JP2016113518A - Active energy ray-curable resin composition having (meth)acrylamide urethane oligomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition having a low viscosity and excellent operability before cured, having high curability even in the presence of oxygen, and giving a cured product that is free from bleed-out of a non-reactive diluent, exhibits good tackiness or adhesiveness, and is useful for a pressure-sensitive adhesive, an adhesive, an electronic material, an ink, a coating agent or a photocurable resist, or for addition production.SOLUTION: A (meth)acrylamide urethane oligomer having a (meth)acrylamide group at a terminal or in a side chain, an N-substituted (meth)acrylamide, and a non-reactive diluent are used in the active energy ray-curable resin composition.SELECTED DRAWING: None

Description

  The present invention is useful for pressure-sensitive adhesives, adhesives, electronic materials, inks, coating agents, photo-curing resist applications, additive manufacturing applications, etc., and has high curability even in the presence of oxygen, and improves handling while keeping viscosity low. The present invention relates to an active energy ray-curable resin composition and a molded product thereof.

  Active energy ray curing technology is fast-curing and high productivity, and is environmentally friendly technology such as solvent-free and high solid, and can be used for patterning and additive manufacturing. It is used in various fields such as electronic materials, inks, coating agents, photo-curable resist applications, and additive manufacturing applications. The active energy ray curing technology includes a photocationic polymerization reaction using a cationic ring-opening polymerizable monomer and a protonic acid as a photoactive species, and a photoradical polymerization reaction using an acrylic monomer and proceeding with a photoradical initiator. Many are used. Although the cationic photopolymerization reaction is not affected by the inhibition of polymerization by oxygen and has a low curing shrinkage rate, it has a drawback that the curing rate is slow. On the other hand, the radical photopolymerization reaction is susceptible to oxygen inhibition and has drawbacks such as high cure shrinkage, but is widely used because it has a high cure rate and can use general-purpose acrylic monomers.

  Furthermore, the active energy ray-curable resin composition using a (meth) acrylic monomer is easy to keep the viscosity low, has good handling during use, and can be used in various applications. For example, in the photocurable adhesive composition, 30 to 3000 mPa · s is considered to be a preferable viscosity region in order to improve the coating performance, and 30 to 50% by mass of oligomer, (meth) acrylates and (meth) Acrylamide is used in an amount of 50 to 70% by mass (Patent Document 1). In addition, when used as an inkjet ink, 2 to 30 mPa · s is a preferable viscosity range from the viewpoint of stable ejection, and not only a (meth) acrylic monomer but also an organic solvent is used to reduce the viscosity. (Patent Document 2).

  In addition, when an active energy ray-curable resin composition is used in a radical photopolymerization reaction, a polymerizable urethane oligomer having a (meth) acryl group introduced therein is used in addition to an acrylic monomer as shown in Patent Document 1. Many things have been reported. This is because the polymerizable urethane oligomer has a variety of skeletal structures in a well-balanced manner, and there are various adhesive properties, tackiness, flexibility, flexibility, flexibility, toughness, solvent resistance, wear resistance, etc. according to the application. This is because it is possible to easily impart the required performance. Such a polymerizable urethane oligomer usually reacts with a polyol and a polyisocyanate to obtain a polyurethane having a hydroxyl group or an isocyanate group at both ends, and then a hydroxyl group-containing (meth) acrylate or an isocyanate group-containing (meth) acrylate and further It is synthesized by reacting (Patent Documents 3 to 5). There has also been proposed a synthesis method in which a hydroxyl group-containing acrylate and a polyisocyanate are reacted and then attached to the end of a polyol (Patent Document 6).

  In addition, in order to improve the curability of the active energy ray-curable resin composition in general, a method of using a hydroxyl group-containing (meth) acrylamide as a polymerizable urethane oligomer or monomer having a (meth) acrylamide group introduced is proposed. (Patent Documents 7 and 8).

  On the other hand, when the active energy ray-curable resin composition is actually used in various fields such as pressure-sensitive adhesives, adhesives, electronic materials, inks, coating agents, photo-curing resist applications, and additional production applications, polymerization is performed. The required physical properties cannot be satisfied only with the reactive urethane oligomer and the acrylic monomer, and a plasticizer or a softening agent may be used as a non-reactive diluent. The non-reactive diluent not only improves the operability by lowering the viscosity but also includes the cured product to reduce the curing shrinkage and adjust the physical properties of the cured product according to the application. For example, when assembling a cover glass and a liquid crystal display unit with a photo-curing adhesive, so-called liquid OCA, in the assembly of a liquid crystal panel, lowering the viscosity to satisfactorily fill the panel and preventing distortion due to curing shrinkage In order to reduce the curing shrinkage rate, liquid polybutadiene or the like is used as a non-reactive diluent (Patent Documents 9 and 10). Moreover, in addition manufacture use, non-reactive diluents, such as alkylene glycol, are added in order to adjust a viscosity, peelability, etc. (patent documents 11, 12).

However, it is extremely difficult to balance the active energy ray-curable resin composition with high curability, low viscosity, and low cure shrinkage. For example, in Patent Document 7 in which a non-reactive diluent is not used, the viscosity is as high as 1000 mPa · s or more, and the resin is poor in handling. Further, in Patent Document 8, although a resin having low viscosity and good adhesiveness is obtained, an integrated light amount of 1000 mJ / cm ² is required for curing, and the curability is insufficient. Furthermore, since the monomer is used in an amount of 80% by mass or more, it cannot contribute to the improvement of the curing shrinkage rate, and there is a concern that it is difficult to use because the distortion becomes large in thick film adhesive sheets and additional production applications. On the other hand, in Patent Document 2 using an organic solvent to reduce the viscosity, although it is excellent in operability as an ink-jet ink, a drying step for removing the organic solvent before curing with active energy rays is required, Productivity was inferior. Furthermore, in the photocurable adhesive using a non-reactive diluent as described in Patent Documents 9 and 10, a high integrated light amount of 6000 mJ / cm ² is required, and the curability is not sufficient. . In addition, a non-reactive diluent is also used in addition manufacturing applications. However, Patent Document 11 attempts to reduce the viscosity, but curing requires an integrated light amount of 1000 mJ / cm ² and is hardened. In the case of using a non-reactive diluent in Patent Document 12, although high curability and low viscosity can be achieved, prevention of bleed-out of the non-reactive diluent from the cured product is insufficient. Therefore, the resin before curing has good handling such as high curability and low viscosity, and an active energy ray-curable resin composition that provides a cured product having excellent physical properties such as adhesion and tackiness after curing. Development was desired.

JP 2007-177169 A JP 2010-092012 A JP 61-21120 A JP 2010-267703 A JP-A-6-145276 WO2013 / 088889 JP 2001-270973 A JP 2013-177547 A JP 2014-095080 A JP 2008-282000 A JP 2012-111226 A JP 2010-155889 A

  The present invention has low viscosity and excellent operability, and has high curability due to active energy rays even in the presence of oxygen, and the cured product has no bleed-out of non-reactive diluent and has good tackiness and adhesiveness. It is an object of the present invention to provide an active energy ray-curable resin composition useful for a pressure-sensitive adhesive, an adhesive, an electronic material, an ink, a coating agent, a photo-curing resist application, an additive production application, and the like.

  As a result of intensive studies to solve the above problems, the present inventor contains a urethane oligomer having a (meth) acrylamide group at the terminal or side chain, N-substituted (meth) acrylamide and a non-reactive diluent. It has been found that the above-mentioned goal can be achieved by using an active energy ray-curable resin composition, and the present invention has been achieved.

That is, the present invention relates to (1) an alcohol compound (a1) having one or more hydroxyl groups in one molecule and a polyisocyanate having two or more isocyanate groups in one molecule with respect to 100% by mass of the total composition. The (meth) acrylamide urethane oligomer (A) obtained by addition reaction between the compound (a2) and the (meth) acrylamide compound (a3) having a hydroxyl group represented by the general formula (1) is 0.5 to 30.0. % By weight, N-substituted (meth) acrylamide (B) is 10.0 to 69.0% by weight and non-reactive diluent (C) is 1.0 to 80.0% by weight. Active energy ray-curable resin composition (D),
(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and R ₃ represents an alkylene group having 1 to 6 carbon atoms or a phenylene group.)
(2) The active energy ray curing according to (1) above, wherein the (meth) acrylamide compound (a3) having a hydroxyl group represented by the general formula (1) is N- (2-hydroxyethyl) acrylamide. Liquid resin composition (D),
(3) The N-substituted (meth) acrylamide (B) is a (meth) acrylamide having a hydroxyl group represented by the general formula (2), either (1) or (2) above Active energy ray-curable liquid resin composition (D),
(In the formula, R ₄ represents a hydrogen atom or a methyl group, R ₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and R ₆ represents an alkylene group having 1 to ₆ carbon atoms, or a phenylene group.)
(4) The active energy ray-curable liquid according to any one of (1) to (3), wherein the (meth) acrylamide having a hydroxyl group is N- (2-hydroxyethyl) acrylamide. Resin composition (D),
(5) The activity according to any one of (1) to (4) above, wherein the non-reactive diluent (C) is a compound containing an alkylene glycol group represented by the general formula (3) Energy ray-curable liquid resin composition (D),
Wherein R ₇ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₈ is a hydrogen atom or methyl group, R ₉ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an acetyl group, and n is 1 to Represents an integer of 100.)
(6) The non-reactive diluent (C) represented by the general formula (3) is a compound containing an ethylene glycol group, as described in any one of (1) to (5) above Active energy ray-curable liquid resin composition (D),
(7) The active energy ray curing according to any one of (1) to (6), wherein the alcohol compound (a1) having one or more hydroxyl groups in one molecule is a polyalkylene glycol. Liquid resin composition (D),
(8) Curing of the active energy ray-curable liquid resin composition according to any one of (1) to (7), wherein the non-reactive diluent (C) is 40.0 to 80.0% by mass. A pressure-sensitive adhesive containing a product,
(9) Curing of the active energy ray-curable liquid resin composition according to any one of (1) to (7), wherein the non-reactive diluent (C) is 1.0 to 40.0% by mass. An adhesive characterized by containing a product,
(10) Curing of the active energy ray-curable liquid resin composition according to any one of (1) to (7), wherein the non-reactive diluent (C) is 30.0 to 80.0% by mass. An ink containing an object,
(11) Curing of the active energy ray-curable liquid resin composition according to any one of (1) to (7), wherein the non-reactive diluent (C) is 1.0 to 25.0% by mass. A model material used for addition manufacturing, characterized by containing a product,
(12) Curing of the active energy ray-curable liquid resin composition according to any one of (1) to (7), wherein the non-reactive diluent (C) is 30.0 to 80.0% by mass. The present invention provides a support material for use in addition manufacturing, characterized by containing a product.

  According to the present invention, an alcohol compound (a1) having one or more hydroxyl groups in the molecule, a polyisocyanate compound (a2) having two or more isocyanate groups in one molecule, and a (meth) acrylamide having a hydroxyl group. The (meth) acrylamide urethane oligomer (A) obtained by addition reaction with the compound (a3) is 0.5 to 30.0% by mass, and the N-substituted (meth) acrylamide (B) is 10.0 to 69.0. By using the active energy ray-curable resin composition (D) characterized by containing 1.0% to 80.0% by mass of the mass% and the non-reactive diluent (C), the viscosity is low and the operability is low. And a curable resin composition having a high curing rate with respect to active energy rays can be provided. Moreover, by using the active energy ray-curable resin composition (D) of the present invention, it is possible to provide a molded article having no stickiness and adhesiveness without bleeding out of the non-reactive diluent. .

The present invention is described in detail below.
The (meth) acrylamide urethane oligomer (A) of the present invention is characterized by having a (meth) acrylamide group at the end or side chain of the molecule. The usage-amount of (meth) acrylamide type urethane oligomer (A) is 0.5-30 mass% with respect to the whole active energy ray-curable resin composition (D). When it is 0.5% by mass or more, the cured product obtained by polymerizing the active energy ray-curable resin composition (D) by irradiation with active energy rays has good tensile strength, hardness, elasticity, etc. This is preferable because the bleed out of the reactive diluent (C) can be suppressed. Moreover, when it is 30 mass% or less, since the viscosity of an active energy ray curable resin composition (D) is low and operativity, such as application | coating operation, is favorable, it is preferable. When the content is 1% by mass or more, the tensile strength, hardness, elasticity and the like of the cured product are further improved, and the bleedout of the non-reactive diluent (C) is further suppressed. It is more preferable because the viscosity of the curable resin composition (D) is further reduced and the operability of the coating process is further improved.

  The synthesis method of the (meth) acrylamide urethane oligomer (A) of the present invention is not particularly limited, and can be synthesized by a known urethanization reaction technique. That is, an alcohol compound (a1) having one or more hydroxyl groups in the molecule, a polyisocyanate compound (a2) having two or more isocyanate groups in one molecule, and a (meth) acrylamide compound (a3) having a hydroxyl group, It can be synthesized from the reaction of Also, a polyol and an isocyanate compound are reacted to synthesize a polyurethane having one or more isocyanate groups in the molecule, and then further reacted with an isocyanate group in the urethane compound using a (meth) acrylamide monomer having a hydroxyl group. There is a method for obtaining a target (meth) acrylamide urethane oligomer. The latter is preferable because generation of a byproduct composed of the polyisocyanate compound (a2) and the (meth) acrylamide compound (a3) having a hydroxyl group can be suppressed.

  One or more isocyanates per molecule by addition reaction of an alcohol compound (a1) having one or more hydroxyl groups in one molecule and a polyisocyanate compound (a2) having two or more isocyanate groups in one molecule. A urethane compound having a group can be obtained. Moreover, it is made to react so that the sum total of the isocyanate group of a polyisocyanate compound (a2) may become an equivalent or more with respect to the sum total of the hydroxyl group of the alcohol compound (a1) which has a 1 or more hydroxyl group in 1 molecule which can react with an isocyanate group. Among them, a method of reacting at a ratio such that the equivalent ratio (molar ratio) (hydroxyl group / isocyanate group) is 1 / 1.01 to 1 / 2.0 is preferable.

  The alcohol compound (a1) having one or more hydroxyl groups in one molecule used in the (meth) acrylamide urethane oligomer (A) of the present invention is a carbon having one or more hydroxyl groups at the terminal or side chain of the main chain skeleton. Examples thereof include alkylene glycols having 2 to 9 carbon atoms, polyalkylene glycols having 2 to 6 carbon atoms, polyester polyols, polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, and hydrogenated polyisoprene polyols. These polyols can be used individually by 1 type or in combination of 2 or more types.

  Alkylene glycol has one or more hydroxyl groups at the end or side chain of the main chain skeleton, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3- Butylene glycol, 1,4-butylene glycol, 1,5-pentane glycol, 2-methyl-1,3-propylene glycol, 2-methyl-1,4-butylene glycol, 1,6-hexanediol, 3-methyl- Examples include 1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol. These alkylene glycols can be used alone or in combination of two or more.

  The polyalkylene glycol has a hydroxyl group at the terminal or side chain containing a polyether skeleton in the molecule, and is preferably liquid at room temperature from the viewpoint of miscibility during the addition reaction. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polymethylpentane glycol, polyhexamethylene glycol, and the like, and commercially available products include, for example, P, BPX, G, T of ADEKA polyether. , EDP, AM, BM, CM, PR, GR series (made by ADEKA), PTMG series (made by Mitsubishi Chemical), PEG series, UNIOX G series, UNIOR D, TG, PB series (made by NOF Corporation), etc. Is mentioned. These polyalkylene glycols can be used alone or in combination of two or more.

  The polyester polyol is composed of a polyvalent carboxylic acid and a diol, and has hydroxyl groups at both ends or side chains including a polyester skeleton in the molecule. Examples of the polyvalent carboxylic acid component include terephthalic acid, isophthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and the diol component includes ethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonane Examples include diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol. A polyester polyol that is liquid at room temperature is preferred from the viewpoint of miscibility during the urethanization reaction in the next step. Moreover, as a commercial item, Adeka New Ace series (made by ADEKA), Kuraray polyol P, F, N series (made by Kuraray), Plaxel series (made by Daicel Chemical Industries) etc. are mentioned, for example. These polyester polyols can be used singly or in combination of two or more.

  Polycarbonate polyol is composed of a carbonyl component and a diol, and has hydroxyl groups at both ends or side chains including a carbonate skeleton in the molecule. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2- And butyl-1,3-propanediol. A polycarbonate polyol that is liquid at room temperature is preferred from the viewpoint of miscibility during the urethanization reaction in the next step. Moreover, as a commercial item, for example, Plaxel CD series (made by Daicel Chemical Industries), ETERNCOLLUH, UHC, UC, UM series (made by Ube Industries), Duranol series (made by Asahi Kasei Chemicals), NIPPOLLAN 982R (Japan) Polyurethane), Kuraray polyol series (Kuraray), and the like. These polycarbonate polyols can be used alone or in combination of two or more.

  Polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol both contain 1,4-vinyl bond and / or 1,2-vinyl bond in the molecule, or contain hydrogenated products of these vinyl groups. It is a liquid resin having a hydroxyl group at the terminal or side chain. Examples of the polybutadiene polyol include commercially available products such as NISSO-PB series (manufactured by Nippon Soda Co., Ltd.) G-1000, G-2000, G-3000, Poly bd series (manufactured by Idemitsu Kosan Co., Ltd.), R-15HT, R-45HT, Examples include Krasol series (manufactured by Clay Valley) LBH2000, LBH-P2000, LBH-3000, LBH-P3000, and the like. Examples of the hydrogenated polybutadiene polyol include GI-1000, GI-2000, GI-3000 of the NISSO-PB series (manufactured by Nippon Soda Co., Ltd.), HLBH-P2000, HLBH-P3000 of the Krasol series (manufactured by Clay Valley), and the like. Is mentioned. Examples of the polyisoprene polyol include Poly ip (manufactured by Idemitsu Kosan Co., Ltd.). Examples of the hydrogenated polyisoprene polyol include EPOL (manufactured by Idemitsu Kosan Co., Ltd.). These polybutadiene polyols can be used singly or in combination of two or more.

  In the type of alcohol compound (a1) having one or more hydroxyl groups in one molecule, a structure similar to that of the non-reactive diluent (C) is used from the viewpoint of preventing bleeding out of the non-reactive diluent (C). It is preferable to select. Since the non-reactive diluent (C) is preferably a substance containing an alkylene glycol group, the alcohol compound (a1) having one or more hydroxyl groups in one molecule is preferably a polyalkylene glycol having 2 to 4 carbon atoms.

  Examples of the polyisocyanate compound (a2) having two or more isocyanate groups in one molecule include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2- Aliphatic isocyanates such as 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 Nate, aromatic isocyanates such as 2,4-diphenylmethane diisocyanate and xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane Examples thereof include alicyclic isocyanates such as diisocyanate and 2,6-norbornane diisocyanate, and multimers such as adduct type, isocyanurate type and burette type. These polyisocyanates can be used alone or in combination of two or more.

The (meth) acrylamide compound (a3) having a hydroxyl group has the general formula (1) (wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, R ₃ represents a compound having a carbon number of 1 to 6 and a phenylene group.

Examples of the (meth) acrylamide compound (a3) having a hydroxyl group represented by the general formula (1) used in the present invention include N-hydroxymethyl (meth) acrylamide, N-methyl-N-hydroxymethyl (meta) ) Acrylamide, N-ethyl-N-hydroxymethyl (meth) acrylamide, N- (n-propyl) -N-hydroxymethyl (meth) acrylamide, N-isopropyl-N-hydroxymethyl (meth) acrylamide, N- (n -Butyl) -N-hydroxymethyl (meth) acrylamide, N- (i-butyl) -N-hydroxymethyl (meth) acrylamide, N- (t-butyl) -N-hydroxymethyl (meth) acrylamide, N- ( n-pentyl) -N-hydroxymethyl (meth) acrylamide, N- (n-he Sil) -N-hydroxymethyl (meth) acrylamide, N, N-dihydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) -N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) ( (Meth) acrylamide, N-methyl-N- (2-hydroxyethyl) (meth) acrylamide, N-ethyl-N- (2-hydroxyethyl) (meth) acrylamide, N- (n-propyl) -N- (2 -Hydroxyethyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxyethyl) (meth) acrylamide, N- (n-butyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- ( i-butyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- (t-butyl) -N -(2-hydroxyethyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxyethyl) ( (Meth) acrylamide, N, N-di (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N-methyl-N- (3-hydroxypropyl) (meth) acrylamide, N-ethyl-N- (3-hydroxypropyl) (meth) acrylamide, N- (n-propyl) -N- (3-hydroxypropyl) (meth) acrylamide, N-isopropyl-N- (3-hydroxypropyl) (Meth) acrylamide, N- (n-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N (I-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (t-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (n-pentyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (n-hexyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (hydroxymethyl) -N- (3-hydroxypropyl) (meth) Acrylamide, N- (2-hydroxyethyl) -N- (3-hydroxypropyl) (meth) acrylamide, N, N-di (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) ) Acrylamide, N-methyl-N- (2-hydroxypropyl) (meth) acrylamide, N-ethyl-N- (2-H Roxypropyl) (meth) acrylamide, N- (n-propyl) -N- (2-hydroxypropyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxypropyl) (meth) acrylamide, N- (n -Butyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (i-butyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (t-butyl) -N- (2 -Hydroxypropyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxypropyl) (meth) acrylamide N- (hydroxymethyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxyethyl) ) -N- (2-hydroxypropyl) (meth) acrylamide, N, N-di (2-hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N-methyl-N -(4-hydroxybutyl) (meth) acrylamide, N-ethyl-N- (4-hydroxybutyl) (meth) acrylamide, N- (n-propyl) -N- (4-hydroxybutyl) (meth) acrylamide, N-isopropyl-N- (4-hydroxybutyl) (meth) acrylamide, N- (n-butyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (i-butyl) -N- (4 -Hydroxybutyl) (meth) acrylamide, N- (t-butyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- ( -Pentyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (n-hexyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (hydroxymethyl) -N- (4- Hydroxybutyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (4-hydroxybutyl) (meth) acrylamide, N, N-di (4-hydroxybutyl) (meth) acrylamide, N- (2 -Hydroxybutyl) (meth) acrylamide, N-methyl-N- (2-hydroxybutyl) (meth) acrylamide, N-ethyl-N- (2-hydroxybutyl) (meth) acrylamide, N- (n-propyl) -N- (2-hydroxybutyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxybutyl) (meth) Acrylamide, N- (n-butyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (i-butyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (t-butyl ) -N- (2-hydroxybutyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxy) Butyl) (meth) acrylamide, N- (hydroxymethyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (2-hydroxybutyl) (meth) acrylamide, N , N-di (2-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N-methyl-N -(5-hydroxypentyl) (meth) acrylamide, N-ethyl-N- (5-hydroxypentyl) (meth) acrylamide, N- (n-propyl) -N- (5-hydroxypentyl) (meth) acrylamide, N-isopropyl-N- (5-hydroxypentyl) (meth) acrylamide, N- (n-butyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (i-butyl) -N- (5 -Hydroxypentyl) (meth) acrylamide, N- (t-butyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (n-pentyl) -N- (5-hydroxypentyl) (meth) acrylamide N- (n-hexyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (hydroxymethyl)- -(5-hydroxypentyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (5-hydroxypentyl) (meth) acrylamide, N, N-di (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N-methyl-N- (6-hydroxyhexyl) (meth) acrylamide, N-ethyl-N- (6-hydroxyhexyl) (meth) acrylamide, N- ( n-propyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N-isopropyl-N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-butyl) -N- (6-hydroxyhexyl) ) (Meth) acrylamide, N- (i-butyl) -N- (6-hydroxyhexyl) (meth) a Rilamide, N- (t-butyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-pentyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-hexyl) ) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (hydroxymethyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (6-hydroxy) (Hexyl) (meth) acrylamide, N, N-di (6-hydroxyhexyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, N-methyl-N- (4-hydroxyphenyl) (meta ) Acrylamide, N-ethyl-N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-propyl) ) -N- (4-hydroxyphenyl) (meth) acrylamide, N-isopropyl-N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-butyl) -N- (4-hydroxyphenyl) (meth) ) Acrylamide, N- (i-butyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (t-butyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (n- Pentyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-hexyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (hydroxymethyl) -N- (4-hydroxy) Phenyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (4-hydroxyphenyl) (meth) acrylamide N, N-di (4-hydroxyphenyl) (meth) acrylamide. (Meth) acrylamide containing these hydroxyl groups can be used alone or in combination of two or more. An acrylamide compound having a hydroxyl group in which R ₁ is a hydrogen atom is preferable because of its high curability, and N- (2-hydroxyethyl) acrylamide is particularly safe because it has low skin irritation (PII = 0). It is easy and more preferable.

  Addition reaction of urethane compound having one or more isocyanate groups in one molecule obtained by addition reaction of alcohol compound (a1) and polyisocyanate compound (a2) with (meth) acrylamide compound (a3) having a hydroxyl group In addition, it is preferable that the equivalent ratio (hydroxyl group / isocyanate group) of the total of hydroxyl groups is 1.0 or more with respect to the total of isocyanate groups. When the amount is 1.0 equivalent or more, it is preferable that all isocyanate groups of the urethane compound having an isocyanate group react and there is no possibility of causing a decrease in stability of the product due to the remaining isocyanate group.

  The urethanization reaction of the present invention has a hydroxyl group and a urethane compound obtained by a reaction between the alcohol compound (a1) and the polyisocyanate compound (a2) and an addition reaction between the alcohol compound (a1) and the polyisocyanate compound (a2). Although there exists reaction with a (meth) acrylamide compound (a3), all can mix a reaction component, raise temperature as needed, and can implement by a well-known method. This reaction is desirably performed at a temperature of 10 to 160 ° C, preferably 20 to 140 ° C. The reaction components can be mixed by a known method. Moreover, the addition of the reaction components can be carried out in several stages as desired. Moreover, although the said reaction is possible even without a solvent, it can be implemented in a reactive diluent in an organic solvent as needed. The organic solvent that can be used is not particularly limited as long as it does not react with isocyanate. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, hexane , Cyclohexane, benzene, toluene, xylene, aliphatic hydrocarbon solvents (petroleum ether, etc.) and the like. The reactive diluent that can be used is not particularly limited as long as it does not react with isocyanate, but methyl acrylate, ethyl acrylate, butyl 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, N-acryloyl Examples include morpholine. The usage-amount of an organic solvent or a reactive diluent is 0-400 mass% with respect to the total weight of the raw material component of (meth) acrylamide type urethane oligomer (A), Preferably it is 0-200 mass%.

  In such a reaction, a catalyst can be added for the purpose of promoting the reaction. Examples of the catalyst include metal salts such as sodium, potassium, nickel, cobalt, cadmium, barium, calcium and zinc of fatty acids having 8 to 20 carbon atoms such as potassium or sodium salts of alkylphosphonic acids, dibutyltin dilaurate, dioctyl. Organic tin compounds such as tin maleate, dibutyldibutoxytin, bis (2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-1,3-diacetoxydistanoxane, which may be used alone or Two or more types can be used in combination. The amount of the catalyst used is usually preferably 5% by mass or less, more preferably 1% by mass or less, based on the total weight of the raw material components of the (meth) acrylamide urethane oligomer (A).

  In order to suppress radical polymerization of the polymerizable double bond of the (meth) acrylamide monomer (a3) having a hydroxyl group, a radical polymerization inhibitor can be used as necessary. Examples of the radical polymerization inhibitor 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; N, N'-diphenyl-p-phenylenediamine, amine polymerization inhibitors such as phenothiazine, N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; dimethyldithiocarbamic acid Copper, copper diethyldithiocarbamate, dibuty Copper dithiocarbamate-based polymerization inhibitors such as copper dithiocarbamate and the like. These may be used alone or in combination of two or more thereof.

  The addition amount of these polymerization inhibitors may be appropriately set according to the type and blending amount of the (meth) acrylamide monomer having a hydroxyl group. From the viewpoints of the polymerization inhibitory effect, production convenience, and economic efficiency. Therefore, it is usually preferably 0.001 to 5 mass%, more preferably 0.01 to 1 mass%, based on the total weight of the raw material components of the (meth) acrylamide urethane oligomer (A).

  The (meth) acrylamide urethane oligomer of the present invention has a weight average molecular weight of 1,000 to 50,000, more preferably 2,000 to 20,000. When the weight average molecular weight is less than 1,000, the ratio of unsaturated groups to the molecular weight is large, and there is a possibility that the curing shrinkage of the obtained cured product cannot be sufficiently suppressed. On the other hand, when the weight average molecular weight exceeds 50,000, the viscosity becomes high and the handling property is deteriorated.

  The glass transition temperature of the (meth) acrylamide-based urethane oligomer of the present invention is not particularly specified, and can be appropriately designed by combining the alcohol compound (a1) and the polyisocyanate compound (a2) according to the application to be used. . For example, when used as an adhesive, the glass transition temperature is as low as less than 0 ° C., while when used as a coating agent, the glass transition temperature can be designed as high as 50 ° C. or higher.

  The N-substituted (meth) acrylamide used in the present invention is N-monosubstituted (meth) acrylamide N, N-disubstituted (meth) acrylamide, specifically, mono- or di-substituted alkyl (meth) acrylamide. Mono- or di-substituted alkoxylalkyl (meth) acrylamide, mono- or di-substituted (meth) acrylamide polymerizable ionic liquid, mono- or di-substituted (meth) acrylamide containing an amino group, mono- or di-substituted (meth) containing a hydroxyl group Examples include acrylamide. These N-substituted (meth) acrylamides may be used alone or in combination of two or more.

Mono- or di-substituted (meth) acrylamide containing a hydroxyl group, that is, (meth) acrylamide having a hydroxyl group is represented by the general formula (2) (wherein R ₄ is a hydrogen atom or methyl group, R ₅ is a hydrogen atom or carbon number) 1-6 alkyl group, hydroxyalkyl group, R ₆ represents a C 1-6 alkylene group, phenylene group.)

Examples of the (meth) acrylamide compound (B) having a hydroxyl group represented by the general formula (2) used in the present invention include N-hydroxymethyl (meth) acrylamide, N-methyl-N-hydroxymethyl (meta) ) Acrylamide, N-ethyl-N-hydroxymethyl (meth) acrylamide, N- (n-propyl) -N-hydroxymethyl (meth) acrylamide, N-isopropyl-N-hydroxymethyl (meth) acrylamide, N- (n -Butyl) -N-hydroxymethyl (meth) acrylamide, N- (i-butyl) -N-hydroxymethyl (meth) acrylamide, N- (t-butyl) -N-hydroxymethyl (meth) acrylamide, N- ( n-pentyl) -N-hydroxymethyl (meth) acrylamide, N- (n-hex) ) -N-hydroxymethyl (meth) acrylamide, N, N-dihydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) -N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) ( (Meth) acrylamide, N-methyl-N- (2-hydroxyethyl) (meth) acrylamide, N-ethyl-N- (2-hydroxyethyl) (meth) acrylamide, N- (n-propyl) -N- (2 -Hydroxyethyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxyethyl) (meth) acrylamide, N- (n-butyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- ( i-butyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- (t-butyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxyethyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxyethyl) (meta ) Acrylamide, N, N-di (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N-methyl-N- (3-hydroxypropyl) (meth) acrylamide, N -Ethyl-N- (3-hydroxypropyl) (meth) acrylamide, N- (n-propyl) -N- (3-hydroxypropyl) (meth) acrylamide, N-isopropyl-N- (3-hydroxypropyl) ( (Meth) acrylamide, N- (n-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- i-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (t-butyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (n-pentyl) -N- ( 3-hydroxypropyl) (meth) acrylamide, N- (n-hexyl) -N- (3-hydroxypropyl) (meth) acrylamide, N- (hydroxymethyl) -N- (3-hydroxypropyl) (meth) acrylamide N- (2-hydroxyethyl) -N- (3-hydroxypropyl) (meth) acrylamide, N, N-di (3-hydroxypropyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) Acrylamide, N-methyl-N- (2-hydroxypropyl) (meth) acrylamide, N-ethyl-N- (2-hydride Xylpropyl) (meth) acrylamide, N- (n-propyl) -N- (2-hydroxypropyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxypropyl) (meth) acrylamide, N- (n- Butyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (i-butyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (t-butyl) -N- (2- Hydroxypropyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (hydroxymethyl) -N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxyethyl) ) -N- (2-hydroxypropyl) (meth) acrylamide, N, N-di (2-hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N-methyl-N- (4-hydroxybutyl) (meth) acrylamide, N-ethyl-N- (4-hydroxybutyl) (meth) acrylamide, N- (n-propyl) -N- (4-hydroxybutyl) (meth) acrylamide, N -Isopropyl-N- (4-hydroxybutyl) (meth) acrylamide, N- (n-butyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (i-butyl) -N- (4- Hydroxybutyl) (meth) acrylamide, N- (t-butyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (n Pentyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (n-hexyl) -N- (4-hydroxybutyl) (meth) acrylamide, N- (hydroxymethyl) -N- (4-hydroxy) Butyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (4-hydroxybutyl) (meth) acrylamide, N, N-di (4-hydroxybutyl) (meth) acrylamide, N- (2- Hydroxybutyl) (meth) acrylamide, N-methyl-N- (2-hydroxybutyl) (meth) acrylamide, N-ethyl-N- (2-hydroxybutyl) (meth) acrylamide, N- (n-propyl)- N- (2-hydroxybutyl) (meth) acrylamide, N-isopropyl-N- (2-hydroxybutyl) (meth) Kurylamide, N- (n-butyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (i-butyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (t-butyl ) -N- (2-hydroxybutyl) (meth) acrylamide, N- (n-pentyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (n-hexyl) -N- (2-hydroxy) Butyl) (meth) acrylamide, N- (hydroxymethyl) -N- (2-hydroxybutyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (2-hydroxybutyl) (meth) acrylamide, N , N-di (2-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N-methyl-N- (5-hydroxypentyl) (meth) acrylamide, N-ethyl-N- (5-hydroxypentyl) (meth) acrylamide, N- (n-propyl) -N- (5-hydroxypentyl) (meth) acrylamide, N -Isopropyl-N- (5-hydroxypentyl) (meth) acrylamide, N- (n-butyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (i-butyl) -N- (5- Hydroxypentyl) (meth) acrylamide, N- (t-butyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (n-pentyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (n-hexyl) -N- (5-hydroxypentyl) (meth) acrylamide, N- (hydroxymethyl) -N (5-hydroxypentyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (5-hydroxypentyl) (meth) acrylamide, N, N-di (5-hydroxypentyl) (meth) acrylamide, N -(6-hydroxyhexyl) (meth) acrylamide, N-methyl-N- (6-hydroxyhexyl) (meth) acrylamide, N-ethyl-N- (6-hydroxyhexyl) (meth) acrylamide, N- (n -Propyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N-isopropyl-N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-butyl) -N- (6-hydroxyhexyl) (Meth) acrylamide, N- (i-butyl) -N- (6-hydroxyhexyl) (meth) act Luamide, N- (t-butyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-pentyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (n-hexyl) ) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (hydroxymethyl) -N- (6-hydroxyhexyl) (meth) acrylamide, N- (2-hydroxyethyl) -N- (6-hydroxy) (Hexyl) (meth) acrylamide, N, N-di (6-hydroxyhexyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide, N-methyl-N- (4-hydroxyphenyl) (meta ) Acrylamide, N-ethyl-N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-propyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N-isopropyl-N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-butyl) -N- (4-hydroxyphenyl) (meth) Acrylamide, N- (i-butyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (t-butyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-pentyl) ) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (n-hexyl) -N- (4-hydroxyphenyl) (meth) acrylamide, N- (hydroxymethyl) -N- (4-hydroxyphenyl) ) (Meth) acrylamide, N- (2-hydroxyethyl) -N- (4-hydroxyphenyl) (meth) acrylamide, , N- di (4-hydroxyphenyl) (meth) acrylamide. (Meth) acrylamide containing these hydroxyl groups can be used alone or in combination of two or more.
Further, an acrylamide compound having a hydroxyl group in which R ₄ is a hydrogen atom is preferable because of its high curability, and N- (2-hydroxyethyl) acrylamide is particularly safe because it has low skin irritation (PII = 0). It is easy to handle and is more preferable.

  Examples of the mono- or di-substituted alkyl (meth) acrylamide used in the present invention include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (n-propyl) (meth) acrylamide, and N-isopropyl. (Meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (i-butyl) (meth) acrylamide, N- (t-butyl) (meth) acrylamide, N- (n-pentyl) (meta ) Acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (n-dodecyl) (meth) acrylamide N- (n-octadecyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, , N-diethyl (meth) acrylamide, N, N-di (n-propyl) (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, N , N-di (i-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide, N, N-di (n-pentyl) (meth) acrylamide, N, N-di ( n-hexyl) (meth) acrylamide, N, N-di (n-heptyl) (meth) acrylamide, N, N-di (n-octyl) (meth) acrylamide, N, N-di (n-dodecyl) ( Examples include meth) acrylamide, N, N-di (n-octadecyl) (meth) acrylamide, and the like.

  Examples of the mono- or di-substituted alkoxylalkyl (meth) acrylamide used in the present invention include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, and N-ethoxy. Examples include ethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, and N- (meth) acryloylmorpholine.

  Examples of the mono- or di-substituted (meth) acrylamide containing an amino group used in the present invention include N- [3- (dimethylamino)] ethyl (meth) acrylamide, N- [3- (diethylamino)] ethyl ( (Meth) acrylamide, N- {3- [di (n-propyl) amino]} ethyl (meth) acrylamide, N- [3- (dimethylamino)] propyl (meth) acrylamide, N- [3- (diethylamino)] Examples thereof include propyl (meth) acrylamide, N- {3- [di (n-propyl) amino]} propyl (meth) acrylamide, 1- (meth) acryloyl imidazole and the like.

Examples of the mono- or di-substituted (meth) acrylamide polymerizable ionic liquid used in the present invention include (meth) acrylamide-based ammonium ions and imidazolium ions as cations and Cl ⁻ , Br ⁻ , I ^{− and the} like as anions. 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 - and inorganic acid anion or an organic acid anions of.

  The usage-amount of the N-substituted (meth) acrylamide compound (B) in this invention is 10-69 mass% with respect to the whole active energy ray-curable resin composition (D). When it is 10% by mass or more, the viscosity of the active energy ray-curable resin composition (D) is low, the operability of coating is improved, and bleeding out of the non-reactive diluent (C) can be suppressed. preferable. Moreover, when it is 69 mass% or less, since the cure shrinkage rate of the hardened | cured material obtained can be restrained low, it is preferable at 20-55 mass% with respect to the whole active energy ray-curable resin composition (D). In some cases, it is more preferable.

  The (meth) acrylamide compound (a3) having a hydroxyl group represented by the above general formula (1) and the (meth) acrylamide having a hydroxyl group represented by the above general formula (2) used in the present invention both have a hydroxyl group ( It is a meth) acrylamide compound, and different compounds may be used or the same compound may be used. Moreover, it is especially preferable to use N- (2-hydroxyethyl) acrylamide as a (meth) acrylamide compound (a3 and B) having a hydroxyl group in the entire production process from the viewpoint of simplifying the production process and improving safety.

  The non-reactive diluent (C) used in the present invention is not particularly limited as long as it does not react with the (meth) acrylamide compound and is non-polymerizable, but alkylene glycols, polyalkylene glycols, glycol ethers , Glycol esters, carboxylic acid esters, polyolefins, polyolefin derivatives, liquid polyesters, liquid polycarbonates, and the like. These non-reactive dilutions may be used alone or in combination of two or more. Can do.

  As alkylene glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentane glycol 2-methyl-1,3-propylene glycol, 2-methyl-1,4-butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl Glycol, 2-ethyl-2-butyl-1,3-propanediol and the like.

  Polyalkylene glycols include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, ditetramethylene glycol, tritetramethylene glycol, polytetramethylene glycol, dimethylpentanediol, trimethylpentanediol, Examples include polymethylpentanediol.

  As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl propyl ether, ethylene Glycol ethyl propyl ether, ethylene glycol dipropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl Glycol diethyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, Triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl propyl ether, triethylene glycol ethyl propyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, Reethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol dimethyl ether, polyethylene glycol methyl ethyl ether, polyethylene glycol diethyl ether, polyethylene glycol methyl propyl ether, polyethylene glycol ethyl propyl ether, polyethylene Glycol dipropyl ether, polyethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, Propylene glycol methyl ethyl ether, propylene glycol diethyl ether, propylene glycol methyl propyl ether, propylene glycol ethyl propyl ether, propylene glycol dipropyl ether, propylene glycol monobutyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol ethyl propyl ether Dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol methyl Ethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol ethyl propyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, Ripropylene glycol monopropyl ether, polypropylene glycol monobutyl ether, polypropylene glycol dimethyl ether, polypropylene glycol methyl ethyl ether, polypropylene glycol diethyl ether, polypropylene glycol methyl propyl ether, polypropylene glycol ethyl propyl ether, polypropylene glycol dipropyl ether, polypropylene glycol dibutyl ether, Tetramethylene glycol monomethyl ether, tetramethylene glycol monoethyl ether, tetramethylene glycol monopropyl ether, tetramethylene glycol monobutyl ether, tetramethylene glycol monopentyl ether, tetramethylene glycol dimethyl ether, Tetramethylene glycol methyl ethyl ether, tetramethylene glycol diethyl ether, tetramethylene glycol methyl propyl ether, tetramethylene glycol ethyl propyl ether, tetramethylene glycol dipropyl ether, tetramethylene glycol dibutyl ether, ditetramethylene glycol monomethyl ether, ditetramethylene Glycol monoethyl ether, ditetramethylene glycol monopropyl ether, ditetramethylene glycol monobutyl ether, ditetramethylene glycol monopentyl ether, ditetramethylene glycol dimethyl ether, ditetramethylene glycol methyl ethyl ether, ditetramethylene glycol diethyl ether, di Tetramethylene glycol Tilpropyl ether, ditetramethylene glycol ethyl propyl ether, ditetramethylene glycol dipropyl ether, ditetramethylene glycol dibutyl ether, tritetramethylene glycol monomethyl ether, tritetramethylene glycol monoethyl ether, tritetramethylene glycol monopropyl ether, Tritetramethylene glycol monobutyl ether, tritetramethylene glycol monopentyl ether, tritetramethylene glycol dimethyl ether, tritetramethylene glycol methyl ethyl ether, tritetramethylene glycol diethyl ether, tritetramethylene glycol methyl propyl ether, tritetramethylene glycol ethyl propyl Ether, tritetrame Lenglycol dipropyl ether, tritetramethylene glycol dibutyl ether, polytetramethylene glycol monomethyl ether, polytetramethylene glycol monoethyl ether, polytetramethylene glycol monopropyl ether, polytetramethylene glycol monobutyl ether, polytetramethylene glycol monopentyl ether , Polytetramethylene glycol dimethyl ether, polytetramethylene glycol methyl ethyl ether, polytetramethylene glycol diethyl ether, polytetramethylene glycol methyl propyl ether, polytetramethylene glycol ethyl propyl ether, polytetramethylene glycol dipropyl ether, polytetramethylene glycol Dibutyl ether, me Tylpentanediol monomethyl ether, methylpentanediol monoethyl ether, methylpentanediol monopropyl ether, methylpentanediol monobutyl ether, methylpentanediol monohexyl ether, methylpentanediol dimethyl ether, methylpentanediol methyl ethyl ether, methylpentanediol diethyl ether , Methylpentanediol methylpropyl ether, methylpentanediol ethylpropyl ether, methylpentanediol dipropyl ether, methylpentanediol dibutyl ether, methylpentanediol dihexyl ether, di (methylpentanediol) monomethyl ether, di (methylpentanediol) mono Ethyl ether, di (methylpentane All) monopropyl ether, di (methylpentanediol) monobutyl ether, di (methylpentanediol) monohexyl ether, di (methylpentanediol) dimethyl ether, di (methylpentanediol) methyl ethyl ether, di (methylpentanediol) diethyl Ether, di (methylpentanediol) methylpropyl ether, di (methylpentanediol) ethylpropyl ether, di (methylpentanediol) dipropyl ether, di (methylpentanediol) dibutyl ether, di (methylpentanediol) dihexyl ether, Tri (methylpentanediol) monomethyl ether, tri (methylpentanediol) monoethyl ether, tri (methylpentanediol) monopropyl ether , Tri (methylpentanediol) monobutyl ether, tri (methylpentanediol) monohexyl ether, tri (methylpentanediol) dimethyl ether, tri (methylpentanediol) methyl ethyl ether, tri (methylpentanediol) methylpropyl ether, tri ( Methylpentanediol) ethylpropyl ether, tri (methylpentanediol) dipropyl ether, tri (methylpentanediol) diethyl ether, tri (methylpentanediol) dibutylether, tri (methylpentanediol) dihexyl ether, poly (methylpentanediol) ) Monomethyl ether, poly (methylpentanediol) monoethyl ether, poly (methylpentanediol) monopropyl ether, poly ( Methylpentanediol) monobutyl ether, poly (methylpentanediol) monohexyl ether, poly (methylpentanediol) dimethylether, poly (methylpentanediol) methylethylether, poly (methylpentanediol) diethylether, poly (methylpentanediol) Examples thereof include methylpropyl ether, poly (methylpentanediol) ethylpropyl ether, poly (methylpentanediol) dipropyl ether, poly (methylpentanediol) dibutyl ether, poly (methylpentanediol) dihexyl ether and the like.

  As glycol esters, ethylene glycol methyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol methyl ether propionate, diethylene glycol ethyl ether Acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol butyl ether Acetate, polyethylene glycol methyl ether acetate, polyethylene glycol ethyl ether acetate, polyethylene glycol propyl ether acetate, polyethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate , Propylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol methyl ether propionate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol buty Ether acetate, Tripropylene glycol methyl ether acetate, Propionic acid tripropylene glycol methyl ether, Tripropylene glycol ethyl ether acetate, Tripropylene glycol propyl ether acetate, Tripropylene glycol butyl ether acetate, Polypropylene glycol methyl ether acetate, Propionic acid polypropylene glycol methyl ether , Polypropylene glycol ethyl ether acetate, polypropylene glycol propyl ether acetate, polypropylene glycol butyl ether acetate, tetramethylene glycol methyl ether acetate, tetramethylene glycol methyl ether propionate, tetramethylene glycol ethyl ether Acetate, tetramethylene glycol propyl ether acetate, tetramethylene glycol butyl ether acetate, ditetramethylene glycol methyl ether acetate, ditetramethylene glycol methyl ether propionate, ditetramethylene glycol ethyl ether acetate, ditetramethylene glycol propyl ether acetate, ditetramethylene glycol propyl ether acetate Tetramethylene glycol butyl ether acetate, tritetramethylene glycol methyl ether acetate, tritetramethylene glycol ethyl ether acetate, tritetramethylene glycol propyl ether acetate, tritetramethylene glycol butyl ether acetate, polytetramethylene glycol methyl ether acetate, dipropionic acid Tramethylene glycol propyl ether, polytetramethylene glycol ethyl ether acetate, polytetramethylene glycol propyl ether acetate, polytetramethylene glycol butyl ether acetate, methyl pentanediol methyl ether acetate, methyl pentanediol methyl ether propionate, methyl pentanediol ethyl ether acetate , Methylpentanediol propyl ether acetate, methylpentanediol butyl ether acetate, methylpentanediol hexyl ether acetate, di (methylpentanediol) methyl ether acetate, propionic acid di (methylpentanediol) methyl ether, di (methylpentanediol) ethyl ether Acetate, di Methylpentanediol) propyl ether acetate, di (methylpentanediol) butyl ether acetate, di (methylpentanediol) hexyl ether acetate, tri (methylpentanediol) methyl ether acetate, propionate tri (methylpentanediol) propyl ether, tri ( Methylpentanediol) ethyl ether acetate, tri (methylpentanediol) propyl ether acetate, tri (methylpentanediol) butyl ether acetate, tri (methylpentanediol) hexyl ether acetate, poly (methylpentanediol) methyl ether acetate, propionic acid poly (Methylpentanediol) propyl ether, poly (methylpentanediol) ethyl ether Examples include acetate, poly (methylpentanediol) propyl ether acetate, poly (methylpentanediol) butyl ether acetate, poly (methylpentanediol) hexyl ether acetate and the like.

  Carboxylic acid esters include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dihexyl phthalate, bis (2-ethylhexyl) phthalate, dioctyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate Bis (methoxyethyl) phthalate, bis (butoxyethyl) phthalate, dimethyl adipate, diethyl adipate, dipropyl adipate, dihexyl adipate, bis (2-ethylhexyl) adipate, dioctyl adipate, dinonyl adipate, Diisononyl adipate, diisodecyl adipate, diundecyl adipate, bis (methoxyethyl) adipate, bis (butoxyethyl) adipate, trimethyl trimellitic acid, triethyl trimellitic acid, trimelli Tripropyl titrate, trihexyl trimellitic acid, tri (2-ethylhexyl) trimellitic acid, trioctyl trimellitic acid, trinonyl trimellitic acid, trisononyl trimellitic acid, trisodecyl trimellitic acid, triundecyl trimellitic acid, tritrimethyl trimellitic acid (Methoxyethyl), trimellitic acid tri (butoxyethyl) and the like.

  Examples of polyolefins and polyolefin derivatives include liquid hydrogenated polybutadiene, hydroxyl-terminated liquid hydrogenated polybutadiene, liquid hydrogenated polyisoprene, and hydroxyl-terminated liquid hydrogenated polyisoprene.

  Liquid polyesters are liquid resins consisting of polyvalent carboxylic acids and diols and containing a polyester skeleton in the molecule. Polyvalent carboxylic acid components include terephthalic acid, isophthalic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid. , Dodecanedioic acid, and the like. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane. Examples include diol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, and the like. . Examples of commercially available polyols include Adeka New Ace series (manufactured by ADEKA), Kuraray polyols P, F, N series (manufactured by Kuraray), Plaxel series (manufactured by Daicel Chemical Industries), and the like.

  Liquid polycarbonates are composed of a carbonyl component and a diol, and include a carbonate skeleton in the molecule. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5 -Pentanediol, 1,9-nonanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol and the like. Examples of commercially available liquid polycarbonates include Plaxel CD series (Daicel Chemical Industries), ETERNCOLLUH, UHC, UC, UM series (Ube Industries), Duranol series (Asahi Kasei Chemicals), NIPPOLLAN 982R. (Made by Nippon Polyurethane Co., Ltd.), Kuraray polyol series (made by Kuraray Co., Ltd.) and the like.

Moreover, since it is highly compatible with (meth) acrylamide (B) having a hydroxyl group and dissolves easily, the non-reactive diluent (C) is represented by the following general formula (3) (wherein R ₇ is A hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₈ represents a hydrogen atom or a methyl group, R ₉ represents a hydrogen atom or an alkyl group or an acetyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 100.) It is preferable that it is a compound containing the alkylene glycol group shown by these. Furthermore, ethylene glycols having a hydroxyethyl group similar to the N- (2-hydroxyethyl) acrylamide are more preferred because they have excellent compatibility and do not bleed out at the same time.

  The usage-amount of the non-reactive diluent (C) used by this invention is 1-80 mass% with respect to the whole active energy ray-curable resin composition (D). When it is 1 mass% or more, the viscosity of the active energy ray-curable resin composition (D) is low and the operability such as coating is good, which is preferable. Moreover, when it is 80 mass% or less, the tensile strength, hardness, elasticity, etc. of the hardened | cured material obtained by superposing | polymerizing with an active energy ray can fully be satisfied, and a non-reactive diluent (C) does not bleed out. ,preferable.

  Moreover, when the active energy ray-curable resin composition (D) of the present invention is used as an adhesive, the content of the non-reactive diluent (C) is 40 to 80% by mass with respect to the whole (D). More preferably. Within this range, the viscosity and application operability of the active energy ray-curable resin composition (D) are good, and no bleed out of the non-reactive diluent (C) is observed in the resulting cured product. Since a flexible cured product having an A hardness of 20 or less is obtained and is excellent in adhesion and adhesiveness to the substrate, it is more preferable.

  When the active energy ray-curable resin composition (D) of the present invention is used as an adhesive, the content of the non-reactive diluent (C) is 1 to 40% by mass with respect to the whole (D). Is more preferable. Within this range, the viscosity and application operability of the active energy ray-curable resin composition (D) are good, the bleed-out of the non-reactive diluent (C) is not observed, and the rubber hardness is as high as 10 or more. This is because the cured product can have sufficient elasticity and cohesive force, and therefore has the highest adhesion to the substrate and the adhesive strength of the resulting molded product. On the other hand, if the amount of the non-reactive diluent (C) used exceeds 40% by mass, the rubber hardness of the cured product is lowered, and sufficient elasticity and cohesive force may not be imparted to the adhesive molded product. In addition, the durability may decrease over time.

When the active energy ray-curable resin composition (D) of the present invention is used as an ink, the content of the non-reactive diluent (C) is 30 to 80% by mass with respect to the whole (D). More preferred. In this range, the viscosity of the active energy ray-curable resin composition (D) is low, the operability is excellent, the adhesion of the cured ink to the substrate is excellent, and the non-reactive diluent (C) bleeds out. Since it is not recognized, it is preferable. On the other hand, when the amount of the non-reactive diluent (C) used is less than 30% by mass, the viscosity of the active energy ray-curable resin composition (D) is 100 mPa · s or more, and the ejection stability during inkjet printing is improved. There is a risk that good printing and image formation cannot be performed.
Furthermore, when the active energy ray-curable resin composition (D) of the present invention is used as an ink, the non-reactive diluent (C) is more preferably a compound containing an ethylene glycol group. In this case, since the viscosity of (D) is 30 mPa · s or less, not only is the ejection stability excellent, but the cured product is whitened, and a white cured film having high concealability can be formed without the addition of a pigment or the like. It can be suitably used as an ink.

  When the active energy ray-curable resin composition (D) of the present invention is used as a model material used for addition production, the content of the non-reactive diluent (C) is 1 to 25 with respect to the whole (D). More preferably, it is mass%. Within this range, the active energy ray-curable resin composition (D) has a low viscosity and excellent operability, and the cured molded article has good tensile strength, hardness, elasticity, etc., and the non-reactive diluent (C) Bleed-out is not recognized, and when the support agent is removed from the molded article by washing or the like, the swelling of the model agent is low and deformation or breakage of the molded article does not occur. Furthermore, when the non-reactive diluent (C) is 1 to 10% by mass, the swelling property is hardly observed, which is more preferable. On the other hand, when the usage-amount of a non-reactive diluent (C) becomes larger than 25 mass%, there exists a possibility that the tensile strength, hardness, elasticity, etc. of hardened | cured material may fall or swelling property may become high.

  When the active energy ray-curable resin composition (D) of the present invention is used as a support material for addition production, the content of the non-reactive diluent (C) is 30 to 80 mass with respect to the whole (D). % Is more preferable. Within this range, the active energy ray-curable resin composition (D) is preferable because the viscosity thereof is low, the operability is excellent, and the non-reactive diluent (C) is not bleed out from the support material after curing. Furthermore, in this range, the support material can be easily peeled from the molded product. Moreover, when it becomes 50 mass% or more, since peeling time is shortened more, it is especially preferable.

  The active energy ray-curable resin composition (D) of the present invention can be cured by irradiation with active energy rays. The active energy ray of the present invention has an energy quantum among electromagnetic waves or charged particle beams, that is, light energy such as visible light, electron beam, ultraviolet ray, infrared ray, X-ray, α-ray, β-ray, and γ-ray. Refers to a line. Examples of the active energy ray source include a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, an ultraviolet LED, an electron beam accelerator, and a radioactive element. As the active energy ray to be irradiated, ultraviolet rays are preferable from the viewpoint of storage stability of the active energy ray-curable resin composition (D), curing speed and low harmfulness.

  When the active energy ray-curable resin composition of the present invention is cured, the photopolymerization initiator (E) is not particularly necessary when an electron beam is used as the active energy ray, but visible light or ultraviolet light is used. It is necessary in some cases. The photopolymerization initiator (E) may be appropriately selected from ordinary ones such as acetophenone series, benzoin series, benzophenone series, α-amino ketone series, xanthone series, anthraquinone series, and polymeric photoinitiator series. For example, as acetophenones, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 As benzoins, benzoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzoylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal Examples of benzophenones include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, and examples of α-aminoketones include 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, 2 -Benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, xanthones include xanthone, thioxanthone, anthraquinones include anthraquinone, 2-methylanthraquinone, 2- Examples of ethyl anthraquinone and polymer photoinitiator include polymers of {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one}. These photopolymerization initiators (E) can be used alone or in combination of two or more.

  As for the usage-amount of the photoinitiator (E) used by this invention, 0.1-10 mass% is preferable with respect to the whole active energy ray-curable resin composition (D). When the content is 0.1% by mass or more, the accumulated light amount necessary for polymerizing the active energy ray-curable resin composition (D) with active energy rays is sufficient, and the residual monomer amount of the obtained cured product is sufficient. Less, good tensile strength, hardness, elasticity, etc. of the cured product. Moreover, since the bleed-out of a non-reactive diluent (C) can be suppressed, it is preferable. When the content is 10% by mass or less, the active energy ray-curable resin composition (D) has a long pot life, and troubles such as gelation during storage do not occur. More preferred is the case.

A necessary amount of active energy ray irradiation (integrated light amount) is not particularly limited. Depending on the type and amount of (meth) acrylamide compound (a3), N-substituted (meth) acrylamide (B) and photopolymerization initiator (E) having a hydroxyl group used in the active energy ray-curable resin composition (D) varies, is preferably 50 mJ / cm ² or more 1000 mJ / cm ² or less, and more preferably 200 mJ / cm ² or more 600 mJ / cm ² or less. When the integrated light quantity is 50 mJ / cm ² or more, sufficient curing proceeds, the cured product has good tensile strength, hardness, elasticity, etc., and bleed-out of the non-reactive diluent (C) is suppressed. preferable. Also, integrated light quantity When it is 1000 mJ / cm ² or less, hardly occur side reactions such as decomposition by excess energy, preferred because coloring is suppressed of the cured product, it is 200 mJ / cm ² or more 600 mJ / cm ² or less It is more preferable. Furthermore, it is particularly preferable that the integrated light amount is 600 mJ / cm ² or less because the irradiation time of the active energy ray is shortened and the productivity is improved.

The active energy ray-curable resin composition (D) of the present invention may further use an ethylenically unsaturated compound (F) other than the N-substituted (meth) acrylamide (B). Examples of the ethylenically unsaturated compound (F) include monofunctional (meth) acrylates and vinyl compounds, polyfunctional (meth) acrylates, polyfunctional (meth) acrylamides, polymerizable ionic liquids, and the like. The saturated compound (F) may be used alone or in combination of two or more. The amount of the ethylenically unsaturated compound (F) added is not particularly limited as long as it does not adversely affect the characteristics exhibited by the active energy ray-curable resin composition (D) according to the present invention. The range of 30 mass% or less is preferable with respect to the resin composition (D).

  Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth) acrylate, hydroxy Ethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meta Acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (Meth) acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylic , Cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) Acrylate, N-methylaminopropyl (meth) acrylate, N-ethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N- Diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclope Tantanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl -2-Adamantyl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate and the like.

  Examples of the vinyl compound include vinyl acetate, methyl vinyl ether, ethyl vinyl ether, styrene, N-vinyl pyrrolidone, N-vinyl caprolactam and the like.

  Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and dipropylene glycol di ( (Meth) acrylate, ditetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-he Tandiol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) Acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di (meth) acrylate, glycerin tri (meth) acrylate and glycerin alkoxy tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate Rate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) ) Acrylate, cyclohexanedimethanol di (meth) acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated hexanediol di (meth) acrylate, alkoxylated cyclohexanedimethanol di (meth) acrylate, epoxy (meth) acrylate, urethane ( Examples thereof include monomers and oligomers such as (meth) acrylate.

  Examples of the polyfunctional (meth) acrylamide include methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, diallyl (meth) acrylamide and the like.

Examples of the polymerizable ionic liquid include ionic vinyl monomers. The ionic vinyl monomer is an onium salt in which a cation and an anion are combined. Specifically, a cation is a (meth) acrylate-based or (meth) acrylamide-based ammonium ion or imidazolium ion, an anion is Cl ⁻ , Hal ion such as Br ⁻ and I ⁻ or OH ⁻ , CH ₃ COO ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , HSO ₄ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , Examples thereof include inorganic acid anions or organic acid anions such as CH ₃ C ₆ H ₆ SO ₃ ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and SCN ⁻ .

As a method for synthesizing the polymerizable ionic liquid used in the present invention, generally, a tertiary amine having a polymerizable group is converted to a quaternizing agent such as an alkyl halide, dialkyl sulfates, or methyl p-toluenesulfonate. The quaternary ammonium salt obtained by quaternization is further subjected to anion exchange using a salt having the target anion, or the quaternary ammonium salt is converted to water using an anion exchange resin. There is a method of neutralizing with an acid having the target anion after conversion to an oxide, and the details of Patent Documents 13 to 17 can be referred to for details (
JP2011-012240, JP2011-074216, JP 2011-140448 A, JP, 2011-140455, A).

  Examples of the tertiary amine having a polymerizable group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N , N-diethylaminopropyl (meth) acrylate, N- [3- (dimethylamino)] propylacrylamide and the like.

  The ions of the polymerizable ionic liquid easily form hydrogen bonds and ionic bonds with the coating substrate, and can impart conductivity and antistatic properties, improving wettability and coating more uniformly. And a film can be formed more stably. Furthermore, since the polymerizable quaternary salt ionic liquid itself is also an active energy ray-curable compound, by copolymerizing with the active energy ray-curable resin composition (D) of the present invention, it does not bleed out and becomes permanent. An auxiliary effect imparting conductivity and antistatic properties and an effect of improving adhesion can be provided.

  Various additives can be used for the active energy ray-curable resin composition (D) of the present invention as necessary. Additives include thermal polymerization inhibitors, antioxidants, antioxidants, UV sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, colorants, plasticizers, A surface lubricant, a leveling agent, a softening agent, etc. are mentioned. The addition amount of these various resins and additives is not particularly limited as long as it does not adversely affect the characteristics expressed by the active energy ray-curable resin composition (D) according to the present invention, and the active energy ray-curable resin composition. The range of 5 mass% or less is preferable with respect to the product (D).

  Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, pyrogallol, β-naphthol and the like.

  Examples of the anti-aging agent include hindered phenol-based compounds such as butylated hydroxytoluene and butylhydroxyanisole, benzotriazole-based compounds, and hindered amine-based compounds.

  Surfactants include, for example, nonylphenol polyethylene oxide adducts, lauric acid polyethylene oxide adducts, alkylene oxide addition nonionic surfactants such as stearic acid polyethylene oxide adducts, sorbitan palmitic acid monoester, sorbitan stearic acid monoester , Polyhydric alcohol type nonionic surfactants such as sorbitan stearic acid triester, fluorine-containing surfactants such as perfluoroalkylpolyethylene oxide adducts, perfluoroalkylcarboxylates and perfluoroalkylbetaines, polyether-modified silicone oils And modified silicone oils such as (meth) acrylate-modified silicone oils.

  The viscosity of the active energy ray-curable resin composition (D) of the present invention is preferably a low viscosity at which the coating operability is good. However, when the viscosity is too low, repellence or the like may easily occur during film formation. Therefore, it is preferably 1 to 2000 mPa · s at 25 ° C., and more preferably 5 to 500 mPa · s because the operability such as coating operation is further improved.

The active energy ray-curable resin composition of the present invention is made of paper, cloth, nonwoven fabric, glass, polyethylene, polypropylene, polyethylene terephthalate, diacetate cellulose, triacetate cellulose, acrylic polymer, urethane polymer, polyvinyl chloride, cellophane, celluloid, High-performance pressure-sensitive adhesive, adhesive, coating layer, ink layer, additional production by applying between active surfaces of plastics and metals such as polycarbonate and polyimide, and curing them by irradiation with active energy rays such as ultraviolet rays. An object model material and a support material for shape support can be obtained. In addition, as a method of applying this resin composition on a substrate, 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, a bar coater method, an ink jet method Ordinary coating film forming methods can be used. Moreover, as a method of apply | coating between base materials, the laminating method, the roll-to-roll method, etc. are mentioned.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following, “part” and “%” are all based on mass unless otherwise specified.

Production Example 1 Production of (Meth) acrylamide-based urethane oligomer (A-1) Polyethylene glycol having a hydroxyl group value of 374 mgKOH / g number-average molecular weight of 300 in a 300 mL Separa flask equipped with a stirrer, thermometer and reflux condenser (a1) -1) 44.07 g, methylhydroquinone (hereinafter abbreviated as MHQ) as a polymerization inhibitor 0.2 g was added, and tolylene diisocyanate (a2-1) (hereinafter abbreviated as TDI) as polyisocyanate. 38.31 g was added and reacted at 60 ° C. for 3 hours with stirring in a nitrogen atmosphere. Furthermore, 17.40 g of N- (2-hydroxyethyl) acrylamide (a3-1) as a (meth) acrylamide compound having a hydroxyl group and dibutyltin dilaurate as a catalyst (hereinafter abbreviated as DBSL) were added to this reaction product. 0.02 g was added and reacted at 60 ° C. for 3 hours, and it was confirmed by IR measurement that the absorption peak of 2230 cm ⁻¹ isocyanate group had disappeared. Thereafter, the reaction vessel was cooled to obtain a (meth) acrylamide urethane oligomer (A-1) having a weight average molecular weight of 4800.

Production Example 2 Production of (Meth) acrylamide Urethane Oligomer (A-2) Polyethylene glycol (a1) having a terminal hydroxyl group with a hydroxyl value of 374 mgKOH / g number average molecular weight of 300 in a 300 mL Separa flask equipped with a stirrer, thermometer and reflux condenser. -1) 39.83 g and MHQ 0.2 g were added, and 44.20 g of isophorone diisocyanate (a2-2) (hereinafter abbreviated as IPDI) as polyisocyanate and 0.02 g of DBSL as catalyst were added. Then, the mixture was reacted at 60 ° C. for 3 hours in a nitrogen atmosphere with stirring. Further, 15.73 g of N- (2-hydroxyethyl) acrylamide (a3-1) as a (meth) acrylamide compound having a hydroxyl group and 0.02 g of DBSL as a catalyst were added to the reaction product, and the mixture was heated at 60 ° C. for 3 hours. It reacted and it confirmed that the absorption peak of the isocyanate group of 2230cm < ^-1 > disappeared by IR measurement. Thereafter, the reaction vessel was cooled to obtain a (meth) acrylamide urethane oligomer (A-2) having a weight average molecular weight of 5000.

Production Examples 3, 4, 6-8 Production of (meth) acrylamide urethane oligomers (A-3), (A-4), (A-6) to (A-8) Production with the composition shown in Table 1 By performing the same operation as in Example 2, the (meth) acrylamide urethane oligomers (A-3), (A-4) and (A-6) to (A-8) having the number average molecular weights shown in Table 1 were obtained. Obtained.

Production Example 5 Production of (meth) acrylamide urethane oligomer (A-5) Polyethylene glycol having a terminal hydroxyl group with a hydroxyl value of 374.0 mgKOH / g number average molecular weight of 300 in a 300 mL Separ flask equipped with a stirrer, thermometer and reflux condenser. (A1-1) 22.82 g and MHQ 0.1 g were added, and further 50.0 g of diethylene glycol ethyl ether acetate was added and stirred until uniform. Thereto, 19.16 g of hexamethylene diisocyanate (a2-3) (hereinafter abbreviated as HDI) as polyisocyanate and 0.01 g of DBSL as catalyst were added and reacted at 60 ° C. for 3 hours in a nitrogen atmosphere with stirring. I let you. Furthermore, 7.90 g of 2-hydroxymethylacrylamide (a3-2) as a (meth) acrylamide compound having a hydroxyl group and 0.01 g of DBSL as a catalyst were added to this reaction product, and reacted at 60 ° C. for 3 hours. It was confirmed by IR measurement that the absorption peak of the isocyanate group at 2230 cm ⁻¹ disappeared. Thereafter, the reaction vessel was cooled to obtain a diethylene glycol ethyl ether acetate solution containing 50% by mass of a (meth) acrylamide urethane oligomer (A-5) having a weight average molecular weight of 13600.

Production Example 9 Production of (Meth) acrylamide-Based Urethane Oligomer (A-9) By performing the same operations as in Production Example 3 with the composition shown in Table 1, the (meth) acrylamide type having the number average molecular weight shown in Table 1 A solution of urethane oligomer (A-9) was obtained.

Molecular weight measurement The weight average molecular weight of the obtained (meth) acrylamide-based urethane oligomer was measured using high performance liquid chromatography (LC-10A manufactured by Shimadzu Corporation) and the column was Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm), and three in series are eluted Tetrahydrofuran was used as the liquid.) And was calculated in terms of standard polystyrene molecular weight.

Table 1

Explanation of Abbreviations in Table 1 A: (Meth) acrylamide-based urethane oligomer a1: Alcohol compound a1-1 having one or more hydroxyl groups in one molecule: polyethylene glycol having a number average molecular weight of 300 and a hydroxyl value of 373 mgKOH / g PEG300 (manufactured by Toho Chemical Co., Ltd.)
a1-2: Uniol D1000 (manufactured by NOF Corporation), which is 1,2-polypropylene glycol having a number average molecular weight of 1000 and a hydroxyl value of 112 mgKOH / g
a1-3: 1,6-hexanediol (hydroxyl value 948 mgKOH / g)
a1-4: GI-1000 (Nippon Soda Co., Ltd.), a hydrogenated polybutadiene having a hydroxyl group obtained by hydrogenating a polybutadiene having a number average molecular weight of 1500, a hydroxyl value of 75 mgKOH / g, and a 1,2-polybutadiene structure having a content of 80% by mass or more. Company-made)
a1-5: Kuraray polyol P510 (made by Kuraray Co., Ltd.) which is a polyester diol composed of methylpentanediol / adipic acid having a number average molecular weight of 500 and a hydroxyl value of 224 mgKOH / g
a1-6: Kuraray polyol C1090 (manufactured by Kuraray Co., Ltd.), which is a polycarbonate diol comprising methylpentanediol / 1,6-hexanediol = 9/1 having a number average molecular weight of 1000 and a hydroxyl value of 112 mgKOH / g
a2: 1 Polyisocyanate compound having two or more isocyanate groups in the molecule a2-1: Tolylene diisocyanate (TDI) (2,4-tolylene diisocyanate 80% and 2,6-tolylene diisocyanate 20% blend)
a2-2: Isophorone diisocyanate (IPDI)
a2-3: 1,6-hexamethylene diisocyanate (HDI)
a3: (meth) acrylamide compound having a hydroxyl group a3-1: N- (2-hydroxyethyl) acrylamide a3-2: N-hydroxymethylacrylamide a3-3: N- (4-hydroxyphenyl) methacrylamide EDGAc: diethylene glycol ethyl Ether acetate MHQ: Methyl hydroquinone DBSL: Dibutyltin dilaurate

Example 1
7.0 parts by mass of (meth) acrylamide urethane oligomer (A-1) produced in Production Example 1, 10.0 parts by mass of N- (2-hydroxyethyl) acrylamide (B-1), Uniol D400 (number average molecular weight) 400, 1,2-polypropylene glycol (manufactured by NOF Corporation)) (C-1) 80.0 parts by mass, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd.)) (E-1) 3.0 parts by mass of each was charged into a container and stirred at 25 ° C. for 1 hour to obtain a uniform and transparent active energy ray-curable resin composition (D-1).

Examples 2-9, 11-15, 17, 18, 20, 22
By performing the same operations as in Example 1 with the compositions shown in Table 2, the active energy ray-curable resin compositions (D-2) to (D-9) and (D-11) having the compositions shown in Table 2 are used. ) To (D-15), (D-17), (D-18), and (D-20) to (D-22) were obtained.

Example 10
10.0 mass parts ((meth) acrylamide urethane oligomer (A-5) 5.0 mass) of 50 mass% diethylene glycol ethyl ether acetate solution of (meth) acrylamide urethane oligomer (A-5) produced in Production Example 5 Parts, diethylene glycol ethyl ether acetate (C-7) 5.0 parts by mass), N- (2-hydroxyethyl) acrylamide (B-1) 69.0 parts by mass, Uniol D1000 (1,2-number average molecular weight 1000 1,2- Polypropylene glycol (manufactured by NOF Corporation)) (C-6) 20.0 parts by mass, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd.)) (E-1) 1.0 part by mass Each container is charged into a container and stirred at 25 ° C for 1 hour to obtain a uniform transparent Give sexual energy ray-curable resin composition (D-10).

Example 16
20.0 parts by mass of a (meth) acrylamide urethane oligomer (A-5) 50% by mass diethylene glycol ethyl ether acetate solution produced in Production Example 5 (1) ((meth) acrylamide urethane oligomer (A-5) 10.0 mass) Parts, diethylene glycol ethyl ether acetate (C-7) 10.0 parts by mass), N- (2-hydroxyethyl) acrylamide (B-1) 20.0 parts by mass, diethylene glycol ethyl ether acetate (C-7) 59.0 Uniform transparent activity by charging 1.0 parts by mass of IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd.)) (E-1) into a container and stirring at 25 ° C. for 1 hour. An energy ray curable resin composition (D-16) was obtained.

Example 19
20.0 parts by mass of a (meth) acrylamide urethane oligomer (A-9) 50% by mass diethylene glycol ethyl ether acetate solution produced in Production Example 9 ((meth) acrylamide urethane oligomer (A-9) 10.0 mass) Parts, diethylene glycol ethyl ether acetate (C-7) 10.0 parts by mass), N- (2-hydroxyethyl) acrylamide (B-1) 20.0 parts by mass, diethylene glycol ethyl ether acetate (C-7) 50.0 Uniform transparent activity by charging 10.0 parts by mass of IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone (BASF Japan Ltd.)) (E-1) in a container and stirring at 25 ° C. for 1 hour. Obtaining energy ray-curable resin composition (D-19) .

Comparative Examples 1-8
By performing the same operations as in Example 1 with the compositions shown in Table 2, Comparative Examples (H-1) to (H-8) of active energy ray-curable resin compositions having the compositions shown in Table 2 are obtained. It was. Here, Comparative Example 1 is Example 2-2 described in Patent Document 9 (Japanese Patent Laid-Open No. 2012-111226), and Comparative Example 2 is an example described in Patent Document 10 (Japanese Patent Laid-Open No. 2010-155889). 9 was used as a reference.

Table 2

Explanation of abbreviations in Table 2 B: N-substituted (meth) acrylamide compound B-1: N- (2-hydroxyethyl) acrylamide B-2: N- (2-hydroxyethyl) methacrylamide B-3: N- Ethylacrylamide B-4: N-Acroylmorpholine B-5: 1-Propanaminium, N, N, N-trimethyl-3-[(1-oxo-2-propen-1-yl) amino]-, 4 -Methylbenzenesulfonate C: Non-reactive diluent C-1: Uniol D400 (manufactured by NOF Corporation) which is 1,2-polypropylene glycol having a number average molecular weight of 400
C-2: Ethylene glycol C-3: PEG200 (manufactured by Toho Chemical Co., Ltd.) which is a polyethylene glycol having a number average molecular weight of 200
C-4: Propylene glycol C-5: Diethylene glycol ethyl ether C-6: Uniol D1000 (manufactured by NOF Corporation) which is 1,2-polypropylene glycol having a number average molecular weight of 1000
C-7: Diethylene glycol ethyl ether acetate C-8: Bis (2-ethylhexyl) phthalate
C-9: ethylene glycol dimethyl ether C-10: ethylene glycol butyl ether acetate C-11: dimethyl phthalate E: photopolymerization initiator E-1: 1-hydroxycyclohexyl phenyl ketone (IRGACURE 184 (manufactured by BASF Japan Ltd.))
E-2: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (IRGACURE 2959 (manufactured by BASF Japan Ltd.))
E-3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE TPO (manufactured by BASF Japan Ltd.))
F: Ethylene biounsaturated compound other than B F-1: 4-hydroxybutyl acrylate F-2: Isobornyl acrylate F-3: 2-hydroxyethyl methacrylate G: Other additives G-1: Emanone 1112 (laurin Acid polyethylene oxide (12E.O.) adduct (manufactured by Kao Corporation))
G-2: KF-6011 (polyethylene oxide (11E.O.) methyl ether dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd.))
G-3: Diacrylate of polyethylene glycol (molecular weight 1000) (manufactured by Sartomer)
G-4: 2,4-diphenyl-4-methyl-pentene

  Evaluation of the active energy ray-curable resin compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 8 was carried out by the following methods, and the results are shown in Tables 3 to 7.

Viscosity measurement Cone plate type viscometer (device name: RE550 type viscometer manufactured by Toki Sangyo Co., Ltd.) was used and obtained in each example and comparative example at 25 ° C. according to JIS K5600-2-3. The viscosity of the active energy ray-curable resin composition was measured.

Curability A 75 μm-thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) (with the treated surface on the front) is adhered to a horizontally placed glass plate, and each example and comparative example is used with a bar coater. The obtained active energy ray-curable resin composition was applied to a thickness of 50 μm and irradiated with ultraviolet rays in the air (apparatus: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: M04 manufactured by iGraphics). -L41, UV illuminance 300 mW / ^cm 2, accumulated light quantity 200 mJ / cm ² in one pass), and the active energy ray curable resin composition was measured number of passes to be cured. The curing described here is a state in which the surface of the coating film is not sticky.

Measurement of rubber hardness of the cured product A 75 μm thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) was adhered to a horizontally placed glass plate, and a spacer with a thickness of 1 mm and an interior of 60 mm × 90 mm was installed. After filling the inside of the spacer with the active energy ray-curable resin composition obtained in each Example and Comparative Example, a 50 μm-thick lightly peeled PET film (polyester film E7002 manufactured by Toyobo Co., Ltd.) is further formed thereon. (Equipment: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by iGraphics, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity in one pass: 200 mJ / cm ² And the active energy ray-curable resin composition was cured. The number of passes for irradiating ultraviolet rays was the number of passes obtained in the above item 91. Thereafter, six cured products prepared by removing the peeled PET films on both sides were stacked, and the Shore A hardness was measured according to JIS K6253 “Rubber Hardness Test Method”.

Bleed-out resistance A 75 μm-thick heavy release PET film (polyester film E7001 manufactured by Toyobo Co., Ltd.) is adhered to a horizontally placed glass plate, and a spacer having a thickness of 1 mm and an inside of 20 mm × 40 mm is installed. After filling the active energy ray-curable resin composition obtained in each Example and Comparative Example inside, a 50 μm-thick lightly peeled PET film (Toyobo Co., Ltd., polyester film E7002) is stacked thereon. , Irradiated with ultraviolet rays (apparatus: made by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: made by igraphics M04-L41, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity in one pass 200 mJ / cm ² ) The active energy ray-curable resin composition was cured. The number of passes for irradiating ultraviolet rays was the number of passes obtained in the above item 91. Then, the cured product prepared by removing the peeled PET film on both sides was used as a test piece, and left in a constant temperature and humidity chamber set at 25 ° C. and 50% RH for 168 hours. Evaluation was performed.
A: Bleed-out product is not observed before and after standing.
○: Bleed-out is not seen before standing, but bleed-out is slightly observed after standing.
(Triangle | delta): Bleed out is recognized slightly before leaving still, and a bleed-out thing is recognized slightly after leaving still.
X: Bleed-out is slightly observed before standing, and bleed-out product is intensely observed after standing.

Adhesion to glass A 100 μm-thick surface-treated PET film (polyester film A4100, manufactured by Toyobo Co., Ltd.) (treated surface is the surface) was placed in close contact with a horizontally placed glass plate, and each example and comparative example was compared with a bar coater. The active energy ray-curable resin composition obtained in the above is applied to a thickness of 50 μm and irradiated with ultraviolet rays in the air (apparatus: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: manufactured by iGraphics) M04-L41, integral light quantity of ultraviolet illuminance 300 mW / ^cm 2, 1 pass 200 mJ / cm ^2), and curing the active energy ray curable resin composition. Moreover, the adhesive sheet was obtained by making the number of passes of irradiating ultraviolet rays the number of passes obtained in the above item 91. The obtained sheet member was cut into a size of 25 × 100 mm, and the exposed adhesive member surface was bonded to a float glass having a width of 30 mm × length of 100 mm × thickness of 2.0 mm without entrainment of bubbles to obtain a test piece. Next, the test piece was placed in an autoclave and treated at 40 ° C. and 0.5 MPa for 30 minutes. After taking out from the autoclave and leaving the test pieces for 24 hours under conditions of 23 ° C. and 50% humidity, 180 ° peeling at 23 ° C. and 50% humidity using a tensile tester (Autograph AGXS-X 500N manufactured by Shimadzu Corporation). The sheet member was peeled from the glass interface at an angle of 300 mm / min, and the adhesive strength (N / 25 mm) to the glass plate was measured.
A: 10.0 (N / 25 mm) or more ○: 5.0 (N / 25 mm) or more, less than 10.0 (N / 25 mm) Δ: 1.0 (N / 25 mm) or more, 5.0 (N / Less than 25 mm) x: less than 1.0 (N / 25 mm)

Adhesion to PET A 100 μm thick surface-treated PET film (Polyester film A4100, manufactured by Toyobo Co., Ltd.) (treated surface is the surface) was adhered to a horizontally placed glass plate and compared with each example using a bar coater. The active energy ray-curable resin composition obtained in the example was applied to a thickness of 50 μm and irradiated with ultraviolet rays in the air (apparatus: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: igraphics) Ltd. M04-L41, UV illuminance 300 mW / ^cm 2, accumulated light quantity 200 mJ / cm ² in one pass), and curing the active energy ray curable resin composition. Further, the cured product sheet was obtained by setting the number of passes of irradiating ultraviolet rays as the number of passes obtained in 91 above. After leaving the obtained sheet member under the condition of 23 ° C. and 50% humidity for 24 hours, 100 squares of 1 mm square were prepared according to JIS K 5600, and cellophane tape [manufactured by Nichiban Co., Ltd., CT24] was used, and was adhered to the cured product layer and then peeled off. For the adhesion to PET, the number of squares not peeled out of 100 squares was expressed as OO / 100. For example, it was expressed as 100/100 when not peeling at all, and 0/100 when peeling completely.

Adhesion to polymethylmethacrylate (PMMA) plate The active energy ray-curable resin composition obtained in each example and comparative example was applied to a thickness of 50 μm with a bar coater on a 1 mm thick PMMA plate installed horizontally. UV irradiation under air (apparatus: made by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: made by iGraphics M04-L41, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity in one pass: 200 mJ / Cm ² ) to cure the active energy ray-curable resin composition. Further, the cured product sheet was obtained by setting the number of passes of irradiating ultraviolet rays as the number of passes obtained in 91 above. After leaving the obtained sheet member under the condition of 23 ° C. and 50% humidity for 24 hours, 100 squares of 1 mm square were prepared according to JIS K 5600, and cellophane tape [manufactured by Nichiban Co., Ltd., CT24] was used, and was adhered to the cured product layer and then peeled off. For the adhesiveness to PMMA, the number of squares not peeled out of 100 squares was expressed as OO / 100. For example, it was expressed as 100/100 when not peeling at all, and 0/100 when peeling completely.

Adhesiveness to polarizing film Each example and comparative example are sandwiched between two acrylic films by using a table-type roll laminator (RSL-382S manufactured by Royal Sovereign). The active energy ray-curable resin composition obtained in (1) was bonded to a thickness of 10 μm. Ultraviolet rays are irradiated from the upper surface of the obtained laminated film (device: Inverter type conveyor device ECS-4011GX manufactured by Eye Graphics, metal halide lamp: M04-L41 manufactured by Eye Graphics, ultraviolet illuminance: 700 mW / cm 2, integrated light amount: 1000 mJ / cm 2 And a polarizing plate having an acrylic film on both sides of the polarizing film was prepared. The obtained polarizing plate was cut into 20 mm × 150 mm under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and a double-sided adhesive tape was used for a test plate attached to a tensile tester (manufactured by Shimadzu Autograph AGXS-X 500N). And pasted. A piece of acrylic film and polarizing film that is not attached with a double-sided adhesive tape is peeled off about 20 to 30 mm in advance, chucked to the upper gripping tool, and peeled at 90 ° at a peeling speed of 300 mm / min (N / 20 mm). ) Was measured.
A: 3.0 (N / 20 mm) or more B: 1.5 (N / 20 mm) or more, less than 3.0 (N / 20 mm) Δ: 1.0 (N / 20 mm) or more, 1.5 (N / Less than 20 mm) x: less than 1.0 (N / 20 mm)

Swellability After peeling the cured product obtained by the method described in 93 above from the peeled PET, the cured product was immersed in 25 ° C. ion exchange water for 24 hours, and then the length of the long side of the cured product was measured. Was used to calculate the swelling ratio.
Swell ratio (%) = {length of cured product after immersion (mm) −length of cured product before immersion (mm)} / length of cured product before immersion (mm) × 100

Detergency
A PMMA plate with a thickness of 1 mm and a spacer with a thickness of 30 mm x 40 mm are installed on a horizontally installed PMMA plate, and the active energy ray-curable resin composition obtained in each of the examples and comparative examples is filled inside the spacer. After that, ultraviolet rays are irradiated (apparatus: manufactured by iGraphics, inverter type conveyor device ECS-4011GX, metal halide lamp: M04-L41 manufactured by iGraphics, ultraviolet illuminance of 300 mW / cm ² , integrated light quantity of 200 mJ / cm ^{2 in} one pass. And the active energy ray-curable resin composition was cured. The number of passes for irradiating ultraviolet rays was the number of passes obtained in the above item 91. Then, the hardened | cured material on the obtained PMMA board was wash | cleaned with the water flow, the peeling state from the PMMA board of hardened | cured material was confirmed, and the following evaluation method evaluated.
(Double-circle): Hardened | cured material is not sticking to a PMMA board, and peels easily from a PMMA board without a residue.
○: The cured product is removed from the PMMA plate by washing with water, and no residue derived from the cured product is observed.
(Triangle | delta): Although hardened | cured material is removed from a PMMA board by water washing, the residue derived from hardened | cured material is seen.
X: Hardened | cured material does not peel from a PMMA board in water washing.

Table 3

As is clear from the results in Table 3, the active energy ray-curable resin compositions (D-1) to (D-8) obtained in Examples 1 to 8 have a viscosity of 500 mPa · s or less at 25 ° C. Yes, excellent in film formability and smoothness, bleed-out of the non-reactive diluent is suppressed, and the Shore A hardness of the cured product is 10 or less. , 8 shows the adhesive strength to a glass of 5 N / 25 mm or more, and Examples 2, 3, 5, and 7 show the adhesive strength to a glass of 10 N / 25 mm or more, and can be suitably used as an adhesive. On the other hand, in Comparative Example 1 corresponding to Example 2-2 described in Patent Document 9 (Japanese Patent Application Laid-Open No. 2012-111226), a (meth) acrylamide urethane oligomer is not used and a sufficient crosslinked structure is formed. Since it was not possible, a large amount of non-reactive diluent bleed-out was observed, resulting in a cured product having no tackiness. In Comparative Example 2 corresponding to Example 9 described in Patent Document 10 (JP 2010-155889 A), SR-740A (polyethylene glycol (molecular weight 1000)) diacrylate (Sartomer) instead of (meth) acrylamide urethane oligomer )) And a chain transfer agent. For this reason, although the viscosity is low, the molecular weight of the cured product is not increased by the chain transfer agent, the cured product is brittle, and sufficient strength cannot be maintained, so that tackiness is not observed. Although Comparative Example 3 shows good tackiness, since a hydroxybutyl acrylate was used instead of N-substituted (meth) acrylamide, an amount of accumulated light of 2000 mJ / cm ² was required for curing, and a composition with poor curability was obtained. It has become. In Comparative Example 4, since hydroxyethyl methacrylate was used instead of (meth) acrylamide having a hydroxyl group, physical properties could not be evaluated without curing even with an integrated light amount of 5000 mJ / cm ² . In Comparative Example 5 in which a non-reactive diluent (C) is not used and in Comparative Example 6 in which a large amount of (meth) acrylamide-based urethane oligomer (A) is introduced, the viscosity is 2000 mPa · s or more, and operations such as application of a resin composition are performed. The nature was bad. In Comparative Examples 5, 6, and 8 in which the amount of the non-reactive diluent used is less than 40% by mass, the Shore A hardness of the cured product is as high as 30 or more, and the composition is not applied as an adhesive. It was. In Comparative Example 7 in which the amount of non-reactive diluent (C) used is an excessive amount of 87% by mass, the monomer concentration is low, so that an integrated light amount of 2000 mJ / cm ² is required for curing. There was a problem that bleeding out was observed and the adhesiveness was as low as 5 N / 25 mm or less.

Table 4

As is clear from the results in Table 4, the active energy ray-curable resin compositions (D-9) to (D-15) obtained in Examples 9 to 15 have a viscosity of 1000 mPa · s or less at 25 ° C. It has excellent coating operability, formability and smoothness, and exhibits high curability that can be cured by UV irradiation at 600 mJ / cm ² or less even in the presence of oxygen, and at the same time, suppresses bleeding out of non-reactive diluents. Has been. In addition, it shows good adhesion and adhesion to PET and PMMA base materials, and it can be seen that it is suitably used as an adhesive. On the other hand, in Comparative Example 1, a large amount of non-reactive diluent bleed out was observed, and adhesion and adhesive strength were also low. In Comparative Example 2, the cured product was brittle, no adhesion was observed, and sufficient adhesive strength was not exhibited. In Comparative Example 5 in which the non-reactive diluent (C) was not used, the viscosity of the composition was high and the coating film operability was poor. Moreover, since the plastic effect by a non-reactive diluent was not seen, resin became brittle and adhesiveness and adhesiveness were inadequate. In Comparative Example 6, good adhesion to PET and PMMA was observed, but the viscosity of the composition was 5000 mPa · s or more, and the coating operability, uniformity and adhesive strength were poor. In Comparative Example 7 in which the amount of the non-reactive diluent (C) used was as high as 87% by mass, the curability was inferior due to the low monomer concentration, and bleeding out of the non-reactive diluent was observed. It was not possible to adhere to or adhere to PMMA.

Table 5

As is clear from the results in Table 5, the active energy ray-curable resin compositions (D-15) to (D-17) obtained in Examples 15, 16, and 17 have a viscosity of 30 mPa · s or less at 25 ° C. Since it has a viscosity, it can provide good ejection properties as an inkjet ink. Further, it has high curability that can be cured by irradiation with ultraviolet rays of 200 mJ / cm ² even in the presence of oxygen, and is excellent in drying property as a UV curable ink. Furthermore, since these resin compositions have high adhesion to PET and do not cause bleed-out of non-reactive diluents, they are suitably used for printing on paper, PET films, etc., and can suppress bleeding and transfer of printed products. . The resin compositions of Examples 15 to 17 can be suitably used as a UV curable inkjet ink for recording because they can be whitened by curing and can form a highly concealed white cured film without the addition of a pigment or the like. . On the other hand, in Comparative Examples 1, 2 and 7, the viscosity of the composition at 25 ° C. is 30 mPa · s or more, and the ink-jet ink is not satisfactory in ejection properties, and the viscosity of Comparative Examples 5 and 6 is 2000 mPa. -Since it was more than s, there was also a problem in coating suitability and smoothness. Further, in Comparative Examples 1 and 7, a large amount of non-reactive diluent bleed out was observed, and there was a problem that good drying property and bleed resistance were not obtained as an ink.

Table 6

As is apparent from the results in Table 6, in Examples 11, 12 and 18, the obtained active energy ray-curable resin compositions (D-11), (D-12) and (D-18) were 25 It has a viscosity of 1000 mPa · s or less at ° C, is excellent in operability, and has high curability that can be cured by irradiation with 200 mJ / cm ² of ultraviolet rays even in the presence of oxygen. The cured product has a Shore A hardness of 60 or more, can provide sufficient hardness, and bleed-out of non-reactive diluent is also suppressed. Furthermore, since the swellability with respect to water is suppressed to 5% or less in 24 hours, sufficient shape-retaining properties can be expected without deformation even in the washing step of removing the support material after the production. On the other hand, since Comparative Example 3 used hydroxybutyl acrylate instead of N-substituted (meth) acrylamide, it required an integrated light amount of 2000 mJ / cm ² for curing, and the curability was insufficient as a model material. . The viscosity of the resin compositions of Comparative Examples 5 and 6 was as high as 2000 mPa · s or more, and the operability of the molding process and the delicateness of the molded product were relatively poor. Further, in Comparative Example 7 in which the amount of the non-reactive diluent used was 87% by mass, the cured product was dissolved in water, and the swelling rate could not be measured, indicating that it could not be used as a model material. In Comparative Example 8, the amount of N-substituted (meth) acrylamide was as large as 73% by mass, so that the swelling ratio with respect to water was high, the deformation of the support material in the washing process was large, and it was not suitable for the model material.

Table 7

As is clear from the results in Table 7, the active energy ray-curable resin compositions (D-16) and (D-19) to (D-22) obtained in Examples 16 and 19 to 22 were 25 ° C. The viscosity is 500 mPa · s or less, is excellent in operability, and has high curability that can be cured by ultraviolet irradiation at 1000 mJ / cm ² or less even in the presence of oxygen. The cured product has suppressed bleed-out of non-reactive diluent, and adheres to methacrylic resin (PMMA) used in addition production, but is easily peelable by washing with water, and easy washing in addition production. It can be seen that it can be used as a support material. On the other hand, the cured product of Comparative Example 1 was easily dissolved by washing, and most of the cured product could be removed from the model material. However, oil droplets remained on the surface of the model material and the side surfaces of the gaps, and the surface of the molded product And there was a dirt problem in the internal gap. In Comparative Example 2, the cured product is fragile, and most of the support material collapses at high speed due to washing or the like, and cannot be completely removed at the delicate portion, and remains attached to the model material surface, particularly in the gap. There was a result that was extremely unfavorable as a support material.

As described above, the active energy ray-curable resin composition of the present invention has 0.5 to 30.0% by mass of (meth) acrylamide urethane oligomer (A) with respect to 100% by mass of the total composition. , N-substituted (meth) acrylamide (B) 10.0 to 69.0% by mass and non-reactive diluent (C) 1.0 to 80.0% by mass, so that it is 1000 mPa · s or less at 25 ° C. The active energy ray-curable resin composition having excellent operability can be obtained. Further, by containing the (meth) acrylamide urethane oligomer (A), the cured product can have a crosslinked structure, and a cured product in which bleeding out of the non-reactive diluent is suppressed can be obtained. Further, by using N-substituted (meth) acrylamide (B), an active energy ray-curable resin composition having excellent curability that can be cured by irradiation with ultraviolet rays of 1000 mJ / cm ² or less even in the presence of oxygen. be able to. Furthermore, by controlling the addition amount of the non-reactive diluent (C), a cured product can be obtained in which tackiness and adhesion are imparted, viscosity is further reduced, swelling with respect to water and release from an acrylic resin are controlled. be able to. Furthermore, by using a mixture of monofunctional, polyfunctional monomers, ionic monomers, active energy ray polymerization initiators, pigments, etc. as necessary, pressure-sensitive adhesives, adhesives, electronic materials, inks, coating agents, light It can be suitably used for curable resist applications and additive manufacturing applications.

Claims (12)

An alcohol compound (a1) having one or more hydroxyl groups in one molecule, a polyisocyanate compound (a2) having two or more isocyanate groups in one molecule, and a general formula with respect to 100% by mass of the total amount of the composition The (meth) acrylamide urethane oligomer (A) obtained by addition reaction with the (meth) acrylamide compound (a3) having a hydroxyl group represented by (1) is 0.5 to 30.0% by mass, N-substituted (meta ) Acrylamide (B) contains 10.0 to 69.0% by mass and non-reactive diluent (C) contains 1.0 to 80.0% by mass. (D).
(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and R ₃ represents an alkylene group having 1 to 6 carbon atoms or a phenylene group.) 2. The active energy ray-curable liquid resin composition according to claim 1, wherein the (meth) acrylamide compound (a3) having a hydroxyl group represented by the general formula (1) is N- (2-hydroxyethyl) acrylamide. Object (D). The activity according to claim 1, wherein the N-substituted (meth) acrylamide (B) is (meth) acrylamide having a hydroxyl group represented by the general formula (2). Energy ray-curable liquid resin composition (D).
(In the formula, R ₄ represents a hydrogen atom or a methyl group, R ₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and R ₆ represents an alkylene group having 1 to ₆ carbon atoms, or a phenylene group.) The active energy ray-curable liquid resin composition (D) according to any one of claims 1 to 3, wherein the (meth) acrylamide having a hydroxyl group is N- (2-hydroxyethyl) acrylamide. . The active energy ray-curable liquid resin according to any one of claims 1 to 4, wherein the non-reactive diluent (C) is a compound containing an alkylene glycol group represented by the general formula (3). Composition (D).
Wherein R ₇ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₈ is a hydrogen atom or methyl group, R ₉ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an acetyl group, and n is 1 to Represents an integer of 100.) 6. The active energy ray-curable liquid according to claim 1, wherein the non-reactive diluent (C) represented by the general formula (3) is a compound containing an ethylene glycol group. Resin composition (D). The active energy ray-curable liquid resin composition according to any one of claims 1 to 6, wherein the alcohol compound (a1) having one or more hydroxyl groups in one molecule is a polyalkylene glycol. D). A non-reactive diluent (C) is 40.0-80.0 mass%, containing the hardened | cured material of the active energy ray-curable liquid resin composition as described in any one of Claims 1-7. Characteristic adhesive. A non-reactive diluent (C) is 1.0-40.0 mass%, containing the hardened | cured material of the active energy ray-curable liquid resin composition as described in any one of Claims 1-7. Features an adhesive. A non-reactive diluent (C) is 30.0-80.0 mass%, containing the hardened | cured material of the active energy ray-curable liquid resin composition as described in any one of Claims 1-7. Characteristic ink. A non-reactive diluent (C) is 1.0-25.0 mass%, containing the hardened | cured material of the active energy ray-curable liquid resin composition as described in any one of Claims 1-7. Model material used for additional manufacturing applications. A non-reactive diluent (C) is 30.0-80.0 mass%, containing the hardened | cured material of the active energy ray-curable liquid resin composition as described in any one of Claims 1-7. Support material used for special additive manufacturing applications.