JP2012197436A - Active energy ray curing resin composition and coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curing resin composition excellent in resiliency and elasticity in a level of withstanding practical use when being made to be a cured film, and to provide a coating agent using the same.SOLUTION: The active energy ray curing resin composition is made by containing a urethane(meth)acrylate-based compound (A) obtained by reacting a polyol-based compound (x), a hydroxyl group-containing (meth)acrylate-based compound (y), and a polyvalent isocyanate-based compound (z), wherein the urethane(meth)acrylate-based compound has a weight-average molecular weight of 10,000 to 800,000. The polyol-based compound (x) contains a polyol-based compound (x1) containing 3 or more hydroxyl groups.

Description

  The present invention relates to an active energy ray-curable resin composition and a coating agent, and more particularly, to an active energy ray-curable resin composition for forming a cured coating film excellent in resilience and stretchability against scratches, and the same It is related with the coating agent which uses this.

  Conventionally, an active energy ray-curable resin composition is cured by irradiation with an active energy ray such as radiation for a very short time, so it is widely used as a coating agent, adhesive or anchor coating agent for various substrates. It has been.

  Among them, as the coating agent, an active energy ray curable resin capable of forming a cured film on the surface of a plastic substrate and forming a cured coating film having resilience against scratches as a coating agent for protecting the outermost surface of the substrate. Development of a composition is desired. For example, an ultraviolet curable coating composition using a urethane acrylate oligomer obtained by reacting a polycaprolactone-containing polyfunctional alcohol, an isocyanate and a hydroxyl group-containing (meth) acrylate (for example, patent literature) 1) is proposed.

Japanese Patent Laid-Open No. 2004-35599

  However, in the disclosed technique of Patent Document 1, by using a caprolactone-containing polyfunctional alcohol as a constituent raw material of the urethane (meth) acrylate compound, it shows some resilience when it is a cured coating film. The urethane (meth) acrylate compound of Patent Document 1 described above has a molecular weight in terms of design structure, although it requires a relatively high molecular weight and elasticity like a polymer rubber in order to restore and recover a scratch. It was designed to be relatively small, and a practically sufficient level of resilience could not be obtained.

  Therefore, the present invention has an active energy ray-curable resin composition excellent in resilience and stretchability that can withstand practicality when used as a cured coating film under such a background, and a coating agent using the same. It is intended to provide.

However, as a result of intensive studies in view of such circumstances, the present inventors have made a relatively high molecular weight urethane (meth) obtained by reacting a polyol compound, a hydroxyl group-containing (meth) acrylate compound and a polyvalent isocyanate compound. In the acrylate compound, by using a polyol compound containing three or more hydroxyl groups as the polyol compound, a three-dimensional network structure is maintained while maintaining the coating film stretch characteristic unique to the urethane structure when a cured coating film is formed. A rubber elastic coating film having stretch / shrink performance can be obtained. Therefore, it discovered that the cured coating film excellent in the recoverability with respect to a damage | wound can be formed, and completed this invention.
In the present invention, when a polyol compound containing three or more hydroxyl groups and a polyol compound containing two hydroxyl groups are used as the polyol compound as a constituent raw material of the urethane (meth) acrylate compound, Since excessive molecular network formation can be alleviated and gelation can be suppressed, it becomes possible to stably produce urethane (meth) acrylate compounds, and after the formation of a cured coating film, the remarkable effects of the present invention can be obtained. Will be demonstrated.

That is, the gist of the present invention is that the weight average molecular weight obtained by reacting the polyol compound (x), the hydroxyl group-containing (meth) acrylate compound (y), and the polyvalent isocyanate compound (z) is 10,000 to 800,000. This is an active energy ray-curable resin composition containing the urethane (meth) acrylate compound (A), and the polyol compound (x) contains a polyol compound (x1) containing three or more hydroxyl groups. The present invention relates to an active energy ray-curable resin composition.
Moreover, in this invention, the coating agent containing the said active energy ray curable resin composition, especially the coating agent used for the outermost surface are also provided.

  The active energy ray-curable resin composition of the present invention has an excellent effect on resilience, stretchability, and transparency when it is used as a cured coating film, and as a coating agent, particularly as a coating agent for the outermost surface. Useful.

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 resin composition of the present invention contains a urethane (meth) acrylate compound (A).

[Urethane (meth) acrylate compound (A)]
The urethane (meth) acrylate compound (A) used in the present invention includes a polyol compound (x) containing a polyol compound (x1) containing 3 or more hydroxyl groups, and a hydroxyl group-containing (meth) acrylate compound (y). , And a polyisocyanate compound (z).

  The polyol compound (x) essentially contains a polyol compound (x1) containing at least three hydroxyl groups (hereinafter sometimes referred to as “trifunctional or more polyol compound (x1)”). If it is.

Examples of the trifunctional or higher functional polyol compound (x1) include various polyol compounds containing three or more hydroxyl groups. Specific examples include polyester polyols, polyether polyols, polycarbonate polyols, and polyolefins. And polyols, hydrogenated polybutadiene polyols, (meth) acrylic polyols, polysiloxane polyols, and the like.
Moreover, it is preferable that it is a trifunctional or more functional polyol type compound which does not contain an unsaturated group in a molecule | numerator from the point which is excellent in transparency of a coating film.

  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. In which each raw material is selected so as to contain three or more hydroxyl groups.

  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, methane Triol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol) Etc., and the like.

  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 (lactone) include γ-butyrolactone, δ-valerolactone, and ε-caprolactone.

Examples of the polyether-based polyol include polyether-based polyols obtained by dehydrating and condensing a polyol as a raw material so that three or more hydroxyl groups are contained at molecular ends (molecular side chains).
Such a polyol may contain at least one trifunctional or higher functional polyol such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol and the like. Examples thereof include polyols and polyoxyalkylene polyols which are adducts of these polyols with alkylene oxides.

  Examples of the polycarbonate polyol include a reaction product of a polyhydric alcohol and phosgene, wherein the polyhydric alcohol is selected so as to contain three or more hydroxyl groups; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.) And those containing three or more hydroxyl groups.

The polyhydric alcohol may contain at least one trifunctional or higher functional polyol such as methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol and the like. Examples thereof include molecular weight polyols, and polyoxyalkylene polyols, which are alkylene oxide adducts of these polyols.
The polycarbonate polyol may be a compound having a carbonate bond in the molecule and a terminal containing three or more hydroxyl groups, and may have an ester bond together with the carbonate bond.

  Any polyolefin-based polyol may be used as long as it has a total of three or more hydroxyl groups at the molecular ends (side chains) of the hydrocarbon skeleton having at least one branched structure.

  The hydrogenated polybutadiene-based polyol is a structure in which all of the ethylenically unsaturated groups contained in the structure of the polybutadiene-based polyol are hydrogenated, and has a total of three or more hydroxyl groups at the molecular ends (side chains). If it is.

  As said (meth) acrylic-type polyol, what contains at least 3 or more hydroxyl groups in the polymer of a (meth) acrylic ester or a copolymer should just be contained. Examples of monomers constituting the polymer and copolymer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , Hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters such as hexyl acid, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, etc. Can be mentioned.

  As the polysiloxane-based polyol, a polysiloxane having 3 or more hydroxyl groups at the molecular end (main chain) may be used.

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

The trifunctional or higher functional polyol compound (x1) preferably has a hydroxyl value of 30 to 3,500 mgKOH / g, particularly preferably 40 to 1,750 mgKOH / g, and still more preferably 50 to 1,200 mgKOH / g. If the hydroxyl value is too high, the three-dimensional structure becomes too dense at the synthesis stage, a sudden increase in viscosity occurs, and there is a tendency to gel during the production of the urethane (meth) acrylate compound, and the hydroxyl value is too low. Then, there is a tendency that the hardness of the surface of the coating film after the curing of active energy rays, particularly ultraviolet rays, tends to decrease.
The hydroxyl value is a value measured according to JIS K 1557.

  The weight average molecular weight of the trifunctional or higher functional polyol compound (x1) is preferably 50 to 6,000, particularly preferably 100 to 3,500, and further preferably 100 to 2,500. If the weight average molecular weight is too high, the hardness of the coating surface after curing of active energy rays, particularly ultraviolet rays, tends to decrease. If the weight average molecular weight is too low, the three-dimensional network structure becomes too dense at the synthesis stage. As a result, a sudden increase in viscosity occurs and the gelation tends to occur during the production of the urethane (meth) acrylate compound.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and is a high performance liquid chromatography (Nippon Waters Co., Ltd., "Waters 2695 (main body)" and "Waters 2414 (detector)"), Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / pack, packing material: styrene-divinylbenzene copolymer, packing It is measured by using three series of agent particle size: 10 μm).

  The polyol compound (x) may be described as a polyol compound (x2) (hereinafter referred to as “bifunctional polyol compound (x2)”) containing two hydroxyl groups and having a hydroxyl value of less than 450 mgKOH / g. )), The three-dimensional network structure becomes too dense to prevent gelation during the production of the urethane (meth) acrylate compound, and the urethane (meth) acrylate compound is stably produced. It is preferable in that it is easy to do.

The hydroxyl value of the bifunctional polyol compound (x2) needs to be smaller than 450 mgKOH / g, preferably 200 mgKOH / g or less, particularly preferably 180 mgKOH / g or less. The lower limit of the hydroxyl value is usually 20 mgKOH / g.
If the hydroxyl value is too high, the three-dimensional network structure becomes too dense at the synthesis stage, which causes a rapid viscosity increase and tends to gel during the production of the urethane (meth) acrylate compound. If it is too low, there is a tendency that the hardness of the surface of the coating film after curing of active energy rays, particularly ultraviolet rays, tends to decrease.
The hydroxyl value is a value measured according to JIS K 1557.

Examples of the bifunctional polyol compound (x2) include various polyol compounds containing two hydroxyl groups, and specific examples include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, and water. Examples of the additive polybutadiene-based polyol, (meth) acrylic polyol, and polysiloxane-based polyol.
Specifically, it may be in accordance with each polyol compound exemplified in the description of the above-described trifunctional or higher functional polyol compound (x1), and is obtained by selecting and combining raw material compounds so that there are two hydroxyl groups. Any bifunctional polyol may be used.

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

  The weight average molecular weight of the bifunctional polyol compound (x2) is preferably 250 to 6,000, particularly preferably 300 to 5,000, more preferably 500 to 4,000, and the weight average molecular weight is high. If it is too high, there is a tendency that the hardness of the coating surface after curing of active energy rays, particularly ultraviolet rays, tends to decrease. If the weight average molecular weight is too low, the three-dimensional network structure becomes too dense at the synthesis stage, Increase in viscosity tends to occur during the production of urethane (meth) acrylate compounds.

Regarding the polyol compound (x), the blending ratio (weight ratio) of the trifunctional or higher functional polyol compound (x1) and the bifunctional polyol compound (x2) when using the bifunctional polyol compound (x2) is as follows: (X1) :( x2) = 1: 99 to 99: 1 is preferable, (x1) :( x2) = 2: 98 to 50:50 is particularly preferable, and (x1) :( x2) = 3 is more preferable. : 97-30: 70.
If the blending ratio of the trifunctional or higher polyol-based compound (x1) is too large, the three-dimensional network structure becomes excessive and the molecular weight becomes too high, and the gel tends to be gelled at the time of production. There is a tendency for the structure to be too small and to be excellent in balance between elasticity and elasticity.

  Further, as the polyol compound (x), a polyol compound (x3) containing two hydroxyl groups and having a hydroxyl value of 450 mgKOH / g or more (hereinafter sometimes referred to as “bifunctional polyol compound (x3)”). In particular, in addition to the trifunctional polyol compound (x1) and the bifunctional polyol compound (x2) described above, a polyol further containing two hydroxyl groups and having a hydroxyl value of 450 mgKOH / g or more. It is preferable to contain a compound (x3) from the viewpoint of further relaxing the three-dimensional network structure of the urethane (meth) acrylate compound and improving the stretchability of the coating film.

The hydroxyl value of the bifunctional polyol compound (x3) needs to be 450 mgKOH / g or more, preferably 500 mgKOH / g or more, particularly preferably 550 mgKOH / g or more. The upper limit of the hydroxyl value is usually 2,000 mgKOH / g.
The hydroxyl value is a value measured according to JIS K 1557.

Examples of the bifunctional polyol compound (x3) include a low molecular weight diol compound having a weight average molecular weight of about 250 or less. Specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, Dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylene Diol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1, 5-pentamethylenediol, pentaerythritol Acrylates, aliphatic alcohols such as 1,9-nonanediol and 2-methyl-1,8-octanediol, cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldimethanol, bisphenols such as bisphenol A, tri Examples thereof include sugar alcohols such as cyclodecanedimethanol, xylitol and sorbitol, and these can be used alone or in combination of two or more.
Among these, from the viewpoint of yellowing of the cured coating film, compounds having a structure not containing an aromatic ring or an unsaturated group are preferable, aliphatic alcohols are particularly preferable, and neopentyl glycol is more preferable.

The blending amount of the bifunctional polyol compound (x3) is 0 to 50% by weight based on the total amount of the trifunctional or higher polyol compound (x1) and the bifunctional polyol compound (x2). It is preferably 0.3 to 40% by weight, more preferably 0.5 to 25% by weight.
If the blending amount is too large, the three-dimensional network structure becomes too dense, which causes a sudden increase in viscosity and tends to cause gelation during the production of the urethane (meth) acrylate compound.

The polyol compound (x) preferably has an average number of hydroxyl groups of 2.01 to 6 mol, particularly preferably 2.05 to 5 mol, and more preferably 2.1 to 4 mol.
If the average number of hydroxyl groups is too small, the three-dimensional network structure tends to be too small, and it tends to be difficult to achieve a good balance between stretchability and elasticity. Tends to be too gelled during production.

The average number of hydroxyl groups is determined by the following calculation formula [I] or [II].
[I]
Average number of hydroxyl groups = [{number of hydroxyl functional groups of trifunctional or higher functional polyol compound (x1) × number of moles of trifunctional or higher functional polyol based compound (x1)} / {hydroxyl group of trifunctional or higher functional polyol based compound (x1) Molecular weight calculated from the valence + molecular weight calculated from the hydroxyl value of the bifunctional polyol compound (x2)}] + [{number of moles charged in the 2 × 2 functional polyol compound (x2)} / {trifunctional or higher polyol system Molecular weight calculated from hydroxyl value of compound (x1) + molecular weight calculated from hydroxyl value of bifunctional polyol compound (x2)}]
[II]
Average number of hydroxyl groups = [{number of hydroxyl functional groups of trifunctional or higher functional polyol compound (x1) × number of moles of trifunctional or higher functional polyol based compound (x1)} / {hydroxyl group of trifunctional or higher functional polyol based compound (x1) Molecular weight calculated from valence + molecular weight calculated from hydroxyl value of bifunctional polyol compound (x2) + molecular weight calculated from hydroxyl value of bifunctional polyol compound (x3)}] + [{2 × 2 functional polyol compound (x2) charged mole number} / {molecular weight calculated from hydroxyl value of trifunctional or higher functional polyol compound (x1) + molecular weight calculated from hydroxyl value of bifunctional polyol compound (x2) + bifunctional polyol compound ( x3) Molecular weight calculated from hydroxyl value}] + [{number of moles of 2 × 2 functional polyol compound (x3)} / {trifunctional or higher polyol compound Molecular weight calculated from the hydroxyl value of the molecular weight +2 functional polyol compound (x3) calculated from the hydroxyl value of the molecular weight is calculated from the hydroxyl value +2 functional polyol compound (x2) of (x1)}]

  Examples of the hydroxyl group-containing (meth) acrylate compound (y) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, dipropylene glycol (meth) acrylate, Fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxip Hydroxyl-containing (meth) acrylate compounds containing one ethylenically unsaturated group such as pill (meth) acrylate; glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meta ) Hydroxyl group containing two or more ethylenically unsaturated groups such as acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate ( (Meth) acrylate compounds; these may be used alone or in combination of two or more.

  Among these, a hydroxyl group (meth) acrylate compound containing one ethylenically unsaturated group is preferable, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) are preferable in terms of reactivity and versatility. Acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are particularly preferable, and 2-hydroxyethyl (meth) acrylate is more particularly preferable.

  Further, as the hydroxyl group-containing (meth) acrylate compound (y), it is possible to use a hydroxyl group-containing (meth) acrylate compound having an acid value of 1 mgKOH / g or less (preferably 0.75 mgKOH / g or less). Is preferable in that it is difficult to produce a stable urethane (meth) acrylate compound. Specific examples of the hydroxyl group-containing (meth) acrylate compound having an acid value of less than 1 mgKOH / g include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). An acrylate and 4-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.

  Among the hydroxyl group-containing (meth) acrylate compounds, caprolactone-modified 2-hydroxyethyl (meth) acrylate is generally available as a raw material of caprolactone 1 mol-modified 2-hydroxyethyl (meth) acrylate and 2.0 mgKOH. / G, caprolactone 2 mol modified 2-hydroxyethyl (meth) acrylate, which has an acid value of about 2.5 mg KOH / g, and when the caprolactone modification amount further increases, the acid value tends to increase. When caprolactone-modified 2-hydroxyethyl (meth) acrylate is used, the effect of the present invention tends to be hardly obtained.

  Examples of the polyvalent isocyanate compound (z) 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, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) cyclo Cycloaliphatic polyisocyanates such as xanthone, trimer compounds or multimeric compounds of these polyisocyanates, allophanate type polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd. "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.).

  Among these, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, etc. Aliphatic diisocyanates; Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and other alicyclic diisocyanates; Preferably, the cured coating yellow The viewpoint of less points or cure shrinkage smaller, particularly preferably alicyclic diisocyanate compound include isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, is hydrogenated xylylene diisocyanate more preferred.

  The urethane (meth) acrylate compound (A) can be obtained by reacting the constituent materials containing the above (x) to (z).

  The production method of the urethane (meth) acrylate compound (A) is usually a batch of the polyol compound (x), the hydroxyl group-containing (meth) acrylate compound (y), and the polyvalent isocyanate compound (z) in a reactor. Alternatively, the reaction may be carried out separately, but the reaction product obtained by reacting the polyol compound (x) and the polyvalent isocyanate compound (z) in advance with the hydroxyl group-containing (meth) acrylate compound (y) Is preferable from the viewpoints of reaction stability and reduction of by-products.

  In the method of reacting a hydroxyl group-containing (meth) acrylate compound (y) with a reaction product obtained by reacting the polyol compound (x) and the polyvalent isocyanate compound (z) in advance, the polyol compound A known reaction method can be used for the reaction between (x) and the polyvalent isocyanate compound (z). For example, the isocyanate group in the polyvalent isocyanate compound (z): polyol compound (x) The reaction product containing an isocyanate group at the terminal can be obtained by reacting with the functional group molar ratio with the hydroxyl group in the isocyanate group being usually about mol: (polyol hydroxyl group-hydroxyl group mol of hydroxyl group-containing acrylate). That's fine.

  Also in the case of reacting the hydroxyl group-containing (meth) acrylate compound (y) with the reaction product of the polyol compound (x) and the polyvalent isocyanate compound (z), known reaction means can be used. The reaction molar ratio between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y) is, for example, two isocyanate groups in the reaction product, and the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (y) When it is 1, the reaction product: hydroxyl group-containing (meth) acrylate compound (y) is reacted at about 1: 2, and the reaction product has three isocyanate groups, and the hydroxyl group-containing (meth) acrylate compound. When (y) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (y) may be reacted at about 1: 3.

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

In addition, when a trifunctional or higher functional polyol compound (x1) and a bifunctional polyol based compound (x2) are used in combination, the trifunctional or higher functional polyol compound (x1) can be mixed and reacted together. However, in order to avoid localization of the branched structure in the urethane (meth) acrylate molecule and to disperse the branched structure in the urethane (meth) acrylate molecule, the reaction is carried out in multiple stages. Is preferred.
When the trifunctional or higher functional polyol compound (x1) is divided and blended, it can be divided and blended at an arbitrary distribution. For example, when blended in two stages, urethane ( In terms of efficiently dispersing the branched structure in the (meth) acrylate molecule, it is preferable to add by dividing the weight ratio in the range of 1st stage: 2nd stage = 10-90: 90-10.

  In the reaction between the polyol compound (x) and the polyvalent isocyanate compound (z), and the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), a catalyst is used for the purpose of promoting the reaction. The catalyst is preferably an organic metal compound such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octoate, tin octoate, cobalt naphthenate, stannous chloride. Metal salts such as stannic chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, Amine catalysts such as N′-tetramethyl-1,3-butanediamine and N-ethylmorpholine, bismuth nitrate, bismuth bromide, Organic bismuth compounds such as dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, etc. Organic acid bismuth salts such as salts, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc. Among them, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferable.

  In the reaction between the polyol compound (x) and the polyvalent isocyanate compound (z), and in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), it reacts with an 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.

  Further, instead of such an organic solvent, a (meth) acrylate monomer having no functional group that reacts with an isocyanate group can be used. As such a (meth) acrylate monomer, a bifunctional (meth) acrylate monomer is used. A monofunctional (meth) acrylate monomer is preferable, and a monofunctional (meth) acrylate monomer is particularly preferable in that the stretchability of the coated film after curing is less disturbed.

  Examples of such bifunctional (meth) acrylate monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 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, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexa Examples include dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and isocyanuric acid ethylene oxide-modified diacrylate. It is done.

  Examples of such monofunctional (meth) acrylate monomers include styrene monomers such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) -methyl ( ) Acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (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 (n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, tetrahydrofur Acrylate monomers such as ril (meth) acrylate, carbitol (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, (meth) acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate; N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, and vinyl acetate.

  In the reaction between the polyol compound (x) and the polyvalent isocyanate compound (z), and the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), the reaction temperature is usually 30 to 30. It is 100 degreeC, Preferably it is 40-90 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

The ethylenically unsaturated group content (mmol / g) of the urethane (meth) acrylate compound (A) used in the present invention is preferably 0.01 to 10 mmol / g, particularly preferably 0.05. -5 mmol / g, more preferably 0.1-1 mmol / g, particularly preferably 0.1-0.5 mmol / g.
If the content of the ethylenically unsaturated group (mmol / g) of the urethane (meth) acrylate compound (A) is too small, curing at the time of irradiation with active energy rays tends to be insufficient, and if too large, active energy rays As a result of the increase in the number of components that form a crosslink, the stretchability and elasticity of the desired cured coating film tend to be difficult to obtain.

  In addition, the urethane (meth) acrylate compound (A) preferably has 10 or less ethylenically unsaturated groups in terms of utilizing structural properties such as stretchability and elasticity, and 6 or less. It is particularly preferred that it has an ethylenically unsaturated group, and it is more preferred that it has 4 or less ethylenically unsaturated groups. In general, the lower limit of the ethylenically unsaturated group is two.

The urethane (meth) acrylate compound (A) used in the present invention must have a weight average molecular weight of 10,000 to 800,000, particularly preferably 20,000 to 500,000, and more preferably 2 10,000 to 300,000.
If the weight average molecular weight is too small, the stretchability and elasticity of the cured coating film tend to decrease, and if 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.

In the present invention, when the urethane (meth) acrylate compound (A) is dissolved so as to contain 40% of toluene, the viscosity at 20 ° C. is preferably 500 to 1,000,000 mPa · s. Preferably, it is 500 to 500,000 mPa · s, and more preferably 500 to 200,000 mPa · s.
When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured using a B-type viscometer.

  Thus, the urethane (meth) acrylate compound (A) used in the present invention can be produced, and the active energy ray-curable resin composition of the present invention can be produced using the urethane (meth) acrylate compound (A). can get.

  In the active energy ray-curable resin composition of the present invention, if necessary, an ethylenically unsaturated monomer (C) other than the photopolymerization initiator (B), the urethane (meth) acrylate compound (A), an acrylic resin , Surface conditioning agents, leveling agents, polymerization inhibitors, etc., and oils, antioxidants, flame retardants, antistatic agents, fillers, stabilizers, reinforcing agents, matting agents, abrasives, It is also possible to blend organic fine particles, inorganic particles and the like.

  Examples of the photopolymerization initiator (B) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) 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 Benzo such as ether 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 Benzophenones such as chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy ) -3, -Thioxanthones such as dimethyl-9H-thioxanthone-9-one mesochloride; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl Acylphosphine oxides such as phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; In addition, as for these photoinitiators (B), 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, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin 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 (B), it is preferable that it is 0.1-20 weight part with respect to 100 weight part of urethane (meth) acrylate type compounds (A), Most preferably, it is 0.5- 10 parts by weight, more preferably 1 to 10 parts by weight.
If the content of the photopolymerization initiator (B) is too small, curing tends to be poor and film formation tends to be difficult, and if too large, yellowing of the cured coating tends to occur, and coloring problems tend to occur.

  Examples of the ethylenically unsaturated monomer (C) other than the urethane (meth) acrylate compound (A) include monofunctional monomers, bifunctional monomers, and trifunctional or higher monomers.

  Examples of such monofunctional monomers include styrene monomers such as styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2-methoxyethyl (meth) acrylate, 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 Rate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate (2-methyl-2-ethyl-1,3-dioxolan-4-yl) -methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan-4-yl) -methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) Acu Rate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene Half (meth) acrylates of phthalic acid derivatives such as oxide-modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) (Meth) acrylate monomers such as acrylate, (meth) acryloylmorpholine, polyoxyethylene secondary alkyl ether acrylate, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine And vinyl acetate.

  Examples of such bifunctional monomers include 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, and di Propylene 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, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (me ) Acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) Acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, ethylene isocyanurate Examples thereof include oxide-modified diacrylate.

  Examples of the tri- or higher functional monomer include 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, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, capro Kuton modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol Examples include tetra (meth) acrylate and ethoxylated glycerin triacrylate.

Further, a Michael adduct of acrylic acid or 2-acryloyloxyethyldicarboxylic acid monoester can be used in combination, and as such a Michael adduct of acrylic acid, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, An acrylic acid tetramer, a methacrylic acid tetramer, etc. are mentioned.
The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl. Examples include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, other oligoester acrylates may be mentioned.

  Examples of the surface conditioner include cellulose resin and alkyd resin. Such a cellulose resin has an action of improving the surface smoothness of the coating film, and an alkyd resin has an action of imparting a film-forming property at the time of coating.

  As the leveling agent, a known general leveling agent can be used as long as it has an effect of imparting wettability to the substrate of the coating liquid and a function of reducing the surface tension. 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. -Butyl hydroquinone, pt-butyl catechol, etc. can be mentioned.

  Moreover, it is also preferable to use the organic solvent for dilution for the active energy ray curable resin composition of this invention as needed, in order to make the viscosity at the time of coating appropriate. 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.

  When two or more of the above are used in combination, it is preferable from the viewpoint of the appearance of the coating film that two or more of glycol ethers, ketones, and alcohols are selected and combined.

  In addition, in manufacturing the active energy ray-curable resin composition of the present invention, the method of mixing the urethane (meth) acrylate compound (A) and other components is not particularly limited, and is mixed by various methods. be able to.

  The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for coating film formation, such as a topcoat agent and an anchor coat agent on various substrates, and is active energy ray-curable. After applying the functional resin composition to the substrate (after drying further when the composition diluted with the organic solvent is applied), it is cured by irradiating with active energy rays.

  Examples of the base material to which the active energy ray-curable resin composition of the present invention is applied include polyolefin resin, polyester resin, polycarbonate resin, acrylic resin acrylonitrile butadiene styrene copolymer (ABS), polystyrene. Metals (aluminum, copper, etc.) such as plastic base materials such as plastic resins and their molded products (films, sheets, cups, etc.), composite base materials thereof, or composite base materials of the above materials mixed with glass fibers or inorganic substances , Iron, SUS, zinc, magnesium, alloys thereof, and the like), and substrates having a primer layer on a substrate such as glass.

  Examples of the coating method of the active energy ray-curable resin composition include wet coating methods such as spraying, showering, dipping, roll, spinning, screen printing, etc. You just apply to.

  Moreover, the active energy ray-curable resin composition of the present invention is diluted with the organic solvent so that the solid content concentration is usually 3 to 60% by weight, preferably 5 to 40% by weight. It is preferable to work.

  The drying conditions for dilution with the organic solvent are as follows: the temperature is usually 40 to 120 ° C., preferably 50 to 100 ° C., and the drying time is usually 1 to 20 minutes, preferably 2 to 10 minutes. That's fine.

  Active energy rays used for curing the active energy ray-curable resin composition coated on the substrate include rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, and electromagnetic waves such as X-rays and γ rays. In addition, electron beams, proton beams, neutron beams, and the like can be used, but curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like. In addition, when performing electron beam irradiation, it can harden | cure even without using a photoinitiator (B).

When curing by ultraviolet irradiation, using a high-pressure mercury lamp emitting ultra-high pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED, etc. Usually, ultraviolet rays of 30 to 3000 mJ / cm ² (preferably 100 to 1500 mJ / cm ² ) may be irradiated.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  The coating thickness (thickness after curing) is related to the flaw depth assumed as the flaw resilience, so if the flaw depth does not exceed the coating thickness, In general, in view of light transmission so that the photopolymerization initiator (B) can react uniformly as an ultraviolet curable coating film, it may be 3 to 1000 μm, preferably 5 to 500 μm, particularly preferably 10 to 10 μm. 200 μm.

  A polyol compound (x) containing a polyol compound (x1) containing three or more hydroxyl groups of the present invention, a hydroxyl group-containing (meth) acrylate compound (y), and a polyvalent isocyanate compound (z) are reacted. The active energy ray-curable resin composition characterized by containing the urethane (meth) acrylate compound (A) is a cured coating film, while maintaining the stretchability characteristic of the urethane structure, The coating film shrinkage due to the three-dimensional network structure provides a coating film with stretching / shrinking performance. Therefore, it is possible to form a cured coating film with high practicality as a resilience against scratches, and paints and inks. It is particularly useful as a coating agent, especially as a coating agent for the outermost surface.

  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 basis.

  The following were prepared as urethane (meth) acrylate compounds (A) (see Table 1).

<Production Example 1: Urethane (meth) acrylate-based compound (A-1)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 66.7 g of toluene, 19.8 g of hydrogenated xylylene diisocyanate (z) (0.10 mol), neopentyl glycol (x3 ) (Hydroxyl value 1078 mgKOH / g) 2.80 g (0.027 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 7.30 g (0.011 mol), bifunctional polyester polyol (x2) ) (Hydroxyl value 62.8 mgKOH / g) 42.6 g (0.024 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, and reacted at 60 ° C. for 2 hours, Trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 20 g (0.0040 mol), 21.3 g (0.012 mol) of a bifunctional polyester polyol (x2) (hydroxyl value 63 mgKOH / g) were added and reacted at 60 ° C. for 2 hours to give 2-hydroxyethyl acrylate ( y) 4.00 g (0.034 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A- 1) A toluene solution (resin content 60%) of (weight average molecular weight (Mw); 85,000) was obtained.

<Production Example 2: Urethane (meth) acrylate-based compound (A-2)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 66.7 g of toluene, 19.0 g of hydrogenated xylylene diisocyanate (z) (0.098 mol), neopentyl glycol (x3 ) (Hydroxyl value 1078 mg KOH / g) 3.40 g (0.033 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mg KOH / g) 7.30 g (0.011 mol), 1,5-pentanediol, Bifunctional polycarbonate polyol (x2) (hydroxyl value 55 mgKOH / g) 66.5 g (0.033 mol) using 1,6-hexanediol as a raw material, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and dibutyltin as a reaction catalyst 0.02 g of dilaurate was charged and reacted at 60 ° C. for 3 hours. 3.80 g (0.033 mol) of roxyethyl acrylate (y) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and the urethane (meth) acrylate type A toluene solution (resin content 60%) of compound (A-2) (weight average molecular weight (Mw); 57,000) was obtained.

<Production Example 3: Urethane (meth) acrylate compound (A-3)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 66.7 g of toluene, 18.4 g of hydrogenated xylylene diisocyanate (z) (0.095 mol), neopentyl glycol (x3 ) (Hydroxyl value 1078 mg KOH / g) 2.50 g (0.024 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mg KOH / g) 10.1 g (0.016 mol), 1,6-hexanediol Bifunctional polycarbonate polyol (x2) (hydroxyl value 60 mgKOH / g) 65.1 g (0.035 mol) as a raw material, hydroquinone methyl ether 0.02 g as a polymerization inhibitor, dibutyltin dilaurate 0.02 g as a reaction catalyst, Reaction at 60 ° C. for 3 hours, 2-hydroxyethyl acrylate y) 3.90 g (0.033 mol) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A- 3) A toluene solution (resin content 60%) of (weight average molecular weight (Mw); 78,000) was obtained.

<Production Example 4: Urethane (meth) acrylate compound (A-4)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, 66.7 g of toluene, 29.6 g of hydrogenated xylylene diisocyanate (z) (0.15 mol), neopentyl glycol (x3 ) (Hydroxyl value 1078 mg KOH / g) 5.00 g (0.048 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mg KOH / g) 17.8 g (0.028 mol), 2-methyl-1,3 -Bifunctional polycarbonate polyol (x2) (hydroxyl value 130 mgKOH / g) 41.7 g (0.048 mol) using propanediol and 1,4-butanediol as raw materials, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 60 ° C for 3 hours. Then, 5.90 g (0.051 mol) of 2-hydroxyethyl acrylate (y) was charged and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 0.3%, the reaction was terminated, and urethane (meta ) A toluene solution (resin content 60%) of an acrylate compound (A-4) (weight average molecular weight (Mw); 135,000) was obtained.

<Production Example 5: Urethane (meth) acrylate-based compound (A-5)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 66.7 g of toluene, 29.5 g of hydrogenated xylylene diisocyanate (z) (0.15 mol), neopentyl glycol (x3 ) (Hydroxyl value 1078 mg KOH / g) 3.70 g (0.035 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mg KOH / g) 9.70 g (0.015 mol), 1,5-pentanediol Bifunctional polycarbonate polyol (x2) (hydroxyl value 150 mgKOH / g) 51.1 g (0.068 mol) using 1,6-hexanediol as a raw material, hydroquinone methyl ether 0.02 g as a polymerization inhibitor, and dibutyltin as a reaction catalyst 0.02 g of dilaurate was charged and reacted at 60 ° C. for 3 hours. Charged 6.00 g (0.052 mol) of roxyethyl acrylate (y) and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and the urethane (meth) acrylate type A toluene solution (resin content 60%) of compound (A-5) (weight average molecular weight (Mw); 119,000) was obtained.

<Production Example 6: Urethane (meth) acrylate-based compound (A-6)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 66.7 g of toluene, 19.5 g (0.10 mol) of hydrogenated xylylene diisocyanate (z), tricyclodecane dimethanol (X3) (hydroxyl value 572 mg KOH / g) 5.20 g (0.026 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mg KOH / g) 7.30 g (0.014 mol), bifunctional polyester polyol (X2) (hydroxyl value 63 mg KOH / g) 62.1 g (0.035 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, dibutyltin dilaurate 0.02 g as a reaction catalyst, and reacted at 60 ° C. for 3 hours, 2.90 g (0.034 mol) of 2-hydroxyethyl acrylate (y) is prepared. The reaction was terminated at 60 ° C. for 3 hours, and when the residual isocyanate group became 0.3%, the reaction was terminated, and the urethane (meth) acrylate compound (A-6) (weight average molecular weight (Mw); 51, 000) toluene solution (resin content 60%).

<Production Example 7: Urethane (meth) acrylate-based compound (A-7)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 66.7 g of toluene, 22.2 g (0.10 mol) of isophorone diisocyanate (z), neopentyl glycol (x3) (hydroxyl group) 2.80 g (0.027 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 9.20 g (0.014 mol), bifunctional polyester polyol (x2) (hydroxyl group) 63.4 mg KOH / g) 61.9 g (0.035 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. for 3 hours. Charge 3.90 g (0.034 mol) of ethyl acrylate (y) The reaction was terminated at 60 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-7) (weight average molecular weight (Mw); 29,000) A toluene solution (resin content 60%) was obtained.

<Production Example 8: Urethane (meth) acrylate-based compound (A-8)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 66.7 g of toluene, 17.8 g (0.11 mol) of hexamethylene diisocyanate (z), neopentyl glycol (x3) ( Hydroxyl value 1078 mgKOH / g) 2.90 g (0.028 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 9.70 g (0.015 mol), bifunctional polyester polyol (x2) ( (Hydroxyl value 63 mg KOH / g) 65.4 g (0.037 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor and dibutyltin dilaurate 0.02 g as a reaction catalyst were charged and reacted at 60 ° C. for 3 hours to give 2-hydroxyethyl Charge 4.10 g (0.035 mol) of acrylate (y) The reaction was terminated at 60 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-8) (weight average molecular weight (Mw); 158,000) A toluene solution (resin content 60%) was obtained.

<Production Example 9: Urethane (meth) acrylate-based compound (A-9)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 100 g of toluene, 23.8 g (0.12 mol) of hydrogenated xylylene diisocyanate (z), neopentyl glycol (x3) ( Hydroxyl value 1078 mgKOH / g) 3.40 g (0.033 mol), trifunctional polyether polyol (x1) (hydroxyl value 77 mgKOH / g) 40.1 g (0.018 mol), bifunctional polyether polyol (x2 ) (Hydroxyl value 168 mg KOH / g) 28.0 g (0.042 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60 ° C. for 3 hours, 4.70 g (0.040 mol) of hydroxyethyl acrylate (y) is charged, The reaction was terminated at 0 ° C. for 3 hours, and the reaction was terminated when the residual isocyanate group reached 0.3%, and the urethane (meth) acrylate compound (A-9) (weight average molecular weight (Mw); 50,000) A toluene solution (resin content 50%) was obtained.

<Production Example 10: Urethane (meth) acrylate-based compound (A-10)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and nitrogen gas inlet, tetrahydrofurfuryl acrylate 66.7 g, hydrogenated xylylene diisocyanate (z) 19.8 g (0.10 mol), neopentyl Glycol (x3) (hydroxyl value 1078 mgKOH / g) 2.80 g (0.027 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 7.30 g (0.011 mol), bifunctional polyester Polyol (x2) (hydroxyl value 63 mgKOH / g) 42.6 g (0.024 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. for 2 hours. Trifunctional polyester polyol (x1) (hydroxyl value) 64 mg KOH / g) 2.20 g (0.0040 mol), bifunctional polyester polyol (x2) (hydroxyl value 63 mg KOH / g) 21.3 g (0.012 mol) was added and reacted at 60 ° C. for 2 hours. -4.00 g (0.034 mol) of hydroxyethyl acrylate (y) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and urethane (meth) acrylate A tetrahydrofurfuryl acrylate solution of the compound (A-10) (weight average molecular weight (Mw); 52,000) was obtained.

<Production Example 11: Urethane (meth) acrylate-based compound (A′-1)>
To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 12.9 g (0.058 mol) of isophorone diisocyanate (z), bifunctional polyester polyol (x2) (hydroxyl value 54 mgKOH / g) 82.6 g (0.040 mol) and 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged and reacted at 60 ° C. for 2 hours to give 4.40 g (0.038 mol) of 2-hydroxyethyl acrylate (y), polymerization 0.04 g of hydroquinone methyl ether was added as an inhibitor and reacted at 60 ° C. for 3 hours. The reaction was terminated when the residual isocyanate group became 0.3%, and the urethane (meth) acrylate compound (A′-1) (Weight average molecular weight (Mw); 17,000) was obtained.

<Production Example 12: Urethane (meth) acrylate-based compound (A′-2)>
Into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, isophorone diisocyanate (z) 26.5 g (0.12 mol), trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g) 9.40 g (0.015 mol), bifunctional polyether polyol (x2) (hydroxyl value 63 mg KOH / g) 47.4 g (0.027 mol), 0.02 g of dibutyltin dilaurate as a reaction catalyst were charged at 60 ° C. For 2 hours, 16.6 g (0.14 mol) of 2-hydroxyethyl acrylate (y) and 0.02 g of hydroquinone methyl ether as a polymerization inhibitor were allowed to react at 60 ° C. for 3 hours. The reaction was terminated when the amount reached 3%, and the urethane acrylate compound (A′-2) ( Weight average molecular weight (Mw); 4,000) was obtained.

<Production Example 13: Urethane (meth) acrylate-based compound (A'-3)>
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 42.9 g of toluene, 32.3 g (0.17 mol) of hydrogenated xylylene diisocyanate (z), neopentyl glycol (w ) 11.6 g (0.11 mol), bifunctional polyester polyol (x2) (hydroxyl value 63 mg KOH / g) 49.6 g (0.028 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, and as a reaction catalyst 0.02 g of dibutyltin dilaurate was charged and reacted at 60 ° C. for 2 hours, and 6.50 g (0.056 mol) of 2-hydroxyethyl acrylate (y) was charged and reacted at 60 ° C. for 3 hours. The reaction was terminated at the point of 3%, and urethane (meth) acrylate compound (A′-3) (weight average Average molecular weight (Mw); 13,000) was obtained.

The following were prepared as the photopolymerization initiator (B).
(B-1): 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd., “Irgacure 184”)

[Examples 1 to 9]
100 parts of urethane (meth) acrylate compounds (A-1 to A-9) obtained in Production Examples 1 to 9, 2.4 parts of photopolymerization initiator (B-1), and toluene in a solid content concentration of 40% The active energy ray-curable resin composition was obtained.

Example 10
4 parts of a photopolymerization initiator (B-1) was blended with 100 parts of the urethane (meth) acrylate compound (A-10) obtained in Production Example 10 to obtain an active energy ray-curable resin composition.

[Comparative Example 1]
In Example 1, instead of the urethane (meth) acrylate compound (A-1), the urethane (meth) acrylate (A′-1) obtained in Production Example 11 was used, and a photopolymerization initiator (B The active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the amount of -1) used was 4 parts.

[Comparative Example 2]
In Example 1, instead of the urethane (meth) acrylate compound (A-1), the urethane (meth) acrylate (A′-2) obtained in Production Example 12 was used, and a photopolymerization initiator (B The active energy ray-curable resin composition was obtained in the same manner as in Example 1 except that the amount of -1) used was 4 parts.

[Comparative Example 3]
In Example 1, it replaces with a urethane (meth) acrylate type compound (A-1), and Example 1 except having used the urethane (meth) acrylate (A'-3) obtained by the said manufacture example 13. Similarly, an active energy ray-curable resin composition was obtained.

  The active energy ray-curable resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated for transparency.

<Transparency>
The color was compared with an APHA (Hazen unit color number) standard solution, and the APHA value of the active energy ray-curable resin composition was measured and evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation criteria)
○: APHA value is less than 30 ×: APHA value is 30 or more

  Moreover, restoration property and stretchability were evaluated using the obtained active energy ray-curable resin composition.

<Restorability>
The active energy ray-curable resin composition obtained above is applied to a black polycarbonate substrate (manufactured by Nippon Test Panel Co., Ltd., 2 × 70 × 150 mm) with an applicator so that the cured coating film has a thickness of 40 μm. After drying at 90 ° C. for 6 minutes, using one high pressure mercury lamp 80W, 3 passes of UV irradiation (cumulative irradiation amount 1000 mJ / cm ² ) at a conveyor speed of 3.4 m / min from a height of 18 cm. And a cured coating film was obtained. In addition, since the active energy ray-curable resin composition obtained in Example 10 is a solvent-free composition, the cured coating film was obtained by omitting the drying step from the cured coating film forming step.
Using the above-mentioned cured coating film, under a condition of 23 ° C. and 50% Rh, using a brass 2-digit brush, scratching the coating film 5 times with a load of 500 g, and measuring the time when the scratch cannot be visually confirmed And evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation criteria)
○: Scratch is restored within 3 minutes Δ: Scratch is restored after 3 minutes and within 10 ×: Scratch is not restored by confirmation after over 10 minutes after being scratched

<Elasticity>
Apply the active energy ray-curable resin composition obtained above to a glass substrate (manufactured by Nippon Test Panel Co., Ltd., 2 × 70 × 150 mm) so that the cured coating film has a thickness of 40 μm with an applicator, After drying at 90 ° C. for 6 minutes, using one high pressure mercury lamp 80W, 3 passes of UV irradiation (cumulative irradiation amount 1000 mJ / cm ² ) at a conveyor speed of 3.4 m / min from a height of 18 cm. After forming a cured coating film, only the coating film was peeled off to obtain a cured coating film.
In addition, since the active energy ray-curable resin composition obtained in Example 10 is a solvent-free composition, the cured coating film was obtained by omitting the drying step from the cured coating film forming step.
The cured coating film was cut into a width of 10 mm and a length of 30 mm, and the resulting coating film was pulled in the length direction under the condition of 23 ° C. and 50% Rh, and the length was 45 mm (1.5 times longer). In this case, the film was fixed for 60 seconds while being pulled, and then the fixation was removed, and the time during which the elongation of the coating film was the same as before stretching was measured and evaluated according to the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation criteria)
○: Return to the original size within 1 minute. △: Return to the original size within 3 minutes.

  From the above evaluation results, Example 1 obtained by using a polyol compound containing a polyol compound containing 3 or more hydroxyl groups and using a urethane (meth) acrylate compound having a weight average molecular weight of 10,000 to 800,000. It can be seen that the cured coating film of 1 to 10 is excellent in the balance between resilience and stretchability, and also excellent in the transparency of the resin composition.

On the other hand, the cured coating films of Comparative Examples 1 and 3 obtained using a urethane (meth) acrylate compound that contains only a bifunctional polyol compound and does not contain a trifunctional or higher polyol compound are both restorable. It turns out that the cured coating film of Comparative Example 3 is also inferior in stretchability.
In addition, the cured coating film of Comparative Example 2 obtained using a urethane (meth) acrylate compound having a low weight average molecular weight but containing a tri- or higher functional polyol compound may be inferior in both resilience and stretchability. Recognize.

  The active energy ray curable resin composition of the present invention has a coating film contractibility due to a three-dimensional network structure while maintaining a coating film stretch characteristic peculiar to a urethane structure when a cured coating film is formed. An elastic coating film having shrinkage performance can be obtained. Therefore, a cured coating film having high practicality can be formed as a resilience against scratches, and it is useful as a coating material, an ink, a coating agent, particularly as a coating agent for the outermost surface.

Claims (9)

Polyol compound (x),
Hydroxyl group-containing (meth) acrylate compound (y) and polyvalent isocyanate compound (z)
Is an active energy ray-curable resin composition comprising a urethane (meth) acrylate compound (A) having a weight average molecular weight of 10,000 to 800,000,
An active energy ray-curable resin composition, wherein the polyol compound (x) contains a polyol compound (x1) containing three or more hydroxyl groups.   2. The active energy ray-curable resin composition according to claim 1, wherein the polyol compound (x1) containing three or more hydroxyl groups is at least one selected from polyester polyols and polyether polyols.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the polyol compound (x1) containing three or more hydroxyl groups has a weight average molecular weight of 50 to 6,000.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the polyol compound (x) contains a polyol compound (x2) containing two hydroxyl groups and having a hydroxyl value of less than 450 mgKOH / g. Resin composition.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the polyol compound (x) contains a polyol compound (x3) having two hydroxyl groups and a hydroxyl value of 450 mgKOH / g or more. Resin composition.   The active energy ray-curable resin composition according to claim 1, wherein the average number of hydroxyl groups of the polyol-based compound (x) is 2.01 to 6 mol.   7. The active energy ray-curable resin composition according to claim 1, wherein the urethane (meth) acrylate compound (A) has an ethylenically unsaturated group content of 0.01 to 10 mmol / g. object.   A coating agent comprising the active energy ray-curable resin composition according to claim 1.   The coating agent according to claim 8, which is used as a coating agent for the outermost surface.