TW201720851A - Urethane-modified (meth)acrylamide compounds 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 a high curing speed to active energy rays and excellent surface curability, and to provide ultraviolet curing films which have excellent surface hardening resistance, scratch resistance, bending resistance, and high transparency. By using urethane-modified (meth) acrylamide compounds of the present invention which have an urethane bond and one or more (meth) acrylamide group in the molecule, it is possible to obtain active energy ray curable resin compositions which have excellent in compatibility with organic solvents, general purpose acrylic monomers and oligomers, and have high curability to active energy rays, and to obtain curing films which have excellent adhesion, scratch resistance, bending resistance, low curing shrinkage and high transparency.

Description

Ethyl urethane modified (meth) acrylamide compound and active energy ray curable resin composition containing the same

The present invention relates to an organic solvent, a general-purpose acrylic monomer, and an oligomer, and has a high average curing molecular weight of 250 or more and less than 4,500, and (meth)acrylic acid having a high curing rate for active energy rays. Ethyl urethane-modified (meth) acrylamide compound having an equivalent weight of from 250 or more to less than 3,000 and excellent surface hardenability, heat resistance, scratch resistance, and low hardenability and shrinkage A highly transparent active energy ray-curable resin composition and a molded article thereof.

The urethane resin can be structurally designed to be soft to hard by a combination of a polyol of a raw material and a polyisocyanate, and is used in a wide range of industries and fields. In addition, the active energy ray-curable resin which is cured by ultraviolet rays (UV) and electron beam (EB) has characteristics such as productivity, energy saving, and low environmental load as compared with the thermosetting composition and the solvent-based resin composition. Therefore, in recent years, the use is expanding. In the trend of such technological innovation, the development of active energy ray-curable urethane acrylate for the unsaturated group such as acrylate at the end of the urethane resin has been actively applied. get on.

As an active energy ray-curable resin, urethane acrylate is expected to be widely used as a coating for various substrates, a hard coating agent, an adhesive, an adhesive, a sealant, an ink, etc. The structural design of the various desired compounds and the adjustment of the composition blending of the expected properties are not satisfactory and become a major problem. That is, it is extremely difficult to obtain the toughness, extensibility, high hardness, high adhesion property of the urethane structure, the rapidity of hardening associated with active energy ray hardening, surface dryness after hardening, surface hardness, and scratch resistance. , the balance of physical properties such as hardening shrinkage. As a result, in the field of rapid growth, for example, optical film bonding in the field of displays and touch panels, and hard coating and hard coating for thin films in the field of decoration, and thin film formation of optical bonding layers are required. When both high-performance and high-performance are taken into consideration, the status quo is that there is no high performance that can meet the requirements.

For example, Patent Document 1 discloses that a photocurable resin composition containing a 6- or more-functional urethane acrylate as an essential component has a non-tacky surface and is excellent in hardness, scratch resistance, and chemical resistance. Coating film. Further, Patent Document 2 proposes a reaction of a polyol skeleton obtained by reacting a hydroxyl group-containing acrylamide with a polyisocyanate to form an amine urethane acrylamide and a polyhydric alcohol. The oligomeric type of ethyl urethane acrylamide. According to Patent Document 2, by changing the polymerizable group from the acrylate group to the acrylamide group, the curing rate of the addition molding is increased by a factor of two or more, and the hardenability of the oligomer type and the adhesiveness of the surface of the cured film are different. improve. Further, Patent Document 3 discloses that an active energy ray-curable resin obtained by a reaction of a hydroxyl group-containing acrylamide and an isocyanate compound can be used to obtain an uncured state in which the viscosity and adhesion are small, and the formable hard can be wound. The coated film, Patent Document 4 discloses that excellent surface hardness and flexibility are obtained by using a curable resin composition composed of a hydroxyl group-containing acrylamide, trimethylolpropane, a polyvalent isocyanate compound, and a reaction catalyst. A hard coating layer of the formed film in the mold.

However, in these patent documents (1 to 4), there is no mention of hardening shrinkage resistance and bending resistance, and the solubility of the general-purpose monomer, the oligomer, and the resin when used together, and the obtained hardened layer are not described. Transparency, the current situation is that the aforementioned issues have not yet been resolved.

Patent Documents 5 and 6 disclose an oligomer or a polymer of urethane amide which is obtained by reacting a hydroxyl group-containing acrylamide, a polyhydric alcohol, and an isocyanate, and the former is excellent in heat stability. An optical film, which is a material for an electrophotographic apparatus which is improved in strength and which can prevent cracking. Patent Document 5 discloses that an optical film having a specific structural unit, heat resistance characteristics, and the like can be obtained by using a urethane acrylamide polymer obtained by using a specific polyol or a specific isocyanate. Patent Document 6 provides that the cleavage strength is improved by the acrylamide-containing amine group, and the hardenability is improved, and as a result, crack resistance is provided. However, these patent documents do not disclose the hardening shrinkage resistance, the bending resistance, the solubility, the transparency, etc., and the problem that the above-described ethyl urethane acrylamide compound is not balanced is not solved, and it is not possible to cope with it. A high-performance issue that requires rapid growth. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-128849 (Patent Document 3) JP-A-2009-244460 (Patent Document 4) JP-A-2010-128417 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2011-218616 (Patent Document 6) Japanese Laid-Open Patent Publication No. 2012-82288

(Problems to be Solved by the Invention) The first problem is to provide an amino carboxylic acid B which is excellent in compatibility with an organic solvent, a versatile acrylic monomer, and an oligomer, and has high curability and low hardening shrinkage ratio with respect to an active energy ray. Ester-modified (meth) acrylamide compound. Further, the second problem is to provide surface dryness (stick resistance), scratch resistance, bending resistance, and shrinkage resistance (curing resistance) of the (meth)acrylamide compound modified with the urethane. Active energy ray-curable resin which is excellent in high transparency and high adhesion. (method of solving the problem)

In order to solve the above problems, the inventors of the present invention have diligently studied and found that the number average molecular weight of one or more (meth) acrylamide groups in the molecule is 250 by using one or more of the urethane linkages in the molecule. The urethane-modified (meth) acrylamide compound having a (meth)acrylic acid equivalent of from 250 to 3,000 can achieve the above object, and the present invention has been completed.

That is, the present invention is: (1) A urethane-modified (meth) acrylamide compound having at least one urethane bond and one or more (meth) groups in the molecule. The acrylamide group is an isocyanate compound having one or more hydroxyl groups per molecule, an isocyanate compound having two or more isocyanate groups per molecule, and an N-substituted (methyl) group having a hydroxyl group represented by the general formula [1] Addition reaction of acrylamide compound; [Chemical 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 each represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may also be substituted by a hydroxyl group, and carbon. An aliphatic ring or an aromatic ring of 3 to 6, and R ₂ and R ₃ may be integrated with a nitrogen atom carrying them and further formed into a 5-7-membered ring which may also contain a saturated or unsaturated oxygen atom or a nitrogen atom. However, the case where both R ₂ and R ₃ are a hydrogen atom and the case where both R ₂ and R _{3 are} simultaneously an alkyl group are excluded, and the total of the hydroxyl groups possessed by R ₂ and R ₃ is 1 or more. (2) The ethyl methacrylate-modified (meth) acrylamide compound according to (1), wherein the number average molecular weight is from 250 to 4,500, and the (meth)acrylic equivalent is in the range of from 250 to 3,000. (3) The ethyl methacrylate-modified (meth) acrylamide compound according to (1) or (2), wherein the alcohol compound has a selected from the group consisting of an ether skeleton, an ester skeleton, a carbonate skeleton, and a polyoxyl A compound of one or more of a skeleton, an olefin skeleton, and an acrylic skeleton. (4) The ethyl urethane-modified (meth) acrylamide compound according to any one of (1) to (3), which has an ether skeleton, having a number average molecular weight of 250 to 1,500 and an acrylic equivalent of 250~ The scope of 750. (5) An active energy ray-curable resin composition comprising: the ethyl urethane-modified (meth) acrylamide compound (A) of any one of (1) to (4), 1 to 100 by weight %, polyfunctional (meth)acrylic compound (B) 0 to 90% by weight, and monofunctional (meth)acrylic compound (C) 0 to 90% by weight. (6) An active energy ray-curable adhesive composition characterized by containing a urethane-modified (meth) acrylamide compound such as (5). (7) An active energy ray-curable adhesive composition characterized by containing a urethane-modified (meth) acrylamide compound such as (5). (8) An active energy ray-curable ink jet ink composition characterized by containing a urethane-modified (meth) acrylamide compound such as (5). (9) An active energy ray-curable coating composition characterized by containing a urethane-modified (meth) acrylamide compound such as (5). (10) A curable composition for decorative active energy ray-curable nails, which comprises an ethyl carbamate-modified (meth) acrylamide compound as in (5). (11) An active energy ray-curable sealant curable composition characterized by containing an ethyl carbamate-modified (meth) acrylamide compound as in (5). (12) A curable composition for an active energy ray-curable decorative film, which comprises a urethane-modified (meth) acrylamide compound as in (5). (Effect of the invention)

According to the present invention, one or more ethyl urethane bonds in the molecule and one or more (meth) acrylamide-based ethyl carbamate-modified (meth) acrylamide compounds, and an organic solvent It is excellent in compatibility with general-purpose acrylic monomers and oligomers, and has high curability and low hardening shrinkage for active energy rays, and (meth)acrylamide compound is modified by containing the ethyl urethane. It is an active energy ray-curable resin which is excellent in surface hardenability, bending resistance, scratch resistance, and hardening shrinkage resistance, and has high transparency and high adhesion, and a molded article thereof.

The invention is described in detail below. The ethyl urethane-modified (meth) acrylamide compound of the present invention has one or more urethane bonds and one or more (meth) acrylamide groups in the molecule and each An addition reaction of an alcohol compound having one or more hydroxyl groups, an isocyanate compound having two or more isocyanate groups per molecule, and an N-substituted (meth) acrylamide containing a hydroxyl group. The ethyl urethane-modified (meth) acrylamide compound preferably has a number average molecular weight of 250 or more to less than 4,500 and an acrylic equivalent of 250 or more to less than 3,000.

The alcohol compound used in the synthesis of the ethyl urethane-modified (meth) acrylamide compound of the present invention has a hydrocarbon skeleton selected from the group consisting of an ether skeleton, an ester skeleton, a carbonate skeleton, a polyfluorene skeleton, an olefin skeleton, and an acrylic skeleton. One or two or more kinds of skeleton alcohol compounds.

The alcohol compound having an ether skeleton is one having one or more hydroxyl groups at the terminal or side chain of the ether skeleton in the molecule, and commercially available products include diethylene glycol, dipropylene glycol, dibutyl glycol, and PTMG series, for example, PTMG650 (Mitsubishi Chemical Co., Ltd.), Sannix PP, GP, GOP series, for example: Sannix PP-1000, GP-250, GOP-600 (Sanyo Chemical Industry Co., Ltd.), PEG series, for example: PEG300, Uniox Series, Uniol D, TG, HS, PB series, for example: Uniol D-700, TG-1000, HS-1600D, PB-700, Unilube DGP series, Polycerin DC, DCB series (Nippon Oil Co., Ltd.).

The alcohol compound having an ester skeleton is one in which the terminal or the side chain of the ester skeleton has one or more hydroxyl groups in the molecule, and commercially available products include Curadiol polyols P, F, N, and PMNA series, for example, Curaray. Polyols P-1010, N-2010, PMNA-2016 (made by Kuraray Co., Ltd.), Placcel series, for example: Placcel 205 (made by Daicel), Priplast series, for example: Priplast 1900 (Croda Japan) ), Teslac series, for example, Teslac 2456 (Hitachi Chemical Co., Ltd.) and the like.

The alcohol compound having a carbonate skeleton has one or more hydroxyl groups at the terminal or side chain of the carbonate skeleton in the molecule, and a commercially available product includes a Placcel CD series, for example, Placcel CD210 (manufactured by Daicel Co., Ltd.), ETERNACOLL UH. , UHC, UC and UM series, such as ETERNACOLL UH-100, UHC50-100, UC-100, UM-90 (3/1) (Ube Industries, Ltd.), Duranol T and G series, such as Duranol T6001 ( Asahi Kasei Chemicals Co., Ltd., NIPPOLLAN series, for example: NIPPOLLAN 981 (made by Tosoh Co., Ltd.), Curaray Polyol C series, for example: Curaray Polyol C-590 (Kuraray Co., Ltd.) )Wait.

The alcohol compound having a polyfluorene skeleton is a compound having a siloxane chain in the main chain and having one or more hydroxyl groups at both ends or side chains, and commercially available products include KF-6000 and X-21-. 5841 (Shin-Etsu Chemical Industry Co., Ltd.), BY 16-201 (Dongli Dow Corning Co., Ltd.), XF42-B0970 (made by Momentive Performance Materials Co., Ltd.), Silaplane series, for example: Silaplane FM-0411 (JNC) ))).

The alcohol compound having an olefin skeleton is a conjugated or non-conjugated olefin skeleton or a hydrogenated skeleton thereof in the molecule, and has one or more hydroxyl groups at the terminal or side chain. Commercially available products include the NISSO-PB series. For example: NISSO-PB G-1000, GI-1000 (made by Japan Soda Co., Ltd.), Poly bd series (made by Idemitsu Kosan Co., Ltd.), Krasol series, for example: Krasol L BH2000, HLBH-P2000 (Crayvalley Co., Ltd.) , Pripol series (Croda Japan).

The alcohol compound having an acrylic skeleton is a polymer obtained by polymerizing one or more acrylic monomers, and has one or more hydroxyl groups at the terminal or side chain of the molecule. For example, a homopolymer of a hydroxyl group-containing acrylic monomer such as hydroxy (meth)acrylic acid acrylate or hydroxyacrylic (meth)acrylamide or a copolymer thereof with a monomer having an unsaturated group is used. Commercially available products include UMM-1001 and UT-1001 (manufactured by Konica Chemical Co., Ltd.).

The alcohol compound having the above various skeletons may be used alone. Alternatively, two or more kinds of the alcohol compounds of the same skeleton or the alcohol compounds of different skeletons may be used in combination.

The isocyanate compound used for the synthesis of the urethane-modified (meth) acrylamide compound of the present invention has two or more isocyanate groups in one molecule, and examples thereof include trimethylene diisocyanate. Aliphatic isocyanates such as hexamethylene diisocyanate, 1,2-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,4-phenylene diisocyanate, 2, Aromatic isocyanates such as 4-tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylene diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, 4,4'-di Cyclohexyl isocyanate such as cyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate or 2,6-norbornane diisocyanate, and urea-containing isocyanate such as "Desmodur XP2565" (manufactured by Bayer Polyurethane Co., Ltd.) Isocyanates of acid ester groups or polymers of such adducts, isocyanurates, biurets, etc., such as Coronate L, HL, HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), Duranate 24A -100 (Asahi Kasei Industrial Co., Ltd.) and so on. These isocyanate compounds may be used alone or in combination of two or more.

The hydroxyl group-containing N-substituted (meth) acrylamide compound used in the synthesis of the ethyl methacrylate-modified (meth) acrylamide compound of the present invention is a compound represented by the general formula [1], here, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R _{3 are the} same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may also be substituted by a hydroxyl group, and carbon 3 to 6 An aliphatic ring or an aromatic ring, and R ₂ and R ₃ may be further integrated with a nitrogen atom carrying them, and may further contain a saturated or unsaturated 5-7 member ring of an oxygen atom or a nitrogen atom. However, when R ₂ and R _{3 are} both a hydrogen atom and R ₂ and R _{3 are} simultaneously an alkyl group, the total of the hydroxyl groups of R ₂ and R ₃ is 1 or more.

[Chemical 2]

The N-substituted (meth) acrylamide containing a hydroxyl group, specifically, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (Meth) acrylamide, N-hydroxyisopropyl (meth) acrylamide, N-methyl hydroxymethyl (meth) acrylamide, N-methyl hydroxyethyl (meth) propylene oxime Amine, N-ethylhydroxymethyl(meth)acrylamide, N-ethylhydroxyethyl(meth)acrylamide, N-ethylhydroxyisopropyl(meth)acrylamide, n-propyl Hydroxymethyl (meth) acrylamide, n-propyl hydroxyisopropyl (meth) acrylamide, N-isopropyl hydroxyethyl (meth) acrylamide, N, N-dihydroxymethyl (meth)acrylamide, N,N-dihydroxyethyl(meth)acrylamide, N,N-dihydroxypropyl(meth)acrylamide, N,N-dihydroxyisopropyl (Meth) acrylamide, N-[2-(3,4-dihydroxyphenyl)ethyl]propenamide, 4-(hydroxy)methacrylamide, N-[1,1-double (hydroxymethyl)ethyl]propenylamine, N-[1-(hydroxymethyl)propyl]methacrylamide, N-(2-hydroxyphenyl)methacrylamide, N-(2 -hydroxy-5-methylphenyl)propene Indoleamine, 1-[4-(2-hydroxyethyl)-1-piperidin Bis-2-propen-1-one, 1-propenyl-4-hydroxypiperidine. Further, it is particularly preferable that the urethane-modified acrylamide compound obtained by using a hydroxyl group-containing acrylamide is improved in the curability of the urethane-modified acrylamide compound and the surface coating effect of the surface of the coating film formed therefrom is high. These hydroxyl group-containing (meth) acrylamides may be used alone or in combination of two or more.

The method for synthesizing the urethane-modified acrylamide compound of the present invention is not particularly limited, and can be synthesized in accordance with a known urethane reaction technique. In the blending ratio of the raw materials, the total of the hydroxyl groups is preferably an equivalent or more with respect to the total of the isocyanate groups, wherein the hydroxyl group in the hydroxyl group/isocyanate group/(meth)acrylamide of the alcohol compound becomes 1/1/0.5. The ratio of 1/3/2.5 makes the reaction particularly good. If the blending ratio of the isocyanate group exceeds this range, it may cause time-dependent thickening and coloration of the urethane-modified acrylamide compound. On the other hand, when the hydroxyl group of the (meth) acrylamide compound exceeds this range, the obtained urethane-modified acrylamide compound has a reduced water resistance and moisture resistance.

The ethyl carbamate reaction of the present invention can be carried out by mixing an alcohol compound, an isocyanate compound, and a hydroxyl group-containing N-substituted (meth) acrylamide, which are a raw material, and increasing the temperature as needed, and carrying out the method. The reaction is carried out at a temperature of from 10 to 160 ° C, preferably from 20 to 140 ° C. The mixing of the raw materials can be carried out all at once or in several stages. Further, the reaction may be solvent-free, but may be carried out in an organic solvent or a reactive diluent as needed. Can be used in solvents such as: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl acetamide, dimethyl hydrazine, ethyl acetate, butyl acetate, It is carried out in the presence of tetrahydrofuran, hexane, cyclohexane, benzene, toluene, xylene, an aliphatic hydrocarbon solvent (petroleum ether, etc.). Further, the reactive diluent which can be used is not particularly limited as long as it does not react with an isocyanate and does not react with a hydroxyl group, and examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Long-chain aliphatic acrylate, allyl acrylate, cyclohexyl acrylate, 1,6-hexane diacrylate, tetraethylene glycol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane three Acrylate, isodecyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethyl methacrylate, diethyl acrylamide, N-propylene fluorenyl Porphyrin and the like. The organic solvent or reactive diluent is used in an amount of from 0 to 400% by weight, preferably from 0 to 200% by weight, based on the isocyanate compound.

Further, in the ethyl carbamate reaction, a catalyst may be added to promote the reaction. The catalyst is, for example, potassium or sodium salt of alkylphosphonic acid, sodium, potassium, nickel, cobalt, cadmium, barium, calcium, zinc and the like, and dibutyltin dilaurate, of a fatty acid having 8 to 20 carbon atoms. Dioctyltin maleate, dibutyltinbutoxide, bis(2-ethylhexyl)tin oxide, 1,1,3,3-tetrabutyl-1,3-diethoxycarbonyl Organotin compounds such as stannoxanes, N,N,N',N'-tetramethylguanidine, 1,3,5-parade (N,N-dimethylaminopropyl)hexahydro-S-three 1,8-diazabicyclo[5.4.0]undecene-7, N,N'-dimethylperazine N-ethyl A tertiary amine compound such as a porphyrin, N,N-dimethylethanolamine, 1-methylimidazole or triethylenediamine may be used alone or in combination of two or more. The total amount of the catalyst used is preferably 1% by weight or less based on the total weight of the raw material components, and more preferably 0.1% by weight or less.

In order to inhibit the double bond of the N-substituted (meth) acrylamide containing a hydroxyl group and the obtained double bond of the urethane-modified (meth) acrylamide to cause radical polymerization, free radical polymerization may be used as needed. Prohibition agent. a radical polymerization inhibiting agent, for example, hydroquinone, methoxyhydroquinone, benzamidine, an antimony polymerization inhibitor such as p-t-butylcatechol; 2,6-di-t-butylphenol, 2, 4-di-tert-butylphenol, 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri- An alkylphenol-based polymerization inhibitor such as a third butyl phenol; an alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, and a thiophene An amine-based polymerization inhibitor, N-oxyl radicals such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl radical; copper dimethyldithiocarbamate, diethyl A copper dithiocarbamate-based polymerization inhibitor such as copper dithiocarbamate or copper dibutyldithiocarbamate may be used singly or in combination of two or more kinds.

The amount of the polymerization inhibitor may be appropriately set depending on the type, blending amount, and the like of the N-substituted (meth) acrylamide containing a hydroxyl group, and the polymerization inhibitory effect, the ease of production, and the economy are considered. The (meth) acrylamide modified with respect to the obtained urethane is usually 0.001 to 5% by weight, more preferably 0.01 to 1% by weight.

The number average molecular weight of the ethyl urethane-modified (meth) acrylamide of the present invention is from 250 or more to less than 4,500, and further preferably from 250 to less than 3,000. When the number average molecular weight is less than 250, the ratio of the monofunctional low molecular component is high, and the obtained ethyl urethane-modified (meth) acrylamide is hardenable, and for the organic solvent and the general-purpose acrylic monomer. On the other hand, if the number average molecular weight exceeds 4,500, the crosslinking density is lowered, and the curability and the tack resistance are not sufficiently satisfied, which is not preferable.

The ethyl urethane-modified (meth) acrylamide of the present invention has an acrylic acid equivalent of from 250 or more to less than 3,000, more preferably from 250 to 2,500. When the acrylic equivalent is less than 250, the density of the (meth) acrylamide group which is a polymerizable group is high, and the production process of the ethyl urethane-modified (meth) acrylamide and the subsequent polymerization at the time of storage are likely to occur. On the other hand, if the acrylic equivalent is more than 3,000 and the crosslinking density is lowered, the curability and the tack resistance are not sufficiently satisfied, which is not preferable.

The ethyl urethane-modified (meth) acrylamide having an ether skeleton of the present invention preferably has an acrylic acid equivalent of from 250 to 750. When the ethyl acrylate-modified (meth) acrylamide modified with an ether skeleton has an acrylic equivalent of less than 250, it is not preferable as described above, and if the acrylic equivalent is more than 750, the urethane is modified (methyl In the intramolecular or intermolecular hydrogen bond of acrylamide, it is difficult to form a hydrogen bond.

The ethyl urethane-modified (meth) acrylamide of the present invention is used alone, in accordance with the skeleton derived from an alcohol, the type of (meth)acrylamide group, the acrylic acid equivalent and the molecular weight, and the active energy ray hardenability. The surface of the obtained cured film (dryness) (viscosity resistance), physical properties such as adhesion to various substrates, and properties are different, and it is preferably within the following range.

The ethyl urethane-modified (meth) acrylamide of the present invention can be completely hardened by irradiation with active energy rays. The amount of active energy ray irradiation (accumulated light amount) varies depending on the type of (meth) acrylamide group and the acrylic acid equivalent, but is preferably 0.1 to 2,000 mJ/cm ² , and further preferably about 1 to 1,000 mJ/cm. ^{2 is} particularly ideal. When the amount of accumulated light is less than 0.1 mJ/cm ² , the portion where the hardening is incomplete remains, and the hardness, water resistance, and durability of the entire cured product are lowered. When the amount of accumulated light exceeds 2,000 mJ/cm ² , side reactions such as decomposition occur due to excessive energy, and the cured film tends to be easily colored.

The water-repellent film of the cured film composed of ethyl urethane-modified (meth) acrylamide of the present invention preferably has a water absorption ratio of 2% or less, more preferably 1% or less. When the water absorption rate is larger than 2%, when used for a long period of time in a high-humidity environment, the cured film may absorb water over time and deform in shape due to expansion, so adhesion and transparency may be lowered.

The hardening shrinkage ratio of the methyl methacrylate-modified (meth) acrylamide of the present invention is evaluated when the floating height of the cured film by ultraviolet irradiation is evaluated (the evaluation of the curl resistance), and the floating height is preferably It is preferably 1 cm or less, more preferably 0.5 cm or less. When the floating of the cured film is larger than 1 cm, the deformation of the film causes a decrease in the adhesion to the substrate, and as a result, the curable resin composition containing the urethane-modified (meth) acrylamide is used. The molded article of the composition is likely to have a decrease in water resistance, durability, bending resistance, and the like, and may not be able to maintain the shape stably.

The polyfunctional (meth)acrylic compound (B) used in the present invention is a polyfunctional (meth) acrylate or a polyfunctional (meth) acrylamide. For example: alkyl (di) (meth)acrylate, dicyclopentanyl (meth)acrylate, and caprolactone modified dicyclopentanyl (meth)acrylate, such as ethylene di(meth)acrylate Ester ester, neopentyl tetra(meth)acrylate, neopentyl tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate , trimethylolpropane tri (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate, acrylate (two Alkylene glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy (meth)acrylate, Monomers and oligomers such as ethyl urethane (meth) acrylate and ethyl urethane (meth) acrylamide. Further, these polyfunctional (meth) acrylates may be used alone or in combination of two or more.

The monofunctional (meth)acrylic compound (C) used in the present invention is a monofunctional (meth) acrylate or a monofunctional (meth) acrylamide. Further, a polymerizable 4-stage salt ionic compound may be contained as needed. Further, the monofunctional (meth)acrylic compound may be used singly or in combination of two or more.

Monofunctional (meth) acrylate, for example: alkyl (meth) acrylate of methyl (meth) acrylate, ethyl hydroxy acrylate, ethyl alkoxy (meth) acrylate, methoxy (methyl) Diethylene glycol acrylate, ethyl 2-(2-ethoxyethoxy)acrylate, ethyl phenoxy (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate Ethyl phenoxy (meth) acrylate, dicyclopentanyl (meth) acrylate, isodecyl (meth) acrylate, tetrahydrofuran methyl acrylate, 2-methyl-2-adamantane (meth) acrylate A hydroxy (meth) acrylate such as an ester, allyl (meth) acrylate or ethyl hydroxy (meth) acrylate.

The monofunctional (meth) acrylamide used in the present invention is, for example, N-alkyl (meth) acrylamide, N-alkoxyacryl (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N-[3-(dimethylamino)]propylpropenylamine, N,N-dimethyl(meth)acrylamide, N,N-diethyl ( Methyl) acrylamide, N-propylene fluorenyl A hydroxyalkyl (meth) acrylamide such as a porphyrin or a hydroxyethyl acrylamide.

The urethane-modified (meth) acrylamide compound (A) of the present invention is preferably contained in an active energy ray-curable resin composition in an amount of 1% by weight or more. If it is less than 1% by weight, good surface hardenability, bending resistance, scratch resistance, and the like may not be obtained. Further, the content of the polyfunctional (meth)acrylic compound (B) in the curable resin composition is preferably 90% by weight or less. When the content of the (B) exceeds 90% by weight, the liquid viscosity of the curable resin composition rises, and it is difficult to mix and apply, which causes an operational problem, which is not preferable. In addition, when the monofunctional (meth)acrylic compound (C) is blended in the curable resin composition, it is preferably 90% by weight or less in order to maintain sufficient scratch resistance and hardenability.

A polymerizable fourth-order salt ionic compound can be added to the active energy ray-curable resin composition of the present invention. For example, ionic vinyl monomers and/or oligomers or polymers containing them as constituent components. The sulfonium salt in which an ionic vinyl single-system cation and an anion are combined is specifically a (meth) acrylate-based or (meth) acrylamide-based ammonium ion or an imidazolium ion, and an anion can be enumerated. Halogen ions such as Cl ^- , Br ^- , I ^- or OH ^- , CH ₃ COO ^- , NO ₃ ^- , ClO ₄ ^- , PF ₆ ^- , BF ₄ ^- , HSO ₄ ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^{- an} inorganic acid anion or an organic acid anion such as CH ₃ C ₆ H ₆ SO ₃ ^- , C ₄ F ₉ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , SCN ^- or the like.

The ion of the fourth-stage salt ionic compound easily forms a hydrogen bond or an ionic bond with the coated substrate, and imparts conductivity and antistatic property, so that the moisture permeability can be improved, and the coating can be more uniformly applied and stabilized. Film formation. Further, since the polymerizable fourth-order salt ionic compound itself is also an active energy ray-curable compound, it can be copolymerized with the active energy ray-curable resin composition without osmosis, providing permanent impartance of conductivity and antistatic. Auxiliary effect and adhesion improvement effect. The blending amount of these ionic compounds can be adjusted by the number of functional groups and molecular weight of the ion pair, and thus is not particularly limited. In general, 0 to 50% by weight is added to the active energy ray-curable resin composition, and 0 to 10% by weight is preferred. When the blending amount of the ionic compound exceeds 50% by weight, it varies depending on the type, but the transmittance of the cured film may be lowered.

The active energy ray of the present invention is defined as an energy ray capable of decomposing a compound (photopolymerization initiator) which produces an active species 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 the active energy ray-curable resin composition of the present invention is cured, a photopolymerization initiator is added first. The photopolymerization initiator is not particularly necessary when an electron beam is used as the active energy ray, but it is necessary when ultraviolet rays are used. The photopolymerization initiator can be appropriately selected from usual products such as acetophenone-based, benzoin-based, benzophenone-based, and thioxanthone. Among the photopolymerization initiators, commercially available photopolymerization initiators are available under the trade names 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 and so on. These photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator to be used is not particularly limited, and is usually from 0 to 10% by weight, preferably from 1 to 5% by weight, based on the active energy ray-curable resin composition. When it exceeds 10% by weight, there is a possibility that the strength of the cured film is lowered and yellowing is caused.

The pigment, the dye, the surfactant, the anti-blocking agent, the leveling agent, the dispersing agent, and the defoaming can be used together without impairing the characteristics of the active energy ray-curable resin composition of the present invention and the molded article produced thereby. Other optional ingredients such as agents, antioxidants, UV sensitizers, preservatives, etc.

The active energy ray curable resin composition of the present invention can be applied to paper, cloth, nonwoven fabric, glass, polyethylene terephthalate, cellulose diacetate, cellulose triacetate, acrylic polymer Polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide, and other substrates such as plastics and metals, and hardened by active energy rays such as ultraviolet rays. A high performance coating layer, ink layer, adhesive layer or adhesive layer is obtained. In particular, the active energy ray-curable resin composition of the present invention has a highly transparent urethane oligomer, and is suitable as an optical adhesive, an optical adhesive, a coating material for an optical film, or the like. The optical resin composition is used. Further, examples of the method of applying the resin composition on a substrate include a spin coating method, a spray coating method, a dip coating method, a gravure printing roll method, a knife coating method, a reverse roll method, a screen printing method, a coating bar method, and the like. The usual film formation method. Further, a method of applying between the substrates may be a lamination, a roll to roll method, or the like. [Examples]

Hereinafter, the present invention will be specifically described in detail by using the synthesis examples and the evaluation examples, but the present invention is not limited to the examples. Further, among the following, % other than the yield represents % by weight. The physical property analysis of the obtained ethyl urethane-modified (meth) acrylamide was carried out in the following manner.

(1) Determination of the molecular weight and the number average molecular weight of the urethane-modified (meth) acrylamide obtained by the calculation of the acrylic acid equivalent by high-speed liquid chromatography ("LC-10A" manufactured by Shimadzu Corporation) Column: Shodex GPC KF-803L (excluding the limit molecular weight: 7 × 10 ⁴ , separation range: 100 ~ 7 × 10 ⁴ , theoretical number of layers: 18,000 layers / root, filler material: styrene-divinylbenzene copolymerization The particle size of the material and the filler: 10 μm)) and the solution of the tetrahydrofuran in the solution were measured and calculated based on the molecular weight of the standard polystyrene. Further, the acrylic acid equivalent (molecular weight of each (meth) acrylamide group) was calculated. (2) Viscosity measurement: 1 part by weight of ethyl methacrylate-modified (meth) acrylamide, and 1 part by weight of tetrahydrofuran were uniformly mixed, and used in a cone-and-plate type viscometer (device name: RE550 type viscometer Machine Industry Co., Ltd.) The viscosity of the solution at 25 ° C was measured in accordance with JIS K5600-2-3.

The synthesis of the urethane-modified (meth) acrylamide compound (A) is as follows. Synthesis Example 1 Synthesis of ethyl urethane-modified (meth) acrylamide amine YY-1 In a 4-neck flask equipped with a stirrer, a thermometer, a cooler, and a dry gas introduction tube, a volume of 300 mL was charged with isophorone II. Isocyanate (IPDI) 44.4g (0.2mol), ETERNACOLL UC-100 (polycarbonate polyol, manufactured by Ube Industries, Ltd., number average molecular weight: 1,000) 90g (0.09mol), Pripol2033 (dimer diol, Croda Japan The company's system, the average molecular weight: 540) 5.4g (0.01mol), methyl ethyl ketone (MEK) 48.6g, dibutyl hydroxy toluene (BHT) 0.08g, while heating to nitrogen at 70 ° C, add two laurel 16.2 mg of dibutyltin acid was allowed to react at 70 ° C for 4 hours. Then, 23.0 g (0.2 mol) of hydroxyethyl acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademark "HEAA") was added, and stirring was continued for 3 hours while maintaining the internal temperature at 80 ° C under a stream of dry air. . The solvent was distilled off by a reduced pressure method to obtain 161.9 g of a viscous liquid UY-1. Infrared absorption spectroscopy (IR) analysis was carried out, and the characteristic absorption (2260 cm ^-1 ) of the isocyanate group of the raw material IPDI was completely disappeared and the characteristic absorption (1650 cm ^-1 ) of the amine group derived from "HEAA" and the resulting urethane were formed. The characteristic absorption of the ethyl ester bond (1740 cm ^-1 ) confirmed that the desired urethane-modified (meth) acrylamide amine UY-1 had been formed. The obtained UY-1 had a number average molecular weight of 1,600, an acrylic equivalent of 800, and a solution viscosity of 20 mPa·s at 25 °C.

Synthesis Example 2 Synthesis of ethyl urethane-modified (meth) acrylamide amine UY-2 The same apparatus as in Synthesis Example 1 was used, and it was charged with Unilube DGP-700F (polyether polyol, tetrafunctional, and Nippon Oil Co., Ltd. Amount of the average molecular weight: 700) 17.5 g (0.025 mol), ETERNACOLL UH-50 (polycarbonate polyol, manufactured by Ube Industries, Ltd., number average molecular weight: 500) 50 g (0.1 mol), hexamethylene diisocyanate (HDI 52.4 g (0.2 mol), MEK 39.4 g, and BHT 0.07 g were heated to 65 ° C while passing dry nitrogen gas, and 0.13 g of triethylenediamine was added dropwise thereto, and the mixture was reacted at 65 ° C for 5 hours. Then, 11.5 g (0.1 mol) of "HEAA" was charged, and stirring was continued for 3 hours while maintaining the internal temperature of the system under a stream of dry air at 65 °C. The solvent was distilled off by a reduced pressure method to obtain 131.4 g of a viscous liquid UY-2. In the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane-modified (meth) acrylamide amine UY-2 was produced. The obtained UY-2 had a number average molecular weight of 4,480, an acrylic equivalent of 1,120, and a solution viscosity of 25 mPa·s at 25 °C.

Synthesis Example 3 Synthesis of ethyl urethane-modified (meth) acrylamide amine YY-3 The same apparatus as in Synthesis Example 1 was used, and dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI) was charged. 16.8 g (0.1 mol), UMMA-1001 (acrylic-based polyol (methacrylate main skeleton, monofunctional, manufactured by Amika Chemical Co., Ltd., number average molecular weight: 1,000) 50 g (0.05 mol), UH-100 (polycarbonate polyol) Manufactured by Ube Hiroshi Co., Ltd., the average molecular weight of the product: 1000) 50g (0.05mol), BHT 0.06g, while heating to 65 ° C while passing dry nitrogen, adding 12.3 mg of dibutyltin dilaurate, and making it at 65 ° C After reacting for 4 hours, "HEAA" 5.8 g (0.05 mol) was further charged, and stirring was continued for 3 hours while maintaining the internal temperature at 65 ° C under a stream of dry air to obtain 122.6 g of a viscous liquid UY-3. In the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane-modified (meth) acrylamide amine UY-3 was produced. The obtained UY-3 had a number average molecular weight of 2,700 and an acrylic equivalent of 2,700. The solution viscosity at 25 ° C was 23 mPa·s.

Synthesis Example 4 Synthesis of ethyl urethane-modified (meth) acrylamide amine UY-4 The same apparatus as in Synthesis Example 1 was used, and an IPDI-containing isocyanurate (IPDInurate) 16.7 g (0.025 mol) was charged. Kuraray polyol P-530 (polyester polyol, manufactured by Kuraray Co., Ltd., number average molecular weight 500) 37.5g (0.075mol), MEK 24.2g, BHT 0.04g, dibutyltin dilaurate 8.1mg Dry nitrogen gas was passed through, and 16.3 g (0.075 mol) of IPDI was added dropwise while maintaining the dropping rate to maintain a state of 65 ° C, and the reaction was allowed to proceed at 65 ° C for 2 hours. Then, N-methylhydroxyethyl decylamine (MHEAA) 9.7 g (0.08 mol) was charged, and stirring was continued for 5 hours under a flow of dry air while maintaining the internal temperature at 65 °C. The solvent was distilled off by a reduced pressure method to obtain 80.5 g of a viscous liquid UY-4, and it was confirmed by IR analysis in the same manner as in Synthesis Example 1 to form a desired ethyl urethane-modified (meth) acrylamide amine UY. -4. The obtained UY-4 had a number average molecular weight of 3,200, an acrylic equivalent of 1,100, and a solution viscosity of 28 mPa·s at 25 °C.

Synthesis Example 5 Synthesis of ethyl urethane-modified (meth) acrylamide amine UY-5 The same apparatus as in Synthesis Example 1 was used, and GI-1000 (manufactured by Japan Soda Co., Ltd., number average) was used. After molecular weight 1,500) 75 g (0.05 mol), MEK 34.2 g, BHT 0.06 g, and pentamethyldiethylenetriamine 0.11 g, while passing dry nitrogen gas, the hydrogenation MDI 26.2 g (0.1 mol) was added while adjusting the dropping rate. It was kept at 70 ° C and allowed to react at 70 ° C for 4 hours. Then, 12.9 g (0.10 mol) of hydroxyethylmethacrylamide (HEMAA) was fed, and stirring was continued for 4 hours while maintaining the internal temperature at 70 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 114.1 g of a viscous liquid UY-5, and the same analysis as in Synthesis Example 1 was carried out by IR analysis to confirm that the desired ethyl urethane-modified (meth) acrylamide was formed. UY-5. The obtained UY-5 had a number average molecular weight of 2,250, an acrylic equivalent of 1,130, and a solution viscosity of 80 mPa·s at 25 °C.

Synthesis Example 6 Synthesis of ethyl urethane-modified (meth) acrylamide amide UY-6 The same apparatus as in Synthesis Example 1 was used, and KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd. Number average molecular weight: 1,000) 50g (0.05mol), trimethylhexamethylene diisocyanate (TMHDI) 21.0g (0.1mol), BHT 0.04g, while passing dry nitrogen, heating to 70 ° C, adding two 8.3 mg of dibutyltin laurate was allowed to react at 70 ° C for 5 hours. Then, 11.5 g (0.1 mol) of "HEAA" was fed, and stirring was continued for 3 hours while maintaining the internal temperature of the system under a flow of dry air at 80 °C. 82.5 g of the viscous liquid UY-6 was obtained, and in the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane-modified (meth) acrylamide amine UY-6 was produced. The obtained UY-6 had a number average molecular weight of 1,700, an acrylic equivalent of 830, and a solution viscosity of 12 mPa·s at 25 °C.

Synthesis Example 7 Synthesis of ethyl urethane-modified (meth) acrylamide amide UY-7 The same apparatus as in Synthesis Example 1 was used, and it was charged with Uniol D-250 (polypropylene glycol, Nippon Oil Co., Ltd., number average molecular weight: 250 25 g (0.1 mol), HDI 33.6 g (0.2 mol), and BHT 0.04 g, while passing dry nitrogen gas, while raising the temperature to 75 ° C, 8.2 mg of dibutyltin dilaurate was added dropwise, and the reaction was carried out at 75 ° C for 3 hours. . Then, 23.0 g (0.2 mol) of "HEAA" was fed, and stirring was continued for 3 hours while maintaining the internal temperature of the system under a flow of dry air at 75 °C. 81.6 g of the viscous liquid UY-7 was obtained, and in the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane-modified (meth) acrylamide amine UY-7 was produced. The obtained UY-7 had a number average molecular weight of 820, an acrylic equivalent of 400, and a solution viscosity of 8 mPa·s at 25 °C.

Comparative Synthesis Example 1 Synthesis of urethane acrylate oligomer (UA-1) was carried out in the same manner as in Synthesis Example 1, and charged in Duranol T4672 (polycarbonate polyol, manufactured by Asahi Kasei Chemical Co., Ltd., number average molecular weight: 2,000) 100g (0.05mol), IPDInurate 11.1g (0.02mol), MEK38.4g, BHT 0.06g, after heating to 80 ° C, add 12.8mg of dibutyltin dilaurate, while passing dry nitrogen, adjust the drop acceleration IPDI 14.7 g (0.07 mol) was added thereto, maintained at 80 ° C, and reacted at 80 ° C for 4 hours. Then, "HEAA" 9.4 g (0.08 mol) was charged, and stirring was continued for 3 hours while maintaining the internal temperature at 80 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 135.2 g of a viscous liquid UA-1. In the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the urethane acrylate oligomer UA-1 was produced. The obtained UA-1 had a number average molecular weight of 7,700, an acrylic equivalent of 2,600, and a solution viscosity of 250 mPa·s at 25 °C.

Comparative Synthesis Example 2 Synthesis of urethane acrylate oligomer (UA-2) was carried out in the same manner as in Synthesis Example 1, and charged into Uniol D-400 (polypropylene glycol, manufactured by Nippon Oil Co., Ltd., number average molecular weight: 400) 53.3 g After (0.13 mol), BHT 0.06 g, and dibutyltin dilaurate (12.1 mg), 52.4 g (0.2 mol) of hydrogenated MDI was added dropwise while adjusting the dropping rate while maintaining dry nitrogen gas to maintain at 80 ° C and at 80 ° C. It reacted for 5 hours. Then, "HEAA" 15.3 g (0.13 mol) was fed, and stirring was continued for 3 hours while maintaining the internal temperature of the system under a flow of dry air at 80 °C. 121.0 g of the viscous liquid UA-2 was obtained, and in the same manner as in Synthesis Example 1, it was confirmed by IR analysis that the urethane acrylate oligomer UA-2 was produced. The obtained UA-2 had a number average molecular weight of 1,900, an acrylic equivalent of 950, and a solution viscosity of 24 mPa·s at 25 °C.

Comparative Example Synthesis 3 The urethane acrylate oligomer UA-3 was synthesized in the same manner as in Synthesis Example 1, and charged with KF-6000 60 g (0.06 mol), IPDI 26.6 g (0.12 mol), and BHT 0.05 g. While drying with dry nitrogen gas, the temperature was raised to 80 ° C, and 10.1 mg of dibutyltin dilaurate was added dropwise, and the mixture was reacted at 80 ° C for 4 hours. Then, 13.9 g (0.12 mol) of hydroxyethyl acrylate (HEA) was fed, and stirring was continued for 3 hours while maintaining the internal temperature at 70 ° C under a stream of dry air. 100.6 g of a viscous liquid was obtained, and in the same manner as in Synthesis Example 1, it was confirmed by IR analysis that urethane acrylate oligomer UA-3 was produced. The obtained UA-3 had a number average molecular weight of 1,500, an acrylic equivalent of 850, and a solution viscosity of 10 mPa·s at 25 °C.

Comparative Example Synthesis 4 The urethane acrylate oligomer UA-4 was synthesized in the same manner as in Synthesis Example 1, and charged into Uniol TG-330 (polyoxypropylene glyceryl ether, trifunctional, Nippon Oil Co., Ltd., number average). Molecular weight: 330) 13.2g (0.04mol), IPDInurate 79.9g (0.12mol), MEK 36.3g, BHT 0.06g, while drying nitrogen gas, while heating to 65 ° C, adding 12.1 mg of dibutyltin dilaurate, The reaction was allowed to proceed at 65 ° C for 4 hours. Then, HEA 27.8 g (0.24 mol) was charged, and stirring was continued for 4 hours while maintaining the internal temperature at 65 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 121.0 g of a solid urethane acrylate oligomer UA-4. In the same manner as in Synthesis Example 1, it was confirmed by IR analysis that UA-4 was produced. The obtained UA-4 had a number average molecular weight of 3,000, an acrylic equivalent of 500, and a solution viscosity of 23 mPa·s at 25 °C.

Comparative Example Synthesis 5 Adductate Type Ethyl Carbamate Acrylamide UA-5 Synthesis Referring to Example 2 of Patent Document 2 (JP-A-2002-37849), tolyldiisocyanate (TDI) was added. 74.8 g (0.43 mol) and "HEAA" 100 g (0.87 mol) were reacted in 180 g of N,N-dimethylformamide (DMF) at 40 ° C for 4 hours to carry out synthesis, and the solvent was distilled off by a reduced pressure method. The urethane acrylamide UA-5 was obtained as a solid addition type. The obtained UA-5 had a number average molecular weight of 400 and a solution viscosity of 8 mPa·s at 25 °C.

The synthesis of the polyfunctional (meth)acrylic compound (B) is as follows. Synthesis Example 8 Synthesis of Reactive Ethyl Carbamate Polymer UP-1 Using the same apparatus as in Synthesis Example 1, ETERNACOLL UC-100 75 g (0.075 mol), MEK 51.5 g, BHT 0.06 g, and dibutyltin dilaurate were charged. 11.1 mg, while raising the temperature to 65 ° C while passing dry nitrogen, IPDI 26.2 g (0.12 mol) was added dropwise, and the reaction was allowed to proceed at 65 ° C for 4 hours. Thereafter, 10.0 g (0.09 mol) of "HEAA" was fed, and stirring was continued for 4 hours while maintaining the internal temperature of the system under a stream of dry air at 65 °C. The solvent was distilled off by a reduced pressure method to obtain 111.1 g of a viscous liquid UP-1. In the same manner as in Synthesis Example 1, the desired reactive urethane polymer UP-1 was confirmed by IR analysis. The obtained UP-1 had a number average molecular weight of 4,700, an acrylic equivalent of 1,560, and a solution viscosity of 55 mPa·s at 25 °C.

Synthesis Example 9 Synthesis of reactive urethane polymer UP-2 was carried out in the same manner as in Synthesis Example 1, and charged with TDI 8.7 g (0.05 mol) and PTMG2000 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, The number average molecular weight: 2,000) 90 g (0.045 mol), MEK 50.0 g, BHT 0.05 g, and the temperature was raised to 75 ° C while passing dry nitrogen gas, and 10.0 mg of dibutyltin dilaurate was added dropwise, and the reaction was carried out at 75 ° C for 3 hours. . Then, 1.3 g (0.01 mol) of hydroxyethyl methacrylate (HEMA) was fed, and stirring was continued for 3 hours while maintaining the internal temperature at 75 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 100.0 g of a viscous liquid UP-2. In the same manner as in Synthesis Example 1, the desired reactive urethane polymer UP-2 was confirmed by IR analysis. The obtained UP-2 had a number average molecular weight of 20,000, an acrylic equivalent of 10,000, and a solution viscosity of 180 mPa·s at 25 °C.

Synthesis Example 10 Synthesis of Reactive Ethyl Formate Polymer UP-3 Using the same apparatus as in Synthesis Example 1, IPDI 11.1 g (0.05 mol) and ETERNACOLL UHC-50-200 (polycarbonate polyol, Ubeshin) were charged. Manufactured by the company, the average molecular weight: 2,000) 80g (0.04mol), MEK 46.7g, BHT 0.05g, heated to 70 ° C while drying with dry nitrogen, 9.3 mg of dibutyltin dilaurate was added dropwise, at 70 ° C It reacted for 4 hours. Then, 2.3 g (0.02 mol) of HEA was fed, and stirring was continued for 4 hours while maintaining the temperature inside the system at 70 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 93.4 g of a viscous liquid UP-3. In the same manner as in Synthesis Example 1, the desired reactive urethane polymer UP-3 was confirmed by IR analysis. The obtained UP-3 had a number average molecular weight of 9,000, an acrylic equivalent of 4,600, and a solution viscosity of 80 mPa·s at 25 °C.

Synthesis Example 11 Synthesis of Reactive Ethyl Carbamate Polymer UP-4 Using the same apparatus as in Synthesis Example 1, IPDI nurate 1.11 g (2 mmol), IPDI 11.1 g (50 mmol), Uniol D-2000 (polypropylene glycol, Made by Nippon Oil Co., Ltd., number average molecular weight: 2,000) 91g (0.045mol), MEK 51.8g, BHT 0.05g, while heating to 70 ° C while passing dry nitrogen, adding 10.4 mg of dibutyltin dilaurate at 70 ° C It was allowed to react for 3 hours. Then, 0.5 g (5 mmol) of HEA was fed, and stirring was continued for 3 hours while maintaining the internal temperature at 80 ° C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 103.6 g of a viscous liquid UP-4. In the same manner as in Synthesis Example 1, the desired reactive urethane polymer UP-4 was confirmed by IR analysis. The obtained UP-4 had a number average molecular weight of 68,000, an acrylic equivalent of 22,500, and a solution viscosity of 1200 mPa·s at 25 °C.

The urethane-modified (meth) acrylamide obtained by the synthesis examples 1 to 7 and the urethane acrylate oligomer obtained in Comparative Synthesis Example 5 were evaluated for the general-purpose organic solvent by the following method. The solubility characteristics of the acrylic monomer are shown in Table 1. Further, the solvent and monomer used were evaluated as follows. IPA: isopropanol MEK: methyl ethyl ketone THF: tetrahydrofuran "ACMO": N-acrylonitrile Porphyrin (registered trademark "ACMO") HDDA: 1,6-hexanediol diacrylate BA: butyl acrylate IBOA: isodecyl acrylate 2EHA; 2-ethylhexyl acrylate THFA; tetrahydrofuran methyl acrylate

(3) Solubility: 1 part by weight of a commonly used solvent or acrylic monomer as a diluent is added to 1 part by weight of the obtained urethane-modified (meth) acrylamide, and the mixture is stirred and allowed to stand. At a glance, the degree of dissolution was visually confirmed. ◎: The transparency was high, and no turbidity or separation was observed at all. ○: The transparency was high, but white turbidity was slightly observed. △: No layer was separated but it was cloudy. ×: white turbid and layer separation

【Table 1】

As shown by the results of the evaluation examples and the evaluation of the comparative examples, the addition type of ethyl urethane acrylamide has poor solubility in a general-purpose solvent or an acrylic monomer, and is particularly insoluble in a hydrophobic solvent. It is difficult to operate as an active energy ray curable resin composition. The reason is that the intramolecular and intermolecular hydrogen bonds of the urethane amide of the addition type are very strong, and it is difficult to disperse the solvent and other monomers due to self-coagulation.

The composition of the active energy ray-curable resin was prepared by using the urethane-modified (meth) acrylamide obtained in Synthesis Examples 1 to 6 and the urethane acrylate oligomer obtained in Comparative Synthesis Examples 1 to 4. Things. Further, using these resin compositions, the production of the ultraviolet curable film and the evaluation of the properties of the cured film were carried out, and the results are shown in Table 2.

Example A-1 100 parts by weight of methyl methacrylate-modified (meth) acrylamide UY-1 obtained in Synthesis Example 1, 100 parts by weight of MEK, and 3 parts by weight of Darocur 1173 as a photopolymerization initiator The mixture was mixed to prepare an active energy ray curable resin composition. Then, using the obtained curable resin composition, an ultraviolet curable film was produced in the following manner.

A method for producing an ultraviolet curable film is applied to a polyethylene terephthalate (PET) film having a thickness of 100 μm by a coating bar (RDS 12) ("Cosmoshine A4100" manufactured by Toyobo Co., Ltd., single-sided tackifying coating treatment) The coated surface was adhered to prepare a coating film so that the thickness of the dried coating film became 10 μm. The obtained coating film was dried in an explosion-proof dryer at 80 ° C for 2 minutes, and then hardened by ultraviolet irradiation (device: Ey-graphics conversion belt conveyor ECS-4011GX, metal halide lamp: M04-L41 manufactured by Eyegraphics). A UV cured film is produced. The curability of the resin composition, the tack resistance of the obtained cured film, the shrinkage resistance, the transparency, the water absorption, and the adhesion were evaluated. The results are shown in Table 2.

(4) Curability: A dried coating film having a thickness of 10 μm was produced in the same manner as described above, and ultraviolet rays having an illuminance of 2 mW/cm ^{2 were} irradiated at a temperature of 70 ° C for 120 seconds (accumulated light amount: 240 mJ/cm ² ), and the resin composition was measured by an instantaneous FT-IR. The height of the peak of the vinyl group (1630 cm ^-1 ) was calculated, and the hardening rate (%) of the coating film was calculated (the height from the peak of the vinyl group before curing - the height of the peak from the vinyl group after hardening) / The height of the peak from the vinyl before hardening × 100). ◎: Hardening rate is 90% or more ○: Hardening rate is 80% or more and less than 90% Δ: Hardening rate is 50% or more and less than 80% ×: Hardening rate is less than 50% (5) Adhesive resistance is 10 μm in the same manner as described above The dried coating film was irradiated with ultraviolet rays having an illuminance of 700 mW/cm ² for 3 seconds (accumulated light amount: 2100 mJ/cm ² ) at a temperature of 70 ° C to prepare a completely cured coating film (completely cured film). Touch the surface of the fully cured film with your fingers and evaluate the degree of stickiness. ◎: Completely non-adhesive. ○: There is some adhesiveness, but no fingerprint remains on the surface. △: There is adhesiveness and fingerprints remain on the surface. ×: The adhesiveness is severe and the finger sticks to the surface. (6) Curl resistance (shrinkage resistance) A completely cured film having a thickness of 60 μm was produced in the same manner as described above. The obtained fully cured film was cut into 10 cm squares, and the floating heights of the four corners were measured, and the average enthalpy was determined from the five cut pieces which were also cut out. ◎: The floating height is less than 0.5 mm. ○: The floating height is 0.5 mm or more and less than 1 mm. △: The floating height is 1 mm or more and less than 3 mm. ×: The floating height is 3 mm or more. (7) Transparency (visual) The fully cured film obtained by the above-mentioned shrinkage resistance test was visually observed and evaluated for transparency. ◎: Transparent and completely without extinction. ○: Transparent and slightly matt. △: There is matting but the transparent portion remains. ×: Extremely extinction, the transparent portion could not be confirmed. (8) Water absorption rate The curable resin composition was poured into a Teflon sheet having a depth of 1 mm and vacuum-dried (50 ° C, 400 torr), and then irradiated with ultraviolet rays (700 mW/cm ² , 2000 mJ/cm ² ). Hardened to make an ultraviolet curing sheet. The obtained sheet was cut into 3 cm squares and used as a test piece. The obtained test piece was allowed to stand in an environment of a temperature of 50 ° C and a relative humidity of 95% for 24 hours, and the water absorption rate was calculated (water absorption rate (%) = (weight after constant temperature and humidity - weight before constant temperature and humidity) / constant temperature constant Weight before wetness × 100) (10) Adhesiveness A completely cured film having a thickness of 10 μm was formed on a substrate of various materials in the same manner as described above. 100 square cells of 1 mm square were produced in accordance with JIS K 5600, and a scotch tape was attached, and the number of square eyes having a coating film remaining on the substrate side at the time of peeling off was counted and evaluated.

Examples A-2 to A-7 and Comparative Examples A-8 to A-11 were prepared in the same manner as in Example A-1 except that the composition shown in Table 2 was used, and a cured film was prepared. Evaluation according to the above method. The results are shown in Table 2.

【Table 2】

As shown in the results of the evaluation example and the evaluation comparative example, the molecular weight and the acrylic acid equivalent of the ethyl urethane-modified (meth) acrylamide of the present invention are within a specific range, so that the active energy ray hardenability is high, and the obtained The cured film has good surface drying property (viscosity resistance), curl resistance, and water resistance, and is excellent in transparency and adhesion to various substrates. However, if the molecular weight or the acrylic acid equivalent is out of the specific range of the present invention, the curing property, the tack resistance, and the curl resistance are not all satisfactory, and as a result, the transparency, adhesion, and water resistance of the cured film are also lowered. In particular, when the molecular weight is too high, the properties derived from the carbonate skeleton and the ether skeleton are remarkably exhibited, and as the crystallinity is improved, the transparency is lowered, and the adhesion of the cured film is lowered (Evaluation Comparative Example A-8), and the surface of the cured film is adhesive. The sex (evaluation of Comparative Example A-9) became remarkable. On the other hand, the (meth) acrylate-containing urethane acrylate oligomer has a molecular weight and an acrylic equivalent even within the specific range of the present invention, and is hardenable, tack-resistant, and hardenable and shrinkable. Any of the above properties is unsatisfactory and the adhesion is also low. Further, in Comparative Example A-11 having 6 acrylate groups per molecule, the appearance was excellent in tack resistance, but the curing ratio of the vinyl group was less than 50%, and the hardening shrinkage ratio was also high. The molecular weight and the acrylic acid equivalent of the ethyl urethane-modified (meth) acrylamide of the present invention are within a specific range, and a cured film excellent in curl resistance can be obtained even when the curability is high. The inventors and the like presumably have a strong hydrogen bond between the guanamine groups or the guanamine group and the urethane bond, and the urethane-modified (meth) acrylamide of the present invention is even before hardening. When it exists in a cohesive state, the distance between molecules before and after hardening is not greatly reduced, and the shrinkage of the entire cured film is also suppressed.

The urethane-modified (meth) acrylamide obtained by the synthesis of Examples 1 to 7 and the urethane acrylate oligomer obtained in Comparative Synthesis Examples 1 to 5 were evaluated for characteristics in each application field. The materials used in the examples and comparative examples are as follows. "HEAA"; hydroxyethyl acrylamide (manufactured by KJ Chemicals Co., Ltd.) "DMAA"; N,N-dimethyl methacrylate (KJ Chemicals Co., Ltd.) "DEAA"; N, N-II Acrylamide (KJ Chemicals Co., Ltd.) "ACMO"; N-acrylonitrile Porphyrin (manufactured by KJ Chemicals Co., Ltd.) "DMAPAA"; dimethylaminopropyl acrylamide (manufactured by KJ Chemicals Co., Ltd.) HEA; ethyl hydroxyacrylate 2EHA; 2-ethylhexyl acrylate EEA; (2-ethoxyethoxy)ethyl esterTHFA; tetrahydrofuran methacrylate IBOA; isodecyl acrylate IBMA; isodecyl methacrylate VEEA; 2-(2-vinyloxyethoxy)ethyl acrylate CHA; cyclohexyl acrylate CHMA; cyclohexyl methacrylate 4HBA; 4-hydroxybutyl acrylate A-LEN-10; ethoxylated o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) HDDA; 1,6-hexanediol ester TPGDA; tripropylene glycol diacrylate PETA; neopentyl glycol triacrylate DPHA; dipentaerythritol hexaacrylate DMAEA-TFSIQ; propylene methoxyethyl trimethyl Ammonium bis(trifluoromethanesulfonyl) quinone imine (manufactured by KJ Chemicals Co., Ltd.) DMAPAA-TFSIQ; propylene decylaminopropyltrimethylammonium bis(trifluoromethanesulfonyl) quinone imine (KJ Chemicals (manufactured by Chemicals Co., Ltd.) Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan) Irgacure 1173; 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF Japan) Irgacu Re TPO; 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (manufactured by BASF Japan) Irgacure 819; bis(2,4,6-trimethylbenzylidene)-phenyl Phosphine oxide (manufactured by BASF Japan) Irgacure 127; 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propenyl)benzyl]phenyl]-2-methyl-propane- 1-ketone (manufactured by BASF Japan) Hitaloid 7851; epoxy acrylate oligomer (manufactured by Hitachi Chemical Co., Ltd.) Hitaloid 7975; Acrylic acrylate oligomer (manufactured by Hitachi Chemical Co., Ltd.) (solvent-type material, after solvent removal by evaporator) use)

Evaluation Example B-1 8 parts by weight of the ethyl carbamate-modified (meth)acrylamide amine UY-1 synthesized in Synthesis Example 1, 30 parts by weight of the reactive urethane synthesized in Synthesis Example 12. 10 parts by weight of polymer UP-4, "HEAA", 30 parts by weight of "DEAA", 4 parts by weight of CHA, 15 parts by weight of EEA, and 3 parts by weight of DMAPAA-TFSIQ, and 1 part by weight of a photopolymerization initiator was added. Irgacure 184, uniformly mixed, to prepare an ultraviolet curable adhesive. Thereafter, using the obtained adhesive, an adhesive sheet was produced by ultraviolet curing in the following manner and evaluated.

Method for producing ultraviolet curing type adhesive sheet The above-prepared ultraviolet curing type adhesive is applied to a heavy peeling separator (polyoxynitride coated PET film) to lightly peel the separator (polyoxynitride coated PET film) The surface-type roll laminator (RSL-382S made by Royal Sovereign) was attached to the adhesive layer so as to have a thickness of 25 μm, and the ultraviolet ray was irradiated (device: Ey-graphics conversion belt conveyor ECS-4011GX) Metal halide lamp: M04-L41 manufactured by Eyegraphics, ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ), and made into a transparent adhesive sheet for optical use. The characteristics of the obtained adhesive sheets were evaluated by the following methods, and the results are shown in Table 3.

(10) Transparency (transmittance) The peeled surface of the light-peeling separator which was cut into a 25 mm-wide adhesive sheet was attached to a glass substrate as a adherend under the conditions of a temperature of 23 ° C and a relative humidity of 50%. Then peel off the heavy peeling separator and measure the transmittance. Measurement Using a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance of the glass substrate was measured in accordance with JIS K 7105, and the transmittance of the glass plate was subtracted to calculate the transmittance of the adhesive layer itself. And evaluate transparency in the form of numbers. The higher the transmittance, the better the transparency. (11) Surface resistivity measurement Using a template (vertical 110×180 mm), the bonding piece was cut with a dicing blade, and placed in a constant temperature and humidity machine adjusted to a temperature of 23 ° C and a relative humidity of 50%, and allowed to stand for 3 hours to obtain A sample for measuring surface resistivity. The measurement was carried out using a digital electrometer (Model R8252: manufactured by ADC Co., Ltd.) in accordance with JIS K 6911. (12) The adhesive force is transferred to a polyethylene terephthalate (PET) film (thickness 100 μm) or a glass substrate as a adherend under the conditions of a temperature of 23 ° C and a relative humidity of 50%, and the weight is 2 kg. The pressure roller was pressure-applied twice and back and placed in the same gas atmosphere for 30 minutes. Thereafter, a tensile tester (device name: Tensilon RTA-100 ORIENTEC Co., Ltd.) was used, and 180° peel strength (N/25 mm) was measured at a peeling speed of 300 mm/min. ◎: 15 (N/25 mm) or more ○: 10 (N/25 mm) or more and less than 15 (N/25 mm) △: 3 (N/25 mm) or more and less than 10 (N/25 mm) ×: not up to 3 (N) /25mm) (13) Corrosion resistance The adhesive sheet and the above-mentioned adhesive force were attached to the adherend in the same manner, and after being left at 80 ° C for 24 hours, the surface of the adherend after the adhesive sheet was peeled off was visually observed. Pollution. ◎: No pollution ○: There is little pollution. △: There is a slight pollution. ×: There is a paste (adhesive) remaining. (14) Yellowing resistance The adhesive sheet was attached to a glass substrate, and mounted on a 氙 fading tester (SC-700-WA: manufactured by Suga Test Machine Co., Ltd.), and irradiated with ultraviolet rays of 70 mW/cm ² for 120 hours, and visually observed. Observe the discoloration of the adhesive sheet. ◎: Yellowing was not confirmed at all by visual observation. ○: Yellowing was slightly confirmed by visual observation. △: Yellowing can be confirmed visually. ×: Obvious yellowing can be visually confirmed. (15) Moisture and heat resistance The adhesive sheet and the yellowing resistance test were bonded to the glass substrate in the same manner, and were kept at a temperature of 85 ° C and a relative humidity of 85% for 100 hours, and then visually observed and evaluated whether or not floating occurred. Peeling, air bubbles, white turbidity. ◎: It was transparent and did not float, peel, or bubble. ○: There was little extinction, but no floating, peeling, or air bubbles occurred. △: There is a slight matting or floating, peeling, and air bubbles. ×: Extremely extinction, floating, peeling, and air bubbles. (16) Height difference follow-up A black tape having a thickness of 20 μm was bonded to a glass substrate to produce a glass having a height difference. The adhesive sheet is transferred to a glass having a height difference, and is subjected to pressure bonding at a temperature of 23 ° C and a relative humidity of 50% in a gas flow of 2 kg (a crimping speed of 300 mm/min) at a temperature. After standing at 80 ° C for 24 hours, the state of the difference portion was confirmed by an optical microscope. ◎: No bubble was observed at all: A small number of small spherical bubbles were observed Δ: Large bubbles were observed, and the bubbles were connected to each other ×: Large bubbles were connected to each other and expanded on the line at the height difference (17) The press-formed sheet obtained by the press workability was cut by a Thomson press method (a press method in which ten straight edges were arranged in parallel at intervals of 5.0 mm with straight edges). ◎: There is no residue at all on the stamping edge. 〇: There is a small amount of adhesive residue on the stamping edge. △: There is adhesive residue on the punching edge. ×: There is a significant residue of the adhesive on the press blade, and the cut surface cannot be clearly determined.

Evaluation Examples B-2 to 7, Evaluation Comparative Examples B-8 to 11 An ultraviolet curable resin composition was prepared in the same manner as in Evaluation Example B-1 except that the composition described in Table 3 was used, and an adhesive sheet was produced. Evaluation of the above method. The results are shown in Table 3.

【table 3】

As shown in the results of the evaluation examples and the evaluation comparative examples, the ethyl methacrylate-modified (meth) acrylamide, or the amine having a molecular weight and the acrylic acid equivalent, within a certain range, having a blending molecular weight and an acrylic acid equivalent are within a certain range When the ethyl methacrylate-modified (meth) acrylate has a tendency to lower the adhesive strength and the moist heat resistance, and the stain resistance of the adhesive sheet after curing and the press workability are poor, it is difficult to use. By using (meth) acrylamide modified with the urethane of the present invention, a pressure-sensitive adhesive sheet having transparency, adhesion, stain resistance, and press workability can be obtained.

Evaluation Example C-1 22 parts by weight of the ethyl carbamate synthesized in Synthesis Example 1 was modified with (meth)acrylamide amine UY-1, and 15 parts by weight of the reactive urethane synthesized in Synthesis Example 10. Polymer UP-3, "ACMO" 18 parts by weight, "HEAA" 9 parts by weight, "DMAA" 14 parts by weight, THFA 10 parts by weight, IBOA 12 parts by weight, and added 3 parts by weight as a photopolymerization initiator. Irgacure 1173 was uniformly mixed to prepare an ultraviolet curable adhesive. Then, using the obtained adhesive, the polarizing plate was produced by ultraviolet curing in the following manner, and the physical properties of the polarizing plate were evaluated.

Polarizing plate was produced by UV irradiation using a tabletop roll laminator (RSL-382S manufactured by Royal Sovereign), and a polarizing film was sandwiched between two transparent films (protective film, retardation film or optical compensation film), and The adhesive of the example or the comparative example was bonded between the transparent film and the polarizing film to have a thickness of 10 μm. Ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ) were irradiated from the top surface of the laminated transparent film to prepare a polarizing plate having a transparent film on both sides of the polarizing film.

(18) Observation of surface shape The surface of the obtained polarizing plate was visually observed and evaluated according to the following criteria. ◎: The surface of the polarizing plate was not confirmed by minute streaks or irregularities. ○: It was confirmed that the surface portion of the polarizing plate had minute streaks. △: It was confirmed that there were minute streaks and irregularities on the surface of the polarizing plate. ×: It was confirmed that there were significant streaks and unevenness on the surface of the polarizing plate. (19) Peeling strength The polarizing plate (test piece) cut into 20 mm × 150 mm was attached to a tensile tester (manufactured by Shimadzu Corporation) under the conditions of a temperature of 23 ° C and a relative humidity of 50%. Test plate for autograph AGXS-X 500N). The transparent protective film on the side where the double-sided tape was not attached and one of the polarizing film were peeled off by about 20 to 30 mm, and the upper clamp was sandwiched, and the 90° peel strength (N/25 mm) was measured at a peeling speed of 300 mm/min. ◎: 3.0 (N/25 m) or more ○: 1.5 (N/25 m) or more, less than 3.0 (N/25 m) Δ: 0.5 (N/25 m) or more, less than 1.5 (N/25 m) ×: not up to 0.5 (N/25m) (20) Water resistance The obtained polarizing plate was cut into 20 × 80 mm, and after immersing in warm water of 60 ° C for 48 hours, it was confirmed whether the interface between the polarizing plate and the protective film, the retardation film, and the optical compensation film was There is stripping. The judgment was made on the basis of the following criteria. ◎: There was no peeling (less than 1 mm) at the interface between the polarizing plate and the protective film. ○: A part of the interface between the polarizing plate and the protective film was peeled off (1 mm or more and less than 3 mm). △: Partial peeling (3 mm or more, less than 5 mm) was formed at the interface between the polarizing plate and the protective film. ×: Peeling (5 mm or more) at the interface between the polarizing plate and the protective film. (21) Durability The polarizing plate obtained was cut into 150 mm × 150 mm, placed in a thermal shock device (TSA-101L-A manufactured by Espec Co., Ltd.), and subjected to a thermal shock of -40 ° C to 80 ° C for 30 minutes each for 100 times. Evaluation according to 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 end. However, the polarizing plate is not separated into two or more portions due to the line. ×: Cracks occurred outside the end. The polarizing plate is thus divided into two or more portions by lines.

Evaluation Examples C-2 to 7 and Evaluation Comparative Examples C-8 to 11 An ultraviolet curable resin was prepared in the same manner as in Evaluation Example C-1 except that the composition described in Table 4 was used, and a polarizing plate was produced. Evaluation. The results are shown in Table 4.

【Table 4】

As shown in the results of the evaluation examples and the evaluation comparative examples, the ethyl methacrylate-modified (meth) acrylamide, or the amine having a molecular weight and the acrylic acid equivalent, within a certain range, having a blending molecular weight and an acrylic acid equivalent are within a certain range When the ethyl methacrylate-modified (meth) acrylate has high flexibility from a main skeleton such as an ether or an ester, peel strength and water resistance tend to be lowered, and peel strength and durability are caused by incomplete curing of the adhesive. Low, so it is difficult to use. It is known that the adhesive using the urethane-modified (meth) acrylamide of the present invention has high cross-linking density, so that the peel strength and durability are high, and the balance between flexibility and strength is good, and water resistance is good. Sex is also excellent.

Evaluation Example D-1 48 parts by weight of the urethane synthesized by Synthesis Example 1 was modified with (meth)acrylamide amine UY-1, HDDA 15 parts by weight, TPGDA 24 parts by weight, and "DEAA" 8 parts by weight. 5 parts by weight of IBOA, 3 parts by weight of the pigment, and 3 parts by weight of the pigment dispersing agent were mixed, and 2 parts by weight of Irgacure 819 and 3 parts by weight of Irgacure 127 as a photopolymerization initiator were added and uniformly mixed to prepare a photocurable printing. Ink composition. Thereafter, inkjet printing was carried out in the following manner, and evaluation of the obtained printed matter was carried out.

(22) Viscosity The viscosity of the obtained ink composition was measured in accordance with JIS K5600-2-3 using a cone-and-plate type viscometer (device name: RE550 type viscometer, manufactured by Toki Sangyo Co., Ltd.). According to ink jet printing, the viscosity of the ink composition at 20 ° C is preferably 3 to 20 mPa·s or less, and further preferably 5 to 18 mPa·s. If it is less than 3 mPa·s, it is observed that the printing is oozing out after the discharge, and the printing deviation is caused, and the discharge followability is lowered. When the discharge nozzle is clogged at 20 mPa·s or more, the discharge stability is lowered, which is not preferable. (23) Compatibility The compatibility of the ink composition prepared by the above method was visually confirmed. ◎: The ink composition has no insoluble matter. 〇: A small amount of insoluble matter was observed in the ink composition. △: Insoluble matter was observed in the entire ink composition. ×: The ink composition has a precipitate.

The printed matter was prepared by UV irradiation, and the obtained ink composition was applied to a polyethylene terephthalate (PET) film having a thickness of 100 μm by a coating bar (RDS 12), and irradiated with ultraviolet rays (device: LED type by HOYA) The UV irradiation system H-10MAH20-1T18, 385 nm) was hardened to prepare a printed matter.

(24) Curability The cumulative amount of light until the ink composition was completely cured in the environment at room temperature of 23 ° C when the printed matter was produced by the above method was measured. ◎: at 500mJ / cm ² completely cured ○: at 500 ~ 1000mJ / cm ² completely cured △: in 1000 ~ 2000mJ / cm ² completely hardened ×: completely cured until needed 2000mJ / cm ² or more (25) surface drying properties will The printed matter produced by the above method was allowed to stand in an environment of room temperature of 23 ° C and a relative humidity of 50% for 5 minutes, and high-grade paper was placed 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 ink to the paper. ◎: The ink was dried and not transferred to the paper at all. ○: The ink is dry and slightly transferred to the paper. △: The ink is substantially dry and the transfer paper is transferred. ×: The ink is hardly dried, and the transfer to the paper is large.

Inkjet printing and printing suitability evaluation using an inkjet type color printer (PM-A890 manufactured by Seiko Epson), printing a full-surface image, and irradiating ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ) The printed matter was produced and evaluated in the following manner. The results are shown in Table 5.

(26) Spittling stability The printing state of the printed matter was visually evaluated by printing on the above-mentioned ink jet printer. ◎: No nozzle was left white and printed well. 〇: There are a few nozzles left white. △: There are nozzles left in a wide range. ×: Do not spit out. (27) Sharpness The brightness of the printed image was visually observed. ◎: The ink was not observed to be oozing at all, and the image was sharp. ○: Almost no ink was oozing, and the image was good. △: Several inks were observed to seep. ×: Ink bleeding was observed remarkably. (28) Water resistance The printed surface was exposed to running water for 1 minute to visually observe changes in the image. ◎: The sharpness of the image is completely unchanged. ○: The sharpness of the image was hardly changed, but the ink was slightly observed to seep. △: The sharpness of the image was lowered and the ink was observed to seep. ×: The sharpness of the image was remarkably lowered and the ink bleeding was observed remarkably.

Evaluation Examples D-2 to 7, Evaluation Comparative Examples D-8 to 11 An ink composition was prepared in the same manner as in Evaluation Example D-1 except that the composition described in Table 5 was replaced, and a printed matter was produced according to the above method. Evaluation of the above method. The results are shown in Table 5.

【table 5】

As shown in the results of the evaluation examples and the evaluation comparative examples, the ethyl methacrylate-modified (meth) acrylamide, or the amine having a molecular weight and the acrylic acid equivalent, within a certain range, having a blending molecular weight and an acrylic acid equivalent are within a certain range When the ethyl methacrylate-modified (meth) acrylate has a high viscosity after preparation of the ink composition, there is a tendency that the discharge stability is low, the hardenability, and the surface dryness are also low. Further, due to the viscosity of the main skeleton and the low curability of (meth) acrylate, bleeding was observed in the printed matter after the discharge was cured. When the (meth) acrylamide is modified with the urethane of the present invention, an ink composition having high curability and high hardening density and excellent in surface dryness, sharpness, and water resistance can be obtained.

Evaluation Example E-1 15 parts by weight of the ethyl carbamate-modified (meth) acrylamide amine UY-1 synthesized in Synthesis Example 1 and 20 parts by weight of the reactive urethane synthesized in Synthesis Example 8 Polymer UP-1, 30 parts by weight of the reactive urethane polymer UP-3 synthesized in Synthesis Example 10, 25 parts by weight of PETA, and 10 parts by weight of IBOA were mixed, and 3 parts by weight as a photopolymerization initiator was added. Darocur 1173 was uniformly mixed to prepare a photocurable coating composition.

(29) Compatibility The compatibility of the coating composition obtained by the above method was visually confirmed. ◎: The coating composition had high transparency, and no white turbidity or separation was observed at all. 〇: The coating composition was highly transparent, but was slightly cloudy. △: The entire coating composition was cloudy. ×: The coating composition was cloudy and separated. (30) Moisture permeability The obtained coating composition was applied onto a substrate, and the state of adhesion of the coating film was visually observed. ◎: There was no shrinkage at the time of application and standing for 5 minutes, and a smooth coating film was formed. 〇: There was no shrinkage at the time of coating, but a slight shrinkage was observed after standing for 5 minutes. △: A slight shrinkage hole was observed just after coating. ×: Most of the shrinkage cavities were observed immediately after coating, and a uniform coating film was not obtained.

The coating film was prepared by ultraviolet irradiation, and the obtained coating composition was coated with a coating bar (RDS 12) on a PET film having a thickness of 100 μm, and irradiated with ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² ) to prepare a coating film (thickness). 10 μm), evaluated according to the following method. The results are shown in Table 6. Further, when a solvent is used, it is dried at 80 ° C for 3 minutes after application, and then irradiated with ultraviolet rays.

(31) A composition of a curable coating agent, which was irradiated with an ultraviolet ray of 700 mW/cm ^{2 in an} environment of 23 ° C at room temperature, and the cumulative amount of light until the resin composition was completely cured. Complete hardening refers to a state in which the surface of the cured film is not traced when it is traced by a rubber. ◎: Completely hardened at a cumulative light amount of 1000 mJ/cm ² . 〇: Completely hardened at a cumulative light amount of 1000 mJ/cm ² to 2000 mJ/cm ² . △: Completely hardened at a cumulative light amount of 2000 mJ/cm ² to 5000 mJ/cm ² . ×: The cumulative light amount is required to be 5000 mJ/cm ² or more until it is completely cured. (32) Adhesion resistance The surface of the coating film obtained by the above method was touched with a finger, and the degree of adhesiveness was evaluated. ◎: There is no adhesive at all. ○: There is some adhesiveness, but no fingerprint remains on the surface. △: It has adhesiveness and fingerprints remain on the surface. ×: The adhesiveness is severe and the finger sticks to the surface. (33) Curing resistance (shrinkage resistance) The coating film obtained by the above method was irradiated with ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ), and the obtained coating film was cut into 10 cm squares, and four were measured. The average of the floats of the corners. ◎: The floating height is less than 0.5 mm. ○: The floating height is 0.5 mm or more and less than 1 mm. △: The floating height is 1 mm or more and less than 3 mm. ×: The floating height is 3 mm or more. (34) Scratch resistance Steel wool of #0000 was used, and a load of 200 g/cm ^{2 was} applied thereto 10 times to visually evaluate whether or not a flaw occurred. ◎: Almost no film peeling or scratching was observed. ○: A slight flaw was confirmed in one part of the film. △: The film was confirmed to have a striped flaw. ×: Film peeling occurred. (35) Self-healing property After the coating film obtained by the above method was injured by a spoon, it was allowed to stand in an environment of a temperature of 25 ° C and a relative humidity of 50%, and the recovery state of the scar was visually evaluated. ◎: The wound completely recovered within 30 minutes. ○: The scar is completely recovered within 30 minutes to 5 hours. △: The flaw completely recovered within 5 hours to 24 hours. ×: The wound still did not completely recover after standing for 24 hours. (36) Adhesiveness According to JIS K 5600, 100 square squares of 1 mm square were produced, and a scotch tape was attached, and the number of square eyes which have a coating film remaining on the substrate side at the time of one breath peeling was calculated and evaluated. (37) Moisture resistance The coating film obtained on the PET film (100 μm) was allowed to stand in an environment of a temperature of 50 ° C and a relative humidity of 95% for 24 hours, and the film after evaluation by visual inspection or adhesion test. ◎: Transparency was maintained under high temperature and high humidity, and no decrease in adhesion was observed. 〇: Transparency was maintained under high temperature and high humidity, but slight decrease was observed in adhesion. △: Transparency was maintained under high temperature and high humidity, but the adhesion was observed to be greatly lowered. X: When the high temperature and high humidity were observed, the transparency was lowered, and the adhesion was lowered.

Evaluation Examples E-2 to 7 and Evaluation Comparative Examples E-8 to 11 A coating film was prepared in the same manner as in Evaluation Example E-1 except that the composition described in Table 6 was used instead of the composition described in Table 6. And 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 the evaluation comparative examples, the ethyl methacrylate-modified (meth) acrylamide, or the amine having a molecular weight and the acrylic acid equivalent, within a certain range, having a blending molecular weight and an acrylic acid equivalent are within a certain range When the ethyl methacrylate-modified (meth) acrylate is used, the hardenability of the coating agent and the surface drying property (stickiness) of the obtained coating film are low, and the scratch resistance and self-healing property tend to be reduced. When the (meth) acrylamide is modified with the urethane of the present invention, since the crosslinking density inside the cured film is high, it is possible to prepare a hardening which is more resistant to scratching and self-healing except for hardenability and surface dryness. membrane.

Evaluation Example F-1 32 parts by weight of a urethane-modified (meth) acrylamide-based UY-1 synthesized in Synthesis Example 1, 5 parts by weight of a synthetic urethane synthesized in Synthesis Example 6 (meth)acrylamide amine UY-6, 22 parts by weight of the reactive urethane polymer UP-2 synthesized in Synthesis Example 9, "ACMO" 5 parts by weight, IBMA 21 parts by weight, CHMA 15 parts by weight After mixing, 3 parts by weight of Irgacure 184 as a photopolymerization initiator was added and uniformly mixed to prepare a coating composition for nail decoration.

Nail decoration method The obtained coating composition for nail decoration was uniformly applied to the nail using a flat brush, and irradiated with LED light (12 W) for gel-shaped nails for 20 seconds to form a nail decoration on the nail.

(38) Sturability The surface of the nail decoration obtained by the above method was touched with a finger and the degree of adhesiveness was evaluated. ◎: Completely non-adhesive. ○: There are some adhesiveness but no fingerprint residue on the surface. △: It has adhesiveness and fingerprints on the surface. ×: The adhesiveness is severe and the finger sticks to the surface. (39) Smoothness The surface of the nail decoration obtained by the above method was visually confirmed. ◎: The surface was smooth, and no unevenness was observed on the coated surface. ○: The whole was smooth but some irregularities were observed. △: A part of the bristles caused by the flat brush remains after application. ×: bristles caused by the flat brush remaining after application. (40) Glossiness The surface of the nail decoration obtained by the above method was visually observed. ◎: There is a surface gloss. ○: Light reflection was confirmed, but a little extinction was observed. △: The surface is completely dull. ×: Surface extinction. (41) Adhesiveness The appearance change after nail decoration obtained by the above method by other nails was visually confirmed. ◎: No change in appearance. ○: One part of the nail decoration floats and confirms whitening. △: A part of the nail decoration was confirmed to be peeled off. ×: Significant peeling of the nail decoration was confirmed. (42) Removability A cotton sheet containing acetone was placed 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 with a cloth. ◎: The nail decoration can be easily peeled off even without using a cloth. ○: If the cloth is lightly rubbed, the nail decoration can be easily peeled off. △: If the cloth is continuously rubbed for about 1 minute, the nail decoration can be peeled off. ×: The acetone was not swollen, and it could not be peeled off by the cloth.

Evaluation Examples F-2 to 7 and Evaluation Comparative Examples F-8 to 11 A composition for coating a nail decoration was prepared in the same manner as in Evaluation Example F-1 except that the composition described in Table 7 was used. Nail decoration was made and evaluated in the above manner. The results are shown in Table 7.

[Table 7]

As shown in the results of the evaluation examples and the evaluation comparative examples, the ethyl methacrylate-modified (meth) acrylamide, or the amine having a molecular weight and the acrylic acid equivalent, within a certain range, having a blending molecular weight and an acrylic acid equivalent are within a certain range When the ethyl methacrylate-modified (meth) acrylate is used, the curability of the composition and the gloss of the obtained decorative film are low, and the flexibility and adhesiveness from the main skeleton are imparted, so that the nail decoration is formed on the nail. The smoothness is poor, and there is a tendency for dripping liquid and residual brush bristles. When the (meth) acrylamide is modified with the urethane of the present invention, the adhesiveness of the decorative film after curing is suppressed, and the floating of the nail is low during hardening, so that it can be formed without lifting from the nail. It is decorated with nails which are also highly removable with acetone.

Evaluation Example G-1 24 parts by weight of the urethane-modified (meth) acrylamide-modified UY-1 synthesized in Synthesis Example 1, 12 parts by weight of the modified urethane modified by Synthesis Example 2 (Methyl) acrylamide amine UY-2, 25 parts by weight of the reactive urethane polymer UP-1, 5 parts by weight of Synthesis Example 9 synthesized by reactive urethane polymerization 10 parts by weight of "UPMO", "ACMO", 4 parts by weight of "DEAA", 10 parts by weight of 4-HBA, and 10 parts by weight of A-LEN-10, and added as 2 parts by weight of a photopolymerization initiator. Irgcure 184, Irgacure TPO 2 parts by weight, uniformly mixed to prepare a photocurable sealant.

A method for producing a cured film of a light-curing type sealant resin is placed on a glass plate (length 50 mm × width 50 mm × thickness 5 mm) with a spacer (length 30 mm × width 15 mm × thickness 3 mm), and the above-mentioned preparation is injected into the spacer. Photohardenable sealant. After sufficiently deaerating, ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ) were irradiated to prepare a sealant resin cured product. The properties of the obtained cured product were evaluated by the following methods, and the results are shown in Table 8.

(43) Transparency The obtained cured product was allowed to stand in a gas atmosphere at a temperature of 23 ° C and a relative humidity of 50% for 24 hours. Then, the transmittance of the cured film was measured by a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the transparency was classified into the following four grades and evaluated. ◎: transmittance is 90% or more ○: transmittance is 85% or more and less than 90% Δ: transmittance is 50% or more and less than 85% ×: transmittance is less than 50% (44) Light resistance The obtained cured product was bonded to a glass substrate, and the yellowness was measured with a spectrophotometer (CM-3600d: manufactured by Konica Minolta Co., Ltd.). After that, it was placed on a 氙 fading measuring instrument (SC-700-WA: manufactured by Suga Test Instruments Co., Ltd.), and irradiated with ultraviolet rays having an intensity of 4 W/cm ² at 30 ° C for 100 hours. After the irradiation, the yellowness was measured in the same manner as before the irradiation, and visually observed. Observe the discoloration of the hardened material. ◎: Yellowing was not confirmed by visual inspection. ○: It was confirmed by visual observation that there was little yellowing. △: Yellowing can be confirmed visually. ×: Obvious yellowing can be visually confirmed. (45) Water resistance 1 g of the obtained cured product was cut out and placed in a constant temperature and humidity machine at a temperature of 85 ° C × 95% relative humidity as a test piece, and allowed to stand for 48 hours, and then the weight of the test piece was measured, and the weight was calculated. Water absorption rate (water absorption rate (%) = (weight after constant temperature and humidity - weight before constant temperature and humidity) / weight before constant temperature and humidity × 100). ◎: water absorption rate is less than 1.0% ○: water absorption rate is 1.0% or more and less than 2.0% △: water absorption rate is 2.0% or more and less than 3.0% ×: water absorption rate is 3.0% or more (46) fugitive gas In the test, 1 g of the obtained cured product was cut out, and it was allowed to stand in a thermostatic chamber at a temperature of 100 ° C as a test piece, and a flow of dry nitrogen gas was passed for 24 hours, and then the weight of the test piece was measured to calculate the incidence of the fugitive gas (dissipating). Gas incidence rate (%) = (weight after constant temperature - weight before constant temperature) / weight before constant temperature × 100). ◎: The incidence rate is less than 0.1% ○: The incidence rate is 0.1% or more and less than 0.3% △: The incidence rate is 0.3% or more and less than 1.0% ×: The incidence rate is 1.0% or more (47) Heat-resistant period The cured product obtained was placed at -40 ° C for 30 minutes and then placed at 100 ° C for 30 minutes as one cycle, and repeated 10 times to visually observe the state of the cured product. ◎: No change was observed at all: Some microbubbles were observed, but no cracking was observed. It is transparent. △: Some bubbles or cracks were observed, and some were slightly matted. ×: Bubbles or cracks occur comprehensively and are translucent.

Evaluation Examples G-2 to 7 and Evaluation Comparative Examples G-8 to 12 An ultraviolet curable resin was prepared in the same manner as in Evaluation Example G-1 except that the composition described in Table 8 was used, and a sealant cured product was produced. Method evaluation. The results are shown in Table 8.

[Table 8]

As shown by the results of the evaluation example and the evaluation comparative example, the ethyl urethane-modified (meth) acrylamide containing a molecular weight and an acrylic acid equivalent are in a certain range, or the amine group having a molecular weight and an acrylic acid equivalent within a certain range When ethyl formate is modified (meth) acrylate, the transmittance of the obtained cured product is low, the crosslinking density inside the cured product is low, the occurrence of fugitive gas is remarkable, and the water resistance tends to be low. Further, when the addition type of urethane acrylamide is used, the transmittance and light resistance of the composition are low, and the crystallinity inside the cured product is high, so that the degree of freedom of the vinyl is hindered, and the vinyl It is difficult to completely disappear. When (meth)acrylamide is modified with the urethane of the present invention, light resistance is observed to be low, but the sealant has high hardenability and high crosslink density inside the cured product, so water resistance is high. It is also high, and can sufficiently suppress the occurrence of fugitive gas, and the heat resistance periodicity is also high.

Evaluation Example H-1 3 parts by weight of the ethyl carbamate-modified (meth) acrylamide amine UY-1 synthesized in Synthesis Example 1, 5 parts by weight of the modified urethane modified by Synthesis Example 2 (Methyl) acrylamide amine UY-2, 28 parts by weight of the reactive urethane polymer UP-1 synthesized in Synthesis Example 8, 50 parts by weight of the synthetic urethane polymerization synthesized in Synthesis Example 10. 10 parts by weight of DP-3, DPHA, 4 parts by weight of IBOA, and 50 parts by weight of MEK were mixed, and 3 parts by weight of Irgacure 184 as a photopolymerization initiator was added and uniformly mixed to prepare a resin composition for a decorative film.

The method for producing a photocurable decorative film is obtained by applying a resin composition for a decorative film obtained by coating a resin film (RDS 30) to a PET film having a thickness of 125 μm ("Softshine TA009" manufactured by Toyobo Co., Ltd.) so as to have a dry film thickness of 20 μm. It was dried at 100 ° C for 1 minute to prepare a film before UV curing. Thereafter, ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light amount: 2000 mJ/cm ² ) were irradiated to prepare a decorative film, and the ultraviolet-cured pre-formed film and the decorative film were each evaluated by the following methods. The results are shown in Table 9.

(48) The transmittance of the cured film was measured by a haze meter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the transparency was classified into the following four grades and evaluated. ◎: Transmittance is 90% or more ○: Transmittance is 85% or more and less than 90% Δ: Transmittance is 50% or more and less than 85% ×: Transmittance is less than 50% (49) Adhesive resistance The film formed by superposition of the UV-cured pre-formed film was laminated with untreated PET (thickness 100 μm, "Cosmoshine A 4100", manufactured by Toyobo Co., Ltd., tack-coated untreated surface), and pressed back and forth twice with a pressure roller weighing 2 kg. The mixture was allowed to stand under a temperature of 23 ° C and a humidity of 50% for 30 minutes. Thereafter, untreated PET was peeled off, and the blocking resistance was evaluated by visual observation. ◎: No adhesion to untreated PET, no change in appearance of the formed film. ○: No adhesion to untreated PET, but some residual marks on the surface of the formed film △: No transfer to untreated PET, but traces of traces on the surface of the formed film X: The film was transferred to the untreated PET, and peeling and floating (50) elongation at break were observed on the surface of the formed film. The obtained film was formed by ultraviolet pre-curing, and measured at a temperature of 130 ° C and 10 mm/min. Measuring equipment; Tensilon universal material testing machine RTA-100 (manufactured by Orientec) Elongation at break [%] = length of sheet at break / length of sheet before test × 100 ◎: elongation at break is 100% or more ○: elongation at break 50% or more and less than 100% △: elongation at break is 10% or more and less than 50% ×: elongation at break is less than 10% (51) Forming processability test The machine SDF400 (Sodick Co., Ltd.) was subjected to molding at a heating temperature of 130 ° C, and after cooling to 25 ° C, the state of the decorative layer of the molded article was visually confirmed. ◎: No cracks were observed at all, and the surface was also highly transparent. ○: No crack was observed, but the thickness of the decorative layer was uneven, and a part of the transparency was observed to be lowered. △: Cracks and cracks were observed, and a part of the decorative layer was observed to have uneven thickness and reduced transparency. ×: Most cracks were observed, and the thickness of the decorative layer was uneven, and the transparency was significantly lowered. (52) A resin composition for a curable coating decorative film, which was dried at 100 ° C for 1 minute, and then irradiated with a UV illuminance of 700 mW/cm ² at room temperature of 23 ° C, and measured until the resin composition was completely hardened. The cumulative amount of light up to that. Complete hardening refers to a state in which the surface of the cured film is not traced when it is traced by a rubber. ◎: Completely hardened at a cumulative light amount of 1000 mJ/cm ² . 〇: Completely hardened at a cumulative light amount of 1000 mJ/cm ² to 2000 mJ/cm ² . △: Completely hardened at a cumulative light amount of 2000 mJ/cm ² to 5000 mJ/cm ² . ×: The cumulative light amount is required to be 5000 mJ/cm ² or more until it is completely cured. (52) Adhesively obtained the decorative film obtained by making 100 1 mm square squares according to JIS K 5600, attaching a scotch tape, and calculating the number of square eyes remaining on the substrate side in one breath stripping and Evaluation. (53) Pencil hardness The obtained decorative film was used, and according to JIS K 5600, the pencil was rubbed at an angle of 45° by about 10 mm, and the pencil which was the hardest on the surface of the decorative film without scratches was defined as pencil hardness. ◎: pencil hardness is 2H or more ○: pencil hardness HB~H △: pencil hardness is 3B~B ×: pencil hardness is 4B or less (54) scratch resistance. Steel wool of #0000 is used, and a load of 200 g/cm ² is applied. The back and forth were 10 times on the decorative film to visually evaluate whether or not a scar occurred. ◎: Almost no film peeling or scratching was observed. ○: A slight flaw was confirmed in one part of the film. △: The film was confirmed to have a striped flaw. ×: Film peeling occurred. (55) Bending resistance The decorative film obtained above was bent so that the coated surface became the outer side, and a weight of 1 kg was placed and left for 10 minutes to visually observe whether or not the surface of the decorative film was cracked. ◎: No cracks were observed at all. ○: Part of the bend is whitened. △: A part of the crack was observed in the bent portion. ×: A crack was observed in the bent portion.

Evaluation Example H-2 to 7, Evaluation Comparative Example H-8 to 11 A resin composition for a decorative film was prepared in the same manner as in Evaluation Example H-1 except that the composition described in Table 9 was used, and the decoration was produced by the above method. The film was evaluated according to the above method. The results are shown in Table 9.

[Table 9]

As shown by the results of the evaluation example and the evaluation comparative example, the ethyl urethane-modified (meth) acrylamide containing a molecular weight and an acrylic acid equivalent are in a certain range, or the amine group having a molecular weight and an acrylic acid equivalent within a certain range When ethyl formate is modified (meth) acrylate, the formed film is soft before ultraviolet curing, and viscosity is observed, so that the blocking resistance is poor, and it tends to be difficult to stretch under high temperature conditions. Moreover, although the obtained decorative film was confirmed to have high bending resistance, the cured product was soft and the scratch resistance was low. When the (meth) acrylamide is modified with the urethane of the present invention, the agglomeration of the guanamine or urethane bond forms a pseudo hard segment, so that high blocking resistance can be obtained. Molding processability, crack-free UV-cured pre-formed film. Further, when the temperature is higher than the Tg of the urethane polymer or the urethane-modified (meth) acrylamide, the pseudo-hard segment is temporarily dispersed, so that the high elongation at break is exhibited and the Tg is obtained. A decorative film having pencil hardness and scratch resistance can be obtained in the vicinity of the following high normal temperature. [Industry Utilization]

As described above, the ethyl urethane-modified (meth) acrylamide of the present invention has a urethane bond and one or more (meth) acrylamide groups in the molecule, and the molecular weight and the acrylic acid equivalent. Within a certain range, the crosslinking density inside the cured product is increased by ultraviolet curing, and the hardened segment can be formed by the aggregation of the amide group or the urethane bond, so that not only hardening is formed. It is excellent in properties and tack resistance, and also exhibits hardness, shrinkage resistance, durability, etc., and also exhibits softness due to the main skeleton portion derived from the alcohol compound other than the (meth) acrylamide bond and the (meth) acrylamide. Water resistance, lubricity and other properties. The ethyl urethane-modified (meth) acrylamide of the present invention has a balance of hydrophilicity and hydrophobicity, hardness and flexibility, and by using it, transparency and adhesion to various substrates can be obtained. A curable resin composition having high scratch resistance. Further, the curable resin composition of the present invention may be used alone or in combination with a monofunctional monomer, a polyfunctional monomer, a general-purpose oligomer, a pigment, or the like, and is preferably used for bonding an adhesive or an electron. Materials, optics, semiconductors, inks, coatings, gel-like nails, sealants, decorative films, photo-curing photoresists.

no

Claims (12)

A urethane-modified (meth) acrylamide compound having at least one urethane bond and one or more (meth) acrylamide groups in the molecule, having a molecular weight per molecule An addition reaction of one or more hydroxyl group alcohol compounds, an isocyanate compound having two or more isocyanate groups per molecule, and an N-substituted (meth) acrylamide compound having a hydroxyl group represented by the general formula [1]; [Chemical 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 each represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may also be substituted by a hydroxyl group, and carbon. An aliphatic ring or an aromatic ring of 3 to 6, and R ₂ and R ₃ may be integrated with a nitrogen atom carrying them and further formed into a 5-7-membered ring which may also contain a saturated or unsaturated oxygen atom or a nitrogen atom. However, the case where both R ₂ and R ₃ are a hydrogen atom and the case where both R ₂ and R _{3 are} simultaneously an alkyl group are excluded, and the total of the hydroxyl groups possessed by R ₂ and R ₃ is 1 or more. The ethyl urethane-modified (meth) acrylamide compound according to the first aspect of the patent application, wherein the number average molecular weight is from 250 to 4,500, and the (meth)acrylic equivalent is in the range of from 250 to 3,000. The ethyl urethane-modified (meth) acrylamide compound according to claim 1 or 2, wherein the alcohol compound has a selected from the group consisting of an ether skeleton, an ester skeleton, a carbonate skeleton, and a polyfluorene skeleton. A compound of one or two or more kinds of an olefin skeleton or an acrylic skeleton. The ethyl urethane-modified (meth) acrylamide compound according to any one of claims 1 to 3, which has an ether skeleton having a number average molecular weight of 250 to 1,500 and an acrylic equivalent of 250 to 750. range. An active energy ray-curable resin composition comprising: 1 to 100% by weight of a urethane-modified (meth) acrylamide compound (A) according to any one of claims 1 to 4, The polyfunctional (meth)acrylic compound (B) is 0 to 90% by weight and the monofunctional (meth)acrylic compound (C) is 0 to 90% by weight. An active energy ray-curable adhesive composition characterized by containing a urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. An active energy ray-curable adhesive composition characterized by containing a urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. An active energy ray-curable ink jet ink composition characterized by containing a urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. An active energy ray-curable coating composition characterized by containing a urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. A curable composition for decorative active energy ray-curable nails, which comprises an ethyl urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. An active energy ray-curable sealant hardenable composition characterized by containing a urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4. A curable composition for an active energy ray-curable decorative film, which comprises the urethane-modified (meth) acrylamide compound according to any one of claims 1 to 4.