TWI708792B - 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 compound

The present invention relates to excellent compatibility with organic solvents, general acrylic monomers, and oligomers, and has a high curing speed for active energy rays. The number average molecular weight is 250 or more to less than 4,500, and (meth)acrylic acid An urethane modified (meth)acrylamide compound with an equivalent weight of 250 or more to less than 3,000 and the surface hardenability, heat resistance, abrasion resistance, and low curing shrinkage that contain the compound Highly transparent active energy ray-curable resin composition and its molded products.

Urethane resin, through the combination of raw material polyol and polyisocyanate, can be structured with soft to hard characteristics, and used in a wide range of industries and fields. In addition, the active energy ray-curable resin cured by ultraviolet (UV) and electron beam (EB) is compared with thermosetting compositions and solvent-based resins. The resin composition has the characteristics of productivity, energy saving, and low environmental load, so in recent years, its use is expanding. In such a trend of technological innovation, the research and development of active energy ray-curable urethane acrylate, which is obtained by bonding unsaturated groups such as acrylate to the end of urethane resin, has been actively applied in particular. get on.

Urethane acrylate, as an active energy ray curable resin, is expected to be widely used as coating, hard coating agent, adhesive, adhesive, sealant, printing ink, etc. for various substrates, but it is suitable for blending with various substrates. The structural design of various required compounds and the adjustment of the blending of the composition with expected characteristics are not satisfactory and become a major problem. That is to say, it is extremely difficult to obtain the physical properties of the urethane structure such as toughness, elongation, high hardness, and high adhesion, which are related to the rapid hardening of active energy ray hardening, surface dryness after hardening, surface hardness, and scratch resistance. , The balance of physical properties such as curing shrinkage. As a result, in the rapidly growing fields, for example, optical film bonding in the display and touch panel fields, hard coating for films from the decorative field to the optical field, hard coating field, and optical adhesive layer separation are required. When balancing with high performance, the current situation is that there is no high performance that can meet the requirements.

For example, Patent Document 1 discloses that by using a photocurable resin composition with 6 or more functional urethane acrylate as an essential component, the surface becomes non-sticky, and the hardness, scratch resistance, and chemical resistance are excellent. Coating film. In addition, Patent Document 2 proposes that by reacting an addition-molded ethyl urethane acrylamide and a polyol obtained by reacting a hydroxyl-containing acrylamide with a polyisocyanate, a polyol skeleton is obtained. The oligomer type of ethyl urethane acrylamide. As in Patent Document 2, by changing the polymerizable group from an acrylate group to an acrylamide group, the curing speed of addition molding is increased by more than 2 times, and the curability of the oligomer type is better than the adhesiveness of the cured film surface. improve. Furthermore, Patent Document 3 discloses that by Using an active energy ray curable resin obtained by the reaction of a hydroxyl-containing acrylamide and an isocyanate compound to obtain an uncured state of viscosity, less adhesion, and a hard coating film for forming that can be wound. Patent Document 4 discloses Hard coating of in-mold film with excellent surface hardness and flexibility by using a curable resin composition composed of hydroxyl-containing acrylamide, trimethylolpropane, polyvalent isocyanate compound and reaction catalyst Floor.

However, these patent documents (1 to 4) do not mention curing shrinkage resistance and bending resistance at all, and do not describe the solubility of general-purpose monomers, oligomers, and resins when they are used together, and the resulting cured layer Transparency, the status quo is that the aforementioned issues have not been resolved.

Patent Documents 5 and 6 disclose the use of oligomers and polymers of ethyl urethane acrylamide obtained by reacting hydroxyl-containing acrylamide, polyol, and isocyanate. The former is excellent in heat stability Optical film, the latter is a material for electronic photo equipment that has improved strength and can prevent cracking. Patent Document 5 describes that since it is an ethyl urethane acrylamide polymer obtained by using a specific polyol and a specific isocyanate, an optical film with specific structural units and its heat resistance properties can be achieved. Patent Document 6 provides that the fracture strength is improved due to the inclusion of an acrylamide group, and the hardenability is improved. As a result, they provide fracture resistance. However, these patent documents also do not describe curing shrinkage resistance, bending resistance, solubility, transparency, etc., and still have not solved the problem of unbalanced urethane acrylamide-based compounds, and cannot respond to High-performance topics required by the rapidly growing field.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2005-281412

[Patent Document 2] JP 2002-37849 A

[Patent Document 3] JP 2009-244460 A

[Patent Document 4] JP 2010-128417 A

[Patent Document 5] Japanese Patent Application Publication No. 2011-218616

[Patent Document 6] JP 2012-82288 A

The first task is to provide urethane modified (methyl) with excellent compatibility with organic solvents, general acrylic monomers and oligomers, high curability to active energy rays and low curing shrinkage. Acrylamide compound. In addition, the second task is to provide surface dryness (stickiness resistance), scratch resistance, bending resistance, and curing shrinkage resistance (curl resistance) containing the urethane-modified (meth)acrylamide compound. Performance) Active energy ray curable resin with excellent transparency and high adhesion.

The inventors of the present case worked hard to solve the aforementioned problems, and found that by using more than one urethane bond and one or more (meth)acrylamide groups in the molecule, the number average molecular weight is 250 A urethane modified (meth)acrylamide compound with a (meth)acrylic equivalent of ~4,500 and a (meth)acrylic equivalent in the range of 250 to 3,000 can achieve the aforementioned goals and complete the present invention.

That is, the present invention is:

(1) An urethane modified (meth)acrylamide compound, which simultaneously has more than one urethane bond and more than one (meth)acrylamide group in the molecule, which is used Addition of alcohol compounds having more than one hydroxyl group per molecule, isocyanate compounds having more than two isocyanate groups per molecule, and N-substituted (meth)acrylamide compounds containing hydroxyl groups represented by the general formula [1] Response obtained

In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R _{3 are the} same or different, and represent a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbons which may be substituted by a hydroxyl group, carbon 3 to 6 aliphatic or aromatic rings, and R ₂ and R ₃ can also be integrated with the nitrogen atom supporting them and further form a saturated or unsaturated 5- to 7-membered ring that can also contain oxygen or nitrogen atoms ; However, the case where R ₂ and R _{3 are} both hydrogen atoms and the case where R ₂ and R _{3 are} both alkyl groups are excluded, and the total of the hydroxyl groups possessed by R ₂ and R ₃ is 1 or more.

(2) The urethane modified (meth)acrylamide compound according to (1), wherein the number average molecular weight is 250 to 4,500, and the (meth)acrylic acid equivalent is in the range of 250 to 3,000.

(3) The urethane-modified (meth)acrylamide compound according to (1) or (2), wherein the alcohol compound has an ether skeleton, an ester skeleton, a carbonate skeleton, and a polysiloxane A compound of one or more of skeletons, olefin skeletons, and acrylic skeletons.

(4) The urethane modified (meth)acrylamide compound according to any one of (1) to (3), which has an ether skeleton, a number average molecular weight of 250 to 1,500 and an acrylic acid equivalent of 250 to The range of 750.

(5) An active energy ray-curable resin composition containing: the ethyl carbamate modified (meth)acrylamide compound (A) of any one of (1) to (4) by 1 to 100 weight %, 0 to 90% by weight of the polyfunctional (meth)acrylic compound (B) and 0 to 90% by weight of the monofunctional (meth)acrylic compound (C).

(6) An active energy ray-curable adhesive composition characterized by containing the ethyl urethane modified (meth)acrylamide compound as in (5).

(7) An active energy ray-curable adhesive composition characterized by containing an ethyl urethane modified (meth)acrylamide compound as in (5).

(8) An active energy ray-curable inkjet ink composition characterized by containing the ethyl urethane modified (meth)acrylamide compound as in (5).

(9) An active energy ray-curable coating composition characterized by containing an ethyl urethane modified (meth)acrylamide compound as in (5).

(10) A curable composition for decoration of active energy ray-curable nails, characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in (5).

(11) A curable composition for an active energy ray-curable sealant, characterized by containing an ethyl urethane modified (meth)acrylamide compound as in (5).

(12) A curable composition for an active energy ray-curable decorative film, which is characterized by containing an ethyl urethane modified (meth)acrylamide compound as in (5).

According to the present invention, a (meth)acrylamide modified (meth)acrylamide compound with more than one urethane bond and more than one (meth)acrylamide group in the molecule, and an organic solvent 、Universal acrylic monomers and oligomers have excellent compatibility, and have high curability and low curing shrinkage to active energy rays. The modified (meth)acrylamide compound containing the ethyl urethane can provide surface hardening, bending resistance, scratch resistance, excellent curing shrinkage resistance, high transparency, and high adhesion activity. Energy ray curable resins and their molded products.

The present invention will be described in detail below.

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

The alcohol compound used in the synthesis of the urethane-modified (meth)acrylamide compound of the present invention is selected from ether skeletons, ester skeletons, carbonate skeletons, polysiloxane skeletons, olefin skeletons, and acrylic skeletons. One or more alcohol compounds with a skeleton.

Alcohol compounds with ether skeletons are those with more than one hydroxyl group at the end or side chain of the ether skeleton. Commercially available products include diethylene glycol, dipropylene glycol, dibutylene glycol, and PTMG series, such as: PTMG650 (manufactured by Mitsubishi Chemical Corporation), Sannix PP, GP, GOP series, such as: Sannix PP-1000, GP-250, GOP-600 (manufactured by Sanyo Chemical Co., Ltd.), PEG series, such as: PEG300, Uniox Series, Uniol D, TG, HS, PB series, such as: Uniol D-700, TG-1000, HS-1600D, PB-700, Unilube DGP series, Polycerin DC, DCB series (Nippon Oil Corporation), etc.

Alcohol compounds with an ester skeleton are those having more than one hydroxyl group at the end or side chain of the ester skeleton in the molecule. Commercially available products include Curaray polyols P, F, N, PMNA series, for example: Curaray Polyol P-1010, N-2010, PMNA-2016 (Curaray (stock) system), Placcel series, such as: Placcel 205 (Daicel (stock) system), Priplast series, such as: Priplast 1900 (Croda Japan (stock) ) System), Tesla series, for example: Tesla 2456 (Hitachi Chemical Co., Ltd.) and so on.

Alcohol compounds with a carbonate skeleton are those with more than one hydroxyl group at the end or side chain of the carbonate skeleton in the molecule. Commercially available products include the Placcel CD series, such as Placcel CD210 (manufactured by Daicel (Stock)), ETERNACOLL UH , UHC, UC and UM series, such as ETERNACOLL UH-100, UHC50-100, UC-100, UM-90 (3/1) (manufactured by Ube Industries Co., Ltd.), Duranol T and G series, such as Duranol T6001 ( Asahi Kasei Chemical Co., Ltd.), NIPPOLLAN series, such as: NIPPOLLAN 981 (Tosoh Co., Ltd.), Curaray polyol C series, such as: Curaray Polyol C-590 (Curaray (stock) system )Wait.

Alcohol compounds with a polysiloxane skeleton are those that contain siloxane bonds in the main chain skeleton in the molecule and have more than one hydroxyl group at both ends or side chains. Commercially available products include KF-6000 and X-21- 5841 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY 16-201 (manufactured by Toray and Dow Corning Co., Ltd.), XF42-B0970 (manufactured by Momentive Performance Materials), Silaplane series, such as Silaplane FM-0411 (JNC (shares) )System) etc.

Alcohol compounds with olefin skeletons are those with conjugated or unconjugated olefin skeletons or their hydrogenated skeletons in the molecule, and have more than one hydroxyl group at the end or side chain. Commercially available products include the NISSO-PB series. For example: NISSO-PB G-1000, GI-1000 (manufactured by Soda Co., Ltd.), Poly bd series (manufactured by Idemitsu Kosan Co., Ltd.), Krasol series, for example: KrasolL BH2000, HLBH-P2000 (manufactured by Crayvalley) , Pripol series (Croda Japan (stock) system), etc.

The alcohol compound with an acrylic skeleton is a polymer formed by polymerizing more than one acrylic monomer, and has more than one hydroxyl group at the end or side chain of the molecule. For example, homopolymers of acrylic monomers with hydroxyl groups such as hydroxy (meth) acrylate, hydroxy acrylate (meth) acrylamide, etc., or copolymers with monomers with unsaturated groups are used. Commercial products include UMM-1001, UT-1001 (manufactured by Soken Chemical Co., Ltd.), etc.

The alcohol compound having the aforementioned various skeletons can be used alone. Or use two or more kinds of alcohol compounds with the same skeleton or alcohol compounds with different skeletons in combination.

The isocyanate compound used in the synthesis of the urethane-modified (meth)acrylamide compound of the present invention is one having 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, 4- extending tolylene diisocyanate, 4,4 '- aromatic isocyanate-based diphenylmethane diisocyanate, xylylene diisocyanate and the like, cycloalkyl extending cyclohexyl diisocyanate, isophorone diisocyanate, 4,4'- Cyclohexylmethane diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate and other alicyclic isocyanates, ``Desmodur XP2565'' (manufactured by Sumika Bayer Polyurethanes Co., Ltd.) Acid ester-based isocyanates or their adducts, isocyanurates, biurets and other polymers, such as Coronaate L, HL, HX (manufactured by Japan Polyurethane Industry Co., Ltd.), Duranate 24A -100 (Asahi Kasei Industry Co., Ltd.), etc. These isocyanate compounds can be used individually by 1 type or in combination of 2 or more types.

The hydroxyl-containing N-substituted (meth)acrylamide used in the synthesis of the ethyl carbamate modified (meth)acrylamide compound of the present invention is a compound represented by the general formula [1], where R ₁ represents a hydrogen atom or a methyl group, R ₂ and R _{3 are the} same or different, and represent a hydrogen atom, or a linear or branched alkyl group with carbon numbers of 1 to 6 that may be substituted by a hydroxyl group, and a carbon group of 3 to 6 An aliphatic ring or an aromatic ring, and R ₂ and R ₃ may be integrated with the nitrogen atom supporting them to further form a saturated or unsaturated 5- to 7-membered ring that may contain an oxygen atom or a nitrogen atom. The exception is when R ₂ and R _{3 are} both hydrogen atoms and when R ₂ and R _{3 are} both alkyl groups, and the total number of hydroxyl groups possessed by R ₂ and R ₃ is 1 or more.

基]-2-丙烯-1-酮、1-丙烯醯基-4-羥基哌啶。又，藉由使用含有羥基之丙烯醯胺，獲得之胺基甲酸乙酯改性丙烯醯胺化合物之硬化性改善、由其形成之塗膜表面之整面塗覆改善效果高，故特別理想。該等含羥基之(甲基)丙烯醯胺可單獨使用1種或組合使用2種以上。 N-substituted (meth)acrylamide containing hydroxyl group, specifically N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (Meth)acrylamide, N-hydroxyisopropyl(meth)acrylamide, N-methylhydroxymethyl(meth)acrylamide, N-methylhydroxyethyl(meth)acrylamide Amine, N-ethylhydroxymethyl(meth)acrylamide, N-ethylhydroxyethyl(meth)acrylamide, N-ethylhydroxyisopropyl(meth)acrylamide, n-propyl Hydroxymethyl(meth)acrylamide, n-propylhydroxyisopropyl(meth)acrylamide, N-isopropylhydroxyethyl(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]acrylamide, 4-(hydroxy)methacrylate anilide, N-[1,1-bis (Hydroxymethyl)ethyl)acrylamide, N-[1-(hydroxymethyl)propyl]methacrylamide, N-(2-hydroxyphenyl)methacrylamide, N-(2 -Hydroxy-5-methylphenyl)acrylamide, 1-[4-(2-hydroxyethyl)-1-piper

Group]-2-propen-1-one, 1-propenyl-4-hydroxypiperidine. In addition, by using acrylamide containing a hydroxyl group, the curability of the ethyl carbamate-modified acrylamide compound obtained is improved, and the coating film surface formed by it has a high coating improvement effect on the entire surface, which is particularly desirable. These hydroxyl-containing (meth)acrylamides can be used individually by 1 type or in combination of 2 or more types.

The method for synthesizing the ethyl carbamate modified acrylamide compound of the present invention is not particularly limited, and can be synthesized according to the known ethyl carbamate reaction technology. In the blending ratio of the raw materials, the total of the hydroxyl groups is preferably equal to or more than the total of the isocyanate groups. Among them, the hydroxyl group of the alcohol compound/the isocyanate group/the hydroxyl group of (meth)acrylamide becomes 1/1/0.5~ The ratio of 1/3/2.5 makes the response particularly good. If the blending ratio of isocyanate groups exceeds this range, the urethane-modified acrylamide compound may become thickened and colored over time. On the other hand, if the hydroxyl group of the (meth)acrylamide compound exceeds this range, the water resistance and moisture resistance of the obtained ethyl urethane modified acrylamide compound may decrease.

啉等。有機溶劑或反應性稀釋劑之使用量相對於異氰酸酯化合物為0~400重量%，宜為0~200重量%。 The ethyl carbamate reaction of the present invention can mix the raw material alcohol compound, isocyanate compound and hydroxyl-containing N-substituted (meth)acrylamide, raise the temperature as necessary and implement it according to a known method. This reaction is carried out at a temperature of 10 to 160°C, preferably 20 to 140°C. The mixing of the raw materials can be carried out all at once or in several stages. In addition, the reaction may be solvent-free, but if necessary, it may be carried out in an organic solvent or a reactive diluent. Solvents that can be used such as: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethylacetamide, dimethyl sulfide, ethyl acetate, butyl acetate, It is carried out in the presence of tetrahydrofuran, hexane, cyclohexane, benzene, toluene, xylene, aliphatic hydrocarbon solvents (petroleum ether, etc.). In addition, the reactive diluent that can be used is not particularly limited as long as it does not react with isocyanate and does not react with hydroxyl. Examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Long-chain aliphatic acrylate, allyl acrylate, cyclohexyl acrylate, 1,6-hexane diacrylate, tetraethylene glycol diacrylate, dineopentyl erythritol hexaacrylate, trimethylolpropane Acrylate, isobornyl acrylate, dimethylamino ethyl acrylate, diethylamino ethyl acrylate, dimethyl acrylamide, diethyl acrylamide, N-acrylamide

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

、1,8-二氮雜雙環[5.4.0]十一烯-7、N,N'-二甲基哌

、N-乙基

啉、N,N-二甲基乙醇胺、1-甲基咪唑、三乙二胺等三級胺化合物類，它們可單獨使用或組合使用2種以上。觸媒之使用量相對於原料成分之合計重量通常為1重量%以下較佳，0.1重量%以下又更佳。 In addition, in the ethyl urethane reaction, a catalyst may be added to promote the reaction. The catalyst, for example: potassium or sodium salt of alkyl phosphonic acid, sodium, potassium, nickel, cobalt, cadmium, barium, calcium, zinc and other metal salts of fatty acids with carbon number of 8-20, dibutyltin dilaurate, Dioctyl tin maleate, dibutyl dibutoxy tin, bis(2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-1,3-diacetoxydi Organotin compounds such as stannoxane, N,N,N',N'-tetramethylguanidine, 1,3,5-ginseng (N,N-dimethylaminopropyl)hexahydro-S-tri

, 1,8-diazabicyclo[5.4.0]undecene-7, N,N'-dimethylpiperidine

, N-ethyl

Tertiary amine compounds such as morpholine, N,N-dimethylethanolamine, 1-methylimidazole, and triethylenediamine can be used alone or in combination of two or more. The amount of the catalyst used is generally preferably 1% by weight or less with respect to 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 hydroxyl-containing N-substituted (meth)acrylamide and the obtained double bond of the ethyl urethane modified (meth)acrylamide from causing free radical polymerization, free radical polymerization can be used if necessary Inhibitor.

等胺系聚合禁止劑、4-羥基-2,2,6,6-四甲基哌啶-N-氧自由基等N-氧自由基類；二甲基二硫胺甲酸酸銅、二乙基二硫胺甲酸銅、二丁基二硫胺甲酸銅等二硫胺甲酸銅系聚合禁止劑等，它們可單獨使用，也可併用2種以上。 Free radical polymerization inhibitors, such as: hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol and other quinone-based polymerization inhibitors; 2,6-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri- Alkylphenol-based polymerization inhibitors such as tertiary butylphenol; alkylated diphenylamine, N,N ' -diphenyl-p-phenylenediamine, phenanthrene

Amine-based polymerization inhibitors, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy radicals and other N-oxygen radicals; copper dimethyl dithiocarbamate, diethyl Copper dithiocarbamate-based polymerization inhibitors, such as copper dithiocarbamate and copper dibutyl dithiocarbamate, can be used alone or in combination of two or more.

The addition amount of these polymerization inhibitors can be appropriately set according to the type and blending amount of the hydroxyl-containing N-substituted (meth)acrylamide, taking into account the polymerization inhibition effect, the ease of production, and the economic point of view, Relative to the obtained urethane-modified (meth)acrylamide, it is usually 0.001 to 5% by weight, preferably 0.01 to 1% by weight.

The number average molecular weight of the urethane-modified (meth)acrylamide of the present invention is 250 or more and less than 4,500, and more preferably 250 or more and less than 3,000. When the number average molecular weight is less than 250, the proportion of monofunctional low-molecular components is high, and the curability of the obtained urethane-modified (meth)acrylamide is good for organic solvents and general acrylic monomers. Solubility may decrease. On the other hand, if the number-average molecular weight exceeds 4,500, the crosslink density will decrease, and the curability and adhesion resistance will not be sufficiently satisfied, which is not desirable.

The urethane-modified (meth)acrylamide of the present invention has an acrylic equivalent of 250 or more to less than 3,000, and more preferably 250 to 2,500. When the acrylic acid equivalent is less than 250, the density of the (meth)acrylamide group, which is a polymerizable group, is high, and it is prone to the production process of urethane-modified (meth)acrylamide and the subsequent steps. There are problems such as polymerization during storage. On the other hand, if the acrylic equivalent exceeds 3,000, the crosslinking density is reduced, and the curability and adhesion resistance cannot be sufficiently satisfied, which is undesirable.

The acrylic acid equivalent of the ethyl urethane modified (meth)acrylamide with ether skeleton of the present invention is preferably in the range of 250 to 750. When the acrylic equivalent of the ethyl urethane modified (meth)acrylamide with ether skeleton is less than 250, it is not ideal as the above. Moreover, if the acrylic equivalent exceeds 750, the urethane modified (methyl) ) It is difficult to form intra- or intermolecular hydrogen bonds of acrylamide, which may reduce the hardening speed.

When the urethane-modified (meth)acrylamide of the present invention is used alone, it depends on the alcohol skeleton, the type of (meth)acrylamide group, acrylic acid equivalent and molecular weight, active energy ray curability, The surface dryness (adhesion resistance) of the obtained cured film, the adhesion to various substrates, and other physical properties and performance will vary, and it is generally preferable to be within the following ranges.

The ethyl carbamate modified (meth)acrylamide of the present invention can be completely cured by active energy ray irradiation. The necessary amount of active energy ray irradiation (cumulative light amount) varies depending on the type of (meth)acrylamide group and the equivalent of acrylic acid, but it is preferably 0.1 to 2,000 mJ/cm ² and then about 1 to 1,000 mJ/cm ² Especially ideal. If the cumulative amount of light is less than 0.1mJ/cm ² , incompletely hardened areas will remain, and the hardness, water resistance, and durability of the entire hardened product may decrease. In addition, if the cumulative amount of light exceeds 2,000 mJ/cm ² , side reactions such as decomposition will occur due to excessive energy, and the cured film tends to be easily colored.

The water absorption rate of the cured film composed of urethane modified (meth)acrylamide of the present invention is preferably 2% or less, and particularly preferably 1% or less. If the water absorption rate is greater than 2%, when used for a long time in a high-humidity environment, the cured film may absorb water over time, and the shape may be deformed due to swelling, which may reduce adhesion and transparency.

The curing shrinkage rate of the urethane-modified (meth)acrylamide of the present invention is evaluated by the lifting height of the cured film caused by ultraviolet radiation (crimp resistance evaluation), the lifting height is preferably It is preferably less than 1 cm, particularly preferably less than 0.5 cm. If the lift of the cured film is larger than 1cm, the deformation of the film will reduce the adhesion to the substrate. As a result, the curable resin composition containing ethyl urethane modified (meth)acrylamide is used Molded products of this composition are prone to decrease in water resistance, durability, bending resistance, etc., and may not be able to maintain their shape stably.

烷二醇二丙烯酸酯)、烷氧基化己烷二醇二(甲基)丙烯酸酯、烷氧基化環己烷二甲醇二(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、胺基甲酸乙酯(甲基)丙烯酸酯、胺基甲酸乙酯(甲基)丙烯醯胺等單體與低聚物。又，該等多官能(甲基)丙烯酸酯可單獨使用也可併用2種以上。 The polyfunctional (meth)acrylic compound (B) used in the present invention is a polyfunctional (meth)acrylate or a polyfunctional (meth)acrylamide. For example: ethylene di(meth)acrylate and other alkylene glycol di(meth)acrylates, dicyclopentyl di(meth)acrylate, caprolactone modified dicyclopentane di(meth)acrylate Alkenyl ester, neopentyl erythritol tetra (meth) acrylate, neopentyl erythryl tri (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, dine pentaerythritol penta (meth) acrylate , Trimethylolpropane tri(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate (two

Alkyl glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy (meth)acrylate, Monomers and oligomers such as urethane (meth)acrylate and urethane (meth)acrylamide. Moreover, these polyfunctional (meth)acrylates may be used individually or may use 2 or more types together.

The monofunctional (meth)acrylic compound (C) used in the present invention is a monofunctional (meth)acrylate or a monofunctional (meth)acrylamide. Moreover, it may contain a polymerizable quaternary salt ionic compound as needed. In addition, a monofunctional (meth)acrylic compound may be used individually or may use 2 or more types together.

Monofunctional (meth)acrylates, for example: (meth)alkyl (meth)acrylate of methyl (meth)acrylate, ethyl hydroxyacrylate, alkoxy ethyl (meth)acrylate, methoxy (meth) Diethylene glycol acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, phenoxy ethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate , Phenoxy ethyl (meth)acrylate, dicyclopentyl (meth)acrylate, isobornyl (meth)acrylate, methyl tetrahydrofuran acrylate, 2-methyl-2-adamantane (meth)acrylate Hydroxy (meth)acrylic acid alkyl esters such as esters, allyl (meth)acrylate, and hydroxy ethyl (meth)acrylate.

啉、羥基乙基丙烯醯胺等羥基烷基(甲基)丙烯醯胺。 The monofunctional (meth)acrylamide used in the present invention, for example: N-alkyl (meth)acrylamide, N-alkoxyacryl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N-[3-(dimethylamino)]propyl allylamine, N,N-dimethyl(meth)acrylamide, N,N-diethyl( (Meth)acrylamide, N-acrylamide

Hydroxyalkyl (meth)acrylamides such as morpholine and hydroxyethylacrylamide.

The urethane-modified (meth)acrylamide compound (A) of the present invention is preferably contained in an active energy ray curable resin composition at 1% by weight or more. If it is less than 1% by weight, good surface hardening properties, bending resistance, scratch resistance, etc. may not be obtained. In addition, the content of the polyfunctional (meth)acrylic compound (B) in the curable resin composition is preferably 90% by weight or less. If the content of (B) exceeds 90% by weight, the liquid viscosity of the curable resin composition will increase, making it difficult to mix and apply, and handling problems may occur. miss you. Furthermore, when a monofunctional (meth)acrylic compound (C) is blended in the curable resin composition, in order to maintain sufficient scratch resistance and curability, it is preferably 90% by weight or less.

In the active energy ray-curable resin composition of the present invention, a polymerizable quaternary salt ionic compound can be added. For example: ionic vinyl monomers and/or oligomers and polymers using them as constituents. An onium salt composed of an ionic vinyl single-system cation and an anion. Specifically, the cation includes (meth)acrylate-based or (meth)acrylamide-based ammonium ions and imidazolium ions, and the anions include cl ^-, Br ^-, I ^- halogen ion or _{^{OH -, CH 3 COO -,}} NO 3 -, ClO 4 -, PF 6 -, BF 4 -, HSO 4 -, CH 3 SO 3 -, CF 3 SO 3 _{^{-, CH 3 C 6 H 6}} SO 3 -, C 4 F 9 SO 3 -, (CF 3 SO 2) 2 N -, SCN - inorganic acid anion or organic acid anion.

The ions of the grade 4 salt ionic compound can easily form hydrogen bonds and ionic bonds with the coated substrate, and can impart conductivity and antistatic properties, so it can improve the moisture permeability, can be coated more uniformly, and be more stable地成膜。 Ground film. Furthermore, the polymerizable quaternary salt ionic compound itself is also an active energy ray curable compound, so it can be copolymerized with an active energy ray curable resin composition without bleeding, providing permanent conductivity and antistatic properties. The auxiliary effect of sex and the effect of improving adhesion. The blending amount of these ionic compounds can be adjusted by the number of functional groups and molecular weight of the ion pair, so there is no particular limitation. Generally speaking, 0 to 50% by weight is added to the active energy ray curable resin composition, and 0 to 10% by weight is preferred. If the blending amount of the ionic compound exceeds 50% by weight, although it depends on the type, the transmittance of the cured film may decrease.

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

When curing the active energy ray-curable resin composition of the present invention, a photopolymerization initiator is added first. The photopolymerization initiator is not particularly necessary when using electron beams as active energy rays, but is necessary when using ultraviolet rays. The photopolymerization initiator can be appropriately selected from general products such as acetophenone series, benzidine series, benzophenone series, and thioxanthone series. Among the photopolymerization initiators, commercially available photopolymerization initiators can be used 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 , IrgacureTPO, UCB company system, trade name Ubecryl P36, etc. These photopolymerization initiators can be used 1 type or in combination of 2 or more types.

The amount of the photopolymerization initiator used is not particularly limited, and it is generally added at 0-10% by weight relative to the active energy ray-curable resin composition, and preferably 1 to 5% by weight. If it exceeds 10% by weight, the strength of the cured film may decrease and yellowing may occur.

Pigments, dyes, surfactants, anti-blocking agents, leveling agents, dispersing agents, and defoaming agents can be used together within the range that does not interfere with the characteristics of the active energy ray-curable resin composition of the present invention and the molded articles made therefrom Other optional ingredients, such as agents, antioxidants, ultraviolet sensitizers, preservatives, etc.

The active energy ray-curable resin composition of the present invention can be coated on paper, cloth, non-woven fabric, glass, polyethylene terephthalate, cellulose diacetate, cellulose triacetate, acrylic polymer , Polyvinyl chloride, cellophane, celluloid, polycarbonate, polyimide and other plastic and metal substrate surfaces and between, and irradiate it with ultraviolet and other active energy rays to harden it, To obtain high-performance coating layer, ink layer, adhesive layer or adhesive layer. In particular, the active energy ray-curable resin composition of the present invention has a highly transparent urethane oligomer, which can be suitably used as optical adhesives, optical adhesives, coating materials for optical films, etc. Used for optical resin composition. In addition, methods for coating the resin composition on the substrate include spin coating, spray coating, dip coating, gravure printing roll method, knife coating method, reverse roll method, screen printing method, coating bar method, etc. The usual coating film formation method. In addition, the method of coating between the substrates may include a lamination method, a roll to roll method, and the like.

[Example]

Hereinafter, the present invention will be specifically explained in more detail using synthesis examples and evaluation examples, but the present invention is not limited to these examples. In addition, in the following,% other than the yield represents% by weight. The physical property analysis of the obtained ethyl carbamate modified (meth)acrylamide was carried out according to the following method.

(1) Determination of molecular weight and calculation of acrylic acid equivalent

The number average molecular weight of the ethyl carbamate-modified (meth)acrylamide, etc., was obtained by high-speed liquid chromatography ("LC-10A" manufactured by Shimadzu Corporation, column: Shodex GPC KF-803L ( Exclude limit molecular weight: 7×10 ⁴ , separation range: 100~7×10 ⁴ , theoretical number of layers: 18,000 layers/piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10μm) ), eluate tetrahydrofuran) measured and calculated based on the standard polystyrene molecular weight. Also, calculate the acrylic acid equivalent (the corresponding molecular weight of each (meth)acrylamide group).

(2) Viscosity measurement

Mix 1 part by weight of ethyl carbamate-modified (meth)acrylamide, etc., and 1 part by weight of tetrahydrofuran, and mix them in a cone-plate viscometer (device name: RE550 viscometer Toki Industry Co., Ltd.) Manufactured by the company), in accordance with JIS K5600-2-3, the solution viscosity measured at 25°C.

The synthesis example of the urethane-modified (meth)acrylamide compound (A) is shown below.

Synthesis Example 1 Synthesis of (meth)acrylamide UY-1 modified by ethyl carbamate

A 4-necked flask with a capacity of 300 mL equipped with a stirrer, thermometer, cooler, and dry gas introduction tube is charged with 44.4 g (0.2 mol) of isophorone diisocyanate (IPDI), ETERNACOLL UC-100 (polycarbonate polyol, Ube Industries Co., Ltd., number average molecular weight: 1,000) 90 g (0.09 mol), Pripol 2033 (dimer diol, manufactured by Croda Japan, number average molecular weight: 540) 5.4 g (0.01 mol), methyl ethyl ketone (MEK) 48.6 g , 0.08g of dibutylhydroxytoluene (BHT), heated to 70°C while blowing in dry nitrogen, 16.2mg of dibutyltin dilaurate was added dropwise, and reacted at 70°C for 4 hours. Then, 23.0g (0.2mol) of hydroxyethyl acrylamide (manufactured by KJ Chemicals Co., Ltd., registered trademark "HEAA") was added, and under a stream of dry air, the temperature in the system was kept at 80°C and stirring was continued for 3 hours . The solvent was distilled off using a reduced pressure method to obtain 161.9 g of viscous liquid UY-1. Analysis by infrared absorption spectrometry (IR), and detects the feature of the isocyanate groups of the starting material IPDI absorption (2260cm ^-1) and from the complete disappearance of the characteristic acyl group "HEAA" of absorption (1650cm ^-1) and generates the amino acid The characteristic absorption of the ethyl ester bond (1740cm ^-1 ) confirms that the desired ethyl urethane modified (meth)acrylamide UY-1 has been produced. The obtained UY-1 has a number average molecular weight of 1,600, an acrylic acid equivalent of 800, and a solution viscosity of 20mPa‧s at 25°C.

Synthesis Example 2 Synthesis of (meth)acrylamide UY-2 modified by ethyl carbamate

Using the same equipment as in Synthesis Example 1, Unilube DGP-700F (polyether polyol, 4-functional, manufactured by NOF Corporation, number average molecular weight: 700) 17.5g (0.025mol), ETERNACOLL UH-50 (polycarbonate polycarbonate) Alcohol, manufactured by Ube Industries Co., Ltd., number average molecular weight: 500) 50g (0.1mol), hexamethylene diisocyanate (HDI) 52.4g (0.2mol), MEK 39.4g, BHT 0.07g, while blowing in dry nitrogen After raising the temperature to 65°C, 0.13 g of triethylenediamine was added dropwise, and reacted at 65°C for 5 hours. Then add 11.5g (0.1mol) of "HEAA" and continue to stir for 3 hours while maintaining the internal temperature of the system at 65°C under a stream of dry air. The solvent was distilled off by a reduced pressure method to obtain 131.4 g of viscous liquid UY-2. As in Synthesis Example 1, it was confirmed by IR analysis that the intended urethane-modified (meth)acrylamide UY-2 was produced. The obtained UY-2 has a number average molecular weight of 4,480, an acrylic acid equivalent of 1,120, and a solution viscosity of 35mPa‧s at 25°C.

Synthesis Example 3 Synthesis of (meth)acrylamide UY-3 modified by ethyl carbamate

Using the same device as in Synthesis Example 1, 16.8 g (0.1 mol) of dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), UMMA-1001 (acrylic polyol (methacrylate main skeleton, single Functional, manufactured by Soken Chemical Co., Ltd., number average molecular weight: 1,000) 50 g (0.05 mol), UH-100 (polycarbonate polyol, manufactured by Ube Industries Co., Ltd., number average molecular weight: 1000) 50 g (0.05 mol), BHT 0.06 g After blowing in dry nitrogen and heating to 65°C, 12.3mg of dibutyltin dilaurate was added dropwise and reacted at 65°C for 4 hours. Then 5.8g (0.05mol) of "HEAA" was fed into the stream of dry air Keep the temperature inside the system as Stirring was continued for 3 hours at 65°C to obtain 122.6 g of viscous liquid UY-3. As in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane-modified (meth)acrylamide UY-3 was produced. The obtained UY-3 has a number average molecular weight of 2,700, an acrylic acid equivalent of 2,700, and a solution viscosity of 23mPa‧s at 25°C.

Synthesis Example 4 Synthesis of (meth)acrylamide UY-4 modified by ethyl carbamate

Using the same device as in Synthesis Example 1, 16.7g (0.025mol) of IPDI-containing isocyanurate body (IPDInurate), Curaray polyol P-530 (polyester polyol, manufactured by Curaray company, average quantity Molecular weight 500) 37.5g (0.075mol), MEK 24.2g, BHT 0.04g, dibutyltin dilaurate 8.1mg, and then add dry nitrogen while adjusting the dripping rate while adding IPDI 16.7g (0.075mol) to maintain At 65°C, react at 65°C for 2 hours. Then, 9.7 g (0.08 mol) of N-methylhydroxyethyl acrylamide (MHEAA) was fed, and stirring was continued for 5 hours under a stream of dry air while maintaining the temperature in the system at 65°C. The solvent was distilled off by a reduced pressure method to obtain 80.5 g of viscous liquid UY-4. The same as in Synthesis Example 1, IR analysis was used to confirm the production of the intended ethyl carbamate modified (meth)acrylamide UY. -4. The obtained UY-4 has a number average molecular weight of 3,200, an acrylic acid equivalent of 1,100, and a solution viscosity of 28mPa‧s at 25°C.

Synthesis Example 5 Synthesis of (meth)acrylamide UY-5 modified by ethyl carbamate

Using the same device as in Synthesis Example 1, GI-1000 (both terminal hydroxybutadiene, manufactured by Soda Corporation, number average molecular weight 1,500) 75g (0.05mol), MEK 34.2g, BHT 0.06g, and pentamethyldiethylene were charged After 0.11 g of triamine, 26.2 g (0.1 mol) of hydrogenated MDI was added dropwise while blowing dry nitrogen gas and adjusting the dropping rate, maintaining 70°C, and reacting at 70°C for 4 hours. Then feed hydroxyethyl methyl 12.9 g (0.10 mol) of acrylamide (HEMAA), under a stream of dry air, keep the temperature in the system at 70°C and continue stirring for 4 hours. The solvent was distilled off by a reduced pressure method to obtain 114.1 g of viscous liquid UY-5. The IR analysis was performed in the same way as in Synthesis Example 1, and it was confirmed that the desired ethyl urethane modified (meth)acrylamide was produced. UY-5. The obtained UY-5 has a number average molecular weight of 2,250, an acrylic acid equivalent of 1,130, and a solution viscosity of 80mPa‧s at 25°C.

Synthesis Example 6 Synthesis of (meth)acrylamide UY-6 modified by ethyl carbamate

Using the same equipment as in Synthesis Example 1, 50 g (0.05 mol) of KF-6000 (both-terminal methanol-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 1,000), trimethylhexamethylene diisocyanate ( TMHDI) 21.0g (0.1mol), BHT 0.04g, while blowing in dry nitrogen, after the temperature was raised to 70°C, 8.3mg of dibutyltin dilaurate was added dropwise and reacted at 70°C for 5 hours. Then 11.5 g (0.1 mol) of "HEAA" is fed, and the temperature in the system is maintained at 80°C under a stream of dry air and stirring is continued for 3 hours. 82.5 g of viscous liquid UY-6 was obtained, and as in Synthesis Example 1, it was confirmed by IR analysis that the desired urethane modified (meth)acrylamide UY-6 was produced. The obtained UY-6 has a number average molecular weight of 1,700, an acrylic acid equivalent of 830, and a solution viscosity of 12mPa‧s at 25°C.

Synthesis Example 7 Synthesis of (meth)acrylamide UY-7 modified by ethyl carbamate

Using the same device as in Synthesis Example 1, load Uniol D-250 (polypropylene glycol, manufactured by NOF Corporation, number average molecular weight: 250) 25 g (0.1 mol), HDI 33.6 g (0.2 mol), and BHT 0.04 g. After drying the nitrogen gas and raising the temperature to 75°C, 8.2 mg of dibutyltin dilaurate was added dropwise and reacted at 75°C for 3 hours. Then feed 23.0g (0.2mol) of "HEAA", and keep the temperature in the system at 75°C under a stream of dry air and continue stirring for 3 hours. Obtain 81.6g of viscous liquid UY-7, same as Synthesis Example 1, using IR Analysis confirmed that the desired urethane modified (meth)acrylamide UY-7 was produced. The obtained UY-7 has a number average molecular weight of 820, an acrylic acid equivalent of 400, and a solution viscosity of 8mPa‧s at 25°C.

Comparative synthesis example 1 Synthesis of urethane acrylic oligomer (UA-1)

Using the same equipment as in Synthesis Example 1, Duranol T4672 (polycarbonate polyol, manufactured by Asahi Kasei Chemicals, number average molecular weight: 2.000) 100g (0.05mol), IPDInurate 11.1g (0.02mol), MEK38.4g, BHT 0.06g After the temperature was raised to 80℃, 12.8mg of dibutyltin dilaurate was added dropwise. While blowing in dry nitrogen, 14.7g (0.07mol) of IPDI was added dropwise while adjusting the dropping rate to maintain the temperature at 80℃ and react at 80℃4 hour. Then, 9.4g (0.08mol) of "HEAA" was fed, and the temperature in the system was maintained at 80°C under a stream of dry air to continue stirring for 3 hours. The solvent was distilled off by a reduced pressure method to obtain 135.2 g of viscous liquid UA-1. As in Synthesis Example 1, it was confirmed by IR analysis that the urethane acrylic oligomer UA-1 was produced. The number average molecular weight of the obtained UA-1 is 7,700, the acrylic acid equivalent is 2,600, and the solution viscosity at 25°C is 250mPa‧s.

Comparative synthesis example 2 Synthesis of urethane acrylic oligomer (UA-2)

Using the same device as in Synthesis Example 1, 53.3g (0.13mol) of Uniol D-400 (polypropylene glycol, manufactured by NOF, number average molecular weight 400), 0.06g of BHT, and 12.1mg of dibutyltin dilaurate were loaded, and then passed in The nitrogen was dried, 52.4 g (0.2 mol) of hydrogenated MDI was added dropwise while adjusting the dropping rate to maintain the temperature at 80°C, and the reaction was carried out at 80°C for 5 hours. Then, 15.3 g (0.13 mol) of "HEAA" is fed, and the temperature in the system is maintained at 80°C under a stream of dry air and stirring is continued for 3 hours. 121.0 g of viscous liquid UA-2 was obtained. As in Synthesis Example 1, it was confirmed by IR analysis that urethane acrylic oligomer UA-2 was produced. obtain The number average molecular weight of UA-2 is 1,900, the acrylic acid equivalent is 950, and the solution viscosity at 25°C is 24mPa‧s.

Comparative Example Synthesis 3 Synthesis of urethane acrylic oligomer UA-3

Using the same equipment as in Synthesis Example 1, 60g (0.06mol) of KF-6000, 26.6g (0.12mol) of IPDI, 0.05g of BHT were charged, and then the temperature was raised to 80°C while adding dry nitrogen, and dilauric acid was added dropwise. 10.1 mg of dibutyltin was reacted at 80°C for 4 hours. Then, 13.9 g (0.12 mol) of ethyl hydroxyacrylate (HEA) was fed, and the system was kept at 70° C. under a stream of dry air and stirred for 3 hours. 100.6 g of a viscous liquid was obtained. As in Synthesis Example 1, it was confirmed by IR analysis that the urethane acrylic oligomer UA-3 was produced. The number average molecular weight of the obtained UA-3 is 1,500, the acrylic acid equivalent is 850, and the solution viscosity at 25°C is 10mPa‧s.

Comparative Example Synthesis 4 Synthesis of urethane acrylic oligomer UA-4

Using the same device as in Synthesis Example 1, Uniol TG-330 (polyoxypropylene glycerol ether, trifunctional, manufactured by NOF Corporation, number average molecular weight: 330) 13.2g (0.04mol), IPDInurate 79.9g (0.12mol), After 36.3 g of MEK and 0.06 g of BHT, the temperature was raised to 65°C while blowing dry nitrogen, 12.1 mg of dibutyltin dilaurate was added, and the reaction was carried out at 65°C for 4 hours. Then, 27.8 g (0.24 mol) of HEA was fed, and under the flow of dry air, the temperature in the system was maintained at 65° C. and the stirring was continued for 4 hours. The solvent was distilled off by a reduced pressure method to obtain 121.0 g of a solid ethyl urethane acrylic oligomer UA-4. As in Synthesis Example 1, IR analysis confirmed that UA-4 was produced. The number average molecular weight of the obtained UA-4 is 3,000, the acrylic acid equivalent is 500, and the solution viscosity at 25°C is 23mPa‧s.

Comparative Example Synthesis 5 The synthesis of adduct type ethyl urethane acrylamide UA-5

Referring to Example 2 of Patent Document 2 (Japanese Patent Laid-Open No. 2002-37849), 74.8 g (0.43 mol) of tolylene diisocyanate (TDI) and 100 g (0.87 mol) of "HEAA" were added to N,N-dimethyl 180 g of dimethanamide (DMF) was reacted at 40°C for 4 hours to synthesize, and the solvent was distilled off by a reduced pressure method to obtain a solid adduct type ethyl carbamate acrylamide UA-5. The number average molecular weight of the obtained UA-5 is 400, and the solution viscosity at 25°C is 8mPa‧s.

The synthesis example of the polyfunctional (meth)acrylic compound (B) is shown below.

Synthesis Example 8 Synthesis of Reactive Urethane Polymer UP-1

Using the same device as in Synthesis Example 1, put 75g (0.075mol) of ETERNACOLL UC-100, 51.5g of MEK, 0.06g of BHT, and 11.1mg of dibutyltin dilaurate with the same device as in Synthesis Example 1. After blowing in dry nitrogen, the temperature was raised to 65°C and then added dropwise IPDI 26.2g (0.12mol) was reacted at 65°C for 4 hours. After that, 10.0g (0.09mol) of "HEAA" was fed, and under the flow of dry air, the temperature in the system was maintained at 65°C and stirring was continued for 4 hours. The solvent was distilled off using a reduced pressure method to obtain 111.1 g of viscous liquid UP-1. As in Synthesis Example 1, it was confirmed by IR analysis that the desired reactive urethane polymer UP-1 was produced. The obtained UP-1 has a number average molecular weight of 4,700, an acrylic acid equivalent of 1,560, and a solution viscosity of 55mPa‧s at 25°C.

Synthesis Example 9 Synthesis of Reactive Urethane Polymer UP-2

Using the same device as in Synthesis Example 1, 8.7g (0.05mol) of TDI, PTMG2000 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) 90g (0.045mol), MEK 50.0g, BHT 0.05 g, after the temperature was raised to 75°C while blowing in dry nitrogen, 10.0 mg of dibutyltin dilaurate was added dropwise and reacted at 75°C for 3 hours. Then feed 1.3 g (0.01 mol) of hydroxy ethyl methacrylate (HEMA), Under a stream of dry air, keep the temperature in the system at 75°C and continue stirring for 3 hours. The solvent was distilled off using a reduced pressure method to obtain 100.0 g of viscous liquid UP-2. As in Synthesis Example 1, it was confirmed by IR analysis that the target reactive urethane polymer UP-2 was produced. The number average molecular weight of the obtained UP-2 is 20,000, the acrylic acid equivalent is 10,000, and the solution viscosity at 25°C is 180mPa‧s.

Synthesis Example 10 Synthesis of Reactive Urethane Polymer UP-3

Using the same device as in Synthesis Example 1, it was charged with 11.1g (0.05mol) of IPDI, ETERNACOLL UHC-50-200 (polycarbonate polyol, manufactured by Ube Industries Co., Ltd., number average molecular weight: 2,000) 80g (0.04mol), MEK 46.7 g and 0.05 g of BHT were heated to 70°C while blowing in dry nitrogen, 9.3 mg of dibutyltin dilaurate was added dropwise, and the reaction was carried out at 70°C for 4 hours. Then, HEA 2.3g (0.02mol) was fed, and the system temperature was maintained at 70°C under a stream of dry air to continue stirring for 4 hours. The solvent was distilled off by a reduced pressure method to obtain 93.4 g of viscous liquid UP-3. As in Synthesis Example 1, it was confirmed by IR analysis that the target reactive urethane polymer UP-3 was produced. The obtained UP-3 has a number average molecular weight of 9,000, an acrylic acid equivalent of 4,600, and a solution viscosity of 80mPa‧s at 25°C.

Synthesis Example 11 Synthesis of Reactive Urethane Polymer UP-4

Using the same device as in Synthesis Example 1, charged with IPDI nurate 1.11g (2mmol), IPDI 11.1g (50mmol), Uniol D-2000 (polypropylene glycol, manufactured by NOF Corporation, number average molecular weight: 2,000) 91g (0.045mol), MEK 51.8g and BHT 0.05g were heated to 70°C while blowing dry nitrogen, 10.4 mg of dibutyltin dilaurate was added dropwise and reacted at 70°C for 3 hours. Then, 0.5g (5mmol) of HEA was fed, and under a stream of dry air, the temperature in the system was maintained at 80°C and stirring was continued for 3 hours. The solvent was distilled off by a reduced pressure method to obtain 103.6 g of a viscous liquid UP-4. Same as Synthesis Example 1, IR analysis confirmed that the target reactive urethane polymer UP-4 was produced. The obtained UP-4 has a number average molecular weight of 68,000, an acrylic acid equivalent of 22,500, and a solution viscosity of 1200mPa‧s at 25°C.

Using the urethane-modified (meth)acrylamide obtained in Synthesis Examples 1-7 and the urethane acrylic oligomer obtained in Comparative Synthesis Example 5, the following methods were used to evaluate the general organic solvents , The solubility characteristics of acrylic monomers, the results are shown in Table 1. In addition, the solvents and monomers used in the evaluation are as follows.

IPA: isopropanol

MEK: methyl ethyl ketone

THF: Tetrahydrofuran

啉(註冊商標「ACMO」) "ACMO": N-Acrylic

Morin (registered trademark "ACMO")

HDDA: 1,6-hexanediol diacrylate

BA: Butyl acrylate

IBOA: Isobornyl acrylate

2EHA; 2-ethylhexyl acrylate

THFA; tetrahydrofuran methyl acrylate

(3) Solubility

Add 1 part by weight of a general solvent or acrylic monomer as a diluent to 1 part by weight of the obtained carbamate-modified (meth)acrylamide, etc., stir and let stand overnight for visual inspection Confirm the degree of dissolution.

◎: The transparency is high, and white turbidity and separation are not confirmed at all.

○: The transparency is high, but white turbidity is slightly observed.

△: No layer separation but white turbidity.

×: White turbidity and layer separation

As shown in the results of evaluation examples and evaluation comparative examples, the adduct type of ethyl urethane acrylamide has poor solubility in general solvents and acrylic monomers, especially insoluble in hydrophobic solvents and monomers. It is difficult to handle as an active energy ray curable resin composition. The reason is that the intramolecular and intermolecular hydrogen bonds of the adduct type ethyl urethane acrylamide are very strong, which makes it difficult to disperse in solvents and other monomers due to self-aggregation.

The urethane-modified (meth)acrylamide obtained in Synthesis Examples 1 to 6 and the ethyl urethane acrylic oligomer obtained in Comparative Synthesis Examples 1 to 4 were used to prepare active energy ray curable resin composition Things. And using these resin compositions, the production of an ultraviolet cured film and the evaluation of the characteristics of the cured film were performed. The results are shown in Table 2.

Example A-1

The urethane-modified (meth)acrylamide UY-1100 parts by weight, 100 parts by weight of MEK, and 3 parts by weight of Darocur 1173 as a photopolymerization initiator obtained in Synthesis Example 1 were uniformly mixed to prepare a reactive Energy ray curable resin composition. Then, using the obtained curable resin composition, an ultraviolet curable film was produced by the following method.

Production method of UV curing film

Coated with a coating rod (RDS 12) on the thickening coating surface of a 100μm thick polyethylene terephthalate (PET) film ("Cosmoshine A4100" manufactured by Toyobo Co., Ltd., single-sided thickening coating treatment) , Make the coating film so that the thickness of the dried coating film becomes 10μm. After drying the obtained coating film with an explosion-proof dryer at 80°C for 2 minutes, it was cured by ultraviolet radiation (device: Inverter conveyor device ECS-4011GX manufactured by Eyegraphics, and metal halide lamp: M04-L41 manufactured by Eyegraphics). Production of UV curing film. The curability of the resin composition and the adhesion resistance, shrinkage resistance, transparency, water absorption, and adhesion of the cured film obtained were evaluated. The results are shown in Table 2.

(4) Hardening

Prepare a dry coating film with a thickness of 10μm in the same manner as above, and irradiate ultraviolet rays with an illuminance of 2mW/cm ² at a temperature of 70°C for 120 seconds (accumulated light quantity 240mJ/cm ² ), and measure the peaks derived from vinyl in the resin composition by instant FT-IR Section (1630cm ^-1 ) height, calculate the curing rate of the coating film

(Curing rate (%) = (the height of the peak from the vinyl before curing-the height of the peak from the vinyl after curing)/the height of the peak from the vinyl before curing × 100).

◎: Hardening rate is over 90%

○: The curing rate is more than 80% and less than 90%

△: The curing rate is more than 50% but not 80%

×: Hardening rate is less than 50%

(5) Adhesion resistance

A dry coating film with a thickness of 10 μm was produced in the same manner as above, and ultraviolet rays with an illuminance of 700 mW/cm ^{2 were} irradiated at a temperature of 70° C. for 3 seconds (cumulative light quantity 2100 mJ/cm ² ) to produce 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.

◎: No stickiness at all.

○: There is some adhesiveness, but no fingerprints remain on the surface.

△: Adhesive and fingerprints remain on the surface.

×: The adhesiveness is severe, and the fingers are stuck to the surface.

(6) Curl resistance (shrink resistance)

A fully cured film with 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 value was calculated from the measured values of 5 pieces cut out in the same way.

◎: The floating height is less than 0.5mm.

○: 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 inspection)

The fully cured coating film obtained in the aforementioned shrinkage resistance test was used to visually observe and evaluate the transparency.

◎: Transparent and no matting at all.

○: Transparent with a little matte.

△: There is matte but transparent parts remain.

×: Extremely matte, and the transparent part cannot be confirmed.

(8) Water absorption

Pour the curable resin composition on the Teflon sheet with a depth of 1mm, vacuum dry it (50°C, 400torr), and cure it with ultraviolet radiation (700mW/cm ² , 2000mJ/cm ² ) to produce ultraviolet curing sheet. The obtained piece was cut into 3 cm squares and used as a test piece. Place the obtained test piece in an environment with a temperature of 50°C and a relative humidity of 95% for 24 hours, and calculate its water absorption

(Water absorption (%) = (weight after constant temperature and humidity-weight before constant temperature and humidity) / weight before constant temperature and humidity × 100)

(10) Adhesion

As before, a fully cured film with a thickness of 10μm is produced on a substrate of various materials. According to JIS K 5600, 100 squares of 1mm square were made, and scotch tape was attached, and the number of squares with residual coating film on the substrate side was counted and evaluated.

Examples A-2~A-7, Comparative Examples A-8~A-11

The composition described in Table 2 was replaced, except that the ultraviolet curable resin composition was prepared in the same manner as in Example A-1, and a cured film was prepared, and the evaluation was performed according to the above method. The results are shown in Table 2.

【Table 2】

As shown in the results of the evaluation examples and evaluation comparative examples, the molecular weight and acrylic acid equivalent of the urethane-modified (meth)acrylamide of the present invention are within a specific range, so the active energy ray hardenability is high, and The cured film has good surface dryness (adhesion resistance), curl resistance and water resistance, and its transparency and adhesion to various substrates are all satisfactory. However, if the molecular weight or acrylic equivalent is out of the specific range of the present invention, the curability, tack resistance and curl resistance cannot all be satisfactory. As a result, The transparency, adhesion and water resistance of the cured film are also reduced. Especially when the molecular weight is too high, the characteristics derived from the carbonate skeleton and the ether skeleton will be significantly exhibited. With the increase in crystallinity, the transparency will decrease, and the adhesion of the cured film will decrease (Evaluation Comparative Example A-8), and the adhesion of the cured film surface Sex (evaluation comparative example A-9) becomes remarkable.

On the other hand, the (meth)acrylate-containing urethane acrylic oligomer, even if its molecular weight and acrylic equivalent are all within the specified range of the present invention, is among the properties of curability, adhesion resistance, and curing shrinkage resistance. The performance of any one or more is not satisfactory, and the adhesion is also low. In addition, the evaluation comparative example A-11 with 6 acrylate groups per molecule has good adhesion resistance in appearance, but the curing rate of vinyl is less than 50%, and the curing shrinkage rate is also high.

The urethane-modified (meth)acrylamide of the present invention has a molecular weight and an acrylic equivalent within a specific range, and even if the curability is high, a cured film with excellent curl resistance can be obtained. The inventors speculated that the hydrogen bond between the amide groups or between the amide group and the urethane bond is strong, and the urethane-modified (meth)acrylamide of the present invention is still strong even before curing. Exists in a cohesive state, as a result, the distance between the molecules before and after curing will not be greatly reduced, and the shrinkage of the entire cured film is also suppressed.

The urethane-modified (meth)acrylamide obtained in Synthesis Examples 1 to 7 and the ethyl urethane acrylic oligomer obtained in Comparative Synthesis Examples 1 to 5 were used to evaluate the characteristics of each application field. The materials used in the examples and comparative examples are as follows.

"HEAA"; Hydroxyethyl acrylamide (manufactured by KJ Chemicals)

"DMAA"; N,N-Dimethacrylamide (manufactured by KJ Chemicals)

"DEAA"; N,N-Diethylacrylamide (manufactured by KJ Chemicals)

啉(KJ Chemicals(股)製) "ACMO"; N-acryloyl

Morin (manufactured by KJ Chemicals Co., Ltd.)

"DMAPAA"; Dimethylaminopropyl acrylamide (manufactured by KJ Chemicals)

HEA; ethyl hydroxyacrylate

2EHA; 2-ethylhexyl acrylate

EEA; 2-(2-ethoxyethoxy) ethyl acrylate

THFA; Tetrahydrofuran methacrylate

IBOA; Isobornyl acrylate

IBMA; Isobornyl 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 Shinnakamura Chemical Industry Co., Ltd.)

HDDA; 1,6-hexanediol diacrylate

TPGDA; Tripropylene glycol diacrylate

PETA; neopentyl erythritol triacrylate

DPHA; Dineopentaerythritol hexaacrylate

DMAEA-TFSIQ; Allyloxyethyl trimethylammonium bis(trifluoromethanesulfonyl)imide (manufactured by KJ Chemicals)

DMAPAA-TFSIQ; acrylamidopropyl trimethylammonium bis(trifluoromethanesulfonyl)imidine (manufactured by KJ Chemicals)

Irgacure 184; 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan)

Irgacure 1173; 2-hydroxy-2-methyl-1-phenyl-propane-1-one (manufactured by BASF Japan)

Irgacure TPO; 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide (manufactured by BASF Japan)

Irgacure 819; Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (manufactured by BASF Japan)

Irgacure 127; 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propanyl)benzyl]phenyl]-2-methyl-propan-1-one (manufactured by BASF Japan )

Hitaloid 7851; epoxy acrylate oligomer (manufactured by Hitachi Chemical)

Hitaloid 7975; Acrylic acrylate oligomer (manufactured by Hitachi Chemical Co., Ltd.)

Evaluation Example B-1

8 parts by weight of the ethyl urethane modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1 and 30 parts by weight of the reactive urethane polymer UP-4 synthesized in Synthesis Example 12, 10 parts by weight of "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 were mixed, and 1 part by weight of Irgacure 184 as a photopolymerization initiator was added and mixed uniformly. Prepared into ultraviolet curable adhesive. Then, using the obtained adhesive, the adhesive sheet was made and evaluated by ultraviolet curing in the following method.

Manufacturing method of UV-curing adhesive sheet

Apply the UV-curing adhesive prepared above to the heavy-release separator (polysiloxy-coated PET film) to use it without trapping air bubbles on the light-release separator (polysiloxy-coated PET film) A desktop roll laminator (RSL-382S manufactured by Royal Sovereign) is used to attach the adhesive layer to a thickness of 25μm, and irradiate ultraviolet rays (device: Eyegraphics inverter conveyor device ECS-4011GX, metal halide lamp: Eyegraphics M04 -L41, ultraviolet illuminance: 700mW/cm ² , cumulative light quantity: 2000mJ/cm ² ), made into a transparent adhesive sheet for optics. The properties of the obtained adhesive sheet were evaluated according to the following methods, and the results are shown in Table 3.

(10) Transparency (transmittance)

At a temperature of 23℃ and a relative humidity of 50%, on the glass substrate as the adherend, attach the peeled surface of the lightly peelable separator cut into a 25mm wide adhesive sheet, and then peel off the heavy peelable separator. Measure the transmittance. The measurement uses a haze meter (Nippon Denshoku Kogyo Co., Ltd., NDH-2000), in accordance with JIS K 7105, after measuring the total light transmittance of the glass substrate, subtracting the transmittance of the glass plate, and calculating the transmittance of the adhesive layer itself , And evaluate transparency in numerical form. The higher the transmittance, the better the transparency.

(11) Surface resistivity measurement

Using a template (length 110 × width 110 mm), cut the adhesive sheet with a cutting knife, put it in a constant temperature and humidity machine adjusted to a temperature of 23°C and a relative humidity of 50%, and let it stand for 3 hours to obtain a sample for surface resistivity measurement . According to JIS K 6911, the measurement was performed using a digital electrometer (R8252 type: manufactured by ADC).

(12) Adhesion

Under the conditions of temperature 23℃ and relative humidity 50%, transfer to a polyethylene terephthalate (PET) film (thickness 100μm) or glass substrate as the adherend, using a pressure bonding roller weighing 2kg back and forth Apply pressure for 2 times and place it in the same gas environment for 30 minutes. Thereafter, a tensile tester (device name: Tensilon RTA-100 manufactured by ORIENTEC) was used to measure the 180° peel strength (N/25 mm) at a peel speed of 300 mm/min.

◎: 15(N/25mm) or more

○: 10 (N/25mm) or more and less than 15 (N/25mm)

△: 3(N/25mm) or more and less than 10(N/25mm)

×: less than 3 (N/25mm)

(13) Pollution resistance

The adhesive sheet was attached to the adherend in the same manner as the aforementioned measurement of the adhesive force, and after standing at 80°C for 24 hours, the contamination on the surface of the adherend after peeling off the adhesive sheet was visually observed.

◎: No pollution

○: There is very little contamination.

△: Slight contamination.

×: Paste (adhesive) remains.

(14) Yellowing resistance

The adhesive sheet was attached to the glass substrate and installed in a xenon fading tester (SC-700-WA: manufactured by Suga Testing Machine Co., Ltd.). After 120 hours of exposure to ultraviolet rays with an intensity of 70mW/cm ² , the discoloration of the adhesive sheet was visually observed .

⊚: No yellowing was confirmed visually.

○: Yellowing can be slightly confirmed visually.

△: Yellowing can be confirmed visually.

×: Remarkable yellowing can be confirmed visually.

(15) Humidity and heat resistance

The adhesive sheet was attached to the glass substrate in the same manner as the aforementioned yellowing resistance test, and after keeping it at a temperature of 85°C and a relative humidity of 85% for 100 hours, visual observation was made to evaluate whether floating, peeling, bubbles, and turbidity occurred.

◎: Transparent and no floating, peeling, or bubbles occurred.

○: There is very little extinction, but no floating, peeling, and bubbles.

△: There is slight dullness or floating, peeling, bubbles.

×: Extremely dull or floating, peeling, bubbles.

(16) High-low difference followability

A black tape with a thickness of 20 μm is bonded to the glass substrate to produce glass with a difference in height. Transfer the adhesive sheet to a glass with a difference in height, and press it back and forth once with a roller with a load of 2kg (pressing speed 300mm/min) under a gas environment with a temperature of 23℃ and a relative humidity of 50%. After standing at 80°C for 24 hours, confirm the state of the height difference with an optical microscope.

◎: No bubbles are observed at all

○: A few small spherical bubbles are observed

△: Large bubbles are observed, sometimes the bubbles are connected to each other

×: Large bubbles are connected to each other and expand on the line at the height difference part

(17) Stamping processability

The obtained adhesive sheet was cut using a Thomson punching method (a punching method in which 10 punching blades are arranged parallel to each other at 5.0 mm intervals).

◎: There is no residue on the punching blade.

○: A small amount of adhesive remains on the punching blade.

△: Adhesive remains on the punching blade.

×: The adhesive remains significantly on the punching blade, and the cutting surface cannot be clearly identified.

Evaluation Examples B-2~7, Evaluation Comparative Examples B-8~11

Except that the composition described in Table 3 was replaced, an ultraviolet curable resin composition was prepared in the same manner as in Evaluation Example B-1, an adhesive sheet was produced, and the evaluation was carried out by the above method. The results are shown in Table 3.

【table 3】

As shown in the results of the evaluation example and the evaluation comparative example, blended urethane modified (meth)acrylamide with molecular weight and acrylic equivalent outside a certain range, or amines with molecular weight and acrylic equivalent within a certain range Ethyl formate-modified (meth)acrylate has a tendency to decrease adhesion and heat resistance, and the adhesive sheet after curing has poor stain resistance and punching processability, so it is difficult to use. By using this hair It is clear that urethane modified (meth)acrylamide can obtain an adhesive sheet with transparency, adhesion, stain resistance, and excellent punching processability.

Evaluation Example C-1

22 parts by weight of the ethyl urethane modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1 and 15 parts by weight of the reactive urethane polymer UP-3 synthesized in Synthesis Example 10, 18 parts by weight of "ACMO", 9 parts by weight of "HEAA", 14 parts by weight of "DMAA", 10 parts by weight of THFA, and 12 parts by weight of IBOA were mixed, and 3 parts by weight of Irgacure 1173 as a photopolymerization initiator was added and mixed uniformly. Prepared into ultraviolet curable adhesive. Afterwards, using the obtained adhesive, a polarizing plate was made by ultraviolet curing by the following method and the physical properties of the polarizing plate were evaluated.

Making polarizing plates by UV irradiation

Using a desktop roll laminator (RSL-382S manufactured by Royal Sovereign), sandwich the polarizing film between two transparent films (protective film, retardation film or optical compensation film), and place the polarizing film between the transparent film and the polarizing film. The adhesives of the examples or comparative examples were bonded together so that the thickness was 10 μm. Irradiated with ultraviolet rays from the transparent film bonded to the top surface (ultraviolet illuminance: 700mW / cm ^2, accumulated light quantity: 2000mJ / cm ^2), at both sides of the polarizing film made of a transparent film of a polarizing plate.

(18) Surface shape observation

The surface of the obtained polarizing plate was visually observed and evaluated according to the following criteria.

◎: The surface of the polarizing plate has not even slight streaks or unevenness.

○: It can be confirmed that there are micro streaks on the surface of the polarizer.

△: It can be confirmed that there are micro streaks and unevenness on the surface of the polarizing plate.

×: It can be confirmed that there are obvious streaks and unevenness on the surface of the polarizing plate.

(19) Peel strength

Under the conditions of a temperature of 23°C and a relative humidity of 50%, the polarizing plate (test piece) cut into 20mm×150mm is pasted with double-sided tape on the tensile tester (automatic stereograph made by Shimadzu Corporation) (autograph) AGXS-X 500N) test board. Peel off one of the transparent protective film and the polarizing film on the side where the double-sided tape is not attached in advance for about 20-30mm, clamp it in the upper clamp, and measure the 90° peel strength (N/25mm) at a peeling speed of 300mm/min.

◎: 3.0(N/25m) or more

○: 1.5 (N/25m) or more, less than 3.0 (N/25m)

△: 0.5 (N/25m) or more, less than 1.5 (N/25m)

×: less than 0.5 (N/25m)

(20) Water resistance

The obtained polarizing plate was cut into 20×80 mm and immersed in 60°C warm water for 48 hours, and then it was confirmed whether there was peeling at the interface between the polarizer and the protective film, retardation film, and optical compensation film. The judgment is based on the following criteria.

◎: No peeling at the interface between the polarizer and the protective film (less than 1mm).

○: A part of peeling occurred at the interface between the polarizer and the protective film (1 mm or more, less than 3 mm).

△: A part of peeling at the interface between the polarizing plate and the protective film (3 mm or more, less than 5 mm).

×: There is peeling (5 mm or more) at the interface between the polarizer and the protective film.

(21) Durability

Cut the obtained polarizing plate into 150mm×150mm, put it into a thermal shock device (TSA-101L-A manufactured by Espec), and perform thermal shock at -40°C to 80°C for 30 minutes each for a total of 100 times, and evaluate according to the following criteria.

◎: No cracks occurred.

○: Only short cracks of 5 mm or less occur at the end.

△: Short-line cracks occurred outside the ends. However, the polarizing plate is not separated into two or more parts by this line.

×: Cracks occurred outside the ends. The polarizing plate is divided into two or more parts by this line.

Evaluation Examples C-2~7, Evaluation Comparative Examples C-8~11

Except that the composition described in Table 4 was replaced, an ultraviolet curable resin was prepared in the same manner as in Evaluation Example C-1, a polarizing plate was prepared, and the evaluation was performed in accordance with the above method. The results are shown in Table 4.

【Table 4】

As shown in the results of the evaluation example and the evaluation comparative example, blended urethane modified (meth)acrylamide with molecular weight and acrylic equivalent outside a certain range, or amines with molecular weight and acrylic equivalent within a certain range When the (meth)acrylate is modified by ethyl formate, the flexibility from the main skeleton such as ether and ester is high, the peel strength and water resistance tend to decrease, and the peel strength and durability are caused by incomplete curing of the adhesive Low, it is difficult to use. It is learned that the adhesive using the urethane modified (meth)acrylamide of the present invention has high crosslinking density, so it has high peel strength and durability, good balance between flexibility and strength, and water resistance The sex is also excellent.

Evaluation Example D-1

48 parts by weight of the urethane modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1; 15 parts by weight of HDDA, 24 parts by weight of TPGDA, 8 parts by weight of "DEAA", 5 parts by weight of IBOA, Mix 3 parts by weight of pigment and 3 parts by weight of pigment dispersant, add 2 parts by weight of Irgacure 819 and 3 parts by weight of Irgacure 127 as a photopolymerization initiator, and mix them uniformly to prepare a photocurable ink composition. After that, inkjet printing was carried out according to the following method, and the evaluation of the 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-plate viscometer (device name: RE550 viscometer manufactured by Toki Sangyo Co., Ltd.). According to inkjet printing, the viscosity of the ink composition at 20°C is preferably 3-20mPa‧s or less, and 5-18mPa‧s is more preferable. If it is less than 3mPa‧s, printing bleeding after discharge and printing deviation will be observed, resulting in a decrease in discharge followability. Above 20mPa‧s, a decrease in discharge stability due to clogging of the discharge nozzle will be observed, which is not ideal.

(23) Compatibility

Visually confirm the compatibility of the ink composition prepared by the above method.

◎: The ink composition has no insoluble matter.

○: A small amount of insoluble matter is observed in the ink composition.

△: Insoluble matter is observed in the entire ink composition.

×: There are deposits in the ink composition.

Use UV irradiation to make printed matter

The obtained ink composition was coated with a coating rod (RDS 12) on a polyethylene terephthalate (PET) film with a thickness of 100 μm, and irradiated with ultraviolet rays (device: HOYA LED UV irradiation system H- 10MAH20-1T18, 385nm) to harden it to make a printed matter.

(24) Hardening

Measure the cumulative amount of light until the ink composition is completely cured in an environment at room temperature of 23°C when the printed matter is produced by the above method.

◎: Completely hardened at 500mJ/cm ²

○: Fully hardened at 500~1000mJ/cm ²

△: Fully hardened at 1000~2000mJ/cm ²

×: 2000mJ/cm ² or more is required until complete hardening

(25) Surface dryness

The printed matter produced by the above method was allowed to stand for 5 minutes at a room temperature of 23°C and a relative humidity of 50%. The high-quality paper was superimposed on the printing surface, and a load of 1kg/cm ^{2 was} applied for 1 minute to evaluate the degree of transfer of the ink to the paper.

◎: The printing ink is dry and does not transfer to paper at all.

○: The printing ink is dry and slightly transferred to the paper.

△: The ink is almost dry and transfers to paper.

×: The ink is almost not dried, and there is much transfer to paper.

Inkjet printing and printing suitability evaluation

Use an inkjet color printer (PM-A890 manufactured by Seiko Epson) to print the entire surface image and irradiate ultraviolet light (ultraviolet illuminance: 700mW/cm ² , cumulative light quantity: 2000mJ/cm ² ) to make printed matter, and follow the following Method evaluation. The results are shown in Table 5.

(26) Spit out stability

Print with the above-mentioned inkjet printer, and visually evaluate the printing state of the printed matter.

◎: There is no nozzle blanking, and printing is good.

○: Some nozzles are left blank.

△: There is nozzle blanking in a wide range.

×: There is no vomiting.

(27)Sharpness

Visually observe the sharpness of the printed image.

⊚: No bleeding of ink is observed at all, and the image is clear.

○: There is almost no ink bleeding, and the image is good.

△: Slight ink bleeding is observed.

×: Bleeding of ink is significantly observed.

(28)Water resistance

Expose the printed surface to running water for 1 minute, and observe the changes in the image visually.

◎: There is no change in the sharpness of the image.

○: The sharpness of the image is hardly changed, but ink bleeding is slightly observed.

△: The sharpness of the image is reduced and ink bleeding is observed.

×: The sharpness of the image is significantly reduced and ink bleeding is significantly observed.

Evaluation Examples D-2~7, Evaluation Comparative Examples D-8~11

The composition described in Table 5 was replaced, except that the ink composition was prepared in the same manner as in Evaluation Example D-1, and printed matter was prepared according to the above method and evaluated according to the above method. The results are shown in Table 5.

As shown in the results of the evaluation example and the evaluation comparative example, blended urethane modified (meth)acrylamide with molecular weight and acrylic equivalent outside a certain range, or amines with molecular weight and acrylic equivalent within a certain range In the case of ethyl formate-modified (meth)acrylate, the viscosity of the ink composition after preparation is high, so the ejection stability is low, the hardenability, and the surface dryness tend to be low. In addition, due to the viscosity derived from the main skeleton and the low curability of (meth)acrylate, bleeding was observed in the printed matter after ejection and curing. When the ethyl urethane modified (meth)acrylamide of the present invention is used, an excellent ink composition with curability, high curing density, and excellent surface dryness, sharpness, and water resistance can be obtained.

Evaluation Example E-1

15 parts by weight of the urethane modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1 and 20 parts by weight of the reactive urethane polymer UP-1 synthesized in Synthesis Example 8 30 parts by weight of synthesis example 10 synthetic reactive urethane polymer UP-3, 25 parts by weight of PETA, 10 parts by weight of IBOA were mixed, 3 parts by weight of Darocur 1173 as a photopolymerization initiator was added, and mixed uniformly , Prepared into a photocurable coating composition.

(29) Compatibility

The compatibility of the coating composition obtained by the above method was confirmed visually.

⊚: The coating composition has high transparency, and white turbidity and separation are not confirmed at all.

○: The coating composition has high transparency, but slightly white turbidity is observed.

△: The entire coating composition is cloudy.

×: The coating composition is cloudy and separated.

(30) Moisture permeability

The obtained coating agent composition was coated on a substrate, and the adhesion state of the coating film was visually observed.

◎: There was no shrinkage at the time of application and after standing for 5 minutes, and a smooth coating film was formed.

○: There is no shrinkage hole immediately after coating, but some shrinkage hole is observed after standing for 5 minutes.

△: Some shrinkage holes are observed immediately after coating.

×: Many shrinkage holes were observed immediately after coating, and a uniform coating film could not be obtained.

Utilize ultraviolet radiation to make coating film

The coating agent composition obtained was coated on a PET film with a thickness of 100μm using a coating bar (RDS 12), and irradiated with ultraviolet rays (ultraviolet illuminance: 700mW/cm ² ) to produce a coating film (thickness 10μm), and evaluated according to the following methods . The results are shown in Table 6. In addition, when a solvent is used, it is irradiated with ultraviolet rays after drying at 80°C for 3 minutes after coating.

(31) Hardening

The coating agent composition was applied, and the obtained coating film was irradiated with an ultraviolet illuminance of 700 mW/cm ^{2 in an} environment of room temperature 23° C., and the cumulative light amount until the resin composition was completely cured was measured. Completely hardened refers to the state where there will be no traces on the surface of the cured film when traced with silicone rubber.

◎: It is completely cured at a cumulative light intensity of 1000 mJ/cm ² .

○: It is completely cured at a cumulative light intensity of 1000mJ/cm ² ~2000mJ/cm ² .

△: It is completely cured at a cumulative light intensity of 2000mJ/cm ² ~5000mJ/cm ² .

×: A cumulative light quantity of 5000 mJ/cm ² or more is required until complete curing.

(32) Adhesion resistance

Touch the surface of the coating film obtained by the above method with a finger, and evaluate the degree of adhesiveness.

◎: There is no adhesiveness at all.

○: There is some adhesiveness, but no fingerprints remain on the surface.

△: Adhesive, and fingerprints remain on the surface.

×: The adhesiveness is severe and the fingers stick to the surface.

(33) Curl resistance (shrink resistance)

For the coating film irradiated with ultraviolet rays (ultraviolet illuminance of 700mW / cm ^2, accumulated light quantity of 2000mJ / cm ²⁾ of the above-mentioned method, the obtained coating film was cut into 10cm square and measuring the average of the four corners of the float.

◎: The floating height is less than 0.5mm.

○: 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

Use #0000 steel wool to go back and forth 10 times while applying a load of 200g/cm ² to visually evaluate whether there is a scar.

◎: Film peeling and scratches were hardly confirmed.

○: A slight flaw is confirmed in a part of the film.

△: Streak-like scars are confirmed across the film.

×: Film peeling occurred.

(35) Self-healing

After the coating film obtained by the above method was injured with a spoon, it was allowed to stand in an environment with a temperature of 25°C and a relative humidity of 50% to visually evaluate the recovery state of the scar.

◎: The scar is completely recovered within 30 minutes.

○: The scar is completely recovered within 30 minutes to 5 hours.

△: The scar is completely recovered within 5 hours to 24 hours.

×: The scar has not fully recovered even after being left for 24 hours.

(36) Adhesion

According to JIS K 5600, make 100 1mm square grid eyes, attach scotch tape, count and evaluate the number of grid eyes with coating film remaining on the substrate side when stripping off in one go.

(37) Humidity resistance

The coating film obtained on the PET film (100μm) was left to stand for 24 hours in an environment with a temperature of 50°C and a relative humidity of 95%, and the film was evaluated by visual inspection or adhesion test.

⊚: Transparency is maintained under high temperature and high humidity, and no decrease in adhesion is observed.

○: The transparency is maintained under high temperature and high humidity, but a slight decrease in adhesion is observed.

△: The transparency is maintained under high temperature and high humidity, but the adhesion is greatly reduced.

×: Decrease in transparency is observed under high temperature and high humidity, and adhesion is further reduced.

Evaluation Examples E-2~7, Evaluation Comparative Examples E-8~11

The composition was replaced with the composition described in Table 6, except that the coating composition was prepared in the same manner as in Evaluation Example E-1, and a cured film was prepared according to the above method and evaluated according to the above method. The results are shown in Table 6.

【Table 6】

As shown in the results of the evaluation example and the evaluation comparative example, blended urethane modified (meth)acrylamide with molecular weight and acrylic equivalent outside a certain range, or amines with molecular weight and acrylic equivalent within a certain range When the (meth)acrylate is modified by ethyl formate, the curability of the coating agent and the surface dryness (adhesion resistance) of the obtained coating film are low, and the scratch resistance and self-healing properties also tend to be reduced. When the ethyl carbamate modified (meth)acrylamide of the present invention is used, because the cross-linking density inside the cured film is high, it is possible to prepare a cured product that combines scratch resistance and self-healing properties in addition to curing properties and surface drying properties. membrane.

Evaluation Example F-1

32 parts by weight of the urethane modified (meth)acrylamide system UY-1 synthesized in Synthesis Example 1 and 5 parts by weight of the urethane modified (meth)acrylic acid in Synthesis Example 6 Amide UY-6, 22 parts by weight of Synthesis Example 9 Synthesized reactive urethane polymer UP-2, 5 parts by weight of "ACMO", 21 parts by weight of IBMA, 15 parts by weight of CHMA were mixed and added as photopolymerization 3 parts by weight of Irgacure 184 as the starting agent are uniformly mixed to prepare a coating composition for nail decoration.

Nail decoration method

The obtained coating composition for nail decoration was evenly coated on the nail using a flat brush, and irradiated with a gel-like nail special LED light (12W) for 20 seconds to form nail decoration on the nail.

(38) Hardening

Touch the surface of the nail decoration obtained by the above method with your fingers and evaluate the degree of adhesiveness.

◎: No stickiness at all.

○: There is some adhesiveness but no fingerprints remain on the surface.

△: Adhesive, with fingerprints remaining on the surface.

×: The adhesiveness is severe and the fingers stick to the surface.

(39) Smoothness

Visually confirm the surface of the nail decoration obtained by the above method.

⊚: The surface is smooth, and unevenness is not observed on the coated surface.

○: The whole is smooth but some irregularities are observed.

△: Brush marks caused by flat brushes remain partly after application.

×: Brush marks caused by flat brushes remain after coating.

(40) Glossiness

The surface of the nail decoration obtained by the above method was visually observed.

◎: There is surface gloss.

○: Light reflection can be confirmed, but slight extinction is observed.

△: The entire surface is somewhat dull.

×: The surface is matted.

(41) Adhesion

Visually confirm the appearance change of nails obtained by scratching with other nails after the above method is decorated.

◎: No change in appearance.

○: A part of the nail decoration is floating and whitening is confirmed.

△: Peeling of part of nail decoration is confirmed.

×: Remarkable peeling of 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 soak in warm water for 10 minutes. Remove the aluminum foil and cotton sheet, and wipe gently with a cloth.

◎: The nail decoration can be easily peeled off even without cloth.

○: The nail decoration can be easily peeled off by wiping lightly with a cloth.

△: If you keep rubbing with a cloth for about 1 minute, the nail decoration can be peeled off.

×: Acetone is not swollen, and it cannot be peeled even when wiped with a cloth.

Evaluation Examples F-2~7, Evaluation Comparative Examples F-8~11

The composition described in Table 7 was replaced, except that the coating composition for nail decoration was prepared in the same manner as in Evaluation Example F-1, and the nail decoration was prepared by the above method and evaluated by the above method. The results are shown in Table 7.

【Table 7】

As shown in the results of the evaluation example and the evaluation comparative example, blended urethane modified (meth)acrylamide with molecular weight and acrylic equivalent outside a certain range, or amines with molecular weight and acrylic equivalent within a certain range When the ethyl carboxylate modified (meth)acrylate is used, the hardening of the composition and the gloss of the decorative film obtained are low, and the softness and adhesiveness from the main skeleton are imparted. Therefore, when forming nail decoration on the nail The smoothness is poor, and there is a tendency to sag and leave the bristles of the flat brush. When the ethyl carbamate modified (meth)acrylamide of the present invention is used, the adhesiveness of the decorative film after curing is inhibited, and the lifting from the nail is low during curing, so it can form a high density without lifting from the nail. It is also decorated with nails that are highly removable with acetone.

Evaluation Example G-1

24 parts by weight of the urethane modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1 and 12 parts by weight of the urethane modified (meth)acrylamide synthesized in Synthesis Example 2 Amine UY-2, 25 parts by weight of synthetic example 8 synthetic reactive urethane polymer UP-1, 5 parts by weight of synthetic example 9 synthetic reactive ethyl urethane polymer UP-2, " Mix 10 parts by weight of "ACMO", 4 parts by weight of "DEAA", 10 parts by weight of 4-HBA and 10 parts by weight of A-LEN-10, and add 2 parts by weight of Irgcure 184 and Irgacure TPO 2 as a photopolymerization initiator Parts by weight, uniformly mixed to prepare a light-curing sealant.

Manufacturing method of light-curing sealant resin cured product

A spacer made of silicon (30mm in length×15mm in width×3mm in thickness) was placed on a glass plate (50mm in length×50mm in width×5mm in thickness), and the light-curing sealant prepared above was injected into the spacer. After sufficient degassing, ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light intensity: 2000 mJ/cm ² ) were irradiated to produce a cured sealant resin. The properties of the obtained cured product were evaluated by the following methods, and the results are shown in Table 8.

(43) Transparency

Use the obtained hardened product and let it stand for 24 hours in a gas environment with a temperature of 23°C and a relative humidity of 50%. After that, the transmittance of the cured film was measured with a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., NDH-2000), and the transparency was divided into the following 4 levels and evaluated.

◎: Transmittance is above 90%

○: Transmittance is over 85% and less than 90%

△: The transmittance is more than 50% and less than 85%

×: The 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). After that, it was placed in a xenon fading tester (SC-700-WA: manufactured by Suga Testing Machine Co., Ltd.) and irradiated with ultraviolet rays with an intensity of 4W/cm ² at 30°C for 100 hours. After the irradiation, the yellowness was measured in the same way as before the irradiation, and visually observed Observe the discoloration of the hardened object.

⊚: The yellowing cannot be confirmed visually.

○: Very little yellowing can be confirmed visually.

△: Yellowing can be confirmed visually.

×: Remarkable yellowing can be confirmed visually.

(45)Water resistance

Cut 1g from the obtained hardened product, set it as a test piece in a constant temperature and humidity machine at a temperature of 85℃×relative humidity 95%, let it stand for 48 hours, and then measure the weight of the test piece to calculate its water absorption rate

(Water absorption (%) = (weight after constant temperature and humidity-weight before constant temperature and humidity) / weight before constant temperature and humidity × 100).

◎: The water absorption rate is less than 1.0%

○: The water absorption rate is 1.0% or more and less than 2.0%

△: The water absorption rate is more than 2.0% and less than 3.0%

×: Water absorption rate is above 3.0%

(46) Fugitive gas test

Cut 1g from the obtained hardened product, and leave it as a test piece in a constant temperature bath with a temperature of 100°C, circulate a stream of dry nitrogen for 24 hours, and then measure the weight of the test piece to calculate the generation rate of escaped gas

(Occurrence rate of escaped gas (%) = (weight after constant temperature-weight before constant temperature)/weight before constant temperature × 100).

◎: The incidence rate is less than 0.1%

○: Incidence rate is more than 0.1% and less than 0.3%

△: The incidence rate is more than 0.3% and less than 1.0%

×: Incidence rate is 1.0% or more

(47) Periodic heat resistance

The obtained cured product was placed at -40°C for 30 minutes and then at 100°C for 30 minutes as a cycle, repeated 10 times, and the state of the cured product was visually observed.

◎: No change is observed at all

○: The generation of slight bubbles is observed, but the generation of cracks is not observed. For transparency.

△: Some bubbles or cracks are observed, and some are slightly dull.

×: Bubbles or cracks occur all-round and are in a translucent state.

Evaluation Examples G-2~7, Evaluation Comparative Examples G-8~12

Except that the composition described in Table 8 was replaced, an ultraviolet curable resin was prepared in the same manner as in Evaluation Example G-1, and a cured sealant was produced, and the evaluation was performed in accordance with the above method. The results are shown in Table 8.

【Table 8】

As shown in the results of the evaluation example and the evaluation comparative example, it contains urethane modified (meth)acrylamide whose molecular weight and acrylic acid equivalent are outside a certain range, or amine groups whose molecular weight and acrylic acid equivalent are within a certain range When the (meth)acrylate is modified by ethyl formate, the transmittance of the cured product obtained is low, the cross-linking density inside the cured product is low, the generation of escape gas is remarkable, and the water resistance tends to be low. Also, use bonus In the case of urethane acrylamide, the transmittance and light resistance of the composition are low, and the crystallinity inside the cured product is high, so the freedom of the vinyl group is hindered and the vinyl group is difficult to completely disappear.

When the (meth)acrylamide modified with ethyl carbamate of the present invention is used, although some low light resistance can be observed, the sealant has high curing properties and high crosslinking density inside the cured product, so water resistance It is also high, can sufficiently suppress the generation of escape gas, and the heat resistance period is also high.

Evaluation Example H-1

3 parts by weight of the ethyl carbamate modified (meth)acrylamide UY-1 synthesized in Synthesis Example 1 and 5 parts by weight of the ethyl carbamate modified (meth)acrylamide synthesized in Synthesis Example 2 Amine UY-2, 28 parts by weight of synthetic example 8 synthetic reactive urethane polymer UP-1, 50 parts by weight of synthetic example 10 synthetic reactive urethane polymer UP-3, DPHA 10 parts by weight, 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 mixed uniformly to prepare a resin composition for decorative film.

Manufacturing method of light hardening type decorative film

The obtained resin composition for decorative film was coated on a 125μm thick PET film ("Softshine TA009" manufactured by Toyobo Co., Ltd.) with a coating bar (RDS 30) to make the dry film thickness 20μm, and then dried at 100°C for 1 minute , Make the film before UV curing. After that, ultraviolet rays (ultraviolet illuminance: 700 mW/cm ² , cumulative light quantity: 2000 mJ/cm ² ) were irradiated to produce a decorative film, and the molded film and decorative film before ultraviolet curing were evaluated by the following methods. The results are shown in Table 9.

(48) Transparency

Using the obtained molded film before ultraviolet curing, the transmittance of the cured film was measured with a haze meter (Nippon Denshoku Kogyo Co., Ltd., NDH-2000), and the transparency was divided into the following 4 levels and evaluated.

◎: Transmittance is above 90%

○: Transmittance is over 85% and less than 90%

△: The transmittance is more than 50% and less than 85%

×: The transmittance is less than 50%

(49) Adhesion resistance

On the obtained UV-curing film, untreated PET (thickness 100μm, "Cosmoshine A 4100" manufactured by Toyobo Co., Ltd., thickened and coated untreated surface) is overlapped, and laminated with pressure using a pressure bonding roller weighing 2kg twice. Place in a gas environment with a temperature of 23°C and a humidity of 50% for 30 minutes. After that, the untreated PET was peeled off, and the blocking resistance was evaluated by visual observation.

◎: It has not adhered to untreated PET, and the appearance of the formed film has not changed

○: Not adhered to untreated PET, but some traces remain on the surface of the molded film

△: No transfer to untreated PET, but traces remain on the entire surface of the molded film

×: There is transfer to untreated PET, and peeling and floating are observed on the surface of the molded film

(50) Elongation at break

Using the obtained film before UV curing, it was measured at a temperature of 130°C and a speed of 10 mm/min.

Measuring equipment; Tensilon universal material testing machine RTA-100 (manufactured by Orientec)

Elongation at break [%] = piece length at break / piece length before test × 100

◎: Elongation at break is more than 100%

○: The elongation at break is more than 50% but not 100%

△: The elongation at break is more than 10% but less than 50%

×: The elongation at break is less than 10%

(51) Formability test

The molded film obtained before ultraviolet curing was molded using a pressure forming machine SDF400 (Sodick Co., Ltd.) at a heating temperature of 130°C, and after cooling to 25°C, the state of the decorative layer of the molded product was visually confirmed.

⊚: No cracks are observed at all, and the surface has high transparency.

○: No cracks are observed, but the thickness of the decorative layer is uneven, and transparency is lowered in part.

△: Cracks and some cracks are observed, and the thickness of the decorative layer is uneven and the transparency is lowered in part.

×: Many cracks are observed, and the thickness of the decorative layer is uneven and the transparency is significantly reduced.

(52) Hardening

After coating the resin composition for a decorative film and drying it at 100°C for 1 minute, the obtained coating film was irradiated with an ultraviolet illuminance of 700mW/cm ² at a room temperature of 23°C, and the cumulative amount of light until the resin composition was completely cured was measured. Fully hardened refers to the state where there will be no traces on the surface of the hardened film when traced with silicone rubber.

◎: It is completely cured at a cumulative light intensity of 1000 mJ/cm ² .

○: It is completely cured at a cumulative light intensity of 1000mJ/cm ² ~2000mJ/cm ² .

△: It is completely cured at a cumulative light intensity of 2000mJ/cm ² ~5000mJ/cm ² .

×: A cumulative light quantity of 5000 mJ/cm ² or more is required until complete curing.

(52) Adhesion

Using the obtained decorative film, make 100 1mm square grid eyes in accordance with JIS K 5600, attach transparent tape, count and evaluate the number of grid eyes remaining on the substrate side when stripping off in one go.

(53) Pencil hardness

Using the obtained decorative film, in accordance with JIS K 5600, the pencil is rubbed at an angle of 45° for about 10 mm, and the hardest pencil without scratches on the surface of the decorative film is defined as the pencil hardness.

◎: Pencil hardness is more than 2H

○: Pencil hardness HB~H

△: Pencil hardness is 3B~B

×: Pencil hardness is below 4B

(54) Scratch resistance

Using #0000 steel wool, while applying a load of 200g/cm ² , apply a load of 200g/cm ² back and forth on the decorative film 10 times, and visually evaluate whether there are scars.

◎: Film peeling and scratches were hardly confirmed.

○: A slight flaw is confirmed in a part of the film.

△: Streak-like scars are confirmed across the film.

×: Film peeling occurred.

(55) Bend resistance

The decorative film obtained above is bent so that the coating surface becomes the outer side, a weight of 1 kg is placed and left for 10 minutes, and the surface of the decorative film is visually observed for cracks.

⊚: No cracks are observed at all.

○: A part of the bent part is whitened.

△: A part of cracks are observed in the bent portion.

×: Cracks are observed in the bent portion.

Evaluation Examples H-2~7, Evaluation Comparative Examples H-8~11

The composition described in Table 9 was replaced, except that the resin composition for a decorative film was prepared in the same manner as in Evaluation Example H-1, and the decorative film was prepared by the above method and evaluated by the above method. The results are shown in Table 9.

As shown in the results of the evaluation example and the evaluation comparative example, it contains urethane modified (meth)acrylamide whose molecular weight and acrylic equivalent are outside a certain range, or amino groups whose molecular weight and acrylic equivalent are within a certain range In the case of ethyl formate modified (meth)acrylate, the formed film is soft before UV curing, and stickiness is observed, so it has poor blocking resistance and tends to be difficult to stretch under high temperature conditions. In addition, although it was confirmed that the obtained decorative film had high bending resistance, the hardened material was soft, so the scratch resistance was low.

When using the urethane modified (meth)acrylamide of the present invention, the agglomeration of the amide group and the urethane bond will form a pseudo-hard segment, so it can display high blocking resistance, Molding processability, crack-free molding film before UV curing. In addition, at high temperatures above the Tg of the urethane polymer and urethane-modified (meth)acrylamide, the pseudo-hard segment will temporarily disperse, so it exhibits a high elongation at break and becomes Tg Near the following high normal temperature, a decorative film with pencil hardness and scratch resistance can be obtained.

[Industrial Utilization]

As explained above, the urethane modified (meth)acrylamide of the present invention has an urethane bond and more than one (meth)acrylamide group in the molecule, and the molecular weight is equivalent to the acrylic acid equivalent. Within a certain range, the cross-linking density inside the cured product increases due to ultraviolet curing, and the agglomeration of the amide group and the urethane bond site can form a pseudo-hard segment, so it is not only cured It also exhibits excellent flexibility and adhesion resistance, and also shows hardness, shrinkage resistance, durability, etc., and also shows the flexibility brought by the urethane bond and the main skeleton part of the alcohol compound other than (meth)acrylamide. Water resistance, lubricity and other properties. The urethane modified (meth)acrylamide of the present invention has a balance of hydrophilicity and hydrophobicity, hardness and flexibility. By using it, transparency and adhesion to various substrates can be obtained. , Curable resin composition with high scratch resistance. Furthermore, the curable resin composition of the present invention can be singly or mixed as needed Monofunctional monomers, multifunctional monomers, general-purpose oligomers, pigments, etc. are used, which can be ideally used in adhesives, electronic materials, optics, semiconductor fields, printing inks, coating agents, and gels Use of nails, sealants, decorative films, and photo-curing photoresists.

Claims (11)

A urethane modified (meth)acrylamide compound with more than one urethane bond and more than one (meth)acrylamide group in the molecule, wherein the number average molecular weight It is 250~4,500, and the (meth)acrylic equivalent (corresponding molecular weight of each (meth)acrylamide group) is in the range of 250~3,000, using alcohol compounds with more than 1 hydroxyl group per molecule. Obtained by the addition reaction of an isocyanate compound with more than two isocyanate groups and a hydroxyl-containing N-substituted (meth)acrylamide compound represented by the general formula [1];

In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R _{3 are the} same or different, and represent a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbons which may be substituted by a hydroxyl group, carbon 3 to 6 aliphatic or aromatic rings, and R ₂ and R ₃ can also be integrated with the nitrogen atom supporting them and further form a saturated or unsaturated 5- to 7-membered ring that can also contain oxygen or nitrogen atoms ; However, the case where R ₂ and R _{3 are} both hydrogen atoms and the case where R ₂ and R _{3 are} both alkyl groups are excluded, and the total of the hydroxyl groups possessed by R ₂ and R ₃ is 1 or more. For example, the ethyl urethane modified (meth)acrylamide compound of the first item of the scope of patent application, wherein the alcohol compound has a structure selected from ether skeleton, ester skeleton, carbonate skeleton, polysiloxane skeleton, olefin skeleton , A compound with one or more than two types of acrylic skeletons. For example, the ethyl urethane modified (meth)acrylamide compound in the first or second item of the scope of patent application has an ether skeleton, a number average molecular weight of 250 to 1,500 and an acrylic equivalent in the range of 250 to 750. An active energy ray-curable resin composition containing: 1 to 100% by weight of the ethyl carbamate modified (meth)acrylamide compound (A) of any one of items 1 to 3 in the scope of patent application, 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, which is characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in any one of items 1 to 3 in the scope of patent application. An active energy ray-curable adhesive composition characterized by containing an ethyl carbamate modified (meth)acrylamide compound as described in any one of items 1 to 3 in the scope of the patent application. An active energy ray-curable inkjet printing ink composition, which is characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in any one of items 1 to 3 in the scope of patent application. An active energy ray-curable coating composition characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in any one of items 1 to 3 in the scope of patent application. A curable composition for decoration of active energy ray curable nails, which is characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in any one of items 1 to 3 in the scope of patent application. A curable composition for active energy ray curable sealant, which is characterized by containing an ethyl carbamate modified (meth)acrylamide compound as described in any one of items 1 to 3 in the scope of patent application. A curable composition for an active energy ray curable decorative film, which is characterized by containing an ethyl carbamate modified (meth)acrylamide compound as in any one of items 1 to 3 in the scope of patent application.