JP6425986B2 - Urethane (meth) acrylate, active energy ray-curable urethane (meth) acrylate composition and cured product thereof - Google Patents

Description

  The present invention mainly relates to urethane (meth) acrylates (active energy ray-curable urethane (meth) acrylates) useful for coating, coating applications, etc., and compositions containing the same as a curing component (active energy ray-curable urethanes (meta ) Acrylate composition and its cured product.

  In recent years, non-solvent-based active energy ray-curable coatings that are cured by active energy rays have been widely used instead of organic solvent-based paints in view of environmental pollution problems and energy saving. Such an active energy ray-curable coating contains a resin that can be cured by active energy rays and a curable monomer, and the monomer simultaneously has the function of a solvent, so it is necessary to volatilize the solvent when forming a coating film There is an advantage that there is no As these resins and monomers, for example, oligomers having a (meth) acryloyl group at molecular terminals such as urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and acrylic monomers are used. ing. Among these, urethane (meth) acrylate resin has a good balance of physical properties, and a paint composition using the resin is, for example, a decorative paper coating, gloss for paper (OPV), paint for woodwork, hard coating for plastics, It is widely used for ink etc.

  In particular, in the application of the coating agent, the coating film to be formed is required to have performance such as hardness, curl resistance, flexibility, adhesion, etc., and the above-mentioned active energy ray-curable material For the purpose of improving the performance of various types, in order to satisfy these required performances.

  Conventionally, as the above-mentioned urethane (meth) acrylate resin, for example, a hydroxyl group-containing polyfunctional (meth) acrylate compound having one or more polymerizable unsaturated bonds, and an isocyanate containing isocyanate group and an isocyanurate ring structure in one molecule An unsaturated urethane compound containing six or more polymerizable unsaturated groups in one molecule obtained by the reaction of an isocyanate group-containing urethane compound comprising a compound and a hydroxyl group-containing compound having a hydroxyl group and an isocyanurate ring structure in one molecule (See Patent Document 1); and an isocyanate group-containing unsaturated urethane compound obtained by reacting a hydroxyl group-containing (meth) acrylate compound having one or more polymerizable unsaturated bonds in one molecule and an isocyanate group-containing isocyanurate compound , Hydroxyl having two or more hydroxyl groups in one molecule Unsaturated urethane compound having 10 or more polymerizable unsaturated bonds in one molecule, which is obtained by the reaction with an alkyl group-containing alkylene glycol compound (see Patent Document 2); two or more isocyanate groups in one molecule Compounds such as hexafunctional or higher urethane (meth) acrylates (see Patent Document 3) obtained by reacting organic isocyanates having hydroxyl groups with trifunctional or higher functional (meth) acrylates having hydroxyl groups have been known.

JP 2005-281412 A JP, 2012-17404, A JP, 2010-238299, A

  A coating agent containing an unsaturated urethane compound or a urethane (meth) acrylate disclosed in Patent Documents 1 to 3 is applied to an object to be coated (for example, a substrate such as a film), and cured by ultraviolet irradiation. It can form a film. The surface of the cured coating film (hard coating layer) obtained in this manner is hard, but on the other hand, it has a problem of causing curling in the coated object after ultraviolet irradiation. On the other hand, although there are materials (coating agents) which do not cause curling of the coated object even after ultraviolet irradiation (that is, even after curing), the cured coating film formed by such materials has a surface The problem is that the hardness of the As described above, materials capable of forming a cured coating film having well-balanced performance of the surface hardness and the property of causing less curling of the object to be coated (sometimes referred to as "curl resistance") have hitherto been described. It is the present condition that it was not obtained.

  Therefore, an object of the present invention is to use a material (urethane (Meta (meta) which can form a coating (hardened coating) having a good balance between high surface hardness (for example, abrasion resistance, scratch resistance) and curl resistance). An object of the present invention is to provide a) an acrylate) and an active energy ray-curable resin composition (active energy ray-curable urethane (meth) acrylate composition) containing the material.

  MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors have high surface hardness according to the urethane (meth) acrylate which uses a specific compound as a raw material, and the active energy ray hardening urethane (meth) acrylate composition containing this. It has been found that a coating film (cured coating film) can be formed which is equipped with both performances of the toner and the curl resistance in a well-balanced manner, and the present invention has been completed.

That is, the present invention provides the following inventions.
[1] Lactone modified hydroxyl group-containing poly (meth) acrylate (A) in which 1 to 6 moles of lactone is added per 1 mole of hydroxyalkyl poly (meth) acrylate, and one or more isocyanate groups per molecule Urethane (meth) acrylate obtained by reacting an isocyanate compound (B).

[2] Lactone modified hydroxyl group-containing poly (meth) acrylate (A) in which 1 to 6 moles of lactone is added per 1 mole of hydroxyalkyl poly (meth) acrylate, and having 2 or more isocyanate groups per molecule The urethane (meth) acrylate obtained by making an isocyanate compound (B1) and the polyol (C) which has a 2 or more hydroxyl group per molecule react.

[3] The urethane (meth) acrylate according to [1] or [2], wherein the hydroxyalkyl poly (meth) acrylate is pentaerythritol tri (meth) acrylate.

[4] An active energy ray-curable urethane (meth) acrylate composition comprising the urethane (meth) acrylate according to any one of [1] to [3].

[5] The active energy ray curable urethane (meth) acrylate composition according to [4], further comprising a (meth) acryloyl group-containing monomer.

[6] The active energy ray-curable urethane (meth) acrylate composition according to [4] or [5], further comprising a photopolymerization initiator.

[7] A cured product obtained by curing the active energy ray curable urethane (meth) acrylate composition according to any one of [4] to [6].

  Since the urethane (meth) acrylate of the present invention has the above-mentioned constitution, a cured product formed by curing an active energy ray-curable urethane (meth) acrylate composition containing the urethane (meth) acrylate as an essential component has a high surface Both the hardness (for example, abrasion resistance and scratch resistance) and the curl resistance are well balanced. Therefore, the active energy ray-curable urethane (meth) acrylate composition of the present invention is, in particular, a coating agent (coating application), a paint (coating application), an adhesive (adhesive agent) that forms a cured coating on the surface of an article. Applications) can be preferably used.

1 is a chart of the ¹ H-NMR spectrum of the product obtained in Synthesis Example 1. 3 is a chart of the ¹ H-NMR spectrum of the product obtained in Synthesis Example 2. 1 is a chart of the ¹ H-NMR spectrum of a urethane acrylate (UA1) obtained in Example 1. BRIEF DESCRIPTION OF THE DRAWINGS The chart of IR spectrum of urethane acrylate (UA1) obtained in Example 1 is shown. 1 shows a GPC elution curve of the urethane acrylate (UA1) obtained in Example 1. FIG. 3 is a chart of the ¹ H-NMR spectrum of the urethane acrylate (UA2) obtained in Example 2. The chart of IR spectrum of urethane acrylate (UA2) obtained in Example 2 is shown. 7 shows a GPC elution curve of the urethane acrylate (UA2) obtained in Example 2.

<Urethane (Meth) Acrylate>
The urethane (meth) acrylate of the present invention is a lactone modified by adding 1 to 6 moles of lactone to 1 mole of hydroxyalkyl poly (meth) acrylate (that is, 1 mole of hydroxyl group of hydroxyalkyl poly (meth) acrylate). Hydroxyl group-containing poly (meth) acrylate (A) ("lactone modified hydroxyl group-containing poly (meth) acrylate (A)", "component (A)", sometimes referred to as "A") and one or more per molecule The compound is a urethane (meth) acrylate obtained by at least reacting with a compound having an isocyanate group ("isocyanate compound (B)", "component (B)", or "B"). More specifically, as the urethane (meth) acrylate of the present invention,
[1] Urethane (meth) acrylate obtained by reacting lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with isocyanate compound (B), and [2] lactone-modified hydroxyl group-containing poly (meth) acrylate (A) And, an isocyanate compound having two or more isocyanate groups per molecule ("isocyanate compound (B1)", "component (B1)", and "B1"), and two or more per molecule) Urethane (meth) acrylate obtained by reacting with a compound having a hydroxyl group (sometimes referred to as “polyol (C)”, “component (C)”, “C”),
Can be mentioned. However, the urethane (meth) acrylate of the present invention is not limited to these embodiments as long as it is obtained by at least reacting the lactone modified hydroxyl group-containing poly (meth) acrylate (A) with the isocyanate compound (B). .

  In the present specification, “(meth) acrylate” means acrylate and / or methacrylate (either or both of acrylate and methacrylate), and the same applies to “(meth) acryloyl” and the like.

  Although the average functional group number of the urethane (meth) acrylate of this invention is not specifically limited, 2-20 are preferable, More preferably, it is 3-15. By setting the average number of functional groups to 2 or more, the surface hardness (scratch resistance, abrasion resistance, etc.) of the cured product (cured coating film) tends to be higher. On the other hand, when the average number of functional groups is 20 or less, the curl resistance of the cured product (cured coating film) tends to be further improved.

The "average number of functional groups" of the urethane (meth) acrylate of the present invention is the average number of (meth) acryloyl groups possessed by one urethane (meth) acrylate of the present invention. For example, a lactone modified hydroxyl group-containing poly (meth) acrylate (A) having one hydroxyl group and three (meth) acryloyl groups per molecule, and an isocyanate compound (B) having one isocyanate group per molecule Are reacted at a molar ratio of 1: 1, and the average functionality of urethane (meth) acrylate obtained is 3. It is as follows when the structure is shown typically.

Also, a polyol (C) which is a diol having two hydroxyl groups per molecule, an isocyanate compound (B1) which is a diisocyanate having two isocyanate groups per molecule, and three hydroxyl groups per molecule The average functional group number of the urethane (meth) acrylate obtained by reacting the lactone modified hydroxyl group-containing poly (meth) acrylate (A) having a (meth) acryloyl group of the following at a molar ratio of 1: 2: 2 is 6. It is as follows when the structure is shown typically.

Further, a polyol (C) which is a diol having two hydroxyl groups per molecule, an isocyanate compound (B1) which is a triisocyanate having three isocyanate groups per molecule, and one hydroxyl group per molecule The average functionality number of urethane (meth) acrylates obtained by reacting lactone-modified hydroxyl group-containing poly (meth) acrylates (A) having individual (meth) acryloyl groups at a molar ratio of 1: 2: 4 is 12. It is as follows when the structure is shown typically.

The urethane (meth) acrylate of the present invention may be a mixture of two or more of the same or different average functional group numbers. The average functionality of the mixture can be determined by weighted averaging. For example, 0.3 moles of urethane (meth) acrylate having an average functionality of 3 and 0.2 moles of urethane (meth) acrylate having an average functionality of 6 and 0.5 moles of urethane (meth) acrylate having an average functionality of 12 When three types are mixed, the average functional group number of the mixture (urethane (meth) acrylate of the present invention) is calculated according to the following formula: 8.1.
(3 × 0.3 + 6 × 0.2 + 12 × 0.5) / (0.3 + 0.2 + 0.5) = 8.1 / 1.0 = 8.1

  Although the weight average molecular weight of the urethane (meth) acrylate of this invention is not specifically limited, 500-30000 are preferable, More preferably, it is 800-10000. By setting the weight average molecular weight to 500 or more, the surface hardness and the mechanical strength of the cured product (cured coating film) tend to be further improved. On the other hand, by setting the weight average molecular weight to 30,000 or less, the viscosity of the active energy ray-curable urethane (meth) acrylate composition does not become too high, and the handleability in coating operation and the like is further improved. Tends to be obtained. In addition, the weight average molecular weight of the urethane (meth) acrylate of this invention is computed from the molecular weight of standard polystyrene conversion measured by gel permeation chromatography.

[Lactone modified hydroxyl group-containing poly (meth) acrylate (A)]
The lactone modified hydroxyl group containing poly (meth) acrylate (A) which is a raw material of urethane (meth) acrylate of this invention is demonstrated. The lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is a compound in which 1 to 6 moles of lactone is added to 1 mole of hydroxyalkyl poly (meth) acrylate, and 1 mole of hydroxyalkyl poly (meth) acrylate The compound is a compound corresponding to one obtained by reacting (addition reaction) 1 to 6 moles of lactone. For this reason, the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) has a specific amount of a lactone-modified structure (that is, a structure in which a lactone is ring-opened), and one hydroxyl group per molecule It has two or more (meth) acryloyl groups per molecule. In addition, as a raw material of urethane (meth) acrylate of this invention, lactone modified | denatured hydroxyl group containing poly (meth) acrylate (A) can also be used individually by 1 type, and can also be used combining 2 or more types. .

A hydroxyalkyl poly (meth) acrylate which is a raw material of lactone-modified hydroxyl group-containing poly (meth) acrylate (A) has one hydroxyl group per molecule and at least two (meth) acryloyl groups per molecule. It is a compound which it has. The above hydroxyalkyl poly (meth) acrylate does not have a lactone-modified structure. As the hydroxyalkyl poly (meth) acrylate, known or commonly used compounds can be used, and not particularly limited, for example, compounds represented by the following formula (1) can be used.

In Formula (1), R ¹ represents a (p + 1) -valent hydrocarbon group. As described later, p is an integer of 2 or more, so (p + 1) is an integer of 3 or more. As the above-mentioned hydrocarbon group, a trivalent or higher linear, branched or cyclic aliphatic hydrocarbon group; a trivalent or higher aromatic hydrocarbon group; a linear aliphatic hydrocarbon group, a branched fatty acid Group hydrocarbon groups, cyclic aliphatic hydrocarbon groups, and trivalent or higher hydrocarbon groups formed by combining two or more selected from the group consisting of aromatic hydrocarbon groups, and the like. Examples of the trivalent linear, branched or cyclic aliphatic hydrocarbon group include an alkane-triyl group [for example, a methane-triyl group, an ethane-triyl group ((meth) acryloyloxy group and a bonding position of a hydroxyl group The same is true for the following exemplary groups where the bonding position is not specified.), Propane-triyl group, 1,1,1-trimethylpropane-triyl group, etc.], cycloalkane-triyl group [eg cyclohexane-triyl group , Methylcyclohexane-triyl group, dimethylcyclohexane-triyl group etc.] and the like. Examples of the trivalent aromatic hydrocarbon group include groups formed by removing three hydrogen atoms on the structural formula from an aromatic compound such as benzene, naphthalene or fluorene. As the tetravalent linear, branched or cyclic aliphatic hydrocarbon group, for example, alkane-tetrayl group [eg, methane-tetrayl group, ethane-tetrayl group, propane-tetrayl group, butane-tetrayl group, 2 , 2-Dimethylpropane-tetrayl group etc.], cycloalkane-tetrayl group [eg cyclohexane-tetrayl group, methylcyclohexane-tetrayl group, dimethylcyclohexane-tetrayl group] etc. may be mentioned. Examples of the tetravalent aromatic hydrocarbon group include a group formed by removing four hydrogen atoms from the aromatic compound on the structural formula. The same applies to hydrocarbon groups having 5 or more valences.

Among them, a linear or branched aliphatic hydrocarbon group having a (p + 1) value is preferable as R ^{1 because} it is excellent in the balance between the surface hardness of the cured coating and the curl resistance.

In formula (1), R ² represents a hydrogen atom or a methyl group. In addition, each R ² may be the same or different. P represents an integer of 2 or more (for example, an integer of 2 to 10), preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

  More specifically, as the hydroxyalkyl poly (meth) acrylate, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, dipentaerythritol penta (meth) An acrylate etc. are mentioned. Among them, a compound having three or more (meth) acryloyl groups (total) per molecule is preferable, and pentaerythritol tri (meth) is more preferable, in terms of the balance between the surface hardness of the cured coating and the curl resistance. It is an acrylate.

  The above-mentioned hydroxyalkyl poly (meth) acrylate can also be produced by a known or conventional method, or a commercially available product (for example, trade names "PETRA", "PETIA" (all manufactured by Daicel Ornex Co., Ltd.) Trade name "ALONIX M305" (manufactured by Toagosei Co., Ltd.) and the like can also be obtained.

  The lactone which is a raw material of the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) may be any known or commonly used lactone, and is not particularly limited. For example, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, lower alkyl substituted products of these lactones, and the like can be mentioned. Among these, ε-caprolactone is preferable in that it is more excellent in the balance between the surface hardness of the cured coating film and the curl resistance. In addition, lactone can also be used individually by 1 type, and can also be used in combination of 2 or more type. Also, lactone can be produced by known or conventional methods, or commercially available products can be obtained.

  Specifically, the reaction of the above-described hydroxyalkyl poly (meth) acrylate with lactone is a reaction in which a lactone is added (ring-opening addition reaction or ring-opening addition polymerization) to a hydroxyl group possessed by hydroxyalkyl poly (meth) acrylate. is there. That is, the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is a compound having a structure in which lactone is added (ring-opening addition or ring-opening addition polymerization) starting from the hydroxyl group in hydroxyalkyl poly (meth) acrylate. As described above, the amount of lactone to be added to the hydroxyalkyl poly (meth) acrylate is 1 per 1 mole of hydroxyalkyl poly (meth) acrylate (ie, 1 mole of hydroxyl group of hydroxyalkyl poly (meth) acrylate). It is ~ 6 molar times, preferably 1 to 5 molar times. By controlling the number of moles of lactone (addition number of lactone added) to be added to the hydroxyalkyl poly (meth) acrylate in the above range, the surface hardness and the curl resistance of the cured coating film can be compatible at extremely high levels.

  The above reaction (reaction of hydroxyalkyl poly (meth) acrylate and lactone) can be carried out by a known or conventional method, and is not particularly limited, but can usually be carried out by heating both. In the above reaction, other components such as a cocatalyst and a polymerization inhibitor can be used, if necessary. The above reaction may be allowed to proceed in one step or may be proceeded in two or more steps sequentially.

  The reaction can be carried out in an organic solvent or in the absence of an organic solvent. It does not specifically limit as said organic solvent, For example, what was illustrated as a volatile organic solvent in reaction of the below-mentioned component (A) and component (B) etc. can be used.

  The procedure for carrying out the above reaction is not particularly limited. For example, hydroxyalkyl poly (meth) acrylate and lactone may be charged at once into a reaction vessel and reacted, or hydroxyalkyl poly (meth) acrylate and lactone may be reacted. One of them may be charged into the reaction vessel, and the other may be added (for example, sequentially added) for reaction.

  The temperature (reaction temperature) in the above reaction is not particularly limited, and can be appropriately selected, for example, from the range of 80 to 250 ° C. (eg, 100 to 200 ° C.). Moreover, the time (reaction time) which implements the said reaction is not specifically limited, either, For example, it can select suitably from the range of 0.2 to 20 hours (for example, 1 to 8 hours).

  The reaction can be carried out under normal pressure, increased pressure or reduced pressure. Moreover, the atmosphere which implements the said reaction is not specifically limited, either, In inert gas (for example, nitrogen, argon etc.), it can implement in any atmosphere, such as in air.

  By the above reaction, a lactone modified hydroxyl group-containing poly (meth) acrylate (A) is produced. The lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is, for example, known or commonly used separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, separation means combining these, etc. Can be separated and purified. The lactone-modified hydroxyl group-containing poly (meth) acrylate (A) can be used as it is without separation and purification.

  The number of hydroxyl groups per molecule and the number of (meth) acryloyl groups contained in the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) obtained by the above reaction are usually hydroxyalkyl poly (meth) acrylates which are raw materials. It is the same as the number of hydroxyl groups per molecule and the number of (meth) acryloyl groups.

When the hydroxyalkyl poly (meth) acrylate is a compound represented by the above formula (1), the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) is represented by, for example, the following formula (2).

In Formula (2), R < ¹ >, R < ² > and p are the same as the thing in Formula (1), respectively. R ³ in the formula (2) represents a linear or branched alkylene group having 2 or more carbon atoms. As the said alkylene group, C2-C6 alkylene groups, such as ethylene group, a propylene group, trimethylene group, tetramethylene group, isobutylene group, pentamethylene group, hexamethylene group, etc. are mentioned, for example. Among them, pentamethylene group is preferable. When q is an integer of 2 or more, each R ³ may be the same or different.

  Q in Formula (2) is a repetition number of the structure in the parenthesis attached with q, and shows the integer of 1-6. As q, the integer of 1-5 is preferable.

The urethane (meth) acrylate of the present invention is presumed to be particularly due to the above-described characteristic structure of the lactone-modified hydroxyl group-containing poly (meth) acrylate (A), for example, R in formula (2) These properties are higher in surface hardness and further excellent in curl resistance as compared with the case where a compound having a lactone-modified structure between ¹ and a (meth) acryloyloxy group is used. It is possible to form a well-balanced cured coating.

[Isocyanate Compound (B)]
The isocyanate compound (B) which is a raw material of urethane (meth) acrylate of this invention is demonstrated. The isocyanate compound (B) is a compound having one or more isocyanate groups per molecule. In addition, an isocyanate compound (B) can also be used individually by 1 type as a raw material of urethane (meth) acrylate of this invention, and it can also be used combining 2 or more types.

  Although the number of the isocyanate group which an isocyanate compound (B) has in 1 molecule is not specifically limited, 1-10 are preferable, More preferably, it is 1-6, More preferably, it is 1-4. As described above, in the present specification, among the isocyanate compounds (B), those having two or more isocyanate groups per molecule may be referred to as "isocyanate compound (B1)" in some cases.

  As the isocyanate compound (B), aromatic isocyanate compounds, aliphatic isocyanate compounds, cycloaliphatic isocyanate compounds, alicyclic isocyanate compounds, mixtures of these isocyanate compounds, adducts of the above isocyanate compounds, and the above isocyanate compounds Known isocyanate compounds such as modified products of the above and polymers of the above-mentioned isocyanate compounds can be used. More specifically, as the isocyanate compound (B), for example, 2-acryloyloxyethyl isocyanate (AOI), 2-methacryloyloxyethyl isocyanate (MOI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), water Additive diphenylmethane diisocyanate (H12 MDI), polyphenylmethane isocyanate compound (crude MDI), modified diphenylmethane diisocyanate (modified MDI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HDI) ), Trimethylhexamethylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), norbornene diisocyanate Isocyanate compounds such as (NDI); 1, two or more of the trimer compounds of these isocyanate compounds, and the like.

  The isocyanate compound (B) can be produced by a known or conventional method, or a commercially available product can be obtained. As a commercial item, for example, trade name "VESTANAT IPDI" (isophorone diisocyanate, manufactured by Evonik Co., Ltd.), trade name "2-acryloyloxyethyl isocyanate" (made by Showa Denko KK), trade name "Takenate D-170N" (trade name) Trimer of 1,6-hexamethylene diisocyanate, Mitsui Chemicals Co., Ltd., trade name “Sumidur N3300” (trimer of 1,6-hexamethylene diisocyanate, Sumitomo Bayer Urethane Co., Ltd.), etc. It can be mentioned.

[Polyol (C)]
The polyol (C) which is a raw material of urethane (meth) acrylate of this invention is demonstrated. The polyol (C) is a compound having two or more hydroxyl groups per molecule. In addition, as a raw material of urethane (meth) acrylate of this invention, a polyol (C) can also be used individually by 1 type, and can also be used combining 2 or more types.

As the polyol (C), compounds known or commonly used as compounds having two or more hydroxyl groups per molecule can be used, and although not particularly limited, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, polyoxy C _2-4 alkylene glycol (polyethylene glycol, polypropylene glycol, poly Oxy tetramethylene glycol etc.), polyester diol, polyether diol, polycarbonate diol, bisphenol A and its alkylene oxide adduct, bisphenol F and its Alkylene oxide adduct, hydrogenated bisphenol A and its alkylene oxide adduct, hydrogenated bisphenol F and its alkylene oxide adduct, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, isosorbide, diol such as xylene glycol, glycerin, 1,1,1-tris (hydroxymethyl) propane, D-sorbitol, xylitol, D-mannitol, D-mannitol, diglycerin, polyglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polyether polyol, polyester Polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluoropoly , Polyols having 3 or more hydroxyl groups in the molecule, such as a polyolefin polyol.

  The polyol (C) can be produced by a known or conventional method, or a commercially available product can be obtained. As a commercial item, the brand name "Nipporan" series (made by Nippon Polyurethane Industry Co., Ltd.) etc. are mentioned, for example.

[Method of producing urethane (meth) acrylate]
The urethane (meth) acrylate of the present invention is obtained by at least reacting the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with the isocyanate compound (B) as described above.

  Urethane (meth) acrylate of the present invention is obtained, for example, by reacting urethane (meth) acrylate (lactone modified hydroxyl group-containing poly (meth) acrylate (A) of the above [1] with isocyanate compound (B) When it is (meth) acrylate, the said urethane (meth) acrylate can be manufactured by making component (A) and component (B) react.

The method of reacting the component (A) and the component (B) described above is not particularly limited, and examples thereof include the following methods.
[Method 1a] Method of mixing component (A) and component (B) together and reacting them [Method 2a] method of sequentially adding component (B) into component (A) and reacting them [Method 3a] A method of sequentially adding component (A) into component (B) and reacting them

  In addition, the above-mentioned "sequential addition" means continuous addition (an embodiment added over a fixed time) or intermittent addition (an embodiment divided and added in multiple times). As an aspect of sequential addition, the aspect of dripping etc. are mentioned, for example. The same applies to [Method 2b-2] described later.

  Among the above-mentioned [Method 1a] to [Method 3a], [Method 2a] and [Method 3a] are preferred from the viewpoint of control of reaction heat.

  The reaction of the component (A) with the component (B) is preferably carried out in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine or 4-methoxyphenol for the purpose of preventing polymerization. The addition amount (use amount) of the polymerization inhibitor is not particularly limited, but it is preferably 1 to 10000 ppm, more preferably 100 to 1000 ppm, still more preferably 1 to 10000 ppm by weight based on the urethane (meth) acrylate of the present invention to be produced. 400 to 500 ppm. If the addition amount of the polymerization inhibitor is less than 1 ppm, a sufficient polymerization inhibition effect may not be obtained. On the other hand, when the addition amount of the polymerization inhibitor exceeds 10000 ppm, various physical properties of the urethane (meth) acrylate of the present invention may be adversely affected.

  Moreover, in order to prevent polymerization similarly, it is preferable to carry out the reaction of the above-mentioned component (A) and component (B) in a gas atmosphere containing molecular oxygen. The oxygen concentration is appropriately selected in consideration of safety.

  In the reaction of the component (A) and the component (B) described above, it is preferable to use a catalyst in order to obtain a sufficient reaction rate. Examples of the catalyst include dibutyltin dilaurate, tin octylate, tin chloride and the like. Among them, dibutyltin dilaurate and the like are preferable from the viewpoint of reaction rate. Although the addition amount (use amount) of the above-mentioned catalyst is not particularly limited, in general, 1 to 3000 ppm is preferable, and more preferably 50 to 1000 ppm by weight. If the amount of catalyst added is less than 1 ppm, a sufficient reaction rate may not be obtained. On the other hand, if it exceeds 3000 ppm, various physical properties of the urethane (meth) acrylate of the present invention may be adversely affected.

  The reaction of the components (A) and (B) described above can proceed in the presence of known volatile organic solvents. The volatile organic solvent is not particularly limited, and examples thereof include ethyl acetate, butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl acetate, xylene, toluene and the like. Be Among them, ethyl acetate, butyl acetate and the like are preferable from the viewpoint of boiling point and economy. In the above reaction, a volatile organic solvent may not be used.

  In the reaction of the component (A) with the component (B) described above, a reactive diluent can also be used instead of the volatile organic solvent. Although it does not specifically limit as said reactive diluent, The below-mentioned (meth) acryloyl group containing monomer etc. can be used. When a reactive diluent is used, a composition comprising the urethane (meth) acrylate of the present invention and a reactive diluent is obtained as a product. In addition, the above-mentioned reactive diluent is used for the purpose of adjusting the viscosity of the active energy ray-curable urethane (meth) acrylate composition described later, adjusting the surface hardness of the cured coating film, etc. It can also be compounded after producing the meta) acrylate.

  A commercial item can also be used as said reactive diluent, For example, 1, 6- hexanediol diacrylate (For example, the product name of the product made by Daicel Ornex, product name "HDDA"), trimethylol propane triacrylate (for example, a company It is commercially available under the product name "TMPTA"), tricyclodecane dimethanol diacrylate (for example, product manufactured by the same company, product name "IRR214-K"), and the like.

  The reaction of the component (A) with the component (B) is not particularly limited, but is preferably allowed to proceed at a temperature of 130 ° C. or less (reaction temperature), more preferably 50 to 130 ° C. When the reaction temperature exceeds 130 ° C., radical polymerization by heat may proceed to crosslink double bonds, and gelation may occur. On the other hand, when the reaction temperature is less than 50 ° C., a practically sufficient reaction rate may not be obtained.

  The above-mentioned reaction of the component (A) and the component (B) is usually carried out until the isocyanate group concentration (remaining isocyanate group concentration) becomes 0.1% by weight or less. The isocyanate group concentration can be analyzed, for example, by IR (infrared spectroscopy), titration method or the like.

(Measurement of isocyanate group concentration)
The measurement of the isocyanate group concentration by the titration method is carried out as follows. The measurement is performed with a 100 mL glass flask under stirring by a stirrer.
First, measure the blank value as follows.
To 15 mL of THF, add 15 mL of a solution of dibutylamine in THF (0.1 N). Further, 3 drops of bromophenol blue (1% by weight methanol dilution solution) is added and added to make it blue, and then titrated with an aqueous solution of HCl having a normality of 0.1 N. The titer of the aqueous HCl solution at the time when the color change was observed is Vb (mL).
Next, the measured isocyanate group concentration is measured. First, the sample is weighed Ws (g), dissolved in 15 mL of THF, and 15 mL of a solution of dibutylamine in THF (0.1 N) is added. After confirmation of solution formation, 3 drops of bromophenol blue (1% by weight methanol diluted solution) are added to make it blue, and then it is titrated with an aqueous HCl solution whose normality is 0.1N. The titer of the aqueous HCl solution at the time when the color change is observed is Vs (mL).
Then, the isocyanate group concentration in the sample is calculated by the following formula.
Isocyanate group concentration (% by weight) = (Vb-Vs) × 1.005 × 0.42 ÷ Ws

  On the other hand, the urethane (meth) acrylate of the present invention has, for example, the urethane (meth) acrylate (lactone modified hydroxyl group-containing poly (meth) acrylate (A) of the above [2] and two or more isocyanate groups per molecule. When it is a urethane (meth) acrylate obtained by reacting an isocyanate compound (B1) with a compound (C) having two or more hydroxyl groups per molecule, the component (A), the component (B1), and the component It can manufacture by making (C) react.

Although the method to which the above-mentioned component (A), component (B1), and component (C) are made to react is not specifically limited, For example, the following method is mentioned.
[Method 1b] A method of mixing component (A), component (B1) and component (C) together and reacting them [Method 2b] reacting component (B1) and component (C) to produce isocyanate group Method of reacting the urethane isocyanate prepolymer with the component (A) after forming the urethane isocyanate prepolymer (urethane prepolymer) having [Method 3b] reacting the component (A) and the component (B1) to obtain an isocyanate group Forming a urethane isocyanate prepolymer (urethane prepolymer) having the following, and reacting the urethane isocyanate prepolymer with the component (C)

  Among the above-mentioned [Method 1b] to [Method 3b], [Method 2b] is preferable.

On the other hand, when manufactured by the above [Method 1b], the urethane (meth) acrylate of the present invention is increased in the by-product amount of the following urethane isocyanate prepolymer by repetition of the isocyanate compound (B1) and the polyol (C), and this is cured It may cause a decrease in scratch resistance and abrasion resistance of the coating. In addition, since various complex compounds are generated irregularly, when the obtained product is used as an active energy ray-curable urethane (meth) acrylate composition or a component thereof, it may be difficult to control the quality. is there.

  Moreover, when manufactured by said [Method 3b], the compound by which all the isocyanate groups of an isocyanate compound (B1) reacted with lactone modified hydroxyl-containing poly (meth) acrylate (A) byproduces.

The synthesis method of the urethane isocyanate prepolymer in the above [Method 2b] is not particularly limited. In particular, in order to obtain a target urethane isocyanate prepolymer with high yield, the following [Method 2b-1] or [Method 2b-2] is preferably used.
[Method 2b-1] A method of mixing the component (B1) and the component (C) together and reacting them [Method 2b-2] sequentially adding the component (C) into the component (B1) and reacting them How to

[Method 2b-1]:
An isocyanate compound (B1), a polyol (C) and, if necessary, a diluting solvent (eg, ethyl acetate, butyl acetate etc.) are charged into a reactor, and the temperature is raised as necessary while stirring until uniform, urethane It is preferable to start the reaction (urethane formation) of the component (B1) and the component (C) by introducing a catalyst for conversion. After charging the urethanization catalyst, the temperature may be raised as required.

  When the urethanization catalyst is initially charged, the urethanation reaction proceeds in a state in which the isocyanate compound (B1) and the polyol (C) are inhomogeneous at the stage of charging the isocyanate compound (B1). The molecular weight and viscosity of the prepolymer may change, and the reaction may end in a state in which the unreacted isocyanate compound (B1) remains in the system. In such a case, a by-product is generated by the reaction of only the lactone-modified hydroxyl group-containing poly (meth) acrylate (A) to be used later and the remaining isocyanate compound (B1). Thus, this method may not be preferred if product uniformity is required. On the other hand, when it is preferable from the viewpoint of required properties to obtain a product containing such by-products, the above-mentioned method can be adopted. However, the content of such by-products is preferably less than 15% by weight with respect to the total amount of the product. When the content is less than 15% by weight, the balance between the surface hardness and the curling resistance of the cured product (cured coating film) tends to be better. The above [Method 2b-1] is industrially excellent in that the urethane (meth) acrylate of the present invention can be produced in one pot.

In the case of [Method 2b-2]:
In the reactor, the isocyanate compound (B1), the urethanization catalyst, and, if necessary, the diluting solvent (eg, ethyl acetate, butyl acetate etc.) are charged and stirred until uniform. Then, while stirring, the temperature is raised as necessary, and the polyol (C) is sequentially added.

The above [Method 2b-2] is preferable in that the following by-products are the least in number.

  In addition, when synthesizing a urethane isocyanate prepolymer by reaction of an isocyanate compound (B1) and a polyol (C) by any method, the isocyanate compound (B1) and the polyol (C), and the isocyanate group concentration in the reaction liquid Preferably, the reaction is carried out until the concentration of the end point isocyanate group is less than or equal to the end point concentration.

  The "end point isocyanate group concentration" is the theoretical isocyanate group concentration (hereinafter sometimes referred to as "theoretical end point isocyanate group concentration") when all the hydroxyl groups charged in the system are assumed to be urethaneified. It means the higher isocyanate group concentration with the isocyanate group concentration when the isocyanate group concentration in the reaction solution no longer changes.

  The reaction of the urethane isocyanate prepolymer and the lactone modified hydroxyl group-containing poly (meth) acrylate (A) in [Method 2b] is to inhibit polymerization of hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-methoxyphenol, etc. for the purpose of preventing polymerization. It is preferred to proceed in the presence of the agent. The addition amount (use amount) of the polymerization inhibitor is preferably 1 to 10000 ppm, more preferably 100 to 1000 ppm, still more preferably 400 to 500 ppm by weight based on the urethane (meth) acrylate of the present invention to be produced . When the addition amount of the polymerization initiator is less than 1 ppm, a sufficient polymerization inhibition effect may not be obtained. On the other hand, when the addition amount of the polymerization initiator exceeds 10000 ppm, various physical properties of the urethane (meth) acrylate of the present invention may be adversely affected.

  Further, in order to similarly prevent the polymerization, it is preferable to carry out the reaction of the above-mentioned urethane isocyanate prepolymer and the component (A) under a gas atmosphere containing molecular oxygen. The oxygen concentration is appropriately selected in consideration of safety.

  In the reaction of the above-mentioned urethane isocyanate prepolymer and component (A), a catalyst is preferably used in order to obtain a sufficient reaction rate. Examples of the catalyst include dibutyltin dilaurate, tin octylate and the like. Among them, dibutyltin dilaurate and the like are preferable from the viewpoint of reaction rate. Although the addition amount (use amount) of the above-mentioned catalyst is not particularly limited, in general, 1 to 3000 ppm is preferable, and more preferably 50 to 1000 ppm by weight. If the amount of catalyst added is less than 1 ppm, a sufficient reaction rate may not be obtained. On the other hand, if it exceeds 3000 ppm, various physical properties of the product may be adversely affected.

  The reaction of the above-mentioned urethane isocyanate prepolymer and component (A) can be carried out in the presence of known volatile organic solvents. It does not specifically limit as a volatile organic solvent, For example, the volatile organic solvent etc. which were illustrated above can be used. Among them, ethyl acetate, butyl acetate and the like are preferable from the viewpoint of boiling point and economy. In the above reaction, a volatile organic solvent may not be used.

  In the reaction of the above-mentioned urethane isocyanate prepolymer and component (A), a reactive diluent can be used instead of the volatile organic solvent. Although it does not specifically limit as said reactive diluent, The below-mentioned (meth) acryloyl group containing monomer etc. can be used. The significance of the use of the reactive diluent and the effects obtained are as described above.

  Although the reaction of the above-mentioned urethane isocyanate prepolymer and component (A) is not particularly limited, it is preferable to proceed at a temperature (reaction temperature) of 130 ° C. or less, more preferably 50 to 130 ° C. When the reaction temperature exceeds 130 ° C., radical polymerization by heat may proceed to crosslink double bonds, and gelation may occur. On the other hand, when the reaction temperature is less than 50 ° C., a practically sufficient reaction rate may not be obtained.

  The reaction of the above-mentioned urethane isocyanate prepolymer and component (A) is usually carried out until the isocyanate group concentration (remaining isocyanate group concentration) becomes 0.1% by weight or less. The measuring method of the isocyanate group concentration is as described above.

  The urethane (meth) acrylate of the present invention obtained by the above production method can also be used as it is (for example, active energy ray curable urethane (meth) acrylate composition as it is in the state of a composition containing volatile organic solvent etc. Can be used as a component of (1) and purified. In the purification of the urethane (meth) acrylate of the present invention, known or conventional methods can be used. For example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc. A separation means combining the above can be used.

The urethane (meth) acrylate of the present invention is obtained by reacting a lactone-modified hydroxyl group-containing poly (meth) acrylate (A) with an isocyanate compound (B) (including the component (B1)). When A) is a compound represented by Formula (2), the urethane (meth) acrylate of this invention is represented by following formula (3).

In Formula (3), R ¹ , R ² , R ³ , p and q are respectively the same as those in Formula (1) and Formula (2). In formula (3), R ⁴ is a group (residue) formed by removing an isocyanate group from the isocyanate compound (B) (a compound having r isocyanate groups) on the structural formula, for example, r Hydrocarbon group (eg, linear, branched or cyclic aliphatic hydrocarbon group; aromatic hydrocarbon group etc.), r-valent heterocyclic group, hydrocarbon group and heterocyclic group are bonded And the like (more specifically, groups formed by removing the isocyanate group on the structural formula from the isocyanate compound (B) exemplified above, etc.) and the like. r represents an integer of 1 or more.

When the urethane (meth) acrylate of the present invention is obtained by reacting the lactone modified hydroxyl group-containing poly (meth) acrylate (A), the isocyanate compound (B1) and the polyol (C), the urethane (meth Acrylate is represented by the following formula (4).

In Formula (4), R ¹ , R ² , R ³ , p, and q are the same as those in Formula (1) and Formula (2), respectively. In formula (4), R ⁵ is an isocyanate on the structural formula from a urethane isocyanate prepolymer (urethane prepolymer having s number of isocyanate groups) obtained by reacting an isocyanate compound (B1) with a polyol (C) It is a group (residue) formed by removing a group. s represents an integer of 2 or more.

<Active energy ray curable urethane (meth) acrylate composition>
The active energy ray curable urethane (meth) acrylate composition of the present invention is a composition containing the urethane (meth) acrylate of the present invention as an essential curing component (curable component) (active energy ray curable resin composition) It is. In the active energy ray-curable urethane (meth) acrylate composition of the present invention, the urethane (meth) acrylate of the present invention may be used alone or in combination of two or more. it can.

  The content (blending amount) of the urethane (meth) acrylate of the present invention in the active energy ray-curable urethane (meth) acrylate composition of the present invention is not particularly limited, but the active energy ray-curable urethane (meth) acrylate composition 30 weight% or more (for example, 30-99 weight%) is preferable with respect to the total amount (100 weight%) of, 50-98 weight% is more preferable, More preferably, it is 55-90 weight%. By setting the content of the urethane (meth) acrylate of the present invention to 30% by weight or more, both the surface hardness (abrasion resistance, scratch resistance, etc.) and curl resistance of the cured coating (cured product) are more improved. It tends to be fulfilled at a high level.

[Photoinitiator]
The active energy ray-curable urethane (meth) acrylate composition of the present invention may contain a photopolymerization initiator (photoinitiator). For example, when the active energy ray-curable urethane (meth) acrylate composition of the present invention is cured by electron beam irradiation, it is not necessary to use a photopolymerization initiator, but when it is cured by ultraviolet irradiation It is preferred to include an initiator.

  As the photopolymerization initiator, known or commonly used photoradical polymerization initiators can be used, and it is not particularly limited. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one On, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether , Benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether Ter, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl -4-Methoxy benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- diethyl thio Xanson, 2,4-diisopropylthioxanthone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, methyl phenyl glyoxylate, benzyl, camphor quinone, etc. That. In the active energy ray-curable urethane (meth) acrylate composition of the present invention, one type of photopolymerization initiator can be used alone, or two or more types can be used in combination.

  The content (compounding amount) of the photopolymerization initiator is not particularly limited, but is preferably 1 to 10% by weight with respect to the total amount (100% by weight) of the active energy ray-curable urethane (meth) acrylate composition Preferably, it is about 1 to 5% by weight, more preferably about 3% by weight (e.g., 2 to 4% by weight). By setting the content of the photopolymerization initiator to 1% by weight or more, the curing speed tends to be faster. On the other hand, when the content of the photopolymerization initiator is 10% by weight or less, a cured product having a high curing speed and excellent physical properties tends to be obtained. For example, when the content of the photopolymerization initiator exceeds 10% by weight, no further improvement of the curing rate is observed, and the physical properties of the cured product tend to be impaired, which is not preferable.

[(Meth) Acryloyl Group-Containing Monomer]
The active energy ray-curable urethane (meth) acrylate composition of the present invention is a compound ("(meth) acryloyl group-containing monomer") having a (meth) acryloyl group other than this in addition to the urethane (meth) acrylate of the present invention Is preferred to include. The (meth) acryloyl group-containing monomer is a compound having one or more groups selected from the group consisting of an acryloyl group and a methacryloyl group per molecule. By using the (meth) acryloyl group-containing monomer, it is possible to adjust the viscosity of the active energy ray-curable urethane (meth) acrylate composition and to adjust the surface hardness of the cured coating film.

  As the (meth) acryloyl group-containing monomer, a compound (monomer) having a known or commonly used (meth) acryloyl group can be used, and is not particularly limited. However, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate , Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, polycaprolactone modified hydroxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, (meth) acryloyl morpholine, 1,6-hexanediol mono (meth) Monofunctional monomers such as acrylate, lactone modified product of pentaerythritol mono (meth) acrylate (for example, caprolactone modified product, the same applies hereinafter); 1,6-hexanediol di (meth) acrylate, triplypipi 3 moles of glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane Tri (meth) acrylate of propylene oxide adduct, tri (meth) acrylate of 6 mole propylene oxide adduct of trimethylolpropane, glycerin propoxy tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone of dipentaerythritol Modified hexa (meth) acrylate, di (meth) acrylate of caprolactone modified of pentaerythritol, caprola of pentaerythritol Tri (meth) acrylate tons modified product, lactone-modified product of pentaerythritol di (meth) acrylate, polyfunctional monomers such lactone-modified products of pentaerythritol tri (meth) acrylate. In addition, as the above (meth) acryloyl group-containing monomer, for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, unsaturation, etc. Other examples include oligomers such as polyester. In the active energy ray-curable urethane (meth) acrylate composition of the present invention, the (meth) acryloyl group-containing monomer may be used alone or in combination of two or more. .

  The content (compounding amount) of the (meth) acryloyl group-containing monomer in the active energy ray curable urethane (meth) acrylate composition of the present invention is not particularly limited, but it is based on 100 parts by weight of the urethane (meth) acrylate of the present invention The amount is preferably 1 to 1000 parts by weight, more preferably 1 to 500 parts by weight, and still more preferably 1 to 100 parts by weight. If the content is less than 1 part by weight, it does not have the meaning of being added as a solvent, and if it exceeds 1000 parts by weight, the characteristic of using the urethane (meth) acrylate of the present invention tends to be lost.

[Organic solvent]
An organic solvent etc. can also be added to the active energy ray-curable urethane (meth) acrylate composition of the present invention, as needed, for viscosity adjustment and the like. As the organic solvent, known or commonly used organic solvents can be used, and there is no particular limitation. Ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; Esters such as methyl acetate, ethyl acetate, butyl acetate and methoxyethyl acetate Solvents: Ether solvents such as diethyl ether, ethylene glycol methyl ether and dioxane; Aromatic solvents such as toluene and xylene; Aliphatic solvents such as pentane and hexane; Halogen solvents such as methylene chloride, chlorobenzene and chloroform; Alcohol solvents, such as butanol, etc. are mentioned. In the active energy ray-curable urethane (meth) acrylate composition of the present invention, one organic solvent can be used alone, or two or more organic solvents can be used in combination. The content (blending amount) of the organic solvent is not particularly limited, but is preferably 0 to 30% by weight with respect to the total amount (100% by weight) of the active energy ray-curable urethane (meth) acrylate composition.

  Moreover, other various additives can be mix | blended with the active energy ray hardening-type urethane (meth) acrylate composition of this invention. As the additives, known or commonly used additives can be used and are not particularly limited. For example, fillers, dyes and pigments, leveling agents, UV absorbers, light stabilizers, antifoaming agents, dispersing agents, thixotropic properties A imparting agent etc. are mentioned. In addition, an additive can also be used individually by 1 type in the active energy ray hardening-type urethane (meth) acrylate composition of this invention, and it can also be used combining 2 or more types. The content (blending amount) of the additive is not particularly limited, but it is preferably 0 to 10% by weight, more preferably 0. to 10% by weight based on the active energy ray-curable urethane (meth) acrylate composition (100% by weight). It is 05-5% by weight.

  The active energy ray-curable urethane (meth) acrylate composition of the present invention can be obtained by mixing the urethane (meth) acrylate of the present invention and other components such as a photopolymerization initiator and an organic solvent as required. Can. As means for mixing, known or conventional means can be used, and it is not particularly limited, but for example, various mixers such as dissolver and homogenizer, kneader, roll, bead mill, self-revolution type stirring device and the like can be used. Moreover, conditions, such as temperature in the case of mixing and rotation speed, are not specifically limited, It can set suitably.

<Cured product>
By curing the active energy ray-curable urethane (meth) acrylate composition of the present invention by active energy ray irradiation, a cured product (sometimes referred to as "the cured product of the present invention") can be obtained. The cured product of the present invention has well-balanced performance of high surface hardness (for example, abrasion resistance, scratch resistance) and curl resistance.

  More specifically, the active energy ray-curable urethane (meth) acrylate composition of the present invention is applied to an object to form a coating, and then irradiated with active energy rays such as ultraviolet rays and electron beams. Cure to give a cured coating. Although it does not specifically limit as a light source at the time of irradiating an ultraviolet-ray, For example, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp etc. are used. The irradiation time of the ultraviolet light varies depending on the type of light source, the distance between the light source and the coated surface, other conditions, etc., but is at most several tens of seconds and usually several seconds. After the irradiation with ultraviolet light, heating may be further performed as needed to achieve complete curing. On the other hand, in the case of electron beam irradiation, although not particularly limited, for example, it is preferable to use an electron beam having an energy in the range of 50 to 1000 KeV and to have an irradiation amount of 2 to 5 Mrad. Usually, a radiation source with a lamp output of about 80 to 300 W / cm is used. The thickness of the cured coating (the film of the cured product of the present invention) is not particularly limited, but is usually about 50 to 300 μm.

  The active energy ray-curable urethane (meth) acrylate composition of the present invention is, for example, used for forming a cured coating on the surface of an article, specifically, coating agent (coating application), paint (coating application), adhesion It can be preferably used as an agent (adhesive use) and the like. The cured coating film formed from the active energy ray-curable urethane (meth) acrylate composition of the present invention has high surface hardness and is excellent in the protection of the surface of the object (article) and also in the curl resistance. Since the product is excellent, high quality products can be obtained without causing problems such as curling of the target.

  The target (application) to which the active energy ray-curable urethane (meth) acrylate composition of the present invention is applied (for example, coated) is not particularly limited, and for example, polyethylene terephthalate (PET), polymethacrylate, polycarbonate, Articles made of plastic such as vinyl chloride resin; those obtained by vapor-depositing metal on the plastic surface of the above-mentioned article; wood; metal plates; various articles such as paper. Further, the shape of the target (object to be coated) is not particularly limited. The above-mentioned plastics, wood, metal, paper, etc. in which the active energy ray-curable urethane (meth) acrylate composition of the present invention is used as a coating or an adhesive etc. are various building materials, furniture, printing paper, can products, It is useful in various products such as home appliances and digital video discs (DVDs). The active energy ray-curable urethane (meth) acrylate composition of the present invention is excellent in hydrolysis resistance, and the formed coating film or adhesive is also excellent in flexibility and adhesion.

  EXAMPLES The present invention will be described in more detail based on examples given below, but the present invention is not limited by these examples.

Synthesis example 1
[Synthesis of Lactone Modified Body of Multifunctional Acrylic Compound (Lactone Polymer (1))]
In a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction pipe, and condenser, pentaerythritol (tri / tetra) acrylate (trade name "Alonix M305", manufactured by Toagosei Co., Ltd.) 342.2 g, ε- 157.4 g of caprolactone (trade name "Placcel M", manufactured by Daicel Co., Ltd.), 0.36 g (720 ppm) of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and tin octylate (trade name "Stanocto", 0.055 g (110 ppm) (manufactured by AP Corporation) was charged. Then, while blowing a mixed gas with an air / nitrogen ratio (volume ratio) of 1/2 at 30 ml / min into this mixture, the amount of ε-caprolactone remaining is 1 wt. The reaction was carried out until the amount charged was reduced to 100% by weight to obtain a liquid product at normal temperature. The obtained product is a mixture of ε-caprolactone modified product of pentaerythritol triacrylate (lactone polymer (1); corresponding to the component (A) described above) and pentaerythritol tetraacrylate, and the hydroxyl value is 77 It was .3 mg KOH / g. FIG. 1 shows a chart (solvent: deuterated chloroform) of ¹ H-NMR spectrum of the above-mentioned product.

Synthesis example 2
[Synthesis of Lactone Modified Body of Multifunctional Acrylic Compound (Lactone Polymer (2))]
In a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser, pentaerythritol (tri / tetra) acrylate (trade name "Alonix M305", manufactured by Toagosei Co., Ltd.) 232.4 g, ε- 267.2 g of caprolactone (trade name "Placcel M", manufactured by Daicel Co., Ltd.), 0.36 g (720 ppm) of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and tin octylate (trade name "Stanocto", A charge of 0.055 g (110 ppm) (manufactured by AP Corporation) and remaining at 130 ° C. while blowing a mixed gas having an air / nitrogen ratio (volume ratio) of 1/2 at 30 ml / min. The reaction is carried out until the amount of ε-caprolactone to be added is less than 1% by weight in GC analysis (the charged amount is 100% by weight). A cocoon-like product was obtained. The obtained product is a mixture of pentaerythritol triacrylate ε-caprolactone modified product (lactone polymer (2); corresponding to the component (A) described above) and pentaerythritol tetraacrylate, and the hydroxyl value is 52 It was .5 mg KOH / g. FIG. 2 shows a chart (solvent: deuterated chloroform) of ¹ H-NMR spectrum of the above-mentioned product.

Synthesis example 3
[Synthesis of Lactone Modified Body of Multifunctional Acrylic Compound (Lactone Polymer (3))]
In a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction pipe, and condenser, 191.5 g of pentaerythritol (tri / tetra) acrylate (trade name "Alonix M305", manufactured by Toagosei Co., Ltd.), ε- 308.0 g of caprolactone (trade name “Placcel M”, manufactured by Daicel Co., Ltd.), 0.36 g (720 ppm) of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.), and tin octylate (trade name “Stanocto”, A charge of 0.055 g (110 ppm) (manufactured by AP Corporation) and remaining at 130 ° C. while blowing a mixed gas having an air / nitrogen ratio (volume ratio) of 1/2 at 30 ml / min. The reaction is carried out until the amount of ε-caprolactone to be added is less than 1% by weight in GC analysis (the charged amount is 100% by weight). A cocoon-like product was obtained. The obtained product is a mixture of ε-caprolactone modified product of pentaerythritol triacrylate (lactone polymer (3); corresponding to the component (A) described above) and pentaerythritol tetraacrylate, and the hydroxyl value is 43 It was .3 mg KOH / g.

  The trade name "ALONIX M 305" is a mixture of pentaerythritol triacrylate (tri) and pentaerythritol tetraacrylate (tetra) in a ratio (by weight) of 60: 40 (tri: tetra). is there. That is, the addition mole number of ε-caprolactone to 1 mole of pentaerythritol triacrylate in Synthesis Example 1 is 2 moles, the addition mole number in Synthesis Example 2 is 5 moles, and the addition mole number in Synthesis Example 3 is 7 moles It is a mole.

Example 1
[Synthesis of Urethane Acrylate (UA1)]
898 g of the product obtained in Synthesis Example 1, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 100 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) was continuously added dropwise over 3 hours. Subsequently, the reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA1). In addition to urethane acrylate (urethane (meth) acrylate of the present invention), UA1 contains pentaerythritol tetraacrylate.
Moreover, the residual isocyanate group concentration is measured by the above-mentioned titration method, and the same applies to the following examples.
FIG. 3 shows a chart (solvent: heavy chloroform) of ¹ H-NMR spectrum of the obtained urethane acrylate (UA1). Moreover, the chart of IR spectrum of the obtained urethane acrylate (UA1) is shown in FIG. The GPC elution curve of the obtained urethane acrylate (UA1) is shown in FIG. As a result of molecular weight measurement in terms of standard polystyrene, the weight average molecular weight (Mw) of urethane acrylate (component of peak top holding time 20.88 minutes) in UA1 is 2772, number average molecular weight (Mn) is 1840, and molecular weight distribution ( Mw / Mn) was 1.51.

Example 2
[Synthesis of Urethane Acrylate (UA2)]
928 g of the product obtained in Synthesis Example 2, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 70 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) was continuously added dropwise over 3 hours. Subsequently, the reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA2). In addition to urethane acrylate (urethane (meth) acrylate of the present invention), pentaerythritol tetraacrylate is contained in UA2.
FIG. 6 shows a chart (solvent: heavy chloroform) of ¹ H-NMR spectrum of the obtained urethane acrylate (UA2). Moreover, the chart of IR spectrum of the obtained urethane acrylate (UA2) is shown in FIG. FIG. 8 shows the GPC elution curve of the resulting urethane acrylate (UA2). As a result of the molecular weight measurement in terms of standard polystyrene, the weight average molecular weight (Mw) of urethane acrylate (component with peak top holding time of 20.13 minutes) in UA2 is 4248, the number average molecular weight (Mn) is 2436, and the molecular weight distribution ( Mw / Mn) was 1.74.

Example 3
[Synthesis of Urethane Acrylate (UA3)]
899 g of the product obtained in Synthesis Example 1, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 99 g of 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK) was continuously added dropwise over 3 hours. Subsequently, the reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA3). In addition to urethane acrylate (urethane (meth) acrylate of the present invention), pentaerythritol tetraacrylate is contained in UA3.

Example 4
[Synthesis of Urethane Acrylate (UA4)]
Charge 129g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) and 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) into a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction pipe, and condenser, and measure the internal temperature. The temperature was raised to 60 ° C., and 290 g of polyester polyol (trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was continuously added dropwise over 2 hours. Further, after aging for 1 hour, 1.0 g of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 580 g of the product obtained in Synthesis Example 1 were continuously added dropwise over 2 hours. The reaction was performed until the residual isocyanate group concentration was less than 0.1% by weight to obtain urethane acrylate (UA4). In addition to urethane acrylate (urethane (meth) acrylate of the present invention), pentaerythritol tetraacrylate is contained in UA4.

Example 5
[Synthesis of Urethane Acrylate (UA5)]
Charge 101 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) and 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) into a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction pipe, and condenser, and measure the internal temperature. The temperature was raised to 60 ° C., and 228 g of polyester polyol (trade name “Nipporan 4002”, manufactured by Nippon Polyurethane Industry Co., Ltd.) was continuously added dropwise over 2 hours. Further, after aging for 1 hour, 1.0 g of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) and 670 g of the product obtained in Synthesis Example 2 were continuously added dropwise over 2 hours. The reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA5). In addition, in addition to urethane acrylate (urethane (meth) acrylate of this invention), pentaerythritol tetraacrylate is contained in UA5.

Example 6
[Synthesis of Urethane Acrylate (UA6)]
839 g of the product obtained in Synthesis Example 1, 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 160 g of trimers of hexamethylene diisocyanate (trade name "Takenate D-170N", manufactured by Mitsui Chemicals, Inc.) were continuously added dropwise over 3 hours. The reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain urethane acrylate (UA6). In addition, in addition to urethane acrylate (urethane (meth) acrylate of this invention), pentaerythritol tetraacrylate is contained in UA6.

Example 7
[Synthesis of Urethane Acrylate (UA7)]
884 g of the product obtained in Synthesis Example 2, 0.5 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 114 g of hexamethylene diisocyanate trimer (trade name "Takenate D-170N", manufactured by Mitsui Chemicals, Inc.) was continuously added dropwise over 3 hours. The reaction was performed until the residual isocyanate group concentration was less than 0.1% by weight to obtain urethane acrylate (UA7). In addition to urethane acrylate (urethane (meth) acrylate of the present invention), UA7 contains pentaerythritol tetraacrylate.

Comparative Example 1
[Synthesis of Urethane Acrylate (UA8)]
In a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser, 859 g of pentaerythritol (tri / tetra) acrylate (trade name "Alonix M 305", manufactured by Toagosei Co., Ltd.), dibutyltin dilaurate (Nitto 1.0g of chemical conversion (made) and 1.0g of 4-methoxy phenol (made by Kawaguchi Chemical Industry Co., Ltd.) were prepared, and the internal temperature was raised to 60 degreeC. Next, 139 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) was continuously added dropwise over 3 hours. The reaction was carried out until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA8).

Comparative example 2
[Synthesis of Urethane Acrylate (UA9)]
In a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube, and condenser, a compound in which caprolactone (4 moles per 1 mole of pentaerythritol) has been modified and which is further triacrylated (ie, pentaerythritol) A monomer obtained by acrylated lactone-modified product, 940 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 1.0 g of 4-methoxyphenol (manufactured by Kawaguchi Chemical Industry Co., Ltd.) are charged, and the internal temperature is 60 ° C. The temperature was raised. Next, 58 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) was continuously added dropwise over 3 hours. The reaction was performed until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA9).

Comparative example 3
[Synthesis of Urethane Acrylate (UA10)]
940 g of the product obtained in Synthesis Example 3, 1.0 g of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.), and 4-methoxyphenol in a reaction vessel equipped with a stirrer, thermometer, mixed gas introduction tube and condenser 1.0 g (manufactured by Kawaguchi Chemical Industry Co., Ltd.) was charged, and the internal temperature was raised to 60 ° C. Next, 58 g of isophorone diisocyanate (manufactured by Evonik Co., Ltd.) was continuously added dropwise over 3 hours. The reaction was performed until the residual isocyanate group concentration was less than 0.1% by weight to obtain a urethane acrylate (UA10).

Below, the brief description about each urethane acrylate obtained by Examples 1-7 and Comparative Examples 1-3 is shown. In addition, although a pentaerythritol tetraacrylate is also contained in UA1-UA8 and UA10, the point was abbreviate | omitted.
UA1: reaction product of lactone polymer (1) and isophorone diisocyanate (IPDI) UA2: reaction product of lactone polymer (2) and IPDI UA3: reaction product of lactone polymer (1) and 2-acryloyloxyethyl isocyanate UA4: Reactant of polyester diol and lactone polymer (1) and IPDI UA5: Reactant of polyester diol and lactone polymer (2) and IPDI UA6: Reactant of lactone polymer (1) and hexamethylene diisocyanate (HDI nurate) UA7: Reactant of lactone polymer (2) and HDI nurate UA8: Reactant of pentaerythritol triacrylate and IPDI UA9: Reactant of lactone modified product of pentaerythritol and acrylated monomer and IPDI UA10: Lactone polymer 3) a reaction product of IPDI

Examples 8 to 20, Comparative Examples 4 to 7
[Preparation of active energy ray curable urethane (meth) acrylate composition]
The components shown in Table 1 are sequentially introduced into the stainless beaker at a ratio shown in Table 1 while stirring and mixing using a stirring motor to obtain each composition (active energy ray curable urethane (meth) acrylate composition) The

  The following evaluation was performed about the hardened | cured material (hardened coating film) of the active energy ray hardening-type urethane (meth) acrylate composition obtained above.

(Taber abrasion test)
First, an active energy ray-curable type obtained above with a bar coater # 4 on a polycarbonate plate having a thickness of 1 mm, a length of 100 mm, and a width of 100 mm (trade name "standard test plate" manufactured by Nippon Test Panels Ltd.) After the urethane (meth) acrylate composition is applied, it is irradiated with ultraviolet light (5 m / min × 2 kW, irradiation distance 11 cm, irradiation frequency twice, accumulated light amount 900 mJ / cm ² ) to cure the above composition, and the film thickness is 20 μm. A cured coating (coating) was prepared. This was used as a sample.
The Taber abrasion test was performed in the following procedure using the above samples.
In accordance with ASTM D-1044, using a Taber abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the cured film on the above sample is abraded under the conditions of abrasion wheel CS-10F, load 500 g, rotation speed 300 cycles I did. After abrasion, the cured coating film of the sample is cleaned, and the haze of the sample (referred to as "haze after abrasion") is measured with a haze meter (trade name "HAZE METER NDH 2000" manufactured by Nippon Denshoku Co., Ltd.). The difference (ΔHaze; post-abrasive haze (%)-initial haze (%)) from the haze of the previous sample (this is referred to as “initial haze”) was calculated. The abrasion resistance (friction resistance) was evaluated based on the obtained value of ΔHaze. The results are shown in the "Taber abrasion" column of Table 1.
((Very good wear resistance): 摩 耗 Haze less than 5% ○ (good wear resistance): H Haze 5% or more and less than 10% ((defective wear resistance): H Haze 10% or more Less than 20% × (very poor in wear resistance): ΔHaze is 20% or more

(Steel wool resistance)
First, the same sample as that produced by the Taber abrasion test was prepared. Evaluation of steel wool resistance (scratch resistance) was performed according to the following procedure using the sample.
For the surface of the cured coating on the sample, the 60 ° gloss before the test was measured with a gloss meter, and then the surface of the cured coating was rubbed 100 times back and forth under a load of 1 kg / cm ² using # 0000 steel wool. . After the test, the 60 ° gloss (60 ° gloss after the test) of the rubbing portion was measured in the same manner as before the test, and the gloss retention was calculated by the following equation. The steel wool resistance was evaluated based on the value of the gloss retention based on the following criteria. The results are shown in the "Steel wool resistance" column of Table 1.
Formula: gloss retention% = gloss value after test 試 験 gloss value before test × 100
((Very good scratch resistance): gloss retention of 95% or more ○ (good scratch resistance): gloss retention of 90% or more and less than 95% Δ (poor scratch resistance): gloss retention of 80 % Or more and less than 90% x (very poor in scratch resistance): gloss retention less than 80%

(Curl resistance)
First, using the wire bar # 4, a 100 μm thick polyethylene terephthalate film (PET film; trade name “O321E”, Mitsubishi Resins Co., Ltd.) using the active energy ray-curable urethane (meth) acrylate composition obtained above It cast-coated on the whole surface on the product made; length 10 cm x width 10 cm. Thereafter, the composition is cured by ultraviolet irradiation (5 m / min × 2 kW, irradiation distance 11 cm, irradiation twice, integrated light quantity 900 mJ / cm ² ), and the obtained PET film / cured product laminate is used as a sample. Using.
It is checked visually whether the sample has curled. If curled, place it on a horizontal surface with the convex direction down and measure the height from the horizontal surface of the four corners (four corners) The average value of these was calculated. From the value of this average value (average value of height), the following criteria evaluated curl resistance. The results are shown in the "curl resistance" column of Table 1.
((Very good curl resistance): average height of 0 cm or more and less than 1 cm ○ (good curl resistance): average height of 1 cm or more and less than 3 cm Δ (defective to curl resistance): Average height is 3 cm or more and less than 5 cm × (very poor in curl resistance): average height is 5 cm or more

The meanings of the abbreviations shown in Table 1 are as follows. The meanings of UA1 to UA10 in Table 1 are as described above.
PETIA: trade name “PETIA” (pentaerythritol (tri / tetra) acrylate), manufactured by Daicel Ornex Co., Ltd. IRR 214 K: trade name “IRR 214 K” (tricyclodecane dimethanol diacrylate), Daicel Ornex Co., Ltd. TPGDA : Trade name "TPGDA" (tripropylene glycol diacrylate), Daicel Ornex Co., Ltd. DPHA: Trade name "DPHA" (dipentaerythritol hexaacrylate), Daicel Ornex Co., Ltd. Irg 184: Trade name "IRGACURE 184"(Photoinitiator; 1-hydroxycyclohexyl phenyl ketone), manufactured by BASF

  As shown in Table 1, according to the composition (the active energy ray-curable urethane (meth) acrylate composition of the present invention; Examples 8 to 20) containing the urethane (meth) acrylate of the present invention as an essential component, the surface hardness It was confirmed that a cured product (cured coating film) excellent in any of (wear resistance, scratch resistance) and curl resistance was obtained. On the other hand, according to compositions (Comparative Examples 4 to 7) using other urethane (meth) acrylates or polyfunctional (meth) acrylates instead of the urethane (meth) acrylates of the present invention, the abrasion resistance and scratch resistance Only cured products inferior in one or more of the curl resistance properties were obtained. Further, as in Comparative Examples 5 and 7, when the lactone modified hydroxyl group-containing poly (meth) acrylate is used in which the addition molar number of lactone is 0 mol times or 7 mol times with respect to 1 mol of hydroxyalkyl poly (meth) acrylate. In contrast, it is shown that remarkable effects are exhibited in the surface hardness and the curl resistance when the above-mentioned addition mole number is 1 to 6 mole times (Examples 8 to 20).

  The urethane (meth) acrylate of the present invention and the active energy ray-curable urethane (meth) acrylate composition containing the same are used, for example, in coating applications, coating applications, adhesive applications, etc. (eg, coatings, coatings, adhesives etc. Can be preferably used).

Claims (7)

Lactone modified hydroxyl group-containing poly (meth) acrylate (A) in which 1 to 6 moles of lactone is added to 1 mole of hydroxyalkyl poly (meth) acrylate (A), and isocyanate compound having one or more isocyanate groups per molecule B) and a urethane (meth) acrylate obtained by reacting,
Urethane (meth) acrylate wherein the poly (meth) acrylate (A) is a (meth) acrylate having one hydroxyl group per molecule and two or more (meth) acryloyl groups per molecule . Lactone modified hydroxyl group-containing poly (meth) acrylate (A) in which 1 to 6 moles of lactone is added to 1 mole of hydroxyalkyl poly (meth) acrylate (A), and isocyanate compound having two or more isocyanate groups per molecule Urethane (meth) acrylate obtained by reacting B1) with a polyol (C) having two or more hydroxyl groups per molecule ,
Urethane (meth) acrylate wherein the poly (meth) acrylate (A) is a (meth) acrylate having one hydroxyl group per molecule and two or more (meth) acryloyl groups per molecule .   The urethane (meth) acrylate according to claim 1 or 2, wherein the hydroxyalkyl poly (meth) acrylate is pentaerythritol tri (meth) acrylate.   An active energy ray-curable urethane (meth) acrylate composition comprising the urethane (meth) acrylate according to any one of claims 1 to 3.   The active energy ray curable urethane (meth) acrylate composition according to claim 4, further comprising a (meth) acryloyl group-containing monomer.   Furthermore, the active energy ray curable urethane (meth) acrylate composition according to claim 4 or 5, further comprising a photopolymerization initiator.   A cured product obtained by curing the active energy ray-curable urethane (meth) acrylate composition according to any one of claims 4 to 6.

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