JPH07102030A - Radiation curable polyurethane polymer emulsion composition and method for producing the same - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a radiation curable polyurethane emulsion composition having a high molecular weight polyurethane polymer skeleton and capable of being polymerized by a double bond. A double bond-containing polyol compound containing (A) a compound containing two or more active hydrogens and (B) at least one group of an acryloyl group, a methacryloyl group and an isopropenyl group and a plurality of hydroxy groups. When,
(C) A urethane prepolymer having an isocyanate group at its end is obtained by a reaction with an organic polyisocyate, and this is dispersed in water. The terminal isocyanate of the urethane prepolymer in this dispersion is polymerized with a polyamine compound, a ketimine compound, or water to obtain a radiation curable polyurethane emulsion composition. [Effect] Since the polyurethane contained in this emulsion composition has sufficiently high molecular weight, a coating film using this can form a film having excellent strength and the like only by drying, and can be further improved by photopolymerization. Exhibits excellent physical properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation curable polyurethane polymer emulsion which is polymerized by irradiation with radiation and a method for producing the same.

[0002]

2. Description of the Related Art Polyurethane resins have hitherto been widely used as useful materials for adhesives, paints, modifiers and the like. On the other hand, recently, when a solvent-based resin is used, the solvent scatters into the air when used, polluting the environment and damaging the human body. Therefore, an aqueous solution or an aqueous emulsion-based synthetic resin has been regarded as beneficial in each market. . Also in the polyurethane resin, a water-soluble or aqueous emulsion type is being used in the field of adhesives, paints and the like, instead of the conventional solvent type using an organic solvent, and its use study is rapidly progressing. As described above, the present situation is that the water-soluble or water-based emulsion type polyurethane resin is in the direction of expanding its use in the future.

As one of the water-soluble or aqueous emulsions used in these, there is an emulsion using a thermoplastic polyurethane polymer having a relatively high molecular weight region mainly composed of a linear structure. These emulsions are
A hydrophilic group such as anion, cation, or nonion is introduced into the urethane skeleton for self-emulsification or dispersion, or an emulsifier is added to the hydrophobic polyurethane resin to forcibly disperse in water.

On the other hand, in recent years, radiation curable resins which are polymerized by various kinds of radiation such as ultraviolet rays and electron beams have the advantages of energy saving, low temperature processing in a short time, and thus the demand is rapidly expanding especially in the paint industry. ing.
Among these conventional radiation-curable resin technologies, non-aqueous type resins predominate. Since these radiation curable resins are directed to energy saving, low temperature, and short-time processing as described above, 100% of the constituent components are composed of these resin components, and the mainstream is radiation curable in the medium molecular weight range. It contains a resin and a large amount of a low molecular component of a monomer for adjusting viscosity for improving coating suitability, that is, a so-called reactive diluent monomer. As the reactive diluent monomer, for example, vinyl acetate, vinylpyrrolidone,
Alkyl acrylic ester etc. can be mentioned.

[0005]

However, such a conventional water-soluble or aqueous polyurethane polymer emulsion has the following problems.

That is, since the above-mentioned prior art polyurethane polymer emulsion uses a linear thermoplastic polyurethane having a relatively high molecular weight, for example, heat resistant adhesiveness,
At present, the performance such as solvent resistance and chemical resistance is insufficient, and improvement of these performances is desired. Further, in order to improve various drawbacks of these conventional polyurethane polymer emulsions, it has been attempted to blend various crosslinking agents such as melamine type such as trimethylolmelamine, epoxy type and blocked isocyanate type. As a result, although some improvement in performance has been recognized, most of them are still insufficient in performance. Further, when crosslinking is carried out by adding these cross-linking agents, a coating film having high film strength at the temperature required for drying, for example, because a treatment temperature higher than the reaction temperature of the reactive group of the cross-linking agent body is required. The advantage of conventional polyurethane polymer emulsions that they can be formed is compromised. Further, considering the heat resistance of the adherend material, the processing conditions are restricted and the applicable range is limited.

Therefore, the actual situation is that no satisfactory material has been developed yet.

This lack of performance is primarily due to the fact that the prior art polyurethane polymer emulsions do not have functional groups which react with these crosslinkers. That is, it is considered that the conventional modification with these crosslinking agents is due to the entanglement of polymer molecules such as an interpenetrating network (IPN) between the polyurethane resin and the self-polymer of these crosslinking agents.

Therefore, the polyurethane having the advantage of the polyurethane polymer emulsion of the prior art that a high-strength coating film can be formed with energy of about dryness, and further, the polyurethane having the function of forming a network structure that improves various drawbacks of the prior art. Polymer emulsions are highly desirable and their presence is beneficial.

On the other hand, in the radiation curable resin of the prior art, a low molecular weight reactive diluent monomer for adjusting viscosity and film thickness is added to the medium molecular weight resin component in a proportion of 20 to 70 parts by weight. Therefore, the problem of safety management due to the addition of the reactive diluent monomer, that is, the problem of being harmful to the human body and the problem of odor pollution of the reactive diluent monomer are caused.

Further, when a large amount of these low molecular weight reactive diluent monomers are used in combination and polymerized, there are the following problems.

Many of the cured films or coatings have an odor characteristic of the starting resin, which is primarily due to the reactive diluent monomer. This odor is a very troublesome problem.

The excellent flexibility of a coating film obtained by using a radiation curable resin having a medium molecular weight region as a main ingredient is significantly impaired, and the coating film tends to become brittle.

Since the curing shrinkage that occurs during the polymerization of the low molecular weight reactive diluent monomer is significant, there is a problem in that poor adhesion between the coating film and the adherend material easily occurs.

In order to reduce or completely eliminate the above-mentioned drawbacks, it is an important subject to take chemical and industrial measures. A simple method to solve this problem is to reduce the amount of reactive diluent monomer used by adding water, but since the radiation curable resin in the prior art is insoluble in water, a small amount of it is used. Although water can be used and compounded, it cannot be compounded in a large amount. Therefore, this problem cannot be fundamentally solved. As a chemical method for solving this problem, it is the current situation that the radiation curable resin is made water-based.

On the other hand, Japanese Examined Patent Publication (Kokoku) No. 62-22816 discloses an ionomer urethane acrylate and a method for producing the same, which have these problems in view. Similarly, Japanese Patent Publication No. 3-166216 discloses an ionomer urethane acrylate and a method for producing the same.

In the former case, first, in the first step, the hydroxy acrylate is reacted with the organic diisocyanate, and then the remaining isocyanate group is reacted with the polyol compound. Then, a production method has been proposed in which an aminocarboxylic acid is reacted in water to convert it into a salt thereof, and the residual isocyanate group is subjected to chain extension reaction with water or diamine.

In the latter, first, a polyol compound, a carboxyl group-containing diol and an organic diisocyanate are reacted, and then a hydroxy acrylate is reacted,
Furthermore, a production method has been proposed in which the carboxyl group is converted into a salt and the remaining isocyanate group is subjected to a chain extension reaction with water or diamine.

According to the production methods of these publications, the hydroxyacrylate used in each of the methods has only one hydroxyl group, and therefore each has the following problems.

In the former method, a monohydroxy acrylate and an organic diisocyanate are first reacted to synthesize a partial acrylate of the isocyanate, and then reacted with a polyol to synthesize a urethane acrylate containing isocyanate. Therefore, all the terminals of the urethane acrylate containing isocyanate are not converted into isocyanate groups, and a state in which they are partially double bond groups occurs, and the number of isocyanate groups may be 2 or less. .

Therefore, in the chain extension reaction with the isocyanate group and water or diamine, which is carried out at the final stage, an ideal high molecular weight reaction may not be realized in some cases. Further, even when an ideal high molecular weight reaction can be realized, there is a problem that the range of the urethane structure is considerably limited.

Since the latter also uses monohydroxy acrylate in the same manner, the terminal of urethane acrylate is not completely converted to isocyanate group, and a state in which a double bond is partially generated occurs, and the same problem as the former is caused. Have

The present invention has been made to solve the above problems, and the object of the present invention is to further improve the polyurethane polymer skeleton so that the function of the polyurethane polymer skeleton can be sufficiently exhibited. It is an object of the present invention to provide a radiation-curable polyurethane polymer emulsion composition capable of improving the coating film strength by being sufficiently formed and capable of polymerizing a double bond, and a method for producing the same.

[0024]

The radiation curable polyurethane polymer emulsion composition of the present invention comprises (A) a compound containing two or more active hydrogens, and (B) an acryloyl group, a methacryloyl group and an isopropenyl group. A double bond-containing polyol compound containing at least one group selected from the group and a plurality of hydroxy groups,
(C) obtained by reaction with organic polyisocyate,
A water-based emulsion dispersion of a urethane prepolymer having an isocyanate group at the terminal, wherein the terminal isocyanate of the urethane prepolymer in the emulsion dispersion is a polyamine compound containing a primary amino group and / or a secondary amino group. A diamine and / or triamine ketimine compound,
And a compound selected from the group consisting of water and obtained by a high molecular weight reaction.

Further, the method for producing the radiation-curable polyurethane polymer emulsion composition of the present invention comprises the group consisting of (A) a compound containing two or more active hydrogens and (B) an acryloyl group, a methacryloyl group and an isopropenyl group. A double bond-containing polyol compound containing at least one group selected from and a plurality of hydroxy groups,
(C) a step of obtaining a urethane prepolymer having an isocyanate group at an end by a reaction with an organic polyisocyate, a step of emulsifying and dispersing the urethane prepolymer in water, and an end of the urethane prepolymer in the emulsion dispersion. A step of reacting an isocyanate with a polyamine compound containing a primary amino group and / or a secondary amino group, a ketimine compound of a diamine and / or a triamine, and a compound selected from the group consisting of water, to obtain a high molecular weight compound; It is characterized by including.

The urethane prepolymer used in the present invention has an isocyanate group at the terminal and contains an acryloyl group, a methacryloyl group and an isopropenyl group in the molecule and / or the side chain.

Examples of the compound containing two or more active hydrogens include compounds having a plurality of hydroxyl groups at the terminal and / or side chain. For example, polyether polyols obtained by single or copolyaddition of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, low molecular weight glycols, polyether polyols obtained by polyadding the alkylene oxides to triols, polyester polyols, polycarbonates. Examples thereof include polyols, caprolactone polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, and silicone polyols. The molecular weight of the compound containing two or more active hydrogens is 500.
It is preferably in the range of to 5,000.

If necessary, low molecular weight 1,4-butanediol, 1,6-hexanediol, 3-methyl-
1,5-Pentanediol, ethylene glycol, neopentyl glycol, diethylene glycol, trimethylolpropane, glycol such as cyclohexanedimethanol, triol and the like may be used.

The double bond-containing polyol compound contains at least one group selected from the group consisting of an acroyl group, a methacryloyl group and an isopropenyl group, and a plurality of hydroxy groups. Specific examples include monoacrylates and monomethacrylates of triols such as glycerol and tomethylolpropane. Further, tetraol mono- or diacrylates such as pentaerythritol and mono- or dimethacrylates may be mentioned. Furthermore, mono- or di-acrylates or methacrylates of alkylene oxide adducts such as the above triols and tetraols can be mentioned. As mentioned above, acrylic acid ester and methacrylic acid ester derivatives containing at least two hydroxyl groups are one group.

For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and other monohydroxyalkyl acrylates and methacrylates, and hexamethylene diisocyanate,
Diisocyanates such as xylylene diisocyanate, cyclohexylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and tetramethyl xylylene diisocyanate, and triols such as trimethylolpropane, glycerol, caprolactone triol, diethanolamine and toethanolamine, amino alcohols And an addition reaction product thereof with.

In this case, the molar ratio of each is preferably monohydroxyalkyl acrylate, methacrylates: diisocyanates: triol, amino alcohols = 1: 1: 1 to 1.2.

In addition to the above, monohydroxyalkyl acrylates and methacrylates, triisocyanates which are trimers of the diisocyanates such as burette and malate, ethylene glycol, 1,4-butanediol and 1,6 -Hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol,
Diethylene glycol, cyclohexanedimethanol,
Examples thereof include addition reaction products with glycols such as monoethanolamine and amino alcohols.

In this case, the respective molar ratios are as follows: monohydroxy acrylate, methacrylates: triisocyanates: glycol, aminoacoles =
It is preferable that the ratio is 1: 1: 1 to 2.2.

These addition reactions are carried out by reacting the monohydroxy acrylates with the isocyanates,
The addition reaction of the triol and amino alcohol is carried out.

The reaction temperature is preferably 20 ° C. to 80 ° C., and a polymerization inhibitor such as benzoquinone, hydroquinone, hydroquinone monomethyl ether, phenothiazine or the like which is generally used for preventing the polymerization of double bonds. And a reaction catalyst such as commonly used dibutyltin dilaurate, stanas octoate, triethylamine, etc., which accelerates the reaction between the hydroxyl group and the isocyanate group, and further, in the reaction with an organic solvent that does not react with the isocyanate group. Alternatively, it may be added after completion of the reaction. As these organic solvents, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane,
There are ethyl acetate and the like.

As described above, a polyol compound containing an acryloyl group and a methacryloyl group, which is a urethane compound of at least two acrylates and methacrylates, can be obtained.

As other examples of the double bond-containing polyol compound, 2-methacryloyloxyisocyanate represented by the structural formula of Chemical formula 1 and m represented by the structural formula of Chemical formula 2 are given.
-Addition reaction products of isopropenyl-α, α-dimethylbenzyl isocyanate, methacryloyl isocyanate represented by the structural formula of Chemical formula 3 and the like, and amino alcohols such as the triols, diethanolamine and triethanolamine. In this case, the respective molar ratios are such that the isocyanates of Chemical Formula 1 to Chemical Formula 3 above: the triol, aminoalcohols = 1: 1 to 1.2, and these addition reactions are carried out according to the reaction procedure described above. The same is done.

[0038]

[Chemical 1]

[0039]

[Chemical 2]

[0040]

[Chemical 3]

Next, as the organic polyisocyanate compound used in the present invention, an aromatic, aliphatic or alicyclic organic polyisocyanate which has been conventionally used is used. For example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, water-added xylylene diisocyanate, organic polyisocyanates such as tetramethyl xylylene diisocyanate or a mixture thereof. .

Incidentally, after the urethane prepolymer described below is emulsified and dispersed in water, the reaction with water, diamine or triamine, or a ketimine compound of diamine or triamine, and subsequent maintenance of the emulsion-dispersed state, storage stability, etc. When considering, as the organic polyisocyanate used here, dicyclohexylmethane diisocyanate, isophorone diisocyanate, alicyclic organic polyisocyanate typified by water-added xylylene diisocyanate, and typified by tetramethyl xylylene diisocyanate Organic polyisocyanate compounds having a tertiary isocyanate group are preferred. It is also preferable to mix these organic polyisocyanates with aromatic polyisocyanates such as the above-mentioned tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and xylylene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate. In this case, it is preferable to mix and use at least an equimolar amount or more of the alicyclic polyisocyanate and a polyisocyanate compound having a tertiary isocyanate group with respect to the isocyanate group located at the terminal of the urethane polymer.

The reaction between the compound containing two or more of these active hydrogens, the double bond-containing polyol compound and the excess amount of the organic polyisocyanate is carried out by acryloyl group,
Considering the prevention of polymerization of the double bond of the methacryloyl group or the isopropenyl group, it is preferably carried out at a temperature of 50 to 80 ° C. At this time, in order to prevent the polymerization of the acryloyl group, the methacryloyl group or the isopropenyl group, benzoquinone, hydroquinone, hydroquinone monomethyl ether, or using a polymerization inhibitor such as phenothiazine,
Dry air may be introduced. Furthermore, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannas octoate, or triethylamine, which is commonly used to accelerate the reaction between the hydroxyl group and the isocyanate group, may be used.

Depending on the viscosity of the reaction system, an organic catalyst that does not react with an isocyanate group may be added so that the reaction system can be smoothly stirred. Examples of these organic catalysts include acetone, methyl ethyl ketone, tetrahydrofuran and dioxane. , Ethyl acetate toluene and the like. In consideration of the action of the double bond as a chain transfer agent, the concern about the generation of peroxide due to oxidation, and the solvent recovery described later, ethyl acetate is a more preferable solvent. However, these solvents are preferably selected for each case.

If necessary, a stabilizer such as an antioxidant can be added during the reaction or after the reaction. As a preferable antioxidant, a semicarbazide type antioxidant is preferable. The reason is that when the radiation curable polyurethane polymer emulsion composition, which is the final product of the present invention, is used and radiation curing is performed as the final processing,
This is because there is relatively little adverse effect on the curability.

The content of the isocyanate group at the terminal of the urethane polymer obtained here is preferably 5.0 to 0.3% by weight, more preferably 4.0 to 0.3% by weight, and 3.0.
˜1.0 wt% is more preferred.

When the content of the terminal isocyanate group is more than 5.0% by weight, when the reaction with water or a polyamine or ketimine compound described later is performed, the emulsion is broken and gels.
Alternatively, the stability and the temporal stability of the emulsion composition become poor. When the content of the terminal isocyanate group is less than 0.3% by weight, physical properties such as large coating film strength and chemical resistance of the polyurethane polymer skeleton can be obtained even when a high molecular weight reaction with water, polyamine or ketimine compound described below is carried out. It cannot be expressed and is not preferable.

The amount of the double bond-containing polyol compound used here is set so that the radiation-curable polyurethane polymer emulsion composition of the present invention exhibits physical properties such as high coating strength and chemical resistance. In order to exhibit high coating film strength, chemical resistance, and other physical properties when used in combination with other diluent monomers described later, at least a double bond number having a bromine number of 1.0 g or more per 100 g of resin solids is contained. It is preferable to design it.

When the amount of the double bond component of the double bond-containing polyol compound is designed to be a value lower than 1.0 g of bromine, not only the cured physical properties of the resin itself, that is, the strength of the coating film after curing, When used in combination with other diluent monomers described later, the physical properties such as coating film strength are also unsatisfactory, which is not preferable.

As described above, the urethane prepolymer having an isocyanate group at the terminal of the molecule and containing at least one group selected from the group consisting of an acryloyl group, a methacryloyl group and an isopropenyl group in the molecule and / or in the side chain. (Hereinafter referred to as "urethane prepolymer") is obtained.

Next, the urethane prepolymer is emulsified and dispersed in water. The following method can be adopted as the method.

In the above-mentioned urethane prepolymer preparation step, a carboxyl group is previously introduced into the molecule by reacting a carboxyl group-containing polyol component such as dimethylolpropionic acid with an organic polyisocyanate.
A method in which the carboxyl group is neutralized with a basic compound such as triethylamine, trimethylamine, diethanolmonomethylamine, diethylethanolamine, caustic soda, or potassium hydroxide to convert to a carboxyl group salt.

In the above-mentioned urethane prepolymer preparation step, a tertiary amino group is previously introduced into the molecule by the reaction of a tertiary amino group-containing polyol component such as triethanolamine, N-methyldiethanolamine or the like with an organic polyisocyanate. Then, the tertiary amino group is reacted with an organic acid such as formic acid and acetic acid, an inorganic acid such as phosphoric acid, hydrochloric acid and sulfuric acid, a quaternizing agent such as diethyl sulfuric acid and an alkyl halide, and a tertiary amine salt or A method of converting to a quaternary amine salt form.

In the above-mentioned urethane prepolymer preparation step, a nonionic activator having an oxyethylene chain content of 5 to 20% by weight in the molecule and an HLB value of 6 to 18 is prepared at 50 ° C. after preparation of the urethane prepolymer. The method of adding and mixing below.

However, the amount of the activator used is preferably 2 to 15% by weight based on the urethane prepolymer in consideration of the emulsifying dispersibility, the water resistance of the obtained film and the like.

After preparing the above-mentioned urethane prepolymer, 50 to 5% of the terminal isocyanate groups is more preferably 30
A method of reacting an aqueous solution of sodium ethane, potassium salt such as aminoethanesulfonic acid or aminoacetic acid corresponding to ˜5% at 5 to 50 ° C., preferably 20 to 40 ° C. for 60 minutes can be mentioned.

After performing any of the above operations,
Water is added and emulsified and dispersed using an emulsifying and dispersing device such as a homomixer and a homogenizer. When emulsifying and dispersing, in order to suppress the reaction between the terminal isocyanate group of the urethane prepolymer and water, the emulsifying and dispersing temperature is preferably low, 5 to 40 ° C, and more preferably 5 to 30 ° C. It is preferably carried out in the range of 5 to 20 ° C.

Next, the urethane prepolymer having an isocyanate group at the molecular end is subjected to a high molecular weight reaction in an emulsion. As the method, the following method can be adopted. A method for carrying out a high molecular weight reaction while forming a urea bond by the reaction between a terminal isocyanate group and water. A method of carrying out a high molecular weight reaction while forming a urea bond by reacting a terminal isocyanate group with a polyamine such as diamine or triamine. A method of carrying out a high molecular weight reaction while forming a urea bond by a reaction between a terminal isocyanate group and a ketimine compound.

In the above case, after the emulsification operation described above is carried out, a urea bond is formed by the reaction between the terminal isocyanate group and water contained in the polymer emulsion composition. This reaction is carried out at an emulsification system temperature of 5 to 40 ° C., preferably 1
It is usually carried out in the range of 5 to 30 ° C. for 30 to 120 minutes.

Examples of the polyamines used above include diamines and triamines. Specifically, those having two primary amino groups and / or two secondary amino groups in the inside thereof include, for example, ethylenediamine, piperazine and N. −
Examples include aminoethylpiperazine, isophoronediamine, dicyclohexyldiamine, hexamethylenediamine, and other hydrazine. As one having three primary amino groups and / or secondary amino groups, for example, diethylenetriamine, a low-molecular-weight triamine composed of ethyleneimine can give.

These diamine and triamine compounds are
Used so that the ratio of (the number of moles of terminal isocyanate groups of the urethane prepolymer) / (the number of moles of the primary and / or secondary amino groups of the polyamine compound) is 1/1 to 1 / 0.7. It is preferable to determine the amount. This ratio is
In particular, if it is less than 1/1 (the molar ratio of amino groups is large), effective high molecular weight tends to be hindered or the emulsion system tends to be destroyed, which is not preferable.

In the reaction here, an emulsifying and dispersing device such as a homomixer or a homogenizer is used in order to carry out a uniform reaction. Further, in consideration of rapid reaction, gelation caused by emulsion destruction due to local reaction, product stability afterwards, stability over time, 5 to 40 ° C, preferably 5 to 30 ° C,
More preferably, the reaction is carried out in the temperature range of 5 to 20 ° C,
Usually, the high molecular weight reaction of diamine and triamine is carried out for 10 to 60 minutes.

Examples of the ketimine compound used in the above include the ketimine compounds dehydrated between the primary amino groups of the above-mentioned diamines and triamines and isobutyl ketone.

The amount of these ketimine compounds used is set so that the number of moles of the primary amino group produced by hydrolysis and the contained secondary amino group and the number of moles of the terminal isocyanate group are the same as described above. It The reaction temperature, time and operating method are the same as those described above.

By the above reaction, the radiation-curable polyurethane polymer emulsion composition of the present invention is obtained.

[0066]

The radiation-curable polyurethane polymer emulsion composition of the present invention and the method for producing the same are characterized in that a double bond-containing polyol compound containing an acryloyl group, a methacryloyl group or an isopropenyl group is used to introduce a polymerizable double bond. To do. A compound containing two or more active hydrogens, a polymerizable double bond-containing polyol,
By the reaction with an excessive amount of organic polyisocyanate, the polymerizable double bond is introduced into the molecule and / or the side chain of the polyurethane skeleton, so that all the molecular terminals become isocyanate groups. Therefore, the problem of the prior art using monohydroxyalkyl acrylate or the like that the molecular terminal is partially converted into a double bond component and not entirely converted into an isocyanate group does not occur. Therefore, the final reaction of the present invention is to sufficiently increase the molecular weight of the isocyanate group and the amine, and the insufficient strength of the final cured product due to insufficient formation of the polyurethane skeleton is also improved.

Since the radiation curable polyurethane polymer emulsion composition of the present invention is an aqueous emulsion,
Water can be used as the dilution medium. Therefore, viscosity control and film thickness adjustment can be easily performed. That is, there is a problem of residual odor peculiar to the monomer after curing caused by the reactive diluent monomer used together for the purpose of viscosity control and film thickness adjustment, which is caused by the radiation curable resin of the prior art, and resin curing shrinkage. It is possible to solve the problem of insufficient adhesion to the adherend material and the like.

The radiation-curable polyurethane polymer emulsion composition of the present invention comprises a fiber knitted fabric, a woven fabric, a non-woven fabric,
It can be used by being soaked or coated on wood, paper, leather, metal, plastic, etc., and can also be used for a wide range of applications such as vehicles for paint ink.

When it is necessary to increase the hardness of the cured film, a water-soluble reactive diluent monomer can be used in combination with the radiation-curable polyurethane polymer emulsion composition of the present invention. Examples of the water-soluble reactive diluent monomer include dimethylacrylamide, vinylpyrrolidone, ethylene glycol, diethylene glycol diacrylate, and low molecular weight polyethylene glycol diacrylate.

Further, since the radiation-curable polyurethane polymer emulsion composition of the present invention contains a polyurethane skeleton having a sufficiently high molecular weight, it can be dried to a similar degree to a conventional polyurethane emulsion of the prior art. It develops physical properties such as film strength and chemical resistance. for that reason,
For example, it can be used as a primer agent for a conventional ultraviolet curable coating material. That is, the emulsion composition of the present invention is applied to various substrates, dried, and then, a conventional ultraviolet curable coating material is applied and cured by irradiation with ultraviolet rays to improve the adhesiveness of the coating film. be able to.

Furthermore, the radiation-curable polyurethane polymer emulsion composition obtained in the present invention can be used in combination with other water-based resin emulsions. For example, it can be used as a modifier in combination with a general polyurethane emulsion, vinyl acetate, ethylene vinyl acetate copolymer, acrylic ester resin emulsion and synthetic rubber latex such as natural rubber, SBR and NBR.

A system in which the water-soluble reactive diluent monomer is used in combination with the radiation-curable polyurethane polymer emulsion composition obtained in the present invention may be added to the other water-based resin emulsion and used as a modifier. It is useful.

Further, the radiation-curable polyurethane polymer emulsion composition obtained by the present invention can be applied to curing by electron beam irradiation, curing by heat treatment, etc., in addition to curing by ultraviolet irradiation. Particularly in the case of curing by heat treatment, the emulsion composition of the present invention achieves sufficient curing, as compared with urethane acrylate having an oligomer-level molecular weight. It is considered that this is because the composition of the present invention has a polyurethane polymer skeleton, and thus, when forming a film by drying, inhibition of curing of double bonds by air (oxygen) is prevented.

[0074]

The radiation-curable polyurethane emulsion composition according to the present invention has the following unique effects.

Since it is an aqueous emulsion, it is possible to adjust the viscosity for adjusting the coating film thickness and the like by adding water.

From the viewpoint of physical properties, since the polyurethane skeleton is sufficiently formed, and thus the high molecular weight has been achieved, physical properties such as coating strength and chemical resistance equivalent to those of a polyurethane emulsion generally obtained only by drying are obtained. And further excellent physical properties are exhibited by radiation polymerization.

The use of double bond-containing polyols instead of conventional hydroxy acrylates provides greater freedom in the design of polyurethane structures and, therefore, meets the performance requirements of various applications.

The method for producing the radiation-curable polyurethane polymer emulsion composition of the present invention has the following features. That is, by reacting a compound containing two or more active hydrogens, a double bond-containing polyol compound containing an acryloyl group, a methacryloyl group, or an isopropenyl group, and an organic polyisocyanate, a urethane molecule and / or a side chain is formed. All the terminals of the urethane prepolymer containing an acryloyl group, a methacryloyl group, or an isopropenyl group are converted into isocyanate groups. Thereby, it is possible to sufficiently increase the molecular weight in the final step.

[0079]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
Unless otherwise specified, "parts" and "%" in Examples, Experimental Examples, Comparative Examples and Comparative Experimental Examples described below represent parts by weight and% by weight, respectively.

Example 1 Polyether polyol (P
O / EO = 90/10, molecular weight 2,000) 300 parts,
Trimethylolpropane 13.0 parts, polyethylene glycol (molecular weight 600) 35 parts, polyether polyol (PO / EO = 30/70, random copolymer, molecular weight 3,400) 35 parts, 1,4-cyclohexanedimethanol 93 Part, glycerol monomethacrylate (hydroxyl value (OH · V) = 678, molecular weight 165.4) 36
Parts and 0.4 parts of hydroquinone monomethyl ether were dissolved in 300 parts of ethyl acetate. Under the condition of a temperature of 50 ° C., 310 parts of isophorone diisocyanate and 0.08 part of dibutyltin dilaurate were added, and the reaction was carried out at 75 ° C. for 3 hours to obtain a terminal isocyanate group of 1.8.
A urethane polymer having a% (relative solid content) was obtained.

Next, 55 parts of a nonionic surfactant (ethylene oxide polyaddition product of distyrenated phenol, HLB = 15) was added and mixed under the condition that the system temperature was 50 ° C., and then a homomixer (rotation speed 4, 2,000 rpm), 1,200 parts of ion-exchanged water was added little by little with stirring, and emulsification was carried out under the condition of the system temperature of 30 ° C.

Next, the system temperature was cooled to 25 ° C., 97.4 parts of an aqueous solution of ethylenediamine (10% strength aqueous solution) was added dropwise over 5 minutes, and then, continuously, using a homomixer at 4,000 rpm. Polymerization and dispersion operation with 60
It was carried out for a minute.

Next, heat using an evaporator,
90% of the ethyl acetate solvent used under the condition of hot water 60 ℃
It was collected under reduced pressure over a period of minutes.

As described above, a white liquid radiation-curable polyurethane polymer emulsion composition having a solid content of 40% was obtained. The bromine number (Br.
V) is 3.90 (converted value per 100 g of solid content).

(Example 2) Polyether polyol (P
O / EO = 90/10, molecular weight 2,000) 300 parts,
12.9 parts of trimethylolpropane, 92.0 parts of 1,4-cyclohexanedimethanol, 36.0 parts of glycerol monomethacrylate, and 0.38 part of hydroquinone monomethyl ether were dissolved in 300 parts of ethyl acetate. Isophorone diisocyanate, 333 parts, and dibutyltin dilaurate 0.04 parts were added under the condition of the system temperature of 50 ° C., and the reaction was carried out for 60 minutes under the condition of 75 ° C.,
A urethane prepolymer having 3.8% of terminal isocyanate groups (based on solid content) was obtained.

Next, 26 parts of dimethylolpropionic acid and 0.04 part of dibutyltin laurate were added under the condition of the system temperature of 50 ° C., and the reaction was carried out at 75 ° C. for 300 minutes to obtain a terminal isocyanate. A urethane prepolymer having 1.60% groups (relative to solids) was obtained.

Next, 19.6 parts of triethylamine was added and mixed for 15 minutes under a system temperature of 50 ° C. to carry out a neutralization reaction.

Next, 1,100 parts of ion-exchanged water was added, and emulsification was carried out with a homomixer while stirring at a rotation speed of 4,000 rpm.

Next, 96.0 parts of an aqueous solution of ethylenediamine (10% concentration aqueous solution) was added to the solution under the condition of the system temperature of 20 ° C.
Drip over a period of minutes, then use a homomixer to 40
Polymerization and dispersion were carried out at 00 rpm for 60 minutes.

Next, heat using an evaporator,
90% of the ethyl acetate solvent used under the condition of hot water 60 ℃
It was collected under reduced pressure over a period of minutes.

As described above, a white liquid radiation curable polyurethane polymer emulsion composition having a solid content of 40% was obtained. The bromine number (Br · V) indicating the double bond amount of the composition is 4.30 (converted value per 100 g of solid content).

Example 3 Polyester polyol (butylene adipate, molecular weight 2,000) 300 parts, trimethylolpropane 12.9 parts, polyethylene glycol (molecular weight 600) 35 parts, polyether polyol (PO / EO = 30/70) , Random copolymer, molecular weight 3,400) 35 parts, glycerol monomethacrylate (hydroxyl value (OH · V) = 678, molecular weight 165.4)
80 parts, and hydroquinone monomethyl ether 0.3
Parts were dissolved in 300 parts ethyl acetate. Next, 164 parts of hexane methylene diisocyanate at 50 ° C.,
0.01 part of dibutyltin dilaurate was added.

The reaction was carried out for 180 minutes at a temperature of 75 ° C. to obtain 1.80% of terminal isocyanate groups (on solid content).
A urethane prepolymer having

Then, 50 parts of a nonionic surfactant (ethylene oxide polyadduct of distyrenated phenol, HLB = 15) was added under the condition of 50 ° C. in the system and mixed for 15 minutes.

Then, using a homomixer, 4,000 r
While stirring at pm, 1,000 parts of ion-exchanged water was added little by little, and emulsification was carried out under the condition of 30 ° C.

Next, an aqueous solution prepared by mixing 7.5 parts of hydrazine hydrate and 63 parts of ion-exchanged water was added, and polymerization and dispersion operations were carried out for 90 minutes at 25 ° C.

Next, heat using an evaporator,
90% of the ethyl acetate solvent used under the condition of hot water 60 ℃
It was collected under reduced pressure over a period of 1 minute.

As described above, a white liquid radiation curable polyurethane polymer emulsion composition having a solid content of 40% was obtained.

The bromine number (Br · V) showing the amount of double bonds in this composition was 11.5 (converted value per 100 g of solid content).
Is.

(Example 4) Polyether polyol (P
O / EO = 90/10, molecular weight 2,000) 300 parts,
Trimethylolpropane 12.9 parts, polyethylene glycol (molecular weight 600) 35 parts, polyether polyol (PO / EO = 30/70, random copolymer, molecular weight 3,400) 35 parts, 1,4-cyclohexanedimethanol 92 0.5 parts, 137 parts of a urethane acrylate diol ethyl acetate solution separately prepared by the procedure described below (solid content 60%, hydroxyl value (OH · V) = 176), and 0.4 parts of hydroquinone monomethyl ether were added to 300 parts of ethyl acetate. Dissolved in part. Next, 287 parts of isophorone diisocyanate and 0.08 part of dibutyltin dilaurate were added, and then the reaction was carried out for 170 minutes under the condition of 75 ° C. to obtain urethane having terminal isocyanate groups of 1.60% (solid content). A prepolymer was obtained.

Next, under the condition of 50 ° C., 59 parts of a nonionic surfactant (ethylene oxide polyadduct of distyrenated phenol, HLB = 15) was added and mixed.

Then, using a homomixer, 4,000 r
At pm, add 1,600 parts of ion-exchanged water to 30
The emulsification was carried out under conditions of ° C.

Next, 115 parts (10% concentration) of an ethylenediamine aqueous solution was added under the condition of 20 ° C., and thereafter, polymerization and dispersion operations were carried out for 60 minutes at 4,000 rpm using a homomixer.

Then, the solvent was recovered in the same manner as in Example 3.

As described above, a white liquid radiation curable polyurethane polymer emulsion composition having a solid content of 35% was obtained. The bromine number (Br.
V) is 2.23 (converted value per 100 g of solid content).

<Preparation of Urethane Acrylate Diol>
Isophorone diisocyanate 222 parts ethyl acetate 42
Dissolved in 0 parts, dibutyltin dilaurate 0.03
Parts, and 0.3 parts of hydroquinone monomethyl ether.

Next, 120 parts of hydroxyethyl acrylate was added dropwise over 90 minutes under the condition that the system temperature was 60 ° C. Next, the reaction was carried out at 70 ° C. for 120 minutes to obtain a urethane acrylate having 12.5% of terminal isocyanate groups (versus solid content).

Next, 310 parts of caprolactone triol (molecular weight 300) was added and the reaction was carried out at 70 ° C. to confirm that the isocyanate group had completely disappeared.

By the above, the urethane acrylate polyol was prepared. The hydroxyl value (OH · V) of the obtained urethane acrylate polyol was 176.

Comparative Example 1 Polyether polyol (P
O / EO = 90/10, molecular weight 2,000) 300 parts,
12.9 parts of trimethylolpropane, polyethylene glycol (molecular weight 600), polyether polyol (P
O / EO = 30/70, random copolymer, molecular weight 3,
400) 35 parts, 1,4-cyclohexanedimethanol 129 parts, hydroxyethyl acrylate 35 parts, and hydroquinone monomethyl ether 0.4 parts were dissolved in ethyl acetate 300 parts. Next, 360 parts of isophorone diisocyanate and 0.08 part of dibutyltin dilaurate were added and the reaction was carried out for 250 minutes at 75 ° C. to give a urethane prepolymer having 1.90% of isocyanate groups (relative to solid content). Obtained.

Then, under conditions of 50 ° C., 61 parts of a nonionic surfactant (ethylene oxide polyadduct of distyrenated phenol, HLB = 15) was added and mixed.

Then, using a homomixer, 4,000 r
At pm, 1,300 parts of ion-exchanged water was added to emulsify.

Next, 110 parts (10% concentration) of an ethylenediamine aqueous solution was added under the condition of 25 ° C., and thereafter,
Polymerization and dispersion were carried out for 60 minutes at 4,000 rpm using a homomixer.

Then, the solvent was recovered in the same manner as in Example 3.

As described above, a white liquid polyurethane acrylate emulsion composition having a solid content of 40% using hydroxyethyl acrylate according to the prior art was obtained.

The bromine number (Br · V) indicating the double bond amount of this composition is 3.9 (converted value per 100 g of solid content).

(Experimental Examples 1-10) The radiation-curable polyurethane emulsion compositions prepared in Examples 1-4 were used, and in the case of Experimental Examples 5-10, the photosensitizer shown in Chemical formula 4 was added and blended. The coating film was adjusted. The coating used in each experimental example was coated on a Teflon plate, dried overnight at room temperature, and
It was prepared by drying at 0 ° C. for 2 hours. Experimental Example 5
In the case of 10, the high pressure mercury lamp (irradiation intensity 80
Photopolymerization was carried out by irradiating with ultraviolet rays using W / cm and an illumination point distance of 8 cm. The film thickness of each coating is 200 microns.

[0118]

[Chemical 4]

The physical properties of the coating film after curing were measured by the methods described below. The results are shown in Table 1. Table 1 also shows the case where no photosensitizer was added. The photosensitizer is a photosensitizer shown in Chemical formula 4 / polyoxyethylene allylphenol ether type nonionic surface activity (HLB = 15) / water = 10.
It was added as a mixed aqueous solution of 1 part / 8 parts / 82 parts.

(Comparative Experimental Examples 1 to 3) The radiation curable polyurethane emulsion of the prior art obtained in Comparative Example 1 was used. In Comparative Experimental Example 1, Comparative Experimental Examples 2 and 2 were conducted in the same manner as in Experimental Examples 1 to 4. In the case of 3, a photosensitizer was added and photopolymerization was carried out in the same manner as in Experimental Examples 5 to 10 to obtain a coating film. The physical properties of the coating film after curing were measured, and the physical property measurement results are also shown in Table 1.

[0121]

[Table 1]

Among the physical properties shown in Table 1, strength, elongation and 1
00% modulus (100% MO) and 200% modulus (200% MO) are tensile tester (Autograph manufactured by Shimadzu Corporation) according to JIS-K-6301.
Was measured at a pulling speed of 100 mm / min.

Solvent resistance is ethyl acetate / toluene = 1 /
Immerse a 2 x 4 cm piece of film in the solvent of 1 and leave at 24
It was measured by the coefficient of expansion (%) of the coating area after time immersion with respect to the coating area before immersion. The expansion coefficient is obtained by the following equation (1). The smaller the value of the expansion coefficient, the better the solvent resistance. Coefficient of film expansion = 100 × (area after immersion−initial area) /
(Initial area) (1) The water resistance was measured by immersing a 2 × 4 cm film piece in hot water at 70 ° C. and swelling the film area at 70 ° C. for 24 hours. The expansion coefficient is obtained by the above equation (1). The smaller the value of the expansion coefficient, the better the water resistance.

The following results show that the coating films of Experimental Examples 5 to 10 in which the radiation-curable polyurethane emulsion composition of each of the above Examples was added and the photosensitizer was added and the photopolymerization were Compared with the coating film of No. 4, obviously the film strength,
Elongation, modulus, solvent resistance, and water resistance are improved.

Further, the coating films of Experimental Examples 1 to 4 in which no photosensitizer was added exhibited the same or higher physical properties as those of the coating film of Comparative Experimental Example 1 prepared from a general polyurethane emulsion. .

As described above, since the polyurethane contained in the radiation-curable polyurethane emulsion composition of each of the above-described examples has a sufficiently high molecular weight, a coating film using this is generally dried only. The same physical properties as a coating film prepared from a polyurethane emulsion are exhibited, and more excellent physical properties such as film strength are exhibited by photopolymerization.

On the other hand, the prior art radiation-curable polyurethane emulsion using hydroxy acrylate is
Since it has not been sufficiently polymerized, the physical properties of the urethane film are extremely low only by drying. Further, although the physical properties are improved by photopolymerization, it is obviously low.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 11, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

The urethane prepolymer used in the present invention has an isocyanate group at the terminal and contains an acryloyl group, a methacryloyl group or an isopropenyl group in the molecule and / or the side chain.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

[0029] The double bond-containing polyol compound, A
It contains at least one group selected from the group consisting of acryloyl group , a methacryloyl group and an isopropenyl group and a plurality of hydroxy groups. Specific examples thereof include monoacrylates and monomethacrylates of triols such as glycerol and trimethylolpropane . Also,
Tetraol mono- or diacrylates such as pentaerythritol, mono- or dimethacrylates may be mentioned.
Furthermore, mono- or di-acrylates or methacrylates of alkylene oxide adducts such as the above triols and tetraols can be mentioned. As mentioned above, acrylic acid ester and methacrylic acid ester derivatives containing at least two hydroxyl groups are one group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In addition, the monohydroxyalkyl acrylates and methacrylates, triisocyanates which are trimers of the diisocyanates such as burette and nurate , ethylene glycol, 1,4-butanediol and 1,6 -Hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol,
Diethylene glycol, cyclohexanedimethanol,
Examples thereof include addition reaction products with glycols such as monoethanolamine and amino alcohols.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

Depending on the viscosity of the reaction system, an organic catalyst that does not react with an isocyanate group may be added so that the reaction system can be smoothly stirred. Examples of these organic catalysts include acetone, methyl ethyl ketone, tetrahydrofuran and dioxane. , Ethyl acetate toluene and the like.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

If necessary, a stabilizer such as an antioxidant can be added during the reaction or after the reaction.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

When the amount of the double bond component of the double bond-containing polyol compound is designed so that the bromine number is lower than 1.0 g, the cured physical properties of the resin itself, that is, the strength of the coating film after curing is, of course, obtained. However, when used in combination with other diluent monomers described later, the physical properties such as coating film strength are also unsatisfactory, which is not preferable.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

After carrying out any of the above operations, water is added, and the mixture is emulsified and dispersed by using an emulsifying and dispersing device such as a homomixer and a homogenizer. When emulsifying and dispersing, in order to suppress the reaction between the terminal isocyanate group of the urethane prepolymer and water, the emulsifying and dispersing temperature is preferably low, 5 to 40 ° C, preferably 5 to 30 ° C.
It is more preferably carried out in the range of 5 to 20 ° C.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

<Preparation of Urethane Acrylate Diol>
Isophorone diisocyanate 222 parts ethyl acetate 42
Dissolved in 0 parts, dibutyltin dilaurate 0.03
Parts, and 0.3 parts of hydroquinone monomethyl ether.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Delete

Claims (2)

[Claims] 1. At least one selected from the group consisting of (A) a compound containing two or more active hydrogens and (B) an acryloyl group, a methacryloyl group and an isopropenyl group.
An emulsified dispersion of a urethane prepolymer having an isocyanate group at the terminal in water, which is obtained by reacting a double bond-containing polyol compound containing one group and a plurality of hydroxy groups with (C) an organic polyisocyanate. The terminal isocyanate of the urethane prepolymer in the emulsion dispersion is selected from the group consisting of polyamine compounds containing primary amino groups and / or secondary amino groups, diamine and / or triamine ketimine compounds, and water. A radiation-curable polyurethane polymer emulsion composition obtained by a high molecular weight reaction using a compound according to claim 1. 2. At least one selected from the group consisting of (A) a compound containing two or more active hydrogens and (B) an acryloyl group, a methacryloyl group and an isopropenyl group.
A double bond-containing polyol compound containing a single group and a plurality of hydroxy groups, and (C) an organic polyisocyanate,
The step of obtaining a urethane prepolymer having an isocyanate group at the terminal by the reaction of, the step of emulsifying and dispersing the urethane prepolymer in water, the terminal isocyanate of the urethane prepolymer in the emulsified dispersion is treated with a primary amino group and And / or a polyamine compound containing a secondary amino group, a ketimine compound of a diamine and / or a triamine, and a step of causing a high molecular weight reaction using a compound selected from the group consisting of water, A method for producing a radiation curable polyurethane polymer emulsion composition.