JP2014065903A - 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 at a level of withstanding practical use and excellent in blocking resistance when being made to be a cured film, and a coating agent using the same.SOLUTION: An active energy ray curing resin composition contains a urethane (meth)acrylate-based compound (A) with a weight-average molecular weight of 10,000 to 800,000 obtained by reacting a polyol-based compound (x) containing a polyol-based compound (x1) containing 3 or more hydroxyl groups, a hydroxyl group-containing (meth)acrylate-based compound (y) and a polyvalent isocyanate-based compound (z), and a polysiloxane structure-containing compound (B).

Description

  The present invention relates to an active energy ray-curable resin composition and a coating agent. More specifically, the present invention relates to an active energy ray-curable resin for forming a cured coating film excellent in resilience to scratches, blocking resistance, and transparency. The present invention relates to a composition and a coating agent using the composition.

  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.

  In addition, in order to exhibit excellent resilience when a cured coating film is used, the molecular weight of the urethane (meth) acrylate compound is preferably higher than usual, but the relatively high molecular weight urethane (meth) acrylate compound is When the cured coating film is formed, the coating film tends to be sticky (tack generation), that is, the blocking resistance tends to deteriorate.

  In view of this, the present invention provides an active energy ray-curable resin composition that is excellent in resilience at a level that can withstand practicality and has excellent blocking resistance and transparency when used as a cured coating film under such a background. The object is to provide a product and a coating agent using the product.

  However, as a result of intensive studies in view of such circumstances, the present inventors have made a relatively high molecular weight urethane (meth) acrylate obtained by reacting a polyol compound, a hydroxyl group-containing (meth) acrylate compound and a polyisocyanate compound. When using a polyol compound containing three or more hydroxyl groups as the polyol compound in the system compound, when a cured coating film is obtained, the coating film stretchability unique to the urethane structure is maintained and the three-dimensional network structure is maintained. It is provided with a coating film shrinkage property, and a rubber elastic coating film having stretching / shrinking performance is obtained. Further, by containing a polysiloxane structure-containing compound (B), it is possible to restore resilience to scratches, block resistance, and transparency. The present inventors have found that a cured coating film excellent in balance can be formed, and the present invention has been completed.

  Further, in the present invention, the synthesis is performed 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 material of the urethane (meth) acrylate compound. Since excessive molecular network formation at the time can be alleviated and gelation can be suppressed, it becomes possible to stably produce a urethane (meth) acrylate-based compound. It will be effective.

That is, the gist of the present invention is that a polyol compound (x) containing a polyol compound (x1) containing three or more hydroxyl groups, a hydroxyl group-containing (meth) acrylate compound (y), and a polyisocyanate compound (z) ), A urethane (meth) acrylate compound (A) having a weight average molecular weight of 10,000 to 800,000 and a polysiloxane structure-containing compound (B). It is about things.
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, blocking resistance, and transparency to scratches when formed into a cured coating film. Useful as a surface coating agent.

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 comprises a urethane (meth) acrylate compound (A) and a polysiloxane structure-containing compound (B).
First, the urethane (meth) acrylate compound (A) will be described.

[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 methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1 , 2,6-hexanetriol, pentaerythritol and other low molecular weight (preferably molecular weight 64 to 250) polyols, polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, hydrogenated polybutadiene polyols, ( Examples include (meth) acrylic polyols and polysiloxane polyols.
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, 1,2,6-hexanetriol, pentaerythritol, cyclohexanediol (such as 1,4-cyclohexanediol), bisphenol (such as bisphenol A) ), And the like sugar alcohols (such as xylitol or 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 (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 raw material polyol so that three or more hydroxyl groups are contained in the molecular terminals (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 a polyol having a molecular weight (preferably a molecular weight of 64 to 250) and a polyoxyalkylene polyol which is an alkylene oxide adduct 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 terminals (side chains) may be used.

  Among these, polyester-based polyols and polyether-based polyols are preferable because they have excellent 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 active energy rays, particularly the hardness of the coating film surface after UV curing, tends to decrease. If the weight average molecular weight is too low, the three-dimensional network structure becomes dense at the synthesis stage. If it is too high, a sudden increase in viscosity tends to occur 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).
Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described later is measured according to the above method.

  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) is preferably less than 450 mgKOH / g, more preferably 200 mgKOH / g or less, and 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.

  In addition, 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 above-described trifunctional polyol compound (x1) and bifunctional polyol compound (x2), the compound further contains two hydroxyl groups and has a hydroxyl value of 450 mgKOH / g or more. It is preferable to contain (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) is preferably 450 mgKOH / g or more, 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 cyclodecane dimethanol, 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 difference in hydroxyl value ((x3)-(x2)) between the bifunctional polyol compound (x3) and the bifunctional polyol compound (x2) is preferably 0 to 1980 mgKOH / g, particularly preferably 400 to 1600 mgKOH / g. g, more preferably 800 to 1200 mg KOH / g.
If the difference in hydroxyl value is too large, gelation tends to occur during the production of the urethane (meth) acrylate compound, and if it is too small, it tends to be difficult to provide excellent balance between elasticity and elasticity.

The blending amount of the bifunctional polyol compound (x3) is preferably 0 to 50% by weight, particularly preferably 0.3 to 40% by weight, and more preferably based on the bifunctional polyol compound (x2). Is 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 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.

Regarding the polyol compound (x), a trifunctional or higher functional polyol compound (x1) and a bifunctional polyol compound (x2) when the bifunctional polyol compound (x2) and the bifunctional polyol compound (x3) are used. The blending ratio (weight ratio) with the total amount of the bifunctional polyol compound (x3) is preferably (x1): {(x2) + (x3)} = 1:99 to 70:30, particularly preferably ( x1): {(x2) + (x3)} = 5:95 to 50:50, more preferably (x1): {(x2) + (x3)} = 10:90 to 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.

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. If the average number of hydroxyl groups is too large, the three-dimensional network structure becomes excessive and the molecular weight is too high. 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)} / {preparation of trifunctional or higher functional polyol compound (x1) Number of moles + number of moles of bifunctional polyol compound (x2)}] + [number of moles of 2 × 2 functional polyol compound (x2)} / {number of moles of trifunctional or higher polyol compound (x1) + Number of moles of charged 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)} / {preparation of trifunctional or higher functional polyol compound (x1) Number of moles + number of moles charged of bifunctional polyol compound (x2) + number of moles charged of bifunctional polyol compound (x3)}] + [{number of moles charged of 2 × 2 functional polyol compound (x2)} / {trifunctional Charged moles of polyol compound (x1) above + charged moles of bifunctional polyol compound (x2) + charged moles of bifunctional polyol compound (x3)}] + [{2 × 2 functional polyol compound (x3) ) Charged mole number} / {trifunctional polyol compound (x1) charged mole number + bifunctional polyol compound compound (x2) charged mole number + bifunctional polyol compound ( Molar number of 3)}]

  Examples of the hydroxyl group-containing (meth) acrylate compound (y) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy. Hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, 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) acrylate Hydroxyl-containing (meth) acrylate compounds containing one ethylenically unsaturated group such as leuoxypropyl (meth) acrylate; glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tris Hydroxyl group containing two or more ethylenically unsaturated groups such as (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate Containing (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 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). An acrylate is 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 having an acid value of about 2.5 mg KOH / g, and further, when the amount of caprolactone modification 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 polyisocyanate compound (z) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aromatic polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1, 3-bis (isocyanato Cyl) cyclohexane and other alicyclic polyisocyanates, or trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, 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 polyisocyanate compound (z) in a reactor. The reaction may be carried out separately, but the reaction product obtained by reacting the polyol compound (x) and the polyisocyanate compound (z) in advance reacts with the hydroxyl group-containing (meth) acrylate compound (y). The method of making it preferable from the point which is excellent in stability.

  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 polyisocyanate compound (z) in advance, the polyol compound ( For the reaction between x) and the polyisocyanate compound (z), a known reaction method can be used. For example, first, an isocyanate group in the polyisocyanate compound (z): a hydroxyl group in the polyol compound (x). The reaction product containing an isocyanate group at the terminal may be obtained by reacting with a functional group molar ratio of generally about isocyanate group mol: (polyol hydroxyl group mol-hydroxyl group mol of hydroxyl group-containing acrylate).

  Even when the hydroxyl group-containing (meth) acrylate compound (y) is reacted with the reaction product of the polyol compound (x) and the polyisocyanate compound (z), a 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, that the reaction product has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (y) has one hydroxyl group. In the case of a single group, the reaction product: the hydroxyl group-containing (meth) acrylate compound (y) is reacted at about 1: 2, 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 ( The weight ratio of the first stage: second stage = 10: 90 to 90:10 (preferably 30:70 to 90:10, particularly preferably 50) in that the branched structure can be efficiently dispersed in the (meth) acrylate molecule. : 50 to 90:10, and more preferably 55:45 to 90:10).

  In the reaction between the polyol compound (x) and the polyisocyanate 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. It is also preferable to use such a catalyst as, for example, dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zirconium tris (acetylacetonate) ethyl acetoacetate, zirconium tetrakisacetylacetonate or the like, Hexoate zinc (zinc hexanoate) zinc, zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, stannic chloride and the like, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2, 2] Octane, 1,8-diazabicyclo 5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine, amine catalysts such as N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, sulfide In addition to bismuth, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate Bismuth catalysts such as organic acid bismuth salts such as salts, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc. Among them, among them, dibutyltin dilaurate, 1, - diazabicyclo [5,4,0] undecene is preferred.

  In the reaction between the polyol compound (x) and the polyisocyanate compound (z), and the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), a functional group that reacts with an isocyanate group. An organic solvent having no 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 polyisocyanate compound (z), and the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), the reaction temperature is usually 30 to 100. ° C, preferably 40 to 90 ° C, and the reaction time is usually 2 to 10 hours, preferably 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 will be lowered, and if it is too large, the viscosity becomes 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 ethyl acetate, the viscosity at 20 ° C. is preferably 300 to 1,000,000 mPa · s. Particularly preferably, it is 400 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 is obtained.

  Next, the polysiloxane structure-containing compound (B) will be described.

  As the polysiloxane structure-containing compound (B), a compound containing a known general polysiloxane structure may be used, for example, an ethylenically unsaturated group-containing polysiloxane structure-containing compound, an ethylenically unsaturated group-free polysiloxane structure. Containing compounds.

Examples of the ethylenically unsaturated group-containing polysiloxane structure-containing compound include:
Polysiloxane structure-containing (meth) acrylate monomer;
Polysiloxane structure-containing urethane (meth) acrylate compounds (for example, “Shikko UT-3841”, “Shikko UT-3971” manufactured by Nippon Synthetic Chemical Industry Co., Ltd.),
Polyether-modified polysiloxane structure-containing (meth) acrylate compound (for example, “BYK-UV3500”, “BYK-UV3530” manufactured by Big Chemie Japan),
Polyester-modified polysiloxane structure-containing (meth) acrylate compound (for example, “BYK-UV3570” manufactured by BYK Japan)
Polyether ester-modified polysiloxane structure-containing (meth) acrylate compound,
Polycarbonate modified polysiloxane structure-containing (meth) acrylate compound,
Polysiloxane structure-containing (meth) acrylate compounds such as
Unsaturated group-containing polysiloxane structure-containing (meth) acrylates other than the above;
And the compound etc. which introduce | transduced the fluorine atom into the said compound are mentioned.

The number of unsaturated groups contained in the ethylenically unsaturated group-containing polysiloxane structure-containing compound is preferably 1-30, particularly preferably 2-25, and more preferably 3-20.
When there are too many ethylenically unsaturated groups, there exists a tendency for the stretchability and elasticity of a cured coating film to be hard to be obtained, and when too few, there exists a tendency for an unreacted polysiloxane structure containing compound to bleed and to reduce blocking resistance.

Examples of the ethylenically unsaturated group-free polysiloxane structure-containing compound include:
Polyether-modified polysiloxane (for example, “BYK-SILCLEAN 3720”, “BYK-377”, “BYK-UV3510” manufactured by Big Chemie Japan, excluding the above-mentioned polyether-modified polysiloxane structure-containing (meth) acrylate compound);
Polyester-modified polysiloxane (for example, “BYK-370” manufactured by BYK Japan, excluding the above-mentioned polyester-modified polysiloxane structure-containing (meth) acrylate compound);
Polyester-modified polysiloxane structure-containing compound (excluding the above-mentioned polyester-modified polysiloxane structure-containing (meth) acrylate compound);
Polyether-modified polysiloxane structure-containing compound (excluding the above-mentioned polyether-modified polysiloxane structure-containing (meth) acrylate compound);
Polyether ester-modified polysiloxane structure-containing compound (for example, “BYK-375” manufactured by BYK Japan, excluding the above-mentioned polyether ester-modified polysiloxane structure-containing (meth) acrylate compound);
Polycarbonate-modified polysiloxane structure-containing compound (excluding the above-mentioned polycarbonate-modified polysiloxane structure-containing (meth) acrylate compound);
And a polysiloxane structure-containing (meth) acrylic polymer (for example, “BYK-SILCLEAN 3700” manufactured by BYK Japan).

  Among these, a polysiloxane structure-containing (meth) acrylate compound is preferable from the viewpoint of forming a crosslinked structure when irradiated with ultraviolet rays to form a cured coating film and exhibiting excellent durability, and further, urethane ( A polysiloxane structure-containing urethane (meth) acrylate compound (b) is preferred because it is excellent in compatibility with the (meth) acrylate compound.

  The polysiloxane structure-containing urethane (meth) acrylate compound (b) (hereinafter sometimes referred to as “urethane (meth) acrylate compound (b)”) will be described.

The polysiloxane structure-containing urethane (meth) acrylate compound (b) only needs to contain a polysiloxane structure in its structure. In particular, as a component of the urethane (meth) acrylate compound, the following general formula It is a urethane (meth) acrylate compound obtained by using a polysiloxane compound having a hydroxyl group at one end represented by (1) and a polysiloxane compound having a hydroxyl group at both ends represented by the following general formula (2). It is preferable.
In addition, the said urethane (meth) acrylate type compound (b) may have a structure site | part derived from both general formula (1) and (2).

〔式中、Ｒ¹はアルキル基を示し、Ｒ²はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、Ｒ³は炭化水素基又はヘテロ原子を含む有機基を示す。ａは１以上の整数であり、ｂは１〜３の整数である。〕

[Wherein, R ¹ represents an alkyl group, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and R ³ represents a hydrocarbon group or an organic group containing a hetero atom. a is an integer of 1 or more, and b is an integer of 1 to 3. ]

〔式中、Ｒ¹、Ｒ³は炭化水素基又はヘテロ原子を含む有機基を示し、Ｒ²はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、ａは１以上の整数であり、ｂ、ｃは１〜３の整数である。〕

[Wherein R ¹ and R ³ represent a hydrocarbon group or an organic group containing a hetero atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more, b and c are integers of 1 to 3. ]

  First, a polysiloxane structure-containing urethane (meth) acrylate compound (b1) (hereinafter referred to as “urethane (meth) acrylate system) obtained by using a polysiloxane compound having a hydroxyl group at one end represented by the general formula (1). Compound (b1) ”may be described.

  The urethane (meth) acrylate compound (b1) is a polysiloxane compound (p1) having a hydroxyl group at one end represented by the general formula (1) (hereinafter referred to as “polysiloxane compound (p1)”). ), A polyisocyanate compound (p2), a hydroxyl group-containing (meth) acrylate compound (p3), and, if necessary, a polyol compound (p4).

For such a polysiloxane compound (p1), R ¹ in the general formula (1) is an alkyl group, and the alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.

R ² in the general formula (1) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.
As carbon number of a cycloalkyl group, it is C3-C10 normally, Preferably it is 5-8, for example, a cyclopentyl group, a cyclohexyl group, norbornyl group etc. are mentioned.

The alkyl group, cycloalkyl group, and phenyl group may have a substituent. Examples of the substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. In the case where the substituent has a carbon atom, said carbon atom shall not included in the number of carbon atoms is specified in the description of the R ^2.

R ³ in the general formula (1) is a hydrocarbon group or an organic group containing a hetero atom.
As a hydrocarbon group, it is C1-C30 normally, Preferably it is C1-C20, and a bivalent or trivalent hydrocarbon group is mentioned.
Examples of the divalent hydrocarbon group include an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
Examples of the organic group containing a hetero atom include an oxyalkylene group, a polyoxyalkylene group, a polycaprolactone group, and an amino group.

  A in general formula (1) is an integer greater than or equal to 1, Preferably it is 5-200, Most preferably, it is an integer of 5-120. b is an integer of 1 to 3, preferably an integer of 1 to 2.

  The weight average molecular weight of the polysiloxane compound (p1) used in the present invention is usually preferably 100 to 50,000, particularly 500 to 10,000, more preferably 1,000 to 10,000. It is preferable. If the weight average molecular weight is too low, the blocking resistance tends to decrease, and if it is too high, the transparency tends to decrease.

  Specific examples of the polysiloxane compound (p1) represented by the general formula (1) include, for example, “X-22-170BX”, “X-22-170DX”, “X-22-” manufactured by Shin-Etsu Chemical Co., Ltd. 176DX "," X-22-176F "," Silaplane FM-0411 "," Silaplane FM-0421 "," Silaplane FM-0425 "," Silaplane FM-DA11 "," Silaplane "manufactured by Chisso Corporation Products such as “FM-DA21”, “Silaplane FM-DA26”, and the like.

Examples of the polyisocyanate compound (p2) used in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Aromatic polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1 , 3-bis Alicyclic polyisocyanates such as natomethyl) cyclohexane, trimer compounds or multimer compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.). These can be used alone or in combination of two or more.
Among these, an isocyanate compound having three or more isocyanate groups in one molecule, particularly a polyisocyanate trimer or multimer compound, can reduce unreacted low molecular weight components that cause bleeding. More preferable in terms.

Examples of the hydroxyl group-containing (meth) acrylate compound (p3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and 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 modification -glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Cole 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 pentaerythritol 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, succinic acid-modified pentaerythritol tri (meth) acrylate, tripentaerythritol acrylate (E.g., manufactured by Osaka Organic Chemical Industry Ltd., "Viscoat # 802", etc.) and the like. These can be used alone or in combination of two or more.
Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable in that bleeding of the unreacted polysiloxane structure-containing compound can be reduced.

  Furthermore, you may use a polyol type compound (p4) in the range which does not impair the effect of this invention. Examples of the polyol compound (p4) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2,2-diane Methylol heptane, trimethylene glycol, 1,4-tetramethylene glycol, dipropylene glycol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 2,4-diethyl-1,5-penta Methylene diol, hydrogenated bisphenol A, hydroxy Rulylated bisphenol A, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 2,2-dimethyl-3-hydroxypropyl, 2,2-dimethyl-3-hydroxypropionate, 2,2,4- Trimethyl-1,3-pentanediol, N, N-bis- (2-hydroxyethyl) dimethylhydantoin, glycerin, sorbitol, anitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipenta Low molecular weight polyhydric alcohols such as erythritol and tris- (hydroxyethyl) isocyanurate, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadienes Polyol, (meth) acrylic polyols, and the like.

  Examples of polyether polyols include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.

Examples of the polyester-based polyol include 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 reactants.
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.

  As a weight average molecular weight of a polyol type compound (p4), 50-8000 are preferable, Especially preferably, it is 50-5000, More preferably, it is 600-3000. If the weight average molecular weight of the polyol (p4) is too large, the blocking resistance tends to be reduced during curing, and if it is too small, the resin liquid tends to be highly viscous and difficult to handle.

The urethane (meth) acrylate compound (b1) preferably has one or more ethylenically unsaturated groups, and has three or more ethylenically unsaturated groups in terms of the hardness of the cured coating film. It is particularly preferable that it has 6 or more ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (b1) contains is 30 normally, Preferably it is 25 or less.

The method for producing the urethane (meth) acrylate compound (b1) is not particularly limited.
(A): Polysiloxane compound (p1), polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)), a hydroxyl group-containing (meta ) A method in which the acrylate compound (p3) is charged and reacted together,
(B): After reacting a polysiloxane compound (p1) and a polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)) , A method of reacting a hydroxyl group-containing (meth) acrylate compound (p3),
(C): a polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)) and a hydroxyl group-containing (meth) acrylate compound (p3). A method of reacting the polysiloxane compound (p1) after the reaction,
(D): polyisocyanate compound (p2) (if necessary, a polyisocyanate compound (p2) previously reacted with a polyol compound (p4)) and a hydroxyl group-containing (meth) acrylate compound (p3) A method of reacting a part of the polysiloxane compound (p1) and then reacting the remaining hydroxyl group-containing (meth) acrylate compound (p3);
Among these, the method (b) or (2) is preferable, and the method (b) is particularly preferable from the viewpoint of stability of reaction control.

  In addition, what is necessary is just to follow the manufacture example of a well-known general urethane type polyol, when making a polyol type compound (p4) and a polyisocyanate type compound (p2) react previously, for example.

  In the method (b), after reacting the hydroxyl group of the polysiloxane compound (p1) with the isocyanate group of the polyisocyanate compound (p2) under the condition that the isocyanate group remains, the polyisocyanate compound ( The residual isocyanate group of p2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (p3).

  The reaction molar ratio between the polysiloxane compound (p1) and the polyisocyanate compound (p2) is, for example, that the polysiloxane compound (p1) has one hydroxyl group and the polyisocyanate compound (p2) has 2 isocyanate groups. Polysiloxane compound (p1): polyisocyanate compound (p2) 1: about 0.8 to 10, and the polysiloxane compound (p1) has one hydroxyl group. When the number of isocyanate groups in (p2) is 3, it may be about polysiloxane compound (p1): polyisocyanate compound (p2) 1: 0.2-5.

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (p3), the reaction is terminated when the residual isocyanate group in the reaction system is 0.5% by weight or less. ) An acrylate compound (b1) is obtained.

  The weight of the structural portion derived from the polysiloxane compound (p1) contained in 100 parts by weight of the urethane (meth) acrylate compound (b1) is 0.1 to 80 parts by weight within the above molar ratio range. It is preferable that

  In this reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such a catalyst include dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zirconium tris (acetylacetonate) ethylacetate. Organometallic compounds such as acetate and zirconium tetrakisacetylacetonate, zinc hexate zinc (zinc hexanoate), zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, stannic chloride and the like, triethylamine, Benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl-1,3-butanediamine , Amine catalysts such as N-ethylmorpholine, bismuth nitrate In addition to bismuth bromide, bismuth iodide, bismuth sulfide, etc., organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate Organics such as bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate Examples thereof include bismuth-based catalysts such as acid bismuth salts, among which dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are suitable.

  In such a reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene An organic solvent such as can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  The reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

  The urethane (meth) acrylate compound (b1) thus obtained preferably has a weight average molecular weight of 500 to 50,000, more preferably 500 to 30,000. If the weight average molecular weight is too small, the blocking resistance tends to decrease, and if it is too large, the transparency of the cured coating film tends to decrease.

The viscosity of the urethane (meth) acrylate compound (b1) at 20 ° C. in a 40 wt% methyl isobutyl ketone solution is preferably 5 to 5,000 mPa · s, particularly 5 to 2,500 mPa · s, and more preferably 5 It is preferable that it is-10 million 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.

  As for the said urethane (meth) acrylate type compound (b1), only 1 type may be used independently and 2 or more types may be used together.

  Next, a polysiloxane structure-containing urethane (meth) acrylate compound (b2) (hereinafter referred to as “urethane (meth) acrylate) obtained by using a polysiloxane compound having hydroxyl groups at both ends represented by the general formula (2). The compound (b2) ”may be described.)

〔式中、Ｒ¹、Ｒ³は炭化水素基又はヘテロ原子を含む有機基を示し、Ｒ²はそれぞれ独立にアルキル基、シクロアルキル基又はフェニル基を示し、ａは１以上の整数であり、ｂ、ｃは１〜３の整数である。〕

[Wherein R ¹ and R ³ represent a hydrocarbon group or an organic group containing a hetero atom, R ² independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more, b and c are integers of 1 to 3. ]

  The urethane (meth) acrylate compound (b2) is a polysiloxane compound (q1) having a hydroxyl group at both ends represented by the general formula (2) (hereinafter referred to as “polysiloxane compound (q1)”). ), A polyvalent isocyanate compound (q2), a hydroxyl group-containing (meth) acrylate compound (q3), and, if necessary, a polyol compound (q4).

In the polysiloxane compound (q1), R ¹ and R ³ in the general formula (2) are hydrocarbon groups or organic groups containing a hetero atom.
As a hydrocarbon group, it is C1-C30 normally, Preferably it is C1-C20, and a bivalent or trivalent hydrocarbon group is mentioned.
Examples of the divalent hydrocarbon group include an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
Examples of the organic group containing a hetero atom include an oxyalkylene group, a polyoxyalkylene group, a polycaprolactone group, and an amino group.

R ² in the general formula (2) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
The alkyl group preferably has a relatively short carbon number. Specifically, it is C1-C15 normally, Preferably it is 1-10, Most preferably, it is 1-5, for example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.
As carbon number of a cycloalkyl group, it is C3-C10 normally, Preferably it is 5-8, for example, a cyclopentyl group, a cyclohexyl group, norbornyl group etc. are mentioned.

The alkyl group, cycloalkyl group, and phenyl group may have a substituent. Examples of the substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group. In addition, when the substituent has a carbon atom, the carbon atom is not included in the number of carbons defined in the description of R ² above.

  A in general formula (2) is an integer greater than or equal to 1, Preferably it is 5-200, Most preferably, it is an integer of 5-120. b is an integer of 1 to 3, preferably an integer of 1 to 2.

  The weight average molecular weight of the polysiloxane compound (q1) is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. If the weight average molecular weight is too low, the blocking resistance tends to decrease, and if it is too high, the transparency tends to decrease.

  Specific examples of the polysiloxane compound (q1) include “X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., “ "Silaplane FM-4411", "Silaplane FM-4421", "Silaplane FM-4425", "XF42-B0970" manufactured by Momentive Performance Materials Japan, "BY 16" manufactured by Toray Dow Corning -004 "," SF 8427 "," Macromonomer HK-20 "manufactured by Toagosei Co., Ltd.," DMS-C21 "," DMS-C23 "," DBL-C31 "," DMS-CA21 "manufactured by GELEST, etc. Products.

  As a polyisocyanate type compound (q2), the thing similar to what was illustrated as a polyisocyanate type compound (p2) in the description regarding the said urethane (meth) acrylate (b1) is mentioned, for example.

  Examples of the hydroxyl group-containing (meth) acrylate compound (q3) are the same as those exemplified as the hydroxyl group-containing (meth) acrylate compound (p3) in the description of the urethane (meth) acrylate (b1). Is mentioned.

  Furthermore, a polyol compound (q4) may be used as long as the effects of the present invention are not impaired. For example, those exemplified as the polyol compound (p4) in the description of the urethane (meth) acrylate (b1). The same thing is mentioned.

The urethane (meth) acrylate compound (b2) preferably has 2 or more ethylenically unsaturated groups, and has 4 or more ethylenically unsaturated groups in terms of the hardness of the cured coating film. It is particularly preferable that it has 6 or more ethylenically unsaturated groups.
Moreover, the upper limit of the ethylenically unsaturated group which a urethane (meth) acrylate type compound (b2) contains is 30 normally, Preferably it is 25 or less.

The method for producing the urethane (meth) acrylate compound (b2) is not particularly limited, and for example,
(A): Polysiloxane compound (q1), polyisocyanate compound (q2) (if necessary, polyisocyanate compound (q2) previously reacted with polyol compound (q4)), hydroxyl group-containing (meta ) A method in which the acrylate compound (q3) is charged and reacted together,
(B): After reacting a polysiloxane compound (q1) and a polyisocyanate compound (q2) (if necessary, a polyisocyanate compound (q2) previously reacted with a polyol compound (q4)) , A method of reacting a hydroxyl group-containing (meth) acrylate compound (q3),
(C): Polyisocyanate compound (q2) (if necessary, polyisocyanate compound (q2) previously reacted with polyol compound (q4)) and hydroxyl group-containing (meth) acrylate compound (q3) A method of reacting the polysiloxane compound (q1) after the reaction,
(D): Polyisocyanate compound (q2) (polyisocyanate compound (q2) previously reacted with polyol compound (q4) if necessary) and hydroxyl group-containing (meth) acrylate compound (q3) A method of reacting a part of the polysiloxane compound (q1) and further reacting the remaining hydroxyl group-containing (meth) acrylate compound (q3),
Among these, the method (b) or (d) is preferable, and the method (2) is particularly preferable from the viewpoint of stability of reaction control and compatibility.

  In addition, what is necessary is just to follow the manufacture example of a well-known general urethane type polyol, for example, when making a polyol type compound (q4) and a polyisocyanate type compound (q2) react beforehand.

  In the method (b), after reacting the hydroxyl group of the polysiloxane compound (q1) with the isocyanate group of the polyvalent isocyanate compound (q2) under the condition that the isocyanate group remains, the polyisocyanate compound is then reacted. The residual isocyanate group of (q2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (q3).

  The reaction molar ratio between the polysiloxane compound (q1) and the polyisocyanate compound (q2) is, for example, that the polysiloxane compound (q1) has 2 hydroxyl groups and the polyisocyanate compound (q2) has 2 isocyanate groups. Polysiloxane compound (q1): polyisocyanate compound (q2) is about 1: 1.1 to 2.2, and polysiloxane compound (q1) has two hydroxyl groups, In the case where the number of isocyanate groups in the system compound (q2) is 3, the polysiloxane compound (q1): polyisocyanate compound (q2) may be about 1: 0.5 to 2.2.

  In the addition reaction between the reactive organism and the hydroxyl group-containing (meth) acrylate compound (q3), the reaction is terminated when the residual isocyanate group in the reaction system becomes 0.5% by weight or less. ) An acrylate compound (b2) is obtained.

  Moreover, the weight of the structural part derived from the polysiloxane compound (q1) contained in 100 parts by weight of the urethane (meth) acrylate compound (b2) is 0.1 to 80 parts by weight within the above molar ratio. Preferably there is.

  In such a reaction, it is also preferable to use a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include the same as described above.

  In such a reaction, an organic solvent having no functional group that reacts with an isocyanate group, for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene An organic solvent such as can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  The reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.

  The weight average molecular weight of the urethane (meth) acrylate compound (b2) thus obtained is usually preferably 500 to 50,000, and more preferably 500 to 30,000. If the weight average molecular weight is too small, the blocking resistance tends to decrease, and if it is too large, the transparency of the cured coating film tends to decrease.

The viscosity at 20 ° C. of the 40 wt% methyl isobutyl ketone solution of the urethane (meth) acrylate compound (b2) is preferably 5 to 5,000 mPa · s, more preferably 10 to 2,500 mPa · s, The pressure is preferably 15 to 1,000 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.

  As for the said urethane (meth) acrylate type compound (b2), only 1 type may be used independently and 2 or more types may be used together.

  As the polysiloxane structure-containing urethane (meth) acrylate compound (b), it is preferable to use the urethane (meth) acrylate compound (b1) and / or the urethane (meth) acrylate compound (b2). It is particularly preferable to use urethane (meth) acrylate (b2) from the viewpoint that the polysiloxane compound hardly remains.

  Moreover, when using together urethane (meth) acrylate type compound (b1) and (b2), the mixture ratio (weight ratio) of urethane (meth) acrylate type compound (b1) and urethane (meth) acrylate type compound (b2) ) Is preferably (b1) / (b2) = 5/95 to 95/5, particularly preferably (b1) / (b2) = 20/80 to 80/20.

The polysiloxane structure-containing compound (B) preferably has a silicon atom content of 0.1 to 80% by weight, particularly preferably 0.3 to 60% by weight, more preferably 0.5 ~ 30% by weight.
If the silicon atom content is too large, the compatibility with other components tends to decrease, and if it is too small, the blending amount required for improving the blocking resistance increases, making it difficult to balance the physical properties of the coating film. Tend to be.

The content of the polysiloxane structure-containing compound (B) is preferably 0.01 to 100 parts by weight, particularly preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). 75 parts by weight, more preferably 1 to 50 parts by weight.
When the content is too large, the compatibility tends to decrease, and when the content is too small, the blocking resistance tends to be difficult to improve.

  The active energy ray-curable resin composition of the present invention is obtained using the urethane (meth) acrylate compound (A) and the polysiloxane structure-containing compound (B).

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

  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-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 (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), urethane (meth) acrylate type compound (A), polysiloxane structure containing compound (B) (and the below-mentioned ethylenically unsaturated monomer (D used as needed) )) Is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, and more preferably 1 to 7.5 parts by weight with respect to 100 parts by weight.
If the content of the photopolymerization initiator (C) 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 (D) 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 can also 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.

  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), the polysiloxane structure-containing compound (B) and other components is particularly limited. They can be mixed by various methods.

  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 (C).

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 30~3000mJ / cm ² (preferably 100~1500mJ / cm ²⁾ may be irradiated with ultraviolet rays of).
After UV irradiation, heating can be performed as necessary to complete 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, the photopolymerization initiator (C) as a UV curable coating film should be 3 to 1000 μm, preferably 5 to 500 μm, particularly preferably 10 to 10 μm in consideration of light transmission so that the photopolymerization initiator (C) can react uniformly. 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 polyisocyanate compound (z) are reacted. The active energy ray-curable resin composition comprising the urethane (meth) acrylate compound (A) and the polysiloxane structure-containing compound (B), which is a coating film peculiar to the urethane structure, is used as a cured coating film. While maintaining film stretchability, it has a three-dimensional network-structured film shrinkage, so a film with stretch / shrinkage performance can be obtained. Can form a cured coating film with excellent blocking resistance and transparency, and is particularly useful as a coating agent, ink, coating agent, especially the coating agent for the outermost surface A.

  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.

  In addition, regarding the measurement of the hydroxyl value and the weight average molecular weight in the following Examples, it measured according to the above-mentioned method.

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

<Production Example 1: Urethane (meth) acrylate-based compound (A-1)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, ethyl acetate 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, molecular weight calculated from hydroxyl value 638) 7.30 g (0.011) Mol) Bifunctional polyester polyol (x2) (hydroxyl value 62.8 mgKOH / g, molecular weight 1787 calculated from hydroxyl value) 42.6 g (0.024 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor, Prepared with 0.02g of dibutyltin dilaurate as a reaction catalyst and reacted at 60 ° C for 2 hours Trifunctional polyester polyol (x1) (hydroxyl value 264 mgKOH / g, molecular weight 638 calculated from hydroxyl value) 2.20 g (0.0040 mol), bifunctional polyester polyol (x2) (hydroxyl value 62.8 mgKOH) / G, 21.3 g (0.012 mol) of molecular weight calculated from hydroxyl value 1787) and reacted at 60 ° C. for 2 hours to give 4.00 g (0.034 mol) of 2-hydroxyethyl acrylate (y). The reaction was completed for 3 hours at 60 ° C., and the reaction was terminated when the isocyanate group disappeared, and an ethyl acetate solution of urethane (meth) acrylate compound (A-1) (weight average molecular weight (Mw); 85,000). (Solid content concentration 60%) was obtained.

<Production Example 2: Urethane (meth) acrylate-based compound (A-2)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 66.7 g of ethyl acetate, 20.1 g (0.10 mol) of hydrogenated xylylene diisocyanate (z), neopentyl glycol ( x3) (hydroxyl value 1078 mgKOH / g) 2.90 g (0.028 mol), trifunctional polyether polyol (x1) (hydroxyl value 280 mgKOH / g, molecular weight 601 calculated from hydroxyl value) 6.92 g (0. 012 mol), bifunctional polyester polyol (x2) (hydroxyl value 63.4 mgKOH / g, molecular weight 1770 calculated from hydroxyl value) 42.7 g (0.024 mol), hydroquinone methyl ether 0.02 g as a polymerization inhibitor , 0.02g of dibutyltin dilaurate was added as a reaction catalyst and reacted at 60 ° C for 2 hours Trifunctional polyether polyol (x1) (hydroxyl value 280 mgKOH / g, molecular weight 601 calculated from hydroxyl value) 2.08 g (0.0035 mol), bifunctional polyester polyol (x2) (hydroxyl value 63. 4 mg KOH / g, molecular weight calculated from hydroxyl value 1770) 21.3 g (0.012 mol) was added and reacted at 60 ° C. for 2 hours to give 4.10 g (0.035 mol) 2-hydroxyethyl acrylate (y). Was reacted at 60 ° C. for 3 hours, and the reaction was terminated when the isocyanate group disappeared. Ethyl acetate of urethane (meth) acrylate compound (A-2) (weight average molecular weight (Mw); 35,000) A solution was obtained (solid content concentration 60%).

The following were prepared as the polysiloxane structure-containing compound (B) <Production Example 3: Polysiloxane structure-containing compound (B-1)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, hexamethylene diisocyanate trimer (q2) 69.1 g (isocyanate group content 21.0%), general formula (2 ) Polysiloxane compound (q1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, b = 1, c = 1, weight average molecular weight 6000) 172.6 g, methyl isobutyl ketone 500 g, hydroquinone methyl ether 1.0 g as a polymerization inhibitor, and dibutyltin dilaurate 0.1 g as a reaction catalyst, reacted at 60 ° C. for 3 hours, and residual isocyanate Is 4.0%, dipentaerythritol pentaacrylate (q3) [dipentaerythritol pentaacrylate And 258.3 g of a mixture of dipentaerythritol hexaacrylate (hydroxyl value 50 mg KOH / g)], the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared, and the polysiloxane group-containing urethane (meth) acrylate A compound (B-1) solution was obtained (solid content concentration 50%).

<Production Example 4: Polysiloxane structure-containing compound (B-2)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 115.7 g of isophorone diisocyanate trimer (q2) (isocyanate group content 17.2%), general formula (2) A polysiloxane compound (q1) (R ¹ = —C ₂ H ₄ OC ₃ H ₆ —, R ² = methyl group, R ³ = —C ₃ H ₆ OC ₂ H ₄ —, b = 1, c = 1, weight average molecular weight 6000) 236.7 g, methyl isobutyl ketone 500 g, 2,6-di-tert-butylcresol 0.5 g as a polymerization inhibitor, 0.05 g of dibutyltin dilaurate as a reaction catalyst, 3 at 60 ° C. When the residual isocyanate is 3.8% after reacting for a period of time, pentaerythritol triacrylate [pentaerythritol triacrylate and The mixture (q3) of pentaerythritol tetraacrylate (hydroxyl value 120 mgKOH / g)] 147.6 g was charged, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared, and the polysiloxane group-containing urethane (meth) acrylate type A compound (B-2) solution was obtained (solid content concentration 50%).

<Production Example 5: Polysiloxane structure-containing compound (B-3)>
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 41.8 g of isophorone diisocyanate (q2) (isocyanate group content 37.8%), a polymer represented by the general formula (2) siloxane compound ^{_{(q1) (R 1 = -C}} 2 H 4 OC 3 H 6 -, R 2 = ^{_{methyl, R 3 = -C 3 H 6}} OC 2 H 4 -, b = 1, c = 1, by weight (Average molecular weight 6000) 282.2 g, methyl isobutyl ketone 500 g, hydroquinone methyl ether 0.1 g as a polymerization inhibitor, and dibutyltin dilaurate 0.01 g as a reaction catalyst were allowed to react at 60 ° C. for 3 hours, and the remaining isocyanate was 2.4%. The pentaerythritol triacrylate (q3) [pentaerythritol triacrylate and pentaerythritol A mixture of lithol tetraacrylate (hydroxyl value 120 mg KOH / g)] 176.0 g was charged, the reaction was continued as it was, and the reaction was terminated when the isocyanate group disappeared, and the polysiloxane group-containing urethane (meth) acrylate compound (B -3) A solution was obtained (solid content concentration 50%).

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

The following were prepared as the ethylenically unsaturated monomer (D).
(D-1): Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., “KAYARAD DPHA”)

[Example 1]
100 parts of the urethane (meth) acrylate compound (A-1) obtained in Production Example 1, 0.5 part of the polysiloxane structure-containing compound (B-1) obtained in Production Example 3, a photopolymerization initiator ( C-1) 2.5 parts and 3 parts of ethylenically unsaturated monomer (D-1) are blended using methyl isobutyl ketone so as to have a solid concentration of 40% to obtain an active energy ray-curable resin composition. It was.

[Example 2]
In Example 1, active energy ray curing was carried out in the same manner except that the urethane (meth) acrylate compound (A-1) was changed to the urethane (meth) acrylate compound (A-2) obtained in Production Example 2. A functional resin composition was obtained.

Example 3
In Example 1, the blending amount of the polysiloxane structure-containing compound (B-1) is 1.2 parts, the blending amount of the photopolymerization initiator (C-1) is 2.7 parts, and the ethylenically unsaturated monomer (D- An active energy ray-curable resin composition was obtained in the same manner except that the blending amount of 1) was changed to 8 parts.

Example 4
An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that the polysiloxane structure-containing compound (B-1) was changed to the polysiloxane structure-containing compound (B-2) obtained in Production Example 4. Obtained.

Example 5
An active energy ray-curable resin composition was prepared in the same manner as in Example 3, except that the polysiloxane structure-containing compound (B-1) was changed to the polysiloxane structure-containing compound (B-3) obtained in Production Example 5. Obtained.

[Comparative Example 1]
In Example 1, the polysiloxane structure-containing compound (B-1) and the ethylenically unsaturated monomer (D-1) were not blended, and the blending amount of the photopolymerization initiator (C-1) was changed to 2.4 parts. An active energy ray-curable resin composition was obtained in the same manner except that.

[Comparative Example 2]
In Example 2, the polysiloxane structure-containing compound (B-1) and the ethylenically unsaturated monomer (D-1) were not blended, and the blending amount of the photopolymerization initiator (C-1) was changed to 2.4 parts. An active energy ray-curable resin composition was obtained in the same manner except that.

  Using the active energy ray-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2, the restorability, blocking resistance, and transparency were evaluated as follows.

<Restorability>
Apply the active energy ray-curable resin composition obtained above to a transparent polycarbonate substrate (Mitsubishi Resin polycarbonate plate STELLA, 2 × 70 × 150 mm) so that the cured coating film has a thickness of 25 μm with an applicator. After drying for 5 minutes at 90 ° C., using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes at a conveyor speed of 3.4 m / min from a height of 18 cm (accumulated dose 800 mJ / cm ²⁾ ) To obtain a cured coating film.
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.
(Evaluation criteria)
○: Scratch recovers within 3 minutes Δ: Scratch recovers within 3 minutes exceeding 10 minutes ×: Scratch is not recovered by confirmation after 10 minutes have passed since scratching

<Blocking resistance>
Apply the active energy ray-curable resin composition obtained above to a transparent polycarbonate substrate (Mitsubishi Resin polycarbonate plate STELLA, 2 × 70 × 150 mm) so that the cured coating film has a thickness of 25 μm with an applicator. After drying for 5 minutes at 90 ° C., using a high pressure mercury lamp lamp 80W and one lamp, UV irradiation of 2 passes at a conveyor speed of 3.4 m / min from a height of 18 cm (accumulated dose 800 mJ / cm ²⁾ ) To obtain a cured coating film having an application area of 50 mm × 130 mm.
Place the same transparent polycarbonate substrate as above on the surface of the cured coating that is not attached to the substrate, and paste it back and forth with a 2 kg load roller. The adhesiveness of the surface of the cured coating film was measured as a surface peeling load by peeling off the plate on the upper surface, and the peeling load per unit area was calculated. The evaluation criteria are as follows.
(Evaluation criteria)
○: The peeling load per unit area is less than 10 g / cm ² ×: The peeling load per unit area is 10 g / cm ² or more

<Transparency>
The active energy ray-curable resin composition obtained above was applied to a 125 μm easy-adhesion PET film (Toyobo A4300) with an applicator so that the cured coating film had a thickness of 25 μm, and dried at 90 ° C. for 5 minutes. Thereafter, using a high pressure mercury lamp lamp 80W and one lamp, two passes of ultraviolet irradiation (accumulated irradiation amount 800 mJ / cm ² ) were performed at a conveyor speed of 3.4 m / min from a height of 18 cm to obtain a cured coating film. .
The haze value which combined the PET film and the cured coating film was measured with respect to the cured coating film obtained above using a haze meter ("NDH 2000" manufactured by Nippon Denshoku Industries Co., Ltd.). The haze value of the PET film itself was 0.52.
The evaluation criteria are as follows.
(Evaluation)
○ ・ ・ ・ Haze value is less than 1.0 △ ・ ・ ・ Haze value is 1.0 or more, less than 3.0 × ・ ・ ・ Haze value is 3.0 or more

  From the above evaluation results, the active energy ray-curable resin compositions of Examples 1 to 5 obtained by blending the polysiloxane structure-containing compound (B) with the urethane (meth) acrylate-based compound (A) have a resilience to scratches, A cured coating film having a well-balanced blocking resistance and transparency can be obtained, whereas it can be obtained from the active energy ray-curable resin compositions of Comparative Examples 1 and 2 that do not contain the polysiloxane structure-containing compound (B). The cured coating film was excellent in resilience and transparency, but the coating film surface was sticky and the blocking resistance was poor.

  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 (10)

  Weight average obtained by reacting a polyol compound (x) containing a polyol compound (x1) containing three or more hydroxyl groups, a hydroxyl group-containing (meth) acrylate compound (y), and a polyisocyanate compound (z). An active energy ray-curable resin composition comprising a urethane (meth) acrylate compound (A) having a molecular weight of 10,000 to 800,000 and a polysiloxane structure-containing compound (B).   The active energy ray-curable resin composition according to claim 1, 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.   The active energy ray-curable resin composition according to claim 1 or 2, wherein the polyol compound (x) contains a polyol compound system (x3) containing two hydroxyl groups and having a hydroxyl value of 450 mgKOH / g or more. object.   The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the urethane (meth) acrylate compound (A) has an ethylenically unsaturated group content of 0.01 to 10 mmol / g. object.   The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the polysiloxane structure-containing compound (B) contains at least one ethylenically unsaturated group.   The active energy ray-curable resin composition according to claim 1, wherein the polysiloxane structure-containing compound (B) is a polysiloxane structure-containing urethane (meth) acrylate compound (b).   The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the silicon atom content relative to the entire polysiloxane structure-containing compound (B) is 0.1 to 80% by weight.   The content of the polysiloxane structure-containing compound (B) is 0.01 to 100 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate compound (A). An active energy ray-curable resin composition according to any one of the above.   A coating agent comprising the active energy ray-curable resin composition according to claim 1.   The coating agent according to claim 9, wherein the coating agent is used as an outermost surface coating agent.