.

[0356] [Emulsion Stability (Emulsion Particle) Evaluation]

[0357] The emulsified particles in the sample were observed using an optical microscope.

[0358] ◎: The emulsion particles are uniform, and no coagulation or aggregation was detected.

[0359] ○: The emulsion particles are basically uniform, and no coagulation or aggregation has been confirmed.

[0360] △: The emulsion particles are basically uniform, but slight cohesion or aggregation can be observed.

[0361] ×: The emulsion particles are not uniform, and obvious coagulation or aggregation has been confirmed.

[0362] [Skin irritation test]

[0363] A 24-hour occlusion patch was applied to the inner side of the upper wrist of 10 sensitive skin testers (panels), and the skin condition was assessed according to the following criteria.

[0364] 0…No anomalies detected.

[0365] 1…Slightly confirmed that it was turning red.

[0366] 2…Confirmed to be red.

[0367] 3…Redness and rashes were observed.

[0368] The evaluation criteria for the "skin irritation test" are as follows.

[0369] ◎: The average value of the 10 inspectors is above 0 to below 0.15.

[0370] ○: The average value of the 10 inspectors was between 0.15 and less than 0.2.

[0371] △: The average value of the 10 inspectors was between 0.2 and less than 0.3.

[0372] ×: The average value of 10 inspectors is above 0.3.

[0373] [User Experience Review]

[0374] Ten professional inspectors evaluated the user experience of the sample when it was applied to the skin according to the following criteria: "non-sticky", "moisturizing", and "rapid skin affinity".

[0375] ◎: 7 or more people answered "good" or "can actually feel it".

[0376] ○: 5 to 7 people answered "good" or "can actually feel it".

[0377] △: 3 to 5 people answered "good" or "can actually feel it".

[0378] ×: Less than 2 people answered "good" or "can actually feel it".

[0379] [Time-bound stability evaluation]

[0380] The state of the water-in-oil emulsion cosmetic was observed with the naked eye one month after its manufacture.

[0381] ◎: The sample remains in the emulsified state it was in during manufacturing.

[0382] ○: Some sedimentation / floating can be seen, but the sample basically remains in an emulsified state.

[0383] △: The settling / floating of emulsified particles also confirmed the uniformity of the particles.

[0384] ×: The emulsified particles in the sample settle / float and merge, and the oil phase is completely separated.

[0385] [Table 10]

[0386]

[0387] Examples 98 to 105 and Comparative Examples 29 and 30 (Preparation and evaluation of coating composition)

[0388] According to the proportions (solids conversion) recorded in Table 11, the polymer obtained in Table 1, the polymeric composition obtained in Table 2, and other components were weighed and mixed uniformly at room temperature to prepare a coating composition. Coated sample sheets (coating films) were prepared by the following method, and the wettability, pencil hardness, and adhesion of the coating film to various substrates (substrates) were evaluated. The results are shown in Table 11.

[0389] [Preparation of Coated Samples (Coating)]

[0390] The coating agent composition was applied in a strip dropper onto the front end of various substrates (substrates), coated using a rod coater (RDS 3), and dried at 90°C for 2 minutes. Then, it was cured using the curing methods shown in Table 11 (UV, EB, thermal, UV thermal, EB thermal) to form a coating layer on the substrate (substrates). Subsequently, the samples were placed in an environment at 23°C and 50% relative humidity for 1 day to obtain evaluation coated samples. Furthermore, the UV curing method involved irradiating the coated surface with ultraviolet light (device: Eyegraphics ECS-4011GX inverter-type conveyor device, metal halide lamp: Eyegraphics M04-L41, UV irradiance: 700 mW / cm²). 2 Integrated light intensity: 1000 mJ / cm 2The curing method involves using an electron beam instead of ultraviolet light for curing. The EB irradiation device used is a Curetron EBC-200-AA3 (accelerating voltage: 200kV, irradiation linear dose: 20kGy) manufactured by Nissin High Voltage Co., Ltd. UV thermal curing refers to a method that, after UV curing, further ages the material at 40°C for 72 hours to complete the crosslinking reaction caused by the crosslinking agent. EB thermal curing refers to a method that, after EB curing, further ages the material at 40°C for 72 hours to complete the crosslinking reaction caused by the crosslinking agent.

[0391] [Evaluation of the wettability of the coating composition]

[0392] The coating composition was applied to various substrates using a bar coater (RDS 3), and the rejection of the coating liquid was observed visually.

[0393] ◎: No rejection, produces a uniform coating film.

[0394] ○: There is very little rejection, but the coating is basically uniform.

[0395] △: There is some rejection, but the overall coating is basically uniform.

[0396] ×: High rejection rate, indicating an uneven coating film.

[0397] [Pencil Hardness Evaluation]

[0398] The evaluation is based on JIS K 5400 8.4 handwriting method (1990 edition).

[0399] [Closeness Assessment]

[0400] 100 1mm square grids were made according to JIS K 5600, and celluloid tape was applied. The number of grids with adhesive layer remaining on the substrate side when peeled off in one go was counted, and the adhesion was evaluated according to the following criteria.

[0401] ◎: 100 without peeling.

[0402] 〇: 95 to 99 without stripping.

[0403] △: 70 to 94 without peeling.

[0404] ×: 0 to 69 without peeling.

[0405] [Table 11]

[0406]

[0407] The parts by weight of the adhesive composition are the parts by weight of the solids after drying.

[0408] Examples 106 to 113 and Comparative Examples 31 to 33

[0409] According to the proportions (solids conversion) listed in Table 12, the polymer obtained in Table 1, the polymeric composition obtained in Table 2, and other components were weighed and uniformly mixed at room temperature to prepare an ink composition. The viscosity of the prepared ink composition was measured to evaluate the dispersibility of the raw materials. Furthermore, inkjet printing was performed using the prepared ink composition, and the physical properties of the resulting printed matter were evaluated. In addition, no pigment or pigment dispersant was added to the transparent ink composition, while the black ink composition was formulated with Pigment Black 7 pigment. The ink compositions with and without the pigment dispersant Ajisper PB821 were evaluated separately. The evaluation results are summarized in Table 12.

[0410] [Viscosity Measurement and Evaluation]

[0411] The viscosity of the ink composition was determined according to JIS K5600-2-3 using a cone-plate viscometer (RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.). As an ink composition for inkjet printing, the viscosity was evaluated in four grades as described below.

[0412] ◎: 5 mPa·s to less than 100 mPa·s.

[0413] ○: 100 mPa·s to less than 500 mPa·s.

[0414] △: 500 mPa·s to less than 2000 mPa·s.

[0415] ×: Above 2000 mPa·s.

[0416] [Evaluation of Pigment Dispersibility]

[0417] Using the prepared ink composition, the aggregation or precipitation state of the pigment was observed visually immediately after preparation and after standing for 2 months. The pigment dispersibility was evaluated in four stages as described below.

[0418] ◎: No pigment aggregation or precipitation was observed immediately after preparation or after standing for 2 months.

[0419] 〇: No pigment aggregation or precipitation was observed immediately after preparation, but slight pigment precipitation was observed after standing for 2 months.

[0420] △: Slight aggregation or precipitation of pigments was observed immediately after preparation, and obvious aggregation or precipitation of pigments was observed after standing for 2 months.

[0421] ×: Pigment aggregation or precipitation was clearly observed immediately after preparation.

[0422] Methods for producing printed materials using ultraviolet light irradiation

[0423] The obtained ink composition was coated onto a 100μm thick PET film (10μm thick after drying) using a rod coater (RDS12), and then cured by ultraviolet irradiation (Eyegraphics (Stock) Co., Ltd. inverter type conveyor device ECS-4011GX, metal halide lamp M04-L41) to produce printed materials.

[0424] [Cureability Evaluation]

[0425] When producing printed materials using the above method, the cumulative light intensity is measured until the ink composition is completely cured (in a non-sticky state) to evaluate the curing performance.

[0426] ◎: 1000mJ / cm 2 Completely cured.

[0427] ○: 1000mJ / cm 2 Up to 2000mJ / cm 2 Completely cured.

[0428] △: 2000mJ / cm 2 Up to 5000mJ / cm 2 Completely cured.

[0429] ×: 5000 mJ / cm² is required until complete curing. 2 above.

[0430] [Surface Dryness Evaluation]

[0431] The printed material produced by the above method is left to stand for 5 minutes at room temperature (23°C) and relative humidity (50%). High-grade paper is then overlapped on the printed surface, and a load of 1 kg / cm² is applied. 2 The load is used to evaluate the degree of ink transfer to paper.

[0432] ◎: The ink is dry and has not been transferred to the paper at all.

[0433] ○: The ink has dried and slightly transferred to the paper.

[0434] △: The ink is basically dry and is being transferred to the paper.

[0435] ×: The ink is almost dry, resulting in more transfer to the paper.

[0436] [Closeness Assessment]

[0437] The resulting ink composition was applied to various substrates and irradiated with ultraviolet light (device: Eyegraphics ECS-4011GX inverter-type conveyor device, metal halide lamp: Eyegraphics M04-L41, ultraviolet irradiance: 700mW / cm²). 2 Integrated light intensity: 1000 mJ / cm 2 The cured film was then fully cured. A checkerboard test was used to create 100 1mm square grids on the resulting cured film. Cellulose tape was then applied to each grid, and the number of grids remaining on the substrate side after peeling off in one go was counted for evaluation.

[0438] ◎: The number of remaining grid cells is 100.

[0439] 〇: The number of remaining grid cells is 90 or more but less than 100.

[0440] △: The number of remaining grid cells is between 50 and 90.

[0441] ×: The number of remaining grid cells is less than 50.

[0442] [Inkjet Printing and Printability Evaluation]

[0443] The ink composition prepared above was filled into a commercially available inkjet printer (LuxelJetU V350GTW manufactured by Fujifilm), and the entire image was printed on coated paper. The printability of the ink was evaluated by the following method.

[0444] [Emission stability assessment]

[0445] The printing condition of the printed matter is evaluated visually.

[0446] ◎: No missing prints, excellent printing quality.

[0447] 〇: There was a slight overspray.

[0448] △: Widespread missed spraying.

[0449] ×: Some are not discharged.

[0450] [Clarity Rating]

[0451] Visually inspect the image sharpness of printed materials obtained from ink compositions containing pigments.

[0452] ◎: No ink bleeding was observed, and the image was clear.

[0453] ○: Almost no ink bleeding, good image.

[0454] △: Some ink seepage is visible.

[0455] ×: Ink bleeding is clearly visible.

[0456] [Evaluation of yellowing resistance]

[0457] The obtained transparent ink composition was applied to a substrate (#125-E20) with a film thickness of 10 μm using a rod coater (RDS12), and cured using a metal halide lamp as described above. The hue of the resulting coating was measured using a Spcetrolino (manufactured by GretagMacbeth), and the coating was placed in a thermostat maintained at 60°C for one week. The hue of the coating was then measured again, and the resistance to yellowing was evaluated by the change in hue value before and after heating (ΔE = hue after heating - hue before heating).

[0458] ◎:0≤ΔE≤0.2

[0459] 〇: 0.2<ΔE≤0.5

[0460] △: 0.5 < ΔE ≤ 1.0

[0461] ×: 1.0 < ΔE [Table 12]

[0462]

[0463] Examples 114 to 122 and Comparative Examples 34 and 35

[0464] According to the proportions (solids conversion) listed in Table 13, the polymer obtained in Table 1, the polymeric composition obtained in Table 2, and other components were weighed and uniformly mixed at room temperature to prepare a three-dimensional shaping ink composition. The curing shrinkage rate of the three-dimensional shaping ink composition was determined using the following method. In addition, the strength, heat resistance, water resistance, and shaping accuracy of the cured three-dimensional shaping ink composition were measured. The evaluation results are shown in Table 13.

[0465] [Evaluation of Curing Shrinkage Resistance]

[0466] The curing shrinkage rate was calculated according to JIS K5600 2-4, as shown in the following formula (1), based on the density change of the three-dimensional shaping ink composition before and after curing. The density of the three-dimensional shaping ink composition before and after curing was measured using an electronic hydrometer (MDS-300 manufactured by Alfamirage Co., Ltd.) according to JIS K7112. The cured product was prepared in the same manner as the specimen used for the tensile test. The following evaluation was performed based on the obtained curing shrinkage rate.

[0467] (Cure shrinkage rate) = (Ds - Dl) / Dl × 100 ··· Calculation formula (1)

[0468] (In the formula, Ds is the density of the three-dimensional modeling ink composition after curing, and Dl is the density of the three-dimensional modeling ink composition before curing).

[0469] ◎: Curing shrinkage rate did not reach 6%.

[0470] ○: Curing shrinkage rate is 6% or more but less than 7%.

[0471] △: Curing shrinkage rate is 7% or more but less than 8%.

[0472] ×: Curing shrinkage rate is 8% or more.

[0473] [Strength Assessment]

[0474] A 75μm thick heavy-release PET film (Polyester film E7001 manufactured by Toyobo Co., Ltd.) was tightly bonded to a horizontally placed glass plate. A 1mm thick spacer, internally stamped into a dumbbell shape according to JIS K6251, was placed on the plate. The three-dimensional modeling ink compositions obtained in the respective examples and comparative examples were filled into the inside of the spacer. A 50μm thick light-release PET film (Polyester film E7002 manufactured by Toyobo Co., Ltd.) was then stacked on top. Ultraviolet light was irradiated from both sides (applied by an inverter-type conveyor device ECS-4011GX manufactured by Eyegraphics, metal halide lamp M04-L41 manufactured by Eyegraphics, ultraviolet irradiance 200mW / cm²). 2 The total light intensity is 1000 mJ / cm². 2 The ink composition for three-dimensional shaping is cured. Then, the release PET film on both sides is removed to obtain sample pieces of the cured products for the examples and the cured products for the comparative examples. According to JIS K7161, the tensile strength is measured using a benchtop precision universal testing machine (Autograph AGS-X manufactured by Shimadzu Corporation) at a temperature of 25°C, a tensile speed of 10 mm / min, and a clamping distance of 50 mm. The strength is evaluated according to the following criteria.

[0475] ◎: Tensile strength is above 40MPa.

[0476] ○: Tensile strength is above 30MPa but less than 40MPa.

[0477] △: Tensile strength is above 20MPa but less than 30MPa.

[0478] ×: Tensile strength did not reach 20MPa.

[0479] [Heat Resistance Evaluation]

[0480] Cured products were prepared in the same manner as the specimens used in the tensile test, and the glass transition temperature (Tg) of the cured products was measured using a differential scanning calorimeter (DSC-60plus manufactured by Shimadzu Corporation). The heat resistance was evaluated based on the measured glass transition temperature (Tg) of the cured products as follows.

[0481] ◎: The solidified product has a Tg of 80℃ or higher.

[0482] ○: The Tg of the cured material is above 40℃ but below 80℃.

[0483] ×: The solidified material's Tg did not reach 40℃.

[0484] [Water Resistance Evaluation]

[0485] A 75μm thick heavy-release PET film (Polyester film E7001 manufactured by Toyobo Co., Ltd.) was tightly bonded to a horizontally placed glass plate. A 10mm thick spacer with an internal dimension of 10cm x 1cm was placed inside the spacer. The inner side of the spacer was filled with the 1mm thick three-dimensional modeling ink composition obtained in each of the embodiments and comparative examples. After smoothing the surface by holding it at 60°C for 30 seconds, ultraviolet light was applied (applied to an inverter-type conveyor device ECS-4011GX manufactured by Eyegraphics, metal halide lamp M04-L41 manufactured by Eyegraphics, ultraviolet irradiance 200mW / cm²). 2 The ink composition for three-dimensional shaping is cured to obtain a cured product with a length of 10cm × width of 1cm × thickness of 1mm. The weight of the cured product immediately after manufacturing is measured, and then it is immersed in a beaker containing 100ml of water. The weight after immersion is measured after one day. The water absorption rate is determined by substituting the weights before and after immersion into the following formula, and the water resistance is evaluated according to the criteria shown below.

[0486] ◎: Water absorption rate is less than 2%.

[0487] ○: Water absorption rate is 2% or more but less than 2.5%.

[0488] △: Water absorption rate is 2.5% or more but less than 3%.

[0489] ×: Water absorption rate is 3% or higher.

[0490] [Evaluation of Shaping Accuracy]

[0491] A 75μm thick heavy-release PET film (Polyester film E7001 manufactured by Toyobo Co., Ltd.) was tightly bonded to a horizontally placed glass plate. A 10mm thick spacer with an internal 10×10mm spacer was placed. The inner side of the spacer was filled with a 1mm thick three-dimensional modeling ink composition obtained in each of the embodiments and comparative examples. After smoothing the surface by holding at 60°C for 30 seconds, the surface was irradiated with ultraviolet light (applied by Eyegraphics ECS-4011GX inverter-type conveyor device, metal halide lamp M04-L41 manufactured by Eyegraphics, ultraviolet irradiance 200mW / cm²). 2 The ink composition for 3D modeling was cured. Then, this process was repeated a total of 10 times, with each layer of the ink composition filled to a thickness of 1 mm and cured to obtain a cured product of 10 mm × 10 mm × 10 mm. The height of the resulting cured product was measured. Additionally, the side surface of the resulting cured product was visually observed. These results were combined, and the modeling accuracy was evaluated according to the following criteria.

[0492] ◎: The height is 10mm ± less than 0.1mm, and there are no bumps or dents on the sides.

[0493] ○: The height is more than 10mm ± 0.1mm but less than ± 0.2mm, or there are very few bumps or depressions on the side.

[0494] △: The height is more than 10mm ± 0.2mm but less than ± 0.3mm, or there are slight bumps or depressions on the side.

[0495] ×: The height is 10mm ± 0.3mm or more, or there are obvious bumps or depressions on the side.

[0496] [Table 13]

[0497]

[0498] As shown in the evaluation results of the above embodiments and comparative examples, the polymeric composition containing N-substituted (meth)acrylamide (A) having the specific structure of the present invention exhibits high transparency and good curability due to the well-balanced amphiphilicity of A. It also demonstrates excellent wettability on a wide range of substrates with varying polarities, from low to high polarity, composed of organic, inorganic, and organic-inorganic mixed substrates. Furthermore, the polymer or cured product of this polymeric composition exhibits excellent water resistance due to the hydrophobic substituents of A. Adhesive compositions containing the above-mentioned polymeric composition and / or its polymers, and laminates of adhesive layers composed of such adhesive compositions with various substrates, exhibit strong adhesion and bonding to various substrates, and possess high transparency, stain resistance, yellowing resistance, and durability. Adhesive compositions containing the above-mentioned polymeric composition and / or its polymers, etc., exhibit high adhesion, impact resistance, and water resistance to various substrates and can be used as adhesive compositions for similar or dissimilar materials. Cosmetic compositions containing the above-mentioned polymeric compositions and / or their polymers can be used as hair cosmetics with moisture resistance, smoothness, non-stickiness, good hand feel, and long-term stability, or as water-in-oil emulsion cosmetic compositions that do not cause skin irritation and have excellent emulsification stability, user experience, and long-term stability. Furthermore, coating compositions containing the above-mentioned polymeric compositions and / or their polymers exhibit high wettability and adhesion to various substrates, and show high surface hardness and water resistance upon curing. Ink compositions exhibit high adhesion to various substrates, excellent printing properties such as pigment dispersion, surface drying, discharge stability, and clarity, and also possess high curability and resistance to yellowing. In addition, three-dimensional shaping ink compositions containing the above-mentioned polymeric compositions and / or their polymers can precisely shape three-dimensional objects with high strength, heat resistance, and water resistance. On the other hand, it is shown that various molded articles, such as adhesive compositions, bonding agent compositions, cosmetic compositions, coating agent compositions, ink compositions, and three-dimensional shaping ink compositions, obtained using polymeric compositions and / or polymers without N-substituted (meth)acrylamide (A) are inferior in effect to various molded articles obtained from polymeric compositions and / or polymers containing A.

[0499] [Industry Availability]

[0500] As explained above, the polymerizable composition of the present invention, by containing a specific N-substituted (meth)acrylamide (A), exhibits high transparency and good curability, excellent wettability on a wide range of substrates with polarity ranging from low to high, and the polymer system of the polymerizable composition has excellent water resistance. Therefore, the above-described polymerizable composition and / or its polymer can be used as an adhesive composition capable of polymerization and curing via active energy lines and / or heat, and can be used in a wide range of fields such as industrial, medical, and household applications for adhesives or adhesive-related products. The above-described adhesive composition exhibits good adhesion to a wide range of substrates with broad polarity. For example, by forming an adhesive layer on a film or sheet substrate of polyolefins such as polyethylene and polypropylene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyimide, and polymethyl methacrylate, polyolefin adhesive sheets and polyimide adhesive sheets can be obtained. Furthermore, when an adhesive layer is formed on a glass or metal substrate, glass adhesive sheets and metal adhesive sheets can be obtained. Furthermore, adhesive sheets for electronic materials, adhesive sheets for optical components, and adhesive sheets for automobiles, comprising a substrate for electronic devices and an adhesive layer, can be readily obtained. The adhesive composition formed by the adhesive composition and crosslinking agent of this invention is highly effective for bonding similar materials and various dissimilar materials, from plastics to metals, and can be widely used in electronic materials or optical components, semiconductors, solar cells, etc. Additionally, it can be used in: cosmetic compositions with excellent moisture resistance or emulsion stability and a pleasant user experience; coating compositions with excellent adhesion to various substrates and capable of providing coatings with high surface hardness and water resistance; inks with high adhesion to various substrates, excellent printing characteristics such as pigment dispersion, surface drying, discharge stability, and clarity, and high curability and resistance to yellowing; and three-dimensional shaping ink compositions capable of precisely shaping three-dimensional objects with high strength, heat resistance, and water resistance, and with excellent resistance to curing shrinkage.

Claims

1. A polymerizable composition containing 5% to 90% by weight of N-substituted (meth)acrylamide (A) represented by general formula [1], wherein the saturated water absorption of the cured polymerizable composition is less than 10%. [Chemistry 1] In the formula, R 1 R represents a hydrogen atom or a methyl group. 2 With R 3 One of them represents a chain hydrocarbon group with 6 or more carbon atoms or a cyclic hydrocarbon group with 6 or more carbon atoms, and the other represents a hydrogen atom, a chain hydrocarbon group with 1 or more carbon atoms or a cyclic hydrocarbon group with 3 or more carbon atoms. R 2 and R 3 May include carrying R 2 and R 3 When nitrogen atoms together form a saturated ring with 6 or more members, The N-substituted (meth)acrylamide (A) includes n-hexyl (meth)acrylamide, sec-hexyl (meth)acrylamide, tert-hexyl (meth)acrylamide, n-heptyl (meth)acrylamide, sec-heptyl (meth)acrylamide, tert-heptyl (meth)acrylamide, n-octyl (meth)acrylamide, sec-octyl (meth)acrylamide, tert-octyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, N,N-di-(2-ethylhexyl)acrylamide, n-nonyl (meth)acrylamide, n-decyl (meth)acrylamide, n-undecyl (meth)acrylamide, n-dodecyl (meth)acrylamide, n-tridecyl (meth)acrylamide, n-trimethyldecyl (meth)acrylamide, n-tetradecyl (meth)acrylamide, n-hexadecyl (meth)acrylamide, stearyl (meth)acrylamide, n-eicosyl (meth)acrylamide, n-docosahexadecyl (meth)acrylamide, n-tetra ... N-Cyclohexyl (methyl)acrylamide, N,N-dicyclohexyl (methyl)acrylamide, N-cyclohexyl-N-methyl (methyl)acrylamide, N-cyclohexyl-N-ethyl (methyl)acrylamide, N-cyclohexyl-N-propyl (methyl)acrylamide, N-cyclohexyl-N-butyl (methyl)acrylamide, N-cyclohexyl-N-pentyl (methyl)acrylamide, N-cyclohexyl-N-hexyl (methyl)acrylamide, N-phenyl (methyl)acrylamide, N-(methyl) Acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-(meth)acryloyl-3-methylpiperidine, N-(meth)acryloyl-4-methylpiperidine, N-(meth)acryloyl-2,6-dimethylpiperidine, N-(meth)acryloyl-3,5-dimethylpiperidine, N-(meth)acryloyl-3,3-dimethylpiperidine, N-(meth)acryloyl-4,4-dimethylpiperidine, N-(meth)acryloyl-2,2,6,6-Tetramethylpiperidine, N-(meth)acryloyl-2-methyl-5-ethylpiperidine, N-(meth)acryloyl-4-methyl-4-ethylpiperidine, N-(meth)acryloyl-2-ethylpiperidine, N-(meth)acryloyl-3-ethylpiperidine, N-(meth)acryloyl-4-ethylpiperidine, N-(meth)acryloyl-2-propylpiperidine, N-(meth)acryloyl-3-propylpiperidine, N-(meth)acryloyl-4-propylpiperidine, N-(meth)acryloyl-3-isopropylpiperidine, N-(meth)acryloyl-4-isopropylpiperidine, N-(meth)acryloyl-hexamethyleneimine, N-(meth)acryloyl-2-methylhexamethyleneimine N-(meth)acryloyl-3-methylhexamethyleneimine, N-(meth)acryloyl-4-methylhexamethyleneimine, N-(meth)acryloyl-2-ethylhexamethyleneimine, N-(meth)acryloyl-3-ethylhexamethyleneimine, N-(meth)acryloyl-4-ethylhexamethyleneimine, N-(meth)acryloyl-3-propylhexamethyleneimine, N-(meth)acryloyl-4-propylhexamethyleneimine, N-(meth)acryloyl-3-isopropylhexamethyleneimine, N-(meth)acryloyl-4-isopropylhexamethyleneimine, N-(meth)acryloyl-3,5-dimethylhexamethyleneimine, N-(meth)acryloyl-4,4-Dimethylhexamethyleneimine, N-(meth)acryloylheptamethyleneimine, N-(meth)acryloyloctamethyleneimine, N-(meth)acryloyldedecimethyleneimine, dopamine (meth)acrylamide, 3-(meth)acrylamide phenylboronic acid, hexenyl (meth)acrylamide, heptenyl (meth)acrylamide, octenyl (meth)acrylamide, nonenyl (meth)acrylamide, decenyl (meth)acrylamide, undecenyl (meth)acrylamide, dodecenyl (meth)acrylamide, tetradecenyl (meth)acrylamide, hexadecenyl (meth)acrylamide, oleyl (meth)acrylamide, eicosene (meth)acrylamide, docosene (meth)acrylamide, docosene (meth)acrylamide, octadecadienyl (meth)acrylamide, di At least one of the following: decacarbadienyl (meth)acrylamide, docosadienyl (meth)acrylamide, docosadienyl (meth)acrylamide, octadecadienyl (meth)acrylamide, eicostrienyl (meth)acrylamide, doco ... and docostrienyl (meth)acrylamide.

2. The polymerizable composition of claim 1, wherein the surface tension of the N-substituted (meth)acrylamide (A) is 24.0 mN·m. -1 Up to 46.0 mN·m -1 .

3. The polymerizable composition according to claim 1 or 2, wherein the content of N-substituted (meth)acrylamide (A) is 1% by weight or more relative to the total polymerizable composition.

4. A polymer formed by polymerizing the polymeric composition of any one of claims 1 to 3 by means of an active energy line and / or heat.

5. A polymerizable composition, which is the polymerizable composition according to any one of claims 1 to 3, and further comprises one or more selected from a polymerization initiator, a compound having unsaturated bonds, a nonpolymerizable oligomer and a nonpolymerizable polymer, and the polymer of claim 4, wherein the compound having unsaturated bonds does not include N-substituted (meth)acrylamide (A) and polymers using said N-substituted (meth)acrylamide (A), and the nonpolymerizable oligomer and nonpolymerizable polymer do not include polymers using N-substituted (meth)acrylamide (A).

6. An adhesive composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4, or comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4 and a crosslinking agent.

7. A laminate comprising an adhesive layer comprising the adhesive composition of claim 6 and an organic and / or inorganic substrate, wherein the surface tension of the organic and / or inorganic substrate is 22.6 mN·m. -1 Up to 59.0 mN·m -1 .

8. An adhesive composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4 and a crosslinking agent.

9. An adhesive composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4 and a crosslinking agent, wherein the absolute value of the difference in surface tension between the two dissimilar bonded materials is 37.0 mN·m. -1 the following.

10. A cosmetic composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4.

11. A coating composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4, or comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4 and a crosslinking agent.

12. An ink composition comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4, or comprising the polymeric composition of any one of claims 1 to 3 and 5 or the polymer of claim 4 and a crosslinking agent.

13. An ink composition for three-dimensional shaping, comprising a polymeric composition according to any one of claims 1 to 3 and 5 or a polymer according to claim 4, or comprising a polymeric composition according to any one of claims 1 to 3 and 5 or a polymer according to claim 4 and a crosslinking agent.

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