KR101869579B1 - Active-energy-curable resin compositon and coating agent - Google Patents
Active-energy-curable resin compositon and coating agent Download PDFInfo
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- KR101869579B1 KR101869579B1 KR1020137021266A KR20137021266A KR101869579B1 KR 101869579 B1 KR101869579 B1 KR 101869579B1 KR 1020137021266 A KR1020137021266 A KR 1020137021266A KR 20137021266 A KR20137021266 A KR 20137021266A KR 101869579 B1 KR101869579 B1 KR 101869579B1
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- acrylate
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- polyol
- urethane
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Abstract
The present invention provides an active energy ray curable resin composition and a coating agent using the active energy ray curable resin composition having excellent stability and stretchability at a level that can withstand practicability when applied as a cured coating film, (meth) acrylate compound (A) having a weight-average molecular weight of 10,000 to 800,000, which is obtained by reacting a urethane (meth) acrylate compound (x), a hydroxyl group- Wherein the polyol compound (x) contains a polyol compound (x1) containing at least three hydroxyl groups. The active energy ray-curable resin composition according to claim 1,
Description
The present invention relates to an active energy ray-curable resin composition and a coating agent, and more particularly, to an active energy ray-curable resin composition for forming a cured coating film having excellent scratch resistance and stretchability and a coating agent using the same.
Conventionally, the active energy ray-curable resin composition has been extensively used as a coating agent, an adhesive agent, or an anchor coat agent for various substrates since curing is completed by irradiation of active energy rays such as radiation for a very short period of time.
Among them, as a coating agent, an active energy ray-curable resin composition capable of forming a cured coating film on the surface of a plastic substrate and capable of forming a cured coating film having resilience against scratches as a coating agent for protecting the outermost surface For example, an ultraviolet curable coating composition using a urethane acrylate oligomer obtained by reacting a polycaprolactone-containing polyfunctional alcohol with an isocyanate and a hydroxyl group-containing (meth) acrylate (see, for example, Patent Document 1 .) Have been proposed.
However, in the technique disclosed in Patent Document 1, a caprolactone-containing polyfunctional alcohol is used as a constituent raw material of a urethane (meth) acrylate compound, which shows a somewhat restorable property when used as a cured coating film. (Meth) acrylate-based compound of Patent Document 1 is designed to have a relatively small molecular weight due to its design structure, and a sufficient level of restoration property is obtained practically It was not possible.
Accordingly, an object of the present invention is to provide an active energy ray-curable resin composition excellent in resilience and stretchability at a level that can withstand practicability when applied as a cured coating film under such a background, and a coating agent using the same.
However, the present inventors have made intensive studies in view of such circumstances and as a result, have found that a urethane (meth) acrylate compound having a relatively high molecular weight obtained by reacting a polyol compound, a hydroxyl group-containing (meth) acrylate compound and a polyvalent isocyanate compound By using a polyol compound containing three or more hydroxyl groups as a polyol compound, a coating film shrinkability due to a three-dimensional network structure is provided while maintaining a film stretch characteristic unique to a urethane structure when a cured coating film is formed, A rubber elastic coating film having shrinkage performance was obtained. Thus, it has been found that a cured coating film having excellent scratch resistance can be formed, and thus the present invention has been completed.
In the present invention, when a polyol compound containing three or more hydroxyl groups and a polyol compound containing two hydroxyl groups is used as the polyol compound of the constituent material of the urethane (meth) acrylate compound, (Meth) acrylate-based compound can be stably produced since gelation can be suppressed since the formation of a molecular network of the cured coating film can be suppressed, and the remarkable effect of the present invention can be exhibited after the formation of the cured coating film.
That is, the gist of the present invention is to provide a urethane (meth) acrylate compound having a weight average molecular weight of 10,000 to 800,000, which is obtained by reacting a polyol compound (x), a hydroxyl group containing (meth) acrylate compound (y), and a polyvalent isocyanate compound An active energy ray curable resin composition comprising (meth) acrylate compound (A), wherein the polyol compound (x) comprises a polyol compound (x1) containing at least three hydroxyl groups Energy radiation curable resin composition.
The present invention also provides a coating agent containing the active energy ray-curable resin composition, particularly a coating agent for use on the outermost surface.
The active energy ray-curable resin composition of the present invention is effective as a coating agent, especially as a coating agent for the outermost surface, when it is used as a cured coating film and has an excellent effect on stability against scratches, stretchability and transparency.
Hereinafter, the present invention will be described in detail.
Further, 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).
[Urethane (meth) acrylate compound (A)]
The urethane (meth) acrylate compound (A) used in the present invention is a polyol compound (x) containing a polyol compound (x1) containing three or more hydroxyl groups, a hydroxyl group-containing (meth) y), and a polyvalent isocyanate compound (z).
The polyol compound (x) may be any compound as long as it essentially contains a polyol compound (x1) containing at least three hydroxyl groups (hereinafter sometimes referred to as "trifunctional or higher polyol compound (x1)") .
Examples of the trifunctional or higher polyol compound (x1) include various polyol compounds containing three or more hydroxyl groups. Specific examples thereof include polyester-series polyols, polyether-series polyols, polycarbonate series A polyol, a polyolefin-based polyol, a hydrogenated polybutadiene-based polyol, a (meth) acryl-based polyol, and a polysiloxane-based polyol.
Further, from the viewpoint of excellent transparency of the coating film, it is preferable to be a polyfunctional compound having three or more functional groups which do not contain an unsaturated group in the molecule.
Examples of the polyester-based polyol include a polycondensation reaction product of a polyhydric alcohol and a polyvalent carboxylic acid, a ring-opening polymer of a cyclic ester (lactone), a reaction product of three kinds of components of a polyhydric alcohol, a polyvalent carboxylic acid and a cyclic ester; Etc., and each of the raw materials is selected so as to contain three or more hydroxyl groups.
Examples of the polyhydric alcohol include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, -Trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl- (Such as diethylene glycol, diethylene glycol, etc.), diol, methanetriol, glycerin, trimethylol propane, trimethylol ethane, cyclohexanediol (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol and sorbitol) .
Examples of the polycarboxylic 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; , And cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid and trimellitic acid, etc. .
Examples of the cyclic ester (lactone) include, for example,? -Butylolactone,? -Valerolactone,? -Caprolactone and the like.
Examples of the polyether-based polyol include a polyether-based polyol obtained by dehydration condensation of a polyol as a raw material so as to contain three or more hydroxyl groups at the molecular end (molecular side chain).
Such a polyol may contain at least one trifunctional or higher polyol, and examples thereof include a polyol such as methanetriol, glycerin, trimethiolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol , And polyoxyalkylene polyols, which are alkylene oxide adducts of these polyols, and the like.
Examples of the polycarbonate-based polyol include polyhydric alcohols such as polyhydric alcohols having three or more hydroxyl groups in the reaction product of polyhydric alcohols and phosgene; ring-opening polycarboxylates of cyclic carbonic acid esters (such as alkylene carbonates) And the like.
The polyhydric alcohol may contain at least one trifunctional or higher polyol. Examples of the polyhydric alcohol include methanetriol, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol and the like And polyoxyalkylene polyols, which are alkylene oxide adducts of these polyols, and the like.
The polycarbonate polyol may be a compound having a carbonate bond in the molecule and containing three or more hydroxyl groups at the terminals and may have an ester bond together with a carbonate bond.
The polyolefin-based polyol may be a polyolefin-based polyol having at least three hydroxyl groups at the molecular end (side chain) of the hydrocarbon skeleton having at least one branched structure.
The hydrogenated polybutadiene-based polyol has a structure in which all of the ethylenic unsaturated groups contained in the structure of the polybutadiene-based polyol is hydrogenated and has 3 or more total hydroxyl groups in its powder end (side chain).
The (meth) acryl-based polyol may be one containing at least three hydroxyl groups in a polymer of (meth) acrylic acid ester or in a copolymer. Examples of the constituent monomers of such polymers and copolymers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) (Meth) acrylate such as hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate such as butyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, dicyclomethyl acrylate, dodecyl methacrylate, octadecyl methacrylate, Acrylic acid alkyl esters and the like.
As the polysiloxane-based polyol, a polysiloxane having three or more hydroxyl groups at the molecular end (main chain) may be used.
Among them, a polyester-based polyol and a polyether-based polyol are preferable from the viewpoint of excellent mechanical properties such as flexibility and heat resistance at the time of curing.
The hydroxyl value of the trifunctional or higher polyol compound (x1) is preferably 30 to 3, 500 mgKOH / g, particularly preferably 40 to 1,750 mgKOH / g, and more preferably 50 to 1,200 mgKOH / g to be. If such a hydroxyl value is too high, the three-dimensional structure becomes too dense in the synthesis step, so that the viscosity tends to rise sharply and gelation tends to occur during the production of the urethane (meth) acrylate compound. The lower the hardness of the surface of the coating film after the curing of the active energy rays, particularly ultraviolet rays, tends to be lowered.
Such a hydroxyl value is a value measured in accordance with JIS K 1557.
The weight average molecular weight of the trifunctional or higher polyol compound (x1) is preferably 50 to 6,000, particularly preferably 100 to 3,500, and more preferably 100 to 2,500.
If the weight average molecular weight is too large, the active energy ray, particularly the hardness of the coating film surface after curing of ultraviolet rays, tends to decrease. If the weight average molecular weight is too low, the three dimensional mesh structure becomes too dense in the synthesis step , There is a tendency that the viscosity of the urethane (meth) acrylate compound tends to be increased during the production of the urethane (meth) acrylate compound.
The above weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the weight average molecular weight was measured by high performance liquid chromatography (Waters 2695 (main body) and Waters 2414 (detector), manufactured by Nippon Waters Co., Shodex GPCKF-806L (exclusion limit molecular weight: 2 x 10 7 , separation range: 100 to 2 x 10 7 , theoretical number of steps: 10,000 units / piece, filler material: styrene-divinylbenzene copolymer, filler particle diameter: ≪ / RTI >
As the polyol compound (x), a polyol compound (x2) containing two hydroxyl groups and having a hydroxyl value of less than 450 mgKOH / g (hereinafter sometimes referred to as "bifunctional polyol compound (x2)") (Meth) acrylate compound is too dense to prevent gelation during the production of the urethane (meth) acrylate compound, and it is easy to stably produce the urethane (meth) acrylate compound .
The hydroxyl value of the bifunctional polyol compound (x2) is required to be smaller than 450 mgKOH / g, preferably 200 mgKOH / g or less, and particularly preferably 180 mgKOH / g or less. The lower limit of the hydroxyl value is usually 20 mg KOH / g. When such a hydroxyl value is too high, the three-dimensional network structure becomes too dense in the synthesis step, and the viscosity tends to rise rapidly, so that the urethane (meth) acrylate compound tends to gel during the production of the urethane Is too low, the hardness of the surface of the coating film after the curing of the active energy rays, particularly ultraviolet rays, tends to decrease.
Such a hydroxyl value is a value measured in accordance with JIS K 1557.
Examples of the bifunctional polyol compound (x2) include various polyol compounds containing two hydroxyl groups. Specific examples thereof include polyester polyol, polyether polyol, polycarbonate polyol, polyolefin Based polyol, hydrogenated polybutadiene-based polyol, (meth) acryl-based polyol, and polysiloxane-based polyol.
Concretely, it is sufficient to comply with each of the polyol compounds exemplified above in the description of the trifunctional or higher functional polyol compound (x1), and it may be a bifunctional polyol obtained by selecting and combining raw materials so as to have a hydroxyl value of two.
Among them, a bifunctional polyester-based polyol and a bifunctional polyether-based polyol are preferable from the viewpoint of excellent mechanical properties such as flexibility at the time of curing.
The weight average molecular weight of the bifunctional polyol compound (x2) is preferably 250 to 6,000, particularly preferably 300 to 5,000, and more preferably 500 to 4,000. When the weight average molecular weight is too large, , Particularly, the hardness of the coating film surface after curing of ultraviolet rays tends to decrease. If the weight average molecular weight is too low, the three-dimensional network structure becomes too dense in the synthesis step, resulting in an abrupt increase in viscosity, (Meth) acrylate-based compound is likely to gel.
The mixing ratio (weight ratio) of the trifunctional or higher polyol compound (x1) to the bifunctional polyol compound (x2) when the bifunctional polyol compound (x2) is used in the polyol compound (x) (X2) = 2: 98 to 50: 50, and more preferably (x1) :( x2) = 3 (x2) = 1: 99 to 99: : 97 ~ 30: 70.
If the compounding ratio of the trifunctional or higher polyol compound (x1) is too large, the three-dimensional network structure becomes excessively large, and the molecular weight becomes too large to tend to gel during the production. If too small, It tends to be inferior in balance in terms of stretchability and elasticity.
The polyol compound (x3) containing two hydroxyl groups and having a hydroxyl value of 450 mgKOH / g or more (hereinafter also referred to as " bifunctional polyol compound (x3) " In particular, the polyfunctional polyol compound (x1) and the bifunctional polyol compound (x2) of the above-mentioned base are added with a polyol compound containing two hydroxyl groups and having a hydroxyl value of 450 mgKOH / g or more x3) is preferable in that the three-dimensional network structure of the urethane (meth) acrylate compound is further relaxed to improve the stretchability of the coating film.
The hydroxyl value of the bifunctional polyol compound (x3) is required to be 450 mgKOH / g or more, preferably 500 mgKOH / g or more, and particularly preferably 550 mgKOH / g or more. The upper limit of such a hydroxyl value is usually 2,000 mg KOH / g.
Such a hydroxyl value is a value measured in accordance with JIS K 1557.
Examples of the bifunctional polyol compound (x3) include low molecular weight diol compounds having a weight average molecular weight of about 250 or less. Specific examples thereof include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Methylene glycol, dimethylpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, Methyl-1,3-trimethylenediol, 1,5-pentamethylene diol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-di Ethyl-1,5-pentamethylene diol, pentaerythritol diacrylate, 1,9-nonanediol, and 2-methyl-1,8-octanediol; aliphatic alcohols such as 1,4-cyclohexanediol, cyclo Cyclohexanediol such as hexyldimethanol, bisphenols such as bisphenol A, tricyclodecane dimethanol, and sugar alcohols such as xylitol and sorbitol. These may be used alone or in combination of two or more.
Among them, from the viewpoint of the yellowing property of the cured coating film, compounds having a structure which does not contain an aromatic ring or an unsaturated group are preferable, and aliphatic alcohols, more preferably neopentyl glycol, are particularly preferable.
The blending amount of such a bifunctional polyol compound (x3) is preferably 0 to 50% by weight, particularly preferably 0 to 50% by weight, based on the total amount of the polyfunctional polyol compound (x2) Preferably 0.3 to 40% by weight, more preferably 0.5 to 25% by weight.
When the blending amount is too large, the three-dimensional network structure becomes too dense, and a sharp increase in viscosity occurs, which tends to cause gelation in the production of the urethane (meth) acrylate compound.
The polyol compound (x) preferably has an average number of hydroxyl groups of 2.01 to 6 moles, particularly preferably 2.05 to 5 moles, and more preferably 2.1 to 4 moles. When the average number of hydroxyl groups is too small, the three-dimensional network structure tends to be too small, and the balance between elasticity and elasticity tends to be poor. When the average number of hydroxyl groups is too large, the three- dimensional network structure becomes excessive, And tends to become gelled at the time of production.
The average number of water squares is obtained by the following formula [I] or [II].
(I) Average number of hydroxyl groups = [{number of hydroxyl functional groups of trifunctional or higher polyol compound (x1) number of polyols (x1) having three or more functional groups} / { Of the polyol compound (x1) having a trifunctional or higher functional group (x2)} / {the number of moles of the {2 x bifunctional polyol compound (x2)} / {the molecular weight calculated as the hydroxyl value of the bifunctional polyol compound Molecular weight calculated from hydroxyl value + molecular weight calculated from hydroxyl value of bifunctional polyol compound (x2)}]
(II) Average number of hydroxyl groups = [{number of hydroxyl functional groups of trifunctional or higher polyol compound (x1) number of moles of polyol compound (x1) having three or more functions} / {hydroxyl value of trifunctional or higher polyol compound Molecular weight calculated by the hydroxyl value of the bifunctional polyol compound (x2) calculated from the hydroxyl value of the bifunctional polyol compound (x2) + the molecular weight calculated by the hydroxyl value of the bifunctional polyol compound (x3) Calculated as the hydroxyl value of the polyfunctional polyol compound (x1) + the molecular weight calculated by the hydroxyl value of the bifunctional polyol compound (x2) + the hydroxyl value of the bifunctional polyol compound (x3) The molecular weight calculated by the hydroxyl value of the polyol compound (x1) having three or more functions + the molecular weight of the bifunctional polyol compound (x2) Calculated minutes The molecular weight calculated from the hydroxyl value of the self-excited +2-functional polyol compound (x3)}]
Examples of the hydroxyl group-containing (meth) acrylate compound (y) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate such as 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethyl acryloylphosphate, 2- (Meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate-based compound containing one ethylenically unsaturated group such as 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate;
Acrylate such as glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) Containing (meth) acrylate compounds containing two or more ethylenic unsaturated groups such as dipentaerythritol penta (meth) acrylate and ethylene oxide-modified dipentaerythritol penta (meth) acrylate can be used They may be used alone or in combination of two or more.
Of these, hydroxyl group (meth) acrylate compounds containing one ethylenic unsaturated group are preferable, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
As the hydroxyl group-containing (meth) acrylate compound (y), use is made of a hydroxyl group-containing (meth) acrylate compound having an acid value of 1 mgKOH / g or less (preferably 0.75 mgKOH / g or less) (Meth) acrylate-based compound is easy to prepare. Specific examples of the hydroxyl group-containing (meth) acrylate compound having an acid value of less than 1 mgKOH / g include 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth) Butyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
Among caprolactone-modified 2-hydroxyethyl (meth) acrylates, among the hydroxyl group-containing (meth) acrylate compounds, 1 mol of caprolactone-modified 2-hydroxyethyl (meth) Acrylate having an acid value of about 2.0 mg KOH / g and caprolactone 2 mol modified 2-hydroxyethyl (meth) acrylate having an acid value of about 2.5 mg KOH / g, and when the amount of caprolactone modification is increased, , The effect of the present invention tends to be difficult to obtain by using caprolactone-modified 2-hydroxyethyl (meth) acrylate.
Examples of the polyvalent isocyanate compound (z) include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, Aromatic polyisocyanates such as naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lydidine diisocyanate and lidine triisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene di Alicyclic polyisocyanates such as isocyanate, isophorone diisocyanate, norbornene diisocyanate and 1,3-bis (isocyanatomethyl) cyclohexane; and alicyclic polyisocyanates such as polyisocyanates (For example, " Arcanate 100 ", " Arkane 100, " manufactured by Nippon Polyurethane Industry Co., Ltd.), or a mixture of two or more kinds of polyisocyanate Nate 110 "," Arcanate 200 "," Arcanate 210 "), and the like.
Among them, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, phenylene diisocyanate and naphthalene diisocyanate, hexamethylene diisocyanate, trimethyl Aliphatic diisocyanates such as hexamethylene diisocyanate and lydidine diisocyanate, aliphatic diisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis Alicyclic diisocyanate such as naphthylmethylcyclohexane and natomethylcyclohexane are preferably used. From the viewpoint of low yellowing of the cured coating film and small curing shrinkage, alicyclic diisocyanate The carbonate compound, particularly preferred, and the isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate Chemistry, hydrogenated Chemistry xylene diisocyanate is more preferred.
The urethane (meth) acrylate compound (A) can be obtained by reacting the constituent materials containing (x) to (z).
The method for producing the urethane (meth) acrylate compound (A) is generally a method in which the polyol compound (x), the hydroxyl group-containing (meth) acrylate compound (y) and the polyvalent isocyanate compound (Meth) acrylate compound (y) is reacted with the reaction product obtained by previously reacting the polyol compound (x) and the polyvalent isocyanate compound (z) From the viewpoints of stability of the catalyst and reduction of by-products.
In the method of reacting the hydroxyl group-containing (meth) acrylate compound (y) with a product obtained by previously reacting the polyol compound (x) and the polyvalent isocyanate compound (z), the polyol compound (x) The reaction with the polyvalent isocyanate compound (z) can be carried out according to a known reaction method. For example, the molar ratio of the functional group to the hydroxyl group in the isocyanate group: polyol compound (x) in the polyvalent isocyanate compound (z) Generally, a reaction product containing an isocyanate group at the terminal may be obtained by reacting the isocyanate group in the presence of an isocyanate group mol: (hydroxyl value of the polyol hydroxyl group-hydroxyl group of the hydroxyl group-containing acrylate).
When a reaction product of the polyol compound (x) and the polyvalent isocyanate compound (z) is reacted with the hydroxyl group-containing (meth) acrylate compound (y), known reaction means can be used, (Meth) acrylate compound (y) is 2, the reaction product molar ratio of the hydroxyl group-containing (meth) acrylate compound (y) (Meth) acrylate compound (y) is reacted at a ratio of 1: 2 so that the number of isocyanate groups in the reaction product is 3 and the hydroxyl value of the hydroxyl group-containing (meth) acrylate compound (y) is 1 (Meth) acrylate compound (y) with a reaction product of about 1: 3.
The reaction is terminated when the reaction product and the hydroxyl group-containing (meth) acrylate compound (y) undergo addition reaction at a time when the residual isocyanate group content in the reaction system becomes 0.5 wt% or less. Acrylate compound (A) can be obtained.
When the trifunctional or higher polyol compound (x1) and the bifunctional polyol compound (x2) are used in combination, the trifunctional or higher polyol compound (x1) can be mixed and reacted in a batch, It is preferable to divide the urethane (meth) acrylate molecules into multi-steps and mix them in order to disperse the branched structure in the urethane (meth) acrylate molecules so as to avoid localization in the urethane (meth) acrylate molecule. In the case where the polyfunctional compound (x1) having three or more functional groups is divided and compounded, it can be divided and compounded in an arbitrary proportion. For example, in the case of compounding in two steps, It is preferable to divide the first stage: second stage = 10 to 90: 90 to 10 by weight in order to efficiently disperse the structure.
In the reaction between the polyol compound (x) and the polyvalent isocyanate compound (z) and the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), a catalyst is used Examples of such catalysts include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin and the like, zinc octanoate, tin octanoate, cobalt naphthenate, Metal salts such as stannous chloride and stannic chloride, metal salts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [ Amide catalysts such as N, N, N ', N'-tetramethyl-1,3-butane diamine and N-ethylmorpholine, etc., bismuth acetate, bismuth bromide, bismuth iodide and bismuth sulfide , Dibutyl bismuth dilaurate, dioctyl bismuth dilaurate, etc. Organic bismuth compounds, bismuth salts of 2-ethylhexanoic acid, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, And bismuth organic acid bismuth salts such as salts, bismuth acetate salts, bismuth bisneodecanoate, bismuth salicylate salts and bismuth salt of diimmonic acid, and among these, dibutyltin dilaurate, 1,8 -Diazabicyclo [5,4,0] undecene is very suitable.
In the reaction of the polyol compound (x) with the polyvalent isocyanate compound (z) and the reaction product thereof with the hydroxyl group-containing (meth) acrylate compound (y), a functional group reactive with the isocyanate base Organic solvents such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic solvents such as toluene and xylene can be used.
(Meth) acrylate monomer having no functional group reactive with isocyanate group may be used in place of such an organic solvent, and examples of such a (meth) acrylate monomer include bifunctional (meth) acrylate monomers, Functional (meth) acrylate monomers are preferable, and monofunctional (meth) acrylate monomers are particularly preferable in that they inhibit the stretchability of the coating film after curing is small.
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 Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di Acrylate, dimethyldicyclopentane di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di ) Acrylate, isocyanuric acid ethylene oxide modified acrylate.
Examples of such monofunctional (meth) acrylate monomers include styrene-based monomers such as styrene, vinyltoluene, chlorostyrene and? -Methylstyrene; monomers such as methyl (meth) acrylate, ethyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Methyl (meth) acrylate, cyclohexane spiro-2- (1,3-dioxolane-4-yl) , 3-ethyl-3-oxetanylmethyl (meth) acrylate,? -Butyrolactone (meth) (Meth) acrylate, heptyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (N = 2) (meth) acrylate, nonylphenol propylene oxide denaturation (n = 2.5), n-heptyl (meth) acrylate, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, butoxyethyl (meth) acrylate, aryl (Meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, and the like can be given.
In the reaction between the polyol compound (x) and the polyvalent isocyanate compound (z) or the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (y), the reaction temperature is usually from 30 to 100 ° C, Preferably 40 to 90 DEG C, and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
The content (mmol / g) of the ethylenic unsaturated group in the urethane (meth) acrylate compound (A) used in the present invention is preferably 0.01 to 10 mmol / g, particularly preferably 0.05 to 5 mmol / g, more preferably 0.1 to 1 mmol / g, and particularly preferably 0.1 to 0.5 mmol / g. When the content of the ethylenic unsaturated group (m mol / g) of the urethane (meth) acrylate compound (A) is too small, the curing at the time of active energy ray irradiation tends to become insufficient. There is a tendency that it is difficult to obtain the desired stretchability and elasticity of the cured coating film because the components to be crosslinked are increased.
The urethane (meth) acrylate compound (A) is preferably one having 10 or fewer ethylenically unsaturated groups in terms of elasticity and elasticity, which is a structural characteristic, and preferably has 6 or less ethylenically unsaturated groups , And it is more preferable that it has 4 or fewer ethylenically unsaturated groups. In general, the lower limit of the ethylenic unsaturated group is two.
The weight average molecular weight of the urethane (meth) acrylate compound (A) used in the present invention is preferably from 10,000 to 800,000, particularly preferably from 20,000 to 500,000, more preferably from 20,000 to 30,000 Only. When the weight average molecular weight is too small, the stretchability and elasticity of the cured coating film tend to decrease. When the weight average molecular weight is too large, the viscosity tends to become 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% toluene, the viscosity at 20 ° C is preferably from 500 to 1,000,000 mPa · s, Is 500 to 500,000 mPa · s, and more preferably 500 to 200,000 mPa · s.
When the viscosity is outside the above range, the coating property tends to decrease. The viscosity measurement method is based on the B type clay system.
Thus, the urethane (meth) acrylate compound (A) used in the present invention can be produced. By using such a urethane (meth) acrylate compound (A), the active energy ray- Can be obtained.
(B), an ethylenically unsaturated monomer (C) other than the urethane (meth) acrylate compound (A), an acrylic resin, a surface modifier, a leveling agent , A polymerization inhibitor and the like can be added to the composition of the present invention and the blending of oil, antioxidant, flame retardant, antistatic agent, filler, stabilizer, reinforcing agent, delustering agent, softening agent, organic fine particles, It is possible.
Examples of the photopolymerization initiator (B) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4- (2-hydroxyethoxy) phenyl Methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino Acetophenones such as 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanol oligomer such as benzoin, benzoin methyl ether Benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoyl-N, N-dimethyl-N- [2- (1, 2, 3-trimethylbenzophenone, -Oxo-2-propenyloxy) ethyl] benzenemethanium bromamide, (4-benzoylbenzyl) 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 Thioxanthones such as propoxythioxanthone and 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone 9-one mesochloride; 2,4,6- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like Acylphosphone oxides; and the like. These photopolymerization initiators (B) may be used alone, or two or more of them may be used in combination.
These preparations can also be exemplified by triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Mihira ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoyl isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,4-diethylthioxanthone, It is also possible to use a combination of thioxanthone and the like.
Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- -2-methyl-1-phenylpropan-1-one.
The content of the photopolymerization initiator (B) is preferably from 0.1 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight, more preferably from 1 to 10 parts by weight, per 100 parts by weight of the urethane (meth) To 10 parts by weight. If the content of the photopolymerization initiator (B) is too small, the curing becomes defective and the film formation tends to be difficult. If too large, the yellowing of the cured coating film tends to occur.
Examples of the ethylenically unsaturated monomer (C) other than the urethane (meth) acrylate compound (A) include monofunctional monomers, bifunctional monomers, and trifunctional or higher-functional monomers.
Examples of such a monofunctional monomer include styrene-based monomers such as styrene, vinyltoluene, chlorostyrene and? -Methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, 2- Hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (Meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl Pentenyl (meth) acrylate, dicyclopentane (Meth) acrylate, dicyclopentanyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolane- Methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, -butylolactone (meth) acrylate (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl Acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, nonylphenol propylene oxide modified = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate and 2- (meth) acryloyloxy-2-hydroxypropyl phthalate. (Meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, decyl (meth) acrylate, (Meth) acrylate monomers such as alkyl (meth) acrylates, aryl (meth) acrylates, (meth) acryloylpyrroles and polyoxyethylene secondary alkyl ether acrylates, 2-hydroxyethyl acrylamide, Methacrylamide, N-vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, and the like.
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, neopentyl glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylates such as modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol di (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di Glycidyl ester di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, and isocyanuric acid ethylene oxide-modified diacrylate.
Examples of such trifunctional or higher functional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylol propane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide Caprolactone-modified pentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone- Lactone-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide (Meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethoxylated glycerin triacrylate, and the like. .
Also, a Michael addition product of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester can be used in combination. Examples of the Michael addition product of acrylic acid include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimmer, methacrylic acid trimmer, Acrylic acid tetramer, and methacrylic acid tetramer. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester include carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid mono ester, 2 -Acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloxyethylhexahydrophthalic acid monoester, etc. have. Other oligomeric ester acrylates may also be mentioned.
Examples of the surface modifier include a cellulose resin and an alkyd resin. Such a cellulose resin has an effect of improving the surface smoothness of a coating film, and the alkyd resin has an action of imparting film-forming property at the time of coating.
As the leveling agent, any leveling agent known in the art can be used as long as it has a wetting property-imparting action on the base material of the coating and a function of lowering the surface tension. Examples of the leveling agent include silicone-modified resins, fluorine- Can be used.
Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tricinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methyl Hydroquinone, hydroquinone monomethyl ether, mono-t-butyl hydroquinone, pt-butyl catechol and the like.
The active energy ray-curable resin composition of the present invention may also preferably contain an organic solvent for dilution, if necessary, in order to obtain a suitable viscosity at the time of coating. Examples of such an 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, , Aromatic hydrocarbons such as toluene and xylene, glycol ethers such as propylene glycol monomethyl ether, acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate, and diacetone alcohol.
These organic solvents may be used alone, or two or more of them may be used in combination.
When two or more of them are used in combination, it is preferable to select two or more of glycol ethers, ketones, and alcohols in terms of appearance of the coating film.
In the production of the active energy ray-curable resin composition of the present invention, the mixing method of the urethane (meth) acrylate compound (A) and other components is not particularly limited, and various methods Can be mixed.
The active energy ray-curable resin composition of the present invention is effectively used as a curable resin composition for forming a coating film, such as an overcoat agent or an anchor coat agent for various substrates, and can be obtained by coating an active energy ray- When the composition diluted with an organic solvent is coated, it is cured by irradiating with an active energy ray.
Examples of the substrate to which the active energy ray-curable resin composition of the present invention is applied include a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylic resin acrylonitrile butadiene styrene copolymer (ABS), a polystyrene resin, (Aluminum, copper, iron, SUS, zinc, magnesium, these alloys, etc.), such as a plastic substrate such as a molded product (film, sheet, cup and the like) ), A substrate provided with a primer layer on a substrate such as glass, and the like.
Examples of the coating method of the active energy ray-curable resin composition include wet coating methods such as spraying, showering, dipping, roll, spin, screen printing and the like.
It is preferable that the active energy ray-curable resin composition of the present invention is applied by diluting with the above-mentioned organic solvent so that the solid concentration is usually 3 to 60% by weight, preferably 5 to 40% by weight.
The drying conditions under which the organic solvent is diluted are a temperature of usually 40 to 120 ° C, preferably 50 to 100 ° C, a drying time of usually 1 to 20 minutes, preferably 2 to 10 minutes good.
Examples of the active energy ray used for curing the active energy ray-curable resin composition coated on the substrate include radiation such as a deep ultraviolet ray, ultraviolet ray, near-ultraviolet ray and infrared rays, electromagnetic waves such as X-ray and? , And neutron beams can be used. However, curing by ultraviolet irradiation is advantageous because of the curing rate, the availability of the irradiation apparatus, the price, and the like. In addition, when electron beam irradiation is performed, curing can be performed without using a photopolymerization initiator (B).
Pressure mercury lamps, ultra-high pressure mercury lamps, carbon arc lamps, metal halide lamps, xenon lamps, chemical lamps, electrodeless discharge lamps, and LEDs that emit light in the wavelength range of 150 to 450 nm when cured by ultraviolet irradiation. It may be irradiated with ultraviolet rays of 30 to 3000 mJ / cm 2 (preferably 100 to 1500 mJ / cm 2). After irradiation with ultraviolet rays, heating may be carried out as necessary to achieve complete curing.
The coating film thickness (the film thickness after curing) is related to the depth of the scratches assumed as the scratch resistance. Therefore, the film thickness may be arbitrary so that the depth of the scratches does not exceed the film thickness. Usually, In consideration of light transmission so that the initiator (B) can react uniformly, it is 3 to 1000 mu m, preferably 5 to 500 mu m, particularly preferably 10 to 200 mu m.
(X) containing a polyol compound (x1) containing at least three hydroxyl groups of the present invention, a hydroxyl group-containing (meth) acrylate compound (y) and a polyvalent isocyanate compound (z) The active energy ray-curable resin composition comprising the urethane (meth) acrylate compound (A) comprising a urethane (meth) acrylate compound (A) It is possible to obtain a coating film having stretchability and shrinkability because of its shrinking property. Therefore, it is possible to form a cured coating film having high practicality as a restoration property against flaws, and as a coating material, an ink, a coating agent, useful.
(Example)
Hereinafter, the present invention will be described more concretely with reference to examples, but the present invention is not limited to the following examples without departing from the gist thereof. In the examples, " part " and "% "
The following compounds were prepared as the urethane (meth) acrylate compound (A) (see Table 1).
Production Example 1: urethane (meth) acrylate compound (A-1)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 19.8 g (0.10 mol) of hydrogenated xylene diisocyanate (z), neopentyl glycol (x3) 7.30 g (0.011 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g) and 2.80 g (0.027 mole) of a bifunctional polyester polyol (x2) , 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 2 hours to obtain a polyester polyol (0.012 mol) of 2.20 g (0.0040 mol) of a polyester polyol (x1) (hydroxyl value of 264 mgKOH / g) and a bifunctional polyesterpolyol (x2) (hydroxyl value of 63 mgKOH / g) (0.034 mol) of 2-hydroxyethyl acrylate (y) was added, and the reaction was carried out at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, the reaction was carried out To obtain a toluene solution (60% of resin content) of a urethane (meth) acrylate compound (A-1) (weight average molecular weight (Mw): 85,000).
Production Example 2: urethane (meth) acrylate compound (A-2)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 19.0 g (0.098 mol) of hydrogenated xylene diisocyanate (z), neopentyl glycol (x3) 7.00 g (0.011 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g), 1.50 g (0.033 mole) of 1,6-hexanediol, 66.5 g (0.033 mol) of a bifunctional polycarbonate polyol (hydroxyl value: 55 mgKOH / g) as a raw material, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate (0.033 mol) of 2-hydroxyethyl acrylate (y) was added thereto, and the mixture was allowed to react at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, the reaction was terminated To obtain a toluene solution (resin content 60%) of a urethane (meth) acrylate compound (A-2) (weight average molecular weight (Mw): 57,000).
Production Example 3: urethane (meth) acrylate compound (A-3)
(0.095 mole) of hydrogenated xylene diisocyanate (z), neopentyl glycol (x3) (having a hydroxyl value of 1078 mg) was added to a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 10.0 g (0.016 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g), 2.50 g (0.024 mol) of a polyfunctional poly 65.1 g (0.035 mol) of a carbonate polyol (x2) (hydroxyl value of 60 mgKOH / g), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed, (0.033 mol) of 2-hydroxyethyl acrylate (y) was added thereto and reacted at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, the reaction was terminated to obtain urethane (meth) acrylate To obtain a toluene solution (60% of resin content) of the compound (A-3) (weight average molecular weight (Mw): 78,000).
Production Example 4: urethane (meth) acrylate compound (A-4)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 29.6 g (0.15 mol) of hydrogenated xylene diisocyanate (z), neopentyl glycol (x3) (0.028 mole) of a trifunctional polyester polyol (x1) having a hydroxyl value of 264 mgKOH / g, 0.08 mole of 2-methyl-1,3-propanediol and 1, 4, (0.048 mol) of a bifunctional polycarbonate polyol (x2) having a hydroxyl value of 130 mgKOH / g, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate (0.051 mol) of 2-hydroxyethyl acrylate (y) was added thereto, and the mixture was allowed to react at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, reaction was carried out at 60 ° C for 3 hours. And a toluene solution (60% of resin content) of a urethane (meth) acrylate compound (A-4) (weight average molecular weight (Mw) Obtained.
Production Example 5: urethane (meth) acrylate compound (A-5)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 29.5 g (0.15 mol) of hydrogenated xylene diisocyanate (z), neopentyl glycol (x3) 9.70 g (0.015 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g), 1.70 g (0.035 mole) of 1,6-hexanediol, (0.068 mol) of bifunctional polycarbonate polyol (hydroxyl value: 150 mgKOH / g) serving as a raw material, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst (0.052 mol) of 2-hydroxyethyl acrylate (y) was added thereto and reacted at 60 ° C for 3 hours. When the remaining isocyanate group became 0.3%, the reaction was terminated To obtain a toluene solution (60% of resin content) of a urethane (meth) acrylate compound (A-5) (weight average molecular weight (Mw): 119,000).
Production Example 6: urethane (meth) acrylate compound (A-6)
To a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 19.5 g (0.10 mol) of hydrogenated xylene diisocyanate (z), tricyclodecane dimethanol (x3) 7.30 g (0.014 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g), and 2.40 g (0.026 mole) of a bifunctional polyester polyol (hydroxyl value (0.035 mol), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 3 hours to obtain 2-hydroxy- (Meth) acrylate compound (A-6) ((A-6)) was obtained after completion of the reaction at the time when the remaining isocyanate group became 0.3% (Weight-average molecular weight (Mw): 51,000) was obtained in a toluene solution (resin content 60%).
Production Example 7: urethane (meth) acrylate compound (A-7)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 22.2 g (0.10 mol) of isophorone diisocyanate (z), neopentyl glycol (x3) (hydroxyl value of 1078 mg KOH / (0.014 mole) of a trifunctional polyesterpolyol (x1) (hydroxyl value of 264 mgKOH / g) and a bifunctional polyesterpolyol (x2) (hydroxyl value of 63.4 mgKOH / g) (0.035 mole) as a polymerization inhibitor, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 3 hours to obtain 2-hydroxyethyl acrylate (meth) acrylate compound (A-7) (weight average molecular weight (weight average molecular weight (Mw)) of the urethane (meth) acrylate compound Mw); 29,000) (60% resin content).
Production Example 8: urethane (meth) acrylate compound (A-8)
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet were added 66.7 g of toluene, 17.8 g (0.11 mol) of hexamethylene diisocyanate (z), neopentyl glycol (x3) (hydroxyl value of 1078 mg KOH / 9.70 g (0.015 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g) and 2.40 g (0.028 mole) of a trifunctional polyester polyol (hydroxyl value 63 mg KOH / (0.037 mol) as a polymerization inhibitor, 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 3 hours to obtain 2-hydroxyethyl acrylate (meth) acrylate compound (A-8) (weight average molecular weight (weight average molecular weight (Mw)) of the urethane (meth) acrylate compound Mw); 158,000) in toluene (60% resin content).
Production Example 9: urethane (meth) acrylate-based compound (A-9)
100 g of toluene, 23.8 g (0.12 mol) of hydrogenated xylene diisocyanate (z), and neopentyl glycol (x3) (having a hydroxyl value of 1078 mgKOH) were added to a four-necked flask equipped with a thermometer, a stirrer, (0.018 mole) of a trifunctional polyether polyol (x1) (hydroxyl value of 77 mgKOH / g), and a bifunctional polyether polyol (x2) having a hydroxyl value of 168 mgKOH / g / g), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 3 hours to obtain 2-hydroxyethyl acrylate (meth) acrylate compound (A-9) (weight average (weight average)) was added to the reaction system at a time when residual isocyanate group became 0.3% Molecular weight (Mw): 50,000) (50% of resin content).
≪ Production Example 10: Urethane (meth) acrylate compound (A-10) >
To the four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, 66.7 g of tetrahydrofurfuryl acrylate, 19.8 g (0.10 mol) of hydrogenated xylene diisocyanate (z), neopentyl glycol 7.30 g (0.011 mole) of a trifunctional polyester polyol (x1) (hydroxyl value of 264 mg KOH / g), 2.80 g (0.027 mole) of a hydroxyl group value of 1078 mg KOH / g, (0.024 mole) of hydroxyl group value (63 mg KOH / g), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 DEG C for 2 hours to obtain 3 (0.012 mol) of a polyester polyol (x1) having a hydroxyl value of 264 mgKOH / g (0.0040 mole) and a bifunctional polyesterpolyol (x2) having a hydroxyl value of 63 mgKOH / g were added After reacting at 60 占 폚 for 2 hours, 4.00 g (0.034 mole) of 2-hydroxyethyl acrylate (y) was added and reacted at 60 占 폚 for 3 hours to remove residual isocyanate group 0.3%, the reaction was terminated to obtain a tetrahydrofurfuryl acrylate solution of a urethane (meth) acrylate compound (A-10) (weight average molecular weight (Mw): 52,000).
Production Example 11: urethane (meth) acrylate-based compound (A'-1)
(0.058 mole) of isophorone diisocyanate (z) and a bifunctional polyesterpolyol (x2) (hydroxyl value of 54 mg KOH / g) were added to a four-necked flask equipped with a stirrer, a thermometer, a stirrer, ) And 0.02 g of dibutyltin dilaurate as a reaction catalyst were placed and reacted at 60 캜 for 2 hours to obtain 4.40 g (0.038 mol) of 2-hydroxyethyl acrylate (y) (A'-1) having a weight average molecular weight (Mw (weight average molecular weight (Mw)) of 0.04 g of hydroquinone methyl ether and reacting at 60 ° C for 3 hours to complete the reaction when the residual isocyanate group became 0.3% ); 17,000).
Production Example 12: urethane (meth) acrylate compound (A'-2)
26.5 g (0.12 mol) of isophorone diisocyanate (z) and 3 functional polyester polyol (x1) (hydroxyl value: 264 mg KOH / g) were added to a four-necked flask equipped with a thermometer, a stirrer, 47.4 g (0.027 mol) of dibutyltin dilaurate as a reaction catalyst were added and the mixture was stirred at 60 占 폚 for 3 hours at 60 占 폚. After 16.6 g (0.14 mol) of 2-hydroxyethyl acrylate (y) and 0.02 g of hydroquinone methyl ether as a polymerization inhibitor were added, the mixture was allowed to react at 60 DEG C for 3 hours. When the residual isocyanate group became 0.3% The reaction was terminated to obtain a urethane (meth) acrylate compound (A'-2) (weight average molecular weight (Mw): 4,000).
Production Example 13: urethane (meth) acrylate-based compound (A'-3)
(0.17 mol) of hydrogenated xylene diisocyanate (z) and 11.6 g (0.11 mol) of neopentyl glycol (w) were added to a four-necked flask equipped with a thermometer, a stirrer, a water- (0.028 mole) of bifunctional polyester polyol (x2) (hydroxyl value of 63 mgKOH / g), 0.02 g of hydroquinone methyl ether as a polymerization inhibitor and 0.02 g of dibutyltin dilaurate as a reaction catalyst (0.056 mol) of 2-hydroxyethyl acrylate (y) was added, and the mixture was allowed to react at 60 ° C for 3 hours. When the residual isocyanate group became 0.3%, the reaction was terminated , And a urethane (meth) acrylate compound (A'-3) (weight average molecular weight (Mw): 13,000).
The following photopolymerization initiator (B) was prepared.
(B-1): 1-Hydroxy-cyclohexyl-phenyl-ketone ("IGACURE 184" manufactured by BASF Japan K.K.)
[Examples 1 to 9]
100 parts of the urethane (meth) acrylate compounds (A-1 to A-9) obtained in Production Examples 1 to 9, 2.4 parts of the photopolymerization initiator (B-1) and toluene were blended so as to have a solid content concentration of 40% Ray-curable resin composition.
[Example 10]
4 parts of a photopolymerization initiator (B-1) was blended with 100 parts of the urethane (meth) acrylate compound (A-10) obtained in Preparation Example 10 to obtain an active energy ray curable resin composition.
[Comparative Example 1]
(B-1) was obtained in the same manner as in Example 1, except that the urethane (meth) acrylate (A'-1) obtained in Production Example 11 was used instead of the urethane (meth) Was changed to 4 parts in the same manner as in Example 1 to obtain an active energy ray curable resin composition.
[Comparative Example 2]
(B-1) was obtained in the same manner as in Example 1 except that the urethane (meth) acrylate (A'-2) obtained in Production Example 12 was used instead of the urethane (meth) Was changed to 4 parts in the same manner as in Example 1 to obtain an active energy ray curable resin composition.
[Comparative Example 3]
(A'-3) obtained in Production Example 13 was used instead of the urethane (meth) acrylate compound (A-1) in Example 1, In the same manner, an active energy ray curable resin composition was obtained.
The transparency of the active energy ray curable resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3 was evaluated.
<Transparency>
The APHA value of the active energy ray curable resin composition was measured and evaluated by the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation standard)
○: APHA value is less than 30
X: APHA value is 30 or more
Further, the obtained active energy ray-curable resin composition was used to evaluate stability and stretchability.
<Resilience>
The active energy ray-curable resin composition thus obtained was coated on a black polycarbonate substrate (2 × 70 × 150 mm, manufactured by Nihon Test Panel Co., Ltd.) so that the cured coating film had a thickness of 40 μm in the applicator, and dried at 90 ° C. for 6 minutes , A high-pressure mercury lamp 80 W, and the like, three passes of ultraviolet irradiation (cumulative irradiation amount: 1000 mJ / cm 2 /) were carried out from a height of 18 cm to a conveyor speed of 3.4 m / min to obtain a cured coating film. In addition, since the active energy ray-curable resin composition obtained in Example 10 is a composition of a solvent-free composition, the drying step is omitted from the cured coating film forming step to obtain a cured coating film. Using the cured coating film, the coating film was scratched five times with a brass 2-type brush under a condition of 23 ° C and 50% Rh, and was reciprocated 5 times at a load of 500 g. The time when the scratches were visually unobscured was measured And evaluated by the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation standard)
○: The defect is restored within 3 minutes
DELTA: scratches are restored to within 10 minutes in excess of 3 minutes
X: The defect was not restored by confirmation after the defect was observed for more than 10 minutes
<Elasticity>
The active energy ray-curable resin composition obtained above was coated on a glass substrate (2 x 70 x 150 mm, manufactured by Nihon Test Panel Co., Ltd.) so that the cured coating film had a thickness of 40 탆 in an applicator and dried at 90 캜 for 6 minutes. 3 passes of ultraviolet ray irradiation (cumulative irradiation dose: 1000 mJ / cm 2) was carried out from a height of 18 cm from a height of 18 cm using a lamp 80 W and 1 lamp to form a cured coating film, .
In addition, since the active energy ray-curable resin composition obtained in Example 10 is a composition of a non-solvent, the drying step is omitted from the cured coating film forming step to obtain a cured coating film. The coating film obtained by cutting the cured coating film into a width of 10 mm and a length of 30 mm was drawn in the longitudinal direction under the condition of 23 캜 and 50% Rh and fixed for 60 seconds while pulled at a state of 45 mm length (1.5 times length) Then, the fixation was removed, and the time when the growth of the coating film became the same as before growth was measured and evaluated as the following evaluation criteria. The results are shown in Table 1 below.
(Evaluation standard)
○: Return to original size within 1 minute
△: Return to original size within 3 minutes in excess of 1 minute
X: does not return to its original size even after more than 3 minutes
From the above-mentioned evaluation results, it was confirmed that in Examples 1 to 10 (which were obtained by using a urethane (meth) acrylate-based compound having a weight average molecular weight of 10,000 to 800,000 by using a polyol compound containing a polyol compound containing three or more hydroxyl groups Of the cured coating film is excellent in balance in stability and stretchability, and is also excellent in transparency of the resin composition.
Further, all of the cured coating films of Comparative Examples 1 and 3 obtained using only a bifunctional polyol-based compound and a urethane (meth) acrylate-based compound containing no polyfunctional or higher functional polyol compound are inferior in stability, It can be seen that the cured coating film of Example 3 is inferior to the stretchability.
It is also found that the cured coating film of Comparative Example 2 obtained by using a urethane (meth) acrylate compound having a polyolefin compound having three or more functionalities and having a low weight average molecular weight is poor in both stability and stretchability.
While the present invention has been shown and described with reference to specific embodiments thereof, it is to be understood that these embodiments are merely illustrative and not restrictive. Various modifications apparent to those skilled in the art are also within the scope of the present invention.
(Industrial availability)
The active energy ray-curable resin composition of the present invention has a coating film shrinkability due to a three-dimensional network structure while maintaining a coating film stretch characteristic unique to the urethane structure when used as a cured coating film, so that an elastic coating film having elongation / Therefore, it is possible to form a cured coating film having high practicality as a resilience against flaws, and is useful as a coating material, an ink, a coating material, particularly a coating material for the outermost surface.
Claims (9)
(Meth) acrylate compound (y) having hydroxyl group, and
The polyvalent isocyanate compound (z)
(Meth) acrylate compound (A) having a weight average molecular weight of 10,000 to 800,000, which is obtained by reacting a urethane (meth) acrylate compound
A polyol compound (x1) having at least three hydroxyl groups, a polyol compound (x2) containing two hydroxyl groups and having a hydroxyl value of less than 450 mgKOH / g, and a polyol compound (X1) having a hydroxyl value of 450 mgKOH / g or more and containing at least three hydroxyl groups, wherein the polyol compound (x1) is at least one selected from a polyester-based polyol and a polyether- ≪ / RTI >
Wherein the polyol compound (x1) containing at least three hydroxyl groups has a weight average molecular weight of 50 to 6,000.
Wherein the average number of hydroxyl groups of the polyol compound (x) is 2.01 to 6 moles.
Wherein the content of the ethylenic unsaturated group in the urethane (meth) acrylate compound (A) is 0.01 to 10 mmol / g.
Wherein the urethane (meth) acrylate compound (A) has 10 or less ethylenically unsaturated groups.
A coating agent characterized by being used as a coating agent for a top coat.
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| JPJP-P-2011-050386 | 2011-03-08 | ||
| JP2011050386 | 2011-03-08 | ||
| PCT/JP2012/055897 WO2012121312A1 (en) | 2011-03-08 | 2012-03-08 | Active-energy-curable resin composition and coating agent |
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| KR (1) | KR101869579B1 (en) |
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| US8760728B2 (en) * | 2011-09-22 | 2014-06-24 | Fuji Xerox Co., Ltd. | Transparent plate for platen, document scanning apparatus, and image forming apparatus |
| JP6308774B2 (en) * | 2012-12-28 | 2018-04-11 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
| KR101697402B1 (en) * | 2013-09-30 | 2017-01-17 | 주식회사 엘지화학 | Polarizing plate and image display apparatus comprising the same |
| KR101880431B1 (en) * | 2014-09-11 | 2018-07-20 | 세키스이가세이힝코교가부시키가이샤 | High-recoverability resin particles and use thereof |
| US10005872B2 (en) | 2014-10-24 | 2018-06-26 | Dic Corporation | Active energy ray-curable composition, active energy ray-curable printing ink using same, and printed matter |
| KR102291432B1 (en) * | 2015-02-06 | 2021-08-18 | 도소 가부시키가이샤 | Urethane resin composition for coating and textured coating in which said composition is used |
| CN109071754B (en) * | 2016-03-04 | 2021-09-10 | 陶氏环球技术有限责任公司 | Process for preparing urethane acrylates |
| JP6640624B2 (en) * | 2016-03-23 | 2020-02-05 | 第一工業製薬株式会社 | Active energy ray-curable composition |
| JP6848381B2 (en) * | 2016-11-16 | 2021-03-24 | 東ソー株式会社 | Active energy ray-curable resin composition |
| US11332932B2 (en) | 2017-02-24 | 2022-05-17 | Aica Kogyo Co., Ltd. | Decorative board and method for manufacturing same |
| CN108623779B (en) * | 2017-03-15 | 2022-07-15 | 宇部兴产株式会社 | Polyurethane resin, aqueous polyurethane resin dispersion, method for producing same, use thereof, and cured product thereof |
| WO2018181972A1 (en) * | 2017-03-31 | 2018-10-04 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
| JP7073816B2 (en) * | 2018-03-16 | 2022-05-24 | 三菱ケミカル株式会社 | An active energy ray-curable resin composition, a coating agent using the same, and a sheet. |
| KR102562185B1 (en) * | 2018-07-12 | 2023-07-31 | 아라까와 가가꾸 고교 가부시끼가이샤 | Self-repairing coatings, cured products and films |
| JP7228091B2 (en) * | 2018-12-05 | 2023-02-24 | Dic株式会社 | Active energy ray-curable resin composition, printing ink and printed matter |
| JP7388243B2 (en) * | 2020-03-04 | 2023-11-29 | 三菱ケミカル株式会社 | Urethane (meth)acrylate compound, active energy ray-curable resin composition, and method for producing urethane (meth)acrylate compound |
| US11111334B1 (en) * | 2020-03-13 | 2021-09-07 | Biocellection Inc. | Polymerizable compositions comprising nitro substituted polyester diols |
| JP2021195411A (en) * | 2020-06-10 | 2021-12-27 | 日東シンコー株式会社 | Curable composition |
| JP7285381B1 (en) * | 2023-01-04 | 2023-06-01 | 第一工業製薬株式会社 | Curable resin composition, film and article |
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| JP2009221358A (en) * | 2008-03-17 | 2009-10-01 | Jsr Corp | Curable resin composition, film laminate for transfer, and impact absorbing laminate |
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| JP2012197436A (en) | 2012-10-18 |
| TW201245350A (en) | 2012-11-16 |
| CN103380157A (en) | 2013-10-30 |
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| TWI515272B (en) | 2016-01-01 |
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