JP7166610B2 - Highly safe urethane acrylate and its manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly safe urethane acrylate that contains virtually no poisonous or deleterious substances, and a method for producing the same.

Urethane acrylate is a component of active energy ray-curable resin that cures with ultraviolet rays (UV) and electron beams (EB), and has better productivity and energy saving than thermosetting resin compositions and solvent-based resin compositions. In recent years, its applications have been expanding, especially due to its low environmental impact. When the urethane acrylate is cured, the urethane skeleton becomes a soft segment, while the acrylic portion and the urethane bond portion become a hard segment. By adjusting the combination of the soft segment and the hard segment, curing can be performed according to various purposes. can make things

The urethane skeleton is mainly composed of polyols having structures such as polyester, polyether, and polycarbonate, and the acrylic part is mainly acrylates derived from 2-hydroxyethyl acrylate (HEA) and 2-hydroxypropyl acrylate (HPA). Furthermore, isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), methylenebis(4,1-cyclohexylene ) is bound by diisocyanate (hydrogenated MDI), hexamethylene diisocyanate (HDI), or the like. By the way, these general-purpose diisocyanate compounds have been designated as poisonous and deleterious substances from the past, and in addition to being cautioned against their use, recently 2-hydroxyethyl acrylate (HEA) and 2-hydroxypropyl acrylate (HPA) was also designated as a poisonous and deleterious substance (under the Japanese Poisonous and Deleterious Substances Control Law (Poisonous and Deleterious Substances Law), HEA (CAS No. 818-61-1) is classified as a poisonous substance, 23-3", the HPA (CAS No. 999-61-1) classification is poisonous, and the definition is "Finger 23-4").

Urethane acrylate produced by using toxic substances such as isocyanate compounds, HEA, and HPA may also fall under the category of toxic substances. The reason for this is that the concept of poisonous substances under the Poisonous and Deleterious Substances Control Law is defined by the Ordinance for Designating Poisonous and Deleterious Substances as ``If no exempt concentration is specified, preparations to which the substance is intentionally added are prohibited regardless of its concentration. In principle, it is regarded as a poisonous or deleterious substance.However, even if it contains a poisonous or deleterious substance, if the substance is an impurity derived from the manufacturing process, etc., it is not considered a poisonous or deleterious substance. Therefore, it is a product that intentionally added isocyanate compounds, HEA, and HPA as raw materials for urethane acrylate, and in fact, trace amounts after the reaction, regardless of the content in the product. Even if it contains such residual substances, the product urethane acrylate itself falls under the category of poisonous and deleterious substances.

Conventionally, in order not to leave the isocyanate compound, which is designated as a poisonous substance, in the final step of the urethanization reaction, an excessive amount of HEA or HPA is charged to completely react the isocyanate compound (virtually not contained in the urethane acrylate), Each urethane acrylate manufacturer has adopted a method of removing the urethane acrylate product itself from poisonous and deleterious substances by allowing HEA and HPA to remain (Patent Documents 1 and 2). However, since both HEA and HPA have been designated as poisonous substances, methods such as over-feeding and intentionally leaving them behind will result in the production of urethane acrylate products that are already considered poisonous and deleterious substances.

In addition, urethane acrylate (Patent Document 4) using non-toxic hydroxybutyl acrylate (HBA) instead of HEA or HPA has been reported. Synthetic techniques for urethane acrylamide using ethyl acrylamide (registered trademark “HEAA”) have been reported (Patent Documents 5 and 6). Since it does not contain HEA or HPA, it is a highly safe urethane oligomer that is excluded from toxic substances. , Viscosity, UV curability, coating film formability, thickness of the coating film formed, transparency, adhesion, heat resistance of the cured product, flexibility, scratch resistance, etc. Development of applications suitable for the characteristics of high-safety urethane acrylate is underway, but there is a problem in that existing formulations using general-purpose urethane acrylates with conventional HEA and HPA terminals cannot be used.

JP 2009-053491 A JP 2014-141593 A JP 2012-36290 A JP H05-209038 JP-A-2002-37849 WO2017/047615

A highly safe urethane (meth)acrylate that has the same physical properties as conventional HEA and HPA terminal general-purpose urethane acrylates, practically does not contain HEA or HPA, does not fall under the category of poisonous or deleterious substances, and a method for producing the same. The task is to provide

The present inventors have made intensive studies to solve the above problems, and as a result, have one or more acrylate groups derived from 2-hydroxyethyl acrylate and / or 3-hydroxypropyl acrylate as terminal groups per molecule, The present inventors have found a urethane acrylate that has no isocyanate group in the molecule and does not contain 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate, resulting in the present invention.

That is, the present invention (1) has one or more acrylate groups derived from 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate as terminal groups per molecule, does not have an isocyanate group in the molecule, and 2 - urethane acrylates that do not contain hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate,
(2) 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, and 2-hydroxyethyl methacrylate as terminal groups per molecule a (meth)acryloyl group derived from one or more compounds selected from the group consisting of hydroxyethyl-N-methylacrylamide, 2-hydroxyethyl-N-methylmethacrylamide, 3-hydroxypropylacrylamide, and 3-hydroxypropylmethacrylamide; The urethane acrylate according to (1), characterized by having one or more,
(3) The acrylate groups derived from 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate account for 50 to 99 mol % of the total acryloyl groups in the urethane (meth)acrylate. (1) or urethane acrylate according to (2),
(4) a polyol (A) having two or more hydroxyl groups per molecule, a polyisocyanate (B) having two or more isocyanate groups per molecule, 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate (C); is reacted at a compounding ratio in which the total isocyanate group is equal to or more than the total hydroxyl group, and then 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2- (1 ) to the method for producing the urethane acrylate according to any one of (3),
(5) A highly safe active energy ray-curable resin composition characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(6) An active energy ray-curable highly safe pressure-sensitive adhesive characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(7) An energy ray-curable highly safe adhesive characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(8) an active energy ray-curable high-safety inkjet ink containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3);
(9) An active energy ray-curable highly safe 3D printing ink characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(10) An active energy ray-curable highly safe coating agent characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(11) An active energy ray-curable highly safe nail decorating agent containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above,
(12) An active energy ray-curable highly safe sealant characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above.
(13) An active energy ray-curable highly safe decorative film characterized by containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above.
(14) An active energy ray-curable highly safe vehicle exterior protective agent containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above.
(15) There is provided an active energy ray-curable highly safe architectural paint containing 1% by weight or more of the urethane acrylate according to any one of (1) to (3) above. be.

According to the present invention, it has one or more acrylate groups derived from 2-hydroxyethyl acrylate (HEA) and/or 3-hydroxypropyl acrylate (HPA) as terminal groups per molecule, and does not have isocyanate groups in the molecule. In addition, urethane acrylates that do not contain HEA and/or HPA are practically not poisonous or deleterious substances, and have physical properties equivalent to conventional HEA- and HPA-terminal general-purpose urethane acrylates. ) It is possible to develop new applications as acrylates, and it is possible to use existing formulations using general-purpose urethane acrylates with conventional HEA and HPA terminals without changing them.

The present invention will be described in detail below.
The highly safe urethane acrylate of the present invention has one or more acrylate groups derived from 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate as terminal groups per molecule, and has no isocyanate groups in the molecule, and , 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate.

The highly safe urethane acrylate of the present invention comprises a polyol (A) having two or more hydroxyl groups per molecule, a polyisocyanate (B) having two or more isocyanate groups per molecule, and 2-hydroxyethyl acrylate (HEA, After reacting with C1) and / or 3-hydroxypropyl acrylate (HPA, C2), alkyl (meth) acrylate (D1) having a hydroxyl group excluding C1 and C2 and / or alkyl (meth) acrylamide having a hydroxyl group It is produced by further reacting with (D2). That is, in the first step, A, B, and C are reacted in a proportion equal to or greater than the total amount of isocyanate groups to the total amount of hydroxyl groups to produce a urethane acrylate intermediate having a terminal isocyanate group as an intermediate. In this process, the toxic HEA and/or HPA are completely reacted to produce an intermediate that is virtually free of HEA and HPA. In the second step, the intermediates and D1 and D2 are reacted in a proportion equal to or greater than the total amount of hydroxyl groups with respect to the total amount of isocyanate groups. Acrylates are produced.

The alkyl (meth)acrylate (D1) having a hydroxyl group includes 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate and 6-hydroxyhexyl methacrylate. One or two or more compounds selected from the group consisting of

The alkyl (meth)acrylamide (D2) having a hydroxyl group includes hydroxymethylacrylamide, hydroxymethylmethacrylamide, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethyl-N-methylacrylamide, 2-hydroxy ethyl-N-methylmethacrylamide, 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxypropyl-N-methylacrylamide, 3-hydroxypropyl-N-methylmethacrylamide, 4-hydroxybutylacrylamide, 4- Hydroxybutyl methacrylamide, 4-hydroxybutyl-N-methylacrylamide, 4-hydroxybutyl-N-methylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexylmethacrylamide, 6-hydroxyhexyl-N-methylacrylamide, 6 -hydroxyhexyl-N-methylmethacrylamide, N,N-bishydroxyethylacrylamide, and N,N-bishydroxyethylmethacrylamide.

The polyol (A) having two or more hydroxyl groups per molecule, which is used in the synthesis of the highly safe urethane acrylate of the present invention, includes an ether skeleton, an ester skeleton, a carbonate skeleton, a silicone skeleton, a diene skeleton, and a hydrogenated diene skeleton. , an isoprene skeleton and a hydrogenated isoprene skeleton.

The polyol (A) having an ether skeleton has two or more hydroxyl groups at the ends or side chains containing an ether skeleton in the molecule, and commercially available products include PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (manufactured by Mitsubishi Chemical Corporation), Sannix PP-200, PP-400, PP-600, PP-950, PP-1000, PP-1200, PP-2000, Sannix GP-250, GP-400, GOP- 600, GP-1000, GP-1500 (manufactured by Sanyo Chemical Industries, Ltd.), PEG200T, PEG200, PEG300, PEG400, PEG600, PEG1000, PEG1500, PEG1540, PEG2000, Uniox G-450, G-750, Uniol D-250, D-400, D-700, D-1000, D-1200, D-2000, Uniol TG-330, TG-1000, Unilube DGP-700, DGP-700F, Uniol HS-1600D, Uniol PB-500, PB- 700, PB-1000, PB-2000, 102, 104, polycerine DC-1100, DC-1800E, 60DC-1800, polycerine DCB-1000, DCB-2000 (manufactured by NOF Corporation) and the like.

The polyol (A) having an ester skeleton has two or more hydroxyl groups at the terminal or side chain containing the ester skeleton in the molecule, and commercially available products include Kuraray Polyol P-510, P-1010, P- 2010, F-510, F-1010, F-2010, P-2011, P-2013, P-520, P-1020, P-2020, P-1012, P-2012, P-530, P-2030, P-2050, N-2010, PMNA-2016 (manufactured by Kuraray), Plaxel 205, 205H, L205A, 205U, 208, 210, 210N, 210CP, 212, L212AL, 220, 220N, 220CPB, 220UA, 220NP1, L220AL, 220EB, 220EC (manufactured by Daicel Chemical Industries, Ltd.) and the like.

The polyol (A) having a carbonate skeleton has two or more hydroxyl groups at the ends or side chains containing the carbonate skeleton in the molecule, and commercially available products include Plaxel CD205PL, CD210, CD220, and CD220PL (Daicel Chemical Industries, Ltd.). company), ETERNACOLL UH-50, UH-100, UH-200, UHC50-100, UHC50-200, UC-100, UM-90 (3/1), UM-90 (1/1), UM-90 (1/3) Leeds (manufactured by Ube Industries), Duranol T6001, T6002, T5651, T5652, T5650J, T5450E, G4672, T4671, T4692, T4691 (manufactured by Asahi Kasei Chemicals), NIPPOLLAN 981, 980R, 982R, 963, 964 (manufactured by Nippon Polyurethane Co., Ltd.), Kuraray Polyol C-590, C-1050, C-1090, C-2050 and C-2090 (manufactured by Kuraray Co., Ltd.).

The polyol (A) having a silicone skeleton contains a siloxane bond in the main skeleton in the molecule and has two or more hydroxyl groups at both ends or side chains. -6000, KF-6001, KF-6002, X-21-5841 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY 16-201 (manufactured by Dow Corning Toray), XF42-B0970 (manufactured by Momentive Performance Materials), Silaprene FM-4411 (manufactured by JNC) and the like, and Silaprene FM-0411 and FM-DM110 (manufactured by JNC) containing a hydroxyl group at one end are also included.

The polyol (A) having a diene skeleton, a hydrogenated diene skeleton, an isoprene skeleton, or a hydrogenated isoprene skeleton has two or more hydroxyl groups at the terminals or side chains containing these skeletons in the molecule, and is commercially available. As products, diene-based NISSO-PB series G-1000, G-2000 (manufactured by Nippon Soda Co., Ltd.), Poly bd series R-15HT (manufactured by Idemitsu Kosan Co., Ltd.), Krasol series LBH2000, LBH-P2000 (manufactured by Clay Valley Co., Ltd. ), etc., and hydrogenated diene-based NISSO-PB series GI-1000, GI-2000 (manufactured by Nippon Soda Co., Ltd.), Krasol series HLBH-P2000 (manufactured by Clay Valley) and the like.

These polyols (A) can be used singly or in combination of two or more. Alternatively, a polyol (A) having the same skeleton or a combination of two or more different skeletons can also be used.

The polyisocyanate (B) having two or more isocyanate groups per molecule, which is used in the synthesis of the highly safe urethane acrylate of the present invention, includes, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1 ,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-diphenylmethane Diisocyanates, aromatic isocyanates such as xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane Alicyclic isocyanates such as diisocyanate, or multimers thereof such as adduct type, isocyanurate type and burette type. Specific product names of these products include Coronate L, which is a trimethylolpropane/tolylene diisocyanate adduct type, Coronate HL, which is a trimethylolpropane/hexamethylene diisocyanate adduct type, and Coronate HX, which is an isocyanurate type of hexamethylene diisocyanate ( All of them are manufactured by Nippon Polyurethane Industry Co., Ltd.), and Duranate 24A-100 (manufactured by Asahi Chemical Industry Co., Ltd.), which is a biuret type of hexamethylene diisocyanate. These polyisocyanates (B) can be used singly or in combination of two or more.

The synthesis of the highly safe urethane acrylate of the present invention is performed in two steps. The first step is to react with polyol (A), polyisocyanate (B), 2-hydroxyethyl acrylate (C1) and/or 3-hydroxypropyl acrylate (C2). The ratio of raw materials to be charged is characterized in that the total amount of isocyanate groups is equal to or more than the total amount of hydroxyl groups. That is, at the end of the first stage reaction, neither free 2-hydroxyethyl acrylate (C1) nor 3-hydroxypropyl acrylate (C2) remains, and an intermediate having terminal isocyanate groups and/or acrylate groups is obtained. In the second step, the resulting intermediates are converted to 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, 3 -Reacting with one or more compounds (D) selected from the group consisting of hydroxypropylacrylamide and 3-hydroxypropylmethacrylamide, leaving no isocyanate group, acrylate group, methacrylate group, acrylamide group or methacrylamide group at the end to obtain a urethane acrylate having

The urethane acrylate obtained by the production method of the present invention does not contain toxic substances such as 2-hydroxyethyl acrylate (C1) and 3-hydroxypropyl acrylate (C2), and does not contain a toxic isocyanate group. It is a high urethane acrylate.

When producing the highly safe urethane acrylate of the present invention, the blending ratio of the raw materials was: total of A/total of B/total of C/total of D=1.0/1.1/0.1/0. It is particularly preferable to react at a ratio of 2 to 1.0/3.0/2.0/5.0 (molar ratio). If the raw material blending ratio is within this range, the intermediate and the target product each having a terminal group as designed are obtained by the first-stage reaction and the second-stage reaction, and C does not remain, Only highly safe urethane acrylates that do not have the risk of being classified as poisonous or deleterious substances can be acquired.

The highly safe urethane acrylate of the present invention is characterized by having an acrylate group derived from C and an acrylate group, methacrylate group, acrylamide group or methacrylamide group derived from D as terminal groups. In addition, the total amount of C-derived acrylate groups is 50 to 99% (molar ratio) relative to the total acryloyl groups in the high-safety urethane (meth)acrylate (total of C-derived and D-derived acryloyl groups). is preferred. If the content of the C-derived acrylate group is within this range, the synthesized urethane acrylate is produced using only ordinary C, and is equivalent to or It exhibits physical properties greater than that, and can be used immediately in various fields with a general-purpose formulation as an industrial product. Further, from the viewpoint of stabilizing the production process and improving quality, the total amount of C-derived acrylate groups is more preferably 70 to 95%, more preferably 80 to 90%, of the total acryloyl groups of the urethane acrylate. is most preferred.

In the first stage reaction of the urethanization of the present invention, the raw materials polyol (A), polyisocyanate (B), 2-hydroxyethyl acrylate (C1) and 3-hydroxypropyl acrylate (C2) are mixed at room temperature, The temperature can be increased to a predetermined temperature and the reaction can be carried out while stirring. The reaction is carried out at a temperature of 10-160°C, preferably 20-140°C. Mixing of the raw materials may be performed all at once, or may be performed in several steps. The reaction can be carried out without a solvent, but can be carried out in an organic solvent or a reactive diluent if necessary. Solvents that can be used include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, hexane, cyclohexane, benzene, toluene, xylene, and aliphatic hydrocarbons. It can be carried out in the presence of a solvent (petroleum ether, etc.) or the like. 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 group. Acrylates, allyl acrylate, cyclohexyl acrylate, 1,6-hexanediacrylate, tetraethylene glycol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethyl Acrylamide, diethylacrylamide, N-acryloylmorpholine and the like are exemplified. The organic solvent or reactive diluent is used in an amount of 0 to 200% by weight, preferably 0 to 100% by weight, based on the mixture of A, B and C.

In the second-stage reaction of the urethanization of the present invention, D can be added to the intermediate obtained in the first-stage reaction or the solution of the intermediate, and the mixture can be reacted with stirring at a predetermined temperature. This reaction is also carried out at a temperature of 10-160°C, preferably 20-140°C. The charging of D may be carried out all at once, or may be carried out in several stages. Also, this reaction may or may not have a solvent. If a solvent is present, the solvent in the first step reaction may be used as is, or additional solvent may be added in the second step. The solvent and amount used in the second-stage reaction are the same as in the first-stage reaction.

In the first-stage and second-stage urethanization reactions, a catalyst may be added for the purpose of promoting the reaction. Examples of the catalyst include potassium or sodium salts of alkylphosphonic acids, metal salts of fatty acids having 8 to 20 carbon atoms such as sodium, potassium, nickel, cobalt, cadmium, barium, calcium, and zinc, dibutyltin dilaurate, and dioctyl. and organotin compounds such as tin maleate, dibutyl dibutoxytin, bis(2-ethylhexyl)tin oxide, 1,1,3,3-tetrabutyl-1,3-diacetoxydistannoxane, either alone or Two or more kinds can be used in combination. The amount of the catalyst used is generally preferably 1% by weight or less, more preferably 0.1% by weight or less, relative to the total weight of the raw material components. In the second stage reaction, when highly reactive hydroxyethyl acrylamide is used as D, the urethanization reaction can proceed rapidly even without a catalyst by setting the reaction temperature to 40° C. or higher.

In order to suppress radical polymerization due to the double bonds (acrylate group, methacrylate group, acrylamide group and methacrylamide group) possessed by C and D and the double bonds of the resulting highly safe urethane acrylate, the first step and/or A radical polymerization inhibitor can be used as necessary during the second-stage urethanization reaction. Examples of radical polymerization inhibitors include quinone polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, Alkylphenol polymerization inhibitors such as 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, Amine polymerization inhibitors such as N,N'-diphenyl-p-phenylenediamine and phenothiazine, N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; dimethyldithiocarbamic acid Copper dithiocarbamate-based polymerization inhibitors such as copper, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, etc., may be mentioned, and these may be used alone or in combination of two or more.

The amount of these polymerization inhibitors to be added may be appropriately set according to the type and content of double bonds possessed by C, D and the resulting highly safe urethane acrylate. From the viewpoints of convenience and economy, it is usually preferably 0.001 to 5% by weight, more preferably 0.01 to 1% by weight, based on the obtained urethane acrylate.

The urethane acrylate of the present invention has a number average molecular weight of 500 to 100,000, preferably 800 to 80,000, particularly preferably 1,000 to 50,000. If the number average molecular weight is less than 500, the ratio of monofunctional urethane acrylate having one double bond is high, and the curability of the resulting urethane acrylate as a whole and the solubility in organic solvents and general-purpose acrylic monomers may decrease. On the other hand, when the number average molecular weight exceeds 100,00, the density of double bonds in the urethane acrylate is low, and the hardness of the urethane acrylate and the surface drying property of the resulting cured product cannot be fully satisfied, which is not preferable. .

The acrylic equivalent (molecular weight per double bond) of the urethane acrylate of the present invention is 300 to 75,000, preferably 500 to 50,00. If the acrylic equivalent is less than 300, the density of polymerizable double bonds is high, and troubles such as polymerization during the production process of urethane acrylate and subsequent storage are likely to occur. On the other hand, when the acrylic equivalent exceeds 75,000, the density of double bonds is low, and the urethane acrylate hardness and the surface drying property of the resulting cured product cannot be fully satisfied, which is not preferred.

Although the highly safe urethane acrylate of the present invention may be used alone, an active energy ray-curable resin composition can be prepared by mixing it with other general-purpose acrylic monomers or oligomers. Various compounds such as monofunctional (meth)acrylates and/or monofunctional (meth)acrylamides, polyfunctional (meth)acrylates and/or polyfunctional (meth)acrylamides can be used as general-purpose acrylic monomers and oligomers. It is possible. In general, the highly safe urethane acrylate in the active energy ray-curable resin composition using the highly safe urethane acrylate has a content of 1% by weight or more, preferably 5% by weight or more. If the content of the highly safe urethane acrylate is less than 1% by weight, various effects provided by the urethane acrylate may not be confirmed, which is not preferable.

Monofunctional (meth)acrylates used in the present invention include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ) acrylate, hydroxyethyl acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl ( meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytetra ethylene glycol (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, phenoxyethyl (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxytetraethyleneglycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, Methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl (meth)acrylate, allyl (meth)acrylate, hydroxyethyl (Meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyhexyl (meth)acrylate and the like. These monofunctional acrylates may be used alone or in combination of two or more.

Monofunctional (meth)acrylamides used in the present invention include, for example, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N -Methoxyethyl (meth)acrylamide, N-ethoxyethyl (meth)acrylamide, Nn-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (2-hydroxyethyl)acrylamide, N-[3-(dimethylamino)]propylacrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-acryloylmorpholine, the hydroxyethylacrylamide and hydroxyalkyl (meth)acrylamides such as Moreover, these monofunctional acrylamides may be used alone, or two or more of them may be used in combination.

Examples of polyfunctional (meth)acrylates used in the present invention include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ditetra Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4- butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate ) acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified Phosphate di(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate ) acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di( meth)acrylate, cyclohexanedimethanol di(meth)acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di(meth)acrylate, alkoxylated cyclohexanedimethanol di(meth)acrylate, epoxy(meth)acrylate, urethane Examples include monomers and oligomers such as (meth)acrylates. Moreover, these polyfunctional (meth)acrylates may be used alone or in combination of two or more.

The polyfunctional (meth)acrylamide used in the present invention includes methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, diallyl(meth)acrylamide and the like. Moreover, these polyfunctional (meth)acrylamides may be used alone, or two or more of them may be used in combination.

The various general-purpose acrylic monomers and oligomers used in the present invention can be used singly or in combination of two or more as necessary. The amount of general-purpose acrylic monomers and oligomers blended depends on the skeleton, molecular weight, number of functional groups (number of double bonds in one molecule) of the highly safe urethane acrylate, and the polarity, viscosity, molecular weight and number of functional groups of general-purpose acrylic monomers and oligomers. Since it can be adjusted, it is not particularly limited. The content of the general-purpose acrylic monomer or oligomer is preferably 0 to 99% by weight, more preferably 10 to 80% by weight, based on the active energy ray-curable resin composition. If the content of general-purpose acrylic monomers and oligomers is within this range, by adjusting the blending ratio with the highly safe urethane acrylate of the present invention, the active energy ray curability, the transparency of the resulting cured product, the surface drying property, the surface Good balance of hardness.

The highly safe urethane acrylate of the present invention can be completely cured by irradiation with active energy rays. The necessary amount of active energy ray irradiation (integrated light amount) varies depending on the type of double bond and the acrylic equivalent, but it is preferably 0.1 to 2,000 mJ/cm ² , more preferably 1 to 1,000 mJ/cm ² . degree is particularly preferred. If the integrated amount of light is less than 0.1 mJ/cm ² , insufficiently cured portions may remain and the overall hardness, water resistance and durability of the cured product may be lowered. Further, when the integrated light quantity exceeds 2,000 mJ/cm ² , side reactions such as decomposition occur due to excess energy, and the cured product tends to be colored.

The active energy ray used for curing the active energy ray-curable resin composition having the highly safe urethane acrylate of the present invention decomposes a compound (photopolymerization initiator) that generates active species to generate active species. defined as an energy ray that can 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. A photopolymerization initiator is not particularly necessary when electron beams are used as active energy rays, but is necessary when ultraviolet rays are used. The photopolymerization initiator may be appropriately selected from ordinary ones such as acetophenone series, benzoin series, benzophenone series, and thioxanthone series. Among photopolymerization initiators, commercial photopolymerization initiators manufactured by Ciba Specialty Chemicals, trade names Darocur 1116, Darocur 1173, Irgacure 184, Irgacure 369, Irgacure 500, Irgacure 651, Irgacure 754, Irgacure 819, Irgacure 907, Irgacure 1300, Irgacure 1800, Irgacure 1870, Irgacure 2959, Darocur 4265, Darocur TPO, manufactured by UCB, trade name Uvecryl P36, and the like can be used. These photoinitiators can be used singly or in combination of two or more.

The amount of these photopolymerization initiators to be used is not particularly limited, but generally 0 to 10% by weight, preferably 1 to 5% by weight, is added to the active energy ray-curable resin composition. If it exceeds 10% by weight, the strength of the cured product may be lowered or yellowing may occur.

Pigments, dyes, surfactants, antiblocking agents, leveling agents, dispersants, antifoaming agents, antioxidants, as long as they do not impair the properties of the active energy ray-curable resin composition of the present invention and the molded articles produced therefrom. Other optional components such as agents, UV sensitizers, preservatives, etc. may be used in combination.

The active energy ray-curable resin composition of the present invention can be applied to plastics and metals such as paper, cloth, nonwoven fabric, glass, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymer, polyvinyl chloride, cellophane, celluloid, polycarbonate, and polyimide. A high-performance coating layer, ink layer, pressure-sensitive adhesive layer or adhesive layer can be obtained by coating the surface or between substrates such as the above and curing by irradiation with active energy rays such as ultraviolet rays. In particular, since the active energy ray-curable resin composition of the present invention has a highly transparent urethane oligomer, it is suitably used as an optical resin composition such as an optical pressure-sensitive adhesive, an optical adhesive, and an optical film coating material. be able to. Further, as a method for applying this resin composition onto a substrate, conventional methods such as a spin coating method, a spray coating method, a dipping method, a gravure roll method, a knife coating method, a reverse roll method, a screen printing method and a bar coater method can be used. Film-forming methods can be used. Moreover, the lamination method, the roll-to-roll method, etc. are mentioned as a method of apply|coating between base materials.

The present invention will be described in more detail and more specifically by the following examples, but the present invention is not limited only to these examples. In addition, below, % other than a yield represents the weight%. The physical properties of the obtained highly safe urethane acrylate were analyzed by the following methods.

(1) Measurement of molecular weight of urethane acrylate and measurement of content of C component and D component The number average molecular weight of the obtained urethane acrylate and the content of C component and D component remaining in the urethane acrylate were measured by high performance liquid chromatography (( "LC-10A" manufactured by Shimadzu Corporation, column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ separation range: 100 to 2 × 10 ⁷ theoretical plate number: 10,000 plate/column, Filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm)), eluent: tetrahydrofuran)), and calculated by standard polystyrene molecular weight conversion.
(2) Calculation of acrylic equivalent of urethane acrylate From the obtained molecular weight of urethane acrylate, the acrylic equivalent was calculated by the following formula. Acrylic equivalent = number average molecular weight / number of double bonds

Example 1 Synthesis of highly safe urethane acrylate SUA-1 Uniol D-250 (polypropylene glycol, manufactured by NOF Corporation, manufactured by NOF Corporation, Number average molecular weight: 250) 12.5 g (50 mmol), isophorone diisocyanate (IPDI) 22.2 g (100 mmol), hydroxyethyl acrylate (HEA, C1) 9.5 g (81.9 mmol), dibutylhydroxytoluene (BHT) 0. 02 g of dibutyltin dilaurate and 0.02 g of dibutyltin dilaurate were charged, heated to 80° C. with stirring, and reacted at 80° C. for 4 hours. Next, 3.45 g (30 mmol) of hydroxyethylacrylamide (manufactured by KJ Chemicals Co., Ltd., trademark registration "HEAA") was added, and stirring was continued for 3 hours while maintaining the temperature at 80°C to obtain a slightly viscous liquid. By infrared absorption spectrum (IR) measurement, the characteristic absorption (1720 cm ^-1 ) of the HEA-derived ester group, the characteristic absorption (1650 cm -1 ) of the "HEAA"-derived amide group, and the characteristic absorption (1750 cm ^{-1 )} of the generated urethane bond ¹ ) was detected, the generation of urethane acrylate was confirmed. In addition, it was confirmed that it did not contain an isocyanate group (by IR measurement, the characteristic absorption of the isocyanate group completely disappeared at 2260 cm ⁻¹ ), it was also confirmed that it did not contain HEA, and the content of “HEAA” was 2.3. % and obtained high safety urethane acrylate SUA-1. The obtained SUA-1 had a number average molecular weight of 1,220 and an acrylic equivalent of 610.

Example 2 Synthesis of highly safe urethane acrylate SUA-2 Using the same equipment (500 mL) as in Example 1, Adeka New Ace Y6-30 (polyesterdiol manufactured by Asahi Denka Kogyo Co., Ltd., number average molecular weight: 3000) 150 0 g (50.mmol), hexamethylene diisocyanate (HDI) 9.25 g (55.mmol), hydroxypropyl acrylate (HPA, C2) 0.68 g (5.2 mmol), dibutyltin dilaurate 0.05 g, methylhydroquinone ( 0.2 g of MHQ) was charged, the temperature was raised to 100° C., and the reaction was carried out at 100° C. for 4 hours. After that, the reaction solution was cooled to 60° C., 1.20 g (10.4 mmol) of “HEAA” was added, and stirring was continued for 5 hours while maintaining the temperature at 60° C. to obtain a pale yellow viscous liquid. As in Example 1, formation of the desired urethane acrylate was confirmed by IR analysis. Further, in the same manner as in Example 1, it was confirmed that HPA was not contained in the obtained urethane acrylate, it was confirmed that no isocyanate groups remained, and safe urethane acrylate SUA-2 was obtained. 0.3% of "HEAA" was contained in SUA-2. SUA-2 had a number average molecular weight of 96,500 and an acrylic equivalent of 73,800.

Example 3 Synthesis of highly safe urethane acrylate SUA-3 Using the same equipment as in Example 1, T-5650E (polycarbonate polyol (1,5-pentanediol/1,6-hexanediol), manufactured by Asahi Kasei Chemicals Co., Ltd., several After charging 25.0 g (50 mmol) of average molecular weight 500), 25.8 g (20 mmol) of HEA, 0.06 g of BHT, 0.01 g of dibutyltin dilaurate, and 30 g of methyl ethyl ketone (MEK), the temperature was raised to 65° C. to obtain IPDI nurate. 66.6 g (100 mmol) was added dropwise while adjusting the dropping rate so as to maintain the temperature at 65°C, and further reacted at 65°C for 2 hours. Next, 36.0 g (250 mmol) of hydroxybutyl acrylate (HBA) was added, and stirring was continued for 6 hours while maintaining the temperature at 65°C. The solvent was distilled off under reduced pressure to obtain a slightly viscous liquid. Analysis was performed in the same manner as in Example 1 to confirm that no HEA and isocyanate groups remained, and highly safe urethane acrylate SUA-3 was obtained. The HBA content in SUA-3 was 4.5%, the number average molecular weight of SUA-3 was 1,450, and the acrylic equivalent was 360.

Example 4 Synthesis of highly safe urethane acrylate SUA-4 Using the same apparatus as in Example 1, GI-1000 (both hydroxyl end butadiene, manufactured by Nippon Soda Co., Ltd., number average molecular weight 1500) 75.0 g (50 mmol), HEA 11 .6 g (100 mmol), 39.3 g (150 mol) of dicyclohexylmethane 4,4′-diisocyanate (hydrogenated MDI), and 0.06 g of BHT were charged and reacted at 100° C. for 4 hours. Next, the reaction solution was cooled to 60° C., 17.2 g (150 mmol) of “HEAA” was added, and the reaction was continued at 100° C. for an additional 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature to obtain a viscous liquid. Analysis was performed in the same manner as in Example 1 to confirm that no HEA and isocyanate groups remained, and highly safe urethane acrylate SUA-4 was obtained. The "HEAA" content in SUA-4 was 1.2%, the number average molecular weight of SUA-4 was 5,800, and the acrylic equivalent was 2,900.

Example 5 Synthesis of highly safe urethane acrylate SUA-5 Using the same apparatus as in Example 1, KF-6000 (carbinol-modified silicone at both ends, manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 1,000) 50 g (50 mmol) , 21.0 g (100 mmol) of trimethylhexamethylene diisocyanate (TMHDI), 0.3 g of dibutyltin dilaurate, and 0.04 g of BHT were charged, heated to 70° C., and reacted at 70° C. for 5 hours. Next, 13.0 g (100 mmol) of HPA was charged, and stirring was continued for 3 hours while maintaining the temperature at 70°C. After that, 3.2 g (25 mmol) of hydroxyethyl methacrylamide (HEMAA) was added and reacted at 80° C. for 4 hours to obtain a viscous liquid. Analysis was carried out in the same manner as in Example 1, confirming that no HPA and isocyanate groups remained, and highly safe urethane acrylate SUA-5 was obtained. The HEMAA content in SUA-5 was 0.1%, the number average molecular weight of SUA-5 was 1,600, and the acrylic equivalent weight was 830.

Example 6 Synthesis of highly safe urethane acrylate SUA-6 Using the same device (500 mL) as in Example 1, UT-1001 (acrylic polymer, manufactured by Soken Chemical Co., Ltd., number average molecular weight: 3500) 175.0 g (50 mmol) , IPDI 16.7 g (75 mmol), HEA 1.7 g (15 mmol), and dibutyltin dilaurate 0.1 g were charged and reacted at 80° C. for 3 hours. After that, 3.2 g (25 mmol) of hydroxyethyl methacrylate (HEMA) was added, and stirring was continued for 5 hours while maintaining the temperature at 80°C to obtain a pale yellow viscous liquid. Analysis was performed in the same manner as in Example 1 to confirm that no HEA and isocyanate groups remained, and highly safe urethane acrylate SUA-6 was obtained. The HEMA content in SUA-6 was 0.6%, the number average molecular weight of SUA-6 was 11,800, and the acrylic equivalent was 6,000.

Example 7 Synthesis of highly safe urethane acrylate SUA-7 Using the same device (500 mL) as in Example 1, C-1090 (manufactured by Kuraray Co., Ltd., polycarbonate polyol having hydroxyl groups at both ends, 3-methyl-1 ,5-pentanediol/1,6-hexanediol = 9/1, weight average molecular weight = 1000) 50.0 g (50 mmol), Uniol D-1000 (Uniol D-1000, polypropylene glycol manufactured by NOF Corporation, Weight average molecular weight = 1000) 5.0 g (5.0 mmol), IPDI 17.1 g (77 mmol), HEA 1.7 g (15 mmol), dibutyltin dilaurate 0.03 g, and MHQ 0.10 g were charged and stirred. The reaction was carried out at 80°C for 4 hours. Next, after cooling the reaction solution to 40° C., 1.2 g (10 mmol) of “HEAA” was added, and stirring was continued for 5 hours while maintaining the temperature at 60° C. to obtain a pale yellow viscous liquid. Analysis was performed in the same manner as in Example 1 to confirm that no HEA and isocyanate groups remained, and highly safe urethane acrylate SUA-7 was obtained. The "HEAA" content in SUA-7 was 0.2%, the number average molecular weight of SUA-7 was 26,800, and the acrylic equivalent was 13,400.

Example 8 Synthesis of highly safe urethane acrylate SUA-8 Using the same apparatus as in Example 1, ADEKA NEWACE Y6-30 (polyester diol manufactured by Asahi Denka Kogyo Co., Ltd., number average molecular weight: 3000) 60.0 g (20 mmol) ), 30.0 g (30 mmol) of Uniol D-1000, 9.10 g (100 mmol) of HDI, 8.6 g (75 mmol) of HEA, 0.05 g of dibutyltin dilaurate, and 0.2 g of MHQ, then charged at 80° C. for 4 hours. reacted. Next, after cooling the reaction solution to 40° C., 3.5 g (30 mmol) of “HEAA” and 2.2 g (15 mmol) of HBA were charged, and stirring was continued for 5 hours while maintaining the temperature at 60° C. A pale yellow viscous liquid was obtained. Analysis was performed in the same manner as in Example 1 to confirm that no HEA and isocyanate groups remained, and highly safe urethane acrylate SUA-8 was obtained. The "HEAA" content in SUA-8 was 0.1%, and the HBA content was 0.5%. SUA-8 had a number average molecular weight of 48,600 and an acrylic equivalent of 24,300.

Comparative Example 1 Synthesis of urethane acrylate (UA-1) Using the same apparatus as in Example 1, PTMG 650 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 650) 65.0 g (100 mmol), IPDI 33 3 g (150 mmol) of HEA, 5.8 g (50 mmol) of HEA, 0.05 g of BHT and 0.02 g of dibutyltin dilaurate were charged and reacted at 80° C. for 8 hours to obtain a slightly viscous liquid. IR analysis was performed in the same manner as in Example 1, and a characteristic absorption of the isocyanate group was confirmed at 2260 cm ^-1 . Further, the obtained urethane acrylate UA-1 did not contain HEA, and UA-1 had a number average molecular weight of 4,800 and an acrylic equivalent of 2,400.

Comparative Example 2 Synthesis of urethane acrylate (UA-2) Using the same apparatus as in Example 1, PTMG 650 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 650) 65.0 g (100 mmol), IPDI 33 3 g (150 mmol) of HEA, 11.5 g (100 mmol) of HEA, 0.05 g of BHT and 0.02 g of dibutyltin dilaurate were charged and reacted at 80° C. for 8 hours to obtain a slightly viscous liquid. IR analysis was carried out in the same manner as in Example 1, and residual isocyanate groups were confirmed, and the HEA content in the resulting urethane acrylate UA-2 was 0.8%. UA-2 had a number average molecular weight of 6,200 and an acrylic equivalent of 3,100.

Comparative Example 3 Synthesis of urethane acrylate (UA-3) Using the same apparatus as in Example 1, PTMG 650 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 650) 65.0 g (100 mmol), IPDI 33 3 g (150 mmol) of HEA, 23.0 g (200 mmol) of HEA, 0.05 g of BHT and 0.02 g of dibutyltin dilaurate were charged and reacted at 80° C. for 8 hours to obtain a slightly viscous liquid. IR analysis was conducted in the same manner as in Example 1 to confirm that no isocyanate group remained. The HEA content in the obtained urethane acrylate UA-3 was 5.5%. UA-3 had a number average molecular weight of 5,600 and an acrylic equivalent of 3,000.

Comparative Example 4 Synthesis of urethane acrylate (UA-4) Using the same apparatus as in Example 1, PTMG 650 (polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 650) 65.0 g (100 mmol), IPDI 33 .3 g (150 mmol), 11.5 g (100 mmol) of HEA, 11.6 g (100 mmol) of "HEAA", 0.05 g of BHT, and 0.02 g of dibutyltin dilaurate were charged and reacted at 80° C. for 8 hours until a slightly viscous got the liquid. IR analysis was performed in the same manner as in Example 1, and it was confirmed that no isocyanate group remained. The HEA content in the resulting urethane acrylate UA-4 was 3.5%, and the "HEAA" content was 0.4. %Met. UA-4 had a number average molecular weight of 10,200 and an acrylic equivalent of 5,500.

The urethane acrylates of the present invention obtained in Examples 1 to 8 contained neither toxic isocyanate groups nor poisonous HEA and HPA, confirming that they are highly safe urethane acrylates. On the other hand, the urethane acrylates synthesized in Comparative Examples 1 to 4 contain isocyanate groups, HEA, and HPA, and are highly likely to be poisonous substances. is clear.

As described in Examples 1 to 8, the highly safe urethane acrylate of the present invention has practically no HEA or HPA and no terminal isocyanate groups by the production method of the two-stage urethanization reaction of the present invention. , a high safety urethane acrylate is produced. In the known methods for producing urethane acrylates as described in Comparative Examples 1 to 4, only urethane acrylates corresponding to toxic substances can be obtained because terminal isocyanate groups remain or toxic substances HEA and HPA are contained. I found out.

Various general-purpose An active energy ray-curable resin composition can be prepared by mixing with acrylic monomers, oligomers, photopolymerization initiators and other additives. Moreover, the obtained active energy ray-curable resin composition can be cured by a general-purpose method, for example, by ultraviolet (UV) or electron beam (EB) irradiation. Furthermore, similarly, the obtained highly safe urethane acrylates (SUA-1 to SUA-8) and the urethane acrylates (UA-1 to UA-4) synthesized in Comparative Examples 1 to 4 are known in various fields. It can be used for various urethane acrylate applications. However, by containing only the highly safe urethane acrylate, the active energy ray-curable highly safe pressure-sensitive adhesive, the active energy ray-curable highly safe adhesive, the active energy ray-curable highly safe inkjet ink, the active energy ray-curable highly safe inkjet ink of the present invention, Active energy ray-curable high-safety 3D modeling ink, active energy ray-curable high-safety coating agent, active energy ray-curable high-safety nail decoration agent, active energy ray-curable high-safety sealant, active energy Radiation-curable high-safety decorative films, active-energy-ray-curable high-safety vehicle protective agents and coating agents, and active-energy-ray-curable high-safety building interior and exterior paints can be obtained by general-purpose methods. .

The highly safe urethane acrylate of the present invention has a skeleton, molecular weight, and terminal acrylate group equivalent to those of general-purpose urethane acrylate, and can be utilized without changing the general formulation of general-purpose urethane acrylate. Various highly safe urethane acrylate products can be easily obtained by substituting the highly safe urethane acrylate of the present invention from ordinary urethane acrylates.

As explained above, the highly safe urethane acrylate of the present invention has one or more acrylate groups derived from HEA and/or HPA as terminal groups, does not have an isocyanate group in the molecule, and has HEA and/or Alternatively, it is characterized by not containing HPA, and a highly safe cured product can be obtained by curing with active energy rays such as ultraviolet rays. In addition, the highly safe urethane acrylate of the present invention may be used alone, but if necessary, it can be used by mixing monofunctional monomers, polyfunctional monomers, general-purpose oligomers, pigments, etc. High safety products in various fields such as electronic materials, optics and semiconductor fields, inks, coating agents, gel nails, sealants, decorative films, and photo-curable resists can be suitably manufactured.

Claims (14)

One or more acrylate groups derived from 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate as terminal groups per molecule, no isocyanate groups in the molecule, and 2-hydroxyethyl acrylate and/or 3 - a urethane acrylate that does not contain hydroxypropyl acrylate ,
2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, 2-hydroxyethyl- Having one or more (meth)acryloyl groups derived from one or more compounds selected from the group consisting of N-methylacrylamide, 2-hydroxyethyl-N-methylmethacrylamide, 3-hydroxypropylacrylamide, and 3-hydroxypropylmethacrylamide A urethane acrylate characterized by: Acrylate groups derived from 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate account for 50 to 99 mole percent of all acryloyl groups in the urethane (meth)acrylate. Urethane acrylate as described. Polyol (A) having two or more hydroxyl groups per molecule, polyisocyanate (B) having two or more isocyanate groups per molecule, 2-hydroxyethyl acrylate and/or 3-hydroxypropyl acrylate (C), and hydroxyl groups The total amount of isocyanate is reacted at a compounding ratio of equivalent or more to the total of, then 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylamide, 3. The compound according to claim 1 or 2 , which is obtained by reacting with one or more compounds (D) selected from the group consisting of 2-hydroxyethylmethacrylamide, 3-hydroxypropylacrylamide, and 3-hydroxypropylmethacrylamide. A method for producing urethane acrylate. A highly safe active energy ray-curable resin composition containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe pressure-sensitive adhesive comprising 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An energy ray-curable highly safe adhesive comprising 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe inkjet ink containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable high-safety 3D modeling ink containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe coating agent containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe nail decorating agent containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe sealant containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe decorative film containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable highly safe vehicle exterior protective agent containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 . 3. An active energy ray-curable high-safety paint for buildings containing 1% by weight or more of the urethane acrylate according to claim 1 or 2 .