JP2003226730A - Urethane urea resin and radiation-curable resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a radiation-curable resin composition which exhibits excellent preservation stability not only when a solvent is used but also when water is used as a medium and gives a cured coating film excellent in the balance between solvent resistance and adhesion on a permeable substrate as well as no a smooth and non-permeable substrate, and a urethane urea resin having a specific skeleton used for the radiation-curable resin composition. <P>SOLUTION: The urethane urea resin is represented by general formula 1 (wherein M<SP>1</SP>is represented by formula 2 and M<SP>2</SP>is represented by formula 3). In the formulae, R<SP>1</SP>is a trivalent or higher-valent organic residue; R<SP>2</SP>is a substituted or unsubstituted hydrocarbyl group; R<SP>3</SP>is a bivalent organic residue bearing a urethane bond in the main chain; m is an integer of at least 2; n is an integer of at least 1; and x is an integer of at least 0. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane urea resin and a radiation curable resin composition containing the resin. The resin composition is cured by radiation such as ultraviolet rays and electron beams, and has a hardness, a curing speed and a cross-linking property. It provides a cured film with excellent density, solvent resistance, and water resistance, and is an ink binder applied to coated objects including wood, metal, glass, cloth, leather, paper, plastic, and printed objects,
In particular, the present invention relates to a water-based radiation curable resin composition used for adhesives, coating agents and the like. Furthermore, coated objects including wood, metal, glass, cloth, leather, paper and plastic, which have excellent storage stability and dispersion stability,
More particularly, it relates to an aqueous radiation curable resin composition used as an ink binder, an adhesive, a coating agent or the like applied to a material to be printed.

[0002]

2. Description of the Related Art In recent years, in the adhesive, coating, printing industry, etc., air pollution caused by solvent-based products, fire risk,
As one means for solving occupational health and safety at work, making each product water-based and solvent-free has been proposed and is being promoted.
In fact, water-based and solventless curable products are widely used in various fields, but the curing speed, crosslink density, and
At present, it is limited to some applications because of problems with solvent resistance, water resistance, viscosity, etc. Further, since the solventless type is in a liquid state until it is cured after coating, there is a problem that it is impossible to perform processing such as winding once. Therefore, there is an approach to solve this problem by giving radiation curing performance to an aqueous product. Here, the radiation curing referred to in the present invention means an electron beam,
It means that it is cured by the energy of ionizing radiation such as ultraviolet rays.

For example, a part of the carboxyl group-containing urethane prepolymer having a terminal isocyanato group is reacted with a compound having a hydroxyl group and a (meth) acrylate group, and then made water-based and chain-extended. Although a composition is disclosed (see Patent Document 1), since the disclosed examples have only two (meth) acryloyl groups at the ends in one molecule, the molecular weight and the molecular weight of the final polymer are The density of the (meth) acrylate group therein is inversely proportional, and the water resistance and solvent resistance are not sufficient on a smooth and non-permeable substrate.

On the other hand, the above-mentioned water-borne urethane resin chain-extended in water has poor storage stability, and there is a problem that when it is stored at, for example, 40 ° C., a precipitate is generated. As described above, the conventional techniques have problems in performance and physical properties.

[0005]

[Patent Document 1] Japanese Patent Laid-Open No. 3-166216

[0006]

Not only when a solvent is used as a medium, but also when water is used, the storage stability is excellent, and not only on a permeable substrate but also on a smooth and non-permeable substrate. The present invention aims to develop a radiation curable resin composition that gives a cured coating film having a good balance between solvent resistance and adhesion, and a urethane urea resin having a specific skeleton used in the radiation curable resin composition.

[0007]

The inventors of the present invention have completed the present invention as a result of diligent efforts to solve the above problems. That is, the present invention relates to a urethane urea resin represented by the following general formula 1. General formula 1

[0008]

[Chemical 3]

(In the formula, R ¹ represents an organic residue having a valence of 3 or more. R ² represents a substituted or unsubstituted hydrocarbon group. R ³
Represents a divalent organic residue having a urethane bond in the main chain.
m is an integer of 2 or more, n is an integer of 1 or more, and x is an integer of 0 or more. The present invention also relates to the urethane urea resin, wherein R ³ is a divalent organic residue having at least one anionic functional group in the side chain and a urethane bond in the main chain.

Further, the present invention provides a urethane prepolymer (C) having a terminal isocyanato group obtained by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate.
And a compound (M) having a secondary amino group represented by the following general formula 2 is reacted with the urethane urea resin. General formula 2

[0011]

[Chemical 4]

(Here, R ¹ represents a trivalent to 15-valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P
Is an integer of 2 to 14, and s is an integer obtained by subtracting p from the valence of R ¹ . The present invention is also characterized in that the compound (M) is a compound obtained by Michael-adding the compound (a) having one primary amino group to the compound (x) having three or more acryloyl groups. The above-mentioned urethane urea resin.

The present invention also provides a urethane prepolymer (C) having a terminal isocyanato group obtained by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate.
The present invention relates to a method for producing a urethane urea resin, which comprises reacting the compound (M) with

Further, in the present invention, the compound (M) is a compound obtained by Michael-adding the compound (a) having one primary amino group to the compound (x) having three or more acryloyl groups. The invention relates to a method for producing the urethane urea resin.

The present invention also relates to a radiation curable resin composition containing the above-mentioned urethane urea resin.

The present invention also relates to a radiation curable resin composition containing the urethane urea resin, water and a basic compound as essential components.

The present invention also relates to the above radiation curable resin composition further containing at least one of a compound having one or more α, β-ethylenically unsaturated double bonds and a photopolymerization initiator.

The present invention also relates to a method for producing a cured radiation product, which comprises coating the above radiation-curable resin composition on a substrate and irradiating it with an electron beam or ultraviolet ray to cure it.

The present invention also relates to the method for producing a cured radiation product, wherein the substrate is a non-permeable substrate.

The present invention also relates to a radiation cured product produced by the above production method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
General formula 1

[0022]

[Chemical 5]

(In the formula, R ¹ represents an organic residue having a valence of 3 or more. R ² represents a substituted or unsubstituted hydrocarbon group. R ³
Represents a divalent organic residue having a urethane bond in the main chain.
m is an integer of 2 or more, n is an integer of 1 or more, and x is an integer of 0 or more. In order to obtain the urethane urea resin of the present invention represented by the formula (1), a urethane prepolymer (C) having an isocyanate group at the terminal is used, and the isocyanate group at the terminal and the general formula 2

[0024]

[Chemical 6]

(Here, R ¹ represents a trivalent to 15-valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P
Is an integer of 2 to 14, and s is an integer obtained by subtracting p from the valence of R ¹ . The method of reacting the compound (M) having a secondary amino group represented by the formula (1) is most preferable. The compound (M) can be obtained, for example, by subjecting the compound (a) having one primary amino group to the compound (x) having three or more acryloyl groups by Michael addition.

In this case, R ¹ is a 3- to 15-valent organic residue derived from the compound (x) having three or more acryloyl groups, and R ² is the compound (a) having one primary amino group.
Becomes a substituted or unsubstituted hydrocarbon group derived from R
³ is a divalent organic residue derived from the urethane prepolymer (C). Specific examples of R ^{1 to} R ³ are shown by illustrating the compound (x), the compound (a), and the prepolymer (C), respectively.

The urethane prepolymer (C) is produced by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate.

As the anionic functional group-containing polyol, for example, a carboxyl group which is an anionic functional group,
Although a polyol having a sulfone group or the like can be used, it is particularly preferable to use a carboxyl group-containing polyol.

As the carboxyl group-containing polyol,
Examples thereof include dimethylolalkanoic acid such as dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, and dihydroxypropionic acid, dihydroxysuccinic acid, and dihydroxybenzoic acid. Particularly, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferably used from the viewpoint of reactivity and solubility.

As the polyol other than the anionic functional group-containing polyol, one having two or more hydroxyl groups in one molecule is preferable. For example, as the low molecular weight polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3 , 3'-dimethylolheptane, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, Octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, 3,9
-Bis (1,1-dimethyl-2-hydroxyethyl,
Examples include diols such as 2,2,8,10-tetraoxospiro [5.5] undecane, trimethylolethane, trimethylolpropane, glycerin and pentaerythritol.

Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, epoxy polyol and the like.

Examples of the polyether polyol include polyethylene glycol, polyoxypropylene glycol, poly (ethylene / propylene) glycol, polytetramethylene glycol and the like.

Polyester polyols are obtained by polycondensation of dibasic acids and polyols. As a dibasic acid component,
Examples thereof include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, and isophthalic acid. Examples of the polyol component include the compounds listed as the low molecular weight polyols. Other examples include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

Examples of the polycarbonate polyols, in its backbone, the formula ^{3 - [- O-R 4} -O-CO-] n - ( wherein, R ⁴ is a divalent organic residue, n is 1 The above-mentioned integers are represented), and a known polycarbonate polyol can be used. The polycarbonate polyol is produced, for example, by a known reaction between a polyol or bisphenol and a carbonic acid ester.

Examples of the carbonic acid ester used at this time include dimethyl carbonate, diethyl carbonate,
Examples thereof include diphenyl carbonate, ethylene carbonate and propylene carbonate.

Examples of the polyols include the compounds listed as the low molecular weight polyols. Examples of the bisphenols include bisphenol A and bisphenol F, and compounds obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the bisphenol.

Examples of acrylic polyols include copolymers of monomers having a hydroxyl group. Examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, dihydroxy acrylate, and glycerol methacrylate. These and other α, β-ethylenically unsaturated double bonds It can be obtained by polymerizing the compound possessed by a known method.

Examples of epoxy polyols include amine-modified epoxy resins. In addition, polybutadiene diol, castor oil, etc. may be mentioned.

Among the polyols other than the above-mentioned anionic functional group-containing polyols, it is preferable to use at least a high molecular weight polyol, and further, to partially use a polyether polyol, a polyester polyol and a polycarbonate polyol. Material adhesion, hardness,
It is preferable in terms of ease of production. Further, when it is used as an aqueous solution, it is preferable to use a polyether polyol, a polyester polyol and a polycarbonate polyol which are insoluble in water and have high hydrolysis resistance, from the viewpoint of storage stability.

As such a high-molecular-weight polyol having high hydrolysis resistance, polytetramethylene glycol and polyester polyol or polycarbonate polyol obtained by using 3-methyl-1,5-pentanediol as one raw material are known. It is commercially available from Kuraray Co., Ltd. as Kuraray Polyol C series and the like. The molecular weight of these high molecular weight polyols is preferably 5
100 to 5,000, bifunctional or more, more preferably molecular weight 9
A bifunctional or higher functional polyol of 00 to 4100 is used.

Examples of the polyisocyanate used in the present invention include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates and alicyclic polyisocyanates.

As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate,
Examples thereof include 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

As the araliphatic polyisocyanate,
For example, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-
Examples thereof include diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate,
Methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,
4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

Further, a trimethylolpropane adduct of the above polyisocyanate, a burette reacting with water, a trimer having an isocyanurate ring, etc. can be used in combination.

As the polyisocyanate used in the present invention, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate and the like are preferable.

However, the raw material of the urethane prepolymer (C) is not limited to the anionic functional group-containing polyols exemplified above, polyols other than the anionic functional group-containing polyol, and polyisocyanates. Among polyols other than the anionic functional group-containing polyol and polyisocyanates, trifunctional or higher functional ones are preferably used in an amount within a range not hindering the production of the urethane prepolymer (C).

During the production of the urethane prepolymer (C),
It is not always necessary to add a catalyst because the anionic group of the anionic functional group-containing polyol has a reaction catalytic action between isocyanate and hydroxyl group, but it is necessary to add a catalyst separately in order to accelerate the shortening of the manufacturing time and the manufacturing temperature. You can also As the catalyst used for the reaction between the isocyanate and the hydroxyl group, a known catalyst can be used. Eg 3
Examples include primary amine compounds and organometallic compounds.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-sen and the like. To be

Examples of the organometallic compound include tin compounds and non-tin compounds. Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyl. Examples thereof include tin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate and tin 2-ethylhexanoate.

Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. , Iron such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt such as cobalt benzoate and cobalt such as 2-ethylhexanoate, zinc such as zinc naphthenate and zinc 2-ethylhexanoate, zirconium naphthenate And so on. These can be used alone or in combination.

Of these, dibutyltin dilaurate and tin 2-ethylhexanoate are preferred.

When the urethane prepolymer (C) is produced, it is possible to produce it only with the above-mentioned raw materials, but it is preferable to use a solvent because of problems such as high viscosity and nonuniform reaction. Known solvents can be used as the solvent. For example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, acetonitrile and the like can be mentioned.

Various methods can be used for the urethanization reaction in which a urethane prepolymer (C) is prepared by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate. It is roughly classified into 1) a method of reacting with the whole amount charged, and 2) a method of charging an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol and a catalyst into a flask and dropping polyisocyanate. 2) is preferable for precise control. The reaction temperature for obtaining the urethane prepolymer (C) is preferably 120 ° C. or lower. More preferably, it is 70 to 120 ° C. If it exceeds 120 ° C., the alohanate reaction proceeds and the urethane prepolymer (C) having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably carried out at 70 to 120 ° C. for 2 to 20 hours.

The mixing ratio of the anionic functional group-containing polyol, the polyol other than the anionic functional group-containing polyol, and the polyisocyanate is such that the isocyanate group remains at the terminal so that the anionic functional group-containing polyol and the anionic functional group-containing polyol are mixed. It is necessary that the molar equivalent of the isocyanate group of the polyisocyanate is more than 1 time the total molar equivalent of the hydroxyl groups of the polyols other than. The appropriate compounding ratio depends on the reactivity of the compound, the abundance ratio of the compound having three or more valences, and the like.

General formula 2

[0058]

[Chemical 7]

(Here, R ¹ represents a trivalent to 15-valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. P
Is an integer of 2 to 14, and s is an integer obtained by subtracting p from the valence of R ¹ . The compound (M) having a secondary amino group represented by) is a compound (a) having one primary amino group,
It can be produced by Michael addition to the compound (x) having three or more acryloyl groups.

The compound (a) having one primary amino group is represented by the general formula 4 R ⁷ —NH ₂ (wherein R ⁷ is a monovalent substituted or unsubstituted hydrocarbon group having no active hydrogen group). ). Specifically, benzylamine, phenethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, isopentylamine, n-hexylamine,
1 such as cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine Examples thereof include primary amines, and among them, amines having a substituted or unsubstituted hydrocarbon group having 10 or less carbon atoms are preferable from the viewpoint of reaction control. These can be used alone or in combination.

The compound (x) having three or more acryloyl groups is, for example, glycerin triacrylate,
Glycerin ethylene oxide modified triacrylate, glycerin propylene oxide modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, isocyanuric acid propylene oxide modified triacrylate , Isocyanuric acid ethylene oxide modified ε-caprolactone modified triacrylate, 1,3,5
-Trifunctional acrylates such as triacryloyl hexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Further, for example, tetra- or higher functional groups such as pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate, etc. Acrylates are mentioned. These are not limited to the above compounds, and any compound having three or more acryloyl groups can be used without particular limitation. These can be used alone or in combination. When the compound (x) is preferably a tetrafunctional to 15 functional acrylate, and more preferably a 5 functional to 15 functional acrylate, the number of acryloyl groups that can be introduced into the urethane urea resin increases, and the curability becomes sufficient.

Compound (a) having one primary amino group
Is added to the compound (x) having three or more acryloyl groups by Michael addition, the reaction with the urethane prepolymer (C) during or after this reaction does not cause gelation and may be reacted at any ratio. Good, but the number of moles x of the compound (x) is a / x = the number of moles a of the compound (a).
It is preferable that the reaction is carried out in the range of 0.2 to 2. More preferably, it is a / x = 0.25 to 1.9. When a / x <0.2, a large amount of unreacted compound (x) remains, and the dispersion stability after hydration becomes poor. a / x
When it is> 2, a relatively large amount of the compound having three or more secondary amino groups can be obtained, so that the urethane prepolymer (C) is used.
There is a case where a three-dimensional network cross-linking is caused by the reaction with and gelation occurs.

In the case of a / x = 0.2 to 2, the product after the Michael addition reaction is a compound having two substituted or secondary amino groups, a monosubstituted or secondary amino group. And a 0-substituted compound, that is, an unreacted compound (x). Upon reaction with the urethane prepolymer (C), the 2-substituted product functions as a chain extender that increases the molecular weight, and the 1-substituted product functions as an end-capping agent that stops the polyaddition reaction. When a / x is close to 0.2, the production ratio of the 2-substitution product and the mono-substitution product is large, and as the a / x approaches 2, the mono-substitution product decreases and the 2-substitution product increases.

Here, the compound (M) having a secondary amino group refers to a mixture of the above-mentioned mono-substituted and di-substituted or more compounds.

Compound (a) having one primary amino group
Is added to the compound (x) having three or more acryloyl groups by Michael, a method of sequentially dropping the compound (a) into a reaction tank in which the compound (x) is stirred in order to suppress local reaction is preferable. The dropping time and the reaction time are not limited because they depend on the reactivity between the compound (a) and the compound (x). Further, in order to prevent the secondary amino group of the compound (M) produced from being added to another acryloyl group by Michael, the reaction is carried out at 50 ° C. or lower, preferably 40 ° C. or lower.

Although this reaction can be carried out by using only the above-mentioned raw materials, it is preferable to carry out the reaction by using a solvent because local reaction can be suppressed. At this time, for example, methanol,
Ethanol, n-propyl alcohol, isopropyl alcohol, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, acetonitrile and the like can be used, and these can be used alone or in combination.

It is desirable that the produced compound (M) is immediately reacted with the urethane polymer (C) in order to prevent the secondary amino group from further Michael-adding during storage.

The Michael addition referred to in the present invention is a nucleophilic ion in which a primary amino group is added to an α, β-unsaturated double bond of an acrylate group in a catalyst-free system and, if necessary, in the presence of a catalyst. Indicates a reaction.

The reaction ratio between the urethane prepolymer (C) and the compound (M) having a secondary amino group may be any ratio as long as it does not gel, but isocyanato groups present in the urethane prepolymer (C). The number of moles of <N>,
When the number of moles of the secondary amino group of the compound (M) is <H>, it is preferable to react so that <H> / <N> = 1.0 to 1.1. More preferably <H> /
This is when <N> = 1. When <N> / <H><1, the terminal isocyanato group remains, and after being made aqueous, the isocyanato group reacts with water to become an amine, which reacts with another terminal isocyanato group or acryloyl group to give a high molecular weight. Therefore, deterioration of storage stability and gelation may occur. When <H> / <N >> 1.1, the amount of the compound (M) having a secondary amino group is excessive, and the secondary amino group exists in the system during the long-term storage. The storage stability becomes worse because of Michael addition.

Here, the smaller the value of a / x in producing the compound (M) having a secondary amino group, the higher the degree of extension of the molecular weight of the urethane urea resin formed with respect to the urethane prepolymer (C). The smaller the value of a / x, the greater the degree of extension of the molecular weight of the urethane urea resin produced.

When the reaction between the secondary amino group and the isocyanato group is carried out, the compound (M) is successively added dropwise to the reaction tank in which the reaction solution containing the urethane prepolymer (C) is stirred in order to suppress the local reaction. Is preferred. Further, in order to prevent the secondary amino group of the compound (M) from being Michael-added to the acryloyl group, it is preferably carried out at 50 ° C. or lower, more preferably 40 ° C. or lower.

The weight average molecular weight of the urethane urea resin produced by the above method may be any value as long as there is no problem in use, but it is particularly preferably 5,000 to 200,000 in terms of standard polystyrene equivalent weight average molecular weight by GPC. More preferably, it is 8000 to 150,000. When the weight average molecular weight is less than 5,000, the adhesion to the substrate and the storage stability when made water-based may be poor, and when the weight average molecular weight exceeds 200,000, the viscosity at the time of production and coating becomes extremely high. The productivity of coating may deteriorate.

The amount of acryloyl groups based on the dry weight contained in the urethane urea resin produced by the above method is
It can be easily adjusted by the molecular weight of the urethane prepolymer (C) and the amounts of the secondary amino group and acryloyl group present in the compound (M). The amount of acryloyl group contained in the urethane urea resin may be any value as long as there is no problem in use, but is preferably 0.1 mmol / g or more, more preferably 0.3 mmol / g or more, and most preferably It is 0.4 mmol / g or more. 0.1 mmol
If it is less than / g, the radiation curing reactivity may deteriorate and the cured product may have insufficient solvent resistance.

Since the urethane urea resin has an acryloyl group at its terminal or at the terminal and side chain, it can be used as a radiation curable resin composition.
Furthermore, by neutralizing a part or all of the anionic functional group,
An aqueous radiation curable resin composition can be obtained by adding water simultaneously with or after the neutralization.

At this time, the acid value based on the dry weight of the urethane urea resin is preferably in the range of 5 to 80 mgKOH / g. If the acid value is less than 5 mgKOH / g, the dispersion stability in water may be poor, and aggregates or precipitates may occur over time. If it exceeds 80 mgKOH / g,
The water resistance of the coating film after curing may deteriorate.

As the basic compound used for neutralization, ammonia or an organic basic compound is used, and tertiary amines are particularly preferable. Specifically, triethylamine, tri-n-butylamine, triallylamine, N,
Examples thereof include N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine and the like.

As a method of hydration, it is preferable to neutralize a part or all of the anionic functional groups, then gradually drop water and distill off the solvent used for the reaction by distillation under reduced pressure. As distillation conditions, the temperature is 50 ° C. or lower, and the degree of vacuum is
It is preferable to carry out at 5 to 300 torr. At this time, a known antifoaming agent can be added.

The above radiation curable resin composition further contains at least one of a compound having at least one α, β-ethylenically unsaturated double bond, a photopolymerization initiator, a colorant and a water-soluble compound. be able to.

The compound having one or more α, β-ethylenically unsaturated double bonds is not particularly limited as long as it is a known compound having one or more α, β-ethylenically unsaturated double bonds. Can be used.

Specifically, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-
Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate,
Lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxy polypropylene Alkoxypolyalkylene glycol (meth) acrylates such as glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) Hydroxyl group-containing (meth) acrylates such as acrylate, (meth) acrylamide, and N, N- dimethyl (meth) acrylamide, N, N
-N-substituted (meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N -Amino group-containing (meth) acrylates such as diethylaminoethyl (meth) acrylate, nitriles such as (meth) acrylonitrile,
Styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate and vinyl propionate, and also
Alkylene glycol di (meth) acrylates such as 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, trimethylol Propane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified ε-caprolactone modified tri ( (Meth) acrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol tri (meth) ac Rate, trifunctional (meth) acrylates such as dipentaerythritol tri (meth) acrylate tripropionate. Further, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, oligoester tetra (meth) acrylate, tris Examples include polyfunctional (meth) acrylates such as ((meth) acryloyloxy) phosphate.

Further, in addition to the above compounds, polyester (meth) acrylate, polyurethane (meth)
Examples thereof include acrylate, epoxy (meth) acrylate, and (meth) acrylated maleic acid-modified polybutadiene.

The polyester (meth) acrylate is obtained by polycondensing a polybasic acid and a polyhydric alcohol to obtain a polyester having a hydroxyl group or a carboxyl group, and then the hydroxyl group in the polyester and (meth) acrylic acid or maleic acid. Esterification with unsaturated aliphatic polybasic acid such as acid, or (meth) acrylate having carboxyl group in the polyester and hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate It can be obtained by esterification with. Alternatively, it can also be obtained by reacting an acid anhydride with glycidyl (meth) acrylate and a compound having at least one hydroxyl group.

The polyurethane (meth) acrylate is obtained by reacting a compound having at least two or more isocyanato groups in the molecule with a (meth) acrylate having a hydroxyl group, or by reacting at least two or more isocyanate groups in the molecule. By reacting the compound having with a polyhydric alcohol to obtain a urethane prepolymer having at least two or more isocyanate groups in the molecule, and then reacting the urethane prepolymer having an isocyanate group with a (meth) acrylate having a hydroxyl group. Can be obtained by doing.

The epoxy (meth) acrylate is synthesized by the reaction of a glycidyl group with acrylic acid or methacrylic acid, and examples thereof include bisphenol type, epoxidized oil type, phenol novolac type, alicyclic type and the like. The bisphenol type epoxy (meth) acrylate is obtained by reacting bisphenol type diglycidyl ether obtained by reacting bisphenols with epichlorohydrin and acrylic acid or methacrylic acid, and has a (meth) acryloyl group in one molecule. Have a maximum of two. The epoxidized oil (meth) acrylate is obtained by reacting an oil containing a glycidyl group, an epoxidized soybean oil or the like with acrylic acid or methacrylic acid. The novolac type epoxy (meth) acrylate is obtained by reacting a novolac type epoxy resin with acrylic acid or methacrylic acid. The alicyclic epoxy (meth) acrylate is obtained by reacting an alicyclic epoxy resin with acrylic acid or methacrylic acid.

The (meth) acrylated maleic acid-modified polybutadiene is obtained by adding maleic anhydride to the double bond in polybutadiene, and then the portion derived from maleic anhydride in the maleated polybutadiene and 2-hydroxyethyl (meth). It can be obtained by reacting with a (meth) acrylate having a hydroxyl group such as acrylate.

Here, (meth) acrylate is acrylate or methacrylate, and (meth) acrylamide is acrylamide or methacrylamide.
(Meth) acrylonitrile means acrylonitrile or methacrylonitrile.

When the compound having one or more α, β-ethylenically unsaturated double bonds is used, the compound having a (meth) acryloyl group having a molecular weight of 1000 or less, a vinyl group and an N-substituted type (meth) are preferable. ) Acrylamides, more preferably compounds having an acryloyl group and N-substituted acrylamides, most preferably compounds having a bifunctional or higher functional acryloyl group.

The total amount of α, β-ethylenically unsaturated double bonds in the urethane urea resin and the compound having at least one α, β-ethylenically unsaturated double bond in the radiation curable resin composition of the present invention is The amount may be any value as long as there is no problem in use, but it is 0.2 with respect to the dry weight.
mmol / g or more is preferable, and further 0.3 mmol / g
The above is preferable, and the most preferable is 0.5 mmol / g or more. If it is less than 0.2 mmol / g, the radiation curing reactivity may be poor and the solvent resistance of the cured product may be insufficient.

The photopolymerization initiator is added when the radiation curable resin composition of the present invention is cured by ultraviolet rays. When the radiation curable resin composition of the present invention is cured with an electron beam, no initiator is needed. The photopolymerization initiator is not particularly limited as long as it has a function of initiating vinyl polymerization by photoexcitation, and examples thereof include monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl. A compound etc. can be used.

Specifically, as the monocarbonyl compound,
Benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4 (4-methylphenylthio) phenyl-enetanone, 3,3'-dimethyl-4- Methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,1
0,13-Pentaoxotridecyl) benzophenone, 3,3 '
4,4'-Tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-NNN-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl)
-Phenoxy) -NNN-trimethyl-1-propanamine hydrochloride, 4-benzoyl-NN-dimethyl-N- [2- (1-oxo-2-propenyloxyethyl) methammonium hydrobromide, 2- / 4
-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H thioxanthone-2 -Iroxy) -N, N, N-
Trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline and the like can be mentioned.

Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2,1,1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone and methyl-α. -Oxobenzene acetate, 4-
Phenylbenzil and the like can be mentioned.

As the acetophenone compound, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-
Isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropane
-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropane-1
-One polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1
-One, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butan-1-one , 1-
Examples thereof include phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime and 3,6-bis (2-methyl-2-morpholino-propanonyl) -9-butylcarbazole.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether and the like.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

Examples of aminocarbonyl compounds include methyl
-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl Benzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,
5'-bis- (4-diethylaminobenzal) cyclopentanone and the like can be mentioned.

These may be used alone or in combination, and the amount used is not limited, but the total weight of the urethane urea resin and the compound having at least one α, β-ethylenically unsaturated double bond is 100% by weight. It is preferably added in the range of 1 to 20 parts by weight with respect to parts.

In addition to the above, the radiation curable resin composition of the present invention may contain optional components as long as the purpose is not impaired.
Further, a solvent, pigment, dye, antioxidant, polymerization inhibitor, leveling agent, moisturizer, viscosity modifier, preservative, antibacterial agent, fine powder silica, plasticizer, surfactant, polymer emulsion, etc. may be added. it can.

The radiation-curable aqueous resin composition of the present invention can be applied to coated objects such as wood, metal, glass, cloth, leather, paper and plastics, and materials to be printed. Suitable for use on permeable substrates.

The radiation curable water-based resin composition of the present invention can be applied by brush coating, spray coating, flow coating,
Curtain flow coating, dip coating, vacuum coating, roll coating, reverse coating or gravure printing, flexographic printing, screen printing, inkjet printing, and all other coatings and printing are possible.

The radiation curable aqueous resin composition of the present invention can be used as various adhesives including paints, gravure printing inks, flexographic printing inks, ink binders such as ink jet printing inks, and laminating adhesives. .

The radiation curable aqueous resin composition of the present invention can be cured by a known radiation curing method, and it is particularly preferable to use ultraviolet rays or electron beams.

As the ultraviolet irradiating device, a light source having a light source in the range of 200 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like is used. it can. The cumulative amount of ultraviolet light is not limited because the required minimum cumulative amount of light depends on the application, the film thickness, the presence or absence of a colorant, and the type and amount of the photopolymerization initiator.

When curing with ultraviolet rays, it is not particularly necessary, but the oxygen concentration may be lower than that of air by using an inert gas such as nitrogen.

Examples of the electron beam irradiation apparatus include curtain beam type, area beam type, broad beam type, scanning beam type and vacuum tube type devices. The accelerating voltage of the electron beam is not particularly limited, and a cured product can be formed by setting it in the range of 30 to 500 kV. Also,
The electron beam irradiation dose (DOSE) is preferably 1 to 10
The range is 00 kGy, more preferably 5 to 200 kGy. If it is less than this range, it is difficult to obtain a sufficient cured film, and if it is larger than this range, the coating film and the substrate are largely damaged. In addition, in order to suppress inhibition by oxygen during curing, the oxygen concentration is 500 ppm or less, preferably 200 pp using an inert gas such as nitrogen.
It is preferable to lower it to m or less.

It is also possible to use these ultraviolet rays or electron beams in combination with heat from infrared rays, far infrared rays, hot air, high frequency heating, or the like.

After the radiation curable water-based resin composition of the present invention is applied, it may be naturally or forcibly dried and then may be radiation-cured, or it may be radiation-cured subsequently to the application and then naturally or forcibly-dried. Absent. When curing with electron beam, to prevent water from inhibiting curing,
Radiation curing is preferably performed after natural or forced drying.

[0108]

EXAMPLES The present invention will be described in detail below with reference to production examples and examples, but the present invention is not limited thereto. In the following Production Examples and Examples, “parts” means parts by weight unless otherwise specified. The number average molecular weight and the weight average molecular weight are standard polystyrene equivalent molecular weights measured by GPC.

Production Example 1 (Production of Urethane Prepolymer (C)) A four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer and a dropping funnel was placed in a trade name of Kuraray Polyol P-.
1010 (bifunctional polyester polyol, OH number 11
70.9 mg KOH / g, manufactured by Kuraray Co., Ltd.) 610.9 parts,
Dimethylolbutanoic acid (Nippon Kasei Co., Ltd.) 83.7
Parts, 305.4 parts of isophorone diisocyanate (manufactured by Huls Japan KK) and 280 parts of methyl ethyl ketone were charged, the temperature was gradually raised, and the reaction was carried out at the boiling point of the contents for 3 hours. After confirming the remaining amount of the isocyanato group by titration, 720 parts of methyl ethyl ketone was added, and the mixture was cooled to 40 ° C. to obtain a urethane prepolymer solution (C-1). The reaction solution was transparent and had a solid content of 50% by weight and a number average molecular weight of 580.
0, the weight average molecular weight was 12,600, and the amount of residual isocyanato groups per 0.1 g of the solution was 0.1823 mmol.

Production Examples 2 to 4 The urethane prepolymer (C) shown in Table 1 was synthesized in the same manner as in Production Example 1 to obtain (C-2) to (C-4). Table 1

[0111]

[Table 1]

Abbreviations in Table 1 P-1010: bifunctional polyester polyol, trade name Kuraray polyol P-1010 (OH number 117 mg KO
H / g, manufactured by Kuraray Co., Ltd.) C-1090: bifunctional polycarbonate polyol, trade name Kuraray polyol C-1090 (OH value 112 mg)
KOH / g, manufactured by Kuraray Co., Ltd.) PTG1000: polytetramethylene glycol (OH
Value 109.1 mgKOH / g, Hodogaya Chemical Co., Ltd.) TMP: Trimethylolpropane (Mitsubishi Gas Chemical Co., Ltd.) DMBA: Dimethylolbutanoic acid (Nihon Kasei Co., Ltd.) IPDI: Isophorone diisocyanate (Huls Japan Co., Ltd.) ) DBTDL: dibutyltin dilaurate MEK: methyl ethyl ketone Mn: number average molecular weight, Mw: weight average molecular weight Production Example 5 (Production of compound (M) having secondary amino group) Stirrer, reflux condenser, gas inlet pipe, thermometer , A 4-necked flask equipped with a dropping funnel, ditrimethylol propane tetraacrylate (manufactured by Nippon Kayaku Co., Ltd .: trade name SR-
355) 86.8 parts of methyl ethyl ketone and 28.9 parts of methyl ethyl ketone were charged, and a mixed solution of 13.2 parts of n-butylamine (manufactured by Wako Pure Chemical Industries, Ltd .: special grade reagent) and 4.4 parts of methyl ethyl ketone was added at 25 ° C to 30 with a dropping funnel. The solution was added dropwise at 10 ° C over 10 minutes. Although the temperature of the contents rose due to the heat of reaction, 66.7 parts of methyl ethyl ketone prepared separately was appropriately added and the reaction was carried out while cooling. After dropping, 1 at 25 ℃
The reaction was carried out for 0 minutes to obtain the compound (M-1).

About 2 g of (M-1) was placed in an Erlenmeyer flask, precisely weighed, and dissolved with 30 ml of methyl ethyl ketone. This solution was titrated with a 0.2 mol / L ethanolic hydrochloric acid standard solution using bromophenol blue as an indicator to obtain the total of primary, secondary, and tertiary amine values (total amine value).

Next, about 2 g of (M-1) was placed in an Erlenmeyer flask and precisely weighed, and a mixed solution of acetic anhydride and acetic acid (9: 1) was added.
ml was added and dissolved, and the mixture was left at room temperature for 3 hours. Subsequently, 30 ml of acetic acid was added and 0.1 mol / L was measured with a potentiometric titrator.
The tertiary amine value was determined by titrating with perchloric acid and acetic acid solution and simultaneously performing a blank test.

Next, about 2 g of (M-1) was placed in an Erlenmeyer flask and precisely weighed, and 30 ml of methyl ethyl ketone was added and dissolved. Subsequently, 5 ml of a 25% ethanol solution of salicylaldehyde was added, and the mixture was allowed to stand at room temperature for about 30 minutes (salicylaldehyde is neutralized by reacting with a primary amino group). 0.
The total of secondary and tertiary amine values (partial amine value) was determined by titrating with a 2 mol / L ethanolic hydrochloric acid solution using bromophenol blue as an indicator.

By the above operation, (primary amine value) = (total amine value)-(partial amine value), (secondary amine value) =
It is determined by the formula of (partial amine value)-(tertiary amine value), and as a result, when n-butylamine reacts with ditrimethylolpropane tetraacrylate, the conversion rate for producing the desired secondary amino group is n- It was confirmed to be 99.7% based on butylamine. This gives (M-
The amount of secondary amine per 1 g of the solution of 1) is 0.901 mm
It became ol.

Production Examples 6 to 9 In the same manner as in Production Example 5, compounds (M) having a secondary amino group shown in Table 1 below were synthesized to give (M-2) to (M-
5) was obtained. However, in the case of Production Example 2, after the dropping was completed, 2
The reaction was carried out at 5 ° C for 2 hours. Table 2

[0118]

[Table 2]

Abbreviations in Table 2 SR-355: 4-functional acrylate, trade name SR-35
5 (average molecular weight 482, manufactured by Nippon Kayaku Co., Ltd.) DPCA-20: 6-functional acrylate, trade name KAYA
RAD DPCA-20 (average molecular weight 807, manufactured by Nippon Kayaku Co., Ltd.) Act421 1: 2 functional acrylate, trade name Actil
ane421 (average molecular weight 330, manufactured by Japan Siber Hegner KK) n-BA: n-butylamine BzA: benzylamine MEK: methyl ethyl ketone

Example 1 The number of moles <N> of isocyanato groups present in the urethane prepolymer (C-1) obtained in Production Example 1 by titration, and the compound (M-1 obtained in Production Example 5 in advance. )
The number of moles of the secondary amino group of <H> was determined by titration. Stirrer, reflux cooling pipe, gas introduction pipe, thermometer,
A 4-necked flask equipped with a dropping funnel was charged with 300 parts of the urethane prepolymer obtained in Production Example 1 and 225 parts of methyl ethyl ketone and heated to 40 ° C., where <H> /
Compound (M-1) 60.7 such that <N> = 1.0
Parts were added dropwise over 30 minutes. After completion of dropping, stay at 40 ° C 3
After continuing stirring for 0 minutes, it was confirmed by infrared absorption spectrum that the peak at 2266 cm ^-1 , which is the characteristic absorption of the isocyanato group, disappeared, the reaction was terminated, and a urethane urea resin (U-1) was obtained. This reaction liquid is transparent and has a solid content of 3
0.8% by weight, number average molecular weight 7,000, weight average molecular weight 15800, and calculated amount of acryloyl group per dry weight was 0.90 mmol / g.

Examples 2 to 7 and Reference Examples 1 and 2 By the same apparatus and operation as in Example 1, urethane urea resins (U-2) to (U-9) were obtained at the composition ratios shown in Table 3. An IR chart of the urethane urea resin (U-2) obtained in Example 2 is shown in FIG. 1, an IR chart of the urethane urea resin (U-5) obtained in Example 5 is shown in FIG. The IR chart of the obtained urethane urea resin (U-6) is illustrated in FIG. Table 3

[0122]

[Table 3]

Reference Example 3 A four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, a thermometer, and a dropping funnel was prepared (C-).
1) 300 parts, 2-hydroxyethyl acrylate 7.
0 parts (this amount corresponds to 1.1 equivalents of the number of moles of the isocyanato group present in (C-1)), 0.13 parts of hydroquinone monomethyl ether, and dibutyltin dilaurate of 0.1.
After charging 065 parts to 80 ° C. and continuing the reaction for 5 hours while flowing dry air, the infrared absorption spectrum confirmed that the peak at 2266 cm −1, which is the characteristic absorption of the isocyanato group, disappeared, and the reaction was terminated. Urethane resin (U-
10) was obtained. This reaction liquid was transparent and had a solid content of 52.0% by weight, a number average molecular weight of 6000 and a weight average molecular weight of 1300.
0, calculated amount of acryloyl group per dry weight is 0.36
It was mmol / g.

Reference Example 4 A urethane resin (U-11) having the composition ratio shown in Table 4 was obtained by the same apparatus and operation as in Reference Example 3. Table 4

[0125]

[Table 4]

Abbreviations in Table 4 2HEA: 2-hydroxyethyl acrylate DBTDL: dibutyltin dilaurate HQME: Hydroquinone monomethyl ether

Example 8, Comparative Examples 1 and 2 The urethane urea resin or urethane resin obtained in Example 7 and Reference Examples 2 and 4 was applied to a thickness of 2 using an applicator.
mm polyethylene terephthalate (PET) plate,
The coating was applied so that the thickness after drying was 10 μm, and naturally dried for 1 minute. Low acceleration voltage electron beam irradiation device MIN-EB
(American International Technologies), electron beam acceleration: 50 keV, irradiation dose (DOSE) 50 k
The following test was performed using the samples before and after curing under the condition of Gy. The results are shown in Table 5.

(1) Tack Judge the coating film before electron beam irradiation by touching with a finger. ○: No tack ×: Tuck (2) Adhesive cellophane tape (registered trademark) (manufactured by Nichiban) Uncoated rate of coating film by peel test ○: No peeling at all ×: Partial peeling (3 ) Soak a solvent resistant cotton swab with MEK and rub the surface of the cured coating. Number: The number of times until the base is exposed. Table 5

[0129]

[Table 5]

Examples 9 and 10 and Comparative Examples 3 and 4 To the urethane urea resin or urethane resin obtained in Example 7 and Reference Examples 2 and 4, α, β-ethylenically unsaturated double bond was prepared according to the following Table 6. The compound having one or more of the above and a photopolymerization initiator are added, and the mixture is applied to a polyethylene terephthalate (PET) plate having a thickness of 2 mm with an applicator so that the thickness after drying becomes 10 μm, and naturally dried for 1 minute. Let A belt conveyor type ultraviolet irradiation device (UVC-2534 metal halide lamp type manufactured by Ushio Inc.) was used to irradiate ultraviolet rays with an electric power of 120 W / cm and an integrated light amount of 240 mJ / cm ² , and the same adhesion and solvent resistance test as above. I went. The results are shown in Table 6. Table 6

[0131]

[Table 6]

Abbreviations in Table 6 DPHA: 5.5 functional acrylate, trade name KAYAR
AD DPHA (average molecular weight 535.5, manufactured by Nippon Kayaku Co., Ltd.) Irg907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, trade name Irgacure 907 (Ciba Specialty Chemicals) (Made by corporation)

Example 11 A 5-neck flask equipped with a stirrer, a reflux condenser equipped with a solvent distilling device, a gas introduction tube, a thermometer, and a dropping funnel was stirred with 100 parts of the urethane urea resin obtained in Example 5. Down 1.6
5 parts triethylamine were added. Using a dropping funnel at 40 ° C., 88.2 parts of water was added dropwise over 30 minutes to make it aqueous. Then, methyl ethyl ketone and part of water were distilled off under reduced pressure at 40 ° C. to give an aqueous resin composition (W-1).
Got

This aqueous resin dispersion is treated with water to give a solid content of 20%.
When the storage stability at 40 ° C. was confirmed, no precipitates were found even after 1 month.

Examples 11 to 16, Comparative Examples 5 and 6, Reference Examples 5 to 8 Using the same equipment and operation as in Example 11, the aqueous resin compositions (W-2) were mixed at the mixing ratios shown in Tables 7 and 8. ~ (W-6) were obtained and the storage stability was similarly confirmed. However, compounds having one or more α, β-ethylenically unsaturated double bonds (DP in the table
When HA) and a photopolymerization initiator were added, they were mixed before adding water. Table 7

[0136]

[Table 7]

Table 8

[0138]

[Table 8]

Abbreviations in Tables 7 and 8 DPHA: 5.5 functional acrylate, trade name KAYAR
AD DPHA (average molecular weight 535.5, manufactured by Nippon Kayaku Co., Ltd.) Irg907: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, trade name Irgacure 907 (Ciba Specialty Chemicals) (Made by corporation)

Examples 17 and 18, Comparative Examples 7 and 8 The aqueous resin compositions obtained in Examples 11 and 15 and Reference Examples 5 and 7 were polyethylene terephthalate (PET) films with a thickness of 50 μm using a bar coater. It was coated on the above so that the thickness after drying was 2 μm, and naturally dried at 80 ° C. for 1 minute. Low acceleration voltage electron beam irradiation device MIN-EB
(American International Technologies), electron beam acceleration: 50 keV, irradiation dose (DOSE) 50 k
The following test was performed using the samples before and after curing under the condition of Gy. The results are shown in Table 9.

(1) Tack The coating film before electron beam irradiation is judged by touching with a finger. ○: No tack ×: Tuck (2) Adhesive cellophane tape (registered trademark) (manufactured by Nichiban) Uncoated rate of coating film by peel test ○: No peeling at all ×: Partial peeling (3 ) Soak a solvent resistant cotton swab with MEK and rub the surface of the cured coating. Number: The number of times until the base is exposed. Table 9

[0142]

[Table 9]

Examples 19 to 22 and Comparative Examples 9 and 10 The aqueous resin compositions obtained in Examples 12 to 14 and 16 and Reference Examples 6 and 8 were polyethylene terephthalate (PET) having a thickness of 50 μm using a bar coater. ) A film was coated so that the thickness after drying would be 2 μm, and naturally dried at 80 ° C. for 1 minute. Using a belt conveyor type UV irradiation device (UVC-2534 metal halide lamp type manufactured by Ushio Inc.), electric power 120 W / cm, integrated light intensity 240 mJ /
A test similar to the above was conducted by irradiating with ultraviolet rays of cm ² .
The results are shown in Table 10.

[0144]

[Table 10]

From the above, as shown in Examples 1 to 7, a urethane urea resin having an acryloyl group could be obtained from the urethane prepolymer (C) and the compound (M) having a secondary amino group. Examples 8-10, Comparative Examples 1-
In 4, the coating film provided by the radiation curable resin composition using a solvent as a medium is evaluated.
The comparative examples not using the urethane urea resin of the present invention had poor solvent resistance. In addition, in Examples 11 to 16, α, β-
An aqueous radiation curable resin composition having good storage stability has been obtained regardless of the presence or absence of a compound having one or more ethylenically unsaturated double bonds. However, the urethane urea resin of the present invention was used without α Comparative Example 5 in which a compound having one or more β-ethylenically unsaturated double bonds is added,
In No. 6, storage stability was poor. In addition, Examples 17 to 2
2. In Comparative Examples 7 to 12, the coating films provided by the aqueous radiation curable resin composition were evaluated, but the solvent resistance of the Comparative Examples was clearly poorer than that of the Examples.

[0146]

EFFECTS OF THE INVENTION According to the present invention, not only when a solvent is used as a medium, but also when water is used, the storage stability is excellent, and not only on a permeable substrate but also on a smooth and non-permeable substrate. It is possible to provide a urethane curable resin composition having a specific skeleton used in the radiation curable resin composition and the radiation curable aqueous resin composition that gives a cured coating film having a good balance between solvent resistance and adhesion. It was

[Brief description of drawings]

FIG. 1 is an IR chart of the urethane urea resin obtained in Example 2.

FIG. 2 is an IR chart of the urethane urea resin obtained in Example 5.

FIG. 3 is an IR chart of the urethane urea resin obtained in Example 6.

Claims (12)

[Claims] 1. A urethane urea resin represented by the following general formula 1. General formula 1 (In the formula, R ¹ represents a trivalent or higher valent organic residue. R ² represents a substituted or unsubstituted hydrocarbon group. R ³ represents a divalent organic residue having a urethane bond in its main chain. (m is an integer of 2 or more, n is an integer of 1 or more, and x is an integer of 0 or more.) 2. The urethane urea resin according to claim 1, wherein R ³ is a divalent organic residue having at least one anionic functional group in its side chain and having a urethane bond in its main chain. . 3. A urethane prepolymer (C) having a terminal isocyanato group formed by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate is added to the following general formula 2
A urethane urea resin, which is obtained by reacting a compound (M) having a secondary amino group represented by: General formula 2 (Here, R ¹ represents an organic residue having a valence of ³ to 15, R ² represents a substituted or unsubstituted hydrocarbon group, p is an integer of 2 to 14, and s is a valence of R ¹ minus p. It is an integer.) 4. The compound (M) is a compound obtained by Michael addition of a compound (a) having one primary amino group to a compound (x) having three or more acryloyl groups. Item 3. The urethane urea resin according to item 3. 5. A compound (M) is added to a urethane prepolymer (C) having a terminal isocyanato group obtained by reacting an anionic functional group-containing polyol, a polyol other than the anionic functional group-containing polyol, and a polyisocyanate.
A method for producing a urethane urea resin, which comprises reacting 6. The compound (M) is a compound obtained by Michael-adding a compound (a) having one primary amino group to a compound (x) having three or more acryloyl groups. Item 6. A method for producing a urethane urea resin according to Item 5. 7. A radiation curable resin composition comprising the urethane urea resin according to any one of claims 1 to 4. 8. A radiation curable resin composition comprising the urethane urea resin according to any one of claims 2 to 4, water, and a basic compound as essential components. 9. The radiation curable resin composition according to claim 7, further comprising at least one of a compound having one or more α, β-ethylenically unsaturated double bonds and a photopolymerization initiator. object. 10. A method for producing a cured radiation product, which comprises applying a radiation curable resin composition according to any one of claims 7 to 9 to a substrate and curing it by irradiating it with an electron beam or an ultraviolet ray. . 11. The method for producing a cured radiation product according to claim 10, wherein the substrate is a non-permeable substrate. 12. A radiation cured product produced by the production method according to claim 10.