JP2001151848A - Method for producing active energy ray-curable urethane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an active energy ray-curable urethane composition which scarcely contains residual monomers, has high safety and high hygiene, has excellent storage stability also after the passage of one month or more, and further has sufficient curability and excellent coating film physical properties such as adhesivity and chemical resistance, when used for paints.coatings.printing inks. SOLUTION: This method for producing the active energy ray-curable urethane composition, characterized by having the first process for reacting a (meth)acrylate having one hydroxyl group in the molecule with a divalent isocyanate compound in a hydroxyl group/isocyanate group ratio of <=1/1 in an active energy ray-curable monomer solution and the second process for reacting the residual isocyanate group of the composition obtained in the above process with an acid diol or polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a paint for wooden building materials,
Coating agent for decorative paper for building materials, glossy varnish paint, metal plate such as aluminum, iron, tinplate, galvanized sheet, other metal materials, various plastic films, cardboards, other packaging materials, coated paper, art paper, etc. Also, the present invention relates to an active energy ray-curable urethane composition useful for paints, coatings, inks, etc. for general paper. More specifically, the present invention has a short curing time, excellent adhesion, excellent chemical resistance, high safety and hygiene, low odor, and excellent storage stability. The present invention relates to an active energy ray-curable urethane composition having excellent adhesion to a polyolefin film or an olefin synthetic paper manufactured using high-density polyethylene or polypropylene as a raw material resin.

[0002]

2. Description of the Related Art In recent years, in the fields of paints, coating agents, printing inks, etc., due to environmental pollution problems and energy savings, in the fields of paints, coating agents, printing inks, etc., measures such as electron beams and ultraviolet rays for work environment pollution countermeasures due to discharge of organic solvents or for improving work efficiency. Switching to a so-called active energy ray curing type has been actively performed. This means that the curing time by active energy ray irradiation is shortened, or the resin that can be cured by active energy ray irradiation and a diluent monomer are contained, and the solvent does not volatilize during film formation because the monomer also functions as a solvent. This is because there is an advantage. Examples of the resin having an active energy ray-curing property include polyester acrylate, urethane acrylate, epoxy acrylate and the like having an acrylic double bond at a molecular terminal or a molecular chain, and diluting monomers such as styrene-based and acrylic-based monomers. In the case of a solventless type, a solvent drying step is not necessary, but heating of the paint is necessary to obtain the same coating viscosity as that of the conventional solvent type, The addition of monomers has been undertaken.

[0003] Among them, urethane acrylate resins have a good balance of physical properties, and paints, coating agents and printing ink compositions using the resins are paints for wooden building materials, coating materials for decorative paper for building materials, glossy varnish paints, aluminum varnish paints and the like. Paints, coatings, inks, etc. for metal plates such as iron, tinplate, galvanized sheet, and other metal materials, or for various plastic films, cardboards, and other packaging materials, or for coated paper, art paper, and other general paper Widely used for applications. A urethane acrylate resin system is generally obtained by reacting a polyvalent isocyanate, a polyol and an acid diol, a hydroxyl group-containing (meth) acrylate, etc., and adjusts the combination, reaction sequence or reaction ratio of these components. As a result, various characteristics are maintained.

For example, JP-A-1-170609 discloses a process for producing a terminal isocyanurethane oligomer, a process for producing a carboxyl group-containing terminal isocyanate urethane oligomer for the purpose of transparency, adhesion and dispersibility of a cured film. A production method comprising three steps of obtaining a carboxyl group-containing urethane (meth) acrylate,
Further, JP-A-2-8211 discloses a process for producing a terminal isocyanate diol adduct compound, a process for producing a carboxyl group-containing terminal hydroxyl urethane oligomer, a process for producing a carboxyl group-containing terminal isocyanate urethane oligomer, a process for producing a carboxyl group-containing urethane (meta) A) a production method comprising four steps of obtaining an acrylate,
Furthermore, Japanese Patent Application Laid-Open No. Hei 10-204147 discloses a terminal isocyanate diol for the purpose of adhesion to a substrate, swelling and peeling property with an aqueous alkali solution, and storage stability while maintaining film strength such as elongation and tensile strength. There is disclosed a process comprising three steps of obtaining an adduct compound, obtaining a carboxyl group-containing isocyanate urethane oligomer, and obtaining a carboxyl group-containing urethane (meth) acrylate.

However, each of the disclosed methods described above is a production method comprising three or more steps, and the actual production is inevitably complicated, or all of them mainly involve a reaction in an organic solvent. Therefore, when used as a non-solvent type, an additional step of desolvation is required. Further, since all of these are mainly composed of divalent diols, they do not have a sufficient amount of active energy ray-curable components, and therefore, active energy rays Low curability. Alternatively, when producing an actual paint, coating agent, or printing ink composition, it is usual to use a diluting monomer in combination, and when producing these compositions, there is also a problem that a diluting monomer is added again. Has both. Also, in the above disclosed method,
Among the hydroxyl group-containing (meth) acrylates, P. oleracea exhibiting skin irritation. I. There is an example in which 2-hydroxyethyl acrylate having an I value of 8 is excessively used. However, if such a highly irritating acrylate remains in a high concentration, there is a risk of increasing the skin irritation of the resulting composition. Yes, safety and hygiene are poor.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an active energy ray-curable urethane composition having a low level of residual monomers, a high level of safety and high hygiene by a simple and short-time production method. . Furthermore, the obtained active energy ray-curable urethane composition can be used for paints, coatings and printing inks, and these paints, coatings and printing ink compositions are sufficiently cured by active energy rays, and Maintains excellent coating properties such as adhesion, chemical resistance, and solvent resistance, and has no change in appearance, does not produce precipitates, and has excellent storage stability over one month or more. And to obtain an active energy ray-curable composition having excellent adhesion to olefin and synthetic paper, and having high safety and hygiene.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, in an active energy ray-curable monomer solution, a hydroxyl group of (meth) acrylate having one hydroxyl group in a molecule is 2 By reacting an acid diol and a polyol with an isocyanate residue of the composition obtained by reacting the ratio of isocyanate groups of the monovalent isocyanate at a molar ratio of 1 or more, the reaction is simple, in a short time, and in particular, the amount of the residual monomer is small and the safety is low. Production process that can obtain an active energy ray-curable urethane composition having high hygiene and hygiene properties.

That is, according to the constitution of the present invention, in the active energy ray-curable monomer solution, the ratio of the hydroxyl group of the (meth) acrylate having one hydroxyl group in the molecule to the isocyanate group is 2 or more in a molar ratio of 1 or more. Active energy beam curability characterized by having a first step of reacting a divalent isocyanate and a second step of reacting an acid diol and a polyol with an isocyanate residue of the composition obtained in the step. This is a method for producing a urethane composition.

Further, the active energy ray-curable urethane composition obtained above has a carboxyl group having an acid value of 5 to 150 KOH mg / g, or the active energy ray-curable urethane composition obtained above The polyol constituting the radiation-curable urethane composition is an active energy ray-curable urethane composition comprising an alkyl chain having 4 or more carbon atoms, or an acid diol constituting the active energy ray-curable urethane composition obtained above. , 2,2-
This is a method for producing an active energy ray-curable urethane composition comprising bis (hydroxymethyl) butanoic acid.

When the thus obtained active energy ray-curable urethane composition is used for paints, coatings and printing inks, these paints, coatings and printing ink compositions are sufficiently cured by active energy rays, In addition, it retains excellent coating properties such as adhesion, chemical resistance, and solvent resistance, and does not change its appearance, does not produce precipitates, and has excellent storage stability over time of one month or more. It is an active energy ray-curable composition having excellent adhesion to films and olefin synthetic paper, and having high safety and hygiene.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the first step, the active energy ray-curable monomer solution has one hydroxyl group in the molecule (meth)
By reacting the ratio of the isocyanate group of the divalent isocyanate to the hydroxyl group of the acrylate at a molar ratio of 1 or more, the composition of the composition having the (meth) acrylate and the isocyanate group and the divalent isocyanate not included in the reaction To get things.

The second step is to obtain the desired active energy ray-curable urethane composition by reacting these isocyanate residues with an acid diol and a polyol. In the above-mentioned process, for example, among (meth) acrylates having one hydroxyl group in the molecule, P.I. I. When an acrylate such as 2-hydroxyethyl acrylate having an I value of 8 is used, a small amount of the acrylate is reacted with an excess of isocyanate in the first step. The urethane composition has high safety and hygiene.

Further, in the second step, when the reaction ratio between the isocyanate residue and the acid diol or polyol is less than 1, the reaction rate is up to 100%, or when the reaction is performed at a molar ratio of 1 to 1 or more, The reaction is performed to 95% or more, preferably 98% or more. The reaction rate in this case refers to a value calculated from the calculated NCO% value from the charged equivalent and the actually measured NCO% value after the reaction. The active energy ray-curable urethane composition obtained as described above is excellent in storage stability without a change with time such as formation of a precipitate and thickening.

Further, during the above steps, for example, of the (meth) acrylate having one hydroxyl group in the molecule, the (meth) acrylate
If the acrylate is polyfunctional, or if the polyol has more than two hydroxyl groups, the (meth) acrylate content can be high. Thereby, an active energy ray-curable urethane composition having particularly high active energy ray-curability can be easily obtained.

In the present invention, the active energy ray-curable monomer as the reaction solution used in the step for obtaining the active energy ray-curable urethane composition includes an ethylenically unsaturated bond curable by an active energy ray. A monomer having an ethylenically unsaturated bond curable by an active energy ray other than (meth) acrylate having one hydroxyl group in the molecule, or an amino group, acetoacetyl A monomer having an ethylenically unsaturated bond curable by an active energy ray other than a (meth) acrylate having an active hydrogen such as a group or a thiol, and further dissolving a desired active energy ray-curable urethane composition. And an ethylenically unsaturated bond curable with an active energy ray capable of lowering the viscosity. It is not particularly limited as long as it is a monomer.

For example, known active energy ray-curable compounds include monomers having a (meth) acryloyl group. That is, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, morpholine Monofunctional (meth) acrylates such as acrylates, styrene, vinyltoluene, etc., 1,6-hexane glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol (Meth) acrylate, EO-modified neopentyl glycol di (meth) acrylate, PO-modified neopentyl glycol di (meth) acrylate, neopentyl glycol dihydroxypivalate (meth) acrylate
Bifunctional (meth) acrylates such as EO-modified bisphenol A di (meth) acrylate, 2-ethyl, 2-butyl-propanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, or Trimethylolpropane tri (meth) acryle
EO-modified trimethylolpropanetri (meth) acrylate, PO-modified trimethylolpropanetri (meth) acrylate, ECH-modified trimethylolpropanetri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris ( Trifunctional (meth) acrylates such as methacrylate-ethyl) isocyanurate or ditrimethylolpropanetetra (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol pentaacrylate, dipentaerythritol hexa (meth) acrylate, EO-modified dipentaerythritol hexa (meth) acrylate ) Polyfunctional (meth) acrylates such as acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Further, polyester acrylate, polyether acrylate, polyester type or polyether
Ter type urethane acrylate, unsaturated polyester,
Silicon acrylate and the like can be mentioned. These can be used alone or in combination of two or more.

Of these, more preferred are those which can dissolve the intended active energy ray-curable urethane composition and lower the viscosity, those which have a PII value showing skin irritation of 3 or less, and those which are compounds. High purity of the thing, that the component which can react with the isocyanate group is not mixed,
Further, the CPR value is low.

The (meth) acrylate having one hydroxyl group in the molecule used in the first step for obtaining the active energy ray-curable urethane composition includes, for example,
Monohydroxymono such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 4-hydroxybutyl (meth) acrylate, and caprolactone-modified 2-hydroxyethyl (meth) acrylate (Meth) acrylates or glycerin di (meth) acrylate, light ester G-201P
(Manufactured by Kyoeisha Chemical Co., Ltd.) such as monohydroxyacryl methacrylate, monohydroxytriacrylate such as pentaerythritol triacrylate, monohydroxypentaacrylate such as dipentaerythritol pentaacrylate, and ethylene oxide,
Examples thereof include compounds obtained by addition polymerization of propylene oxide, tetrahydrofuran or ε-caprolactone. These can be used alone or in combination of two or more.

The divalent isocyanate used in the first step for obtaining the active energy ray-curable urethane composition includes, for example, ethylene diisocyanate,
6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4
Aliphatic isocyanates such as trimethylhexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,
Alicyclics such as 4-diisocyanate, 1,3 bis (isocyanatomethyl) cyclohexane, norbornene diisocyanatomethyl, isopropylidenecyclohexyl-4,4'-diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, etc. Diisocyanates. Further, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, aromatic diisocyanates such as toluene diisocyanate, or a composition derived from the reaction of these divalent isocyanate compounds with polyols, A composition having two isocyanate residues in the molecule, or a carbodiimidated 4,4-diphenylmethane diisocyanate and 4,4-diphenylmethane diisocyanate
Examples thereof include a mixture of diphenylmethane diisocyanate (Cosmonate LL, manufactured by Mitsui Chemicals, Inc.) and a terminal aliphatic isocyanate compound having a polycarbodiimide group (Carbodilite V-05, manufactured by Nisshinbo Industries, Ltd.). These can be used alone or in combination of two or more.

Examples of the acid diol used in the second step for obtaining the active energy ray-curable urethane composition include, as an acid group, a phosphate ester group, a sulfonic acid group, a carboxyl group, or any of them. Examples thereof include diols having any one of a sum base and the like. As a specific example, trimethylolpropane monophosphate, trimethylolpropane monosulfate, at least a part of the dibasic acid component is sodium sulfosuccinic acid,
Polyester diol which is sodium sulfoisophthalic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, , 2-bis (hydroxymethyl) butyric acid, 2,2-
Bis-hydroxyalkylalkanoic acid such as bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, or 2,2-bis (hydroxymethyl) propionic acid and ε-caprolactone Carboxyl group-containing polycaprolactone diol, bis (hydroxymethyl) acetic acid, bis (4-
(Hydroxyphenyl) acetic acid, 2,2-bis (hydroxyphenyl) pentanoic acid, 2,2-bis (hydroxymethyl) butanoic acid, tartaric acid and the like. These can be used alone or in combination of two or more.

Of the above-mentioned phosphate groups, sulfonic groups, and carboxyl groups, the introduction of a carboxyl group in particular is easy to balance in various points and easy to operate. In this case, the required amount of the active energy ray-curable urethane composition is from 2 to 150K.
The range of OH mg / g is preferable, and the range of 3 to 50 is more preferable.

Further, among the above-mentioned acid diols,
2-bis (hydroxyalkyl) alkanoic acid is preferred. Particularly, by using 2,2-bis (hydroxymethyl) butanoic acid, the above-mentioned active energy ray-curable monomer used as a reaction solution or active energy ray-curable It is characterized by being relatively easy to dissolve in various raw materials used for obtaining a water-soluble urethane composition, so that it is easy to obtain a desired active energy ray-curable urethane composition.

The polyol used in the second step for obtaining the active energy ray-curable urethane composition is a compound or composition having two or more hydroxyl groups in a molecule other than the above-mentioned acid diol. Examples thereof include polyhydric alcohols, saturated polyester polyols, unsaturated polyester polyols, polyether polyols, caprolactone ring-opening polymers, and hydroxyl-containing fatty acid esters. These can be used alone or in combination of two or more.

Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, cyclosandiol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol and 1,6-hexanediol. , 3-methyl-
1,5-pentanediol, 2-ethyl-1,3 hexanediol, 2-butyl-2ethyl-1,3-propanediol, 2-methyl-1,8 octanediol, 1,
9-nonanediol, cyclohexane-1,4 dimethanol, bisphenol A, hydrogenated bisphenol A,
Trimethylolpropane, glycerin, pentaerythritol and the like can be mentioned. Furthermore, an epoxy resin or the like can be cited as an alcohol component or a component having an equivalent effect thereof.

As the above-mentioned epoxy resin, for example,
Bisphenol A epoxy resin synthesized from bisphenol A, bisphenol F, etc. and epichlorohydrin, or novolak epoxy resin synthesized from phenol novolak, cresol novolak, etc. and epichlorohydrin, or phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid Glycidyl ester-based epoxy resins synthesized from dibasic acids and epichlorohydrin, glycidyl ether epoxy resins synthesized from polyols and epichlorohydrin, and alicyclic epoxy resins.

As the saturated polyester polyols,
For example, the above-mentioned polyhydric alcohols and the same active components thereof, the above-mentioned epoxy resins, or ethyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, decyl glycidyl ether , Monoalkyl glycidyl ethers such as stearyl glycidyl ether, alkyl glycidyl esters (product name: Kadura E10: manufactured by Shell Japan), spiro glycols, etc., and rosin, hydrogenated rosin, coconut oil, methyl stearate, etc. Basic acids, or aliphatic dibasic acids such as succinic acid, sebacic acid, adipic acid, phthalic acid, isophthalic acid, azelaic acid, dimer acid, or phthalic anhydride, isophthalic acid, terephthalic anhydride, and trianhydride Aromatic polybasic acids such as lit acid or anhydride hydrophthalic acid, dimethyl-1,4-cyclohexanedicarboxylic acid or the like alicyclic polybasic resulting from the condensation reaction with an acid such as composition and the like of.

Examples of the unsaturated polyester polyols include a composition obtained by substituting a part of the polybasic acid with a polybasic acid having an unsaturated bond such as maleic acid in the above-mentioned saturated polyester polyol. Can be mentioned.

Examples of the polyether polyols include alkylene oxide adducts such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, PO-modified glycerin, EO-modified bisphenol A, and 1,4-butanediol. .

Examples of polycaprolactone polyols as ring-opening polymers of ε-caprolactone include commercially available products such as Polylite OD-X-2155 and OD-X-21.
25 "Dainippon Ink Chemical Industry Co., Ltd.", Plaxel L
-205AL (manufactured by Daicel Chemical Industries, Ltd.).

Examples of the hydroxyl group-containing fatty acid esters include a reaction product of a fat or oil fatty acid or a synthetic fatty acid with a polyhydric alcohol, or a reaction product obtained by an alcoholysis reaction between a fat or oil and a polyhydric alcohol. Fatty acids include soybean oil, peanut oil, safflower oil, olive oil,
Castor oil and the like can be mentioned.

In addition, polybutadiene polyol, etc.
Polyols such as polyolefin polyols such as polycarbonate polyols can be mentioned.

Among the above-mentioned polyhydric alcohols, examples of the polyhydric alcohol having an alkyl chain having 4 or more carbon atoms include a polyol having an alkyl chain having 4 or more carbon atoms and a polyester polyol synthesized from an alkyl chain having 4 or more carbon atoms. Or polyether polyols can be mentioned.

Alternatively, the general formula (CmH2m) (OH) n
And (CH2) p (COOH) q, and polyester polyols containing an alkyl chain component having 4 or more carbon atoms. In the formula, m is the number of carbon atoms in the polyol molecular chain, n is the number of hydroxyl groups, p is the number of carbon atoms in the polybasic acid molecular chain, q is the number of carboxyl groups, and m and p are 2 to 2.
22, n and q are 2 to 4, and the sum of the average carbon number per equivalent of the polyol and the polybasic acid is (m / n + p / q
≧ 4, preferably m / n + p / q ≧ 8) Number average molecular weight 300 to 30 obtained by reaction at a ratio represented by
00 polyester polyol and the like.

In the case of a polyol or a polybasic acid component other than those described above, the cyclo ring-containing compound counts one cyclo ring as C = 3, and the benzene ring-containing compound converts the benzene ring to C
= 2, compounds having 4 or more carbon atoms as the alkyl chain component can also be used as the polyester component in the range of the above formula.

The above polyols can be used alone or as a mixture of two or more.

In the production process of the present invention, it is desirable to use a polymerization inhibitor such as hydroquinone, tertiary butyl hydroquine and methoquinone. If necessary, a reaction catalyst such as dibutyltin dilaurate, stannasoctoate, triethylamine or the like which promotes the reaction between the hydroxyl group and the isocyanate group can be used.

The active energy ray-curable urethane composition obtained as described above can be used for paints, coating agents, and printing ink compositions. Examples of the compound to be blended at this time include a polymerization initiator for active energy ray curing. These can be used alone or in combination of two or more. Representative examples include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy). ) -Phenyl (2-hydroxy-2-propyl) ketone, 1-
Acetophenones such as hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether;
Benzoin series such as benzoin isopropyl ether and benzyl methyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, etc. Benzophenone, thioxanthone, 2
Active energy ray initiators such as thioxanthones such as -methylthioxanthone, 2,4 dimethylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; Michler's ketone; 4,4'-diethylaminobenzophenone; Sensitizers such as methyl 4-dimethylaminobenzoate can be mentioned.

Others include pigments, dyes, surfactants, matting agents, thickeners, heat stabilizers, leveling agents, defoamers, filling agents, anti-settling agents, antioxidants, antibacterial agents, plastics Agent,
The above-described active energy ray-curable monomer and the like, a crosslinking agent thereof, a wax, a thermal decomposition radical initiator, a known polyester resin, a polyamide resin, shellac or modified shellac, a rosin derivative, a polyurethane resin, an acrylic copolymer, and the like. Can be done. These can be used alone or in combination of two or more.

As the above-mentioned coloring agents, pigments and dyes each alone or as a mixture, for example, organic pigments such as soluble or insoluble azo, phthalocyanine and naphthol, titanium oxide, red iron oxide, carbon black, calcium carbonate And inorganic pigments such as barium sulfate, and organic dyes of metal complex salts. These can be used alone or in combination of two or more.

The paint, coating agent and printing ink composition may be prepared by any method, and for example, may be prepared according to the following formula. That is, as a coloring agent, usually, the active energy ray-curable urethane composition of the present invention is dispersed, if necessary, in one or two or more other active energy ray-curable compositions or various resin compositions. Along with an auxiliary agent or an antifoaming agent, the meat is dispersed by a conventional meat mill such as a ball mill, a sand mill or another media mill, and is used as a colorant base. The colorant base is mixed with other resin components including the remaining active energy ray-curable urethane composition and, if necessary, an antifoaming agent and other additives, and is used as a target paint, coating agent, active energy for printing ink. It is finally prepared as a line-curable composition.

The active energy ray-curable urethane composition of the present invention can be cured by a known method.
First, the base material is painted by any method. Then, when curing with an electron beam, a polymerization initiator is not particularly required, and the acceleration voltage is 50 to 2000 KeV, preferably 50 to 2000 KeV.
Using a 300 KeV electron beam irradiation device, the total irradiation amount is 5 to 20 in a gas atmosphere containing a small amount of oxygen or in an inert gas atmosphere.
Irradiation at 0 kGy, preferably 10 to 100 kGy, can give a cured coating film.

As other curing means, for example, a method of curing in air or an inert gas atmosphere by ultraviolet rays obtained from a mercury lamp, a xenon lamp, or the like, or a method of heating and curing such as infrared rays, high frequency waves, and microwaves. Yes,
In these cases, a photopolymerization initiator or a thermal polymerization initiator is added. The addition amount is, for example, about 0.2 to 20%, preferably 0.5 to 10%, based on the solid content of the active energy ray-curable composition.

[0044]

Next, the present invention will be described with reference to examples and comparative examples. In the following, all parts and percentages represent weight ratios. In the following text, viscosity indicates mPa · S.

Example 1 OTA-4 was added to a reactor equipped with a stirrer equipped with a reflux condenser, a dry air inlet, and a thermometer.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 97.5 parts,
After adding 44.8 parts of HEA (manufactured by Osaka Organic Co., Ltd .: 2-hydroxyethyl acrylate), the temperature was raised to 60 ° C. in 0.5 hour while stirring, and after reacting at 60 to 65 ° C. for 5 hours, castor oil LM was added. 134.8 parts of R (manufactured by Toyokuni Oil Co., Ltd .: low moisture castor oil ester) and 22.9 parts of 2,2-bis (hydroxymethyl) butanoic acid are added, and the temperature is raised to 70 ° C. in 0.5 hours. Then, on the way, dibutyltin dilaurate 0.06
The mixture was reacted at 70 to 75 ° C. for 12 hours while adding 0 parts to obtain a transparent liquid active energy ray-curable urethane composition (J-1) having a solid content acid value of 28.9.

Example 2 OTA-4 was placed in a reactor equipped with a stirrer equipped with a reflux condenser, a dry air inlet, and a thermometer.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 66.4 parts,
HEA (manufactured by Osaka Organic Co., Ltd .: 2-hydroxyethyl acrylate). After adding 35.4 parts and stirring, the temperature was raised to 60 ° C. in 0.5 hours, and after reacting at 60 to 65 ° C. for 4 hours,
Polyol component (equivalent to epoxy resin Mn500 / epoxy resin Mn1000 / coconut oil = 1/1/4) 189.1 parts, 2,2-bis (hydroxymethyl)
Butanoic acid: 9.0 parts was added, and the temperature was raised to 70 ° C. in 0.5 hours. While adding 0.060 parts of dibutyltin dilaurate, the mixture was reacted at 70 to 75 ° C. for 15 hours to obtain a solid acid. A transparent liquid active energy ray-curable urethane composition (J-2) having a value of 11.4 was obtained.

Example 3 OTA-4 was added to a reactor equipped with a stirrer equipped with a reflux condenser, a dry air inlet, and a thermometer.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 74.5 parts,
HEA (manufactured by Osaka Organic Co., Ltd .: 2-hydroxyethyl acrylate). 39.8 parts were added, and the temperature was raised to 60 ° C. in 0.5 hour with stirring, and reacted at 60 to 65 ° C. for 4 hours,
OD-X-2155 (Dainippon Ink & Chemicals, Incorporated: Polycaprolactone polyol Mn1000 or equivalent) 17
5.6 parts and 2,2-bis (hydroxymethyl) butanoic acid: 10.1 parts were added, and the temperature was raised to 70 ° C. in 0.5 hours. While adding 0.060 parts of dibutyltin dilaurate, The mixture was reacted at 70 to 75 ° C. for 12 hours to obtain a transparent liquid active energy ray-curable urethane composition (J-3) having a solid content acid value of 12.8.

Comparative Example 1 A reactor equipped with a stirrer equipped with a reflux condenser, a dry air inlet, and a thermometer was charged with OTA-4.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 97.5 parts,
134.8 parts of castor oil LM-R (manufactured by Toyokuni Oil Co., Ltd .: low moisture castor oil ester) and 22.9 parts of 2,2-bis (hydroxymethyl) butanoic acid: 70
When the temperature was raised to 0.5 ° C. in 0.5 hour and the reaction was carried out at 70 to 75 ° C., it gelled on the way.

Comparative Example 2 OTA-4 was added to a reactor equipped with a stirrer equipped with a reflux cooling pipe, a dry air introduction pipe, and a thermometer.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 84.7 parts,
After adding 53.8 parts of HEA (manufactured by Osaka Organic Co., Ltd .: 2-hydroxyethyl acrylate), the temperature was raised to 60 ° C. in 0.5 hour with stirring, and after reacting at 60 to 65 ° C. for 5 hours, castor oil LM was added. -R: Add 161.5 parts and add 0.1 to 70 ° C.
The temperature was raised in 5 hours, and dibutyltin dilaurate was added in the middle.
The reaction was carried out at 70 to 75 ° C. for 12 hours while adding 060 parts to obtain a transparent liquid active energy ray-curable urethane composition (H-2) having no solid acid value.

Comparative Example 3 OTA-4 was added to a reactor equipped with a stirrer equipped with a reflux condenser, a dry air inlet, and a thermometer.
80 (manufactured by Daicel UCB, Inc .: PO-modified glycerin triacrylate) 300.0 parts, Cosmonate T-10
0 (manufactured by Mitsui Chemicals, Inc .: 2,4-TDI) 74.5 parts,
OD-X-2155: 175.6 parts, 2,2-bis (hydroxymethyl) butanoic acid: 10.1 parts were charged, and the temperature was raised to 70 ° C with stirring for 0.5 hour, and 70 to 75 ° C.
For 12 hours, and HEA (manufactured by Osaka Organic Co., Ltd .: 2-hydroxyethyl acrylate). While adding 39.8 parts, and while adding 0.060 part of dibutyltin dilaurate, the mixture was reacted at 70 to 75 ° C. for 12 hours to cure the active energy ray of a transparent liquid having a solid acid value of 12.8. A water-soluble urethane composition (H-3) was obtained.

(Storage stability test)
3 (J-1, J-2, J-3) and Comparative Examples 2, 3 (H-
2. The active energy ray-curable urethane composition obtained by the method of H-3) was placed in a 250 ml mayonnaise bottle, and then shielded from light with an aluminum foil or the like, and placed in a 60 ° C warm air dryer for one month. Left for a while. Thereafter, the state was visually observed. ：: No gel or precipitate was observed. ×: Generation of a gel or a precipitate is observed.

(Safety and Health Test)
3 (J-1, J-2, J-3) and Comparative Examples 2, 3 (H-
The active energy ray-curable urethane composition obtained by the method of 2, H-3) was measured by gas chromatography to quantify the remaining 2-hydroxyethyl acrylate. The result was defined as the residual 2-HEA concentration.

(Curability Test) Examples 1 to 3
(J-1, J-2, J-3) and Comparative Examples 2, 3 (H-
2. A composition obtained by adjusting the active energy ray-curable urethane composition obtained by the method of H-3) according to the following formulation so that the coating thickness on art paper becomes 2-3 μm. Apply with a bar coater and use a 80 W metal halide lamp at a line speed of 20 m / min.
After the irradiation, the presence or absence of tack was examined by touching the finger. ：: No surface tack. Δ: Some surface tack remains. ×: There is surface tack.

Formulation: active energy ray-curable urethane composition 100.0 parts OTA-480 (diluted monomer) 50.0 parts Initiator 7.5 parts Sensitizer 4.5 parts

(Adhesion Test) Examples 1 to 3
(J-1, J-2, J-3) and Comparative Examples 2, 3 (H-
2, H-3), the composition obtained by adjusting the active energy ray-curable urethane composition according to the above-mentioned composition was mixed with an olefin synthetic paper (Yupo, manufactured by Oji Yuka Synthetic Paper Co., Ltd .: FGS 130 μm). ) Has a coating thickness of 2-3μ
m was applied by a bar coater and irradiated once with an 80 W metal halide lamp at a line speed of 20 m / min. A sample was cross-hatched with a cutter, and a 24-mm cellophane tape (Nichiban ( Was evaluated. ：: The coating film was not peeled at all or degraded. ×: The coating film is peeled.

(Solvent Resistance Test) Examples 1 to 3
(J-1, J-2, J-3) and Comparative Examples 2, 3 (H-
2. A bar coater for the composition obtained by adjusting the active energy ray-curable urethane composition obtained by the method of H-3) according to the above-mentioned composition so that the coating film thickness on art paper is 2-3 μm. The coating was irradiated once with a 80 W metal halide lamp at a line speed of 20 m / min, and the surface of the coating was rubbed with MEK and washing oil until the base was exposed to about 10% of the area. ：: MEK 30 times or more, washing oil 100 times or more. Δ: MEK 10 to 30 times, washing oil 50 to 100 times. ×: MEK is 10 times or less, and washing oil is 50 times or less.

[0057]

[Table 1]

[0058]

As is clear from the above results, according to the present invention, an active energy ray-curable urethane composition can be obtained by a simple and short-time production method, and the obtained active energy ray-curable urethane composition can be obtained. It is clear that the product has high active energy ray curability and low residual monomer, and thus has high safety and hygiene. Furthermore,
The obtained active energy ray-curable urethane composition can be used for paints, coatings and printing inks, and these paints, coatings and printing ink compositions are sufficiently cured by active energy rays and have good adhesion. It retains excellent film properties such as chemical resistance, solvent resistance, etc., and does not change appearance, does not form precipitates, and has excellent storage stability over time of one month or more, especially in polyolefin films and olefins. It is intended to provide an active energy ray-curable composition having excellent adhesion to synthetic paper, high safety and high hygiene.

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Claims (4)

[Claims] In an active energy ray-curable monomer solution, a hydroxyl group of (meth) acrylate having one hydroxyl group in a molecule is reacted with a divalent isocyanate at a molar ratio of at least one isocyanate group. The first step,
And a second step of reacting an acid diol and a polyol with an isocyanate residue of the composition obtained in the above step. A method for producing an active energy ray-curable urethane composition. 2. The active energy ray-curable urethane composition according to claim 1, wherein the active energy ray-curable urethane composition has a carboxyl group corresponding to an acid value of 2 to 150 KOH mg / g. A method for producing a curable urethane composition. 3. The production of an active energy ray-curable urethane composition according to claim 1, wherein the polyol constituting the active energy ray-curable urethane composition is a polyol having an alkyl chain having 4 or more carbon atoms. Method. 4. The active energy ray-curable composition according to claim 1, wherein the acid diol constituting the active energy ray-curable urethane composition is 2,2-bis (hydroxymethyl) butanoic acid. A method for producing a urethane composition.