TWI683832B - (meth)acrylamide-based urethane oligomer and active energy ray curable resin composition containing the same - Google Patents

Abstract

A problem of the present invention is to provide some active energy ray curable resin compositions which have excellent compatibility with organic solvents, general purpose acrylic monomers and oligomers, have high curing speed to active energy rays, low hardening shrinkages, and excellent surface curability, and to provide molded products which have excellent adhesion, moisture resistance, surface curability and low curing shrinkage. By using (meth)acrylamide-based urethane oligomers of the present invention which have (meth) acrylamide groups in the end or the side chains and wherein the curing shrinkage ratio is 5% or less, it is possible to obtain urethane oligomers which have excellent compatibility with organic solvents, general purpose acrylic monomers and oligomers, and high curability and to obtain active energy ray curable resin compositions which contain the urethane oligomers and have excellent adhesion, moisture resistance and shrinkage resistance.

Description

(Meth)acrylamide urethane oligomer and active energy ray curable resin composition containing the compound

The present invention relates to (meth)acrylamide-based amines which are excellent in compatibility with organic solvents, general-purpose acrylic monomers and oligomers, have high curability for active energy rays, and have a curing shrinkage rate of 5% or less An urethane oligomer and an active energy ray-curable resin composition and molded article thereof that have excellent adhesion, moisture resistance, and surface hardening properties, and have low curing shrinkage and high transparency.

Most of the polymerizable urethane oligomers are urethane acrylates. With a good balance and a variety of skeleton structures, they can easily impart flexibility, flexibility, flexibility, and toughness. Various properties such as resistance, solvent resistance, and abrasion resistance are widely used in various fields such as adhesives, paints, and printing inks. Such urethane acrylate is usually made by reacting a polyol with a polyisocyanate to obtain a polyurethane having a hydroxyl group or an isocyanate group at both ends, and then further reacting with a hydroxyl group-containing acrylate or isocyanate group-containing Acrylic ester is reacted for synthesis (Patent Documents 1 to 3). In addition, there is also a synthesis method in which a hydroxyl-containing acrylate and a polyisocyanate are reacted before being attached to the end of a polyol (Patent Document 4).

Urethane acrylate has a radical polymerizable acrylate group, and it is widely used as a component of an active energy ray-curable resin composition like monofunctional acrylate, multifunctional acrylate, epoxy acrylate, etc. With the increase of the blending amount, the curability of the entire composition decreases. When the resin composition is coated on the substrate and cured by irradiation with active energy rays such as ultraviolet rays, there may be glue remaining on the surface of the coating film. Viscous, it is not easy to become the shortcoming of non-stickiness. In addition, when the seal between the solar cell module and the frame is formed, as a thick elastic layer as a sealing material for semiconductors, liquid crystals, and LEDs, many unhardened components remain in the layer, and satisfactory performance cannot be obtained. And there will be the problem of pollution caused by the exudation of unhardened components over time. In order to solve the residual adhesiveness on the surface and the inside of the thick film is not hardened, it has been reported to use monofunctional or multifunctional acrylic monomers and light sensitizers. For example: Patent Literature 1 provides a photocurable resin composition obtained by blending monofunctional acrylate 20 to 80% and a sensitizer 2% with urethane acrylate having a polybutadiene skeleton. However, urethane acrylate with a polybutadiene skeleton has insufficient solubility for many acrylic monomers due to the influence of the highly hydrophobic polybutadiene structure, and on the other hand, there are polyfunctional acrylic The use of esters leads to the problem of reduced flexibility inherent to the polybutadiene skeleton. Moreover, due to the blending of acrylic monomers, the curing shrinkage rate after ultraviolet (UV) irradiation is difficult to maintain at a low level.

In addition, in order to comprehensively improve the active energy ray curability of the urethane acrylate resin, especially the hardness and surface adhesiveness of the cured product, the adducts and oligomers of the urethane acrylate propionamide have been proposed (Patent Literature 5-8). By changing the polymerizable group from an acrylate group to an acrylamide group, the ultraviolet curability is improved and the adhesiveness of the cured film surface and the hardness of the cured product are improved. However, for the solubility of general organic solvents and acrylic monomers, The transparency, scratch resistance, abrasion resistance and shrinkage resistance of the cured film obtained are not mentioned at all. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-21120 [Patent Document 2] Japanese Patent Laid-Open No. 2010-267703 [Patent Document 3] Japanese Patent Laid-Open No. 6-145276 [Patent Document 4] WO2013/088889 [Patent Document 5] Japanese Patent Laid-Open No. 2002-37849 [Patent Document 6] Japanese Patent Laid-Open No. 2009-244460 [Patent Document 7] Japanese Patent Laid-Open No. 2011-218616 [Patent Document 8] Japanese Patent Laid-Open No. 2012-082288 Bulletin

[Problems to be Solved by the Invention] The present invention provides a (meth)acrylamide-based urethane oligomer, which has excellent compatibility with organic solvents, general-purpose acrylic monomers, and oligomers. The active energy ray has high curability and low curing shrinkage, and provides an active energy ray curable resin composition containing the compound, which has excellent adhesion, moisture resistance and surface hardening, and low curing shrinkage. Its molded products. [Method of solving the problem]

The inventors of the present case worked hard to solve the aforementioned problems, and found that by using one or more skeletons and one or more skeletons selected from ether skeletons, ester skeletons, polysiloxane skeletons, and acrylic skeletons in the molecule. The (meth)acrylamide group, and the (meth)acrylamide-based urethane oligomer having an active energy ray hardening shrinkage rate of 5% or less can achieve the aforementioned objective and complete the present invention.

式中，R₁ 表示氫原子或甲基，R₂ 及R₃ 相同或不同而表示氫原子、或也可經羥基取代之碳數1至6之直鏈狀或分支鏈狀之烷基、碳3至6之脂肪族環或芳香環，又，R₂ 及R₃ 也可以和載持它們的氮原子成為一體並進一步形成也可含有氧原子或氮原子之飽和或不飽和之5~7員環。惟不包括R₂ 及R₃ 同時為氫原子的情形、及R₂ 及R₃ 同時為烷基的情形，且R₂ 與R₃ 擁有之羥基之合計為1以上。 (5) 一種活性能量射線硬化性樹脂組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (6) 一種活性能量射線硬化性黏接劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (7) 一種活性能量射線硬化性黏著劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (8) 一種活性能量射線硬化性塗佈劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (9) 一種活性能量射線硬化性密封劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (10) 一種活性能量射線硬化性噴墨用印墨組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (11) 一種活性能量射線硬化性立體造形用樹脂組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (12) 一種活性能量射線硬化性指甲裝飾劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (13) 一種活性能量射線硬化性車廂外裝保護劑組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 (14) 一種活性能量射線硬化性裝飾薄膜用樹脂組成物，其含有1重量%以上之如(1)至(4)中任一項之(甲基)丙烯醯胺系胺基甲酸乙酯低聚物。 [發明之效果]That is, the present invention is: (1) A (meth)acrylamide-based urethane oligomer, characterized in that it has a molecule selected from the group consisting of an ether skeleton, an ester skeleton, a polysiloxane skeleton and acrylic acid One or more of the skeletons in the skeleton, and having more than one (meth)acrylamide group, the shrinkage rate before and after active energy curing is 5.0% or less. (2) The (meth)acrylamide urethane oligomer of (1), in which the content of components with a molecular weight of less than 1000 (excluding (meth)acrylamide with hydroxyl groups) is 5 wt% or less. (3) The (meth)acrylamide urethane oligomer of (1) or (2) has a number average molecular weight of 4,500 to 30,000 and an acrylic acid equivalent of 750 to 25,000. (4) The (meth)acrylamide-based urethane oligomer according to any one of (1) to (3), wherein (meth)acrylamide (C) having a hydroxyl group is Expression [1]; [Chem 1]

In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R _{3 are the} same or different and represent a hydrogen atom, or a linear or branched alkyl or carbon group having 1 to 6 carbon atoms which may also be substituted with a hydroxyl group 3 to 6 aliphatic ring or aromatic ring, and R ₂ and R ₃ can also be integrated with the nitrogen atom carrying them and further formed into saturated or unsaturated 5 to 7 members that can also contain oxygen or nitrogen atoms ring. It does not include the case where R ₂ and R _{3 are} both hydrogen atoms, and the case where R ₂ and R _{3 are} both alkyl groups, and the total number of hydroxyl groups owned by R ₂ and R ₃ is 1 or more. (5) An active energy ray-curable resin composition containing 1% by weight or more of the (meth)acrylamide-based urethane oligomer according to any one of (1) to (4). (6) An active energy ray-curable adhesive composition containing 1% by weight or more of (meth)acrylamide urethane oligomer as in any one of (1) to (4) Thing. (7) An active energy ray-curable adhesive composition containing 1% by weight or more of (meth)acrylamide-based urethane oligomer as described in any one of (1) to (4) . (8) An active energy ray-curable coating agent composition containing 1% by weight or more of (meth)acrylamide-based urethane oligomer as in any one of (1) to (4) Thing. (9) An active energy ray-curable sealant composition containing 1% by weight or more of (meth)acrylamide-based urethane oligomer as described in any one of (1) to (4) . (10) An active energy ray-curable inkjet ink composition containing 1% by weight or more of (meth)acrylamide-based ethyl carbamate as in any one of (1) to (4) Polymer. (11) An active energy ray-curable resin composition for stereolithography that contains 1% by weight or more of (meth)acrylamide-based urethane as in any one of (1) to (4). Polymer. (12) An active energy ray-curable nail decoration composition containing 1% by weight or more of (meth)acrylamide-based urethane oligomers as described in any one of (1) to (4) Thing. (13) An active energy ray-curable vehicle exterior protection agent composition containing 1% by weight or more of (meth)acrylamide-based ethyl carbamate as in any one of (1) to (4) Oligomer. (14) A resin composition for active energy ray-curable decorative films, containing 1% by weight or more of (meth)acrylamide-based urethane as in any one of (1) to (4) Polymer. [Effect of invention]

According to the present invention, a polyol (A) having one or more skeletons selected from an ether skeleton, an ester skeleton, a polysiloxane skeleton, and an acrylic skeleton having one or more hydroxyl groups in one molecule can be provided 、It is obtained by the addition reaction of polyisocyanate (B) with more than 2 isocyanate groups in one molecule and (meth)acrylamide (C) with hydroxyl groups, and it does not contain isocyanate groups at the end, and the active energy is hardened (Meth)acrylamide-based urethane with a shrinkage rate of 5.0% or less before and after, excellent compatibility with organic solvents, general-purpose acrylic monomers, and oligomers, and high curability to active energy rays Oligomer. In addition, by using the (meth)acrylamide urethane oligomer of the present invention, it can provide excellent adhesion, moisture resistance, and surface hardening, and has low curing shrinkage and high transparency The active energy ray curable resin composition and its molded product.

The present invention will be described in detail below. The (meth)acrylamide urethane oligomer of the present invention is characterized by having one or more types of skeleton selected from the group consisting of ether skeleton, ester skeleton, polysiloxane skeleton and acrylic skeleton, And it has (meth)acrylamide group at the terminal or side chain, and the shrinkage rate before and after active energy hardening is 5.0% or less.

The (meth)acrylamide of the present invention is an urethane oligomer (sometimes referred to as urethane oligomer), which is selected from ethers having one or more hydroxyl groups in one molecule. Polyol (A) of one or more skeletons among skeleton, ester skeleton, polysiloxane skeleton and acrylic skeleton, polyisocyanate (B) with two or more isocyanate groups in one molecule and hydroxyl group A compound obtained by the addition reaction of (meth)acrylamide (C) and having no isocyanate group at the terminal. In the (meth)acrylamide urethane oligomer of the present invention, the content rate of the component with a molecular weight of less than 1,000 (excluding (meth)acrylamide with hydroxyl groups) is preferably 5% by weight or less It is 3% by weight or less, more preferably 1% by weight or less. Most of the low-molecular-weight components with a molecular weight of less than 1,000 are ethyl carbamate addition compounds obtained by the addition reaction of polyisocyanate (B) and hydroxyl-containing (meth)acrylamide (C), the inventors of the present invention speculate The presence of these urethane adducts results in reduced solubility of urethane oligomers, white turbidity, and moisture absorption after active energy ray hardening leads to residual surface adhesion and reduced hardening shrinkage resistance s reason.

The method for synthesizing the (meth)acrylamide urethane oligomer of the present invention is not particularly limited, and it can be synthesized by a well-known urethane reaction technique. That is, it can be synthesized by the reaction of a monofunctional or polyfunctional alcohol (polyol) (A), polyisocyanate (B), and (meth)acrylamide monomer (C) having a hydroxyl group. In addition, considering the viewpoint that the content of components with a molecular weight less than 1000 (hereinafter also referred to as low molecular weight components) can be lowered, it is preferable to first react a polyol with an isocyanate compound to synthesize one or more isocyanate groups in the molecule The compound is then reacted with a (meth)acrylamide monomer having a hydroxyl group to obtain the (meth)acrylamide-based urethane oligomer of the target.

Polyether polyols have a polyether backbone chain in the molecule and have more than one hydroxyl group at the end or side chain of the backbone chain. In addition, considering the viewpoint of easy operation, a liquid at normal temperature and pressure is preferable. Commercial products of polyether polyols include Adekapolyether's P, BPX, G, T, EDP, AM, BM, CM, PR, GR series (manufactured by ADEKA), diethylene glycol, dipropylene glycol, dibutylene Alcohol, PTMG series (manufactured by Mitsubishi Chemical Corporation), Sannix PP, GP, GOP series, for example: Sannix PP-1000, GP-250, GOP-600 (Sanyo Chemical Industry Co., Ltd.), PEG series, Uniox G Series, Uniol D, TG, PB series, Unilube DGP series, Polycerin DC, DCB series (made by Nippon Oil Corporation), etc. These polyether polyols may be used alone or in combination of two or more.

Polyester polyols are those that have a polyester backbone backbone in the molecule and have more than one hydroxyl group at the end or side chain of the backbone backbone. In addition, considering the ease of operation, it is better to use a liquid at normal temperature and pressure. Commercial products of polyester polyols, for example: AdekaNewAce series (manufactured by ADEKA), Kuraray polyols P, F, N, PMNA series (manufactured by Kuraray), Priplast series (manufactured by CRODA), Placcel series (Manufactured by Daicel Chemical Company), Tesla 2456 (manufactured by Hitachi Chemical Co., Ltd.), etc. These polyester polyols may be used alone or in combination of two or more.

Polysilicone polyol has a polysilicone main chain skeleton in the molecule and has more than one hydroxyl group at the end or side chain of the main chain skeleton. Commercial products include KF-6000, X-21-5841 (made by Shin-Etsu Chemical Industry Co., Ltd.), BY 16-201 (made by Toray Dow Corning Co., Ltd.), XF42-B0970 (made by Momentive performance materials), Silaplane Series, for example: Silaplane FM-0411 (manufactured by JNC). These polysiloxane polyols may be used alone or in combination of two or more.

Acrylic polyol is a polymer obtained by polymerizing more than one acrylic monomer and has more than one hydroxyl group at the end or side chain of the molecule. For example, homopolymers of acrylic monomers with hydroxyl groups such as hydroxy(meth)acrylate acrylate, hydroxyacrylic acid (meth)acrylamide, or copolymers with monomers with other unsaturated groups are used. Examples of commercially available products include UMM-1001 and UT-1001 (manufactured by Soken Chemical Co., Ltd.).

As the (meth)acrylamide-based urethane oligomer, one or more than one selected from the above polyether polyols, polyester polyols, polysiloxane polyols, and acrylic polyols can be used alcohol. In particular, (meth)acrylamide-based urethane oligomers composed of two or more types of diols with ester, ether, polysilicone, and acrylic skeletons as essential components are dense to copper. Excellent fit. Among them, the ester polyol preferably contains 30% by weight or more, and more preferably contains 50% by weight or more.

Polyisocyanate (B) having 2 or more isocyanate groups in 1 molecule, for example: trimethylene diisocyanate, hexamethylene diisocyanate, 1,2-butylene diisocyanate, 2,4,4-tris Aliphatic isocyanates such as methylhexamethylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolyl diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate Aromatic isocyanates such as isocyanates, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate Alicyclic isocyanates such as isocyanate, isocyanates containing urea formate groups such as "Desmodur XP2565" (manufactured by Bayer Polyurethanes Co., Ltd.) or their adducts, isocyanurates, biuret Such polymers as Coronate L, HL, HX (manufactured by Japan Polyurethane Industry Co., Ltd.), Duranate 24A-100 (manufactured by Asahi Kasei Industry Co., Ltd.), etc. These isocyanate monomers may be used alone or in combination of two or more.

The (meth)acrylamide having a hydroxyl group (C) is a hydroxyl group-containing methacrylamide and a hydroxyl group-containing acrylamide, which may be used alone or in combination of two or more. In addition, by using hydroxyl-containing acrylamide, the hardenability is significantly improved, so it is particularly desirable.

Examples of (meth)acrylamide having a hydroxyl group include: N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acryl Acetamide, N-hydroxyisopropyl (meth)acrylamide, N-methylhydroxymethyl (meth)acrylamide, N-methylhydroxyethyl (meth)acrylamide, N-methyl Hydroxypropyl(meth)acrylamide, N-methylhydroxyisopropyl(meth)acrylamide, N-ethylhydroxymethyl(meth)acrylamide, N-ethylhydroxyethyl (Meth)acrylamide, N-ethylhydroxypropyl (meth)acrylamide, N-ethylhydroxyisopropyl (meth)acrylamide, N-propylhydroxymethyl (methyl) Acrylamide, N-propyl hydroxyethyl (meth) acrylamide, N-propyl hydroxypropyl (meth) acrylamide, N-propyl hydroxyisopropyl (meth) acrylamide, N-isopropylhydroxyethyl(meth)acrylamide, N-isopropylhydroxypropyl(meth)acrylamide, N-isopropylhydroxyisopropyl(meth)acrylamide, N ,N-dihydroxymethyl(meth)acrylamide, N,N-dihydroxyethyl(meth)acrylamide, N,N-dihydroxypropyl(meth)acrylamide, N,N -Dihydroxyisopropyl (meth) acrylamide. In particular, N-hydroxyethyl (meth) acrylamide has high refractive index (1.502), can provide excellent transparency, and because of low skin irritation (PII = 0), it is safe and easy to handle, and easy It is ideal to obtain high-purity industrial products. These hydroxyl-containing (meth)acrylamide can be used alone or in combination of two or more.

啉等。有機溶劑或反應性稀釋劑之使用量相對於異氰酸酯化合物為0~400重量%，宜為0~200重量%。The urethane reaction can be carried out according to a known method. In addition, the reaction can be carried out without a solvent, and if necessary, it can be carried out in an organic solvent or a reactive diluent. Can be used in solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, It is carried out in the presence of tetrahydrofuran, hexane, cyclohexane, benzene, toluene, xylene, aliphatic hydrocarbon-based solvents (petroleum ether, etc.) and the like. The reactive diluent that can be used is not particularly limited as long as it does not react with isocyanate, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and (meth) ) 2-ethylhexyl acrylate, cyclohexyl (meth)acrylate, 1,6-hexane diacrylate, tetraethylene glycol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane Triacrylate, isobornyl (meth)acrylate, dimethyl (meth) acrylamide, di (meth) ethyl acrylamide, N-(meth) acrylamide

Porphyrin etc. The amount of the organic solvent or reactive diluent used is 0 to 400% by weight relative to the isocyanate compound, preferably 0 to 200% by weight.

、1,8-二氮雜雙環[5.4.0]十一-7-烯、N,N'-二甲基哌

、N,N-二甲基環己胺、N-甲基二環己胺、N,N,N',N'-四甲基丙二胺、N,N,N',N'-四甲基六亞甲基二胺、N-乙基

啉(NEM)、N,N-二甲基乙醇胺(DMEA)、N,N-二乙基乙醇胺、二甲胺基丙胺、二

啉基二乙醚(DMDEE)、雙(2-二甲胺基乙基)醚、1-甲基咪唑、1,2-二甲基咪唑、1-異丁基-2-甲基咪唑、1-二甲胺基丙基咪唑、三乙二胺(TED)等三級胺化合物類，它們可單獨使用或組合使用2種以上。觸媒之使用量相對於原料成分之合計重量通常為1重量%以下較佳，0.1重量%以下又更佳。In this urethane reaction, a catalyst may be added to promote the reaction. The catalyst includes, for example, potassium or sodium salts of alkylphosphonic acid, sodium, potassium, nickel, cobalt, cadmium, barium, calcium, zinc and other metal salts of fatty acids having 8 to 20 carbon atoms, dibutyltin dilaurate, Dioctyl tin maleate, dibutyl dibutoxy tin, bis(2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-1,3-diethyl acetyl dioxy Organotin compounds such as stannoxane, N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), N,N,N',N",N"-pentamethyl-( 3-aminopropyl) ethylenediamine, N,N,N',N",N"-pentamethyldipropylene triamine, N,N,N',N'-tetramethylguanidine, 1,3 ,5-ginseng (N,N-dimethylaminopropyl) hexahydro-S-tri

, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N'-dimethylpiper

, N,N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N,N,N',N'-tetramethylpropanediamine, N,N,N',N'-tetramethyl Hexamethylene diamine, N-ethyl

Porphyrin (NEM), N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine, dimethylaminopropylamine, di

Dinyl diethyl ether (DMDEE), bis(2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1- Tertiary amine compounds such as dimethylaminopropylimidazole and triethylenediamine (TED) can be used alone or in combination of two or more. The amount of catalyst used is usually preferably 1% by weight or less relative to the total weight of the raw material components, and more preferably 0.1% by weight or less.

等胺系聚合禁止劑、4-羥基-2,2,6,6-四甲基哌啶-N-氧自由基等N-氧自由基類；二甲基二硫胺甲酸酸銅、二乙基二硫胺甲酸銅、二丁基二硫胺甲酸銅等二硫胺甲酸銅系聚合禁止劑等，它們可單獨使用，也可併用2種以上。In order to suppress the radical polymerization of (meth)acrylamide having a hydroxyl group in the ethylation reaction of urethane, a radical polymerization inhibitor may be used as necessary. Free radical polymerization inhibitors, such as: hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol and other quinone-based polymerization inhibitors; 2,6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri- Tertiary butylphenol and other alkylphenol polymerization inhibitors; alkylated diphenylamine, N,N′-diphenyl-p-phenylenediamine, phenothiazine

Other amine-based polymerization inhibitors, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxygen radicals and other N-oxygen radicals; copper dimethyldithiocarbamate, diethyl Copper dithiocarbamate-based polymerization inhibitors such as copper dithiocarbamate and copper dibutyldithiocarbamate, etc. These can be used alone or in combination of two or more.

The addition amount of these polymerization inhibitors can be appropriately set according to the type and blending amount of (meth)acrylamide containing hydroxyl groups, considering the viewpoints of polymerization inhibition effect, production convenience and economy, relative to amine The total weight of the raw materials for the ethyl formate reaction is usually preferably 0.001 to 5% by weight, and more preferably 0.01 to 1% by weight.

The (meth)acrylamide urethane oligomer of the present invention has a number average molecular weight of 4,500 to 50,000, more preferably 4,500 to 30,000. When the number average molecular weight is less than 4,500, the solubility may decrease and the transparency may deteriorate when the resin composition is prepared. Furthermore, when the molecular weight is less than 500, the content of low molecular weight components, especially the aforementioned urethane addition compound, is large, so the transparency of the resin composition constituting it is worse, and the adhesion and water resistance of the coating film obtained Also reduced. On the other hand, when the number-average molecular weight exceeds 30,000, it is not desirable because it has high viscosity and poor workability. In particular, if the (meth)acrylamide urethane oligomer having an ether skeleton and an ester skeleton has a number average molecular weight of 4,500 or more, the adhesion and moisture resistance of various substrates tend to be significantly improved. Ideal.

The (meth)acrylamide urethane oligomer of the present invention preferably has an acrylic acid equivalent of 750-25,000. When the acrylic equivalent is less than 750, the hardening speed is accelerated but the hardening shrinkage may not be reduced to less than 5%, which is not ideal. On the other hand, when the acrylic equivalent exceeds 25,000, there is a fear that the presence of the non-polymerizable compound may cause the reduction in active energy ray curability, strength of the cured film, and water resistance.

The viscosity of the (meth)acrylamide urethane oligomer of the present invention at 60°C is preferably 500,000 mPa·s or less, and more preferably 300,000 mPa·s or less. If the viscosity at 60°C exceeds 500,000 mPa·s, it may become non-fluid during operation, and the operability is not good, which is not ideal.

The (meth)acrylamide urethane oligomer of the present invention may be used alone or mixed with other active energy ray-curable monomers, oligomers, etc. to prepare an active energy ray-curable resin composition . When the (meth)acrylamide urethane oligomer of the present invention is used alone, it depends on the type and number of polyol skeleton, (meth)acrylamide group, and the molecular weight of the oligomer. The resin composition The physical properties such as the hardenability of the material, the water absorption rate, strength, elongation, etc. of the obtained hardened product will be different, but it is generally preferably within the following range.

The (meth)acrylamide urethane oligomer of the present invention can be completely hardened by active energy ray irradiation. The necessary amount of active energy ray irradiation (accumulated light amount) varies depending on the type and number of (meth)acryl amide groups of the urethane oligomer, but it is preferably 10 to 2000 mJ/cm ² , and It is particularly ideal for around 100~1000mJ/cm ² . If the accumulated light amount is less than 10 mJ/cm ² , insufficiently cured parts will remain, and the strength, elongation, and water resistance of the entire cured product may be reduced. In addition, if the accumulated light amount exceeds 2000 mJ/cm ² , excessive energy may cause side reactions such as decomposition, and the cured film tends to be easily colored.

The water absorption rate of the cured film composed of the (meth)acrylamide urethane oligomer of the present invention is preferably 5% or less, more preferably 2% or less. If the water absorption rate is greater than 5%, when used in a high humidity environment for a long time, the cured film will absorb water over time, and the shape will be deformed due to swelling, so the adhesion and transparency may be reduced.

The strength (tensile breaking strength) of the cured film composed of the (meth)acrylamide urethane oligomer of the present invention is preferably 0.5 to 40 MPa, and the elongation (tensile breaking elongation) is preferably 5 to 300% is better. The strength and elongation of (meth)acrylamide urethane oligomer can fall within these ranges, so it is an active energy ray composed of a mixture of other active energy ray curable monomers and oligomers The curable resin composition can be used in various fields such as adhesives, adhesives, paints, ink compositions, sealants, nail decoration composition, car exterior protection agents, and hardening compositions for decorative films.

Of the photocurable resin compositions for electronic devices, the urethane oligomer of the present invention can of course be used alone, but it is also possible to adjust the curability, fluidity of the resin composition, and the water resistance of the obtained cured product , Flexibility, adhesiveness and other physical properties, and mixed with other photo-curable monomers, oligomers, etc. The blending amount of the urethane oligomer in the photo-curable resin composition is preferably 1% by weight or more, and more preferably 10-60% by weight. If the urethane oligomer is less than 1% by weight, there is a possibility that it cannot sufficiently provide functions such as curability and low curing shrinkage. Examples of monomers and oligomers that can be used in combination with urethane oligomers include monofunctional (meth)acrylates and/or monofunctional (meth)acrylamide, and polyfunctional (meth)acrylic acid. Ester and/or polyfunctional (meth)acrylamide, etc., and their monomers and oligomers may be used alone or in combination of two or more. Furthermore, if necessary, it may contain a polymerizable fourth-grade salt ionic liquid.

Monofunctional (meth)acrylates used in the present invention are, for example: alkyl (meth)acrylate of methyl (meth)acrylate, ethyl hydroxyacrylate, alkoxy ethyl (meth)acrylate, methoxy Diethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, phenoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, (methyl ) Benzyl acrylate, phenoxyethyl (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl (meth) acrylate, methyl tetrahydrofuran acrylate, 2-methyl (meth) acrylate Hydroxyalkyl (meth)acrylates such as 2-adamantanyl ester, allyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. These monofunctional acrylates can be used alone or in combination of two or more.

啉、前述羥基乙基丙烯醯胺等羥基烷基(甲基)丙烯醯胺等。又，該等單官能丙烯醯胺可單獨使用也可併用2種以上。Examples of monofunctional (meth)acrylamide used in the present invention: N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-methoxymethyl (methyl ) Acrylamide, N-ethoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-( 2-hydroxyethyl) acrylamide, N-[3-(dimethylamino)]propyl acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl (Meth)acrylamide, N-acryl

Hydroxyalkyl (meth)acrylamide and the like such as oxoline and the aforementioned hydroxyethylacrylamide. In addition, these monofunctional acrylamides may be used alone or in combination of two or more.

烷二醇二丙烯酸酯)、烷氧基化己烷二醇二(甲基)丙烯酸酯、烷氧基化環己烷二甲醇二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺基甲酸乙酯(甲基)丙烯酸酯等單體與低聚物。又，該等多官能(甲基)丙烯酸酯可單獨使用也可併用2種以上。The aforementioned multifunctional (meth)acrylates are, for example: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene (meth)acrylate Propylene glycol ester, ditetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth) Acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(meth) 1,6-hexanediol acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol Alcohol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth) Base) acrylate, ethylene oxide modified phosphate di(meth)acrylate, neopentaerythritol tetra(meth)acrylate, neopentaerythritol tri(meth)acrylate, hexa(meth)acrylic acid Dipentaerythritol ester, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylol Propane tri(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di( Meth)acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate (dimethacrylate)

(Alkylene glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexane dimethanol di(meth)acrylate, epoxy (meth)acrylate, Monomers and oligomers such as urethane (meth)acrylate. Furthermore, these polyfunctional (meth)acrylates may be used alone or in combination of two or more.

Examples of the polyfunctional (meth)acrylamide include methylenebis(meth)acrylamide, ethylidenebis(meth)acrylamide, diallyl(meth)acrylamide, and the like. Moreover, these polyfunctional (meth)acrylamide may be used individually or in combination of 2 or more types.

In addition, an organic ionic compound which is a component (F) may be blended. Examples of the organic ionic compound include ionic vinyl monomers and/or oligomers and polymers containing them as constituent components. An onium salt composed of an ionic vinyl monosystem cation and an anion. Specifically, the cation includes (meth)acrylate-based or (meth)acrylamide-based ammonium ions and imidazolium ions, and the anion includes the anion. cl ^-, Br ^-, I ^- halogen ion or _{^{OH -, CH 3 COO -,}} NO 3 -, ClO 4 -, PF 6 -, BF 4 -, HSO 4 -, CH 3 SO 3 -, CF 3 SO 3 _{^{-, CH 3 C 6 H 6}} SO 3 -, C 4 F 9 SO 3 -, (CF 3 SO 2) 2 N -, SCN - inorganic acid anion or organic acid anion.

The method for synthesizing the polymerizable 4-level salt ionic liquid used in the present invention can generally be exemplified by converting the tertiary amine having a polymerizable group into 4-levels such as haloalkanes, dialkyl sulfates, and methyl p-toluenesulfonate. The method of making the agent into 4 levels, the method of using the 4 level of ammonium salt obtained by the 4 leveling of further anion exchange with the purpose of anion salt, using the anion exchange resin to convert the 4 level ammonium salt into hydroxide The method of neutralizing the acid of the target anion etc.

The ions of the polymerizable 4-level salt ionic liquid easily form hydrogen bonds and ionic bonds with the coated substrate, and can impart conductivity and antistatic properties, so the moisture permeability is improved, the coating can be more uniform, and the Stable film formation. In addition, the polymerizable 4-level salt ionic liquid itself is also an active energy ray-curable compound. Therefore, by copolymerizing with the active energy ray-curable resin composition of the present invention, it can provide permanent conductivity and resistance without bleeding. The auxiliary effect of static electricity and the effect of improving adhesion.

The polymerizable 4-level salt ionic liquid can be selected from monomolecular compounds with molecular weights of tens to hundreds, oligomers with molecular weights of hundreds to thousands, polymers with molecular weights of thousands to tens of thousands, or 2 as needed Use more than one combination. The blending amount of the polymerizable 4-level salt ionic liquid can be adjusted by the number of functional groups and molecular weight of the ion pair, so there is no special limit. Generally speaking, it is preferable to add 0 to 50% by weight relative to the urethane oligomer of the present invention, and it is preferable to add 0 to 10% by weight. If the blending amount of the polymerizable grade 4 salt ionic liquid exceeds 50% by weight, depending on the type of the polymerizable grade 4 salt ionic liquid, there is a possibility that the transparency of the cured film may decrease.

The active energy ray of the present invention is defined as an energy ray that can decompose an active species-generating compound (photopolymerization initiator) to produce an active species. Examples of such active energy rays include light energy rays such as visible light, electron beams, ultraviolet rays, infrared rays, X rays, α rays, β rays, and γ rays.

When curing the active energy ray-curable resin composition of the present invention, a photopolymerization initiator is added first. The photopolymerization initiator is not particularly necessary when using an electron beam as an active energy ray, but it is necessary when using ultraviolet rays. The photopolymerization initiator can be appropriately selected from common products such as acetophenone-based, benzophenone-based, benzophenone-based, and thioxanthone-based. Among the photopolymerization initiators, commercially available photopolymerization initiators can use Irgacure 1173, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 819, Irgacure 907, Irgacure 2959 manufactured by BASF Japan. , Irgacure 　 TPO, UCB company, trade name Ubecryl P36, etc. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator used is not particularly limited, and generally it is 0.1 to 10% by weight relative to the active energy ray-curable resin composition, of which 1 to 5% by weight is preferred. If it is less than 0.1% by weight, sufficient hardenability cannot be obtained, and if it exceeds 10% by weight, the strength of the coating film may decrease and yellowing may occur.

Pigments, dyes, surfactants, anti-blocking agents, leveling agents, dispersing agents, defoaming agents can be used in a range that does not hinder the characteristics of the active energy ray-curable resin composition of the present invention and the molded product made therefrom Agents, antioxidants, ultraviolet sensitizers, preservatives and other optional ingredients.

By coating the active energy ray-curable resin composition of the present invention on paper, cloth, non-woven fabric, glass, polyethylene terephthalate, cellulose diacetate, cellulose triacetate, acrylic polymer , PVC, cellophane, celluloid, polycarbonate, polyimide and other plastic and metal substrates, between the surface, and by ultraviolet rays and other active energy rays to harden it, And obtain high-performance coating layer, ink layer, adhesive layer or adhesive layer. In addition, the method of coating this resin composition on the substrate includes spin coating method, spray coating method, dip coating method, gravure printing roll method, knife coating method, reverse roll method, screen printing method, coating bar method, etc. The usual coating film formation method. In addition, the method of coating between the substrates includes a lamination method, a roll to roll method, and the like. [Example]

Hereinafter, the present invention will be described in more detail using Synthesis Examples and Evaluation Examples, but the present invention is not limited to only these Examples. In addition, among the following,% other than the yield represents weight %. The physical properties of the obtained urethane oligomer were analyzed according to the following method.

(1) The number average molecular weight of the urethane oligomer obtained by the molecular weight measurement and the content of the urethane addition compound are high-speed liquid chromatography ("LC-10A" manufactured by Shimadzu Corporation). Column: Shodex GPC KF-806L (exclude limit molecular weight: 2×10 ⁷ , separation range: 100~2×10 ⁷ , theoretical layer number: 10,000 layers/piece, filler material: styrene-divinylbenzene copolymer The particle size of the substance and filler: 10 μm, the dissolved liquid tetrahydrofuran) is measured and calculated according to the molecular weight conversion of standard polystyrene. (2) The viscosity measurement uses a cone-plate type viscometer (device name: RE550 type viscometer Toki Industries Co., Ltd.) Co., Ltd.), according to JIS K5600-2-3, the viscosity of the urethane oligomer obtained in each synthesis example and comparative synthesis example was measured at 60°C.

Synthesis Example 1 Synthesis of urethane oligomer UT-1 In a 500 mL 4-neck flask equipped with a stirrer, thermometer, cooler and dry gas introduction tube, 16.2 g of isophorone diisocyanate (IPDI) was charged (73.1mmol), after 0.1g of dibutyltin dilaurate, while introducing dry nitrogen, UT-1001 (acrylic polymer, manufactured by ZK Chemicals Co., Ltd., number average molecular weight: 3500) was added dropwise while adjusting the drop rate. 189.0g (62.8 mmol), maintaining the temperature at 80°C, and reacting at 80°C for 3 hours. Then, after cooling the reaction liquid to 40°C, 0.2 g of methylhydroquinone (MHQ) was added, and dry air was bubbled for 10 minutes. Then, 5.42 g (45.6 mmol) of hydroxyethyl methacrylamide (HEMAA) was added, and stirring was continued for 5 hours while maintaining the temperature in the system at 80°C under a stream of dry air. 188.16g of UT-1 light yellow viscous liquid was obtained with a yield of 96.5%. Infrared absorption spectrum (IR), and detects the specific absorption of the isocyanate group raw material of IPDI (2250cm ^-1) disappeared completely, and detecting the specific absorption of the acyl group from the "HEAA" of (1650cm ^-1) and generating The specific absorption of the urethane bond (1740 cm ^-1 ) confirms that the target urethane oligomer UT-1 has been produced. The obtained urethane oligomer UT-1 has a number average molecular weight of 11,600, a viscosity at 60°C of 25,100 mPa·s, and a low molecular weight component of 1.5%.

Synthesis Example 2 Synthesis of urethane oligomer UT-2 The same equipment as Synthesis Example 1 was used, after 11.4g (67.8mmol) of hexamethylene diisocyanate (HDI) and 0.06g of dibutyltin dilaurate were charged ，Dry nitrogen gas was added, while dropping speed was adjusted, UNIOL D-2000 (polypropylene glycol, manufactured by NOF Corporation, number average molecular weight: 2000) 100.0g (50.0mmol) was maintained to maintain the temperature at 70℃ and react at 70℃ 4 hours. Then, after cooling the reaction liquid to 40° C., 0.06 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 1.88 g (16.4 mmol) of HEAA and 0.52 g (16.4 mmol) of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and stirring was continued for 3 hours while maintaining the temperature in the system at 80° C. under a stream of dry air. 111.80g of UT-2 light yellow viscous liquid was obtained with a yield of 98.2%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-2 had been produced. The obtained urethane oligomer UT-2 has a number average molecular weight of 6,800, a viscosity at 60°C of 12,000 mPa·s, and a low molecular weight component of 0.4%.

Synthesis Example 3 Synthesis of urethane oligomer UT-3 The same equipment as Synthesis Example 1 was used, and PTMG2000 (polytetramethylene glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2000) was loaded 10.0g ( 5.00mmol), UNIOL D-2000 90.0g (45.0mmol), 0.06g of dibutyltin dilaurate, while adding dry nitrogen while adjusting the drop rate and adding dicyclohexylmethane 4,4' diisocyanate (hydrogenated MDI) 14.8 g (58.0 mmol) was maintained at 90°C, and the reaction was carried out at 90°C for 2 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then 3.20 g (27.8 mmol) of HEAA was added, and stirring was continued for 3 hours under the flow of dry air while maintaining the temperature in the system at 90°C. 112.00 g of light yellow viscous liquid of UT-3 was obtained with a yield of 96.8%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UT-3 had been produced. The obtained urethane oligomer UT-3 has a number average molecular weight of 18,500, a viscosity at 60°C of 25,600 mPa·s, and a low molecular weight component of 0.7%.

Synthesis Example 4: Synthesis of urethane oligomer UT-4 The same equipment as Synthesis Example 1 was used, and UNIOLD-3000 (polypropylene glycol, manufactured by NOF Corporation, number average molecular weight: 3000) 150.0g (50.0 mmol) was used with AdekaEDP-300 (polyether polyol, manufactured by ADEKA Corporation, number average molecular weight: 300) 1.88 g (6.25 mmol) was dissolved in 200 g of dehydrated acetone and stirred for 30 minutes. Then, 16.8 g (75.8 mmol) of IPDI was added and stirred for another 30 minutes. Under a stream of dry air, after the temperature of the reaction liquid was raised to 65°C, 0.08 g of dibutyltin dilaurate and 0.2 g of MHQ were added, and the reaction was carried out for 2 hours. Then, 4.88 g (37.8 mmol) of N-methylhydroxyethylacrylamide (MHEAA) was added, and stirring was continued for 3 hours while maintaining the temperature in the system at 60°C under a stream of dry air. After that, acetone was removed by vacuum drying to obtain 166.36g of UT-4 as a transparent and viscous liquid with a yield of 97.0%. IR analysis was carried out in the same manner as in Synthesis Example 1, and it was confirmed that the intended urethane oligomer UT-4 had been produced. The number average molecular weight of the obtained urethane oligomer UT-4 was 27,000, the viscosity at 60°C was 40,000 mPa·s, and the low molecular weight component contained was 0.2%.

Synthesis Example 5: Synthesis of urethane oligomer UT-5 The same equipment as Synthesis Example 1 was used, and KF-6001 (polysiloxane polyol, manufactured by Shin-Etsu Chemical Industry Co., Ltd., number average molecular weight: 1700) 85.0g (50.0 mmol) and 0.05 g of dibutyltin dilaurate were added with 12.5 g (56.5 mmol) of IPDI while maintaining a temperature of 80°C while passing dry nitrogen gas, and then reacted at 80°C for 4 hours. Then, in the same manner as in Synthesis Example 1, 0.2 g of MHQ and 1.50 g (12.7 mmol) of "HEAA" were charged, and stirring was continued at 80°C for 3 hours. 96.10g of UT-5 light yellow viscous liquid was obtained with a yield of 96.8%. Use IR analysis to confirm that UT-5 has been generated. The weight average molecular weight of UT-5 obtained was 15,600, the viscosity at 60°C was 47,500 mPa·s, and the low molecular weight component contained was 0.4%.

Synthesis Example 6 Synthesis of urethane oligomer UT-6 The same equipment as Synthesis Example 1 was used, and it was charged into AdekaNewAceY6-30 (manufactured by polyester diol Asahi Kasei Chemical Co., Ltd., number average molecular weight: 3000) 60.0g (20.0mmol), UNIOL D-1000 30.0g (30.0mmol), dibutyltin dilaurate 0.05g, while adding dry nitrogen, while adjusting the drop rate, add HDI 9.10g (54.0mmol) dropwise to maintain the temperature at React at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, "HEAA" 0.50g (4.30mmol) was fed, and stirring was continued for 5 hours under the flow of dry air while maintaining the temperature in the system at 60°C. 97.30 g of light yellow viscous liquid of UT-6 was obtained with a yield of 97.3%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-6 had been produced. The obtained urethane oligomer UT-6 has a number average molecular weight of 46,000, a viscosity at 60°C of 93,000 mPa·s, and a low molecular weight component of 0.3%.

Synthesis Example 7 Synthesis of urethane oligomer UT-7 The same equipment as Synthesis Example 1 was used and charged with SONGSTAR (tm) SS-2077 (polyester polyol manufactured by SONGWON Corporation, number average molecular weight 1850-2350) 60.0 g (30.0mmol), UNIOL D-1000 20.0g (20.0mmol), dibutyltin dilaurate 0.06g, while adding dry nitrogen, while adjusting the drop rate, add HDI 9.70g (54.0mmol) dropwise to maintain the temperature The reaction was carried out at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 2.19g (17.0mmol) of "HEAA" was fed, and stirring was continued for 5 hours while maintaining the temperature in the system at 60°C under the flow of dry air. 87.90g of UT-7 light yellow viscous liquid was obtained with a yield of 96.3%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UT-7 had been produced. The obtained urethane oligomer UT-7 has a number average molecular weight of 21,400, a viscosity at 60°C of 90,000 mPa·s, and a low molecular weight component of 0.2%.

Synthesis Example 8 Synthesis of urethane oligomer UT-8 In a 500 mL 4-neck flask equipped with a stirrer, thermometer, cooler and dry gas introduction tube, filled with trimethylhexamethylene diisocyanate (TMDI ) After 14.0g (66.5mmol) and 0.06g of dibutyltin dilaurate, P-2012 (polyester polyol, manufactured by Kuraray Co., Ltd., number average molecular weight: 2000) is added dropwise while adjusting the dripping rate while passing dry nitrogen gas 80.0 g (40.0 mmol), P-1010 (polyester polyol, manufactured by Curaray, number average molecular weight: 1000) 10.0 g (10 mmol), the temperature was maintained at 80°C, and the reaction was carried out at 80°C for 3 hours. After cooling the reaction solution to 40°C, 0.2 g of methylhydroquinone (MHQ) was added, and dry air was bubbled for 10 minutes. Then, 7.46 g (57.9 mmol) of hydroxyethyl acrylamide (HEAA) was fed, and stirring was continued for 5 hours under the flow of dry air while maintaining the temperature in the system at 80°C. 107.5g of UT-8 light yellow viscous liquid was obtained with a yield of 96.5%. Using infrared absorption spectroscopy (IR) analysis, it was detected that the specific absorption of the isocyanate group of the raw material IPDI (2250cm-1) completely disappeared, and the specific absorption (1650cm-1) of the amide group from "HEAA" was detected and the resulting The unique absorption of the urethane bond (1740 cm-1) confirms that the desired urethane oligomer UT-8 has been produced. The obtained urethane oligomer UT-8 has a number average molecular weight of 6,240, a viscosity at 60°C of 267,000 mPa·s, and a low molecular weight component of 0.1%.

Synthesis Example 9 Synthesis of urethane oligomer UT-9 The same equipment as Synthesis Example 1 was used, and P-2010 (polyester polyol, manufactured by Kuraray Co., Ltd., number average molecular weight: 2000) was used 70.0g ( 35.0mmol), KF6001 (polysilicone polyol, manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 1700) 27.0g (15.0mmol), 0.06g of dibutyltin dilaurate, while passing dry nitrogen gas, while adjusting the drop acceleration While dropping 11.8 g (56.3 mmol) of TMDI while maintaining the temperature at 80°C, the reaction was carried out at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 2.17g (16.78mmol) of "HEAA" was fed, and stirring was continued for 5 hours while maintaining the temperature in the system at 60°C under the flow of dry air. 107.90g of UT-9 light yellow viscous liquid was obtained with a yield of 97.2%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-9 had been produced. The obtained urethane oligomer UT-9 has a number average molecular weight of 17,410, a viscosity at 60°C of 150,000 mPa·s, and a low molecular weight component of 0.1%.

Synthesis Example 10 Synthesis of urethane oligomer UT-10 The same equipment as Synthesis Example 1 was used, and P-2010 (polyester polyol, manufactured by Kuraray Co., Ltd., number average molecular weight: 2000) was used 50.0g ( 25.0mmol), UT-1001 (acrylic polymer, manufactured by Zheyan Chemical Co., Ltd., number average molecular weight: 3500) 87.5g (25.0mmol), 0.06g of dibutyltin dilaurate, while passing dry nitrogen gas, while adjusting the dripping acceleration 14.8 g (66.5 mmol) of isophorone diisocyanate (IPDI) was added dropwise, the temperature was maintained at 80°C, and the reaction was carried out at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 5.98g (46.4mmol) of "HEAA" was fed, and stirring was continued for 5 hours while maintaining the temperature in the system at 60°C under a stream of dry air. 155.10g of UT-10 light yellow viscous liquid was obtained with a yield of 98.0%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UT-10 was produced. The obtained urethane oligomer UT-10 has a number average molecular weight of 9,100, a viscosity at 60°C of 70,000 mPa·s, and a low molecular weight component of 0.2%.

Synthesis Example 11 Synthesis of urethane oligomer UT-11 The same equipment as Synthesis Example 1 was used, and P-2012 (polyester polyol, manufactured by Curaray, number average molecular weight: 2000) 90.0g (45.0 mmol), UNIOLD-1000 (polypropylene glycol, manufactured by NOF Corporation, number average molecular weight: 1000) 0.4g (4.0mmol), KF-6001 0.1g (0.18mmol), and AdekaEDP-300 (polyether polyol, ADEKA company) System, number average molecular weight: 300) 0.97g (3.22mmol) was dissolved in 200g of dehydrated acetone and stirred for 30 minutes. Then 16.1 g (72.5 mmol) of IPDI was added and stirred for another 30 minutes. Under a stream of dry air, the temperature of the reaction liquid was raised to 65°C, and then 0.08 g of dibutyltin dilaurate and 0.2 g of MHQ were fed to carry out the reaction for 2 hours. Then, 2.75 g (23.9 mmol) of "HEAA" was fed, and stirring was continued for 3 hours while maintaining the temperature in the system at 60°C under the flow of dry air. Afterwards, the acetone was removed by vacuum drying to obtain 105.10g of UT-11 transparent colored viscous liquid with a yield of 96.1%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-11 had been produced. The obtained urethane oligomer UT-11 has a number average molecular weight of 36,700, a viscosity at 60°C of 475,000 mPa·s, and a low molecular weight component of 0.2%.

Synthesis Example 12: Synthesis of urethane oligomer UT-12 The same equipment as Synthesis Example 1 was used, 20.0g (50.0mmol) of Adeka polyether P-400 was charged, and 0.02g of dibutyltin dilaurate was introduced Dry nitrogen gas and add 24.6g (60.0mmol) of Desmodur XP2580 (polyisocyanate containing urea formate group, manufactured by Sumitomo Bayer Polyurethane Co.) while adjusting the dripping rate, maintain the temperature at 80℃, and react at 80℃ for 4 hours . After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, "HEAA" 1.06g (9.21mmol) was fed, and stirring was continued for 5 hours while maintaining the temperature in the system at 60°C under a stream of dry air. 28.25g of UT-12 light yellow viscous liquid was obtained with a yield of 98.2%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UT-12 had been produced. The obtained urethane oligomer UT-12 has a number average molecular weight of 4,690, a viscosity of 15,000 mPa·s at 60°C, and a low molecular weight component of 0.5%.

Synthesis Example 13 Synthesis of urethane oligomer UT-13 The same equipment as Synthesis Example 1 was used, and PEG-200 (polyethylene glycol, manufactured by ADEKA Corporation, number average molecular weight: 200) 10.0 g (45.0 mmol) 1. With AdekaEDP-300 (polyether polyol, manufactured by ADEKA Corporation, number average molecular weight: 300) 1.88g (6.25mmol) was dissolved in 200g of dehydrated acetone and stirred for 30 minutes. Then, 24.6 g (60.0 mmol) of Desmodur XP2580 (polyisocyanate containing urethane group, manufactured by Sumitomo Bayer Polyurethanes Co., Ltd.) was added, and the mixture was stirred for 30 minutes. After the temperature of the reaction liquid was raised to 65°C under the flow of dry air, 0.08 g of dibutyltin dilaurate and 0.2 g of MHQ were fed to carry out the reaction for 2 hours. Then, 1.27g (13.0mmol) of "HEAA" was fed, and stirring was continued for 3 hours while maintaining the temperature in the system at 60°C under the flow of dry air. Afterwards, the acetone was removed by reduced-pressure drying treatment to obtain 23.60 g of UT-13 as a transparent and viscous liquid with a yield of 97.9%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-13 had been produced. The obtained urethane oligomer UT-13 has a number average molecular weight of 7,300, a viscosity at 60°C of 20,000 mPa·s, and a low molecular weight component of 0.8%.

Synthesis Example 14 Synthesis of urethane oligomer UT-14 The same equipment as Synthesis Example 1 was used, and ETERNACOLL UC-100 (polyester polyol, manufactured by Kuraray Corporation, number average molecular weight: 1000) was added 25.0g ( 25.0mmol), UNIOLD-1000 25.0g (25.0mmol), dibutyltin dilaurate 0.03g, while adding dry nitrogen, while adjusting the drop rate, add IPDI 13.9g (62.5mmol) dropwise to maintain the temperature at 80℃ And react at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 1.53 g (13.3 mmol) of "HEAA" was fed, and stirring was continued for 5 hours while maintaining the temperature in the system at 60°C under a stream of dry air. 58.70g of UT-14 light yellow viscous liquid was obtained with a yield of 98.6%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UT-14 had been produced. The obtained urethane oligomer UT-14 has a number average molecular weight of 5,300, a viscosity at 60°C of 230,00 mPa·s, and a low molecular weight component of 0.1%.

Synthesis Example 15 Synthesis of urethane oligomer UT-15 The same equipment as Synthesis Example 1 was used, and ETERNACOLL UHC-50-200 (polyester polyol, manufactured by Kuraray Corporation, number average molecular weight: 2000) was used After 50.0g (25.0mmol), Curaray Polyol P-1010 25.0g (25.0mmol) and dibutyltin dilaurate 0.04g, while adding dry nitrogen, add IPDI 13.0g (58.3mmol) ), maintaining the temperature at 80°C, and reacting at 80°C for 4 hours. After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 1.97 g (17.2 mmol) of "HEAA" was fed, and stirring was continued for 5 hours under the flow of dry air while maintaining the temperature in the system at 60°C. 80.60g of UT-15 light yellow viscous liquid was obtained with a yield of 96.3%. As in Synthesis Example 1, IR analysis confirmed that the intended urethane oligomer UT-15 had been produced. The obtained urethane oligomer UT-15 has a number average molecular weight of 10,800, a viscosity of 36,000 mPa·s at 60°C, and a low molecular weight component of 0.1%.

Synthesis Example 16 Synthesis of urethane oligomer UT-16 Using the same equipment as Synthesis Example 1, P-1010 (polyester polyol, manufactured by Curaray, number average molecular weight: 1000) 50.0 g (50 mmol ) Dissolve in 200g of dehydrated acetone and stir for 30 minutes. Then, 11.1 g (16.7 mmol) of VESTANATT 1890 (trimer of isophorone diisocyanate, manufactured by Evonik Degussa) was added. After the temperature of the reaction liquid was raised to 65°C, 0.03 g of dibutyltin dilaurate and 0.2 g of MHQ were added, and the reaction was carried out for 3 hours. Then, 13.7 g (61.6 mmol) of IPDI was added, and the reaction was further performed for 3 hours. After that, 6.87g (51.5mmol) of "HEAA" was fed, and stirring was continued for 3 hours under the flow of dry air, keeping the temperature in the system at 65°C. Afterwards, the acetone was removed by a reduced-pressure treatment operation to obtain 65.0 g of UT-16 transparent color viscous liquid with a yield of 95.7%. As in Synthesis Example 1, it was confirmed by IR analysis that urethane oligomer had been produced. The low-molecular-weight component contained in the measurement was 8.0%, so it was further purified. The obtained urethane oligomer was reprecipitated using a mixed solution of MEK and water to remove low molecular weight components. MEK and water were completely removed under reduced pressure to obtain ethyl urethane oligomer UT-16 as a light yellow viscous liquid. The evaluation was carried out by the above method. The weight average molecular weight of UT-16 was 5,200, the viscosity at 60°C was 8,000 mPa·s, and the content of the urethane addition compound was 0.9%.

Comparative Synthesis Example 1 Synthesis of urethane oligomer (UA-1) The unrefined ethyl urethane oligomer (containing 8.0% of low molecular weight component) obtained in Synthesis Example 16 was named UA-1. In addition, the evaluation by the above method revealed that the weight average molecular weight of UA-1 was 5,000, and the viscosity at 60°C was 9,000 mPa·s.

Comparative Synthesis Example 2 Synthesis of urethane oligomer (UA-2) Using the same apparatus as Synthesis Example 1, P-1010 50.0 g (50.0 mmol) was dissolved in 200 g of dehydrated acetone and stirred for 30 minutes. Then, 11.1 g (16.7 mmol) of Coronate HX (polyisocyanate manufactured by Tosoh Corporation) was added. After the temperature of the reaction liquid was raised to 65°C, 0.03 g of dibutyltin dilaurate and 0.2 g of MHQ were charged, and the reaction was carried out for 3 hours. Then, 8.81 g (50.6 mmol) of TDI was added, and the reaction was further performed for 3 hours. Thereafter, 4.31 g (37.2 mmol) of ethyl hydroxyacrylate (HEA) was added, and stirring was continued for 3 hours while maintaining the internal temperature of the system at 65°C under a stream of dry air. After removing the acetone, 60.40g of UA-2 transparent colored and viscous liquid was obtained with a yield of 95.9%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UA-2 had been produced. The obtained urethane oligomer UA-2 has a number average molecular weight of 4,900, a viscosity at 60°C of 6,000 mPa·s, and a low molecular weight component of 0.3%.

Comparative Example Synthesis 3 　Urethane oligomer (UA-3) was synthesized using the same equipment as in Synthesis Example 1 and fed with P-2012 (polyester polyol, manufactured by Curaray, number average molecular weight: 2000) After 50.0 g (50.0 mmol) and 0.04 g of dibutyltin dilaurate, dry nitrogen was introduced, and IPDI 12.0 g (54.1 mmol) was added dropwise while adjusting the dripping rate to maintain the temperature at 80° C. for 6 hours at 80° C. . After cooling the reaction liquid to 40°C, 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 2.17 g (18.74 mmol) of HEA was fed, and stirring was continued for 8 hours while maintaining the temperature in the system at 60°C under the flow of dry air. 113.7 g of light yellow viscous liquid was obtained with a yield of 97.9%. As in Synthesis Example 1, it was confirmed by IR analysis that urethane oligomer had been produced. The number average molecular weight of the obtained urethane oligomer UA-3 was 57,000, the viscosity at 60°C was 450,000 mPa·s, and the contained low molecular weight component was 0.8%.

Comparative Synthesis Example 4 Synthesis of urethane oligomer UA-4 The same equipment as Synthesis Example 1 was used. Dipropylene glycol (manufactured by Nacalaitesque, number average molecular weight: 134) 6.7 g (50.0 mmol) and AdekaEDP-300 (Polyether polyol, manufactured by ADEKA Corporation, number average molecular weight: 300) 15.0 g (50.0 mmol) was dissolved in 100 g of dehydrated acetone, and stirred for 30 minutes. Then, 19.1 g (110.0 mmol) of toluene diisocyanate (TDI) was added and stirred for another 30 minutes. Under a stream of dry air, the temperature of the reaction liquid was raised to 65°C, and then 0.02 g of dibutyltin dilaurate and 0.2 g of MHQ were fed to carry out the reaction for 2 hours. Then, 25.2 g (217.0 mmol) of HEA was fed, and stirring was continued for 3 hours while maintaining the temperature in the system at 60°C under the flow of dry air. After that, the acetone was removed by vacuum drying, and 47.1g of UA-4 was obtained as a transparent and viscous liquid with a yield of 96.5%. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane oligomer UA-4 had been produced. The obtained urethane oligomer UA-4 has a number average molecular weight of 2,700, a viscosity at 60°C of 20,000 mPa·s, and a low molecular weight component of 8.2%.

啉(KJ Chemicals(股)製) HDDA：二丙烯酸1,6-己烷二醇酯 BA：丙烯酸丁酯 IBOA：丙烯酸異莰酯 2EHA；丙烯酸2-乙基己酯 THFA；丙烯酸四氫呋喃甲酯The properties of the urethane oligomers obtained in Synthesis Examples 1 to 16 and Comparative Synthesis Examples 1 to 4 were evaluated according to the following methods. The results are shown in Table 1. The solvents and monomers used for evaluation are as follows. IPA: isopropanol MEK: methyl ethyl ketone THF: tetrahydrofuran "ACMO": N-propenyl

Phospholine (manufactured by KJ Chemicals Co., Ltd.) HDDA: 1,6-hexanediol diacrylate BA: butyl acrylate IBOA: isobornyl acrylate 2EHA; 2-ethylhexyl acrylate THFA; tetrahydrofuran acrylate

(4) Compatibility To 1 part by weight of the obtained urethane oligomer is added 1 part by weight of a general-purpose solvent and acrylic monomer as a diluent, and after stirring, it is left to stand overnight for visual confirmation The degree of dissolution. ◎: The transparency is high, and white turbidity and separation are not confirmed at all. ○: The transparency is high, but white turbidity is slightly observed. △: No layer separation but white turbidity. ╳: White turbidity and layer separation

[Table 1]

As shown in the results in Table 1, if the (meth)acrylamide-based urethane oligomer contains urethane adducts and other low-molecular-weight components exceeding 5 wt%, then it is a general-purpose solvent 2. The compatibility of the monomer is significantly deteriorated, and it is not easy to be widely used as an optical component.

An active energy ray-curable resin composition was prepared using the urethane oligomer obtained in Synthesis Example and Comparative Synthesis Example. Then, using these resin compositions, production of an ultraviolet-cured film and evaluation of the characteristics of the cured film were performed. The results are shown in Table 2.

Example A-1 100 parts by weight of (meth)acrylamide urethane oligomer UT-1 obtained in Synthesis Example 1, 100 parts by weight of methyl ethyl ketone (MEK), and 3 parts by weight were used as photopolymerizations The initiator Irgacure 1173 was uniformly mixed to prepare an active energy ray-curable resin composition. After that, using the obtained curable resin composition, an ultraviolet-cured film was produced according to the following method.

The manufacturing method of the UV-cured film is coated on a polyethylene terephthalate (PET) film with a thickness of 100 μm by a coating rod (RDS 12) (“Cosmoshine A4100” manufactured by Toyobo Co., Ltd., with one-sided adhesion coating) To increase the thickness of the coated surface, make a coating film so that the thickness of the dry coating film becomes 10 μm. The obtained coating film was dried in an explosion-proof dryer at 80° C. for 2 minutes, and then cured by ultraviolet irradiation (device: ECS-4011GX, frequency conversion conveyor device made by Eyegraphics, metal halide lamp: M04-L41 made by Eyegraphics), Production of ultraviolet curing film. The curability of the resin composition, the tack resistance of the obtained cured film, shrinkage resistance (curing shrinkage rate), transparency, water absorption, adhesion, strength, and elongation were evaluated, and the results are shown in Table 2.

(5) The hardenability is the same as described above, and a dry coating film with a thickness of 10 μm is prepared, irradiated with ultraviolet light of 2 mW/cm ² for 120 seconds (cumulative light amount 240 mJ/cm ² ), and the vinyl-derived resin composition is measured by real-time FT-IR Peak (1630cm ^-1 ) height, calculate the curing rate of the coating film (curing rate (%) = (height of peak from vinyl before curing-peak height from vinyl after curing) / height from peak before curing Peak height of vinyl × 100). ◎: Hardening rate 90% or more ○: Hardening rate 80% or less but not 90% △: Hardening rate 50% or more but not 80% ╳: Hardening rate 50% or less (6) Tack resistance The thickness is 10 μm in the same way as above The dried coating film was irradiated with ultraviolet light having an illuminance of 700 mW/cm ² for 3 seconds (cumulative light amount 2100 mJ/cm ² ) to produce a completely cured coating film (completely cured film). Touch the surface of the completely hardened film with your fingers and evaluate the degree of adhesiveness. ◎: No stickiness at all. ○: There is some adhesiveness, but no fingerprint remains on the surface. △: There is adhesiveness and fingerprints remain on the surface. ╳: The adhesiveness is serious, and the finger sticks to the surface. (7) Shrinkage resistance (hardening shrinkage rate) The curing shrinkage rate is measured using a laser hardening shrinkage measuring device CUSTRON EU201C (manufactured by Acroedge) with a laser displacement meter, and the hardening shrinkage is calculated according to the method described in Japanese Patent Laid-Open No. 2013-104869 rate. ◎: Shrinkage resistance less than 2.0% ○: Shrinkage resistance more than 2.0% and less than 4.0% △: Shrinkage resistance more than 4.0% and less than 5.0% ╳: Shrinkage resistance more than 5.0% (8) Transparency (Visual inspection) Using the completely cured coating film obtained in (6) above, the transparency was visually observed and evaluated. ◎: Transparent and completely without matting. ○: Transparent and slightly extinct. △: There is matting but there is also a transparent part. ╳: Extremely extinct, the transparent part cannot be confirmed. (9) The water absorption rate was poured into a Teflon sheet hollowed out to a depth of 1 mm, and the curable resin composition was dried in vacuum (50°C, 400 torr), and then irradiated with ultraviolet rays (700 mW/cm ² , 2000 mJ/cm ² ) Harden and produce UV-cured sheets. The obtained piece was cut into 3 cm squares and used as a test piece. The obtained test piece was allowed to stand in an environment with a temperature of 50°C and a relative humidity of 95% for 24 hours, and its water absorption rate was calculated according to Equation 1. [Equation 1] (Water absorption rate (%) = (weight after constant temperature and humidity-weight before constant temperature and humidity) / weight before constant temperature and humidity × 100) (10) Adhesiveness is completely obtained by using (6) above For the cured coating film, 100 square eyes of 1 mm square were produced in accordance with JIS K 5600, a transparent tape was attached, and the number of square eyes with a coating film remaining on the substrate side was peeled off and evaluated. (11) Breaking strength and breaking elongation Using the fully cured coating film obtained in (6) above, it was measured in a gas environment at a temperature of 25°C and a relative humidity of 50% in accordance with JIS K 7127. Measuring equipment; Tensilon universal material testing machine RTA-100 (manufactured by Orientec) Test conditions; test speed 10mm/min test piece size; distance between marking lines 25mm, width 15mm, thickness 50μm

Examples A-2 to 16 and Comparative Examples A-17 to 20 were replaced with the compositions described in Table 2, except that the ultraviolet curable resin composition was prepared and a cured film was prepared in the same manner as in Example A-1, according to the above method Make an evaluation.结果如表2。 The results are shown in Table 2.

[Table 2]

According to the results of the evaluation examples and comparative examples, the (meth)acrylamide-based ethyl urethane oligomer having a content of low molecular weight component compounds such as ethyl urethane adducts exceeding 5 wt% was obtained The hardened product has poor shrinkage resistance, water absorption, and poor transparency. The present inventors believe that because the low-molecular-weight component is a high-polarity component and the low-molecular-weight component is contained, the polarity of the urethane oligomer will also increase as a whole, and the water absorption rate will decrease. Moreover, the solubility of the low molecular weight component is low, and the resulting coating film has poor transparency and shrinkage resistance. In addition, the polyfunctional (meth)acrylamide-based urethane oligomer has a curing shrinkage rate of less than 5%, but the multifunctional (meth)acrylate-based urethane oligomer, The curing shrinkage rate is more than 5%, and the shrinkage resistance is poor. Presumably because of the cohesive force of the acrylamide groups (hydrogen bonds formed between the amide groups, the amide groups and the ethylcarbamate groups), even before UV curing, the molecules are closely aligned with each other to ease hardening Cause it to shrink. Moreover, even if the content of the low-molecular-weight component exceeds 5% by weight, satisfactory hardenability and tack resistance cannot be obtained like the (meth)acrylamide system. The (meth)acrylamide urethane oligomer system of the present invention has satisfactory shrinkage resistance, and the curable resin composition has excellent curability, tack resistance, transparency, and water resistance. The adhesion between the untreated PET surface and PMMA has also been improved.

啉(KJ Chemicals(股)製) 「DMAPAA」；二甲胺基丙基丙烯醯胺(KJ Chemicals(股)製) HEA；羥基丙烯酸乙酯 2EHA；丙烯酸2-乙基己酯 EEA；丙烯酸2-(2-乙氧基乙氧基)乙酯 THFA；丙烯酸四氫呋喃甲酯 IBOA；丙烯酸異莰酯 IBMA；甲基丙烯酸異莰酯 CHA；丙烯酸環己酯 HDDA；二丙烯酸1,6-己烷二醇酯 TPGDA；二丙烯酸三丙二醇酯 PETA；三丙烯酸新戊四醇酯 DPHA；六丙烯酸二新戊四醇酯 4HBA：丙烯酸4-羥基丁酯 TMPTA：三羥甲基丙烷三丙烯酸酯 DMAEA-TFSIQ；丙烯醯氧基乙基三甲基銨雙(三氟甲烷磺醯基)醯亞胺(KJ Chemicals(股)製) DMAPAA-TFSIQ；丙烯醯基胺基丙基三甲基銨雙(三氟甲烷磺醯基)醯亞胺(KJ Chemicals(股)製) UV7600B：紫外線硬化型胺基甲酸乙酯丙烯酸酯樹脂(日本合成化學工業(股)公司) A-LEN-10；乙氧基化鄰苯基苯酚丙烯酸酯(新中村化學工業(股)製) CHMA：甲基丙烯酸環己酯 Light Acrylate PE-4A：四丙烯酸新戊四醇酯 二氧化矽微粒：商品名 IPA-ST-L(日產化學工業(股)公司製)固體成30% IBMA：N-異丁氧基甲基丙烯醯胺 Irgacure 184；1-羥基-環己基-苯基-酮(BASF Japan 製) 8019add：東麗道康寧(股)製聚矽氧系表面改質劑 Irgacure 1173；2-羥基-2-甲基-1-苯基-丙烷-1-酮(BASF Japan 製) UV3700B：胺基甲酸乙酯丙烯酸酯樹脂(日本合成化學工業公司製) UV4200B：胺基甲酸乙酯丙烯酸酯樹脂(日本合成化學工業公司製) Irgacure TPO；2,4,6-三甲基苯甲醯基-二苯基-氧化膦(BASF Japan 製)Evaluation of the characteristics of the urethane oligomers obtained in Synthesis Examples 1 to 16 and Comparative Synthesis Examples 1 to 4 in various application fields. The materials used in Examples and Comparative Examples are as follows. "HEAA"; hydroxyethylacrylamide (manufactured by KJ Chemicals) "DMAA"; N,N-dimethylacrylamide (manufactured by KJ Chemicals) "DEAA"; N,N-diethyl Acryloylamide (manufactured by KJ Chemicals Co., Ltd.) "ACMO"; N-acryloylamide

Porphyrin (manufactured by KJ Chemicals) "DMAPAA"; dimethylaminopropyl acrylamide (manufactured by KJ Chemicals) HEA; ethyl hydroxyacrylate 2EHA; 2-ethylhexyl acrylate EEA; acrylic 2- (2-ethoxyethoxy) ethyl ester THFA; tetrahydrofuran methyl acrylate IBOA; isobornyl acrylate IBMA; isobornyl methacrylate CHA; cyclohexyl acrylate HDDA; 1,6-hexanediol diacrylate Ester TPGDA; Tripropylene glycol diacrylate PETA; Neopentaerythritol triacrylate DPHA; Dipentaerythritol hexaacrylate 4HBA: 4-Hydroxybutyl acrylate TMPTA: Trimethylolpropane triacrylate DMAEA-TFSIQ; Propylene Acetyloxyethyltrimethylammonium bis(trifluoromethanesulfonyl) amide imide (manufactured by KJ Chemicals Co., Ltd.) DMAPAA-TFSIQ; propylene amide aminopropyl trimethylammonium bis(trifluoromethanesulfonate Acyl) amide imine (manufactured by KJ Chemicals) UV7600B: UV-curable urethane acrylate resin (Japan Synthetic Chemical Industry Co., Ltd.) A-LEN-10; ethoxylated o-phenyl Phenol acrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) CHMA: cyclohexyl methacrylate Light Acrylate PE-4A: neopentyl tetraacrylate tetraacrylate silica particles: trade name IPA-ST-L (Nissan Chemical Industries (Made by a company) 30% solids IBMA: N-isobutoxymethacrylamide Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan) 8019add: Toray Dow Corning (share) Polysilicone surface modifier Irgacure 1173; 2-hydroxy-2-methyl-1-phenyl-propane-1-one (manufactured by BASF Japan) UV3700B: urethane acrylate resin (Japan Synthetic Chemicals) Industrial Co., Ltd.) UV4200B: Urethane acrylate resin (manufactured by Japan Synthetic Chemical Industry Corporation) Irgacure TPO; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (manufactured by BASF Japan)

Evaluation Example B-1 (meth)acrylamide-based urethane oligomer UT-1 synthesized in Synthesis Example 1 25 parts by weight, "HEAA" 10 parts by weight, 2EHA 40 parts by weight, CHA 9 parts by weight Parts, 15 parts by weight of EEA, 1 part by weight of DMAEA-TFSIQ as an ionic vinyl monomer, add 3 parts by weight of Irgacure 184 as a photopolymerization initiator, uniformly mix and prepare an ultraviolet curing adhesive . After that, using the obtained adhesive, the preparation and evaluation of the adhesive sheet by ultraviolet curing were performed according to the following method.

Method for manufacturing ultraviolet-curable adhesive sheet The ultraviolet-curable adhesive prepared above is coated on a heavy peeling separator (polysilicone coated PET film) to lightly peel the separator (polysilicone coated PET film) ) Use a desktop roll laminator (RSL-382S made by Royal Sovereign) to stick the adhesive layer so that the thickness is 25 μm, and irradiate ultraviolet rays (device: frequency conversion conveyor belt device ECS-4011GX made by Eyegraphics) , Metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , cumulative light amount: 1000mJ/cm ² ), made into transparent adhesive sheet for optics. The characteristics of the obtained adhesive sheet were evaluated according to the following methods, and the results are shown in Table 3.

(12) Transparency (transmittance) At a temperature of 23°C and a relative humidity of 50%, the peeled surface of the light peeling separator cut into 25mm wide adhesive sheets is attached to the glass substrate to be adhered , And then peel off the separator again, and measure the transmittance. Measurement using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000), according to JIS K 7105, after measuring the total light transmittance of the glass substrate, deduct the transmittance of the glass plate, and calculate the transmittance of the adhesive layer itself And evaluate the transparency in the form of numbers. The higher the transmittance, the better the transparency. (13) The surface resistivity is measured using a template (110 mm long x 110 mm wide), and the adhesive sheet is cut with a cutting knife, the peeled surface of the light peeling separator is attached to the glass substrate as the adherend, and put into adjustment A constant temperature and humidity machine with a temperature of 23° C. and a relative humidity of 50% was allowed to stand for 3 hours to obtain a sample for surface resistivity measurement. According to JIS K 6911, the measurement was performed using a digital electrometer (R8252 type: manufactured by ADC Corporation). (14) Adhesion is transferred to polyethylene terephthalate (PET) film (thickness 100μm) or glass substrate as adherend under the condition of temperature 23℃ and relative humidity 50%, using a weight of 2kg The pressure roller is pressed back and forth twice and placed in the same gas environment for 30 minutes. Thereafter, using a tensile tester (device name: Tensilon RTA-100 manufactured by ORIENTEC), a 180° peel strength (N/25 mm) was measured at a peel speed of 300 mm/min. ◎: 30 (N/25mm) or more ○: 15 (N/25mm) or more but less than 30 (N/25mm) △: 8 (N/25mm) or more but less than 15 (N/25mm) ╳: less than 8 (N /25mm) (15) Contamination resistance The adhesive sheet is attached to the adherend in the same way as the previous measurement of the adhesive force, and after being left at 80°C for 24 hours, the surface of the adherend after the peeling of the adhesive sheet is visually observed Pollution. ◎: No pollution ○: Very little pollution. △: There was slight contamination. ╳: There is paste (adhesive) remaining. (16) Yellowing resistance The adhesive sheet is attached to a glass substrate, mounted on a xenon discoloration tester (SC-700-WA: manufactured by Suga Testing Machine Co., Ltd.), and irradiated with ultraviolet light with an intensity of 70mW/cm ² for 120 hours. Observe the discoloration of the adhesive sheet. ◎: Yellowing was not confirmed at all by visual inspection. ○: Yellowing can be confirmed slightly by visual observation. △: Yellowing can be confirmed visually. ╳: The obvious yellowing can be confirmed visually. (17) Moisture and heat resistance The adhesive sheet and the aforementioned yellowing resistance test were also bonded to a glass substrate, and after 100 hours of holding at a temperature of 85°C and a relative humidity of 85%, visual observation was performed to evaluate whether floating occurred, Peeling, bubbles, and cloudiness. ◎: Transparent without floating, peeling, or bubbles. ○: There is very little matting, but no floating, peeling, or bubbles occur. △: There is slight matting or floating/peeling, and bubbles. ╳: Extreme matting or floating, peeling, air bubbles. (18) Height difference followability A black tape with a thickness of 20 μm is bonded to a glass substrate to produce glass with height difference. Transfer the adhesive sheet to the glass with high and low difference, and press it back and forth once with a 2kg load roller (pressure bonding speed 300mm/min) under a gas environment with a temperature of 23°C and a relative humidity of 50%. After standing at 80°C for 24 hours, the state of the height difference part was confirmed with an optical microscope. ◎: No bubbles were observed at all ○: A few small spherical bubbles were observed △: Large bubbles were observed and sometimes the bubbles were connected to each other ╳: Large bubbles were connected to each other and expanded on the line at the height difference part (19) Press workability The obtained adhesive sheet was cut by the Thomson punching method (a punching method in which 10 punching blades are arranged in parallel with linear blades at 5.0 mm intervals). ◎: There is no residue on the punching blade. ○: A small amount of adhesive remains on the punching edge. △: There is adhesive residue on the punching edge. ╳: There is a significant residue of adhesive on the punching edge, which cannot be surely the cutting surface.

Evaluation Examples B-2 to 9 and Evaluation Comparative Examples B-10 to 13 were replaced with the compositions described in Table 3, except that the ultraviolet curing resin was prepared in the same manner as Evaluation Example B-1 and used as an adhesive sheet, as described above Method evaluation. The results are shown in Table 3.

[table 3]

As shown in the results of the evaluation examples and comparative examples, (meth)acrylamide-based urethane oligomers with a content of low molecular weight components such as urethane adducts exceeding 5% by weight are transparent It has a tendency to decrease the adhesiveness, adhesive strength, and heat and humidity resistance. After curing, the adhesive sheet has poor stain resistance and stamping workability, so it is difficult to use. On the other hand, even if the content of the low molecular weight component of the (meth)acrylate urethane oligomer is 5% by weight or less, poor adhesion resistance leads to poor stain resistance and poor press workability. In addition, oligomers with a number average molecular weight of less than 3500 tend to have a large number of by-products of urethane adducts with a molecular weight of less than 500, and have poor followability, moisture resistance, and adhesion. The (meth)acrylamide urethane oligomer of the present invention can obtain an adhesive sheet with high transparency, adhesive strength, and excellent stain resistance and stamping processability.

Evaluation Example B-14 Addition of (meth)acrylamide urethane oligomer UT-1 synthesized in Synthesis Example 1 40 parts by weight, "HEAA" 15 parts by weight, "DEAA" 15 parts by weight, 2EHA 30 parts by weight, 3 parts by weight of DMAPAA-TFSIQ as an ionic vinyl monomer, and 3 parts by weight of Irgacure 184 as a photopolymerization initiator are uniformly mixed and used for the adhesive layer of the laminate for touch panels. The laminated system is composed of 2 transparent electrode sheets and cover glass. It is a type of electrostatic capacitive touch panel sensor in which two electrode sheets of the transparent substrate are used to detect the position of the electrode on a single mask. The opening of the line pattern is laminated to the above prepared adhesive and irradiated with ultraviolet rays (device: frequency conversion conveyor device made by Eyegraphics ECS-4011GX, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illumination: 700mW/ cm ² , accumulated light quantity: 1000mJ/cm ² ), forming an adhesive layer.

(20) Transparency (transmittance) The same test method as the above 0082 was used for evaluation. (21) Adhesive strength The same test method as the above 0082 was used for evaluation. (22) Yellowing resistance Evaluation was carried out by the same test method as described above for 0082. (23) The presence or absence of bubbles Evaluate the size and number of bubbles formed in the adhesive layer at the opening of the electrode sheet when the electrode sheet is formed with the adhesive layer. ◎: Less than 10 bubbles less than 0.5mm in diameter ○: More than 10 bubbles less than 30 in diameter less than 0.5mm △: More than 30 bubbles less than 0.5mm in diameter ╳: More than 0.5mm in diameter One or more bubbles (24) Visibility Put the touch panel assembled with electrode pads on the display screen of the liquid crystal display device, and visually confirm whether the lines are noticeable when driving the liquid crystal display device to display white. ◎: The line could not be confirmed visually. ○: Very few lines can be confirmed visually. △: The line can be confirmed visually. ╳: Obvious lines can be confirmed visually.

Evaluation Examples B-14 to 18 and Evaluation Comparative Examples B-19 and 20 were replaced with the compositions described in Table 3-2, except that the adhesive layer was prepared in the same manner as Evaluation Example B-14 and evaluated according to the above method. The results are shown in Table 3-2.

[Table 3-2]

It can be seen from Table 3-2 that the adhesive used in the laminate for a touch panel of the present invention has excellent adhesion to copper, and can obtain an adhesive with a high effect of suppressing bubbles in the adhesive layer when the adhesive layer is formed Agent.

Evaluation Example C-1 25 parts by weight of (meth)acrylamide urethane oligomer UT-1 synthesized in Synthesis Example 1, 15 parts by weight of "ACMO", 20 parts by weight of "DMAA", 25 parts by weight of HEA and 15 parts by weight of THFA were mixed, and 3 parts by weight of Irgacure 1173 as a photopolymerization initiator was added, uniformly mixed and prepared as an ultraviolet curing adhesive. After that, the obtained adhesive was used to make a polarizing plate by ultraviolet curing according to the following method and the physical properties of the polarizing plate were evaluated.

Use UV irradiation to make polarizing plates. Use a desktop roll laminator (RSL-382S manufactured by Royal Sovereign). For any of the two transparent films (protective film, retardation film, or optical compensation film), the present invention uses acrylic The film serves as a protective film) with a polarizing film interposed therebetween, and the adhesive of the example or the comparative example is laminated between the transparent film and the polarizing film to have a thickness of 10 μm. Ultraviolet rays are irradiated from the top surface of the attached transparent film (device: frequency conversion conveyor device ECS-4011GX made by Eyegraphics, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , cumulative light amount: 1000mJ/cm ² ), making polarizing plates with transparent films on both sides of the polarizing film.

(25) Observation of surface shape The surface of the polarizing plate obtained was visually observed and evaluated according to the following criteria. ◎: Even slight streaks and unevenness on the surface of the polarizing plate were not confirmed. ○: Micro streaks can be confirmed on the surface part of the polarizing plate. △: It can be confirmed that there are minute stripes and unevenness on the surface of the polarizing plate. ╳: It can be confirmed that there are obvious stripes and unevenness on the surface of the polarizing plate. (26) Peeling strength: polarized plate (test piece) cut into 20mm×150mm under the condition of temperature 23°C and relative humidity 50%, attached to the tensile tester (made by Shimadzu Corporation) using double-sided tape The test board of autograph AGXS-X 500N). One of the transparent protective film and the polarizing film on the side where the double-sided tape is not attached is peeled off about 20 to 30 mm in advance, clamped in the upper jig, and the 90° peel strength (N/20 mm) is measured at a peeling speed of 300 mm/min. ◎: 3.0 (N/20mm) or more ○: 1.5 (N/20mm) or more, less than 3.0 (N/20mm) △: 1.0 (N/20mm) or more, less than 1.5 (N/20mm) ╳: less than 1.0 (N/20m) (27) Water resistance Cut the obtained polarizer to 20×80mm, and immerse it in warm water at 60℃ for 48 hours, then confirm whether the interface between the polarizer and the protective film, retardation film, optical compensation film There is stripping. The judgment is based on the following criteria. ◎: No peeling (less than 1mm) at the interface between polarizer and protective film. ○: Part of the interface between the polarizing plate and the protective film was peeled off (1 mm or more and less than 3 mm). △: Part of the interface between the polarizing plate and the protective film was peeled off (3 mm or more and less than 5 mm). ╳: There is peeling at the interface between polarizer and protective film (more than 5mm). (28) Durability Cut the obtained polarizer into 150mm×150mm, put it into a cold and hot impact device (TSA-101L-A manufactured by Espec Corporation), and perform a thermal shock of -40℃~80℃ for 30 minutes each, a total of 100 times. Evaluation is based on the following criteria. ◎: No cracking occurred. ○: A short crack of 5 mm or less occurred only at the end. △: Short-line cracks occurred outside the ends. However, the polarizing plate is not separated into two or more parts due to the line. ╳: Cracks occurred outside the ends. The polarizing plate is divided into two or more parts due to the line.

Evaluation Examples C-2 to 9 and Evaluation Comparative Examples C-10 to 13 were replaced with the compositions described in Table 4, except that the ultraviolet curing resin was prepared in the same manner as in Evaluation Example C-1 and evaluated according to the above method. The results are shown in Table 4.

[Table 4]

As shown in the results of the evaluation examples and comparative examples, the urethane-modified (meth)acrylamide and urethane-modified (meth)acrylates outside the appropriate range of molecular weight and acrylic acid equivalent , (Meth)acrylamide-based urethane oligomers with a content of low-molecular-weight components exceeding 5% by weight, or (meth)acrylate-based carbamic acids with a content of low-molecular-weight components of less than 5% by weight The ethyl ester oligomer has a low peel strength, and the obtained polarizer has unsatisfactory water resistance and durability. It is considered that the shrinkage resistance is insufficient, which causes the cured film to float. In addition, when a high-viscosity urethane-modified (meth)acrylate is used, streaks appear on the surface of the polarizing plate, and the surface shape has a problem, so it is difficult to use it for this purpose. The polarizing plate obtained from the (meth)acrylamide urethane oligomer of the present invention has no streaks on the surface and unevenness on the entire surface. In addition, an adhesive composition for polarizing plates having water resistance, durability and high peel strength can be obtained.

Evaluation Example D-1 23 parts by weight of (meth)acrylamide urethane oligomer UT-1 synthesized in Synthesis Example 1, 16 parts by weight of UV-7600, 20 parts by weight of PETA, DPHA 12 By weight, 17 parts by weight of "ACMO" and 12 parts by weight of THFA were mixed, and 3 parts by weight of Irgacure 1173 as a photopolymerization initiator was added, uniformly mixed and a photo-curable coating composition was prepared.

(29) Compatibility Visually confirm the compatibility of the coating agent composition obtained by the above method. ⊚: The coating composition has high transparency, and white turbidity and separation are not confirmed at all. ○: The transparency of the coating composition is high, but a slight cloudiness is observed. △: The entire coating composition was cloudy. ╳: The coating composition is cloudy and separated. (30) Moisture permeability The obtained coating agent composition was coated on a substrate, and the adhesion state of the coating film was visually observed. ◎: There was no shrinkage when left for 5 minutes immediately after coating, and a smooth coating film was formed. ○: No shrinkage was observed immediately after application, but a little shrinkage was observed after standing for 5 minutes. △: A little shrinkage was observed immediately after coating. ╳: Most shrinkage holes were observed immediately after coating, and a uniform coating film could not be obtained.

Production of a coating film by ultraviolet irradiation. The obtained coating agent composition was applied to a PET film with a thickness of 100 μm with a coating rod (RDS 12), and ultraviolet rays were irradiated (device: ECS-4011GX, frequency conversion conveyor device manufactured by Eyegraphics, metal halide Lamp: M04-L41 manufactured by Eyegraphics, ultraviolet illuminance: 700 mW/cm ² , accumulated light amount: 1000 mJ/cm ² ) to prepare a coating film, and evaluated according to the following method. The results are shown in Table 6. In addition, when a solvent is used, ultraviolet rays are irradiated after drying at 80°C for 3 minutes after application.

(31) For the curable coating composition, the obtained coating film was irradiated with ultraviolet illuminance of 700 mW/cm ² , and the cumulative light amount until the resin composition was completely cured was measured. Complete hardening refers to the state where no traces are attached when the surface of the hardened film is traced with silicone rubber. ◎: Completely hardened at a cumulative light amount of 1000mJ/cm ² . ○: Completely hardened at a cumulative light intensity of 1000mJ/cm ² to 2000mJ/cm ² . △: It is completely hardened in the accumulated light amount of 2000mJ/cm ² ~ 5000mJ/cm ² . ╳: It needs to accumulate more than 5000mJ/cm ² until it is completely hardened. (32) Tack resistance Touch the surface of the coating film obtained by the above method with fingers, and evaluate the degree of tackiness. ◎: There is no adhesiveness at all. ○: There is some adhesiveness, but no fingerprint remains on the surface. △: Adhesive, and fingerprints remain on the surface. ╳: Severe adhesiveness, fingers stick to the surface. (33) Shrink resistance (curling resistance) The coating film obtained by the above method is irradiated with ultraviolet rays (ultraviolet illuminance 700mW/cm ² , accumulated light amount 2000mJ/cm ² ), and the obtained coating film is cut into 10cm squares and measured The average height of the corners. ◎: There is floating below 0.5mm. ○: There is a float of 1 mm or less. △: There is a float of 3 mm or less. ╳: Large curl. (34) Scratch resistance Use #0000 steel wool, apply a load of 200g/cm ² and make it back and forth 10 times, and visually evaluate whether there are scratches. ◎: Film peeling and scars were hardly confirmed. ○: Slight fine scratches were confirmed on a part of the film. △: The film was confirmed to have streak-like scratches. ╳: Film peeling occurs. (35) Adhesiveness: According to JIS K 5600, 100 square 1mm square grid eyes were made, and scotch tape was attached, and the number of square grid eyes with a coating film remaining on the substrate side during one-off peeling was calculated and evaluated. (31) Moisture resistance The coated film obtained on the PET film (100 μm) was allowed to stand in an environment at a temperature of 50° C. and a relative humidity of 95% for 24 hours, and the film was evaluated by visual inspection or adhesion test. ◎: Transparency is maintained under high temperature and high humidity and no decrease in adhesion is observed. ○: The transparency is maintained under high temperature and high humidity, but a slight decrease in adhesion is observed. △: The transparency was maintained at high temperature and high humidity, but the adhesiveness was significantly reduced. ╳: At high temperature and high humidity, a decrease in transparency is observed, and further a decrease in adhesion. (36) Self-healing After the coating film obtained by the above method is injured with a spoon, it is left in an environment with a temperature of 25°C and a relative humidity of 50% to visually evaluate the recovery state of the scar. ◎: The scar completely recovered within 30 minutes. ○: The wound completely recovered within 30 minutes to 5 hours. △: The wound completely recovered within 5 hours to 24 hours. ╳: The scars have not fully recovered after 24 hours of standing.

Evaluation Examples D-2 to 8 and Evaluation Comparative Examples D-10 to 13 were replaced with the compositions described in Table 5, except that the coating composition was prepared in the same manner as Evaluation Example D-1, and a cured film was produced according to the above method. And evaluate according to the above method. The results are shown in Table 5.

[table 5]

Evaluation Examples D-14 to 17 and Evaluation Comparative Examples D-18 to 19 were replaced with the compositions described in Table 6, except that the self-healing coating composition was prepared in the same manner as Evaluation Example D-1, and hardened according to the above method. The film was evaluated according to the above method. The results are shown in Table 6. [Table 6]

As shown in the results of the evaluation examples and comparative examples, urethane-modified (meth)acrylate and urethane-modified (meth)acrylic acid whose molecular weight, acrylic acid equivalent, and viscosity are outside a certain range Acetamide, its resistance to hardening shrinkage, water resistance, adhesion, hardening, etc. is not satisfactory. In particular, it contains a large amount of oligomers of urethane adducts with a number average molecular weight of less than 1000 and acrylate oligomers. The obtained cured product has poor compatibility, and the transparency and density of the cured film are observed. Reduced compatibility and water resistance. The urethane oligomer of the present invention is a (meth)acrylamide system, and the content of the low molecular weight component is 5 wt% or less, so excellent curability and moisture resistance, adhesion, and resistance can be obtained The coating composition with good viscosity also can be used for decorative film, self-healing coating and hard coating.

Evaluation Example E-1 42 parts by weight of (meth)acrylamide urethane oligomer UT-1 synthesized in the synthesis example, 20 parts by weight of "HEAA", 10 parts by weight of "DEAA", 4- 15 parts by weight of HBA was mixed with 13 parts by weight of A-LEN-10, and 3 parts by weight of Irgacure 1173 as a photopolymerization initiator was added, and the mixture was uniformly mixed to prepare an ultraviolet curable sealant. After that, using the obtained sealant, the cured product of the sealant resin was prepared by ultraviolet curing in the following method and physical properties were evaluated.

Method for manufacturing ultraviolet-curable sealant resin cured product: A silicon spacer (30 mm long × 15 mm wide × 3 mm thick) is placed on a glass plate (50 mm long × 50 mm wide × 5 mm thick), and the above-mentioned preparation is injected into the spacer UV-curable sealant. After fully degassing, irradiate ultraviolet rays (device: frequency conversion conveyor belt device ECS-4011GX made by Eyegraphics, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , cumulative light amount: 1000mJ/cm ² ) to make a seal Hardened resin. The characteristics of the obtained hardened material were evaluated by the following methods, and the results are shown in Table 6.

(37) Transparency (transmittance) Using the obtained hardened product, it was allowed to stand for 24 hours in a gas environment at a temperature of 23°C and a relative humidity of 50%. After that, the transmittance of the cured film was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000), and the transparency was classified into the following 4 levels and evaluated. ◎: Transmittance of 90% or more ○: Transmittance of 85% or more and less than 90% △: Transmittance of 50% or more and less than 85% ╳: Transmittance of less than 50% (38) Light resistance The obtained hardened product was bonded to a glass substrate, and the yellowness was measured with a spectrophotometer (CM-3600d: manufactured by Konica Minolta). After that, it was placed in a xenon discoloration tester (SC-700-WA: manufactured by Suga Testing Machine Co., Ltd.), and the ultraviolet light with an intensity of 4 W/cm ^{2 was} irradiated at 30° C. for 100 hours. After the irradiation, the yellowness was measured in the same manner as before the irradiation, and visually Observe the discoloration of the hardened material ◎: Yellowing cannot be confirmed at all by visual inspection. ○: Very little yellowing can be confirmed visually. △: Yellowing can be confirmed visually. ╳: The obvious yellowing can be confirmed visually. (39) Water absorption test 1g was cut out from the obtained hardened product, placed as a test piece in a constant temperature and humidity machine with a temperature of 85°C x 95% relative humidity, and left for 48 hours, after which the weight of the test piece was measured again, and Evaluation item (9) calculates its water absorption rate in the same way. ◎: Water absorption rate is less than 1.0% ○: Water absorption rate is more than 1.0% and less than 2.0% △: Water absorption rate is more than 2.0% and less than 3.0% ╳: Water absorption rate is more than 3.0% (40) Dissipative gas In the test, 1 g of the obtained cured product was cut off, and it was allowed to stand as a test piece in a thermostat set at 100°C. A dry nitrogen flow was circulated for 24 hours. After that, the weight of the test piece was measured, and the fugitive gas was calculated according to (Equation 2) Occurrence rate [Equation 2] (Occurrence rate of fugitive gas (%) = (weight after constant temperature-weight before constant temperature)/weight before constant temperature × 100). ◎: Incidence rate less than 0.1% ○: Incidence rate 0.1% or more and less than 0.3% △: Incidence rate 0.3% or more and less than 1.0% ╳: Incidence rate 1.0% or more (41) Heat-resistant cycle The obtained hardened product was placed at -40°C for 30 minutes and then at 100°C for 30 minutes as a cycle, which was repeated 100 times to visually observe the state of the hardened product. ◎: No change was observed at all ○: Some micro bubbles were observed, but no cracks were observed. Is transparent. △: A few bubbles or cracks were observed, with a slight extinction. ╳: Bubbles or cracks occur comprehensively and are in a translucent state.

Evaluation Examples E-2 to 8 and Evaluation Comparative Examples E-9 to 12 were replaced with the compositions described in Table 7, except that the ultraviolet curable sealant was prepared in the same manner as in Evaluation Example E-1 and evaluated according to the above method. The results are shown in Table 7.

[Table 7]

As shown in the results of the evaluation examples and comparative examples, the transparency and light resistance of the cured product obtained when the urethane oligomer in which the content of the component with a molecular weight of less than 1000 is blended in 5 wt% or more is blended Reduced and high water absorption. And the urethane modified (meth)acrylate and its molecular weight, acrylic acid equivalent, and viscosity are outside of a certain range, and the urethane modified (meth)acrylamide has reduced water resistance due to hardening shrinkage. The fugitive gas occurs. On the other hand, when the embodiments of the present invention are used, all the required characteristics are excellent, and they can be widely used as sealants for electronic parts, semiconductors, solar cells, and the like.

Evaluation Example F-1 9 parts by weight of (meth)acrylamide urethane oligomer UT-1 synthesized in Synthesis Example 1, 35 parts by weight of HDDA, 30 parts by weight of THFA, and 20 parts by weight of IBOA 3. Mix 3 parts by weight of pigment and 3 parts by weight of pigment dispersant, and add 5 parts by weight of IrgacureTPO as a photopolymerization initiator, uniformly mix and prepare a photo-curable ink composition. After that, inkjet printing was performed according to the following method, and the obtained printed matter was evaluated.

(42) Viscosity The viscosity of the obtained ink composition is measured in accordance with JIS K5600-2-3 using a cone-plate type viscometer (device name: RE550 type viscometer manufactured by Toki Industry Co., Ltd.). For inkjet printing, the viscosity of the ink composition at 20°C is preferably 3-20 mPa·s or less, and more preferably 5-18 mPa·s. If it is less than 3mPa·s, the bleeding of the printing after the discharge and deviation of the printing will reduce the discharge followability. At 20mPa·s or more, the discharge stability due to clogging of the discharge nozzle will be observed, which is not ideal. (43) Compatibility Visually confirm the compatibility of the ink composition prepared by the above method. ◎: There is no insoluble matter in the ink composition. ○: A small amount of insoluble matter was observed in the ink composition. △: Insoluble matter was observed in the entire ink composition. ╳: There is sediment in the ink composition.

Production of printed matter by UV irradiation The obtained ink composition was coated on a polyethylene terephthalate (PET) film with a thickness of 100 μm with a coating rod (RDS 12) and irradiated with ultraviolet rays (device: frequency conversion type manufactured by Eyegraphics) Conveyor belt device ECS-4011GX, metal halide lamp: M04-L41 made by Eyegraphics) is hardened to make a printed matter.

(44) Curability measurement The accumulated light amount until the printing ink composition is completely cured under the environment of room temperature 23°C when the printed matter is produced by the above method. ◎: Completely cured at 1000mJ/cm ² ○: Completely cured at 1000~2000mJ/cm ² △: Completely cured at 2000~5000mJ/cm ² ╳: More than 5000mJ/cm ^{2 is} required until complete curing (45) The surface dryness will be The printed matter produced by the above method was allowed to stand for 5 minutes in an environment of room temperature 23°C and a relative humidity of 50%, and high-grade paper was overlaid on the printing surface, and a load of 1 kg/cm ^{2 was} applied for 1 minute to evaluate the degree of transfer of the printing ink to the paper. ◎: The printing ink was dry and was not transferred to the paper at all. ○: The printing ink was dry and slightly transferred to the paper. △: The ink is almost dry, and there is transfer to the paper. ╳: The printing ink is almost not dry, and there is much transfer to the paper.

Inkjet printing and evaluation of printing suitability Use an inkjet color printer (PM-A890 made by Seiko Epson), print the entire image, and irradiate ultraviolet rays (device: ECS-4011GX, frequency conversion conveyor device made by Eyegraphics, metal halide lamp : M04-L41 manufactured by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , accumulated light amount: 1000mJ/cm ² ) to produce printed matter, and evaluated according to the following method. The results are shown in Table 5.

(46) Discharge stability. The above inkjet printer was used for printing, and the printing state of the printed matter was visually evaluated. ◎: No nozzle blanking and good printing. ○: There is a little nozzle blanking. △: There is nozzle blanking in a wide range. ╳: Do not spit out. (47) Sharpness Visually observe the sharpness of the printed image. ◎: No ink bleeding was observed at all, and the image was clear. ○: There was almost no ink bleeding, and the image was good. △: Some ink bleeding was observed. ╳: Bleeding of ink is noticeably observed. (48) Water resistance Expose the printed surface to running water for 1 minute to visually observe the change in the image. ◎: The sharpness of the image is completely unchanged. ○: The sharpness of the image hardly changed, but ink bleeding was slightly observed. △: The sharpness of the image is reduced and ink bleeding is observed. ╳: The sharpness of the image is significantly reduced and ink bleeding is noticeably observed.

Evaluation Examples F-2 to 9 and Evaluation Comparative Examples F-10 to 13 were replaced with the compositions described in Table 8, except that the printing ink composition was prepared in the same manner as Evaluation Example F-1, and the printed matter was prepared according to the above method. Evaluation by the above method. The results are shown in Table 8.

[Table 8]

As shown in the results of the evaluation examples and comparative examples, (meth)acrylamide-based urethane oligomers containing low-molecular-weight components such as urethane adducts exceeding 5 wt% are hardened Because of its low molecular weight components with high polarity, the printed matter after discharge hardening also has poor water resistance. In addition, the urethane-modified (meth)acrylate and the urethane-modified (meth)acrylamide whose molecular weight and acrylic acid equivalent are outside a certain range have poor stability. The reason is because the viscosity becomes higher, which causes the drawability to become a problem. On the other hand, (meth)acrylate-based urethane oligomers have low curability and surface dryness even if the content of low molecular weight components does not exceed 5% by weight. As a result, the water resistance of the printed matter after curing Also insufficient. The (meth)acrylamide urethane oligomer obtained in the present invention can obtain excellent ink composition with excellent hardenability and surface dryness, and also take into account the stability, sharpness and water resistance of the discharge Thing.

Evaluation Example G-1 15 parts by weight of the urethane-modified (meth)acrylamide synthesized in Synthesis Example 1, 50 parts by weight of "HEAA", 32 parts by weight of UNIOLD400, and 3 parts by weight were added as photopolymerization. Irgacure 184 as the starting agent was uniformly mixed and prepared into a resin composition for active energy ray hardening stereo modeling.

The evaluation of the obtained resin composition for active energy ray curable stereolithography was carried out by the following method, and the results are shown in the table. (49) Curability is measured until the active energy ray-curable resin composition for stereolithography is completely cured. ◎: Completely hardened at 500mJ/cm ² . ○: Completely hardened at 500mJ/cm ² to 1000mJ/cm ² . △: Completely hardened from 1000mJ/cm ² to 3000mJ/cm ² . ╳: It needs more than 3000mJ/cm ^{2 to} completely harden.

For the adhesion of the polarizing film, a desktop roll laminator (RSL-382S manufactured by Royal Sovereign) was used, one polarizing film was sandwiched between two acrylic films, and the examples and comparative examples were laminated between the films The active energy ray-curable resin composition has a thickness of 10 μm. Ultraviolet rays are irradiated from the top surface of the laminated film (device: frequency conversion conveyor device ECS-4011GX made by Eyegraphics, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , cumulative light amount: 1000mJ/cm ² ) Manufacture a polarizing plate with acrylic film on both sides of the polarizing film.

(50) Peel strength The polarizing plate obtained was evaluated according to the same test method as the above 0082.

Measurement of the rubber hardness of the hardened product. A heavy-peeled PET film (made by Toyobo Co., Ltd., polyester film E7001) with a thickness of 75 μm was closely adhered to a horizontal glass plate, and a spacer with a thickness of 1 mm and an internal size of 60 mm × 90 mm was installed. , And after filling the inner side of the spacer with the active energy ray-curable resin composition obtained in each example and comparative example, a light peeling PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) with a thickness of 50 μm is overlaid thereon. ), irradiating ultraviolet rays (device: made by Eyegraphics, frequency conversion conveyor device ECS-4011GX, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance 300mW/cm ² , cumulative light amount of 200mJ/cm ^{2 for} 1 pass) to make the active energy The radiation-curable resin composition is cured. The number of passes of ultraviolet radiation is set to the number obtained by the above [0091]. After that, 6 pieces of hardened products obtained by peeling off the PET film on both sides were overlapped, and Shore A hardness was measured in accordance with JIS K6253 "Rubber Hardness Test Method".

(51) Bleed-out resistance The heavy-peeled PET film (made by Toyobo Co., Ltd., polyester film E7001) with a thickness of 75 μm is closely adhered to a horizontal glass plate, and a spacer with a thickness of 1 mm and an interior of 20 mm × 40 mm is provided. , And after filling the inner side of the spacer with the active energy ray-curable resin composition obtained in each example and comparative example, a light peeling PET film (manufactured by Toyobo Co., Ltd., polyester film E7002) with a thickness of 50 μm is overlaid thereon. ), irradiating ultraviolet rays (device: made by Eyegraphics, frequency conversion conveyor device ECS-4011GX, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance 300mW/cm ² , cumulative light amount of 200mJ/cm ^{2 for} 1 pass) to make the active energy The radiation-curable resin composition is cured. The number of passes of ultraviolet radiation is set to the number obtained by the above [0121]. After that, the cured product obtained by removing the peeled PET film on both sides was used as a test piece, and it was allowed to stand in a constant temperature and humidity bath set at 25°C and 50% RH for 168 hours, and the surface of the test piece before and after standing was visually evaluated . ◎: No exudate was confirmed before and after standing. ○: Exudation was observed before standing, but some slight exudation after standing. △: Some slight exudation was observed before standing, but some exudates were confirmed after standing. ╳: A certain amount of exudation was confirmed before standing, and exudate was strongly considered after standing. (52) Adhesiveness According to JIS K 5600, 100 square 1mm square grid eyes were made, and scotch tape was affixed. The number of square grid eyes with coating film remaining on the substrate side at the time of peeling was calculated and evaluated.

Evaluation Examples G-2 to 8 and Evaluation Comparative Examples G-9 to 12 were replaced with the compositions described in Table 9, and the resin composition for active energy ray-curable stereolithography was prepared in the same manner as in Evaluation Example G-1. Evaluation according to the above method. The results are shown in Table 9.

[Table 9]

The results in Table 9 show that the active energy ray-curable resin compositions obtained in Examples G-1 to 8 are excellent in handleability, formability, and smoothness, and show a factor of 1000 mJ/cm ² even in the presence of oxygen. The following ultraviolet irradiation hardens the high curing properties, and at the same time, the bleeding of the non-reactive diluent is suppressed. In addition, it exhibits good adhesion and adhesion to PET and PMMA substrates, and is suitable as an adhesive. On the other hand, in Comparative Example G-9, a high curing shrinkage rate leads to insufficient adhesion to PET and PMMA substrates. In Comparative Example G-10, the film was not sufficiently cured, and the film was not sufficiently cured. As a result, bleeding of a large amount of non-reactive diluent was observed, and adhesion and adhesion were also low. In Comparative Example G-11, the molecular weight and acrylic acid equivalent of the oligomer in the composition were high, resulting in insufficient hardening, and bleeding of the non-reactive diluent occurred. In Comparative Example G-12, although good curability and bleed suppression were observed, the film after ultraviolet irradiation became rigid, and due to the low degree of operability and formability of the coating film and the high degree of curing shrinkage, it was dense to the plastic substrate. The fit is low and fails to exhibit good adhesion.

Evaluation Example H-1 40 parts by weight of urethane-modified (meth)acrylamide synthesized in Synthesis Example 1, 12 parts by weight of UV3700, 20 parts by weight of "ACMO", 18 parts by weight of IBMA, and 10 parts by weight of CHMA Parts, 20 parts by weight of IBMA, and 10 parts by weight of CHMA are mixed, and 3 parts by weight of Irgacure 1173 as a photopolymerization initiator is added to uniformly mix and prepare a coating agent composition for nail decoration.

Nail decoration method The obtained coating agent composition for nail decoration is evenly applied to the nail using a flat brush, and irradiated with a gel-like LED UV irradiation device (36W) for 60 seconds to form a nail decoration on the nail.

(53) Hardness Touch the surface of the nail decoration obtained by the above method with a finger and evaluate the degree of adhesiveness. ◎: No stickiness at all. ○: There is some adhesiveness but no fingerprint remains on the surface. △: Adhesive, and fingerprints remain on the surface. ╳: Severe adhesiveness, fingers stick to the surface. (54) Smoothness Visually confirm the surface of the nail decoration obtained by the above method. ◎: The surface is smooth, and no unevenness is observed on all the coated surfaces. ○: The whole is smooth but some unevenness is observed. △: A trace of bristles caused by a flat brush remains after coating. ╳: The bristle marks caused by the flat brush remain after coating. (55) Glossiness Visually observe the surface of the nail decoration obtained by the above method. ◎: Surface gloss. ○: The reflection of light can be confirmed, but a little extinction is observed. △: The entire surface is slightly matted. ╳: The surface is matt. (56) Adhesiveness Visually confirm the appearance change of nails obtained by scratching other nails by the above method. ◎: No change in appearance. ○: Part of the nail decoration floated and whitening was confirmed. △: Peeling was confirmed for a part of nail decoration. ╳: Confirm significant peeling of nail decoration. (57) Removability Place a cotton sheet containing acetone to cover the nail decoration obtained by the above method. Then cover the entire nail with aluminum foil, put on thick gloves, and immerse in warm water for 10 minutes. Remove the aluminum foil and cotton sheet and wipe gently with a cloth. ◎: The nail decoration can be easily peeled off without using a cloth. ○: The nail decoration can be easily peeled off by rubbing lightly with a cloth. △: If you continue to wipe with a cloth for about 1 minute, you can peel off the nail decoration. ╳: The acetone is not swollen and cannot be peeled off with a cloth.

Evaluation Examples H-2 to 8 and Evaluation Comparative Examples H-9 to 12 were replaced with the compositions described in Table 10, except that the coating agent composition for nail decoration was prepared in the same manner as in Evaluation Example H-1, and according to the above Methods Make nail decoration and evaluate according to the above method. The results are shown in Table 10.

[Table 10]

As shown in the results of the evaluation examples and comparative examples, the blended molecular weight, acrylic acid equivalent, and viscosity are outside of a certain range of ethyl urethane modified (meth)acrylamide, or ethyl urethane (method Base) acrylic ester, the curability of the composition, the gloss of the obtained decorative film is low, and the coating film is uneven due to high viscosity, the smoothness of the nail decoration formed on the nail is not good, and there are drip and residue Traces of the bristles of a flat brush. Furthermore, due to the increased hardening shrinkage, the adhesion to nails is poor. In addition, (meth)acrylamide-based urethane oligomers and acrylate-based urethane oligomers with a content of low-molecular-weight components exceeding 5 wt. High results in an observable decrease in adhesion. When the urethane-modified (meth)acrylamide of the present invention is used, the adhesiveness of the decorative film after hardening is suppressed, and the hardening shrinkage is also low, so that it can form a high adhesion without floating from the nail. Nail decoration with high acetone removal.

Evaluation Example I-1 25 parts by weight of urethane-modified (meth)acrylamide H-1 synthesized in Synthesis Example 1, 35 parts by weight of Light acrylate PE-4, and 15 parts by weight of "ACMO" Parts, 25 parts by weight of DPHA are mixed, 3 parts by weight of Darocur 1173 as a photopolymerization initiator and 3 parts by weight of 8019add as a surface modifier are added, uniformly mixed and prepared into a car exterior protection agent composition.

Production method of the protective film for the exterior of the car. The surface of the 15cm square polycarbonate resin plate is coated with a coating bar to make the dried coating film about 10μm. After drying with a hot air dryer at 90°C for 15 minutes, it is irradiated. Ultraviolet rays (device: ECS-4011GX, frequency conversion conveyor device made by Eyegraphics, metal halide lamp: M04-L41 made by Eyegraphics, ultraviolet illuminance: 700mW/cm ² , cumulative light amount: 1000mJ/cm ² ), prepared with a cured film on the resin board Of the sample.

The evaluation was performed according to the same test method as 0107 described above.

(59) Weather resistance According to JIS KS5400, a carbon arc solar climatometer is used for a 5,000-hour acceleration test, and every 500 hours, whether there is a decrease in adhesion or cracks is evaluated. In addition, the adhesiveness was evaluated as good if the film was not peeled from the substrate when the test film was attached with a transparent tape and peeled off. The cracks were confirmed visually, and those who did not produce cracks were rated as good. The evaluation results are divided into 4 levels of evaluation as follows. The period during which the decrease in adhesion and cracks are not confirmed is: ◎: 5000 hours or more ○: 4000 hours or more and less than 5000 hours △: 3000 hours or more and less than 4000 hours ╳: 3000 hours or less

(60) Water resistance A 20 μm UV-cured film was made on a polycarbonate resin plate and surface-dried at 70°C for 10 minutes. Then the sensitivity to water swelling is measured. The evaluation results are divided into the following four levels according to the degree of influence. ◎: No effect ○: Very little film dissolves △: Part of the film dissolves ╳: The film dissolves completely

(61) Adhesive use of the exterior protection film of the vehicle compartment, 100 100mm square square eyes are made in accordance with JIS K 5600, with transparent tape attached, counting the square eye with the coating film left on the substrate side when peeled off in one breath And evaluate.

(62) Abrasion resistance According to ASTM D-1044, a push-type abrasion test is carried out. The difference △H (%) in the haze before and after the push-type abrasion test was measured and evaluated. Here, the wear wheel is CS-10F, the load is 500 g each, and the rotation speed is 500 rpm. The transparency is evaluated in the following 4 levels. ◎: The difference in haze △H is less than 7% ○: The difference in haze △H is more than 7% and less than 10% △: The difference in haze △H is more than 10% and less than 15% ╳: The difference of haze △H is more than 15%

(63) Scratch resistance The evaluation was performed according to the same test method as 0100.

Evaluation Examples I-2 to 8 and Evaluation Comparative Examples I-9 to 12 were replaced with the compositions described in Table 11, except that they were prepared in the same manner as Evaluation Example I-1. Evaluation according to the above method. The results are shown in Table 11.

[Table 11]

As shown in the results of the evaluation examples and the comparative examples, the blended molecular weight, acrylic acid equivalent, and viscosity are within a certain range of ethyl urethane modified (meth)acrylamide and ethyl urethane modified When the (meth)acrylate or oligomer with a low molecular weight content of 5% or more, the composition has poor curability, viscosity, and shrinkage resistance, resulting in water resistance and adhesion of the obtained protective film Low, and deterioration in transparency due to poor compatibility was observed. When the urethane-modified (meth)acrylamide of the present invention is used, the protective film has excellent curability after curing, taking into account high cross-linking density and low curing shrinkage, so it can obtain high adhesion without floating, Protective film with excellent abrasion resistance and injury resistance.

Evaluation Example J-1 60 parts by weight of urethane-modified (meth)acrylamide UT-1 synthesized in Synthesis Example 1 and 5 parts by weight of urethane-modified Synthesis Example 2 (Meth)acrylamide UT-2, HDDA 11 parts by weight, DPHA 20 parts by weight, IBOA 4 parts by weight, silica dioxide particles IPL-ST-L 10 parts by weight, add 50 parts by weight of MEK as a solvent, 3 parts by weight One part of Irgacure 184 as a photopolymerization initiator was uniformly mixed with 50 parts by weight of MEK to prepare a resin composition for decorative films.

Method for manufacturing photo-curable decorative film The obtained resin composition for decorative film is applied to a PET film with a thickness of 125 μm (“Softshine TA009” manufactured by Toyobo Co., Ltd.) with a coating bar (RDS 30), after the dry film thickness is 20 μm And dried at 100°C for 1 minute to form a film before ultraviolet curing. After that, ultraviolet rays (ultraviolet illuminance: 2mW/cm ² , cumulative light amount: 50mJ/cm ² ) were irradiated to produce a semi-cured decorative film, and the semi-cured molded film and decorative film were evaluated according to the following methods, respectively. The results are shown in Table 12.

(64) Transparency The obtained semi-cured molded film was used and evaluated according to the same test method as the above 0107. (63) Blocking resistance Overlay the untreated PET (thickness 100μm, "Cosmoshine A4100" made by Toyobo Co., Ltd., coating-coated untreated surface) on the obtained semi-cured molded film, and use a 2kg weight pressure roller 2 The pressure is applied twice, and it is left in a gas environment with a temperature of 23°C and a humidity of 50% for 30 minutes. After that, the untreated PET was peeled off, and the blocking resistance was evaluated by visual observation. ◎: No attachment to untreated PET, no change in appearance of the molded film ○: No attachment to untreated PET, but traces remained on a part of the surface of the molded film △: No transfer to untreated PET, but traces remained on the entire surface of the molded film ╳: There is transfer of untreated PET, and peeling and floating (64) breaking elongation are observed on the surface of the molded film. The obtained semi-hardened molded film is used and measured at a temperature of 130°C and a speed of 10 mm/min. Measuring equipment; Tensilon universal material testing machine RTA-100 (manufactured by Orientec) Elongation at break [%] = sheet length at break/sheet length before test × 100 ◎: Elongation at break is 100% or more ○: Elongation at break 50% or more but less than 100% △: Elongation at break is more than 10% and less than 50% ╳: Elongation at break is less than 10% (65) Molding processability test The semi-hardened molded film obtained will be formed by air pressure Machine SDF400 (Sodick Corporation) was molded at a heating temperature of 130°C, and after cooling to 25°C, the state of the decorative layer of the molded product was visually confirmed. ◎: No cracks were observed at all, and the surface was also highly transparent. ○: No cracks were observed, but the thickness of the decorative layer was uneven, and transparency was partially reduced. △: Cracks and some cracks were observed, and a part of the decorative layer was uneven in thickness and decreased in transparency. ╳: Most cracks were observed, and the thickness of the decorative layer was uneven and the transparency decreased significantly. (66) Curability The decorative film was coated with a resin composition and dried at 100°C for 1 minute. The obtained coating film was irradiated with an ultraviolet illuminance of 700 mW/cm ² to measure the cumulative light amount until the resin composition was completely cured. Complete hardening refers to the state where no traces are attached when the surface of the hardened film is traced with silicone rubber. ◎: Completely hardened at a cumulative light amount of 1000mJ/cm ² . ○: Completely hardened at a cumulative light intensity of 1000mJ/cm ² to 2000mJ/cm ² . △: It is completely hardened in the accumulated light amount of 2000mJ/cm ² ~ 5000mJ/cm ² . ╳: It needs to accumulate more than 5000mJ/cm ² until it is completely hardened. (67) Adhesive use the obtained decorative film, make 100 1mm square grid eyes in accordance with JIS K 5600, attach a transparent tape, calculate the number of square grid eyes remaining on the substrate side when peeled off in one go Evaluation. Obtained outfit (68) Pencil hardness Using the obtained decorative film, scrape the pencil for about 10mm at an angle of 45° according to JIS K 5600, and define the hardness of the hardest pencil with no scratches on the surface of the decorative film at this time as the pencil hardness . ◎: Pencil hardness is 2H or more ○: Pencil hardness HB~H △: Pencil hardness is 3B~B ╳: Pencil hardness is 4B or less (69) Scratch resistance Use #0000 steel wool and apply a load of 200g/cm ² While going back and forth 10 times on the decorative film, visually evaluate whether there are any scratches. ◎: Film peeling and scars were hardly confirmed. ○: Slight fine scratches were confirmed on a part of the film. △: The film was confirmed to have streak-like scratches. ╳: Film peeling occurs. (70) Bending resistance Bend the decorative film obtained above so that the coated surface becomes the outer side, load a 1 kg weight and leave it for 10 minutes to visually observe whether the surface of the decorative film is cracked. ◎: No crack was observed at all. ○: Part of the bent portion is whitened. △: Some cracks were observed in the bent portion. ╳: A crack was observed in the bending part.

Evaluation Examples J-2 to 8 and Evaluation Comparative Examples J-9 to 12 were replaced with the compositions described in Table 12, except that the resin composition for decorative films was prepared in the same manner as in Evaluation Example J-1, and the decoration was prepared according to the above method The film was evaluated according to the above method. The results are shown in Table 12.

[Table 12]

As shown in the results of the evaluation examples and the comparative examples, the blended molecular weight, acrylic acid equivalent, and viscosity are within a certain range of ethyl urethane modified (meth)acrylamide and ethyl urethane modified In the case of (meth)acrylate, the cured film of the semi-cured state has low curability, and viscosity can be observed, so the blocking resistance is not good, and it tends not to be stretched under high temperature conditions. In addition, the obtained decorative film has a problem of low adhesion to various plastic substrates. Moreover, the transparency of oligomers with a low molecular weight content of 5% or more is not good, and it is difficult to use. When the urethane-modified (meth)acrylamide of the present invention is used, the hardenability is excellent, and the agglomeration of the amide group and the urethane bond forms a pseudo-hard segment, so it can exhibit high adhesion resistance Consistency, moldability, and crack-free molded film before UV curing. And the fictitious cohesion is the main reason for achieving low curing shrinkage, and a photo-curable decorative film with good adhesion to various plastic substrates can be obtained. [Industry availability]

As explained above, the (meth)acrylamide-based urethane oligomer of the present invention has at least one (meth)acrylamide group at the terminal or side chain and ethyl urethane is added (Meth)acrylamide urethane oligomers with a content of low molecular weight components such as products of 5 wt% or less, so they are excellent in compatibility with widely used organic solvents and monomers due to their activity Energy ray irradiation shows high curability, and the surface of the cured film has good dryness. The (meth)acrylamide urethane oligomer of the present invention has an active energy ray curing shrinkage rate of 5% or less and has an excellent curing shrinkage rate, so it can be produced with adhesion and shrinkage resistance , Hardened film with high humidity resistance. In addition, if necessary, monofunctional, multifunctional monomers, ionic monomers, active energy ray polymerization initiators, pigments, etc. can be mixed and used, which can be suitably used in adhesives, electronic materials, printing inks, coating agents 1. Light-curing photoresist application.

Claims (13)

A (meth)acrylamide urethane oligomer, characterized by having one or more selected from ether skeleton, ester skeleton, polysiloxane skeleton and acrylic skeleton in the molecule The skeleton has more than one (meth)acrylamide group, and the content of components with a molecular weight of less than 1000 (excluding (meth)acrylamide with hydroxyl groups) is 5 wt% or less, before and after active energy ray hardening The shrinkage rate is 5.0% or less. For example, the (meth)acrylamide urethane oligomer in item 1 of the patent application scope has a number average molecular weight of 4,500 to 30,000 and an acrylic acid equivalent of 750 to 25,000. For example, the (meth)acrylamide urethane oligomer of item 1 or 2 of the patent application scope, wherein (meth)acrylamide (C) having a hydroxyl group is represented by the general formula [1];

In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R _{3 are the} same or different and represent a hydrogen atom, or a linear or branched alkyl or carbon group having 1 to 6 carbon atoms which may also be substituted with a hydroxyl group 3 to 6 aliphatic ring or aromatic ring, and R ₂ and R ₃ can also be integrated with the nitrogen atom carrying them and further formed into saturated or unsaturated 5 to 7 members that can also contain oxygen or nitrogen atoms Ring; except that R ₂ and R _{3 are} both hydrogen atoms, and R ₂ and R _{3 are} both alkyl groups, and the total number of hydroxyl groups owned by R ₂ and R ₃ is 1 or more. An active energy ray-curable resin composition containing 1% by weight or more of the (meth)acrylamide-based urethane oligomer according to any one of items 1 to 3 of the patent application. An active energy ray-curable adhesive composition containing 1% by weight or more of the (meth)acrylamide urethane oligomer according to any one of the patent application items 1 to 3. An active energy ray-curable adhesive composition containing 1% by weight or more of the (meth)acrylamide-based urethane oligomer according to any one of items 1 to 3 of the patent application. An active energy ray-curable coating agent composition containing 1% by weight or more of the (meth)acrylamide-based urethane oligomer according to any one of items 1 to 3 of the patent application. An active energy ray-curable sealant composition containing 1% by weight or more of (meth)acrylamide urethane oligomer according to any one of items 1 to 3 of the patent application. An active energy ray-curable inkjet printing ink composition containing 1% by weight or more of (meth)acrylamide urethane oligomer as described in any one of patent application items 1 to 3 . An active energy ray-curable resin composition for stereolithography, which contains 1% by weight or more of the (meth)acrylamide urethane oligomer as described in any one of items 1 to 3 of the patent application . An active energy ray-curable nail decoration composition comprising 1% by weight or more of the (meth)acrylamide urethane oligomer according to any one of patent application items 1 to 3. An active energy ray-curable car exterior protection agent composition, which contains 1% by weight or more of (meth)acrylamide urethane oligomer as described in any one of patent application items 1 to 3 Thing. A resin composition for active energy ray-curable decorative films, containing 1% by weight or more of (meth)acrylamide urethane oligomer as described in any one of patent application items 1 to 3 .