JP2015143350A - Active energy ray curable composition and coating agent, and novel urethane bond-containing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition and a coating agent having excellent applicability to a base material or the like with low viscosity and being excellent in both strength and flexibility of a formed cured coating film.SOLUTION: An active energy ray curable composition comprises a urethane bond-containing compound (A1) having a specific structure, a urethane bond-containing compound (A2) having a specific structure and a urethane bond-containing compound (A3) having a specific structure.

Description

  The present invention relates to an active energy ray-curable composition and a coating agent. More specifically, the present invention relates to a low viscosity, good coating property to a substrate and the like, and both the strength and flexibility of a formed cured coating film are excellent. The present invention relates to an active energy ray-curable composition and a coating agent containing the composition.

2. Description of the Related Art Conventionally, active energy ray-curable resin compositions have been widely used as coating agents, adhesives, anchor coating agents, and the like for various substrates because curing is completed by irradiation with a very short amount of radiation. Especially, the utility as an active energy ray hardening-type coating agent is high.
In general, polyfunctional urethane (meth) acrylate compounds are used, and from the flexibility of the urethane skeleton, when stretching and molding including the substrate after forming the cured coating film, It has been.

However, since conventional urethane (meth) acrylate compounds show a certain degree of stretchability but lack strength, when used in fields where flexibility and strength are required simultaneously, a polyfunctional urethane ( It was not sufficient to use a meth) acrylate compound alone.
In addition, in order to achieve both strength and flexibility, a general dilution monomer is blended in order to adjust the viscosity of the paint, but in such a method, exposure to heat is caused by the influence of the residual monomer in the cured coating film. Doing so will cause problems such as odor.

  Due to the above circumstances, in recent years, by blending with a general urethane (meth) acrylate compound, flexibility and strength can be imparted to the cured coating film, and it does not volatilize when exposed to heat. There is a need for the development of an oligomer-type compounding agent that has a molecular weight of 1 and does not excessively increase the viscosity of the composition.

  For example, in Patent Document 1, the curable composition contains an oligomer, at least one monomer, and a substantially non-reactive oligomer additive, and does not include the non-reactive oligomer additive. A composition comprising an amount of oligomer additive effective to produce a cured product having a fracture toughness value higher than the fracture toughness value of the cured product of the same composition, What are other non-reactive organic additives that act as harmful plasticizers even though the reactive oligomer additive is substantially free of polymerizable functional groups to chemically bond to the polymer coating network? In contrast, it has been described to improve the mechanical properties and toughness of the coating.

Special table 2009-514994

  However, in the disclosed technique disclosed in Patent Document 1, the cured coating film has high strength but lacks flexibility (for example, elongation), and it is difficult to stretch or stretch the substrate after forming the cured coating film. It was unsuitable for use in fields where strength and strength were required at the same time.

  Therefore, the active energy ray-curable composition according to the present invention, which has a low viscosity and good coatability on a substrate, and is excellent in both strength and flexibility of a formed cured coating film, and The object is to provide a coating agent.

  However, as a result of intensive studies in view of such circumstances, the present inventors have found that, in addition to the urethane bond-containing compound having only an ethylenically unsaturated group, one end is an ethylenically unsaturated group and the other end is a monool. By using a composition containing three types of urethane bond-containing compounds: a urethane bond-containing compound having a urethane bond residue, and a urethane bond-containing compound having a urethane bond residue whose both ends are monools. The present invention was completed by finding that the cured coating film formed in the above has excellent strength and flexibility (particularly elongation).

  That is, the gist of the present invention is represented by the urethane bond-containing compound (A1) represented by the following general formula (1), the urethane bond-containing compound (A2) represented by the general formula (2), and the general formula (3). The present invention relates to an active energy ray-curable composition (A) comprising a urethane bond-containing compound (A3).

[Formula 1]

[Formula 2]

[Formula 3]

(In the above general formulas (1) to (3), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, X ₂ Is a urethane bond residue of the polyvalent isocyanate compound (a2) having n isocyanate groups, X ₃ is a urethane bond residue of the monool compound (a3), and R is hydrogen or a methyl group Yes, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.)

  In the present invention, the active energy ray curable composition (A) and the ethylenically unsaturated curable composition (A) are used as a compounding agent for the ethylenically unsaturated group-containing compound (B). An active energy ray-curable composition [I] comprising the saturated group-containing compound (B) is also provided.

  Furthermore, the present invention also provides a coating agent comprising the active energy ray curable composition (A) or the active energy ray curable composition [I].

  The present invention also provides a novel urethane bond-containing compound represented by the following general formula (4).

[Formula 4]

(In the general formula (4), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, and X ₂ is n The urethane bond residue of the polyisocyanate compound (a2) having an isocyanate group, X ₃ is a urethane bond residue of the aliphatic monool compound (a4) having 3 to 9 or 11 to 30 carbon atoms, R is hydrogen or a methyl group, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.)

  The active energy ray curable composition of the present invention (hereinafter referred to as the active energy ray curable composition (A) or the active energy ray curable composition [I]), and the active energy ray curable composition without reference numerals. ) Is low viscosity and has good coating properties on base materials, etc., and when coated on a base material to form a cured coating film, both strength and flexibility are excellent. In particular, it is very useful as a coating agent, especially as a coating agent for molded substrates.

4 is a ¹ H-NMR chart of a urethane bond-containing compound in the active energy ray-curable composition (A-4) obtained in Example 4. FIG.

The present invention is described in detail below.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.

  The active energy ray-curable composition (A) of the present invention comprises urethane bond-containing compounds (A1) to (A3) represented by the following general formulas (1) to (3).

[Formula 5]

[Formula 6]

[Formula 7]

(In the above general formulas (1) to (3), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, X ₂ Is a urethane bond residue of the polyvalent isocyanate compound (a2) having n isocyanate groups, X ₃ is a urethane bond residue of the monool compound (a3), and R is hydrogen or a methyl group Yes, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.)

In the present invention, the urethane bond-containing compound (A1) can be obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a1), a polyvalent isocyanate compound (a2), and a monool compound (a3). it can.
The urethane bond-containing compound (A2) can be obtained by reacting the hydroxyl group-containing (meth) acrylate compound (a1) and the polyvalent isocyanate compound (a2).
The urethane bond-containing compound (A3) can be obtained by reacting the polyvalent isocyanate compound (a2) and the monool compound (a3).

Each raw material used in the present invention will be described.
[Hydroxyl group-containing (meth) acrylate compound (a1)]
Examples of the hydroxyl group-containing (meth) acrylate compound (a1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable because it can relieve curing shrinkage at the time of coating film formation, and more preferably 2-hydroxyethyl (meth). It is a hydroxyalkyl (meth) acrylate such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, particularly It is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility.
Moreover, these can be used 1 type or in combination of 2 or more types.

[Polyvalent isocyanate compound (a2)]
Examples of the polyvalent isocyanate compound (a2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1 , 3 Bis (isocyanatomethyl) cyclohexane, alicyclic polyisocyanates, or trimers compound or multimeric compounds of these polyisocyanates, allophanate type polyisocyanate, buret type polyisocyanate, and the like.

Among these, aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene from the point of little yellowing Cycloaliphatic diisocyanates such as diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane are preferably used, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate are particularly preferable in terms of low cure shrinkage. More preferably, hydrogenated xylylene diisocyanate and isophorone diisocyanate are used because they are excellent in reactivity and versatility. Sulfonate is used.
Moreover, these can be used 1 type or in combination of 2 or more types.

[Monol compound (a3)]
Examples of the monool compound (a3) include methanol, ethanol, 1-butanol, isobutanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, isohexadecanol, 1-octadecanol, isooctadecanol, 1-eicosanol, isoeicosanol, 1-docosanol, 1-tetracosanol, 1-octacosanol, 1-triacontanol Saturated aliphatic monools such as cis-9-hexadecene-1-ol, 9E-octadecene-1-ol, cis-9-octadecen-1-ol, 9Z, 12Z-octadecadien-1-ol, 9Z , 12Z, 15Z-octadecatrien-1-ol, 9E, 12 , 15E- octadecatrienoic-1-ol, cis-13-docosenoic-1-ol unsaturated aliphatic monool, and aromatic monool such as benzyl alcohol. Moreover, the compound by which alkylene oxide modification or caprolactone modification was carried out to those frame | skeleton may be sufficient.

Among these, saturated aliphatic monools are preferred from the viewpoint of less yellowing, especially saturated aliphatic monools having 1 to 30 carbon atoms, and more bulky, so that the selectivity of the product can be easily controlled, and branching is also possible. A monool having a branched structure having 10 to 25 carbon atoms, such as isohexadecanol, isoeicosanol, and isooctadecanol, which is easy to handle due to its structure and has no crystallinity, is particularly preferable.
Moreover, these can be used 1 type or in combination of 2 or more types.

  In the present invention, the urethane bond-containing compound (A1) has a weight average molecular weight of usually 100 to 10,000, preferably 200 to 5,000, particularly preferably 300 to 3,000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

  The weight average molecular weight of the urethane bond-containing compound (A2) is usually 100 to 10,000, preferably 200 to 5,000, particularly preferably 300 to 3,000. When the weight average molecular weight is too small, the cured coating film tends to be brittle, and when it is too large, the viscosity becomes high and the handling tends to be difficult.

  Furthermore, the weight average molecular weight of the urethane bond-containing compound (A3) is usually 100 to 10,000, preferably 200 to 5,000, particularly preferably 300 to 3,000. When the weight average molecular weight is too small, the cured coating film tends to be brittle, and when it is too large, the viscosity becomes high and the handling tends to be difficult.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, column: Shodex GPC KF-806L (exclusion) in a high performance liquid chromatography (Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). 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) Measured by using series.

  In the present invention, an active energy ray-curable composition (A) containing the urethane bond-containing compound (A1), the urethane bond-containing compound (A2) and the urethane bond-containing compound (A3) is obtained. About a content rate, a urethane bond containing compound (A1) is 40-99.8 weight% with respect to the total amount of a urethane bond containing compound (A1), a urethane bond containing compound (A2), and a urethane bond containing compound (A3). The urethane bond-containing compound (A2) is preferably 0.1 to 50% by weight, and the urethane bond-containing compound (A3) is preferably 0.1 to 50% by weight. Particularly preferably, the urethane bond-containing compound (A1) is 50 to 99% by weight, the urethane bond-containing compound (A2) is 0.5 to 40% by weight, the urethane bond-containing compound (A3) is 0.5 to 40% by weight, More preferably, the urethane bond-containing compound (A1) is 55 to 98% by weight, the urethane bond-containing compound (A2) is 1 to 35% by weight, and the urethane bond-containing compound (A3) is 1 to 35% by weight.

  If the content of the urethane bond-containing compound (A1) is too small, the elongation and strength tend to decrease. When the content ratio of the urethane bond-containing compound (A2) is too small, the strength tends to decrease. When the content is too large, the strength tends to decrease although the strength increases due to an increase in the crosslinking density. If the content of the urethane bond-containing compound (A3) is too small, the elongation tends to decrease. If the content is too large, a sufficient crosslinking density cannot be obtained, the strength decreases, and the cured coating film surface tends to be sticky.

The active energy ray-curable composition (A) in the present invention preferably has a viscosity at 60 ° C. of 10 to 50,000 mPa · s, particularly 15 to 10,000 mPa · s, more preferably 20 to 2. 1,000 mPa · s is preferable. If the viscosity is too low or too high, the coatability of the active energy ray-curable composition tends to decrease.
The viscosity is measured with an E-type viscometer.

  The active energy ray-curable composition (A) of the present invention can be produced, for example, as follows.

(1) A method in which urethane bond-containing compounds (A1) to (A3) are separately produced and then mixed.
(2) A method in which any two types of urethane bond-containing compounds among urethane bond-containing compounds (A1) to (A3) are simultaneously manufactured and then mixed with the remaining urethane bond-containing compounds that have been separately manufactured.
(3) A method in which the urethane bond-containing compounds (A1) to (A3) are simultaneously produced to form a mixture of three types of urethane bond-containing compounds.
Among these, the method (3) is preferable from the viewpoint of production efficiency.

  In addition, when manufacturing each urethane bond containing compound (A1), (A2), (A3) independently, it can carry out according to the method of a conventionally well-known urethane reaction.

Below, the manufacturing method of said (3) is demonstrated.
In the present invention, the above-mentioned hydroxyl group-containing (meth) acrylate compound (a1), polyvalent isocyanate compound (a2), and monool compound (a3) may be charged or reacted together in a reactor. However, in particular, the monool compound (a3) and the polyvalent isocyanate compound (a2) are charged into a reactor and allowed to react in view of advantageous reaction stability and control of product selectivity. Then, it is preferable to charge and react the hydroxyl group-containing (meth) acrylate compound (a1).

  In particular, in order to obtain the urethane bond-containing compound (A1) with good yield, the molar ratio of the hydroxyl group-containing (meth) acrylate compound (a1), the polyvalent isocyanate compound (a2), and the monool compound (a3) is The following is preferable.

  That is, with respect to the polyvalent isocyanate compound (a2), the hydroxyl group-containing (meth) acrylate compound (a1) is 0.5 to 1.5 (molar ratio), particularly 0.7 to 1.3 (mole). Ratio). If the amount of the hydroxyl group-containing (meth) acrylate compound (a1) is too small, a sufficient crosslinking density cannot be obtained and the strength tends to decrease. If the amount is too large, the crosslinking tends to be excessive and the elongation tends to decrease. The monool compound (a3) is 1.5 to 0.5 (molar ratio), particularly 1.3 to 0.7 (molar ratio) with respect to the polyvalent isocyanate compound (a2). preferable. When the monool compound (a3) is too small, it is excessively crosslinked and the elongation tends to decrease, and when it is too large, a sufficient crosslinking density cannot be obtained and the strength tends to decrease.

  The reaction conditions may be determined in consideration of the selectivity of the products of the urethane bond-containing compounds (A1) to (A3). For example, for the reaction temperature, the urethane bond-containing compound (A1) is obtained with a good yield. In addition, it is preferable to set the temperature within the range of about 30 to 80 ° C. However, it is appropriate to carry out the reaction at 60 to 70 ° C. because the reaction time can be shortened. Preferably it is 3 to 8 hours.

  In the urethane reaction in the hydroxyl group-containing (meth) acrylate compound (a1), the polyvalent isocyanate (a2), and the monol (a3), it is also preferable to use a catalyst for the purpose of accelerating the reaction. Organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc bisacetylacetonate, zirconium tris (acetylacetonato) ethylacetoacetate, zirconium tetraacetylacetonate, hexane Zinc acid, zinc octenoate, tin octenoate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannic chloride, potassium acetate and other metal salts, triethylamine, triethylenediamine, benzyl Ethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine, In addition to amine-based catalysts such as N-methylmorpholine and N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, and 2-ethylhexane Bismuth acid salt, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bismuth Neodecanoate, bismuth disalicylate, Bismuth catalysts such as organic bismuth salts such Kosan bismuth salts. Among these, dibutyltin dilaurate, 1,8-diazabicyclo [5,4,0] undecene is preferred. These can be used alone or in combination of two or more.

  The amount of such a catalyst is usually 0.01 to 1000 ppm, preferably 0.1 to 500 ppm, particularly preferably 1 to 300 ppm, based on the total amount of reaction components.

Thus, the active energy ray-curable composition (A) of the present invention comprising the urethane bond-containing compounds (A1), (A2) and (A3) is obtained.
The active energy ray-curable composition (A) of the present invention can be applied as it is on a substrate as a coating agent to form a cured coating film excellent in both flexibility and strength. Using the curable composition (A) as a compounding agent, particularly as a compounding agent for the ethylenically unsaturated group-containing compound (B), the active energy ray-curable composition (A) and the ethylenically unsaturated compound The active energy ray-curable composition [I] containing the group-containing compound (B) is preferable.
Furthermore, in this invention, it is also preferable that a photoinitiator (C) and a solvent (D) are contained in the active energy ray-curable composition (A) or the active energy ray-curable composition [I].

  The ethylenically unsaturated group-containing compound (B) is preferably used for forming a cured coating film having excellent strength. The urethane (meth) acrylate compound (B1) and the ethylenically unsaturated monomer (B2) are used. Etc.

[Urethane (meth) acrylate compound (B1)]
The urethane (meth) acrylate compound (B1) used in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1), a polyvalent isocyanate compound (b2), and a polyol compound (b3). Urethane (meth) acrylate compound (B1-1) or a urethane (meth) acrylate compound (B1) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1) and a polyvalent isocyanate compound (b2) ( B1-2) may be used, and one of these may be used alone, or two or more may be used in combination.

  Among these, the urethane (meth) acrylate compound (B1-1) is preferable from the viewpoint of excellent flexibility of the cured coating film, and the urethane (meth) acrylate compound (B1-2) is preferable from the viewpoint of excellent hardness of the cured coating film. Although it is preferable, it is appropriately selected in consideration of imparting various physical properties of the target coating film.

  The weight average molecular weight of the urethane (meth) acrylate compound (B1) used in the present invention is preferably 500 to 50000, more preferably 1000 to 30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

  The weight average molecular weight is measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (B1) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and further preferably 1000 to 100,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured with an E-type viscometer.

<Urethane (meth) acrylate compound (B1-1)>
The urethane (meth) acrylate compound (B1-1) in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1), a polyvalent isocyanate compound (b2), and a polyol compound (b3). Is.

  Examples of the hydroxyl group-containing (meth) acrylate compound (b1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) Acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate, caprolactone-modified penta Erythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, etc. Is mentioned.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable because it can relieve curing shrinkage at the time of coating film formation, and more preferably 2-hydroxyethyl (meth). It is a hydroxyalkyl (meth) acrylate such as acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, particularly It is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility.
Moreover, these can be used 1 type or in combination of 2 or more types.

  Examples of the polyvalent isocyanate compound (b2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aliphatic polyisocyanates such as polyisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1 , 3 Bis (isocyanatomethyl) cyclohexane, alicyclic polyisocyanates, or trimers compound or multimeric compounds of these polyisocyanates, allophanate type polyisocyanate, buret type polyisocyanate, and the like.

  Among these, aliphatic diisocyanates such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene from the point of little yellowing Cycloaliphatic diisocyanates such as diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane are preferably used, and particularly preferably isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate in terms of low cure shrinkage. More preferably, hydrogenated xylylene diisocyanate and isophorone diisosodium are used because they are excellent in reactivity and versatility. Aneto is used.

  Examples of the polyol compound (b3) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.

  Examples of the polyether polyol include, for example, polyether glycols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Coalescence is mentioned.

  Examples of the polyester-based polyol include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

  Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, trimellitic acid, and the like.

  Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).

  Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.

  In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  Examples of the polyolefin-based polyol include those having a homopolymer or copolymer such as ethylene, propylene, and butene as a saturated hydrocarbon skeleton, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

  Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.

  Examples of the polysiloxane-based polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

  Among these, polyester polyols and polyether polyols are preferable, and polyether polyols are particularly preferable because they are excellent in mechanical properties such as flexibility during curing.

  As a number average molecular weight of the said polyol type compound (b3), 500-8000 are preferable, Especially preferably, it is 550-5000, More preferably, it is 600-3000. If the molecular weight of the polyol compound (b3) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if too small, curing shrinkage tends to increase and stability tends to decrease.

  The production method of the urethane (meth) acrylate compound (B1-1) is usually a reaction between the hydroxyl group-containing (meth) acrylate compound (b1), the polyvalent isocyanate compound (b2), and the polyol compound (b3). The reaction product obtained by reacting the polyol-based compound (b3) and the polyvalent isocyanate-based compound (b2) in advance may be added to the vessel all at once or separately, and the hydroxyl group-containing (meth) acrylate-based compound. The reaction of (b1) is useful in terms of reaction stability and reduction of by-products.

  For the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), known reaction means can be used. At that time, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (b2) to the hydroxyl group in the polyol compound (b3) is usually about 2n: (2n-2) (n is an integer of 2 or more). By doing this, after obtaining a terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (b1) is made possible.

  The addition reaction of the reaction product obtained by reacting the polyol compound (b3) and the polyvalent isocyanate compound (b2) in advance with the hydroxyl group-containing (meth) acrylate compound (b1) is also a known reaction. Means can be used.

  The reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (b1) is, for example, that the polyisocyanate compound (b2) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b1). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 2, and the polyisocyanate compound (b2) has three isocyanate groups. When the hydroxyl group-containing (meth) acrylate compound (b1) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 3.

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (B1-1) is obtained.

  In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), a catalyst is used for the purpose of promoting the reaction. It is also preferable to use a catalyst, and examples of such a catalyst include those described above.

  In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), it reacts with the isocyanate group. Organic solvents having no functional group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and organic solvents such as aromatics such as toluene and xylene can be used.

  Moreover, reaction temperature is 30-90 degreeC normally, Preferably it is 40-80 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

  It is preferable that the weight average molecular weights of the obtained urethane (meth) acrylate type compound (B1-1) are 500-50000, More preferably, it is 1000-30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

  The weight average molecular weight is measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (B1-1) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and further preferably 1000 to 100,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured by an E-type viscometer as described above.

<Urethane (meth) acrylate compound (B1-2)>
The urethane (meth) acrylate compound (B1-2) in the present invention is obtained by reacting a hydroxyl group-containing (meth) acrylate compound (b1) and a polyvalent isocyanate compound (b2).

The urethane (meth) acrylate compound (B1-2) used in the present invention preferably has three or more ethylenically unsaturated groups from the viewpoint of the hardness of the cured coating film, particularly preferably four. Those having the above ethylenically unsaturated groups, more preferably those having 6 or more ethylenically unsaturated groups, and among these, pentaerythritol tri (meth) acrylate and isophorone diisocyanate are reacted. Particularly preferred are urethane (meth) acrylates having 6 ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (B1-2) contains is 30 normally, Preferably it is 25 or less.

  In order to adjust the number of ethylenically unsaturated groups, the hydroxyl group-containing (meth) acrylate compound (b1) and the polyvalent isocyanate compound (b2) may be appropriately selected and used. When using a hydroxyl group-containing (meth) acrylate compound (b1) having three ethylenically unsaturated groups and using a diisocyanate compound as the polyvalent isocyanate compound (b2), urethane (meth) acrylate The number of ethylenically unsaturated groups in the system compound (B1-2) is 6.

  What is necessary is just to manufacture according to the manufacturing method of the said urethane (meth) acrylate type compound (B1-1) about the manufacturing method of a urethane (meth) acrylate type compound (B1-2).

  The reaction molar ratio between the polyvalent isocyanate compound (b2) and the hydroxyl group-containing (meth) acrylate compound (b1) is, for example, that the polyisocyanate compound (b2) has two isocyanate groups and has a hydroxyl group content ( When the hydroxyl group of the (meth) acrylate compound (b1) is one, the polyvalent isocyanate compound (b2): hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 2, and the polyisocyanate compound When the compound (b2) has three isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b1) has one hydroxyl group, the polyvalent isocyanate compound (b2): hydroxyl group-containing (meth) acrylate compound (B1) is about 1: 3.

  In the addition reaction between the polyvalent isocyanate compound (b2) and the hydroxyl group-containing (meth) acrylate compound (b1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. By making it, a urethane (meth) acrylate type compound (B1-2) is obtained.

  It is preferable that the weight average molecular weights of the obtained urethane (meth) acrylate type compound (B1-2) are 500-50000, More preferably, it is 1000-30000. If the weight average molecular weight is too small, the cured coating film tends to be brittle, and if it is too large, the viscosity tends to be high and difficult to handle.

  The weight average molecular weight is measured in the same manner as described above.

The viscosity of the urethane (meth) acrylate compound (B1-2) at 60 ° C. is preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and further preferably 1000 to 100,000 mPa · s. When the viscosity is out of the above range, the coatability tends to be lowered.
The viscosity is measured by an E-type viscometer as described above.

<Ethylenically unsaturated monomer (B2)>
The ethylenically unsaturated monomer (B2) may be any ethylenically unsaturated monomer (excluding the urethane (meth) acrylate compound (B1)) having one or more ethylenically unsaturated groups in one molecule. , For example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer.

  The monofunctional monomer may be any monomer containing one ethylenically unsaturated group, such as styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Fester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  In addition to the monofunctional monomer, there may be mentioned a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, and acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like. Examples of 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The bifunctional monomer may be any monomer containing two ethylenically unsaturated groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) Examples include acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, and 2- (meth) acryloyloxyethyl acid phosphate diester.

  The tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene Oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene Side modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) ) Acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, succinic acid-modified pentaerythritol tri (meth) acrylate, and the like.

  These ethylenically unsaturated monomers (B2) may be used alone or in combination of two or more.

  In the present invention, the content ratio of the active energy ray-curable composition (A) and the ethylenically unsaturated group-containing compound (B) is active with respect to 100 parts by weight of the ethylenically unsaturated group-containing compound (B). The energy ray curable composition (A) is preferably 0.1 to 300 parts by weight, particularly 10 to 200 parts by weight, and more preferably 20 to 100 parts by weight. If the content of the active energy ray-curable composition (A) is too small, it tends to be difficult to obtain sufficient elongation / strength for the cured coating film. The coating tends to be sticky.

[Photopolymerization initiator (C)]
Examples of the photopolymerization initiator (C) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Acetophenones such as phenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether Benzoin etc. Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2, 4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy)- 3,4- Thioxanthones such as methyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphos Acylphosphine oxides such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, as for these photoinitiators (C), only 1 type may be used independently and 2 or more types may be used together.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

  Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.

As content of a photoinitiator (C), with respect to a total of 100 weight part of photopolymerizable components (active energy ray hardening-type composition (A), ethylenically unsaturated group containing compound (B), etc.), The amount is preferably 0.1 to 40 parts by weight, particularly preferably 1 to 20 parts by weight, particularly preferably 2 to 20 parts by weight.
If the content of the photopolymerization initiator (C) is too small, curing tends to be poor, while if too large, solution stability tends to decrease, such as precipitation from the paint, and embrittlement and coloring problems are likely to occur. Tend.

  In the present invention, a surface conditioner, a leveling agent, a polymerization inhibitor and the like can be further blended as necessary.

Examples of the surface conditioner include alkyd resins.
Such an alkyd resin has an effect of imparting a film-forming property at the time of application and an effect of increasing the adhesion to a metal vapor deposition surface.

  As the leveling agent, a known general leveling agent can be used as long as it has a wettability imparting action to the base material of the coating liquid and a surface tension reducing action. For example, a silicone-modified resin, a fluorine-modified resin, An alkyl-modified resin or the like can be used.

  Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t- Examples thereof include butyl hydroquinone and pt-butyl catechol.

  Furthermore, oils, antioxidants, flame retardants, antistatic agents, fillers, stabilizers, reinforcing agents, matting agents, abrasives, organic fine particles, inorganic fine particles, polymer compounds (acrylic resins, polyester resins, epoxy resins) , Etc.) can also be blended.

  Moreover, it is also possible to mix | blend an organic solvent as needed and to use it, adjusting a viscosity. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene And the like, glycol ethers such as propylene glycol monomethyl ether, acetates such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more. In addition, when using in the above-mentioned urethane reaction, it is preferable to select the solvent which does not contain a hydroxyl group.

  The active energy ray-curable composition of the present invention can be diluted to 3 to 60% by weight, preferably 5 to 40% by weight, using the organic solvent, and applied to a substrate.

  The active energy ray curable composition of the present invention is effectively used as a curable composition for forming a coating film such as a topcoat agent or an anchor coat agent on various substrates. After the product is applied to the base material (when the composition diluted with an organic solvent is applied, it is further dried) and then cured by irradiation with active energy rays. The coating method is not particularly limited, and examples thereof include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll, spin, dispenser, ink jet, and screen printing.

  As such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (C).

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. 30~3000mJ / cm ² about may be irradiated.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  The coating film thickness (film thickness after curing) is usually preferably 1 to 300 μm, particularly preferably 3 to 250 μm, more preferably 5 to 200 μm. If the film thickness is too thick, it is difficult to cure the active energy rays deeply, and if it is too thin, not only the coating surface but also the entire coating film will be affected by the inhibition of curing by oxygen. There is a tendency to be poorly cured.

  Examples of the base material to which the active energy ray-curable composition of the present invention is applied include polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS), polystyrene resin, and the like. Molded products (films, sheets, cups, etc.), metals (aluminum, copper, iron, SUS, zinc, magnesium, alloys thereof, etc.), glass and the like.

  The active energy ray-curable composition of the present invention can form a cured coating film excellent in both flexibility and strength, and can be used for paints, pressure-sensitive adhesives, adhesives, adhesives, inks, and protective coatings. It is useful as various film forming materials such as a coating agent, an anchor coating agent, a magnetic powder coating binder, a sandblast coating, and a plate material. Among them, it is very useful as a coating agent for molding base materials and the like.

  Moreover, in this invention, the novel urethane bond containing compound shown by following General formula (4) is provided.

[Formula 8]

(In the general formula (4), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, and X ₂ is n The urethane bond residue of the polyisocyanate compound (a2) having an isocyanate group, X ₃ is a urethane bond residue of the aliphatic monool compound (a4) having 3 to 9 or 11 to 30 carbon atoms, R is hydrogen or a methyl group, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.)

In the present invention, in the general formula (4), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups. Examples of the hydroxyl group-containing (meth) acrylate compound (a1) include the same ones as described above.

X ₂ in the general formula (4) is a urethane bond residue of the polyvalent isocyanate compound (a2) having n isocyanate groups. Examples of the polyvalent isocyanate compound (a2) are the same as described above.

X ₃ in the general formula (4) is a urethane bond residue of the aliphatic monool compound (a4) having 3 to 9 or 11 to 30 carbon atoms. Examples of the aliphatic monool compound (a4) include 1-propanol, isopropanol, 1-butanol, isobutanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-dodecanol, and 1-tetradecanol. 1-hexadecanol, isohexadecanol, 1-octadecanol, isooctadecanol, 1-eicosanol, isoeicosanol, 1-docosanol, 1-tetracosanol, 1-octacosanol, 1-triacone Saturated aliphatic monools such as tanol, cis-9-hexadecene-1-ol, 9E-octadecene-1-ol, cis-9-octadecene-1-ol, 9Z, 12Z-octadecadien-1-ol, 9Z, 12Z, 15Z-octadecatrien-1-ol, 9 , 12E, 15E- octadecatrienoic-1-ol, cis-13-docosenoic-1-ol unsaturated aliphatic monool, and aromatic monool such as benzyl alcohol. In addition, compounds having an alkylene oxide modified or caprolactone modified in their skeleton are exemplified, and among them, saturated aliphatic monools are preferably used from the viewpoint of little yellowing.
R in the general formula (4) is hydrogen or a methyl group, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the examples, “parts” and “%” mean weight standards.

Example 1
<Production of active energy ray-curable composition (A)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas blowing port, 34.4 g (0.15 mol) of isophorone diisocyanate and isoeicosanol having 20 carbon atoms (“Fineoxocol manufactured by Nissan Chemical Co., Ltd.) 2000 ”) 46.8 g (hydroxyl value 185.6 mg KOH / g) (0.15 mol) and 0.001 g of dibutyltin dilaurate as a reaction catalyst were reacted at 60 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 18 .9 g (0.16 mol) and 2,8-di-tert-butylcresol 0.08 g as a polymerization inhibitor were charged and reacted at 60 ° C., when the remaining isocyanate group became 0.3%. After completion, an active energy ray-curable composition (A-1) was obtained.

  The obtained active energy ray-curable composition (A-1) contains the urethane bond-containing compound (A1), the urethane bond-containing compound (A2), and the urethane bond-containing compound (A3). The content ratio is as shown in Table 1.

In addition, the content rate of a urethane bond containing compound (A1), a urethane bond containing compound (A2), and a urethane bond containing compound (A3) was measured as follows.
(Measurement sample preparation)
After 200 mg of the active energy ray-curable composition (A) was dissolved in 5 mL of methanol, the remaining unreacted isocyanate was methylurethanated by heating at 40 ° C. for 30 minutes or more. Then, what was fixedly dissolved in 25 mL with methanol was used as a measurement sample solution (0.8% solution).

(Measuring method)
Agilent Technology HP1100 equipped with Impact Unison UK-C8 50 × 2 mm 3 μm was used as the column, and the urethane bond-containing compound (A2) was quantified by LC analysis. Water / methanol (weight ratio) = 70/30 (0 min) to 0/100 (15 min) was used for the mobile phase, and after injecting 3 μL of the measurement sample solution, conditions of a flow rate of 0.7 mL / min and a column temperature of 40 ° C. Analysis was performed below, and a UV lamp (210 nm) was used to detect the target.

  About the content rate of a urethane bond containing compound (A1) and a urethane bond containing compound (A3), it computed from the quantitative value of the urethane bond containing compound (A2), and the measured value of the raw material at the time of preparation.

(Example 2)
<Production of active energy ray-curable composition (A)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, isophorone diisocyanate 32.5 g (0.15 mol), carbon number 20 isoeicosanol (manufactured by Nissan Chemical Co., Ltd., “Fineoxocol”) 2000 ") 53.1 g (hydroxyl value 185.6 mg KOH / g) (0.18 mol) and 0.001 g of dibutyltin dilaurate as a reaction catalyst were added and reacted at 60 ° C. for 3 hours, and then 2-hydroxyethyl acrylate 14 .4 g (0.12 mol) and 2,8-di-tert-butylcresol 0.08 g as a polymerization inhibitor were added and reacted at 60 ° C., when the remaining isocyanate group became 0.3%. After completion, an active energy ray-curable composition (A-2) was obtained.

  The obtained active energy ray-curable composition (A-2) contains the urethane bond-containing compound (A1), the urethane bond-containing compound (A2), and the urethane bond-containing compound (A3). The content ratio is as shown in Table 1. The content ratio was measured in the same manner as the measurement method in Example 1.

(Example 3)
<Production of active energy ray-curable composition (A)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 41.9 g (0.19 mol) of isophorone diisocyanate and 35.1 g (0.19) of 1-dodecanol (Tokyo Chemical Industry Co., Ltd.) Mol), 0.001 g of dibutyltin dilaurate as a reaction catalyst was added and reacted at 60 ° C. for 3 hours, and then 23.0 g (0.20 mol) of 2-hydroxyethyl acrylate and 2,6-di- 0.08 g of tert-butylcresol was added and reacted at 60 ° C. When the residual isocyanate group became 0.3%, the reaction was terminated to obtain an active energy ray-curable composition (A-3).

  The obtained active energy ray-curable composition (A-3) contains the urethane bond-containing compound (A1), the urethane bond-containing compound (A2), and the urethane bond-containing compound (A3). The content ratio is as shown in Table 1. The content ratio was measured in the same manner as the measurement method in Example 1.

Example 4
<Production of active energy ray-curable composition (A)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 53.1 g (0.24 mol) of isophorone diisocyanate and 17.7 g (0.24 mol) of 1-butanol (manufactured by Kishida Chemical Co., Ltd.) ), 0.001 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 60 ° C. for 3 hours, and then 29.1 g (0.25 mol) of 2-hydroxyethyl acrylate, and 2,6-di-tert as a polymerization inhibitor. -A butyl cresol 0.08g was prepared, it was made to react at 60 degreeC, reaction was complete | finished when the residual isocyanate group became 0.3%, and the active energy ray hardening-type composition (A-4) was obtained.

  The obtained active energy ray-curable composition (A-4) contains the urethane bond-containing compound (A1), the urethane bond-containing compound (A2), and the urethane bond-containing compound (A3). The content ratio is as shown in Table 1. The content ratio was measured in the same manner as the measurement method in Example 1.

In addition, the urethane bond containing compound in the active energy ray hardening-type composition (A-4) obtained in Example 4 is a compound which has the following structure.
[Chemical 9]

FIG. 1 shows a ¹ H-NMR (solvent: CDCl ₃ ) chart of the urethane bond-containing compound. The main attributes of each chart are as follows. For the NMR measurement, “AVANCE III HD” was used.

[ ¹ H-NMR] (see FIG. 1)
_{1.35~1.60ppm: -O-CH 2 C H} 2 C H 2 CH 3
2.90~2.95ppm: -C H ₂ -NHCO-O-
4.01-4.05 ppm: —O—C H ₂ CH ₂ CH ₂ CH ₃
4.30 to 4.35 ppm: —O—C H ₂ C H ₂ —O—CO—CH═CH ₂
5.80 to 5.90 ppm: —O—CO—CH═C H ₂
6.07 to 6.14 ppm: —O—CO—C H ═CH ₂
6.40~6.50ppm: -O-CO-CH = C H 2

(Comparative Example 1)
<Manufacture of active energy ray hardening-type composition (A ')>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 48.3 g (0.22 mol) of isophorone diisocyanate, 51.7 g (0.45 mol) of 2-hydroxyethyl acrylate, polymerization prohibited 2,6-di-tert-butylcresol 0.08 g as an agent and 0.001 g dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C., and the reaction was terminated when the residual isocyanate group reached 0.3%. Then, an active energy ray-curable composition (A′-1) was obtained. The content ratio of each component is as shown in Table 1. The content ratio was measured in the same manner as the measurement method in Example 1.

(Comparative Example 2)
<Manufacture of active energy ray hardening-type composition (A ')>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 26.4 g (0.12 mol) of isophorone diisocyanate and isoeicosanol having 20 carbon atoms (“Fineoxocol manufactured by Nissan Chemical Industries, Ltd. 2000 ") 73.6 g (hydroxyl value 185.6 mg KOH / g) (0.24 mol), 0.001 g of dibutyltin dilaurate as a reaction catalyst was charged and reacted at 60 ° C., resulting in a residual isocyanate group of 0.3%. Reaction was complete | finished at the time and the active energy ray hardening-type composition (A'-2) was obtained. The content ratio of each component is as shown in Table 1. The content ratio was measured in the same manner as the measurement method in Example 1.

The following components were prepared.
<Production of urethane (meth) acrylate compound (B1)>
Into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 11.4 g (0.051 mol) of isophorone diisocyanate, bifunctional polyether polyol (number average molecular weight 2000, hydroxyl value 56.9 mgKOH / g) 86.5 g (0.044 mol), charged with 0.001 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60 ° C. for 3 hours, then further 2.2 g (0.019 mol) of 2-hydroxyethyl acrylate, polymerization As an inhibitor, 0.04 g of 2,6-di-tert-butylcresol was added and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 0.3%, the reaction was terminated, and a bifunctional urethane acrylate ( B1-1) was obtained.

<Photopolymerization initiator (C)>
-As a photoinitiator (C), 1-hydroxy cyclohexyl phenyl ketone (C-1) (the BASF * Japan make, "Irgacure 184") was prepared.

<Solvent (D)>
-Ethyl acetate (D-1) was prepared as a solvent (D).

<Ethylenically unsaturated monomer>
-As the ethylenically unsaturated monomer, a monofunctional monomer isostearyl acrylate (E-1) (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "ISTA") was prepared.

(Example 5)
<Production of active energy ray-curable composition [I]>
100 parts of bifunctional urethane acrylate (B1-1), 43 parts of active energy ray-curable composition (A-1), 5.7 parts of photopolymerization initiator (C-1), solvent (D-1) The active energy ray-curable composition [I-1] was obtained by blending 143 parts.
Using the obtained active energy ray-curable composition [I-1], the elongation and strength of the cured coating film were evaluated as follows.

(Preparation of samples for measuring elongation and strength)
The active energy ray-curable composition [I] was applied onto a release paper with a 400 μm applicator, dried at 60 ° C. for 50 minutes, and then from a height of 18 cm to 3.4 m using one high-pressure mercury lamp 80W. UV irradiation of 2 passes (integrated irradiation amount 800 mJ / cm 2) was performed at a conveyor speed of / min to obtain a cured coating film (film thickness: 100 μm). This cured coating film was punched out with dumbbell No. 3, and a strip-shaped sample was prepared so as to have a width of 15 mm and a length of 75 mm.

(Strength)
A tensile test was performed in accordance with JIS K 7127 using a tensile tester “AG-X 500N” (manufactured by Shimadzu Corporation) at a temperature of 23 ° C. and a humidity of 50%. The tensile speed was 10 mm / min, the strength at the breaking point of the coating film was measured, and evaluated according to the following criteria.
○ ・ ・ ・ 1.0 N / mm ² or more △ ・ ・ ・ 0.5 N / mm ² or more and less than 1.0 N / mm ² × ・ ・ ・ less than 0.5 N / mm ²

(Elongation)
A tensile test was performed in accordance with JIS K 7127 using a tensile tester “AG-X 500N” (manufactured by Shimadzu Corporation) at a temperature of 23 ° C. and a humidity of 50%. The tensile rate was 10 mm / min, the elongation at the breaking point of the coating film was measured, and evaluated according to the following criteria.
○ ・ ・ ・ 400% or more △ ・ ・ ・ 300% or more and less than 400% × ・ ・ ・ less than 300%

(Examples 6-9, Comparative Examples 3-5)
Example 5 is the same as Example 5 except that the type and blending amount of the active energy ray-curable composition (A) and the blending amounts of the photopolymerization initiator (C) and the solvent (D) are changed as shown in Table 2. Similarly, each cured coating film was obtained.
About the obtained cured coating film, it carried out similarly to Example 5, and evaluated the intensity | strength and elongation.
Table 2 shows the evaluation results of Examples and Comparative Examples.

From the above evaluation results, the active energy ray-curable composition A) containing the urethane bond-containing compound (A1) represented by the general formula (1) as a main component was blended with the ethylenically unsaturated group-containing compound (B). The active energy ray-curable compositions [I] of Examples 5 to 9 had excellent effects in both strength and elongation when formed into a cured coating film.
On the other hand, the active energy ray-curable composition of Comparative Example 3 that does not contain the urethane bond-containing compound (A1) represented by the general formula (1) in the ethylenically unsaturated group-containing compound (B) Even if compared with a thing, it is inferior to intensity | strength and elongation, and did not achieve the objective of this invention.
The active energy ray-curable composition of Comparative Example 4 consisting only of the ethylenically unsaturated group-containing compound (B), the photopolymerization initiator (C), and the solvent (D) has a strength when used as a cured coating film. Further, the elongation was inferior, and the object of the present invention was not achieved.
Furthermore, instead of blending the active energy ray-curable composition (A), the active energy ray-curable composition of Comparative Example 5 in which the monofunctional monomer isostearyl acrylate was blended with the ethylenically unsaturated group-containing compound (B). However, when a cured coating film was obtained, the elongation was improved, but it was not sufficient. On the other hand, the strength decreased, and the object of the present invention was not achieved.

  The active energy ray-curable composition of the present invention can form a cured coating film excellent in both flexibility and strength, and can be used for paints, pressure-sensitive adhesives, adhesives, adhesives, inks, and protective coatings. It is useful as various film forming materials such as a coating agent, an anchor coating agent, a magnetic powder coating binder, a sandblast coating, and a plate material. Among them, it is very useful as a coating agent for molding substrates and the like.

Claims (9)

The urethane bond-containing compound (A3) represented by the following general formula (1), the urethane bond-containing compound (A2) represented by the general formula (2), and the urethane bond-containing compound (A3) represented by the general formula (3) An active energy ray-curable composition comprising:
[Formula 1]

[Formula 2]

[Formula 3]

(In the above general formulas (1) to (3), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, X ₂ Is a urethane bond residue of the polyvalent isocyanate compound (a2) having n isocyanate groups, X ₃ is a urethane bond residue of the monool compound (a3), and R is hydrogen or a methyl group Yes, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.) The content ratio of the urethane bond-containing compound (A1), the urethane bond-containing compound (A2) and the urethane bond-containing compound (A3) is the urethane bond-containing compound (A1), the urethane bond-containing compound (A2), and the urethane bond-containing compound (A3). ), The urethane bond-containing compound (A1) is 40 to 99.8% by weight, the urethane bond-containing compound (A2) is 0.1 to 50% by weight, and the urethane bond-containing compound (A3) is 0.8. The active energy ray-curable composition according to claim 1, wherein the content is 1 to 50% by weight. The active energy ray-curable composition according to claim 1 or 2, wherein the monool compound (a3) is a saturated aliphatic monool having 1 to 30 carbon atoms. The active energy ray-curable composition according to any one of claims 1 to 3, wherein the viscosity at 60 ° C is 10 to 50,000 mPa · s. An active energy ray-curable composition comprising the active energy ray-curable composition (A) according to claim 1 and an ethylenically unsaturated group-containing compound (B). The content of the active energy ray-curable composition (A) is 0.1 to 300 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated group-containing compound (B). Active energy ray-curable composition. The active energy ray-curable composition according to claim 1, comprising a photopolymerization initiator (C). A coating agent comprising the active energy ray-curable composition according to claim 1. A urethane bond-containing compound represented by the following general formula (4):
[Formula 4]

(In the general formula (4), X ₁ is a linking group in the urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (a1) having p (meth) acryloyl groups, and X ₂ is n The urethane bond residue of the polyisocyanate compound (a2) having an isocyanate group, X ₃ is a urethane bond residue of the aliphatic monool compound (a4) having 3 to 9 or 11 to 30 carbon atoms, R is hydrogen or a methyl group, p is an integer of 1 or more, r is an integer of 1 or more, n is an integer of 2 or more, and n is the sum of q and r.)

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