JP4535574B2 - Novel urethane acrylamides and ultraviolet and electron beam curable resin compositions containing the urethane acrylamides - Google Patents

Description

【００３３】
試験例
実施例９〜１６及び比較例９〜１６で得られた硬化性組成物の性能を以下の試験により評価し、表２〜表５にその特性評価結果をまとめて示した。
【００３４】
Ａ．塗装と紫外線硬化
ガラス試料板（縦１００×横１００×厚さ５ｍｍ）を動かないように水平面に固定し、板の先方の端に調製した樹脂溶液を帯状に滴下して、バーコーター（ＲＤＳ６０）で全体に均等な力がかかるように両端を押さえ、回転させずに同じ速さ（５ｃｍ／ｓｅｃ）で手前まで引き塗膜を得た。実施例９、１０、１３、１４および比較例９、１０、１３、１４で得られた硬化性組成物については乾燥窒素気流下８０℃１０分間セッティングして溶剤を揮発させた後、実施例１１、１２、１５、１６および比較例１１、１２、１５、１６で得られた硬化性組成物については加熱による溶剤除去を行わず、塗面を上向きにして紫外線照射を行って硬化させた。
紫外線硬化条件は、単位当たり出力５０ｗ／ｃｍの高圧水銀灯一本を設置した紫外線照射装置（オーク製作所：モデルＯＨＤ３２０Ｍ、出力３００ｗ）を使用し、１秒当たりに紫外線エネルギーは１０ｍＪ／ｃｍ^２ であるように試料板とランプの距離を調節した。塗膜の表面がベタ付かなくなるまでに必要な照射時間を硬化時間として測定した。硬化後、各試験板上の塗膜の表面状態、密着性、鉛筆硬度、耐水性と耐溶剤性試験を行った。
【００３５】
Ｂ．表面状態評価の試験
塗膜の表面指で押してべた付き性を判断した。
○：べた付かない、△：少しべた付く、×：べた付く
【００３６】
Ｃ．密着性試験
試料板上の塗膜の上にセロハン粘着テープを貼り付け、気泡がないようにテープを擦り、塗膜に完全に付着させる。１分後テープの一方の端を持って塗面に対して９０度に保ったまま、瞬間的にテープを剥がし、塗膜の付着状態を目視により観察した。
◎：優れている、○：良い、△：やや悪い、×：悪い
【００３７】
Ｄ．鉛筆硬度試験
ＪＩＳ Ｋ５４００ ８．４．２に準じて鉛筆硬度試験を行った。
【００３８】
Ｅ．耐水性試験
試験板から塗膜を剥がし、得られたフィルムを２５℃において水中に２４時間浸漬して、その吸水率を式１に従って算出した。
【００３９】
【式１】
吸水率（％）＝（浸漬後の重量−浸漬前の重量）／浸漬前の重量×１００
【００４０】
Ｆ．耐溶剤性試験
試験板から塗膜を剥がし、得られたフィルムを２５℃においてトルエン中に２４時間浸漬して、その膨潤率を式２に従って算出した。
【００４１】
【式２】
膨潤率（％）＝（浸漬後の重量−浸漬前の重量）／浸漬前の重量×１００
【００４２】
【表２】

【００４３】
【表３】

【００４４】
【表４】

【００４５】
【表５】

【００４６】
実施例９〜１６及び比較例９〜１６の特性評価結果より、ウレタンアクリレート、ウレタンアクリレートオリゴマーに比べてウレタンアクリルアミドおよびウレタンアクリルアミドオリゴマーを配合した方が、硬化に要するエネルギーが少なく、得られた塗膜の硬度が高く、また密着性と耐溶剤性も従来より良くなることが判明した。
【００４７】
【発明の効果】
以上説明してきたように、本発明によると、従来のウレタンアクリレート、あるいはウレタンアクリレートオリゴマーに比べ、優れた硬化性と塗膜硬度を有し、皮膚刺激性と臭気がない安全な、紫外線及び電子線硬化性樹脂組成物、及び該組成物に好適に使用される新規なウレタンアクリルアミド及びウレタンアクリルアミドオリゴマーが提供される。
【図面の簡単な説明】
【図１】実施例１で得られたウレタンアクリルアミドのＩＲスペクトルである。
【図２】実施例２で得られたウレタンアクリルアミドのＩＲスペクトルである。
【図３】実施例５で得られたウレタンアクリルアミドオリゴマーのＩＲスペクトルである。
【図４】実施例６で得られたウレタンアクリルアミドオリゴマーのＩＲスペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel urethane acrylamide and urethane acrylamide oligomer (hereinafter collectively referred to as urethane acrylamide) obtained by reacting a hydroxyl-containing (meth) acrylamide with polyisocyanate and polyol, and the urethane acrylamide. The present invention relates to an ultraviolet ray and electron beam curable resin composition that is used in paints, inks, and the like that have high sensitivity to ultraviolet rays and electron beams.
[0002]
[Prior art]
Traditionally, the surface of furniture, flooring, cans, etc. has been painted to give durability and aesthetics, but in recent years the energy cost required for drying and curing paints, production efficiency, and prevention of volatilization of organic solvents Due to such problems, ultraviolet ray and electron beam curable coating compositions containing urethane acrylate are often used (for example, JP-A-2000-7753, etc.).
Urethane acrylate is generally composed of polyol, polyisocyanate, and acrylate having a hydroxyl group. Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, etc. are used as the acrylate having a hydroxyl group, but these acrylates do not have sufficient photocuring speed, and the polymer Tg is low, so the coating film has insufficient hardness, Since it has a unique odor, the operator has an unpleasant feeling and skin irritation is high. Multifunctional acrylates such as trimethylolpropane triacrylate are also used to improve these, increase the hardness of the coating film, and increase the curing speed, but still have the disadvantage of high skin irritation.
[0003]
[Problems to be solved by the invention]
The present invention was made in order to solve the problems of such conventional urethane acrylate, and has a sufficient speed and hardness, a safe and novel urethane acrylamide having no skin irritation and odor, And an ultraviolet ray / electron beam curable resin composition.
[0004]
[Means for solving the problems]
In the present invention to solve the above problems, instead of the conventional urethane acrylates, and hydroxyethyl acrylamide, by using the novel urethane acrylamides obtained di- isocyanate, a polyol is reacted, fast curing and sufficient coating It came to obtain the safe ultraviolet-ray and electron beam curable resin composition which has film hardness and does not have skin irritation and odor. That is, the present invention
(1) and hydroxyethyl acrylamide, obtained by reacting a di-isocyanate, urethane acrylamide having an acrylamide group,
(2) and hydroxyethyl acrylamide, obtained by reacting a di- isocyanate and polyol, urethane acrylamide oligomers having acrylamide group,
(3) Ultraviolet and electron beam curable resin composition comprising urethane acrylamide and / or urethane acrylamide oligomer of (1) to (2),
Is to provide.
[0005]
Hereinafter, the present invention will be described in detail.
The urethane acrylamide of the present invention refers to one having an acrylamide group obtained by reacting a hydroxyl group-containing (meth) acrylamide represented by the chemical formula 2 and a polyisocyanate.
Specific examples of the hydroxyl-containing (meth) acrylamide represented by Chemical Formula 2 as a raw material compound include hydroxypropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, and hydroxybutyl (meth) acrylamide. Hydroxyethyl (meth) acrylamide is particularly preferable because it not only has an extremely excellent characteristic that PII is 0 and has no skin irritation, but also has excellent miscibility with various polyisocyanates and polyols. .
Specific examples of the polyisocyanate as one raw material compound include 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,3-bisisocyanate methylcyclohexane (CHDI), 1,6-hexane diisocyanate (HMDI), 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate 3,3′-dimethylphenylene diisocyanate, isophorone diisocyanate (IPDI), and the like.
[0006]
The urethane acrylamide oligomer of the present invention refers to one having an acrylamide group, which is obtained by reacting a hydroxyl-containing (meth) acrylamide represented by the chemical formula 2 above, a polyisocyanate and a polyol.
Hydroxyl-containing (meth) acrylamide and polyisocyanate are as described above. Specific examples of polyols include saturated and unsaturated polyether diols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol. 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, diethylene glycol, dipropylene glycol and other polyhydric alcohols, polyester polyol, polycarbonate diol, polybutadiene polyol, hydrogenated polybutadiene polyol Etc.
The polyol is used in combination for adjusting the flexibility and adhesion of the coating film.
[0007]
Urethane acrylamides can be obtained by reacting a hydroxyl-containing (meth) acrylamide represented by Chemical Formula 2 with a polyisocyanate, or a polyisocyanate and a polyol.
The reaction can be carried out without a solvent, but is carried out in an organic solvent or a reactive diluent as necessary.
Examples of the organic solvent that can be used include dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, hexane, cyclohexane, toluene, xylene, and the like.
The reactive diluent that can be used is not particularly limited as long as it does not react with isocyanate, but methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, long-chain aliphatic acrylate, allyl acrylate, cyclohexyl acrylate 1,6-hexane diacrylate, tetraethylene glycol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylacrylamide, diethylacrylamide, acryloylmorpholine, etc. Is exemplified.
The amount of the organic solvent or reactive diluent used is 0 to 90% by weight, preferably 0 to 50% by weight, based on the hydroxyl-containing (meth) acrylamide represented by Chemical Formula 2.
[0008]
In addition, a urethanization catalyst can be added to the reaction to promote the reaction. Examples of the catalyst include dibutyltin dilaurate, dioctyltin diacetate, dibutyltin oxide, lead octenoate, and lead naphthenate.
[0009]
The reaction temperature is 0 to 120 ° C., preferably 0 to 70 ° C. The reaction time is approximately 6 to 12 hours, although it depends on the compound used and the reaction conditions.
In particular, since hydroxyethyl (meth) acrylamide has higher reactivity than the corresponding acrylate, it can react at a lower temperature.
[0010]
After completion of the reaction, the target product can be isolated and purified by reprecipitation or other methods, but it should be used as it is as an ultraviolet ray / electron beam curable resin composition or as a raw material without isolation and purification. Can do.
[0011]
The present invention further provides an ultraviolet ray and electron beam curable resin composition containing the urethane acrylamides.
For the composition, urethane acrylamides and photopolymerization initiators are sufficient, but if necessary, the composition is prepared by blending a reactive diluent, an organic solvent, and other paint additives. Can do.
Examples of the photopolymerization initiator that can be used include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin ethyl ether, 2,2-dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4-tert-butyl-dichloro. Examples include acetophenone compounds such as acetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone compounds such as benzophenone and acrylated benzophene, and thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone. . The photopolymerization initiator is desirably added in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of urethane acrylamide.
As the reactive diluent and the organic solvent, those used at the time of the production of urethane acrylamide can be similarly used as necessary for adjusting the viscosity of the composition, the flexibility of the coating film, and the adhesion.
The composition of the urethane acrylamide is 50 to 99 parts by weight, the organic solvent is 0 to 50 parts by weight, the reactive diluent is 0 to 50 parts by weight, and the photopolymerization initiator is about 0.1 to 5 parts by weight. preferable.
Further, as other additives, sensitizers, stabilizers, ultraviolet and electron beam absorbers, matting agents, anti-blocking agents and the like can be used as necessary.
[0012]
The ultraviolet ray and electron beam curable resin composition of the present invention can be used by a usual method.
[0013]
Although the hydroxyl-containing (meth) acrylamide which is a raw material compound of the present invention can be synthesized from (meth) acrylic acid chloride and N-alkylaminoalcohol by a conventional method, the following method is preferred industrially.
That is, cyclopentadiene obtained by thermally decomposing dicyclopentadiene and (meth) acrylic acid ester are subjected to Diels-Alder addition reaction to obtain an ester adduct, and this and N-alkylamino alcohol in the presence of a basic catalyst. The amide adduct is made to react and then is thermally decomposed in a gas phase of about 200 to 500 ° C. to be converted into a crude hydroxyl group-containing (meth) acrylamide. The crude product can be easily purified by a normal vacuum distillation operation.
[0014]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples.
Production example: Production example of hydroxyethyl (meth) acrylamide (1) Production of ester adduct 1300 g of methyl acrylate was charged into a 3000 ml three-necked flask equipped with a stirrer, thermometer and dropping device, and 1000 g of cyclopentadiene was added thereto. Was gradually added dropwise with stirring. Meanwhile, the temperature of the reaction mixture was kept below 35 ° C. After completion of dropping, the reaction mixture was stirred overnight at 35 ° C. or lower. Unreacted substances and by-produced dicyclopentadiene were recovered by distillation under reduced pressure to obtain 2257 g of an ester adduct. Yield 98%
(2) Production of amide adduct 2200 g of ester adduct, 1060 g of 2-aminoethanol, and 52 g of 30% sodium methylate solution were charged in the same reaction apparatus as described above, and reacted at 60 ° C. for 4 hours. Thereafter, by-product methanol was recovered by distillation under reduced pressure to complete the reaction. After neutralization with concentrated sulfuric acid equivalent to sodium methylate used in the reaction, excess aminoethanol was recovered by distillation to obtain 5- [N- (2-hydroxyethyl) carbamoyl] -2-norbornene (hereinafter referred to as amide adduct and 2490 g was obtained. Yield 95%
(3) Pyrolysis of amide adduct 540 g of a amide adduct was continuously supplied to an evaporator at a pressure of 30 mmHg at 45 g / h, vaporized by heating, and heated to 400 to 420 ° C. (4 mm, length 600 mm). The operation time required about 12 hours. The pyrolysis product was trapped by a condenser maintained at about 50 ° C. and a condenser cooled to −50 ° C., to obtain 336 g of crude hydroxyethylacrylamide from the former and 193 g of crude cyclopentadiene from the latter. The thermal decomposition rate of the amide adduct was 95%, and the purity of the crude hydroxyethyl acrylamide was 97%.
(4) Purification of crude hydroxyethyl acrylamide 0.6 g of phenothiazine was added to 300 g of crude hydroxyethyl acrylamide, and simple distillation was performed under a reduced pressure of 1 mmHg (boiling point 130 ° C.) to obtain 250 g of a colorless transparent liquid. The purity was 99.5%.
[0015]
Example 1
1,4-bisisocyanatomethylcyclohexane (CHDI) 84.4 g (0.43 mol), dibutyltin dilaurate in a 500 mL five-necked flask equipped with a stirrer, thermometer, condenser, dropping funnel and dry air introduction tube 0.1 g and dimethylformamide (DMF) 180 g were charged. Next, 100 g (0.87 mol) of hydroxyethylacrylamide (HEAA) to which 0.3 g of methylhydroquinone (MHQ) was added under a dry air stream was gradually added dropwise over 5 hours at 5 ° C. while paying attention to heat generation. Reaction was performed. After completion of the dropwise addition, aging was performed at 10 ° C. for 4 hours to obtain a urethane acrylamide-containing composition UAAm-1 (HEAA-CHDI-DMF).
The solvent was removed from the composition at 80 ° C. under vacuum, and the formation of urethane acrylamide (HEAA-CHDI-HEAA) was confirmed by infrared absorption spectrum (IR). The IR spectrum is shown in FIG.
[0016]
Example 2
As in Example 1, 0.35.6 g of MHQ and 100 g of HEAA (0.87 mol) were exothermic in a mixture of 75.6 g (0.43 mol) of tolylene diisocyanate (TDI), 0.1 g of dibutyltin dilaurate and 180 g of DMF in a dry air stream. Was slowly added dropwise at 40 ° C. Thereafter, the reaction was aged at 40 ° C. for 4 hours to obtain a urethane acrylamide-containing composition UAAm-2 (HEAA-TDI-DMF).
After removing the solvent, the formation of urethane acrylamide (HEAA-TDI-HEAA) was confirmed by IR. The IR spectrum is shown in FIG.
[0017]
Example 3
In the same manner as in Example 1, 84.4 g (0.43 mol) of CHDI, 0.1 g of dibutyltin dilaurate and 183.6 g of acryloylmorpholine (ACMO) were mixed with 0.4 g of MHQ and 100 g of HEAA (0.87 mol) in a dry air stream. The solution was gradually added dropwise at 5 ° C while paying attention to heat generation. Thereafter, the reaction was aged at 10 ° C. for 4 hours to obtain a urethane acrylamide-containing composition UAAm-3 (HEAA-CHDI-ACMO).
[0018]
Example 4
As in Example 1, 0.4 g of MHQ and 100 g of HEAA (0.87 mol) were added dropwise to a mixture of 75.6 g (0.43 mol) of TDI, 0.1 g of dibutyltin dilaurate and 175 g of ACMO at 40 ° C. while paying attention to heat generation. After aging, urethane acrylamide-containing composition UAAm-4 (HEAA-TDI-ACMO) was obtained.
[0019]
Example 5
Polypropylene glycol (PPG) (number average molecular weight: 3000) 150 g (0.05 mol), CHDI 24.3 g (0.125 mol) in a 500 mL four-necked flask equipped with a stirrer, thermometer, condenser and dry gas introduction tube ), 0.2 g of dibutyltin dilaurate and 180 g of DMF were charged and reacted at 70 ° C. for 2 hours while passing dry nitrogen.
Next, after cooling the reaction solution to 40 ° C., 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 17.25 g (0.15 mol) of HEAA was charged, and stirring was continued for 10 hours while maintaining the temperature in the system at 40 ° C. under a stream of dry air, and a urethane acrylamide oligomer-containing composition UAAmG-1 (HEAA-PPG-CHDI) -DMF).
Solvent removal under vacuum at 80 ° C. and IR measurement were performed to confirm the formation of urethane acrylamide oligomer. The IR spectrum is shown in FIG.
[0020]
Example 6
Example 5 A mixture of PPG 150 g (0.05 mol), TDI 21.75 g (0.125 mol), dibutyltin dilaurate 0.2 g and DMF 180 g was reacted by stirring at 70 ° C. for 2 hours using the same apparatus under a dry nitrogen stream. It was.
After cooling to 40 ° C., 0.2 g of MHQ was added to the reaction solution, and substitution was performed with dry air for 10 minutes. HEAA (17.25 g, 0.15 mol) was charged and reacted at 40 ° C. for 10 hours while blowing dry air to obtain a urethane acrylamide oligomer-containing composition UAAmG-2 (HEAA-PPG-TDI-DMF).
In the same manner as in Example 5, de-DMF was performed and IR measurement was performed to confirm the formation of the target product. The IR spectrum is shown in FIG.
[0021]
Example 7
In Example 5, 174 g of ACMO was charged instead of DMF. Others were carried out similarly to Example 5, and obtained urethane acrylamide oligomer containing composition UAAmG-3 (HEAA-PPG-CHDI-ACMO).
[0022]
Example 8
In Example 6, 172 g of ACMO was charged instead of DMF. Others were the same as in Example 6, and urethane acrylamide oligomer-containing composition UAAmG-4 (HEAA-PPG-TDI-ACMO) was obtained.
[0023]
Comparative Example 1
CHDI 83.7g (0.43mol), dibutyltin dilaurate 0.1g, and DMF180g were put into the 500 mL capacity | capacitance 5-neck flask provided with the stirrer, the thermometer, the cooler, the dropping funnel, and the dry air introduction tube. Under a dry air stream, 100 g (0.86 mol) of hydroxyethyl acrylate (HEA) to which 0.3 g of MHQ was added was gradually added dropwise at 25 to 30 ° C. over 2 hours while paying attention to heat generation. After completion of dropping, reaction aging was performed at 30 ° C. for 6 hours to obtain urethane acrylate-containing composition UA-1 (HEA-CHDI-DMF).
[0024]
Comparative Example 2
In the same manner as in Comparative Example 1, in a dry air stream, pay attention to heat generation of a mixed solution of MHQ 0.3 g and HEA 100 g (0.86 mol) in a mixed solution of TDI 75.0 g (0.43 mol), dibutyltin dilaurate 0.1 g and DMF 180 g. The solution was gradually added dropwise at 40 ° C. Then, it was made to react at 40 degreeC for 8 hours, and urethane acrylate containing composition UA-2 (HEA-TDI-DMF) was obtained.
[0025]
Comparative Example 3
In the same manner as in Comparative Example 1, under a dry air stream, CHDI 84.8 g (0.43 mol), dibutyltin dilaurate 0.1 g and ACMO 183.6 g mixture were mixed MHQ 0.4 g and HEA 100 g (0.86 mol). The solution was gradually added dropwise at 25 ° C. Thereafter, the reaction was aged at 30 ° C. for 6 hours to obtain a urethane acrylate-containing composition UA-3 (HEA-CHDI-ACMO).
[0026]
Comparative Example 4
In the same manner as in Comparative Example 2, under a dry air stream, a mixed solution of 0.4 g of MHQ and 100 g of HEA (0.86 mol) was mixed with 75.0 g (0.43 mol) of TDI, 0.1 g of dibutyltin dilaurate and 175 g of ACMO, while paying attention to heat generation. Dropping at 40 ° C. and aging at 40 ° C. gave urethane acrylate-containing composition UA-4 (HEA-TDI-ACMO).
[0027]
Comparative Example 5
Polypropylene glycol (PPG) (number average molecular weight: 3000) 150 g (0.05 mol), CHDI 24.3 g (0.125 mol) in a 500 mL four-necked flask equipped with a stirrer, thermometer, condenser and dry gas introduction tube ), 0.2 g of dibutyltin dilaurate and 180 g of DMF were added and reacted at 70 ° C. for 2 hours while passing dry nitrogen.
Next, after cooling the reaction solution to 40 ° C., 0.2 g of MHQ was added, and dry air was bubbled for 10 minutes. Then, 17.4 g (0.15 mol) of HEA was added, and stirring was continued at 40 ° C. for 15 hours while bubbling dry air to obtain a urethane acrylate oligomer-containing composition UAG-1 (HEA-PPG-CHDI-DMF). .
[0028]
Comparative Example 6
In the same manner as in Comparative Example 5, a mixed solution of 150 g (0.05 mol) of PPG, 21.75 g (0.125 mol) of TDI, 0.2 g of dibutyltin dilaurate and 180 g of DMF was stirred at 70 ° C. for 2 hours.
After cooling to 40 ° C., 0.2 g of MHQ was added and replaced with dry air for 10 minutes. 17.0 g (0.15 mol) of HEA was charged and reacted at 40 ° C. for 15 hours while blowing dry air to obtain a urethane acrylate oligomer-containing composition UAG-2 (HEA-PPG-TDI-DMF).
[0029]
Comparative Example 7
In Comparative Example 5, 174 g of ACMO was charged instead of DMF. The others were the same as in Comparative Example 5 to obtain a urethane acrylate oligomer-containing composition UAG-3 (HEA-PPG-CHDI-ACMO).
[0030]
Comparative Example 8
In Comparative Example 6, 172 g of ACMO was charged instead of DMF. Otherwise, the urethane acrylate oligomer-containing composition UAG-4 (HEA-PPG-TDI-ACMO) was obtained in the same manner as in Comparative Example 6.
[0031]
Examples 9-16 and Comparative Examples 9-16
Urethane acrylamide-containing compositions UAAm-1 to UAAm-4, urethane acrylamide oligomer-containing compositions UAAmG-1 to UAAmG-4, urethane acrylate-containing composition UA-1 obtained in Examples 1 to 8 and Comparative Examples 1 to 8 -UA-4, urethane acrylate oligomer-containing composition UAG-1 to UAG-4 are added and mixed with 1-hydroxycyclohexyl phenyl ketone (photopolymerization initiator: Ciba Geigy, Irgacure 184) at the ratio shown in Table 1. An ultraviolet and electron beam curable composition was obtained.
[0032]
[Table 1]

[0033]
Test Examples The performances of the curable compositions obtained in Examples 9 to 16 and Comparative Examples 9 to 16 were evaluated by the following tests, and Table 2 to Table 5 collectively show the results of the characteristic evaluation.
[0034]
A. Paint and UV-cured glass sample plate (length 100 × width 100 × thickness 5 mm) are fixed on a horizontal surface so that they do not move, and the prepared resin solution is dropped into a strip at the end of the plate. Bar coater (RDS60) Then, both ends were pressed so that a uniform force was applied to the whole, and a paint film was obtained to the front at the same speed (5 cm / sec) without rotating. The curable compositions obtained in Examples 9, 10, 13, and 14 and Comparative Examples 9, 10, 13, and 14 were set at 80 ° C. for 10 minutes in a dry nitrogen stream to volatilize the solvent. , 12, 15, and 16 and Comparative Examples 11, 12, 15, and 16 were cured by applying ultraviolet rays with the coated surface facing upward, without removing the solvent by heating.
The UV curing conditions were such that an UV irradiation device (Oak Seisakusho: Model OHD320M, output 300 w) with one high-pressure mercury lamp with an output of 50 w / cm per unit was used, and the UV energy per ^second was 10 mJ / cm ^2. The distance between the sample plate and the lamp was adjusted. The irradiation time required until the surface of the coating film was not sticky was measured as the curing time. After curing, the surface condition, adhesion, pencil hardness, water resistance and solvent resistance of the coating film on each test plate were tested.
[0035]
B. The stickiness was judged by pressing with the surface finger of the test coating film for surface condition evaluation.
○: Not sticky, △: Sticky a little, ×: Sticky [0036]
C. Adhesion test A cellophane adhesive tape is affixed on the coating film on the sample plate, and the tape is rubbed so that there are no air bubbles. One minute later, while holding one end of the tape and keeping it at 90 degrees with respect to the coating surface, the tape was instantaneously peeled off, and the state of adhesion of the coating film was visually observed.
◎: Excellent, ○: Good, △: Slightly bad, X: Bad [0037]
D. Pencil hardness test A pencil hardness test was performed according to JIS K5400 8.4.2.
[0038]
E. The coating film was peeled off from the water resistance test test plate, the obtained film was immersed in water at 25 ° C. for 24 hours, and the water absorption rate was calculated according to Formula 1.
[0039]
[Formula 1]
Water absorption (%) = (weight after immersion−weight before immersion) / weight before immersion × 100
[0040]
F. The coating film was peeled off from the solvent resistance test test plate, the obtained film was immersed in toluene at 25 ° C. for 24 hours, and the swelling ratio was calculated according to Formula 2.
[0041]
[Formula 2]
Swelling ratio (%) = (weight after immersion−weight before immersion) / weight before immersion × 100
[0042]
[Table 2]

[0043]
[Table 3]

[0044]
[Table 4]

[0045]
[Table 5]

[0046]
From the characteristic evaluation results of Examples 9 to 16 and Comparative Examples 9 to 16, the blended urethane acrylamide and urethane acrylamide oligomer compared to urethane acrylate and urethane acrylate oligomer required less energy for curing, and the resulting coating film It has been found that the hardness is high, and the adhesion and solvent resistance are also improved.
[0047]
【The invention's effect】
As described above, according to the present invention, compared with conventional urethane acrylates or urethane acrylate oligomers, it has excellent curability and coating film hardness, and is safe and free from skin irritation and odor, and ultraviolet rays and electron beams. A curable resin composition and a novel urethane acrylamide and urethane acrylamide oligomer suitably used for the composition are provided.
[Brief description of the drawings]
1 is an IR spectrum of urethane acrylamide obtained in Example 1. FIG.
2 is an IR spectrum of urethane acrylamide obtained in Example 2. FIG.
3 is an IR spectrum of the urethane acrylamide oligomer obtained in Example 5. FIG.
4 is an IR spectrum of the urethane acrylamide oligomer obtained in Example 6. FIG.

Claims (3)

And hydroxyethyl acrylamide, obtained by reacting a di-isocyanate, urethane acrylamide having an acrylamide group. And hydroxyethyl acrylamide, obtained by reacting a di- isocyanate and polyol, urethane acrylamide oligomers having acrylamide group.  An ultraviolet and electron beam curable resin composition comprising the urethane acrylamide and / or urethane acrylamide oligomer according to claim 1.

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