Urethane (METH)acrylamide and curable composition comprising same

Abstract

[Problem] To provide a urethane (meth)acrylamide oligomer having moisture resistance, weather resistance, transparency, tight adhesiveness, and chemical resistance, exhibiting a high level of heat resistance and good filler dispersibility, and being applicable to a wide range of applications, and to provide a curable composition comprising the urethane (meth)acrylamide oligomer. [Solution] A urethane (meth)acrylamide oligomer having a specific structural unit (general formula (1)) containing a carbonate group was discovered. The oligomer is applicable both as a material for additive manufacturing requiring toughness and as a thermal interface material requiring flexibility and heat resistance.

Description

Urethane (meth)acrylamide and curable compositions containing the same

[0001] The present invention relates to urethane (meth)acrylamide, curable compositions containing the same, and cured products thereof.

[0002] Unsaturated urethane oligomers are widely used as polymerizable oligomers in active energy ray curable compositions, and these compositions are used in the fields of paints, coatings, inks, adhesives, sealants, photoresists, and 3D printing materials.

[0003] Unsaturated urethane oligomers, due to their diverse structures, can impart a wide range of physical properties. In particular, unsaturated urethane oligomers with a polycarbonate (PC) backbone exhibit excellent hydrolysis resistance and moisture resistance derived from carbonate bonds (carbonate groups), high weather resistance (durability), high transparency, and high toughness, making them suitable for long-term use even in harsh environments. For this reason, research and development are actively underway in the fields of optics, electrical and electronic engineering, semiconductors, and medicine.

[0004] WO2015 / 141537 discloses a urethane oligomer as an unsaturated urethane oligomer having one or more skeletons selected from a carbonate skeleton, a diene skeleton, and a hydrogenated diene skeleton within its molecule, and having one or more (meth)acrylamide groups at its termini. The same document shows that by limiting the content of components with a molecular weight of less than 1000 in the (meth)acrylamide urethane oligomer to 5% by weight or less, compatibility with organic solvents and acrylic monomers is improved, and high curability against active energy rays is obtained. Curable compositions containing such urethane oligomers are disclosed to exhibit excellent adhesion, moisture resistance, chemical resistance, and surface curability, as well as low curing shrinkage, high transparency, and high elongation. These properties are the result of the synergistic expression of the properties of the PC skeleton and the (meth)acrylamide group, and the urethane oligomer having the PC skeleton has the properties of a medium-hard material and is widely applied in existing fields.

[0005] In recent years, with the miniaturization and high integration of electronic components and the advancement of 3D printing technology, the properties required of curable compositions have become increasingly stringent. In particular, there is growing demand for both hard and soft materials that take advantage of the properties of PC (polycarbonate) skeletons. Hard materials require higher impact resistance, crack resistance, and toughness that combines strength and elongation, while soft materials require higher flexibility, high elasticity, and excellent wear resistance. Furthermore, there is a strong desire for both hard and soft materials to also possess high heat resistance.

[0006] This disclosure aims to provide a urethane (meth)acrylamide having properties derived from carbonate groups and (meth)acrylamide groups, and exhibiting even better heat resistance and filler dispersibility. By adjusting the structure of the obtained urethane (meth)acrylamide, the aim is to provide a tough urethane oligomer for hard materials with higher impact resistance and a rubber-elastic urethane oligomer for soft materials with better flexibility.

[0007] The inventors of the present invention have diligently studied to solve the above problems and have found that these problems can be solved by urethane (meth)acrylamide having a structural unit represented by general formula (1). General formula (1) In general formula (1), Q is R 1 It contains one or more divalent organic groups represented by general formula (2), general formula (3), or general formula (4), and if Q contains two or more organic groups, they may be bonded in any order. n represents an integer from 1 to 100. R 1 represents a linear alkylene group having 3 to 11 carbon atoms, a branched alkylene group having 3 to 11 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. General formula (2) In general formula (2), R 2 n1 represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n1 represents an integer from 1 to 5. General formula (3) In general formula (3), R 3 and R 4Each of these independently represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n2 represents an integer from 1 to 5. General formula (4) In general formula (4), R 5 R represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 6 to 12 carbon atoms. 6 * represents a linear alkylene group with 1 to 8 carbon atoms, a branched alkylene group with 3 to 8 carbon atoms, or a cyclic alkylene group with 6 to 12 carbon atoms, and n3 represents an integer from 1 to 20. * in general formulas (1) to (4) represents the bond position.

[0008] The urethane (meth)acrylamide of this disclosure possesses excellent properties such as moisture resistance, weather resistance, transparency, adhesion, and chemical resistance derived from carbonate and (meth)acrylamide groups. Furthermore, by adjusting the molecular structure, it exhibits high heat resistance and filler dispersibility. By including such urethane (meth)acrylamide, it is possible to provide curable compositions with excellent heat resistance, filler dispersibility, moisture resistance, weather resistance, transparency, adhesion, and chemical resistance. These curable compositions can be used in the fields of thermal interface materials, inks, 3D printing materials, dental materials, coatings, sealants, photoresist materials, imprint materials, paints, and adhesives.

[0009] The embodiments will be described in detail below, but the scope of the present invention is not limited to these embodiments, and various modifications are possible without departing from the spirit of the invention. When multiple upper and lower limits are given for a particular parameter, a suitable numerical range can be set within the range of these upper and lower limits or by any combination of upper and lower limits.

[0010] One embodiment of the present disclosure relates to urethane (meth)acrylamide (E) having a structural unit represented by general formula (1). General formula (1)

[0011] In general formula (1), Q is R 1contains one or more divalent organic groups represented by General Formula (2), General Formula (3) or General Formula (4). When Q contains two or more types of organic groups, they may be bonded in any order. n is an integer representing a repeating unit, and n is in the range of 1 to 100. n is preferably 1 to 50, more preferably 3 to 30.

[0012] General Formula (1) is a structure composed of a carbonate group and Q. A cured product with high hardness can be obtained from the carbonate group due to the high cohesive energy derived from its rigid structure. The structure of Q adjusts the steric hindrance around the carbonate group and the overlapping state of molecular chains, and also plays a role in imparting various properties to urethane (meth)acrylamide (E).

[0013] R 1 is a linear alkylene group having 3 to 11 carbon atoms, a branched alkylene group having 3 to 11 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. When Q is R 1 , the carbonate groups are linked via a chain or cyclic alkylene group. This structure forms van der Waals forces between alkylene groups, strong cohesive force between carbonate bonds, and strong hydrogen bonds between carbonate bonds, urethane bonds and (meth)acrylamide bonds. As a result, the urethane (meth)acrylamide (E) exhibits excellent properties in mechanical strength, moisture resistance, heat resistance, chemical resistance and weather resistance.

[0014] R 1 is a linear alkylene group, the molecular chain can rotate relatively easily, and the urethane (meth)acrylamide (E) exhibits flexibility. When the number of carbon atoms in R 1 increases, the mobility of the molecular chain is further enhanced, and the flexibility of E improves. When R 1 is a branched alkylene group, overlapping between molecular chains is suppressed due to steric hindrance between the branched alkylene groups, so the flexibility of E is further enhanced. This allows E to maintain flexibility even at low temperatures and further achieve a lower viscosity.

[0015] Examples of linear alkylene groups include propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and undecylene groups. Examples of branched alkylene groups include 1-methylethylene, isopropylene, 1-methylpropylene, 2-methylpropylene, neopentyl, 3-methylpentylene, isopentylene, 2-ethylhexylene, (2R,4R)-2,4-dimethylhexylene, isohexylene, isoheptylene, isooctylene, isononylene, isodecylene, and isoundecylene groups, as well as their structural isomers.

[0016] From the perspective of the balance between flexibility and hardness, R 1 The linear or branched alkylene group preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms. In particular, from the viewpoint of obtaining a cured product with an excellent balance of flexibility and hardness, R 1 It is most preferably a propylene group, a butylene group, a pentylene group, a hexylene group, a 2-methylpropylene group, or a 3-methylpentylene group.

[0017] For more details, see R 1 When the number of carbon atoms is 3 to 4, the hardness of the cured product can be significantly improved. This is because the short alkylene chain reduces the length of the structural unit in general formula (1), resulting in a relatively higher carbonate equivalent. 1 The fewer the number of carbon atoms, the more densely the carbonate groups, which are the high cohesive energy sites, are arranged on the molecular chain. This causes the molecular chains to attract each other strongly, increasing the rigidity of the hardened product. Short alkylene groups have a low degree of spatial freedom, which suppresses the overall mobility of the molecular chain. This makes it easier for the molecular chains to form a more regular and densely arranged structure. As the molecular chain arrangement density improves, the free volume between molecules decreases, and the translational and rotational motion of molecules due to thermal energy is restricted. As a result, the glass transition temperature (Tg) increases, and dimensional stability at high temperatures improves. The high hardness obtained in this way directly contributes to improved scratch resistance and wear resistance of the hardened product surface, and is extremely advantageous in improving shape retention and dimensional accuracy when used as a structural member subjected to high loads.

[0018] R 1 When the number of carbon atoms is between 4 and 6, the flexibility of the cured product can be effectively improved. This is because as the alkylene chain length increases, the rotational degrees of freedom of the carbon-carbon single bond increases, increasing the overall mobility of the molecular chain. The combination of rigid carbonate groups and flexible alkylene chains allows the molecular chain to undergo various changes in response to external stress, such as bending, stretching, and untangling. This high mobility of the molecular chain results in excellent flexibility and elongation of the cured product. That is, when stress is applied to the material, the energy can be absorbed and relieved by the deformation of the molecular chain, resulting in a larger amount of deformation (elongation at break) before the material breaks. The high flexibility obtained in this way enhances the impact resistance of the cured product and improves its resistance to flexural fatigue in applications involving repeated bending. Furthermore, when applied to or bonded to substrates with different coefficients of thermal expansion, it can prevent the relaxation of internal stress caused by thermal cycling, the occurrence of cracks, and delamination, thus ensuring long-term reliability.

[0019] R 1 When the alkylene group is cyclic alkylene, the molecular chain exhibits rigidity, which can improve the glass transition temperature (Tg) and heat resistance of urethane (meth)acrylamide (E). This rigidity also improves the mechanical strength and chemical resistance of E. Furthermore, by combining linear alkylene groups and cyclic alkylene groups, it is possible to adjust the balance between the flexibility and hardness of E.

[0020] Examples of cyclic alkylenes include various cyclic skeletons, including alicyclic, fused, polycyclic, and aromatic rings. Specific examples of alicyclic structures include cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, and cyclododecylene groups. Examples of fused or polycyclic structures include decalin, tetralin, indan, bicyclohexane, adamantane, and norbornane rings. Examples of aromatic structures include phenylene, naphthylene, biphenylene, and diphenylene groups. Among these, R is particularly important from the viewpoint of hardness and flexibility. 1It is preferable that the group is a cyclohexylene group.

[0021] When Q is a divalent organic group represented by general formula (2), urethane (meth)acrylamide (E) has both a carbonate group and an ether group. n1 is preferably an integer from 1 to 5, more preferably an integer from 1 to 4, and even more preferably an integer from 1 to 3. If n1 is within these ranges, E can produce a cured product that combines the flexibility derived from the ether group with the hardness derived from the carbonate group. General formula (2)

[0022] In general formula (2), R 2 R represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. Examples of these groups include the various alkylene groups mentioned above. From the viewpoint of the high wet hardness of urethane (meth)acrylamide (E), 2 It is preferable that the group is a linear alkylene group or a cyclic alkylene group. From the viewpoint of obtaining a cured product with an excellent balance of flexibility and hardness, 2 It is more preferably a linear alkylene group, and most preferably an ethylene group, a propylene group, or a butylene group.

[0023] When Q is a divalent organic group represented by general formula (3), urethane (meth)acrylamide (E) has both a carbonate group and an ester group. n2 is preferably an integer from 1 to 5, and more preferably an integer from 1 to 4. If n2 is within this range, a cured product with an excellent balance of flexibility and hardness can be obtained. Adhesion to polyethylene terephthalate (PET) and acrylic resin substrates is also improved. General formula (3)

[0024] In general formula (3), R 3 and R 4 Each of these independently represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. Examples of these groups include the various alkylene groups mentioned above. From the viewpoint of the high wet hardness of urethane (meth)acrylamide (E), R3 and R 4 It is preferable that the group is a linear or cyclic alkylene group. From the viewpoint of obtaining a cured product with an excellent balance of flexibility and hardness, R 3 It is preferably a linear alkylene group having 2 to 8 carbon atoms, and more preferably a linear alkylene group having 2 to 6 carbon atoms. 4 It is preferable that is a linear or branched alkylene group having 3 to 8 carbon atoms, and more preferably is a linear or branched alkylene group having 3 to 6 carbon atoms. Furthermore, R 3 is a butylene group, a pentylene group, a hexylene group, R 4 It is most preferable that the group be a pentylene group or a hexylene group.

[0025] When Q is a divalent organic group represented by general formula (4), urethane (meth)acrylamide (E) has both a carbonate group and a group containing a siloxane bond. n3 is preferably an integer from 1 to 20, more preferably an integer from 1 to 15, and even more preferably an integer from 5 to 15. If n3 is within these ranges, a cured product with an excellent balance of flexibility and hardness can be obtained. The heat resistance of E can be further improved. General formula (4)

[0026] In general formula (4), R 5The group represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 6 to 12 carbon atoms. Examples of linear alkyl groups include propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and undecyl groups. Examples of branched alkyl groups include isopropyl, isobutyl, neopentyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, and isoundecyl groups, as well as their structural isomers. Examples of cyclic alkyl groups include alicyclic structures of cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups; fused or polycyclic structures of decalyl, tetralyl, indanyl, bicyclohexyl, adamantyl, and norbornyl groups; and aromatic structures of benzyl, phenethyl, naphthylmethyl, and naphthylethyl groups.

[0027] R 6 This represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. Examples of these groups include the various alkylene groups mentioned above. From the viewpoint of the high hardness of urethane (meth)acrylamide (E), R 5 R is preferably a linear alkyl group having 1 to 6 carbon atoms, and more preferably a linear alkyl group having 1 to 4 carbon atoms. 6 It is preferably a linear alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms. From the viewpoint of obtaining a cured product with an excellent balance of flexibility and hardness, R 5 is a methyl group, an ethyl group, R 6 It is most preferable that the group is a butylene group or a hexylene group.

[0028] The carbonate equivalent of urethane (meth)acrylamide (E) is preferably 120 to 170 or 450 to 1200. The carbonate equivalent is directly related to the proportion of carbonate groups contained in the E molecule and is calculated by dividing the weight-average molecular weight (Mw) of E by the average number of carbonate groups per molecule of E. When the carbonate equivalent is in the range of 120 to 1200, the proportion of carbonate groups contained in E is appropriate, and in combination with (meth)acrylamide groups, it exhibits excellent moisture resistance, weather resistance, transparency, adhesion, and chemical resistance. When the carbonate equivalent is 120 to 170, the proportion of carbonate groups contained in E is high, the cohesive force between carbonate groups becomes strong, and the hardness (sometimes referred to as strength as a mechanical property) and toughness of the resulting cured product are improved. Such E is classified as a tough urethane oligomer and is suitable for hard materials with high impact resistance. On the other hand, when the carbonate equivalent is between 450 and 1200, the proportion of carbonate groups in E is low, resulting in a good balance between the cohesive force between carbonate groups and the hydrogen bonds formed between the carbonate groups, urethane groups, and (meth)acrylamide groups, and thus the flexibility (sometimes described as elongation as a mechanical property) of the resulting cured product is high. Such E is classified as a rubber elastic urethane oligomer and is suitable for soft materials with high flexibility. When the carbonate equivalent is between 180 and 440, E possesses both toughness and flexibility and is classified as a medium-hard material with moderate strength and elongation.

[0029] The carbonate equivalent of tough urethane (meth)acrylamide (E) is more preferably 125 to 165, and even more preferably 130 to 160. Cured products obtained from E having a carbonate equivalent in this range exhibit very high strength and heat resistance while maintaining moderate flexibility. Unexpectedly, tough E exhibits excellent dispersibility with fillers. Due to these properties, tough E is suitably used in 3D stereolithography modeling inks, dental materials (e.g., crowns, bridges, inlays), hard coating agents that impart scratch resistance or impact resistance, and coating agents for decorative applications of smartphone casings and automotive interior parts.

[0030] The carbonate equivalent of rubber-elastic urethane (meth)acrylamide (E) is more preferably 450 to 900, and even more preferably 500 to 800. Cured products obtained from E having a carbonate equivalent in this range exhibit very high flexibility and excellent filler dispersibility while maintaining moderate hardness. Unexpectedly, rubber-elastic E exhibits high heat resistance. Due to these properties, rubber-elastic E is suitably used in adhesives, sealants, encapsulants for semiconductors or electronic components, thermal interface materials (TIMs) and materials used for heat dissipation in power semiconductors, optical fiber coatings, gaskets, elastomers for midsoles and packings, cushioning materials in three-dimensional stereolithography, and flexible model materials such as bio-model materials.

[0031] Urethane (meth)acrylamide (E) has one or more (meth)acrylamide groups. These (meth)acrylamide groups allow E to be polymerized and / or cured by active energy and / or heat, either alone or with other polymerizable compounds.

[0032] The (meth)acrylamide group readily forms hydrogen bonds, increasing the intermolecular cohesive force of urethane (meth)acrylamide (E). As a result, it is hypothesized that the resulting cured product would exhibit high strength while its elongation would tend to decrease. However, contrary to this prediction, it was confirmed that the cured product of E exhibited high strength and elongation. From these results, it is thought that the hydrogen bonds formed by the amide group acted cooperatively with the carbonate and urethane groups, functioning as energy relaxation sites under stress.

[0033] The urethane (meth)acrylamide (E) may have two or more (meth)acrylamide groups. When E has two or more (meth)acrylamide groups, E can form a crosslinked structure on its own, and a cured product exhibiting excellent mechanical strength, chemical resistance, heat resistance, and impact resistance can be obtained. From this viewpoint, the number of (meth)acrylamide groups is preferably 2 to 10, and more preferably 2 to 6.

[0034] Urethane (meth)acrylamide (E) may have unsaturated groups other than the (meth)acrylamide group. These unsaturated groups may be one or more groups arbitrarily selected from (meth)acrylate groups, vinyl groups, allyl groups, and maleimide groups.

[0035] Urethane (meth)acrylamide (E) has one or more urethane groups in its molecule. The urethane groups can form hydrogen bonds with each other, as well as with (meth)acrylamide groups and carbonate groups. By adjusting the formation of these hydrogen bonds, the curing shrinkage resistance of E is increased, and the mechanical strength and heat resistance of the resulting cured product are improved. From this viewpoint, the number of urethane groups contained in the molecule is preferably 2 to 400, more preferably 4 to 60, and even more preferably 6 to 30. Within these ranges, the viscosity of urethane (meth)acrylamide (E) can be adjusted to a range that is easy to handle, and the balance between the hardness and flexibility of the resulting cured product is good, which is preferable.

[0036] The compression set of the cured urethane (meth)acrylamide (E) in this embodiment is preferably 10% or less. Compression set is an indicator of how much deformation remains after the material has been compressed and deformed for a certain period of time. The compression set of the cured product is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. A smaller value means that less deformation remains.

[0037] The numerous hydrogen bonds formed by the abundant carbonate, urethane, and (meth)acrylamide groups within the molecule enable urethane(meth)acrylamide(E) to achieve low compression set. When compressive stress is applied to urethane(meth)acrylamide(E), the hydrogen bond network cleverly relieves the stress and dissipates energy by reversibly severing some of its bonds. This allows for large deformations while preventing material fracture. Subsequently, upon release from stress, the severed hydrogen bonds rapidly recombine with other nearby sites, spontaneously attempting to rebuild the original stable network structure, resulting in a very small compression set in the cured material.

[0038] The tough E has strong cohesive forces between the carbonate groups that make up the main chain, making it less susceptible to plastic deformation due to stress. This reduces residual strain after stress release. The rubber-elastic E has an excellent balance between the cohesive forces between carbonate groups and the flexibility of the hydrogen bond network formed between the carbonate groups, urethane groups, and (meth)acrylamide groups. As a result, even while deforming, a strong force acts to restore it to its original shape, and the shape is restored.

[0039] This property can also be adjusted by the structure of Q in general formula (1). For example, if Q is a relatively short linear alkylene group (R1) with 3 to 4 carbon atoms, the carbonate groups are arranged in close proximity on the molecular chain, increasing the density of carbonate groups and thus increasing the cohesive energy. As a result, the cured material becomes more rigid, and deformation due to stress is suppressed, effectively reducing the compression set. If Q is a relatively long linear alkylene group (R1) with 5 or more carbon atoms and / or general formulas (2) to (4), the main chain is given a moderate degree of flexibility. This flexibility allows the cured material to flexibly absorb stress. At the same time, the intrinsic hardness (cohesive force) and strong hydrogen bond network derived from the carbonate groups are maintained, so after being released from stress, it can easily return to its original shape due to its high restorative force, resulting in the achievement of a low compression set.

[0040] The continuous heat resistance temperature of the cured urethane (meth)acrylamide (E) in this embodiment is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. The continuous heat resistance temperature is an indicator that the cured product has long-term heat resistance.

[0041] In this embodiment, the 5% weight loss temperature of the cured urethane (meth)acrylamide (E) by thermogravimetric analysis (TGA) is preferably 180°C or higher, more preferably 220°C or higher, and even more preferably 250°C or higher. The 5% weight loss temperature is an indicator that the cured product has short-term heat resistance.

[0042] Such excellent heat resistance is the result of a combination of factors stemming from the molecular design of urethane (meth)acrylamide (E). Firstly, it is due to the carbonate groups that constitute the main chain skeleton. Carbonate groups have higher bond energy than ester and ether groups and inherently possess high thermal stability. Secondly, it is due to the presence of (meth)acrylamide groups. Due to their high polarity and planar structure, (meth)acrylamide groups promote dense overlapping of molecular chains. That is, molecular chains can be arranged more densely and regularly, suppressing molecular motion due to thermal energy. This high-density overlapping structure of molecular chains contributes to improved heat resistance. Thirdly, it is due to the aforementioned hydrogen bond network. The strong intramolecular and / or intermolecular hydrogen bonds formed by the urethane groups and (meth)acrylamide groups strongly bind the molecular chains together, making thermal decomposition less likely.

[0043] This property can also be adjusted by the structure of Q in general formula (1). For example, if Q is a relatively long alkylene group with 5 or more carbon atoms (R 1 ) and / or general formulas (2) to (4) increase the distance between carbonate groups, giving the main chain moderate mobility. While this is usually expected to result in reduced heat resistance, this moderate degree of freedom allows the entire molecular chain to overlap densely. As a result, intermolecular interactions are maximized, and high heat resistance can be obtained.

[0044] The acrylic equivalent of urethane (meth)acrylamide (E) is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. The acrylic equivalent is directly related to the proportion of (meth)acrylamide groups contained in the E molecule and is calculated by dividing the weight-average molecular weight (Mw) of E by the average number of (meth)acrylamide groups per E molecule. When the acrylic equivalent is within these ranges, a good balance between the flexibility and hardness of the cured product of E is achieved.

[0045] In urethane (meth)acrylamide (E), the ratio of acrylic equivalent to carbonate equivalent (acrylic equivalent / carbonate equivalent) is preferably 5 to 2,000, more preferably 5 to 1,500, and even more preferably 10 to 1,000. By adjusting the ratio of acrylic equivalent to carbonate equivalent, the hardness and flexibility of the cured product can be arbitrarily controlled, and E with toughness or rubber elasticity can be obtained depending on the purpose.

[0046] More specifically, in a tough urethane (meth)acrylamide (E), if the carbonate equivalent is in the range of 120 to 170, a harder cured product can be obtained if the ratio of acrylic equivalent to carbonate equivalent is 28 to 1265. On the other hand, in a rubber-elastic urethane (meth)acrylamide (E), if the carbonate equivalent is in the range of 450 to 1200, a softer cured product can be obtained if the ratio of acrylic equivalent to carbonate equivalent is 28 to 1265.

[0047] The weight-average molecular weight (Mw) of urethane (meth)acrylamide (E) is not particularly limited as long as it is in the range of 2,000 to 400,000, from the viewpoint of ease of handling and the physical properties of the cured product. When Mw is 2,000 or more, the resulting cured product can exhibit sufficient hardness. When Mw is 400,000 or less, the viscosity of urethane (meth)acrylamide (E) is within an industrially manageable range. From these viewpoints, the Mw of E is preferably 5,000 to 100,000, and more preferably 7,000 to 60,000.

[0048] Urethane (meth)acrylamide (E) has one or more structural units represented by general formula (1). In this specification, the structural units represented by general formula (1) are referred to as carbonate segments. The mass percentage of carbonate segments contained in E (carbonate segment content (%)) can be calculated by dividing the total mass of the structural units of general formula (1) by the weight-average molecular weight (Mw) of E. When the carbonate segment content is in the range of 10% to 95%, it is preferable because the various physical properties derived from the carbonate group can be fully expressed. Furthermore, when the carbonate segment content is in the range of 60% to 95%, the mass of the carbonate group-related structure relative to the molecular weight of E is high, and a harder cured product can be obtained. For tough E, the carbonate segment content is more preferably 70% to 95%, and even more preferably 75% to 95%. On the other hand, when the carbonate segment content is in the range of 10% to 60%, the mass of the carbonate group-related structure relative to the molecular weight of E is relatively low, and a softer cured product can be obtained. The carbonate segment content of E having rubber elasticity is more preferably 20% to 55%, and even more preferably 20% to 40%.

[0049] Urethane (meth)acrylamide (E) may have at least one group selected from urea groups, thiourea groups, amide groups, and imide groups. By introducing these groups, the flexibility and hardness of the resulting cured product can be finely adjusted. Depending on the type of group introduced, miscibility with other resins and additives can be improved, as can adhesion to fillers and dispersibility.

[0050] One embodiment of this present invention relates to a curable composition containing urethane (meth)acrylamide (E) (hereinafter referred to as curable composition (I)).

[0051] The content of urethane (meth)acrylamide (E) is preferably 1 to 100% by mass relative to the total curable composition (I). More preferably, the content of E is 5 to 98% by mass relative to the total I, from the viewpoint of adjusting the balance of the physical properties of the cured product obtained from I. The viscosity of I is not particularly limited and can be appropriately adjusted from a low-viscosity liquid to a high-viscosity paste or solid depending on its application.

[0052] The curable composition (I) in this embodiment may contain one or more components selected from polymerizable compounds (F), initiators (G), fillers (H), and other components (K).

[0053] The polymerizable compound (F) is a polymerizable compound other than urethane (meth)acrylamide (E), and is one or more compounds selected from monofunctional polymerizable compounds (F1) and polyfunctional polymerizable compounds (F2). Generally, since F has a lower viscosity than E, it can reduce the viscosity of the curable composition (I) and improve handling. By incorporating F as part of the cured product, the physical properties of the cured product, such as hardness, flexibility, substrate adhesion, and filler adhesion, can be adjusted. F may be used alone or in combination of two or more types.

[0054] The content of the polymerizable compound (F) can be adjusted as appropriate depending on the application. For example, it may be 0 to 99% by mass relative to the total curable composition (I), and is preferably 20 to 90% by mass from the viewpoint of suitably adjusting the physical properties of the cured product.

[0055] The monofunctional polymerizable compound (F1) not only improves the handling properties of the curable composition (I) but can also impart flexibility to the cured product. The content of F1 is preferably 0 to 95% by mass, more preferably 3 to 85% by mass, and even more preferably 5 to 80% by mass, relative to the total curable composition (I).

[0056] The monofunctional polymerizable compound (F1) is a compound containing one unsaturated group selected from a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, an allyl group, and a styryl group. From the viewpoint of obtaining good curability, it is preferable that the compound has a (meth)acrylate group or a (meth)acrylamide group.

[0057] The following are specific examples of monofunctional polymerizable compounds (F1). In this specification, alkyl refers to a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, or a cyclic alkyl group having 3 to 18 carbon atoms, and alkylene refers to an alkylene group having 1 to 4 carbon atoms.

[0058] Compounds containing a (meth)acrylate group include alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkylcarboxylic acids (meth)acrylates, alkyl sulfonic acids (meth)acrylates, alkyl phosphates (meth)acrylates, alkoxyalkylene glycol (meth)acrylates, phenoxyalkylene glycol (meth)acrylates, N,N-dialkylaminoalkyl (meth)acrylates, and (meth)acrylates having a cyclic structure.

[0059] Specifically, alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate and stearyl(meth)acrylate; hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate and 4-hydroxybutyl(meth)acrylate; alkylcarboxylic acids of (meth)acrylates such as 2-(meth)acryloyloxyethyl succinic acid and 2-(meth)acryloyloxyethyl phthalic acid; and 2-sulfoethyl(meth)acrylate. Alkyl sulfonic acids of rilate (meth)acrylate; alkyl phosphates of methacryloyloxyethyl acid phosphate; alkoxyalkylene glycol (meth)acrylates of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; phenoxyalkylene glycol (meth)acrylates of phenoxyethyl (meth)acrylate and phenoxydiethylene glycol (meth)acrylate; N,N-dialkylaminoalkyl (meth)acrylates of N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;Examples include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and cyclic (meth)acrylates such as N-(meth)acryloyloxyethyl norbornene carboxamide.

[0060] Compounds containing a (meth)acrylamide group include N-alkyl(meth)acrylamides, N,N-dialkyl(meth)acrylamides, N-hydroxyalkyl(meth)acrylamides, N,N-di(hydroxyalkyl)(meth)acrylamides, hydroxyphenyl-substituted compounds, N-alkoxyalkyl(meth)acrylamides, N-sulfoalkyl(meth)acrylamides, N-aminoalkyl(meth)acrylamides, N-(meth)acryloylmorpholins, and diacetone(meth)acrylamides.

[0061] Specifically, N-alkyl(meth)acrylamides such as (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-isopropyl(meth)acrylamide and Nn-butyl(meth)acrylamide; N,N-dialkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; N-hydroxyalkyl(meth)acrylamides such as N-hydroxyethyl(meth)acrylamide; N,N-di(hydroxyalkyl)(meth)acrylamides; hydroxyphenyl(meth)acrylamides such as N-alkyl-N-(4-hydroxyphenyl)(meth)acrylamide, 4-hydroxyphenyl(meth)acrylamide and N,N-di(4-hydroxyphenyl)(meth)acrylamide; N-methoxymethyl Examples include N-alkoxyalkyl(meth)acrylamides of N-(meth)acrylamide and N-ethoxyethyl(meth)acrylamide; N,N-di(alkoxyalkyl)(meth)acrylamides of N,N-di(methoxyethyl)(meth)acrylamide; N-sulfoalkylacrylamides of N-(3-sulfopropyl)acrylamide potassium salt; N-alkylamino(meth)acrylamides; N-alkylaminoalkyl(meth)acrylamides; N,N-dialkylaminoalkyl(meth)acrylamides of N-(dimethylamino)propyl(meth)acrylamide; N-hydroxyalkyl-N-(4-hydroxyphenyl)(meth)acrylamide; N-alkyl-N-hydroxyalkyl(meth)acrylamide; and N-alkyl-N-alkoxyalkyl(meth)acrylamide.

[0062] Compounds containing a vinyl group include carboxylic acid esters of vinyl acetate and vinyl propionate; alkyl vinyl ethers of methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; N-vinyl nitrogen-containing cyclic compounds of N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinyloxazoline; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and their mono / dialkyl esters, mono / dialkylamides, alkylimide unsaturated dibasic acids, and derivatives.

[0063] Compounds containing an allyl group include alkylcarboxylic acid allyl esters of allyl acetate and allyl propionate; alkylallyl ethers of allyl methyl ether, allyl ethyl ether and allyl butyl ether; aromatic allyl ethers of phenylallyl ether and alkylphenylallyl ether; and alkylallylamines of allylamine, monoalkylallylamine and dialkylallylamine.

[0064] Examples of compounds containing a styryl group include styrene, α-alkylstyrene, α-methylstyrene, and α-methylstyrene dimers (α-substituted alkylstyrenes); o-methylstyrene, m-methylstyrene, and p-methylstyrene (aromatically substituted styrenes); and p-styrene sulfonic acid (sulfonic acid substituted styrenes).

[0065] The monofunctional polymerizable compound (F1) may have a cyclic structure in its molecule. By using urethane (meth)acrylamide (E) in combination with F1 having a cyclic structure, the cyclic structure of F1 intersects with the molecules of E and functions as a spacer. This action suppresses excessive aggregation of carbonate groups and allows for a more uniform aggregation state. As a result, the viscosity of the curable composition is effectively adjusted, and the hardness and flexibility of the cured product can be balanced.

[0066] Compounds with a cyclic structure include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, isobornyl (meth)acrylate, bornyl (meth)acrylate, camphanyl (meth)acrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, norbornene-derived (meth)acrylate, and the aliphatic cyclic skeleton of dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, α-methylbenzyl (meth)acrylate, naphthyl (meth)acrylate, and phenethyl Examples include compounds with aromatic cyclic skeletons such as (meth)acrylate, coumenyl (meth)acrylate, and tetrahydronaphthyl (meth)acrylate; heterocyclic skeletons such as tetrahydrofurfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylamide, furfuryl (meth)acrylate, morpholinyl (meth)acrylate, piperidinyl (meth)acrylate, oxazinyl (meth)acrylate, thienyl (meth)acrylate, and indanyl (meth)acrylate; and polycyclic skeletons such as adamantyl (meth)acrylate, bicyclooctyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, and spiro-derived (meth)acrylate.

[0067] The polyfunctional polymerizable compound (F2) can improve the hardness of the cured product. The content of F2 is preferably 0 to 70% by mass, more preferably 1 to 55% by mass, and even more preferably 3 to 50% by mass, relative to the total curable composition (I).

[0068] The polyfunctional polymerizable compound (F2) is a compound containing at least two unsaturated groups selected from (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, allyl groups, styrene groups, and acetylene groups. From the viewpoint of obtaining good curability, the unsaturated groups are preferably (meth)acrylate groups and / or (meth)acrylamide groups. The unsaturated groups of F2 may be the same or different from each other.

[0069] Examples of polyfunctional polymerizable compounds (F2) include allyl (meth)acrylate, allyl oxyalkoxy (meth)acrylate, allyl (meth)acrylamide, allyl oxyalkoxy (meth)acrylamide, vinyl oxyalkoxy (meth)acrylate, diallylamine, alkyldiallylamine, dialkyldiallylammonium quaternary salt, divinylbenzene, allylacetylene and diacetylbenzene allyl / vinyl polyfunctional monomers; glycol di(meth)acrylates of alkylene glycol di(meth)acrylates and polyalkylene glycol di(meth)acrylates; polyalkylene glycol di(meth)acrylates of polyethylene glycol diacrylate, polytetramethylene glycol diacrylate and triethylene glycol dimethacrylate; Bisphenol / epoxy polyfunctional (meth)acrylates including sphenol A diglycidyl ether (meth)acrylic acid adducts, alkoxylated bisphenol A di(meth)acrylates, polyethylene glycol (20)-modified bisphenol A diacrylate, epoxy novolac (meth)acrylates, phenol novolac (meth)acrylates, and cresol novolac (meth)acrylates; polyester / polycarbonate polyfunctional (meth)acrylates including polyester di(meth)acrylates and polycarbonate di(meth)acrylates; urethane polyfunctional (meth)acrylates / acrylamides including polyurethane di(meth)acrylates and polyurethane di(meth)acrylamides having an aliphatic, aromatic, polyether, or polyester skeleton;Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri / tetra / penta / hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanurate ethylene oxide modified tri(meth)acrylate, ethylene oxide modified pentaerythritol Examples include polyol-derived polyfunctional (meth)acrylates such as tol-based polyfunctional (meth)acrylates and succinic acid-modified pentaerythritol-based polyfunctional (meth)acrylates; cycloaliphatic polyfunctional (meth)acrylates such as cyclohexanedimethanol di(meth)acrylate, trimethylolpropanecyclohexanedimethanol di(meth)acrylate, and tricyclodecanedimethanol diacrylate; and phosphate-based polyfunctional (meth)acrylates such as di(meth)acryloyloxyethyl phosphate and tris(meth)acryloyloxyethyl phosphate.

[0070] The weight-average molecular weight of the polyfunctional polymerizable compound (F2) is preferably 100 to 100,000. When the molecular weight of F2 is 100,000 or less, the viscosity of the curable composition (I) can be easily adjusted to a desired range. When the molecular weight of F2 is 100 or more, crosslinking points can be introduced at appropriate intervals in the resulting cured product, thus obtaining a cured product with high impact resistance. From these viewpoints, the molecular weight of F2 is more preferably 200 to 50,000, and even more preferably 300 to 30,000.

[0071] Examples of initiators (G) include photopolymerization initiators (G1) and thermal polymerization initiators (G2). When the curable composition (I) contains G, the polymerization reaction is efficiently initiated by active energy rays and / or heat, thereby improving the curability of I. G may be used alone or in combination of two or more types.

[0072] The initiator may be a photopolymerization initiator or a thermal polymerization initiator used alone, or a hybrid curing system combining a photopolymerization initiator and a thermal polymerization initiator. The curing procedure in hybrid curing is not particularly limited. For example, curing with active energy rays (pre-cure) can be performed first, followed by curing with thermal energy (post-cure). The reaction heat generated during curing with high-power active energy rays can also be used to promote thermal polymerization.

[0073] Examples of photopolymerization initiators (G1) include photoradical-based, photocationic-based, and photoanionic initiators. Since urethane (meth)acrylamide (E) and polymerizable compounds (F) have radically polymerizable unsaturated groups, photoradical-based photopolymerization initiators can be suitably used. Using two initiators with different absorption wavelengths as photopolymerization initiators (G1) in combination improves compatibility with the light source used. Improvements in curing depth during the curing of colored curable compositions and thick films can also be expected.

[0074] Intramolecular cleavage type photoradical polymerization initiators are those in which bonds are cleaved intramolecularly upon light irradiation, directly generating radical species. Representative compounds include, for example, acetophenone-based compounds such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; α-aminoketone-based compounds such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; and bis(2,4,6- Examples include acylphosphine oxide systems such as trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphenate, and (2,4,6-trimethylbenzoyl)bis(p-tolyl)phosphine oxide; and oxime ester systems such as 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one and 1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl)ethanone 1-(O-acetyloxime).

[0075] Hydrogen abstraction type photoradical polymerization initiators are those that become excited upon light irradiation and abstract hydrogen from surrounding hydrogen donors to generate radicals. Representative compounds include, for example, benzophenone-based compounds such as benzophenone, methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, and acrylic benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and diethylthiooxanthone; benzoyl ester-based compounds such as methyl benzoylmate, ethyl benzoylmate, and 3,5-dimethoxybenzoylmate; benzoyl amide-based compounds such as N-methylbenzoylamide, N-phenylbenzoylamide, and benzoylamide groups having an ethylenically unsaturated group or a urethane group; and anthraquinones and camphorquinones.

[0076] Examples include self-polymerizing initiators having one or more groups selected from benzophenone groups, thioxanthone groups, benzoyl methyl acid groups, benzoyl methyl acid ester groups, and benzoyl methyl acid amide groups, high molecular weight (weight-average molecular weight of 1000 or more) initiators, and high molecular weight polymerizable polymerization initiators. As a high molecular weight hydrogen abstraction type photopolymerization initiator having an unsaturated group, Kohshylex I-3101 manufactured by KJ Chemicals is an example. Kohshylex I-3101 is self-polymerizable and can be fixed to the cured product via chemical bonds through the photopolymerization reaction, making it more preferable.

[0077] The content of the photopolymerization initiator (G1) is not particularly limited. If G1 is low molecular weight (weight average molecular weight less than 1000), it is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 10% by mass, relative to the total curable composition (I). If G1 is high molecular weight, it is preferably 3 to 50% by mass, and more preferably 5 to 30% by mass, relative to the total I. If high molecular weight Kohshylex I-3101, which has self-polymerizing properties, it is preferably 3 to 95% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, relative to the total I. If the G1 content is within these ranges, I will have sufficient curability, and discoloration of the cured product and deterioration of physical properties due to G1 residue can be avoided.

[0078] As the thermal polymerization initiator (G2), any known one can be used as appropriate. Specifically, examples include azo compounds of 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), and organic peroxides of benzoyl peroxide and dicumyl peroxide. It is preferable to select an initiator with an appropriate 10-hour half-life temperature depending on the curing temperature used. The G2 content is preferably 0.1 to 10.0% by mass, and more preferably 1 to 5% by mass, relative to the total curable composition (I).

[0079] Examples of fillers (H) include organic fillers and inorganic fillers. When the curable composition (I) contains H, it is possible to improve the mechanical strength (tensile strength) and heat resistance of the cured product, as well as impart properties such as thermal conductivity and electrical insulation. H may be used alone or in combination of two or more types.

[0080] The content of filler (H) is not particularly limited. It is preferably 0 to 90% by mass, more preferably 0.5 to 85% by mass, and even more preferably 5 to 80% by mass, relative to the total curable composition (I).

[0081] The shape of the filler (H) is not particularly limited and can be spherical, nearly spherical, needle-shaped, rod-shaped, columnar, hexagonal columnar, fibrous, plate-shaped, flaky, or irregularly shaped fragments. The filler may be solid or hollow, such as a glass balloon or a shirasu balloon.

[0082] The particle size of the filler can be appropriately selected according to the application and required characteristics. For example, for spherical fillers, the particle size can be selected in the range from the nanometer (nm) order to the micrometer (μm) order, and those in the range of 1 nm to 900 μm can be used. For needle-shaped, rod-shaped, or fibrous fillers, the aspect ratio (length of the long side / length of the short side) can be appropriately selected in the range of 1.1 to 50.

[0083] Examples of organic fillers include plant-derived fillers such as cellulose, lignin, and cellulose nanofibers; acrylic / styrene resin beads such as polymethyl methacrylate, polystyrene, cross-linked polystyrene, polyacrylstyrene, and acrylic beads; engineering plastic resin beads such as polycarbonate, polyamide resin, polyimide resin, polyester resin, polyolefin resin, and polyfluoroethylene resin; organic fiber fillers such as cellulose fibers, aramid fibers, and polyamide fibers; and organic pigment fillers such as phthalocyanine blue and quinacridone red.

[0084] Inorganic fillers include metal oxide fillers such as fused silica, crystalline silica, alumina, zirconia, titanium oxide, iron oxide, calcium oxide, magnesium oxide, zinc oxide, tin oxide, indium oxide, and cerium oxide; composite metal oxides such as silica-alumina, silica-zirconia, alumina-titania, spinel-type oxides (MgAl2O4), and perovskite-type oxides (BaTiO3, SrTiO3); glass fillers such as glass beads, glass fibers, glass flakes, glass balloons, borosilicate glass fillers, and low-melting-point glass fillers. Examples include metal salt fillers such as calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, and magnesium hydroxide; mineral fillers such as talc, clay, mica, kaolin, shirasu balloons, zeolite, montmorillonite, hydrotalcite, and whiskers; inorganic pigments such as titanium dioxide, carbon black, iron oxide, ultramarine, cobalt blue, and lead chromate; and carbon-based fillers such as graphite, carbon black, carbon nanotubes, graphene, carbon fibers, carbon nanofibers, and conductive carbon.

[0085] In particular, nitride-based ceramics such as aluminum nitride, boron nitride (hexagonal, cubic), silicon nitride, gallium nitride, indium nitride, and boron nitride can be suitably used as fillers with high thermal conductivity and electrical insulation. Oxide-based ceramics such as aluminum oxide, zinc oxide, magnesium oxide, silica, titanium oxide, zirconium oxide, and cerium oxide can be suitably used as fillers with electrical insulation. Carbide-based ceramics such as silicon carbide, boron carbide, and titanium carbide can be suitably used as fillers with high thermal conductivity and high hardness. Metal fillers such as aluminum, copper, silver, nickel, gold, and tin can be suitably used as fillers with high thermal conductivity and electrical conductivity. Carbon materials such as diamond, graphite, carbon nanotubes, graphene, carbon nanofibers, expanded graphite, and carbon fibers can be suitably used as fillers with high thermal conductivity and light weight.

[0086] These fillers are preferable because they can be used in combination to impart multiple properties simultaneously. For example, aluminum boron nitride-boron nitride (AIN-BN), aluminum nitride-alumina (AlN-Al2O3), alumina-boron nitride (Al2O3-BN), silicon carbide-alumina nitride (SiC-AlN), SiC-BN (silicon carbide-boron nitride), Ni-coated alumina, alumina nitride-graphite, boron nitride-graphene, silicon carbide-carbon nanotubes, and alumina-carbon nanotubes can be used particularly suitably as thermally conductive composite fillers.

[0087] Other components (K) can be various additives depending on the purpose, as long as they do not impair the properties of the curable composition (I) and the resulting cured product. Specifically, these include solvents, sensitizers, thermal polymerization inhibitors, antioxidants, leveling agents, defoamers, plasticizers, surfactants, antistatic agents, UV absorbers, light stabilizers, flame retardants, coupling agents, and pigment dispersants. These K components may be used individually or in combination of two or more.

[0088] The urethane (meth)acrylamide (E) of this disclosure can be synthesized by known methods. For example, it can be synthesized by reacting a polycarbonate polyol (A) with a polyisocyanate (B) and a compound (C) having an unsaturated group and a hydroxyl group. In C, one or more compounds having a (meth)acrylamide group as an unsaturated group are used as essential raw materials. A may be used in combination with other polyols (D). Only one type of raw material may be used, or two or more different types may be used. From the viewpoint of suppressing side reactions, the reaction temperature is preferably in the range of 20 to 90°C, and more preferably in the range of 40 to 80°C.

[0089] Polycarbonate polyol (A) is a polyol having one or more carbonate groups and two or more hydroxyl groups in its molecule, and can introduce carbonate groups into urethane (meth)acrylamide (E).

[0090] The polycarbonate polyol (A) may be a commercially available product or one synthesized by a known method. When synthesized, one method is to transesterify the polyol with a carbonate diester (a2). Examples of polyols include alkylenediol (a1) and polyols other than (a1) (a3). Examples of carbonate diesters (a2) include dialkyl carbonates with 1 to 6 carbon atoms, alkylene carbonates with 2 to 6 carbon atoms, and / or diaryl carbonates with 6 to 12 carbon atoms.

[0091] The polyol may be any one of alkylenediol (a1) and polyol (a3) ​​other than (a1), or two or more different types may be used. If two or more types are used, different (a1) may be mixed in any ratio, or (a1) and (a3) ​​may be mixed in any ratio. (a2) may be of any one type, or two or more different types may be used.

[0092] Examples of alkylenediols (a1) include linear alkylenediols having 2 to 12 carbon atoms, branched alkylenediols having 3 to 12 carbon atoms, and cyclic alkylenediols having 5 to 12 carbon atoms. Examples of linear alkylenediols having 2 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,10-undecanediol, 1,11-undecanediol, 1,2-dodecanediol, and 1,12-dodecanediol. Examples of branched alkylenediols include 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,2-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-butanediol, 2-ethyl-1,3-propanediol, and 2-butyl-2-ethyl-1,3-propanediol. Examples of cyclic alkylenediols include 1,2-, 1,3- and 1,4-cyclohexanediol, 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cycloheptanediol, 1,2- and 1,3-cyclooctanediol, 1,4-cyclohexanedimethanol, 1,2-cyclobutanediol, cyclononanediol, cyclodecanediol, bicyclohexanediol, norbornanediol, bicyclooctanediol, adamantanediol, tricyclodecanediol, catechol, resorcinol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, hydroquinone, and naphthalenediol.

[0093] Examples of dialkyl carbonates having 1 to 6 carbon atoms include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, di-i-propyl carbonate, di-n-butyl carbonate, di-i-butyl carbonate, di-t-butyl carbonate, di-n-pentyl carbonate, di-n-hexyl carbonate, dicyclohexyl carbonate, and dicyclopentyl carbonate. Examples of alkylene carbonates having 2 to 6 carbon atoms include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, tetramethylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate, and neopentyl carbonate. Examples of diaryl carbonates having 6 to 12 carbon atoms include diphenyl carbonate, ditriyl carbonate, dixylyl carbonate, dinaphthyl carbonate, diantryl carbonate, bis(chlorophenyl) carbonate, dimethoxyphenyl carbonate, and dicresol carbonate.

[0094] Examples of polyols (a3) ​​include polyols having polyether groups, polyols having ester groups, and polyols having siloxane bonds.

[0095] Examples of polyols having a polyether group include low molecular weight ether diols of diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, and polytetramethylene glycol, which are polymers of ethylene oxide or propylene oxide.

[0096] Examples of polyols having an ester group include polyols having an ester group obtained by condensing a diol and a dicarboxylic acid, polyols having an ester group obtained by ring-opening polymerization of a cyclic ester compound starting with a diol, and polyols having an ester group obtained by ring-opening polymerization of a cyclic ester compound starting with a polyol having an ester group obtained by condensing a diol and a dicarboxylic acid. Examples of dicarboxylic acids include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Examples of cyclic ester compounds include lactones and lactides. Examples of lactones include α-acetolactone, β-propiolactone, γ-valerolactone, γ-butyrolactone, and ε-caprolactone, and examples of lactides include lactide lactate and glycolide.

[0097] Examples of polyols having a repeating siloxane structure include dihydroxypolysiloxanes of polydimethylsiloxane, polydiphenylsiloxane, and polymethylphenylsiloxane having hydroxyl groups at both ends, block copolymers of polydimethylsiloxane and polyethylene glycol or polypropylene glycol, and block copolymers of polydimethylsiloxane and polyester.

[0098] Polyisocyanates (B) are compounds having two or more isocyanate groups in their molecule, and they react with the hydroxyl groups of polycarbonate polyols (A) and compound (C) to form urethane bonds.

[0099] Polyisocyanates (B) include aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Examples of aromatic polyisocyanates include 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,4-diphenylmethanediisocyanate, 1,3-xylylenediisocyanate, and 1,4-xylylenediisocyanate. Examples of alicyclic polyisocyanates include cyclopentylenediisocyanate, cyclohexylenediisocyanate, isophoronediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, 1,3-hydrogenated xylylenediisocyanate, 1,4-hydrogenated xylylenediisocyanate, 2,5-norbornanediisocyanate, and 2,6-norbornanediisocyanate. Examples of polymers of these polyisocyanates include adducts, isocyanurates, and biuret compounds. An example of an isocyanurate is hexamethylene diisocyanate isocyanurate trimer.

[0100] Examples of polyisocyanates (B) include isocyanate compounds having siloxane bonds. These are compounds in which isocyanate groups are introduced to the terminal or side chains of linear siloxanes, cyclic siloxanes, or branched siloxanes. Examples include isocyanate-terminated polydimethylsiloxanes, isocyanate-containing cyclic siloxanes, isocyanate-containing branched siloxanes, polydimethylsiloxane-alkylenediisocyanate adducts, and polydimethylsiloxane-tolylenediisocyanate adducts.

[0101] Compound (C) having an unsaturated group and a hydroxyl group is a compound having one or more unsaturated groups and one or more hydroxyl groups. The unsaturated group contained in C is one or more groups selected from (meth)acrylamide group, (meth)acrylate group, vinyl group, allyl group, and maleimide group.

[0102] Examples of compounds (C) having a (meth)acrylamide group include N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-methyl-N-(2-hydroxyethyl)(meth)acrylamide, N-ethyl-N-(2-hydroxyethyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, 2,3-dihydroxypropyl(meth)acrylamide, 2-hydroxy-1-(hydroxymethyl)ethyl(meth)acrylamide, polyethylene glycol mono(meth)acrylamide, 2-(2-hydroxyethoxy)ethyl(meth)acrylamide, 2-(2-hydroxyethoxy)propyl(meth)acrylamide, and N-(poly(ethylene oxide))(meth)acrylamide.

[0103] Compounds (C) having a (meth)acrylate group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, γ-butyrolactone acrylate, ε-caprolactone-modified 2-hydroxyethyl acrylate, ε-caprolactone-modified 2-hydroxypropyl acrylate, ω-carboxypolycaprolactone monoacrylate, and caprolactone-modified trimethylolpropane triacrylate.

[0104] Examples of compounds (C) having a vinyl group include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and polyethylene glycol monovinyl ether. Examples of compounds (C) having an allyl group include allyl alcohol, 2-hydroxyethyl allyl A, and polyethylene glycol monoallyl ether. Examples of compounds (C) having a maleimide group include N-(2-hydroxyethyl)maleimide, N-(2-hydroxypropyl)maleimide, N-(2-hydroxybutyl)maleimide, 2-(2-hydroxyethoxy)ethyl maleimide, and polyethylene glycol monomaleimide.

[0105] Polyol (D) is a polyol other than polycarbonate polyol (A). By using A and D in combination, different structural units can be introduced into urethane (meth)acrylamide (E), and the physical properties of the resulting cured product can be easily adjusted according to the purpose. Examples of D include polyols with a molecular weight of 300 or more (D1) and polyols with a molecular weight of less than 300 (D2).

[0106] Examples of polyols (D1) with a molecular weight of 300 or more include linear polyether polyols with 2 to 18 carbon atoms, branched or cyclic polyether polyols with 3 to 18 carbon atoms, polyester polyols, polyalkadienene polyols, hydrogenated polyalkadienene polyols, polyacrylic polyols, polyamide polyols, polyimide polyols, and silicone polyols.

[0107] Examples of polyether polyols include polyoxyethylene polyols, polyoxypropylene polyols, polytetramethylene glycol, and polyoxyethylene-polyoxypropylene copolymer polyols. Examples of polyester polyols include adipic acid / neopentyl glycol condensates, adipic acid / 1,6-hexanediol condensates, adipic acid / methylpentanediol condensates, sebaciate-based polyester polyols, succinate-based polyester polyols, and phthalate-based polyester polyols. Examples of polybutadiene polyols include 1,2-polybutadienediol, 1,4-polybutadienediol, and polyisoprene polyols. Examples of hydrogenated polybutadiene polyols include hydrogenated polyisoprene polyols derived from hydrogenated polybutadienediol. Examples of acrylic polyols include acrylic polyols containing hydroxyl group-containing (meth)acrylate as a copolymer component. Examples of silicone polyols include diol-terminated silicones and silicone-modified polyethers. Other examples include lactone-based or biodegradable polyols such as polycaprolactone polyols, polylactide polyols, and polyhydroxyalkanoate polyols; natural oil-based polyols such as soybean oil polyols, castor oil polyols, and palm oil polyols; special polyols such as polysulfide polyols, polyether-ester hybrid polyols, and polyoxymethylene ether polyols; and lactone-added polyols such as caprolactone-added trimethylolpropane polyols and caprolactone-added pentaerythritol polyols.

[0108] Polyols (D2) with a molecular weight of less than 300 include linear, branched, or cyclic polyols. Specifically, glycols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol. Aliphatic diols include neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and 1,18-octadecanediol. Aliphatic triols include butanetriol and octanediol. Examples of polyhydric alcohols include glycerin, diglycerin, triglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of alicyclic polyols include cyclohexanediol, cyclohexanedimethanol, norbornanediol, norbornanedimethanol, norbornenediol, norbornenedimethanol, tricyclodecanedimethanol, pentacyclopentadecanedimethanol, adamantanediol, adamantanedimethanol, and adamantanetriol. Examples of special structure polyols include spiroglycol, dioxaneglycol, 1,4:3,6-dianhydrosorbitol (isosorbide), 1,4:3,6-dianhydroannitol (isomannide), and 1,4:3,6-dianhydroiditol (isoidoid).

[0109] The amount of polyol (D) used is preferably 0 to 45% by mass, and more preferably 0 to 30% by mass, relative to the total amount of polyol. The mass ratio (D / A) to polycarbonate polyol (A) is preferably 0 to 3.0, and more preferably 0 to 2.0.

[0110] The amount of polyol (D1) used is preferably 0 to 3.0 in mass ratio (D1 / A) with respect to polycarbonate polyol (A), and more preferably 0 to 1.8. Within this range, the carbonate equivalent of urethane (meth)acrylamide (E) can be precisely adjusted to the desired range, and a soft cured product can be obtained.

[0111] The amount of polyol (D2) used is preferably such that the total mass of D2, polyisocyanate (B), and compound (C) is 5 to 50% by mass relative to the total amount of raw materials constituting urethane (meth)acrylamide (E). D2 has a low molecular weight, and its use increases the number of urethane bonds contained in E, thereby strengthening the cohesive force due to hydrogen bonding.

[0112] During the synthesis of urethane (meth)acrylamide (E), solvents, catalysts, and other additives may be used as needed. Only one type of raw material may be used, or two or more different types may be used. The solvent can be appropriately selected and used as long as it does not inhibit the urethane reaction. For example, aliphatic hydrocarbons or polymerizable compounds may be used. Examples of catalysts include quaternary ammonium salts, tertiary phosphine derivatives, tertiary amine derivatives, and organometallic compounds. Specifically, examples include tetrabutylammonium bromide, triethylbenzylammonium chloride, triphenylphosphine, triethylphosphine, triethylamine, dimethylbenzylamine, carboxylates or acetylacetonate compounds of metals such as tin, bismuth, zirconium, and iron. Quaternary ammonium salts, tertiary phosphines, and tin-based, bismuth-based, zirconium-based, and iron-based organometallic compounds are preferred.

[0113] The hardness of the cured urethane (meth)acrylamide (E) in this embodiment is evaluated using the tensile modulus. The tensile modulus is an index that indicates how resistant a material is to deformation when a tensile force is applied to it; a higher value means the material is harder. The tensile elasticity of a hard cured product is preferably 10 MPa or higher, more preferably 50 MPa or higher, even more preferably 100 MPa or higher, and most preferably 300 MPa or higher.

[0114] The flexibility of the cured urethane (meth)acrylamide (E) in this embodiment is evaluated using elongation at break. Elongation at break is the percentage (%) that indicates how much a material stretches before breaking when pulled, and is an index for evaluating the ductility and toughness of a material. The higher the elongation at break, the more flexible and easily stretched the material is. The elongation at break of a soft cured product is preferably 50% or more, more preferably 100% or more, even more preferably 150% or more, and most preferably 200% or more.

[0115] The present invention will be described in detail below with reference to examples, but these examples are merely illustrative to illustrate embodiments of the present invention and do not limit the present invention in any way. In the following, "parts" and "%" all refer to mass unless otherwise specified.

[0116] Alkylenediol (a1), alkyl carbonate or diaryl carbonate (a2), other polyols (a3), polycarbonate polyol (A), polyisocyanate (B), compounds having unsaturated groups and hydroxyl groups (C), other polyols (D), polymerizable compounds (F), polymerization initiators (G), fillers (H), and other components (K) are shown below. (1) Alkylenediols (a1) a1-1: 1,4-butanediol a1-2: 2-methyl-1,3-propanediol a1-3: 1,3-propanediol a1-4: 1,5-pentanediol a1-5: 1,9-nonanediol a1-6: 1,6-hexanediol a1-7: 1,4-cyclohexanedimethanol (cis-,trans-mixture) a1-8: 3-methyl-1,5-pentanediol a1-9: ethylene glycol a1-10: 1,12-dodecanediol (2) Alkyl carbonates or diaryl carbonates (a2) a2-1: diethyl carbonate a2-2: diphenyl carbonate (3) Other polyols (a3) ​​(raw materials for polycarbonate polyols (A)) a3-1: caprolactone a3-2: diethylene glycol a3-3: Carbinol-modified silicone at both ends (Shin-Etsu Silicone Co., Ltd. KF-6000, molecular weight 935, hydroxyl value 120 mg KOH / g) a3-4: Tetraethylene glycol (4) Polyisocyanates (B) B-1: Isophorone diisocyanate B-2: Hexamethylene diisocyanate B-3: m-Xylylene diisocyanate B-4: 4,4'-Dicyclohexylmethane diisocyanate B-5: 1 / 1 (mass ratio) mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate B-6: Norbornane diisocyanate B-7: Hexamethylene diisocyanate isocyanurate trimer B-8: 1,3-Hydrogenated xylylene diisocyanate (5) Compounds having unsaturated and hydroxyl groups (C) C-1: N-(2-hydroxyethyl)acrylamide (registered trademark "Kohshylmer", "HEAA", manufactured by KJ Chemicals) C-2: N-(2-hydroxypropyl)acrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals) C-3: N-(2-hydroxyethyl)methacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals) C-4: 4-Hydroxybutyl vinyl ether C-5: 2-(2-hydroxyethoxy)ethylacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals) C-6: 4-Hydroxybutyl acrylate C-7: N-methyl-N-(2-hydroxyethyl)acrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals) C-8: N-(2-hydroxyethyl)maleimide C-9: Allyl alcohol C-10: 2-Hydroxyethyl acrylate (6) Other polyols (D) (6-1) Polyols with molecular weight of 300 or more (D1) D1-1: Polytetramethylene glycol (molecular weight 850) D1-2: Polytetramethylene glycol (molecular weight 650) D1-3: Polyester diol (adipic acid / methylpentanediol number average molecular weight 1,000) D1-4: Polyethylene glycol (molecular weight 600) D1-5: Polypropylene glycol (molecular weight 400) D1-6: Carbinol-modified silicone at both ends (Shin-Etsu Silicone Co., Ltd. KF-6001, number average molecular weight 1,810, hydroxyl value 62 mg KOH / g) D1-7: Polypropylene glycol (molecular weight 1,000) (6-2) Polyols with a molecular weight of less than 300 (D2) D2-1: Trimethylolpropane D2-2: Glycerin D2-3: Pentaerythritol D2-4: Diglycerin D2-5: Diethylene glycol (7) Polymerizable compounds (F) (7-1) Monofunctional polymerizable compounds (F1) 2-EHA: 2-Ethylhexyl acrylate BA: Butyl acrylate LA: Lauryl acrylate IBOA: Isobornyl acrylate IBOMA: Isobornyl methacrylate PEA: Phenoxyethyl acrylate THFA: Tetrahydrofurfuryl acrylate HEA: Hydroxyethyl acrylate HEMA: Hydroxyethyl methacrylate NVP: N-Vinylpyrrolidone 4-META: Methacryloyloxyethyl acid phosphate HEAA: Hydroxyethyl acrylamide (Registered trademarks "Kohshylmer" and "HEAA" manufactured by KJ Chemicals) DMAA: N,N-dimethylacrylamide (registered trademark "Kohshylmer", "DMAA", manufactured by KJ Chemicals Co., Ltd.) DEAA: N,N-diethylacrylamide (registered trademark "Kohshylmer", "DEAA", manufactured by KJ Chemicals Co., Ltd.) OLAM: oleylacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) ACMO: acroylmorpholine (registered trademark "Kohshylmer", "ACMO", manufactured by KJ Chemicals Co., Ltd.) TBCHA: t-butylcyclohexyl acrylate (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) AENA: N-acryloyloxyethyl norbornene carboxamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) CHAAm: cyclohexylacrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) THFAAm: tetrahydrofurfurylacrylamide (registered trademark "Kohshylmer") (Manufactured by KJ Chemicals) (7-2) Polyfunctional polymerizable compound (F2) TMPTA: Trimethylolpropane triacrylate DPHA: Dipentaerythritol hexaacrylate HDDA: 1,6-Hexanediol diacrylate TCDDA: Tricyclodecanedimethanol diacrylate TPGDA: Tripropylene glycol diacrylate DPGDA: Dipropylene glycol diacrylate TEGDMA: Triethylene glycol dimethacrylate PEGDA: Polyethylene glycol (molecular weight 1,000) diacrylate PTMGDA: Polytetramethylene glycol (molecular weight 650) diacrylate PETA: Pentaerythritol triacrylate PPGDMA: Polypropylene glycol (molecular weight 700) dimethacrylate BisA-EODA: Polyethylene glycol (20) modified bisphenol A diacrylate (8) Polymerization initiator (G) (8-1) Photopolymerization initiator (G1) TPO: Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide TPO-L: Ethyl (2,4,6-trimethylbenzoyl)phenyl phosphine 184: 1-Hydroxycyclohexyl phenyl ketone KI: Kohshylex I-3101 (Unsaturated group-containing hydrogen abstraction type polymer photopolymerization initiator, registered trademark "Kohshylex", manufactured by KJ Chemicals) BAPO:bis(2,4,6-Trimethylbenzoyl)phenylphosphine oxide (8-2) Thermal polymerization initiator (G2) BPO: Benzoyl peroxide DCP: Dicumyl peroxide AIBN: Azobisisobutyronitrile (9) Filler (H) FS: Fumed silica (average particle size 15 nm, spherical) SiO2: Spherical silica (average particle size 0.1 μm, spherical) Al2O3: Aluminum oxide (average particle size 3 μm, α-Al2O3, spherical) TiO2: Titanium dioxide (AEROXIDE TiO2 P25) ZrO2: Zirconium oxide (Tosoh TZ-3Y) ZnO: Zinc oxide (average particle size 0.2 μm, spherical) AlN: Aluminum nitride (average particle size 1.2 μm, angular) BN: Boron nitride (average particle size 45 μm, flaky) mica: Mica (average particle size 70 μm, plate-like, thickness 1 μm, aspect ratio 10) GL: Glass beads (average particle size 20 μm, spherical) CB: Carbon black (average particle size 30 nm) Gr: Graphite (average particle size 60 μm, plate-like) CNT: Multiwall carbon nanotube (diameter 10-20 nm, length 5-15 μm) Al: Metallic aluminum (average particle size 25 μm, plate-like) Ag: Silver nanowire (diameter 30 nm, length 50 μm) Cu: Copper powder (0.8 μm, spherical) PY: Pigment yellow 155 PB: Pigment blue 15 (10) Other components (K) BYK: BYKJET-9151 (pigment dispersant, maleimide-styrene copolymer with ammonium salt structure, manufactured by BYK) PDMA: Polymethylsiloxane Rosin: Hydrogenated rosin ester (DS-70L)

[0117] The following describes the analytical methods and analytical instruments used in the examples and comparative examples of the present invention. (1) Fourier transform infrared spectroscopy (FT-IR analysis) Instrument: Nicolet iS50 (manufactured by Thermo Fisher Scientific) (2) Nuclear magnetic resonance spectroscopy ( 1(H-NMR analysis) Apparatus: FT-NMR spectrometer (JEOL Ltd., 400MHz) The resonance frequency of the methyl group of tetramethylsilane was set to 0.0 ppm. (3) Gel permeation chromatography analysis (GPC analysis) Apparatus: Prominence-I LC-2030C (Shimadzu Corporation) Guard column: Shodex KD-G 1 piece; Column: Shodex KD-803 1 piece (Showa Denko Corporation) Column temperature: 40℃, Mobile phase: N,N-dimethylformamide; Liquid delivery rate: 0.5 mL / min Standard substance: Polystyrene (4) Shore hardness tester: Durometer (Standard: JIS K 6253) (Shore D) GS-720N (Teclock), (Shore A) GS-719N (Teclock) (5) Elongation at break and tensile modulus tester: Autograph AGS-X (Shimadzu Corporation) Chuck distance: 25 mm; Test speed: 10 mm / min (6) Izod impact strength (Standard: ASTM D256) Apparatus: Izod Charby impact tester No. 195-R (Manufactured by Yasuda Seiki Seisakusho Co., Ltd.) Hammer capacity: 5.5J (7) Compression set (Standard: JIS K 6262) Compression jig: Stainless steel plate; Compression ratio 25% (8) 5% weight loss temperature device: TG-DTA (Thermogravimetric analyzer DTG-60, manufactured by Shimadzu Corporation) Heating rate: 10℃ / min; Measurement temperature: 25 to 500℃ (9) Viscosity (Standard: ISO 2884-1) Device: Cone plate viscometer RE550 (manufactured by Toki Sangyo Co., Ltd.) Measurement temperature: 25℃ (10) Thermosetting shrinkage (Standard: JIS K 6941) Device: Electronic specific gravity meter MDS-300 (manufactured by Alpha Mirage Co., Ltd.) (11) Heat resistance (Standard: JIS K 6240) Device: Differential scanning calorimeter DSC60plus (manufactured by Shimadzu Corporation) Measurement temperature: -40 to 200℃; Heating rate: 5℃ / min (12) Knoop hardness (Standard: JIS Z 2251-1) Instrument: Microhardness tester DMH-2 (manufactured by Matsuzawa Seiki Co., Ltd.) Measurement temperature: 23℃; Load: 100gf (13) Bending strength (Standard: ISO 4049) Instrument: Autograph AGS-X (manufactured by Shimadzu Corporation) Measurement temperature: 23℃; Support distance: 20mm; Bending speed: 1mm / min (14) Transparency (Standard: ISO 14782) Instrument: Haze meter NDH-8000 (manufactured by Nippon Denshoku Industries Co., Ltd.) (15) High-performance liquid chromatography analysis (HPLC analysis) Instrument: Prominence-I LC-2030C (manufactured by Shimadzu Corporation) Column: Mightysil RP-18GP, 4.6mm-250mm, 5μm (manufactured by Kanto Chemical Co., Ltd.) Eluent conditions: Methanol / 10mM phosphoric acid aqueous solution = 50 / 50 Measurement wavelength: 258 nm; Column oven temperature: 40°C.

[0118] Synthesis Example 1 A 300 mL four-necked flask equipped with a stirrer, thermometer, and Oldershaw-type distillation column was charged with 22.4 g (0.25 mol) of 1,4-butanediol (a1-1), 22.4 g (0.25 mol) of 2-methyl-1,3-propanediol (a1-2), and 55.3 g (0.47 mol) of diethyl carbonate (a2-1). The mixture was stirred at 70°C until dissolved, and then 0.015 g of lead acetate trihydrate was added. The flask was heated in an oil bath and reacted for 12 hours under conditions of an internal temperature of 140°C and a pressure of 1.0–1.5 kPa, with partial distillation from the reflux head at a reflux ratio of 4. Subsequently, the apparatus was switched to a simple distillation apparatus, the pressure was set to 0.5 kPa, and the internal temperature of the flask was gradually increased to 140-150°C, and then to 160-165°C to remove unreacted raw materials, yielding polycarbonate diol (A-1) as a viscous, colorless, transparent liquid. GPC measurement confirmed that the number-average molecular weight of the obtained A-1 was 2,000. Based on the molecular weight of A-1 and the molecular weight of the raw material a1-1, the number of carbonates in A-1 was calculated to be 16.5. The results are shown in Table 1.

[0119] Synthesis Examples 2-12, 14, 15, and 17-20: Polycarbonate polyols (A-2)-(A-12), (A-14), (A-15), and (A-17)-(A-20) were synthesized in the same manner as in Synthesis Example 1, according to the compositions shown in Table 1. The results are shown in Table 1.

[0120] Synthesis Example 13 A 300 mL four-necked flask was fitted with a stirrer, thermometer, and Oldershaw distillation column. 50.14 g (0.42 mol) of 1,6-hexanediol (a1-6) was charged into the flask and heated to 140°C. While maintaining 140°C, 7.8 g (0.07 mol) of ε-caprolactone (a3-1) was added dropwise over 3 hours and the reaction was allowed to proceed. After the addition was complete, the reaction mixture was cooled, and 42.1 g (0.36 mol) of diethyl carbonate (a2-1) was added at 25°C and dissolved uniformly. Then, 0.015 g of lead acetate trihydrate was added. The flask was heated in an oil bath and reacted for 12 hours under conditions of an internal temperature of 140°C and a pressure of 1.0–1.5 kPa, with partial distillation from the reflux head at a reflux ratio of 4. The procedure was then carried out in the same manner as in Synthesis Example 1 to obtain polycarbonate diol (A-13). GPC measurement confirmed that the number-average molecular weight of the obtained A-13 was 1,000. Based on the molecular weight of A-13 and the molecular weight of raw material a1-6, the number of carbonates in A-13 was calculated to be 5.3. The results are shown in Table 1.

[0121] Synthesis Example 16: Polycarbonate polyol (A-16) was synthesized in the same manner as in Synthesis Example 13, according to the composition shown in Table 1. The results are shown in Table 1.

[0122]

[0123] Example 1 A 500 mL separable flask was fitted with a stirrer, thermometer, condenser, and gas inlet tube. 78.0 g of polycarbonate polyol (A-1), 15.2 g of isophorone diisocyanate (B-1), 6.8 g of N-(2-hydroxyethyl)acrylamide (C-1), and 0.06 g of dibutyltin dilaurate were charged into the flask. These were reacted at 70°C for 6 hours to obtain urethane (meth)acrylamide (E-1) as a pale yellow viscous liquid. Analysis of the obtained E-1 by FT-IR revealed a characteristic absorption of the isocyanate group (2250 cm⁻¹). -1 ) completely disappears, and the unique absorption of urethane bonding (1550cm) -1) was confirmed. GPC measurement revealed that the weight-average molecular weight (Mw) of E-1 was 10,000. Based on compositional analysis, the carbonate segment content of E-1 was calculated to be 75.2%, and the carbonate equivalent was calculated to be 156. NMR measurement confirmed a peak originating from unsaturated groups, and the acrylic equivalent was calculated to be 5,000. The ratio of acrylic equivalent to carbonate equivalent in E-1 was 32. Table 2-2 shows the weight-average molecular weight, carbonate segment content, carbonate equivalent, acrylic equivalent, and the ratio of acrylic equivalent to carbonate equivalent for E-1.

[0124] Examples 2-45 and Comparative Examples 1-4: The same procedure as in Example 1 was followed to synthesize urethane (meth)acrylamide (E-2) to (E-45) based on the composition ratios shown in Tables 2-1 and 2-2. Using the same procedure, urethane oligomers (UT-1) to (UT-4) were synthesized as comparative examples. The weight-average molecular weight, carbonate segment content, carbonate equivalent, acrylic equivalent, and acrylic equivalent to carbonate equivalent ratio for E-2 to E-45 and UT-1 to UT-4 are shown in Tables 2-3 and 2-4.

[0125]

[0126]

[0127]

[0128]

[0129] (Preparation of test cured material) 97.0 g of urethane (meth)acrylamide (E-1) and 3.0 g of photopolymerization initiator BAPO were mixed at 60°C for 1 hour to obtain a test composition. The obtained composition was applied to the release surface of a 100 μm thick heavy-release PET film (manufactured by Toyobo Co., Ltd.) using a bar coater, and adjusted to a dry film thickness of 100 μm. After application, a 38 μm light-release PET film (manufactured by Mitsubishi Plastics, Inc.) was carefully placed on top to prevent air from entering. Subsequently, a wavelength of 365 nm and an illuminance of 400 mW / cm² were applied. 2 Using a UV-LED lamp, the integrated light intensity is 2,000 mJ / cm². 2UV irradiation was performed to form a cured film. The resulting cured film was punched out into a dumbbell shape (size 3), and the release PET film on both sides was removed to prepare a cured product for tensile testing.

[0130] (Tensile modulus of cured urethane (meth)acrylamide (E)) Tensile tests were performed on the prepared cured materials under conditions of 25°C and 50% relative humidity. The tensile modulus was evaluated according to the following criteria. The results are shown in Table 2-2. (◎◎: Tensile modulus of 300 MPa or more, ◎: Tensile modulus of 100 MPa or more and less than 300 MPa, ○: Tensile modulus of 50 MPa or more and less than 100 MPa, △: Tensile modulus of 10 MPa or more and less than 50 MPa, ×: Tensile modulus of less than 10 MPa)

[0131] (Elongation at Breaking of Cured Urethane (Meth)acrylamide (E)) Tensile tests were performed on the test cured material under the same conditions as for measuring the tensile modulus, and the elongation at breaking was evaluated according to the following criteria. The results are shown in Table 2-2. (◎◎: Elongation at breaking of 300% or more, ◎: Elongation at breaking of 150% or more and less than 300%, ○: Elongation at breaking of 100% or more and less than 150%, △: Elongation at breaking of 50% or more and less than 100%, ×: Elongation at breaking less than 50%)

[0132] (Heat resistance of cured urethane (meth)acrylamide (E)) A thermogravimetric analyzer was used to measure the heat resistance of a 10 mg sample taken from a test cured material and heated at a rate of 10°C / min. The temperature at which a 5% weight loss occurred was determined from the resulting thermogravimetric curve. The heat resistance was evaluated according to the following criteria. The results are shown in Table 2-2. (◎: 250°C or higher, ○: 220°C or higher but less than 250°C, △: 180°C or higher but less than 220°C, ×: less than 180°C)

[0133] (Preparation of hardened material for hardness measurement) A 100 μm thick double-peel PET film was placed in close contact with a horizontally positioned glass plate, and a 60 mm × 60 mm × 0.3 mm spacer was placed on top of it. The test composition was filled into the spacer and left to stand in a 60°C constant temperature bath for 1 minute. After that, under a nitrogen atmosphere, at a wavelength of 405 nm and an illuminance of 5 mW / cm², the hardness was measured. 2 Using a UV-LED lamp, the integrated light output was 100 mJ / cm². 2The material was cured by UV irradiation in the following manner. On top of the obtained cured material, cured material was sequentially layered using the same procedure to form a cured material with a thickness of 6 mm. Subsequently, as a post-curing treatment, a wavelength of 405 nm and an irradiance of 100 mW / cm was applied. 2 Using a UV-LED lamp, the integrated light output was 10,000 mJ / cm². 2 UV irradiation was performed to achieve the desired result, and the resulting hardened material was prepared for hardness measurement.

[0134] (Hardness of Cured Urethane (Meth)acrylamide (E)) Shore D or Shore A hardness was measured using cured materials for hardness measurement and evaluated according to the following criteria. For Examples 1 to 28, Shore D hardness was measured, and for Examples 29 to 45, Shore A hardness was measured. The results are shown in Table 2-2. (Shore D hardness: ◎: Shore D hardness of 80 or higher, ○: Shore D hardness of 70 or higher and less than 80, △: Shore D hardness of 60 or higher and less than 70, ×: Shore D hardness of less than 60), (Shore A hardness: ◎: Shore A hardness of less than 50, ○: Shore A hardness of 50 or higher and less than 80, △: Shore A hardness of 80 or higher and less than 100, ×: Shore A hardness of 100 or higher and measurement impossible)

[0135] (Filler dispersibility of urethane (meth)acrylamide (E)) 100 g of the test composition and 30 g of aluminum oxide (average particle size 0.2-0.3 μm) were placed in a container and kneaded for 10 minutes using a planetary stirrer (Sinky Co., Ltd. "Awatori Rentaro AR-310", rotation speed 2000 rpm). The resulting mixture was applied to a PET film to form a coating with a thickness of 50 μm. The appearance of this coating was observed visually, and the filler dispersibility was evaluated according to the following criteria. The results are shown in Table 2-2. (◎: No streaking occurred on the coated surface, and no filler lifting was observed; ○: No streaking occurred on the coated surface, but slight filler lifting was observed; △: Slight streaking occurred on the coated surface, and filler lifting was observed; ×: Streaking occurred on the coated surface, and filler lifting was significant.)

[0136] From the results in Tables 2-3 and 2-4, it was confirmed that the urethane (meth)acrylamides (E-1) to (E-45) synthesized in Examples 1 to 45 all possess specific structural units containing carbonate groups and (meth)acrylamide groups, exhibiting high heat resistance and good filler dispersibility. Examples 1 to 28, with low carbonate equivalents, showed high tensile modulus and high hardness, demonstrating the properties of a hard material. On the other hand, Examples 29 to 45, with high carbonate equivalents, showed high elongation at break and low hardness, clearly demonstrating the properties of a soft material. In Comparative Examples 1 to 4, the urethane oligomers (UT-1) to (UT-4) exhibited low heat resistance and filler dispersibility in the resulting cured products. Furthermore, regardless of the carbonate equivalent value, they did not show satisfactory performance in terms of tensile modulus, elongation at break, or hardness.

[0137] Examples 46-71 and Comparative Examples 5-8 (Preparation and Evaluation of Curable Compositions for Thermal Interface Materials) Raw materials were weighed according to the composition ratios shown in Table 3 and mixed at 25°C for 30 minutes to obtain curable compositions for thermal interface materials. A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and the composition was applied to its release surface, adjusting the film thickness to 200 μm. Subsequently, curing treatment was carried out under the following conditions depending on the polymerization initiator used, and the resulting cured film was used as the thermal interface material. The tensile modulus, compression set, continuous heat resistance, 5% weight loss temperature, and thermal conductivity of the thermal interface material were evaluated by the following method, and the evaluation results are shown in Table 3. (1) When using a photopolymerization initiator: under a nitrogen atmosphere, wavelength 365 nm, illuminance 400 mW / cm 2 The UV-LED lamp provides an integrated light output of 3,000 mJ / cm². 2 UV irradiation was performed to achieve the following: (2) When using an azo-based thermal polymerization initiator: Heating was performed at 70°C for 10 hours under a nitrogen atmosphere. (3) When using a peroxide-based thermal polymerization initiator: Heating was performed at 80°C for 30 minutes under a nitrogen atmosphere. (4) When using both photo- and thermal polymerization initiators: Under a nitrogen atmosphere, at a wavelength of 365 nm and an irradiance of 400 mW / cm 2 The cumulative light intensity is 2,000 mJ / cm². 2 After UV irradiation to achieve the desired result, the sample was heated at 140°C for 60 minutes.

[0138] (Tensile modulus of thermal interface material) Test specimens of JIS No. 3 dumbbell shape were punched out from the obtained thermal interface material, and tensile tests were performed in an environment of 25°C and 50% relative humidity. The evaluation criteria are shown below. (◎: 50 MPa or more, ○: 10 MPa or more and less than 50 MPa, △: 1 MPa or more and less than 10 MPa, ×: less than 1 MPa)

[0139] (Compression Set of Thermal Interface Material) A double-peel PET film was placed in close contact with a horizontally positioned glass plate, and a disc-shaped spacer with a diameter of 13.0 mm and a thickness of 1.0 mm was placed on the peeled surface. The composition was filled into the spacer, left to stand at 40°C for 1 minute, and then cured under the same conditions as for the thermal interface material to produce one cured piece. Six cured pieces were prepared using the same procedure and stacked to form the sample piece for this evaluation. The obtained sample piece was left to stand at 23°C for 30 minutes, and then a compression test was performed in accordance with JIS K 6262, and the compression set was calculated using the following formula. The evaluation criteria for compression set are shown below. (◎: 3% or less, ○: 3% or more and less than 5%, △: 5% or more and less than 10%, ×: 10% or more) Compression set (%) = ((Thickness of pre-compression specimen - Thickness of post-compression specimen)) / ((Thickness of pre-compression specimen - Thickness of test spacer)) × 100

[0140] (Continuous Heat Resistance of Thermal Interface Materials) The thermal interface material was stored at 120°C for 1000 hours, and then stored for 24 hours at 25°C and 50% relative humidity. Subsequently, a JIS No. 3 dumbbell-shaped test specimen was punched out from the heated thermal interface material, and a tensile test was performed at 25°C and 50% relative humidity. Using the obtained tensile modulus, the rate of decrease in tensile modulus was calculated using the following formula, and the continuous heat resistance was evaluated based on this rate of decrease according to the following criteria: (◎: less than 10%, ○: 10% or more and less than 20%, △: 20% or more and less than 30%, ×: 30% or more) Rate of decrease in tensile modulus (%) = |(Tensile modulus after heating - Tensile modulus before heating)| / Tensile modulus before heating × 100

[0141] (5% weight loss temperature of thermal interface material) Using a thermogravimetric analyzer, approximately 10 mg was taken from a 200 μm thick thermal interface material and heated at a heating rate of 10 °C / min to determine the temperature at which a 5% weight loss occurred. The evaluation criteria are as follows: (◎: 250 °C or higher, ○: 220 °C or higher but less than 250 °C, △: 180 °C or higher but less than 220 °C, ×: less than 180 °C)

[0142] (Thermal conductivity of thermal interface material) Thickness 1 mm, area 10 mm 2 A thermal interface material was formed, and its thermal diffusivity was measured using the laser flash method (device: LFA467 nanoFlash, NETZSCH). The pulsed light irradiation conditions were a pulse width of 0.31 ms and an applied voltage of 247 V, and the measurement was performed in an environment of 25°C ± 1°C. Density was measured using an electronic hydrometer (AUX220, Shimadzu Corporation), and the specific heat was obtained according to JIS K 7123 (Method for measuring the specific heat capacity of plastics). Thermal conductivity was calculated using the following formula, and the thermal conductivity was evaluated based on this calculated value according to the following criteria: (◎: 10 W / m·K or more, ○: 5 W / m·K or more and less than 10 W / m·K, △: 2 W / m·K or more and less than 5 W / m·K, ×: less than 2 W / m·K) λ = α × Cp × ρ (λ is thermal conductivity (W / (m·K)), α is thermal diffusivity (m 2 ρ is density (kg / m³), Cp is specific heat (J / (kg·K)), and ρ is density (kg / m³). 3 ) indicates)

[0143]

[0144] As is clear from the results in Table 3, the cured thermal interface materials obtained from the cured compositions of the examples were found to have a high tensile modulus, good elongation at break, low compression set, continuous heat resistance, and a high 5% weight loss temperature. On the other hand, Comparative Examples 5 and 8 had low tensile modulus and elongation at break, and high compression set. Comparative Examples 6 and 7 had low tensile modulus and insufficient continuous heat resistance.

[0145] Examples 72-103 and Comparative Examples 9-14 (Preparation and Evaluation of Curable Ink Compositions) Raw materials were weighed according to the composition ratios shown in Tables 4-1 and 4-2, and mixed at 25°C for 30 minutes to obtain curable ink compositions. The viscosity, curability, and printability (discharge stability, blocking resistance of printed materials, clarity, and transparency) of the obtained compositions were evaluated by the following method, and the results are shown in Tables 4-1 and 4-2.

[0146] (Viscosity of Curable Ink Composition) The viscosity of the curable ink composition was measured using a cone-plate viscometer and evaluated according to the following criteria: (◎: 5 mPa·s or more and less than 50 mPa·s, ○: 50 mPa·s or more and less than 100 mPa·s, △: 100 mPa·s or more and less than 200 mPa·s, ×: 200 mPa·s or more)

[0147] (Preparation of printed materials) A PET film was placed in close contact with a horizontally positioned glass plate with the treatment surface facing upwards. A curable ink composition was applied to the treatment surface of the PET film, and the coating thickness was adjusted to 20 μm using a bar coater. Subsequently, at a wavelength of 395 nm and an illuminance of 1,000 mW / cm²... 2 The printed material was produced by irradiating it with UV light under these conditions.

[0148] (Curability of Ink Curable Composition) When printed materials were prepared using the above method, the cumulative amount of light required for the ink curable composition to fully cure and become non-sticky was measured, and the curability was evaluated based on the measured value according to the following criteria. (◎: 1,000 mJ / cm²) 2 Less than 1,000 mJ / cm² 2 More than 2,000mJ / cm 2 Less than 2,000 mJ / cm² 2 More than 5,000mJ / cm 2 Less than 5,000 mJ / cm² 2 (End)

[0149] (Discharge Stability of Curable Ink Composition) A curable ink composition containing pigment was loaded into an inkjet printer (LuxelJetUV350GTW, manufactured by Fujifilm Corporation), and a solid image was printed on coated paper. The print quality was visually observed and evaluated according to the following criteria: (◎: No nozzle clogging, ○: Slight nozzle clogging, ×: Widespread nozzle clogging)

[0150] (Blocking resistance of printed materials) After curing, the printed material was left to stand for 5 minutes at 23°C and 50% relative humidity, and then a sheet of fine paper was placed on top of the printed surface and a load of 1 kg / cm² was applied. 2 The load was applied for 1 minute. Afterwards, the degree of ink transfer to the paper was visually observed and evaluated according to the following criteria: (◎: No transfer, ○: Slight transfer, △: Transfer present, ×: Significant transfer)

[0151] (Transparency of Printed Materials) The haze of printed materials was measured using a haze meter, and transparency was evaluated according to the following criteria: (◎: Haze less than 1%, ○: Haze 1% to less than 3%, △: Haze 3% to less than 5%, ×: Haze 5% or more)

[0152] (Sharpness of printed material) Printed material was visually inspected and evaluated according to the following criteria: (◎: No smudging, ○: Slight smudging, ×: Smudging present)

[0153]

[0154]

[0155] As is clear from the results in Tables 4-1 and 4-2, the curing compositions for inks in the examples showed high curability, good ejection stability, excellent drying properties, and produced printed materials with high clarity. On the other hand, in all of Comparative Examples 9 to 14, neither the curability, ejection stability, blocking resistance, nor clarity of the obtained printed materials reached a satisfactory level.

[0156] Examples 104-152 and Comparative Examples 15-22 (Preparation and Evaluation of Curable Compositions for Three-Dimensional Stereolithography) Raw materials were weighed according to the composition ratios shown in Tables 5 and 6, and mixed at 25°C for 30 minutes to prepare curable compositions for three-dimensional stereolithography. For the fabrication of three-dimensional objects, a peel-off PET film was placed in close contact with a horizontally positioned glass plate, and a spacer was placed on top of it. The internal dimensions (length × width × thickness) of the spacers used were as follows: (1) For measuring Shore D hardness, Shore A hardness, and elongation at break: 60 mm × 60 mm × 0.3 mm, (2) For measuring Izod impact strength: 63.5 mm × 12.7 mm × 0.3 mm, (3) For measuring compression set: diameter 13.0 mm × thickness 1.0 mm The curable composition for three-dimensional stereolithography was filled into the spacers. After standing in a 60°C constant temperature bath for 1 minute, the sample was subjected to a nitrogen atmosphere at a wavelength of 405 nm and an illuminance of 5 mW / cm². 2 The UV-LED lamp provides an integrated light output of 100 mJ / cm². 2 A cured material was obtained by UV irradiation in the following manner. A similar cured material was then layered on top of the obtained cured material using the same procedure to form a fabricated object. The fabricated object was post-cured at a wavelength of 405 nm and an irradiance of 100 mW / cm². 2 The UV-LED lamp provides an integrated light output of 10,000 mJ / cm². 2 The material was irradiated with UV light to create a three-dimensional object. The durometer hardness, elongation at break, hardening shrinkage resistance, molding accuracy, heat resistance, compression set, and Izod impact strength of the obtained three-dimensional object were evaluated using the following method, and the results are shown in Tables 5 and 6.

[0157] (Hardness of 3D Printed Objects) Shore D hardness or Shore A hardness was measured using 3D printed objects with a thickness of 6.0 mm and evaluated according to the following criteria: (Shore D hardness: ◎: Shore D hardness of 80 or higher, ○: Shore D hardness of 70 or higher but less than 80, △: Shore D hardness of 60 or higher but less than 70, ×: Shore D hardness of less than 60), (Shore A hardness: ◎: Shore A hardness of less than 50, ○: Shore A hardness of 50 or higher but less than 80, △: Shore A hardness of 80 or higher but less than 100, ×: Shore A hardness of 100 or higher and measurement impossible)

[0158] (Fracture Elongation of 3D Printed Objects) A 1.5 mm thick 3D printed object was punched out in the shape of a dumbbell (size 3) to obtain dumbbell-shaped test specimens. The fracture elongation was evaluated according to the following criteria: (◎◎: Fracture elongation of 200% or more, ◎: Fracture elongation of 100% or more but less than 200%, ○: Fracture elongation of 50% or more but less than 100%, △: Fracture elongation of 20% or more but less than 50%, ×: Fracture elongation of less than 20%)

[0159] (Curing Shrinkage Resistance of Three-Dimensional Printed Objects) The density of the curable composition for three-dimensional stereolithography was measured using a Gay-Lussac specific gravity bottle in accordance with ISO 758. The density of the three-dimensional printed object was measured using an electronic hydrometer in accordance with ISO 1183-1. These density measurements were used to calculate the curing shrinkage resistance of the curable composition according to the following criteria: (◎◎: curing shrinkage rate less than 5%, ◎: curing shrinkage rate 5% or more and less than 6%, ○: curing shrinkage rate 6% or more and less than 8%, △: curing shrinkage rate 8% or more and less than 10%, ×: curing shrinkage rate 10% or more) Curing shrinkage rate (%) = (Ds - D1) / D1 × 100 (wherein Ds is the density of the three-dimensional printed object and D1 is the density of the curable composition for three-dimensional stereolithography)

[0160] (Printing accuracy of 3D printed objects) The sides of the 3D printed objects were visually inspected and the height of the objects was measured. These results were combined and evaluated according to the following criteria: (◎: Height within 3mm ± 0.1mm and no irregularities on the sides, ○: Height within 3mm ± 0.2mm or slight irregularities on the sides, △: Height within 3mm ± 0.3mm or slight irregularities on the sides, ×: Height exceeding 3mm ± 0.3mm or obvious irregularities on the sides)

[0161] (Heat resistance of three-dimensional printed objects) The glass transition temperature (Tg) of three-dimensional printed objects was measured using a differential scanning calorimeter and evaluated according to the following criteria: (◎: Tg is 60°C or higher, ○: Tg is 40°C or higher but less than 60°C, △: Tg is 20°C or higher but less than 40°C, ×: Tg is less than 20°C)

[0162] (Izod Impact Strength of 3D Printed Objects) Izod impact tests were conducted on 3D printed objects with a thickness of 3 mm and evaluated according to the following criteria: (◎: Izod impact strength of 70 J / m or more, ○: Izod impact strength of 50 J / m or more and less than 70 J / m, △: Izod impact strength of 30 J / m or more and less than 50 J / m, ×: Izod impact strength of less than 30 J / m)

[0163] (Compression Set of 3D Printed Objects) Using a 3D printed object with a thickness of 6 mm, the evaluation sample was compressed by 25% in the thickness direction using a jig in an environment of 23°C and 50% relative humidity, and strain was applied for 22 hours. After that, it was removed from the jig and left to stand at 23°C for 30 minutes, and the compression set was calculated using the following formula and evaluated according to the following criteria. (◎: Compression set was 3% or less, ○: Compression set was 3% or more and less than 5%, △: Compression set was 5% or more and less than 10%, ×: Compression set was 10% or more) Compression set (%) = ((Sample thickness before compression - Sample thickness after compression) / (Sample thickness before compression - Thickness of jig spacer)) × 100

[0164]

[0165] As is clear from Table 5, the three-dimensional printed objects obtained from the curable compositions for three-dimensional stereolithography in the examples exhibited excellent hardness, printing accuracy, and heat resistance, as well as low curing shrinkage and good impact resistance. Curable compositions for three-dimensional stereolithography with such properties can be suitably used as hard materials, making it possible to obtain three-dimensional printed objects similar to ABS (Acrylonitrile-butadiene-styrene Resin). On the other hand, the three-dimensional printed objects obtained from the comparative examples did not sufficiently satisfy both hardness and elongation at break, and in particular had low impact resistance.

[0166]

[0167] As is clear from Table 6, the three-dimensional printed objects obtained from the curable compositions for three-dimensional stereolithography in the examples exhibited low Shore A hardness and excellent flexibility. The resulting three-dimensional printed objects had high elongation at break and printing accuracy, low curing shrinkage, and good compression set. Curable compositions for three-dimensional stereolithography with such properties can be suitably used as soft materials, making it possible to obtain three-dimensional printed objects similar to rubber-like materials and self-healing materials. On the other hand, the three-dimensional printed objects obtained from the comparative examples had high Shore A hardness and poor flexibility. Satisfactory performance was not obtained in terms of hardness, elongation at break, or compression set.

[0168] Examples 153-168 and Comparative Examples 23-25 ​​(Preparation and Evaluation of Curable Compositions for Dental Materials) Raw materials were weighed according to the composition ratios shown in Table 7 and mixed at 25°C for 30 minutes to obtain curable compositions for dental materials. The compatibility, storage stability, and curability of the obtained curable compositions for dental materials were evaluated by the following methods. For the cured products, the low molecular weight component content, Knoop hardness, surface smoothness, and flexural strength were evaluated. These results are shown in Table 7.

[0169] (Compatibility of curable compositions for dental materials) The state of the curable compositions for dental materials was visually observed, and their compatibility was evaluated according to the following criteria: (◎: The obtained composition was uniform, ○: The obtained composition was slightly non-uniform, △: The obtained composition was somewhat non-uniform, ×: The obtained composition was significantly non-uniform)

[0170] (Storage Stability of Curable Dental Compositions) Curable dental compositions were placed in light-shielding screw-top tubes, sealed, and stored under two conditions: 40°C for one month and 80°C for two weeks. After storage, the composition's condition was checked and evaluated according to the following criteria: (◎: No change in condition after storage under either 40°C for one month or 80°C for two weeks; ○: A change in condition was observed under either 40°C for one month or 80°C for two weeks; ×: A change in condition was observed after storage under either 40°C for one month or 80°C for two weeks.)

[0171] (Curing properties of the dental curable composition) A polytetrafluoroethylene mold (20 mm × 20 mm × 10 mm) with a 6 mm diameter hole in the center was filled with a dental curable composition and pressed with a polypropylene film. Wavelength 405 nm, illuminance 100 mW / cm 2 After irradiating with a UV-LED lamp for 30 seconds, the polypropylene film was peeled off. The curing properties of the resulting cured material were evaluated by touch according to the following criteria: (◎: No stickiness at all, ○: Slight stickiness but no fingerprints left on the surface, △: Stickiness and fingerprints left on the surface, ×: Severe stickiness and fingers stuck to the surface)

[0172] (Low molecular weight component content of cured dental material curable composition) The cured material obtained in the curability evaluation was dried at 90°C for 2 minutes and weighed to obtain the mass of the cured film before extraction. 25 g of acetone and the weighed cured film were placed in a UV-impermeable brown glass bottle, sealed, and rotated at 30°C for 48 hours to extract the soluble components in the cured film. The extracted solution was filtered through a 0.45 μm filter, and the low molecular weight components were quantified by HPLC analysis. The low molecular weight component content was calculated using the following formula: (◎: Low molecular weight component content is 1.0% or less, ○: Low molecular weight component content is 1.0% or more and 2.0% or less, △: Low molecular weight component content is 2.0% or more and 4.0% or less, ×: Low molecular weight component content is 4.0% or more) Low molecular weight component content (%) = (Mass of extracted low molecular weight components / Mass of cured film before extraction) × 100 The evaluation criteria were as follows.

[0173] (Knoop hardness of cured dental material compositions) The surface of the cured material obtained in the curability evaluation was buffed, and the Knoop hardness was measured using a microhardness tester by applying a 100gf load at 23°C for 20 seconds. The evaluation criteria were as follows: (◎: Knoop hardness of 200 KHN or higher, ○: Knoop hardness of 150 KHN or higher and less than 200 KHN, △: Knoop hardness of 70 KHN or higher and less than 150 KHN, ×: Knoop hardness less than 70 KHN)

[0174] (Surface smoothness of cured products of dental materials) The surface of the cured products obtained in the curability evaluation was visually observed and evaluated according to the following criteria: (◎: Surface was smooth and glossy, ○: Surface was almost smooth with slight cloudiness or unevenness, △: Surface was generally cloudy with some unevenness or granular material, ×: Surface was generally cloudy and covered with granular material)

[0175] (Flexural strength of cured dental material curable composition) A 100 μm thick heavy-release PET film (manufactured by Toyobo Co., Ltd.) was placed in close contact with a horizontally positioned glass plate, and a polytetrafluoroethylene spacer (2 mm x 2 mm x 25 mm) was placed on top of it. The dental material curable composition was then filled into the spacer. To avoid air bubbles, a light-release PET film was placed over the liquid surface. Wavelength 405 nm, illuminance 50 mW / cm 2 The UV-LED lamp provides an integrated light output of 3,000 mJ / cm². 2 The material was then irradiated with UV light. After that, the release film was removed, and the cured material was taken out of the spacer to be used as a test specimen. The test specimen was immersed in water at 37°C for 24 hours, and then a bending test was performed and evaluated according to the following criteria: (◎: Bending strength of 100 MPa or more, ○: Bending strength of 90 MPa or more and less than 100 MPa, △: Bending strength of 80 MPa or more and less than 90 MPa, ×: Bending strength less than 80 MPa)

[0176]

[0177] As is clear from the results in Table 7, the curable dental material compositions of the examples showed excellent compatibility, high curability, and high storage stability. The low content of low molecular weight components in the resulting cured products provided high safety as dental materials. Furthermore, the cured products exhibited high hardness and flexural strength, and also had good surface smoothness. On the other hand, the dental material compositions of the comparative examples had low curability, insufficient compatibility, and poor storage stability. Furthermore, the high content of low molecular weight components in the cured products raised safety concerns, and the hardness and flexural strength of the cured products were also low.

[0178] Examples 169-187 and Comparative Examples 26-28 (Preparation and Evaluation of Curable Compositions for Coating Agents) Raw materials were weighed according to the composition ratios shown in Table 8 and mixed at 25°C for 30 minutes to obtain curable compositions for coating agents. The curability of the obtained curable compositions for coating agents was evaluated by the following method. In addition, the adhesion, light yellowing resistance, flexibility, chemical resistance, scratch resistance, durability, and high temperature and high humidity resistance of the coating layers formed by curing these compositions were evaluated. These results are shown in Table 8.

[0179] (Curability of the curable composition for coating agents) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and the curable composition for coating agents was applied on top of it using a bar coater to a film thickness of 20 μm. A light-release PET film was then placed on top of it. Subsequently, at a wavelength of 405 nm and an illuminance of 50 mW / cm², 2 The composition was cured by irradiation with a UV-LED lamp. Afterward, the easily removable PET film was removed, and the presence or absence of tack on the cured film surface was checked. The curability was evaluated according to the following criteria based on the cumulative light dose required for the tack to disappear. (◎: Cumulative light dose of 500 mJ / cm²) 2 Tack disappeared below 500 mJ / cm². ○: Total light intensity 500 mJ / cm² 2 More than 1,000mJ / cm 2 Tack disappeared below △: Total light intensity is 1,000 mJ / cm 2 More than 5,000mJ / cm 2 Tack disappeared below 5,000 mJ / cm². 2 But Tuck stayed.

[0180] (Preparation of the coating layer) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and a curable composition for coating was applied on top of it to a coating thickness of 5 μm. Subsequently, under a nitrogen atmosphere, the film was heated at a wavelength of 405 nm and an illuminance of 500 mW / cm². 2 Using a UV-LED lamp, the integrated light intensity was 2,000 mJ / cm². 2 The coating layer was formed by irradiating the area in this manner.

[0181] (Adhesion of the coating layer) Following the cross-cut method specified in ISO 2409, cuts were made on the surface of the coating layer with a utility knife to form 100 1mm x 1mm grids, which were used as test pieces. Next, commercially available adhesive tape was applied to the test pieces, and after peeling it off, the number of remaining grids was measured and the adhesion was evaluated based on the following criteria: (◎: 100 grids remained, ○: 90 to 99 grids remained, △: 80 to 89 grids remained, ×: 79 or fewer grids remained)

[0182] (Resistance to light-induced yellowing of the coating layer) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and a silicone spacer with an internal volume of 10 mm × 10 mm × 0.5 mm was placed on top of it. The spacer was filled with a curable composition for the coating agent, and a light-release PET film was applied to the liquid surface to prevent the inclusion of air bubbles. Wavelength 405 nm, illuminance 100 mW / cm 2 Using a UV-LED lamp, the integrated light output was 20,000 mJ / cm². 2 The coating layer was formed by irradiating the material to the desired state. Afterward, the release film was removed, and the cured material was taken out of the spacer. The obtained cured material was visually inspected, and its resistance to light-induced yellowing was evaluated based on the following criteria: (◎: No yellowing was observed, ○: Very slight yellowing was observed, △: Yellowing was observed, ×: Significant yellowing was observed)

[0183] (Flexural resistance of the coating layer) Following the cylindrical mandrel method specified in ISO 1519, the test specimen was bent while in contact with a 10 mm diameter mandrel with the coating layer facing outwards. After the bending test, the coating layer was visually inspected and its flexural resistance was evaluated according to the following criteria: (◎: No whitening or cracking at the bend, ○: Partial whitening at the bend, △: Partial cracking at the bend, ×: Cracking at the bend)

[0184] (Chemical Resistance of the Coating Layer) Oleic acid was applied to the surface of the coating layer in a diameter of approximately 1 cm and kept at 23°C for 1 hour. Afterwards, it was washed with a neutral detergent and the surface of the coating layer was visually inspected. Based on the results, the chemical resistance was evaluated according to the following criteria: (◎: No trace of oleic acid was observed at all, ○: A very thin whitening mark was slightly observed in the oleic acid-coated area, △: The oleic acid-coated area turned white and swelling was observed on the surface, ×: The oleic acid-coated area became sticky and peeling was observed on the surface)

[0185] (Scratch resistance of the coating layer) The surface of the coating layer was rubbed back and forth 10 times using steel wool (#0000, load 100g) in an environment of 23℃ and 50% relative humidity. After the test, the surface of the coating layer was visually observed and the scratch resistance was evaluated based on the following criteria: (◎: No scratches were observed on the coating layer, ○: A few fine scratches were observed on a part of the coating layer, △: Streaky scratches were observed on the entire coating layer, ×: Peeling of the coating layer was observed)

[0186] (High temperature and humidity resistance of the coating layer) A curable composition for coating agents was applied to a horizontally positioned glass substrate using a bar coater to a coating thickness of 20 μm. Wavelength 405 nm, illuminance 50 mW / cm 2 Using a UV-LED lamp, the integrated light intensity was 2,000 mJ / cm². 2 The coating layer was formed by irradiating it in such a manner. The formed coating layer was left to stand for 100 hours in a constant temperature and humidity chamber at 85°C and 85% relative humidity, and then left for 30 minutes in an environment of 23°C and 50% relative humidity, and the coating layer was observed visually. Durability was evaluated according to the following criteria: (◎: The laminate was transparent with no peeling or bubbles, ○: The laminate had very slight clouding but no peeling or bubbles, △: The laminate had slight clouding or peeling / bubbles, ×: The laminate had extreme clouding or peeling / bubbles)

[0187]

[0188] As is clear from the results in Table 8, the curable composition for coating agents in the examples showed high curability to long-wavelength light at a wavelength of 405 nm, and the resulting coating layer exhibited good performance in terms of adhesion, resistance to light yellowing, flexibility, chemical resistance, scratch resistance, and resistance to high temperature and humidity. On the other hand, the curable composition for coating agents in the comparative examples had generally low physical properties in the coating layer, and in particular, its flexibility was significantly poor.

[0189] Examples 188-205 and Comparative Examples 29-31 (Preparation and Evaluation of Curable Compositions for Decorative Coatings) Raw materials were weighed according to the composition ratios shown in Table 9 and mixed at 25°C for 30 minutes to obtain curable compositions for decorative coatings. The curability of the obtained curable compositions for decorative coatings was evaluated by the following method. The elongation at break, scratch resistance, Shore D hardness, flexural resistance, and sunscreen resistance of the decorative coatings formed by curing these compositions were evaluated. The evaluation results are shown in Table 9.

[0190] (Curing properties of curable composition for decorative coating) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and the curable composition for decorative coating was applied on top of it using a bar coater to a coating thickness of 20 μm, and a light-release PET film was placed on top. Wavelength 365 nm, illuminance 100 mW / cm 2 Using a UV-LED lamp, the integrated light output was 1,000 mJ / cm². 2 The curable composition for decorative coating was cured by irradiating it in such a manner. After that, the easily removable PET film was removed, and the curing properties of the resulting cured product were evaluated by touch according to the following criteria: (◎: No stickiness at all, ○: Slightly sticky, but no fingerprints remain on the surface, △: Sticky, fingerprints remain on the surface, ×: Very sticky, fingers stick to the surface)

[0191] (Preparation of decorative coating) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and a curable composition for decorative coating was applied on top to a film thickness of 5 μm. Then, a light-release PET film was placed on top, and the wavelength was 365 nm and the illuminance was 100 mW / cm². 2 Using a UV-LED lamp, the integrated light output was 1,000 mJ / cm². 2 The decorative coating was formed by irradiating the surface in such a manner.

[0192] (Elongation at break of decorative coat) A decorative coat was punched into a No. 3 dumbbell shape, and the release PET films on both sides were removed to obtain a cured product for testing. A tensile test was performed on the cured product for testing under an environment of 25°C and 50% relative humidity, and the elongation at break was evaluated according to the following criteria. (⊚: elongation at break of 50% or more, ◯: elongation at break of 30% or more and less than 50%, △: elongation at break of 5% or more and less than 30%, ×: elongation at break of less than 5%)

[0193] (Scratch resistance of decorative coat) The surface of the decorative coat was rubbed 10 reciprocations using steel wool (#0000, load 100 g) under an environment of 23°C and 50% relative humidity. After the test, the surface of the decorative coat was visually observed, and the scratch resistance was evaluated based on the following criteria. (⊚: no scratches occurred, ◯: slight scratches occurred, △: deep scratches occurred, ×: the decorative coat peeled off)

[0194] (Flex resistance of decorative coat) In accordance with the cylindrical mandrel method specified in ISO 1519, the test piece was bent while being brought into contact with a mandrel having a diameter of 10 mm such that the coat layer was positioned on the outer side. After bending, the decorative coat was visually observed, and the flex resistance was evaluated based on the following criteria. (⊚: neither whitening nor cracking occurred in the bent portion, ◯: partial whitening occurred in the bent portion, △: partial cracking occurred in the bent portion, ×: cracking occurred in the bent portion)

[0195] (Shore D hardness of decorative coat) A heavy-release PET film was brought into close contact with a horizontally arranged glass plate, and a 60 mm×60 mm×1.0 mm spacer was placed thereon. The curable composition for a decorative coat was filled into the spacer, and left to stand still in a thermostatic bath at 60°C for 1 minute. Thereafter, under a nitrogen atmosphere, the wavelength is 365 nm, and the illuminance is 100 mW / cm 2 UV-LED lamp was used, integrated light intensity 2,000 mJ / cm 2 was irradiated to obtain the decorative coat. A decorative coat was laminated on the obtained decorative coat by the same procedure to form a laminated cured product having a thickness of 6 mm. As post-curing, the wavelength is 405 nm, and the illuminance is 100 mW / cm 2 UV-LED lamp was used, integrated light intensity 10,000 mJ / cm 2UV irradiation was performed to obtain a laminated cured decorative coating. The Shore D hardness of this cured product was measured and evaluated according to the following criteria: (◎: Shore D hardness of 80 or higher, ○: Shore D hardness of 70 or higher but less than 80, △: Shore D hardness of 60 or higher but less than 70, ×: Shore D hardness less than 60)

[0196] (Sunscreen Resistance of Decorative Coating) A sunscreen (UltraSheer DRY-TOUCH SUNSCREEN SPF100+) was applied to the surface of the decorative coating in a 1 cm diameter area. The surface was then heated at 80°C for 6 hours, washed with a neutral detergent, and observed. Based on the observation results, sunscreen resistance was evaluated according to the following criteria: (◎: No trace of sunscreen was observed; ○: A slight transparent trace was observed in the sunscreen application area; △: A white mark remained in the sunscreen application area and the surface swelled; ×: The sunscreen application area became sticky and the surface peeled off.)

[0197]

[0198] As is clear from the results in Table 9, the curable compositions for decorative coatings in the examples showed high curability, and the resulting coating layers exhibited good performance in terms of elongation at break, scratch resistance, flexure resistance, hardness, and sunscreen resistance. On the other hand, the curable compositions for decorative coatings in the comparative examples showed low curability. Comparative Example 29 had insufficient scratch resistance and flexure resistance, and Comparative Example 30 did not exhibit sufficient performance in terms of elongation at break, scratch resistance, flexure resistance, hardness, and sunscreen resistance.

[0199] Examples 206-220 and Comparative Examples 32-34 (Preparation and Evaluation of Curable Compositions for Sealing Materials) Raw materials were weighed according to the composition ratios shown in Table 10 and mixed at 25°C for 30 minutes to prepare curable compositions for sealing materials. The curability of the obtained curable compositions for sealing materials was evaluated by the following method. Furthermore, the sealing materials obtained by curing these compositions were evaluated for resistance to humid heat yellowing, resistance to outgassing, resistance to heat cycling, corrosion resistance, and stress relaxation. The evaluation results are shown in Table 10.

[0200] (Preparation of Cured Seal Material) A spacer with an internal volume of 30 mm × 15 mm × 3 mm was placed on a horizontally positioned glass plate, and copper foil (5 mm long × 50 mm wide × 80 μm thick) was placed inside the spacer. Subsequently, a curable composition for the sealant was filled into the spacer, and curing was performed under a nitrogen atmosphere at a wavelength of 405 nm and an illuminance of 500 mW / cm². 2 Using a UV-LED lamp, the integrated light output was 1,000 mJ / cm². 2 The material was cured by irradiating it in such a manner.

[0201] (Curability of Curable Composition for Sealant) The cured sealant obtained was evaluated by touching it with the hand according to the following criteria: (◎: A cured product that could maintain its shape was obtained and there was no tackiness when touched, ○: A cured product that could maintain its shape was obtained and there was tackiness when touched, △: A cured product that could maintain its shape was obtained, but there was a liquid residue when touched, ×: Curing was insufficient and a cured product that could not maintain its shape was not obtained)

[0202] (Heat-resistant yellowing of cured sealant) After allowing the cured sealant to stand for 24 hours in an environment of 23°C and 50% relative humidity, the transmission spectrum was measured using a transmission color meter (TZ-7700, manufactured by Nippon Denshoku Industries Co., Ltd.), and this value was taken as the initial b value. Subsequently, the cured material was allowed to stand for 500 hours in a constant temperature and humidity chamber set at 85°C and 85% relative humidity to perform an accelerated test of heat-resistant yellowing. After the test, the material was allowed to stand for 24 hours in an environment of 23°C and 50% relative humidity, and the transmission color was measured again. The obtained b value was taken as the post-heat-resistant b value. The change amount Δb was calculated using the following formula. Based on the observation and measurement results, heat-resistant yellowing was evaluated according to the following criteria. (◎: Both initial b value and post-moist heat b value are 0.2 or less and Δb is 0.1 or less; ○: Either the initial b value or the post-moist heat b value exceeds 0.2, but both are 0.5 or less and Δb is 0.2 or less; △: Either the initial b value or the post-moist heat b value exceeds 0.5, but both are 1.0 or less and Δb is 0.3 or less; ×: Either the initial b value or the post-moist heat b value exceeds 1.0 or Δb exceeds 0.3) Δb = post-moist heat b value - initial b value

[0203] (Outgassing Resistance of Cured Encapsulating Material) A 1g sample was cut from the cured encapsulating material and used as a test specimen. It was placed in a 100°C constant temperature bath and subjected to a flow of dry nitrogen air for 24 hours. The mass of the test specimen was then measured again. The outgassing rate was calculated using the following formula. Based on the calculation results, the following criteria were used for evaluation: (◎: less than 0.1%, ○: 0.1% or more and less than 0.2%, △: 0.2% or more and less than 0.3%, ×: 0.3% or more) Outgassing rate (%) = (Mass after test - Mass before test) / Mass before test × 100

[0204] (Heat Cycle Resistance of Cured Sealants) The cured sealant was subjected to a treatment cycle of leaving it at -40°C for 30 minutes, followed by 100°C for 30 minutes. This cycle was repeated 100 times. After treatment, the cured material was visually inspected, and its heat cycle resistance was evaluated based on the following criteria: (◎: No change was observed, ○: There was some bubble formation, but no clouding or cracking, △: Some bubbles or cracks were observed, and there was slight clouding, ×: Bubbles or cracks were present throughout, and the material was semi-transparent.)

[0205] (Corrosion resistance of the cured sealant) After the moisture and heat yellowing test, the copper foil surface was visually observed and its corrosion resistance was evaluated according to the following criteria: (◎: No corrosion in the copper foil in the cured material, ○: Slight corrosion in the copper foil in the cured material, △: Some corrosion in the copper foil in the cured material, ×: Significant corrosion in the copper foil in the cured material)

[0206] (Stress Relaxation) A curable composition for encapsulating material was applied to a silicon wafer with a diameter of 100 mm and a thickness of 525 μm using a spin coater. A test specimen was prepared by curing it under the same conditions as for preparing a cured encapsulating material, forming a cured film with a thickness of 100 μm. This test specimen was placed in a warpage measuring device and heated from 25°C to 150°C, then cooled to -40°C. The amount of warpage of the wafer at this time was measured with a laser displacement meter, and the amount of warpage at -40°C was measured as an absolute value as an indicator of the stress generated by thermal contraction in a low-temperature environment. A smaller amount of warpage indicates a higher ability to relax stress caused by the difference in thermal expansion coefficients. (◎: Warpage at -40℃ is less than 100μm, ○: Warpage at -40℃ is 100μm or more and less than 200μm, △: Warpage at -40℃ is 200μm or more and less than 400μm, ×: Warpage at -40℃ is 400μm or more or cracks or peeling have occurred in the cured film)

[0207]

[0208] As is clear from the results in Table 10, the curable composition for sealing material in the example showed high curability, and the resulting cured product had excellent resistance to humid heat yellowing, low outgassing, and good heat cycle resistance and corrosion resistance. In addition, it also had excellent stress relaxation properties. On the other hand, the curable composition for sealing material in the comparative example showed low curability, and the resulting cured product had particularly insufficient heat cycle resistance and stress relaxation properties.

[0209] Examples 221-230 and Comparative Examples 35-36 (Preparation and Evaluation of Curable Compositions for Adhesives) Raw materials were weighed according to the composition ratios shown in Table 11 and mixed at 25°C for 30 minutes to obtain curable compositions for adhesives. p-LA represents a polymer syrup of lauryl acrylate, and p-2EHA represents a polymer syrup of 2-ethylhexyl acrylate. These polymer syrups were prepared by the following method: 100 parts by mass of monomer (LA or 2-EHA) and 0.05 parts by mass of Omnirad184 were placed in a four-necked flask and exposed to a nitrogen atmosphere at a wavelength of 365 nm and an illuminance of 60 mW / cm². 2 Using a UV-LED lamp, the integrated light output was 8,400 mJ / cm². 2The polymer syrup was obtained by UV irradiation to achieve the desired result. The curability of the obtained adhesive curable composition was evaluated by the method described below. Furthermore, the adhesive sheet obtained by curing this composition was evaluated for its tackiness to the substrate, reworkability, resistance to high temperature and humidity, and resistance to light-induced yellowing. The results of these evaluations are shown in Table 11.

[0210] (Curing properties of the curable composition for adhesives) A ​​heavy release film was placed in close contact with a horizontally positioned glass plate, and a spacer with a thickness of 1 mm and an internal dimension of 60 mm x 100 mm was placed on top. The curable composition for adhesives was filled into the spacer, and a light release film was placed on top of it. Subsequently, at a wavelength of 405 nm and an illuminance of 100 mW / cm, 2 Using a UV-LED lamp, the integrated light output was 1,000 mJ / cm². 2 UV irradiation was performed to achieve the desired result. Afterward, the light release film was removed, and an adhesive sheet consisting of a cured product of the adhesive curable composition and a heavy release film was obtained. The curability of the adhesive curable composition was evaluated by touching the adhesive layer based on the following criteria: (◎: A cured product that maintained its shape was obtained, with no liquid residue; ○: A cured product that maintained its shape was obtained, with a small amount of liquid residue; △: A cured product that maintained its shape was obtained, with some liquid residue; ×: Curing was insufficient, and a cured product that maintained its shape could not be obtained.)

[0211] (Adhesion) Under conditions of 23°C and 50% relative humidity, the adhesive layer was transferred to the base film or base plate described in Table 11. The two layers were bonded together using a 2kg pressure roller with two passes, and left for 30 minutes under the same conditions. This bonded body was used as a test specimen, and the 180° peel strength (N / 25mm) (peel speed 300mm / min) was measured using a tensile testing machine (ORIENTEC, Tensilon RTA-100) in accordance with ISO 29862, and the adhesiveness was evaluated based on the following criteria: (◎: Peel strength of 20 (N / 25mm) or more, ○: Peel strength of 10 (N / 25mm) or more and less than 20 (N / 25mm), △: Peel strength of 5 (N / 25mm) or more and less than 10 (N / 25mm), ×: Peel strength less than 5 (N / 25mm))

[0212] (Reworkability) The adhesive layer was peeled off from a test piece prepared in the same manner as in the adhesiveness evaluation, and the state of adhesive residue on the substrate side was visually observed. The reworkability of the adhesive layer was evaluated according to the following criteria. (⊚: no adhesive residue, ○: very slight adhesive residue, △: slight adhesive residue, ×: adhesive residue was observed)

[0213] (High temperature and high humidity resistance of adhesive layer) The adhesive layer of the adhesive sheet was transferred to a glass substrate, and left to stand in a thermo-hygrostat at 85°C and a relative humidity of 85% for 100 hours. Thereafter, the adhesive layer was left to stand for 30 minutes in an environment at 23°C and a relative humidity of 50%, the state of the adhesive layer was visually observed, and the high temperature and high humidity resistance was evaluated according to the following criteria. (⊚: the adhesive layer was transparent, with no peeling or bubbles, ○: the adhesive layer had very slight fogging, but no peeling or bubbles, △: the adhesive layer had slight fogging or peeling, with bubbles, ×: the adhesive layer had extreme fogging or peeling, with bubbles)

[0214] (Light-induced yellowing resistance of cured product of curable composition for adhesives) A heavy release film was adhered tightly to a horizontally placed glass plate, and a silicone spacer with an internal volume of 10 mm × 10 mm × 0.5 mm was placed thereon. The curable composition for adhesives was filled into the spacer, and a light release film was covered on the liquid surface while taking care not to incorporate air bubbles. Subsequently, with a wavelength of 405 nm and an illuminance of 100 mW / cm 2 , an accumulated light amount of 20,000 mJ / cm 2 was irradiated with a UV-LED lamp to cure the composition. Thereafter, the light release film was peeled off, and the cured product was taken out from the spacer. The taken-out cured product was visually observed, and the light-induced yellowing resistance was evaluated based on the following criteria. (⊚: no yellowing was observed at all, ○: very slight yellowing was observed, △: yellowing was observed, ×: obvious yellowing was observed)

[0215]

[0216] As is clear from the results in Table 11, the curable compositions for adhesives in the examples showed high curability, and the adhesive layers obtained by curing them showed high adhesion to various substrates. The cured products (adhesive layers) obtained in the examples had excellent resistance to high temperature and humidity and light yellowing, and also exhibited good reworkability when peeled off from the substrate. On the other hand, the curable compositions for adhesives in the comparative examples had low curability, and the resulting adhesive layers not only had low adhesive strength, but also insufficient resistance to high temperature and humidity, light yellowing, and reworkability.

[0217] Examples 231-246 and Comparative Examples 37-38 (Preparation and Evaluation of Curable Adhesive Compositions) Raw materials were weighed according to the composition ratios shown in Table 12 and mixed at 25°C for 30 minutes to prepare curable adhesive compositions. The curability of the obtained curable adhesive compositions was evaluated by the following method. Laminates were fabricated by bonding various substrates using these compositions. The adhesion and durability of the fabricated laminates were evaluated, and the results are shown in Table 12.

[0218] (Curable Adhesive Composition) A PET film was placed in close contact with a horizontally positioned glass plate, and the curable adhesive composition was coated to a thickness of 20 μm using a bar coater. A release film was then placed on top, with a wavelength of 405 nm and an illuminance of 50 mW / cm². 2 The adhesive curable composition was cured by ultraviolet irradiation using a UV-LED lamp. Afterward, the release film was removed, and the presence or absence of tack on the cured film surface was checked. The curability of the adhesive curable composition was evaluated according to the following criteria based on the cumulative light intensity required for the tack to disappear. (◎: 500 mJ / cm²) 2 The tack disappeared below 500 mJ / cm². 2 More than 1,000mJ / cm 2 Tack disappeared below 1,000 mJ / cm². 2 More than 5,000mJ / cm 2 The tack disappeared below 5,000 mJ / cm². 2 But Tuck stayed.

[0219] (Preparation of Laminates) A ​​curable adhesive composition was coated onto various film-like or plate-like substrates as shown below. PET films were stacked and bonded together using a tabletop roll-type laminator (RSL 382S) to ensure no air bubbles were introduced, resulting in an adhesive layer thickness of 20 μm. Afterward, an illuminance of 50 mW / cm² was applied at a wavelength of 405 nm. 2 Using a UV-LED lamp, the integrated light intensity was 2,000 mJ / cm². 2 The laminate was fabricated by irradiating it with ultraviolet light to achieve the desired result.

[0220] (Adhesion) The 180° peel strength (N / 25mm) of the laminate was measured in accordance with ISO 29862 using a tensile testing machine (ORIENTEC, Tensilon RTA-100) at a peeling speed of 300 mm / min. Based on the obtained peel strength, the adhesion was evaluated according to the following criteria: (◎: 20 (N / 25mm) or more, ○: 10 (N / 25mm) or more and less than 20 (N / 25mm), △: 5 (N / 25mm) or more and less than 10 (N / 25mm), ×: less than 5 (N / 25mm))

[0221] (Laminate durability) Similar to the curability evaluation of curable compositions for adhesives, an adhesive layer is formed on a glass substrate (cumulative light intensity 2,000 mJ / cm²). 2 The laminate was left standing for 100 hours in a constant temperature and humidity chamber at 85°C and 85% relative humidity. After that, it was left for 30 minutes in an environment of 23°C and 50% relative humidity, and the condition of the laminate was visually observed. Based on the observation results, durability was evaluated according to the following criteria: (◎: Laminate was transparent with no peeling or bubbles, ○: Laminate had very slight clouding, but no peeling or bubbles, △: Laminate had slight clouding or peeling and bubbles, ×: Laminate had extreme clouding or peeling and bubbles)

[0222]

[0223] As is clear from the results in Table 12, the curable adhesive compositions in the examples showed high curability, and the laminates obtained by curing them had excellent adhesion and good durability. On the other hand, the adhesive and durability of the laminates obtained in the comparative examples were insufficient.

[0224] Examples 247-266 and Comparative Examples 40-42 (Preparation and Evaluation of Photosensitive Curable Compositions) Raw materials were weighed according to the composition ratios shown in Table 13 and mixed at 25°C for 30 minutes to prepare photosensitive curable compositions. Photosensitive resin cured films were prepared from the obtained photosensitive curable compositions by the following method, and the sensitivity of the photosensitive curable compositions was evaluated. In addition, patterned cured products were prepared using the same compositions, and the pattern formation properties, adhesion of the obtained cured products, and heat resistance were evaluated. These results are shown in Table 13.

[0225] (Manufacturing of Photosensitive Resin Cured Film) A photosensitive curable composition was applied to a silicon wafer using a spin coater. Pre-baking was performed on an 80°C hot plate for 3 minutes to obtain a photosensitive resin film with a thickness of 15 μm. Subsequently, a photosensitive resin film was obtained with a dominant wavelength of 405 nm and an illuminance of 0.5 mW / cm². 2 The cumulative light output of the high-pressure mercury lamp is 90 mJ / cm². 2 UV irradiation was performed to obtain a photosensitive resin cured film.

[0226] (Sensitivity) The cured film obtained above was lightly touched with a finger, and its curability was evaluated based on the degree of tackiness (stickiness) of the surface according to the following criteria. (◎: No stickiness at all, ○: Slight stickiness, but no finger marks were left on the surface, △: Stickiness present, and finger marks were left on the surface, ×: Severe stickiness, and fingers stuck to the surface)

[0227] (Manufacturing of patterned cured products) A photosensitive curable composition was applied to a silicon wafer using a spin coater. Pre-baking was performed on an 80°C hot plate for 3 minutes to obtain a photosensitive resin film with a thickness of 15 μm. Next, a high-pressure mercury lamp (dominant wavelength 405 nm) was used to apply an integrated light of 90 mJ / cm² through a negative quartz photomask with a line and space (L / S) of 50 μm. 2 The image was exposed to light in the manner shown. After exposure, paddle development was performed for 60 seconds using cyclopentanone as the developer to remove unexposed areas. Then, the image was rinsed with isopropyl alcohol and dried by nitrogen blow to obtain a patterned cured product.

[0228] (Pattern Formation) The patterned hardened material was observed using a scanning electron microscope (SEM), and its pattern formation was evaluated according to the following criteria: (◎: No pattern distortion or chipping at the edges, ○: No pattern distortion, slight chipping at the edges, △: Slight pattern distortion and chipping at the edges, ×: Both pattern distortion and chipping at the edges were present)

[0229] (Adhesion) A cross-cut test was performed on the cured film fabricated on a silicon wafer in accordance with JIS K 5600-5-6. 100 grid-like cuts were made in the cured film at 1 mm intervals using a utility knife. Cellophane adhesive tape was then applied over the cuts and peeled off in one swift motion. The number of peeled-off sections of the cured film was then counted. (◎: 0 peeled sections / 100, ○: 1-5 peeled sections / 100, △: 6-15 peeled sections / 100, ×: 16 or more peeled sections / 100)

[0230] (Heat Resistance of Cured Patterns) The cured patterns (50 μm L / S) prepared above were heat-treated on a high-precision hot plate at temperatures of 150°C, 180°C, and 200°C for 30 minutes each. The pattern shape before and after heat treatment was observed using SEM, and the degree of pattern deformation was evaluated according to the following criteria. (◎: No change in pattern shape even after heat treatment at 200°C, ○: No change at 180°C, but slight rounding was observed at the corners of the top of the pattern at 200°C, △: No change at 150°C, but clear pattern flow was observed at 180°C, ×: Significant pattern flow and adhesion occurred after heat treatment at 150°C)

[0231]

[0232] As is clear from the results in Table 13, the photosensitive curable compositions of the examples showed high sensitivity. These photosensitive curable compositions exhibited excellent pattern-forming properties, and the resulting cured products and the formed patterns showed excellent properties in terms of adhesion and heat resistance. On the other hand, the photosensitive curable compositions of the comparative examples had low sensitivity, and the resulting cured products were insufficient in terms of pattern-forming properties, adhesion, and heat resistance.

[0233] Examples 267-289 and Comparative Examples 43-45 (Preparation and Evaluation of Imprint Curable Compositions) Raw materials were weighed according to the composition ratios shown in Table 14 and mixed at 25°C for 30 minutes to prepare imprint curable compositions. The viscosity and curability of the obtained imprint curable compositions were evaluated by the following method. Micromolding printing was performed using these imprint curable compositions, and etching resistance, imprint accuracy, pattern formation, and release properties were evaluated. The results are shown in Table 14.

[0234] (Viscosity of Imprint Curable Composition) The viscosity of the imprint curable composition was measured using a cone-plate viscometer and evaluated according to the following criteria: (◎: Viscosity of 10 mPa·s or more and less than 100 mPa·s, ○: Viscosity of 100 mPa·s or more and less than 500 mPa·s, △: Viscosity of 500 mPa·s or more and less than 1,000 mPa·s, ×: Viscosity of 1,000 mPa·s or more)

[0235] (Preparation of cured product of imprint curable composition) A heavy-release PET film was placed in close contact with a horizontally positioned glass plate, and the imprint curable composition was applied thereon with a bar coater to a film thickness of 20 μm. Subsequently, at a wavelength of 365 nm and an illuminance of 100 mW / cm 2 A cured product was prepared by irradiating it with UV light using a UV-LED lamp.

[0236] (Curability of Imprint Curable Compositions) The cumulative light dose required for the imprint curable composition to fully cure and reach a non-sticky state was measured, and the curability was evaluated according to the following criteria. (◎: Cumulative light dose of 500 mJ / cm²) 2 Complete curing is achieved below 500 mJ / cm². ○: Cumulative light intensity 500 mJ / cm². 2 More than 1,000mJ / cm 2 Complete curing is achieved below △: cumulative light intensity of 1,000 mJ / cm². 2 More than 2,000mJ / cm 2 Complete curing is achieved in less than 2,000 mJ / cm². ×: The cumulative light intensity required for complete curing is 2,000 mJ / cm². 2 (The above was required.)

[0237] (Shrinkage Resistance of Imprint Curable Composition) The density of the imprint curable composition was measured using a Gay-Lussac type specific gravity bottle in accordance with ISO 758. The density of the cured product was measured using an electronic specific gravity meter (MDS-300, manufactured by Alpha Mirage Co., Ltd.) in accordance with ISO 1183-1. The shrinkage rate was calculated from the density of the imprint curable composition and the density of the printed product using the following formula, and the shrinkage resistance of the imprint curable composition was evaluated according to the following criteria. (◎: Shrinkage rate less than 5%, ○: Shrinkage rate 5% or more and less than 6%, △: Shrinkage rate 6% or more and less than 7%, ×: Shrinkage rate 7% or more) Shrinkage rate (%) = (Ds - Dl) / D1 × 100 (wherein Ds is the density of the cured product and Dl is the density of the imprint curable composition.)

[0238] (Etching-resistant) Imprintable curable composition was printed to a thickness of 100 nm on a blank template of the Imprio I300 tool, followed by printing at a wavelength of 365 nm and an illuminance of 5 mW / cm². 2 The material was cured using a UV-LED lamp. Subsequently, oxygen etching was performed. For the etching process, a Trion Oracle Etch system with an O2 / Ar plasma using RIE excitation at 10 Torr was used, and the process was performed for 1 minute. The depth of the material removed in the film thickness direction during etching was measured and evaluated according to the following criteria: (◎: etching depth less than 30 nm, ○: etching depth between 30 nm and 40 nm, △: etching depth between 40 nm and 50 nm, ×: etching depth of 50 nm or more)

[0239] (Imprint Accuracy) The imprintable curable composition was printed to a thickness of 100 nm on the blank template of the Imprio I300 tool at a wavelength of 365 nm and an illuminance of 5 mW / cm². 2 The material was cured using a UV-LED lamp. Subsequently, the shape of the cured material was observed using a digital microscope (Keyence VH X DIGITAL MICROSCOPE) and evaluated according to the following criteria: (◎: No irregularities were observed on the sides, ○: Slight irregularities were observed on the sides, △: Some irregularities were observed on the sides, ×: Clear irregularities were observed on the sides)

[0240] (Pattern Formability of Imprint Curable Composition) An imprint curable composition was applied to a glass substrate using a bar coater, and the coating thickness was adjusted to 100 nm. Next, a mold having an equal-pitch structure with a line width of 150 nm and a spacing of 150 nm was pressed onto the coating, and the composition was cured by irradiation with ultraviolet light at a wavelength of 365 to 405 nm. After that, the pattern cured product obtained by peeling off the mold was observed using a scanning electron microscope (SEM) to evaluate the pattern shape, edge clarity, and presence or absence of defects. The evaluation criteria were as follows: (◎: No pattern distortion, clear edges, and no defects were observed; ○: No pattern distortion, slight irregularity was observed at the edges; △: Some pattern distortion or edge chipping was observed; ×: Significant pattern distortion and edge chipping were observed, indicating poor pattern formation.)

[0241] (Release Properties) After forming a cured product using the same method as described above for evaluating pattern formation properties, the release properties were evaluated by observing the state of the mold when it was peeled off at a constant speed (0.1 to 10 mm / s). The degree of peel resistance during mold peeling, and the presence or absence of defects in the cured pattern, peel residue (adhesion to the mold), and deformation of the pattern after peeling were evaluated by visual and microscopic observation. The evaluation criteria were as follows: (◎: Low peel resistance, no adhesion to the mold or pattern defects were observed; ○: Some peel resistance was observed, but almost no adhesion to the mold or pattern defects were observed; △: Some pattern defects or adhesion to the mold were observed during peeling; ×: High peel resistance, pattern defects or significant adhesion to the mold were observed)

[0242]

[0243] As is clear from the results in Table 14, the imprint curable compositions of the examples had low viscosity and high curability. The cured products obtained by curing these compositions had a low curing shrinkage rate and excellent curing shrinkage resistance. The cured products of the examples obtained after imprinting had excellent etching resistance and showed good properties in terms of printing accuracy, pattern formation, and release properties. On the other hand, the imprint curable compositions of the comparative examples had high viscosity and low curability, and the cured products obtained also had insufficient curing shrinkage resistance. Furthermore, the cured products after imprinting had low etching resistance and did not show satisfactory performance in terms of printing accuracy, pattern formation, and release properties.

[0244] As described above, the urethane (meth)acrylamide (E) of the present invention has a specific structural unit containing a carbonate group and a (meth)acrylamide group. E exhibits excellent properties such as moisture resistance, weather resistance, transparency, adhesion, and chemical resistance, derived from the carbonate group and the (meth)acrylamide group. Furthermore, by adjusting the molecular structure, it has high heat resistance and filler dispersibility. By containing such urethane (meth)acrylamide, it is possible to provide a curable composition with excellent heat resistance, filler dispersibility, moisture resistance, weather resistance, transparency, adhesion, and chemical resistance.

[0245] These curable compositions can be used in a wide range of fields, including thermal interface materials, inks, 3D printing materials, dental materials, coatings, sealants, photoresist materials, imprint materials, paints, and adhesives. In particular, when the carbonate equivalent, which reflects the number of carbonate groups contained in E, is between 120 and 1200, the inclusion of E results in a cured product that possesses both high tensile modulus and elongation. This combination of high modulus and high elongation results in low compression set, high shock absorption capacity, and good continuous heat resistance of the cured product.

[0246] A curable composition (I) can be obtained by adding a polymerizable compound (F) and a polymerization initiator (G) to E. I obtained by adjusting F and G with E having a carbonate equivalent of 120 to 170 is useful as a curable composition for hard materials, and the cured product obtained from such I has good Shore D hardness and elongation and exhibits high impact resistance. I obtained by adjusting F and G with E having a carbonate equivalent of 450 to 1200 is useful as a curable composition for soft materials, and the cured product obtained from such I has good Shore A hardness and elongation, exhibits high compression set resistance and good continuous heat resistance.

[0247] By including E, the resulting cured material exhibits excellent shock absorption properties in both hard and soft materials. E and the curable composition (I) containing E of the present invention are suitable for a variety of applications where active energy ray curing or thermal curing is used, and are particularly useful as curable compositions for three-dimensional stereolithography modeling materials, dental materials, coating materials, decorative coating materials, adhesives, sealants, thermal interface materials, and heat-resistant composite materials that utilize active energy ray curing.

[0248] The present invention includes the following: (1) Urethane (meth)acrylamide having a structural unit represented by general formula (1). General formula (1) In general formula (1), Q is R 1 It contains one or more divalent organic groups represented by general formula (2), general formula (3), or general formula (4), and if Q contains two or more organic groups, they may be bonded in any order. n represents an integer from 1 to 100. R 1 represents a linear alkylene group having 3 to 11 carbon atoms, a branched alkylene group having 3 to 11 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. General formula (2) In general formula (2), R 2 n1 represents a linear alkylene group with 1 to 8 carbon atoms, a branched alkylene group with 3 to 8 carbon atoms, or a cyclic alkylene group with 6 to 12 carbon atoms, and n1 represents an integer from 1 to 5. General formula (3) In general formula (3), R 3 and R 4Each of these independently represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n2 represents an integer from 1 to 5. General formula (4) In general formula (4), R 5 R represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 6 to 12 carbon atoms. 6n represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n3 represents an integer from 1 to 20. * in general formulas (1) to (4) represents the bond position. (2) The urethane (meth)acrylamide described in (1) above, wherein the carbonate equivalent is 120 to 170 or 450 to 1200. (3) The urethane (meth)acrylamide described in (1) or (2) above, wherein the compression set of the cured product is 10% or less. (4) The urethane (meth)acrylamide described in any one of (1) to (3) above, wherein the continuous heat resistance temperature of the cured product is 120°C or higher. (5) The urethane (meth)acrylamide described in any one of (1) to (5) above, wherein the carbonate segment content is 10 to 95%. (6) A curable composition containing the urethane (meth)acrylamide described in any one of (1) to (5) above. (7) A curable composition containing urethane (meth)acrylamide (E) as described in any one of (1) to (5) above, and one or more components selected from polymerizable compound (F), initiator (G), filler (H), and other components (K). (8) A curable composition for thermal interface materials containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (9) An ink containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (10) A material for three-dimensional stereolithography containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (11) A dental material containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (12) A coating agent containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (13) A sealing agent containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (14) A photoresist material containing urethane (meth)acrylamide as described in any one of (1) to (5) above. (15) An imprint material containing urethane (meth)acrylamide as described in any one of (1) to (5) above.

[0249] The urethane (meth)acrylamide (E) of this disclosure is suitably used for both active energy ray curing and thermosetting, and by adjusting its carbonate equivalent, cured products having the properties of a tough, hard material and cured products having the properties of a rubber-elastic, soft material can be obtained.

[0250] Curable compositions (I) containing urethane (meth)acrylamide (E) can be suitably used in a wide range of fields, including printing, coating, bonding and sealing, electronic and electrical applications, optical applications, three-dimensional molding applications, cosmetic applications, industrial applications, and functional material applications. Examples of printing applications include curable compositions for inks, inkjet inks, flexographic inks, offset inks, and screen printing inks. Examples of coating applications include curable compositions for general coating agents, automotive coating agents, architectural paints, antifouling paints, hard coat films, and decorative coatings. Examples of bonding and sealing applications include curable compositions for adhesives, curable compositions for sealants, potting materials for electronic components, and LED encapsulants.

[0251] For electronic and electrical applications, examples include curable compositions for thermal interface materials, heat-resistant nanocomposites, optical fiber coatings, insulating varnishes, solder resists, high-voltage cable coatings, and motor winding insulation materials. For optical applications, examples include optical lenses, light guides, optical films, and hard coats for touch panels. For industrial applications, it can be applied to industrial flooring, wear-resistant coatings, and industrial roll coatings. It can also be used as a curable composition for elastomers, self-healing materials, hydrogels, water-dispersible curable compositions, dental materials, photosensitive resins, and nail cosmetics.

[0252] The curable composition (I), when used as a three-dimensional photopolymerization ink composition, can be used to form molded objects requiring a wide range of physical properties, from hard to rubbery, such as structural components for automobiles, electrical appliances, and furniture; dental hygiene components; optical components such as optical lenses and light guides; figurines, toys, artificial nails, jewelry, shoe insoles or outsoles; smartphone cases; cushioning materials; vibration damping components; architectural models; and medical models. It can also be used as a topcoat material, support material, or high-toughness molding material after molding.

[0253] The curable composition (I) can also be used as a curable thermal interface material or a heat-resistant nanocomposite, and can be applied to applications requiring high heat resistance, electrical insulation, and mechanical reliability, such as power semiconductor device encapsulation, various sensor encapsulation, LED encapsulation, potting of electronic components, motor winding insulation, high-voltage cable coating, and optical fiber coating.

Claims

1. A urethane (meth)acrylamide having a structural unit represented by general formula (1). General formula (1) In general formula (1), Q contains one or more of R 1 , a divalent organic group represented by general formula (2), general formula (3) or general formula (4); when Q contains two or more types of organic groups, they may be bonded in any order. n represents an integer of 1 to 100. R 1 represents a linear alkylene group having 3 to 11 carbon atoms, a branched alkylene group having 3 to 11 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms. General formula (2) In general formula (2), R 2 represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n1 represents an integer of 1 to 5. General formula (3) In general formula (3), R 3 and R 4 each independently represent a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n2 represents an integer of 1 to 5. General formula (4) In general formula (4), R 5 represents a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 6 to 12 carbon atoms, R 6 represents a linear alkylene group having 1 to 8 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms, or a cyclic alkylene group having 6 to 12 carbon atoms, and n3 represents an integer of 1 to 20. * in general formulas (1) to (4) represents a bonding position.

2. The urethane (meth)acrylamide according to claim 1, wherein the carbonate equivalent is 120 to 170 or 450 to 1200.

3. The urethane (meth)acrylamide according to claim 1 or 2, wherein the compression set of the cured product is 10% or less.

4. The urethane (meth)acrylamide according to any one of claims 1 to 3, wherein the cured product has a continuous heat resistance temperature of 120°C or higher.

5. The urethane (meth)acrylamide according to any one of claims 1 to 4, wherein the carbonate segment content is 10 to 95%.

6. A curable composition containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

7. A curable composition comprising a urethane (meth)acrylamide (E) as described in any one of claims 1 to 5, and one or more components selected from a polymerizable compound (F), an initiator (G), a filler (H), and other components (K).

8. A thermal interface material curable composition containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

9. An ink containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

10. A three-dimensional stereolithography material containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

11. A dental material containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

12. A coating agent containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

13. A sealant containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

14. A photoresist material containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

15. An imprint material containing urethane (meth)acrylamide as described in any one of claims 1 to 5.

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