JP2000063514A - Water-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having sufficient coating film performance and such low viscosity as to be coatable by converting a solvent-free curable resin composition into an aqueous form. SOLUTION: This water-based resin composition is obtained by dissolving or dispersing in an aqueous medium (A) a multibranched compound described below and (B) a water-soluble unsaturated group-contg. compound in the weight ratio A/B of (1:99) to (60:40). The multibranched compound A is such one as to be prepared by addition of (c) an isocyanate group-contg. vinyl compound to a core compound having at least one active hydrogen and formed by Michael addition reaction between (a) a polyamino compound having primary or secondary amino group in the molecule and three or more active hydrogen atoms in the above amino group and (b) a hydrophilic long-chain group-contg. (meth) acrylic compound of the formula CH2=C(R1)COO-(CnH2nO)mR2 (R1 is H or methyl; R2 is phenyl or a 1-5C alkyl; (n) is 1-3; (m) is 1-25).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a film-forming or cured film without using a large amount of an organic solvent as a resin for a film-forming material such as paint or ink, or as a resin for a sealing agent, a molding agent, an adhesive or a pressure-sensitive adhesive. And a water-based resin composition that can be used as a curing agent or a reactive diluent for a radiation-curable resin composition. Furthermore, the aqueous resin composition obtained by the present invention can be used as a radiation-curable resin composition as a printing ink, a vehicle for paints, an adhesive, or the like.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used as fillers and molding materials. These resin solutions scatter a large amount of organic solvents in the painting, filling and curing / drying steps. With increasing interest in the global environment and working environment, restrictions on the use of such resin solutions are being imposed. As one of the methods, development of resin materials such as water-soluble resin, powder and hot melt has been promoted. In the case of coating or filling of powder or hot melt, it is necessary to introduce new equipment because the method is largely different from the conventional painting and filling equipment. On the other hand, in the case of a water-soluble resin, it is easy to be accepted by society from the viewpoints of resource saving, low pollution, safety, etc., and stable adhesiveness to a material weak against an organic solvent can be secured. There are an emulsion type and a water-soluble dispersion as a method of making the aqueous solution. The water-soluble type is generally one having a hydrophilic group and a double bond in the oligomer. Since the oligomer is water-soluble, it is excellent in leakage to the pigment and the coating workability is also good. However, it is generally a problem that the coating film is inferior in water resistance and moisture resistance. In order to solve the above-mentioned problems, high solidification of the resin solution, improvement of the water-soluble resin, and the like have been carried out, and it is considered that with such efforts, the tendency for the amount of the organic solvent used to decrease further becomes more remarkable in the future. However, the fundamental solutions are pollution, health and safety, flammability,
There is a strong demand for the development of a solventless liquid resin composition which is free from problems such as explosion and can be applied to a wide range and which can be easily applied and filled. A typical example of the solventless liquid resin composition is a radiation curable resin composition.
Conventional radiation-curable resin compositions include low-viscosity compounds such as various acrylic monomers, and urethane acrylates.
It is composed of a reactive oligomer such as epoxy acrylate or ester acrylate and, if necessary, other resin components. The low-viscosity compound is mainly used as a reactive diluent for the purpose of controlling the viscosity of the composition, but if it is contained in a large amount, volume shrinkage during curing is large,
The cured coating film is fragile, and odors and the like due to residual monomers in the coating film have been a problem. Therefore, improvements such as reduction in the amount of reactive diluent used and increase in molecular weight have been desired. Further, in order to improve the mechanical performance of the cured product, it is preferable to compound a polyfunctional reactive diluent, a reactive oligomer, and a high molecular weight resin material, etc., but these materials have high viscosity or solid. Considering the flow characteristics of the pre-curing composition,
A large amount of reaction diluent has to be blended, and the blending amount is limited. Therefore, a cured product obtained by curing a conventional solventless liquid resin composition is poor in cured product properties such as hardness, toughness, mechanical properties, and chemical resistance, and is practically a solvent-based or water-based resin composition. Was of a quality far below. Radiation-curable resin compositions containing large amounts of high-molecular weight reactive oligomers and resin materials have been developed for the purpose of improving coating film performance, but low-molecular weight reactive dilutions are used to reduce the viscosity to a coatable level. It is difficult to say that environmental improvements have been made due to the use of agents and organic solvents.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a water-based resin composition having a solvent-free curable resin composition which is water-based, has sufficient coating performance, and has a low viscosity for coating. The present invention provides a water-based resin composition in which the water resistance after curing is dramatically improved by utilizing a water-soluble vinyl group-containing compound. In addition, by using a multi-branched compound having a high molecular weight but a low viscosity, it is possible to reduce the compounding ratio of low molecular weight compounds such as a reactive diluent or an aqueous solvent having a problem in safety and performance, and drying property. The present invention provides an aqueous resin composition that enables the above. Further, the present invention, a coating method such as conventionally used roll coater, knife coater, offset printing, gravure printing, letterpress printing, screen printing can be formed into a film by a printing method such as heating, ultraviolet ray, infrared ray, electron beam. , An aqueous resin composition that can be cured by a conventional trigger such as γ-ray irradiation and can be cured without using a catalyst or an initiator, particularly in the case of electron beam, γ-ray irradiation, etc. It is a thing.

In order to solve the above-mentioned problems, the present inventor has conducted earnest research on the correlation between the structure of various resin systems and viscosity, and as a result, comb-shaped polymers, and further multi-branched polymers, rather than general linear polymers. By changing the molecular structure of the polymer as described above, it was found that the polymer has a high viscosity and low viscosity, and many functional groups can be introduced at the terminal. Compared to a linear polymer, a multi-branched compound has a high molecular weight, in which the arm is fixed to the central core part, so that the radius of gyration showing the spread of the polymer in the solution becomes small, which is good. It has been found that the water resistance and the drying property are improved because the viscosity can be made lower even in the solvent and the NV can be made higher. Further, they have found that the multi-branched compound has an active hydrogen-containing functional group at the terminal and exhibits good adhesion to a substrate, particularly to a plastic material which has been very difficult in a radiation curing system. Furthermore, by introducing a highly hydrophilic and flexible long chain group having an appropriate chain length, it becomes possible to achieve both high molecular weight and low viscosity before curing, while maintaining curability, and the mechanical properties of the cured product and It has been found that the adhesiveness with the base material is improved.
Although it has a high molecular weight, it is within the viscosity range that can be formed by the conventional film forming method, and by using the conventional curing method, especially electron beam as a curing trigger, it is possible to obtain a high level without using a catalyst or a reaction initiator. We have discovered a new aqueous resin composition that can be cured at a rate.

[0005]

That is, according to the present invention, the following multi-branched compound (A) and water-soluble unsaturated group-containing compound (B) are added (A) :( B) = 5: 95 to 100: 0 ( (% By weight) with respect to the aqueous resin composition dissolved or dispersed in the aqueous medium (C). Hyperbranched compound (A): a polyamino compound (a) having a primary or secondary amino group in the molecule and a hydrophilic long chain group-containing (meth) acrylic compound (b) represented by the following formula (1): A hyperbranched compound obtained by adding an isocyanate group-containing vinyl compound (c) to a core compound having at least one active hydrogen formed by a Michael addition reaction. ^{_{CH 2 = C (R 1)}} COO- (C n H 2n O) m R 2 (1) ( wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a phenyl group or a 1 to 5 carbon atoms Of the above, n is an integer of 1 to 3, and m is an integer of 1 to 25.) Furthermore, in the present invention, the polyamino compound (a) has the following formula (2).
The aqueous resin composition according to claim 1, which is a diamino compound represented by: _{H 2 N-CH 2 -R-} CH 2 -NH 2 (2) ( wherein, R is a direct bond, -C _r H _2r - _(r is from 1 to 20
Indicates an integer. ), A phenylene group or a cycloalkylene group. The present invention also relates to the aqueous resin composition according to claim 1 or 2, wherein the water-soluble unsaturated group-containing compound (B) has a viscosity of 1 to 10000 cps (30 ° C) or less. Further, the present invention is
Number average molecular weight of 200 to 10,000, viscosity of 1000
A water-based resin composition according to any one of claims 1 to 3, which comprises a liquid multi-branched compound (A) of 00 cps (30 ° C) or less. Furthermore, the present invention relates to a film forming material comprising the aqueous resin composition according to any one of claims 1 to 4.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamino compound (a) used in the present invention is used as a starting material for making a compound into a multi-branched structure, and active hydrogen derived from a primary amine or a secondary amine is added in the molecule in a total amount of 3 A compound having at least one,
Examples thereof include straight chain / branched aliphatic polyamino compounds, cyclic aliphatic polyamino compounds, aliphatic aromatic polyamino compounds, and aliphatic aromatic polyaminopolyol compounds.

As the linear / branched aliphatic amine used in the present invention, hydrazine compounds such as hydrazine and adipic acid dihydrazide, ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, diaminooctane, diaminodecane, Examples thereof include diamino compounds represented by the following general formula (2) such as diaminododecane, 2,5-dimethyl-2,5 hexamethylenediamine, polyoxypropylenediamine, diethylenetriamine and tetraethylenepentamine. Further, as the cycloaliphatic polyamino compound, mensendiamine, isophoronediamine, bis (4
-Amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4-bis (2 -Amino-2
-Methylpropyl) piperazine, polycyclohexylpolyamine, bis (aminomethyl) -bicyclo [2,2,2
1] Heptane, methylenebis (furanmethanamine) and the like can be mentioned. Further, examples of the aliphatic aromatic polyamino compound include meta-xylenediamine and para-xylenediamine. Further, examples of the aliphatic aromatic polyaminopolyol compound include ethylene oxide adduct of metaxylenediamine, propylene oxide adduct of metaxylenediamine, ethylene oxide adduct of paraxylenediamine, propylene oxide adduct of paraxylenediamine, and the like. You can Of these, use of a diamino compound generalized by the following formula (2) is preferable in that the shape of the core compound can be variously changed and mechanical properties after curing are improved. In _{H 2 N-CH 2 -R-} CH 2 -NH 2 (2) the general formula (2), R is a direct bond, -C _r H _2r -
(R represents an integer of 1 to 20, preferably 0 to 12.)
Is an alkylene group, a phenylene group, or a cycloalkylene group. Since these polyamino compounds (a) are starting materials for the core compound, it is more effective for the multibranched compound to have a lower viscosity and a higher functionality by containing amino groups at a higher density in one molecule. In order to satisfy such an object, it is preferable to use a low molecular weight diamino compound such as ethylenediamine or tetramethylenediamine or a polyamino compound having three or more primary or secondary amino groups such as diethylenetriamine.

The number average molecular weight of the polyamino compound (a) used in the present invention is not particularly limited,
As a preferable molecular weight range, a number average molecular weight of 30 to
A polyamino compound having a number average molecular weight of 500, particularly 1,000 or more is a compound having a number average molecular weight of 500, particularly 1000 or more, and may be unfavorable in handling because it has a high viscosity or is a solid.

In the present invention, when the polyamino compound (a) contains a primary amino group, two active hydrogens of the amino group and a hydrophilic long chain group-containing (meth) acrylic compound (b).
It is possible to make the core compound hyperbranched by the Michael addition reaction of. In the present invention, the hydrophilic long-chain group-containing (meth) acrylic compound (b) is a high molecular weight multi-branched compound and is a component for making it water-soluble, and can be represented by the following formula (1). CH ₂ = C in _{^{(R 1) COO- (C n}} H 2n O) m R 2 (1) ( the above formulas, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, 1 to phenyl or carbon atoms 5 alkyl group, n
Represents an integer of 2 to 4, m represents an integer of 1 to 25, and preferably 2 to 20. )

In the present invention, the chain length of the hydrophilic long chain group-containing (meth) acrylic compound (b) is preferably within the above range, and when the chain length is shorter than the above range, the water solubility decreases. , Becomes insoluble in water. When the chain length is longer than the above range, there is no problem in solubility in water, but the bulk viscosity of the multi-branched compound (A) may become high, or it may become a solid at room temperature, and the curability is further improved. It is not preferable because it may become scarce. Further, within the above range, when a hard cured product is required, a short chain length is preferable, and a long chain length is preferable for the purpose of improving flexibility. Further, within the above range, the bulk viscosity tends to decrease despite the increase in the molecular weight with the extension of the chain length. Further, in the general formula (1), when R ^{2 of the} hydrophilic long-chain group-containing (meth) acrylic compound (b) is a hydrogen atom, a hydroxyl group has a functional group capable of reacting with active hydrogen. It functions as a reaction site in the reaction with c).

Examples of the alkylene glycol mono (meth) acrylic compound (b) represented by the general formula (1) when R ² is a hydrogen atom include, for example, diethylene glycol mono (meth) acrylate and triethylene glycol. Mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetra Examples thereof include propylene glycol mono (meth) acrylate and polytetramethylene glycol mono (meth) acrylate.

When R ² is an alkyl group, the alkylene glycol (meth) acrylic compound (b) represented by the general formula (1) includes methoxytetraethylene glycol (meth) acrylate and ethoxytetraethylene glycol ( (Meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate,
n-Pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth)
Acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) Examples of the alkylene glycol (meth) acrylic compound (b) represented by the general formula (1) in the case where R ² is a phenyl group include acrylates and methoxypolytetramethylene glycol (meth) acrylate. Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxyte And La propylene glycol (meth) acrylate.

In the present invention, in addition to the hydrophilic long chain group-containing (meth) acrylic compound (b) in order to improve the physical properties after curing and the compatibility with other components, for example, the following general formula (3) is used. Other (meth) acrylic compounds (b ') shown can also be used in the Michael addition reaction with the above polyamino compounds. ^{_{CH 2 = C (R 1)}} COO-R 2 (3) In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² is a phenyl group, an alkyl group having 1 to 22 carbon atoms, -C _n H _2n - O
H or _{-C x H 2x O (COC y} H 2y O) z R 3, and n is 2 to 22, preferably 2 to 16 integer, x is 2-22,
Preferably, it is an integer of 4 to 16, y is an integer of 2 to 15, preferably 3 to 5, z is an integer of 1 to 20, preferably 1 to 5, R ³ is a hydrogen atom, a phenyl group or a carbon number of 1 to 1.
22 and preferably 2 to 16 alkyl groups respectively.

Further specific examples of the (meth) acrylic compound (b ') include methylmethacrylate, ethylmethacrylate and butyl (meth) as the alkyl (meth) acrylic compound in which R ² is represented by the general formula (3). Acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) Acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl ( Data) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, there is docosyl (meth) acrylate of the general formula (3) in R ²
Examples of the hydroxyalkyl (meth) acrylic compound represented by —C _n H _2n —OH include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and - There is hydroxybutyl (meth) acrylate, R ² is -C in the general formula _{(3) x H 2x O (} C
The polylactone (meth) acrylic compound represented by OC _y H _2y O) _z R ³ includes 2- (meth) acryloyloxyethyl hydrogen methoxycaprolactonate and 2- (meth) acryloyloxyethyl hydrogen methoxy dica. Examples include prolactonate, 2- (meth) acryloyloxyethyl hydrogen methoxypoly (polymerization degree 3 to 5) caprolactonate, and 2- (meth) acryloyloxyethyl-2-methoxy-6 hexanolactonate.

In addition to the compound represented by the general formula (3), maleic acid, fumaric acid, itaconic acid, citraconic acid or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester. , Isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, silicic acid Examples thereof include (meth) acrylic compounds having one or more carboxyl groups in the molecule such as cinnamic acid. It is preferable that the terminal of the (meth) acrylic compound (b ′) is an active hydrogen group because it has excellent hydrophilicity, and a vinyl compound (c) having a functional group capable of reacting with active hydrogen when a vinyl group is introduced is used. Also functions as a reaction site for

The amount of the mixture of the hydrophilic long-chain group-containing (meth) acrylic compound (b) and the other (meth) acrylic compound (b ') is as follows. ) It is not particularly limited as long as at least one acrylic compound (b) is added, but it is preferably 10 to 100 relative to the total active hydrogen derived from the polyamino compound.
%, And more preferably 50 to 100%. If it is less than this, a multi-branched structure is difficult to be obtained, and the hydrophilic long chain group-containing (meth) acrylic compound (b) or (meth)
In some cases, it is not preferable because the characteristics of the acrylic compound (b ′) component are not reflected sufficiently. The mixing ratio of the mixture of the hydrophilic long chain group-containing (meth) acrylic compound (b) and the other (meth) acrylic compound (b ') varies depending on the total number of active hydrogens of the polyamino compound compound, but is preferably (B) :( b ') = 20:80 to 100: 0, and is less likely to be water-soluble outside this range.

The reaction for obtaining the above-mentioned core compound can be carried out according to a conventional method, but when alcohol such as methanol or ethanol is used as a reaction solvent, a side reaction hardly occurs. When a solvent is used, it is preferably used 1 to 100 times the blending weight of the polyamino compound (a). Further, although heating is not particularly required, when the polyamino compound (a) or the hydrophilic long chain group-containing (meth) acrylic compound (b) or (b ') has a large molecular weight, 30 ° C to 70 ° C. It is preferable to heat within the range. The reaction time varies depending on the type of amino compound used and the reaction temperature, but is generally 30 minutes to 72 hours, generally 1 day at room temperature, and 1 to 10 when heated to 50 to 100 ° C.
Finish in time.

In the present invention, the vinyl compound (c) having a functional group capable of reacting with active hydrogen is the hydrophilic long-chain group-containing (meth) acrylic compound (b) containing the above-mentioned active hydrogen or other ( It is used to introduce a polymerizable vinyl group into the terminal of the multi-branched compound by reacting with the active hydrogen contained in the (meth) acrylic compound (b ′) or the unreacted amino group in the core compound. The core compound has an active hydrogen terminal functional group such as a hydroxyl group, a carboxyl group and an amino group, and a compound having a functional group capable of reacting with these active hydrogen terminal functional groups is a functional group capable of reacting with active hydrogen. The vinyl compound (c) having is not particularly limited. Examples thereof include epoxy group-containing vinyl compounds, alkoxysilyl group-containing vinyl compounds, phosphoric acid group-containing vinyl compounds, isocyanate group-containing vinyl compounds, and the like.

The epoxy group-containing vinyl compound used in the present invention includes glycidyl (meth) acrylate, allyl glycidyl ether, epoxycyclohexanemethyl (meth) acrylate, epoxycyclohexanemethylpolycaprolactone (meth) acrylate, vinylcyclohexylepoxide, Mention may be made of methylglycidyl methacrylate and the like. Examples of the alkoxysilyl group-containing vinyl compound include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropymethyldimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. You can Further, as the phosphoric acid group-containing vinyl compound, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxyethyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate. Acid phosphooxypolyoxypropylene glycol monomethacrylate and the like. When the active hydrogen terminal functional group of the core compound used in the present invention is a hydroxyl group, it is necessary to introduce a vinyl group into the core compound using an isocyanate group-containing vinyl compound in which the reaction proceeds under mild conditions with the hydroxyl group. It is desirable in consideration of the stability of the vinyl group. This isocyanate group-containing vinyl compound (c
Examples of -1) include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), and 3-isopropenyl-α, α-dimethylbenzyl isocyanate (TMI). In the present invention, a compound obtained by reacting a diisocyanate compound and a vinyl compound (d) having a functional group capable of reacting with an isocyanate group in equimolar amounts can also be used as the isocyanate group-containing vinyl compound (c-1). .

As the above-mentioned diisocyanate compound,
1,6-diisocyanatohexane, isophorone diisocyanate, diisocyanic acid-4,4'-diphenylmethane, polymeric diphenylmethane diisocyanate,
Xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, toluene 2,4-diisocyanate, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate,
Tetramethyl xylylene diisocyanate, cyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethylxylylene diisocyanate Isocyanate, p-tetramethylxylylene diisocyanate, dimer acid diisocyanate and the like can be mentioned.

The vinyl compound (d) having a functional group capable of reacting with an isocyanate group used in the present invention includes vinyl compounds having an amino group, a hydroxyl group, a carboxyl group, etc. Those having a are preferred from the viewpoint of reactivity with an isocyanate group. As the (meth) acrylic compound having a hydroxyl group, for example, among the above-mentioned hydrophilic long chain group-containing (meth) acrylic compound (b) or other (meth) acrylic compound (b '), only one hydroxyl group is contained. Those having a relatively low molecular weight are preferable from the viewpoint of reactivity with diisocyanate, and examples thereof include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2- (meth) acryloyl. Examples thereof include oxyethyl hydrogencaprolactonate. Further, pentaerythritol triacrylate, trimethylolpropane diacrylate, glycerol diacrylate and the like are preferable for the purpose of improving reactivity and increasing crosslink density.

The blending amount of the vinyl compound (c) having a functional group capable of reacting with the formed hydrogen in the present invention is such that unreacted active hydrogen derived from the polyamino compound (a) present in the core compound and a hydrophilic long chain group are contained. There is no particular limitation as long as at least one is added to all active hydrogen groups derived from the (meth) acrylic compound (b) or other (meth) acrylic compound (b ') terminal, but preferably 10
-100%, more preferably 30-95%. If it is less than this range, sufficient curability cannot be obtained, which is not preferable, and if it is more than this range, the viscosity of the obtained multibranched compound (A) may be increased and the water solubility may be lowered, which is not preferable. Further, in the present invention, the hyperbranched compound (A) is obtained by adding the isocyanate group-containing vinyl compound (c-1) to the synthesis solution of the core compound. that time,
A catalyst used during normal urethane synthesis, if necessary,
For example, tin-based catalysts such as tin octylate and tin 2-ethylhexanoate may be added. The preferable addition amount of the catalyst is 1 with respect to the isocyanate group-containing vinyl compound (c-1).
~ 0.01 wt%.

The number average molecular weight of the multi-branched compound (A) obtained by the present invention is 200 to 10,000, preferably 300 to 5,000, more preferably 400 to 4,000.
And 100,000 cps or less, preferably 5000
0-500 cps, more preferably 20000-100
It is a liquid showing a viscosity of 0 cps (30 ° C.). If the molecular weight is lower than this, curing shrinkage becomes severe, which is not preferable. Further, when the molecular weight is high, there is no particular problem when the viscosity is within a film-forming range, but when the molecular weight is higher than the above range, the viscosity tends to increase, which is not preferable from the viewpoint of coating property. If the viscosity exceeds the above range, it is not preferable in terms of solubility with other components and film-forming property.

Further, in the present invention, the multi-branched compound (A)
Has sufficient coating performance even when used alone, but for the purpose of adjusting the viscosity and curability of the curable composition, it is mixed with another water-soluble unsaturated group-containing compound (B) to form a composition You can also do it. Further, the water-soluble unsaturated group-containing compound (B) used in the present invention is not particularly limited as long as it is a compound having one or more unsaturated double bonds in the molecule, but it is water-soluble (meth) Acrylic compounds, vinyl compounds, diene compounds and the like can be exemplified, but among these, it is preferable to use a water-soluble (meth) acrylic compound from the viewpoint of safety and easy availability.

Specific examples of the water-soluble (meth) acrylic compound (B) include polyethylene glycol (meth) acrylic compounds represented by the following formula (6). ^{_{CH 2 = C (R 1)}} COO- (C 2 H 4 O) m R 2 (6) ( wherein, R ¹ represents a hydrogen atom or a methyl group, R ² is a phenyl group or an alkyl group having 1 to 5 carbon atoms , M is 1 to 2000
Represents the integer of each. ) Among these, those having m of 8 to 20 are preferable from the viewpoint of low viscosity. For example, there are methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, and the like.

Further, there is a polyethylene glycol di (meth) acrylic compound represented by the following formula (7). ^{_{CH 2 = C (R 1)}} COO- (C 2 H 4 O) m COC
(R ¹ ) C ═CH ₂ (7) (In the formula, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 6 to 2000.) Of these, those having m of 8 to 20 have low viscosity. It is preferable from the aspect.

Further, as the water-soluble (meth) acrylic compound (B), (meth) acrylic acid, (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, mono (2- (meth) acryloyloxyethyl) acid phosphate, glycerose mono (meth) acrylate, N-vinylpyrrolidone, vinylformamide, N-acryloylmorpholine, 2,2-bis [4-{(meth) acryloxydiethoxy} phenyl] propane, 2,2-bis [4-
{(Meth) acryloxyethoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypolyethoxy} phenyl] propane, ethylene oxide-modified trimethylolpropane tri (meth) acrylate and the like can also be used. .

The use of a (meth) acrylic compound having an oxyalkylene moiety is preferable for the purpose of achieving both hydrophilicity and water resistance since a crosslinking reaction is caused by irradiation with an electron beam or γ-ray.

The viscosity of the water-soluble unsaturated group-containing compound (B) is not particularly limited as long as the viscosity of the composition meets the intended conditions, but preferably 1 to 10000 cps.
It is (30 ° C.), and those lower than this are not preferable in terms of safety such as PII value because many of them have low molecular weight, and those higher than this are not preferable because they contribute little as a viscosity modifier. The number average molecular weight is preferably 1
000 or less, and more preferably 100 to 600.

Further, in the present invention, the multi-branched compound (A)
The compounding ratio of the water-soluble unsaturated group-containing compound (B) is preferably (A) :( B) = 5: 95 to 100: 0.
(% By weight), and more preferably in the range of 20:80 to 90:10. When the amount of the water-soluble unsaturated group-containing compound (B) is more than the above range, the amount of residual monomer after curing is increased and the curability is decreased, volume shrinkage during curing is observed, and the cured product becomes brittle. Not preferable for the reason.

In the present invention, the viscosity of the resin composition comprising the hyperbranched compound (A) and the water-soluble unsaturated group-containing compound (B) is limited depending on the performance or application of the coating machine used. However, the preferable viscosity range is 10 to 1
It is 0000 cps (30 ° C.).

In the present invention, an aqueous medium containing water and a water-soluble solvent can be used to adjust the viscosity to a desired value. Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol and glycerin, and ketone solvents such as acetone and methyl ethyl ketone. The content of the water-soluble solvent in the aqueous medium is 0 to 80% by weight, preferably 20% or less. If the blending ratio of the water-soluble solvent is higher than this, it is not environmentally preferable.

As the compounding ratio of the aqueous composition in the present invention, the total amount of the hyperbranched compound (A) and the water-soluble unsaturated group-containing compound (B) and the aqueous medium (C) are (A) + (B). :
The weight ratio of (C) is 5:95 to 95: 5, preferably 20:80 to 90:10. If the aqueous medium is added too much, the curing speed will be slowed, which is not preferable. On the other hand, if the amount is too small, the viscosity for coating becomes high, which is not preferable. The viscosity of the aqueous resin composition comprising (A), (B) and (C) in the present invention is 5 to 5000 cps (30 ° C.).

In the present invention, a curing agent resin such as an amino resin or a phenol resin may be blended in order to enhance the film-forming property and the curing property of the aqueous resin composition. Also,
In order to improve the coating performance, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, polyesters, general-purpose polymers such as polystyrene, alkyd resins,
You may mix | blend unsaturated modified alkyd resin, such as rosin modified alkyd resin and linseed oil modified alkyd resin, and drying oil, such as linseed oil, tung oil, and soybean oil. However, the blending amount of these is preferably 40% by weight, and more preferably 2% by weight.
It is 0% by weight or less. Further, if necessary, a solvent, a compatibilizer, a surfactant, a lubricant or the like may be added. The blending amount of these is 20% by weight, preferably 10% by weight or less. Various kinds of pigments such as dyes, carbon black, titanium white, phthalocyanine, azo dyes, and pigments such as quinacridone, Si-based fine particles, inorganic fillers such as mica are added to the aqueous resin composition obtained by the present invention in appropriate amounts. It can be used as a printing ink or a coloring paint. Further, in the case of curing by irradiation with radiation, known photopolymerization sensitizers and initiators can be added.

The composition for film-forming material using the aqueous resin composition of the present invention is a roll coater or knife coater for various steel plates, metal plates such as aluminum plates, plastic films, papers, plastic film laminated papers and other base materials. Coating methods such as offset printing, gravure printing, letterpress printing, silk screen printing, and other conventional methods can be used to form films with a thickness of 0.1 to 500 μm. It can be cured by irradiation with radiation such as light rays and infrared rays. When it is cured by electron beam irradiation, it is preferably 10 to 1000 kV, more preferably 30 to 30 kV.
An electron beam irradiation device having an acceleration voltage in the range of 0 kV is used. Irradiation with an electron beam having a low acceleration voltage is more effective for curing a thin film because energy is concentrated on the surface, and is preferable because it causes less damage to a coating film or a substrate. The acceleration voltage in this case is in the range of 30 to 100 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 less than this, it is difficult to obtain a sufficient cured product,
On the other hand, if it is larger than this, damage to the coating film and the substrate is large, which is not preferable. The film formation in the present invention means forming a resin film having a thickness of 0.1 to 500 μm on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting. .

[0036]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. ◎ Structural analysis, number average molecular weight and viscosity measurement method 1) Structural analysis The structure of the multi-branched compound (A) synthesized here is ¹ H-NM.
Confirmed by R. 2) Number average molecular weight: gel permeation chromatography (Tosoh SC-8020) A calibration curve for gel permeation chromatograph (GPC) was independently prepared from several kinds of multi-branched compounds of known structure analyzed by ¹ H-NMR. The result measured by GPC was adopted. Further, as the molecular weight distribution (Mw / Mn), the value obtained by the same measuring device was adopted. 3) Viscosity: Rheometer (RDS-made by Rheometrics Inc.)
II, RFS-II) Rheometer RDS-II (high viscosity type) manufactured by Rheometrics Co., Ltd. or RFS-II according to the viscosity of the sample.
Steady-state viscosity measured with (low viscosity type) (shift rate = 1 to
The value of 10 / sec) was adopted. ◎ Electron beam irradiation equipment and irradiation conditions 1) Area beam type electron beam irradiation equipment Curetron EBC-200
-20-30 (NISSIN HIGH VOLTAGE) Electron beam acceleration: 200kV DOSE was adjusted by the amount of current in the range of 5-80kGy. 2) MIN-EB (manufactured by AIT) Electron beam acceleration: 60 kV DOSE was adjusted at a belt conveyor speed within a range of 5 to 80 kGy.

The abbreviations of the following compounds used in Examples and Comparative Examples are shown below. 1) Polyamino compound (a) ED: ethylenediamine MXDA: metaxylenediamine 2) hydrophilic long chain group-containing (meth) acrylic compound (b) PEG7A: polypropylene glycol (degree of polymerization of PPG chain = 7) acrylate MPEG9A: methoxypolyethylene Glycol (PE
Polymerization degree of G chain = 9) (meth) acrylic compound (b ′) other than acrylate 3) 2) HEA: 2-hydroxyethyl acrylate EHA: 2-ethylhexyl acrylate 4) Isocyanate group-containing vinyl compound (c) MOI: Methacryloyloxyethyl isocyanate and synthetic products shown in the following Synthesis Examples 1 to 5) Water-soluble unsaturated group-containing compound (B) HEA: 2-hydroxyethyl acrylate (Mn = 116,
η = 4 cps) PEG9DA: polyethylene glycol # 400 diacrylate (Mn = 508, η = 36.2 cps) PEG14DA: polyethylene glycol # 600 diacrylate (Mn = 708, η = 76 cps) 6) Water-based medium (C) H2O: water EtOH : Ethanol IPA: Isopropyl alcohol

(Synthesis Example 1) Agitator for equimolar adduct of IPDI (isophorone diisocyanate) and HEA, nitrogen introduction tube, temperature sensor, condenser,
And HEA: 116 g, 120 g of ethyl acetate in a 1000-mL four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution, IPDI: 222 g, ethyl acetate:
220 g and tin 2-ethylhexanoate (0.1 g) were added, and the above solution filled in a dropping funnel was added dropwise over 1 hour while heating and stirring in a water bath set to 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Synthesis Example 2) Stirrer for equimolar adduct of HMDI (hexamethylene diisocyanate) and 4HBA (hydroxybutyl acrylate), nitrogen introducing pipe, temperature sensor, condenser,
And 4HBA: 144 g, and a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of 145 g of ethyl acetate were mixed with 168 g of HMDI, 170 g of ethyl acetate, and 0.1 g of tin 2-ethylhexanoate. The solution filled in the dropping funnel was added dropwise over 1 hour while heating and stirring in a hot water bath set to 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method. (Synthesis Example 3) Stirrer for equimolar adduct of IPDI and PPG6A, nitrogen introducing pipe, temperature sensor, condenser,
And PPG6A: 204 g, ethyl acetate: 204 g in a 1000 ml four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution, IPDI: 88 g, ethyl acetate: 88 g, tin 2-ethylhexanoate: 0.1 g Then, the solution filled in the dropping funnel was dropped in 1 hour while heating and stirring in a hot water bath set at 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Example 1) ED / MPEG9A / MOI
= 1/2/2 (1/5 mol scale) synthetic stirring apparatus, nitrogen inlet tube, temperature sensor, and ED: 12 g, MPEG9A: 193 g, ethyl acetate in a 1000 ml four-neck round bottom flask equipped with a condenser.
When 205 g was blended and refluxed in a hot water bath set at 75 ° C. for 3 hours, a part of the sample was sampled and ¹ H-NMR was measured. As a result, a proton peak derived from an acrylic group was almost disappeared. Therefore, lower the bath temperature to 60 ° C
I: a mixed solution of 62 g and ethyl acetate: 62 g was added,
After a further 10 to 30 minutes, tin 2-ethylhexanoate: 0.3
g was added. The mixture was heated and stirred for 3 to 4 hours, and the time point when the NCO group characteristic absorption (2270 cm ^-1 ) on the IR chart disappeared was taken as the reaction end point. Furthermore, the target multibranched compound was obtained by removing the solvent of ethyl acetate used as a reaction solvent with an evaporator.

(Embodiment 3) ED / (MPEG9A / HE)
A) / MOI = 1 / (3/1) / 1 (1/10 mole scale) synthetic stirrer, nitrogen inlet tube, temperature sensor, and ED: 6 g in a 1000 ml four-neck round bottom flask equipped with a condenser. , MPEG9A: 145g, HEA: 23
g, ethyl acetate: 174 g were mixed, refluxed in a water bath set at 75 ° C. for 3 hours, and then partially sampled, ¹
When H-NMR was measured, the proton peak derived from the acrylic group was almost disappeared. Therefore, set the bath temperature to 60
The mixture was cooled to 0 ° C., a mixed solution of: MOI: 16 g and ethyl acetate: 16 g was added, and 10 to 30 minutes later, tin 2-ethylhexanoate: 0.1 g was added. Continue heating and stirring for 3 to 4 hours, and absorb NCO group characteristic of IR chart (2270 cm
^The end point of the reaction was the point at which ^-1 ) disappeared. Furthermore, the target multibranched compound was obtained by removing the solvent of ethyl acetate used as a reaction solvent with an evaporator.

(Examples 2, 4 to 20) Polyamino compound (a) shown in Table 1 in a four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser, and an equivalent amount of ethyl acetate. Was added, and the active hydrogen-containing (meth) acrylic compound (b-1) and the non-functional (meth) acrylic compound (b-2) were diluted with ethyl acetate to 70% by weight. The solution was added with stirring. Except when HEA is used as the active hydrogen-containing compound, the same molar number of methanol as that of the polyamino compound (a) is further added. After refluxing for 4 hours or more reaction solution water bath set at 75 ° C. and partially sampled, ¹
After measuring the H-NMR and confirming the reaction end point by the proton peak derived from the acrylic group, a diversion tube was set between the reactor and the condenser, and the mixture was heated and stirred under normal pressure in a water bath at 80 ° C. The solvent was distilled off while continuing. Further, a vacuum line was connected from the upper part of the condenser, and ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less with a water bath lowered to 70 ° C., whereby a viscous liquid resin was obtained. Then, ethyl acetate was newly added to NV50% while maintaining the bath temperature at 70 ° C., and the isocyanate group-containing vinyl compound (c) was added to the (meth) acrylic compound (b-1) and non-functional (meth). ) The total number of moles of the acrylic compound (b-2) was added by the number of moles obtained by multiplying the yield, and further diluted with ethyl acetate so that the concentration of the entire reaction system was 50%. After a further 10 minutes, tin 2-ethylhexanoate was added to the vinyl group (c) containing the isocyanate group of 0.
5 wt% was added. Continue heating and stirring for 3 hours or more as it is, and absorb NCO group characteristic of IR chart (2270c
The time when m ⁻¹ ) disappeared was defined as the reaction end point. Furthermore, the target multibranched compound was obtained by removing the solvent of ethyl acetate used as a reaction solvent with an evaporator. Table 1 also shows the raw material composition at the time of synthesis of the obtained multibranched compound and the characteristics of the obtained multibranched compound.

[0043]

[Table 1]

(Examples 21 to 78) Aqueous resin compositions prepared using the hyperbranched compound (A) obtained in Examples 1 to 20 and the water-soluble unsaturated group-containing compound (B) (Table 2). ,
Alternatively, the composition of the total of the multi-branched compound (A) and the water-soluble unsaturated group-containing compound (B) and the aqueous medium (C) (Table 3) is
It is coated on PET film with a 6 bar coater and is 20k
The electron beam of Gy was irradiated. In Tables 2 and 3, the hyperbranched compound used, the water-soluble unsaturated group-containing compound, the type of aqueous medium and the composition viscosity thereof, and the curing characteristics of the coating film obtained by electron beam irradiation (finger touch test → × : With tack, △: Without tack, but with scratches on the nail, ◯: Without tack, without scratching, and solvent resistance (residual rate obtained from weight change before and after 50 times of H ₂ O rubbing test) evaluation results Indicates.

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

INDUSTRIAL APPLICABILITY According to the present invention, a solvent-free curable resin having a high viscosity and a low viscosity is used as an aqueous resin. A roll coater or knife coater that has been used in the past, contributing to the improvement of the work environment by reducing or eliminating the compounding ratio of low molecular weight compounds used in materials that have safety and physical properties problems. A coating method such as, offset printing, gravure printing, letterpress printing, screen printing can be used to form a film, and it can be cured by conventional triggers such as heating, ultraviolet ray, infrared ray, electron beam, γ-ray irradiation. , Especially electron beam, γ
The present invention provides a hyperbranched compound and composition that can be cured without using a catalyst or an initiator in the case of irradiation with rays.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Miki Kawashima             2-3-13, Kyobashi, Chuo-ku, Tokyo Toyo             Nki Manufacturing Co., Ltd. F-term (reference) 4J002 BG07X CH05X CK04W CM01W                       EH056 EH076 FD010 FD090                       GH01 GJ01 GJ02                 4J034 BA02 BA03 CA14 CA15 CA17                       CC12 CC62 CD04 CD06 DA03                       DB03 DB07 DG03 DG04 DG06                       DG14 HA01 HA04 HA18 HB06                       HB07 HB09 HB12 HB15 HC12                       HC73 LA22 LA23 LA33 QA05                       QB11 QC05 RA07 RA08                 4J038 FA011 FA112 FA152 FA281                       MA08 MA10 MA13 MA14                 4J043 PA13 QB58 QC02 QC03 QC05                       RA08 SA06 SA07 SA08 SA11                       SA24 SB01 TA02 TA06 TA12                       TA38 TA53 TA72 TB01 TB03                       UA041 UA081 UA091 UA121                       UA381 UA621 UA681 UA761                       UB011 VA011 VA041 WA05                       WA16 ZB01 ZB02 ZB03 ZB22

Claims (5)

[Claims] 1. A multi-branched compound (A) and a water-soluble unsaturated group-containing compound (B) shown below (A) :( B) = 5: 95-
An aqueous resin composition which is dissolved or dispersed in an aqueous medium (C) at a ratio of 100: 0 (% by weight). Hyperbranched compound (A): a polyamino compound (a) having a primary or secondary amino group in the molecule and a hydrophilic long chain group-containing (meth) acrylic compound (b) represented by the following formula (1): A multi-branched compound obtained by adding a vinyl compound (c) having a functional group capable of reacting with active hydrogen to a core compound having at least one active hydrogen formed by a Michael addition reaction. ^{_{CH 2 = C (R 1)}} COO- (C n H 2n O) m R 2 (1) ( wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a phenyl group or a 1 to 5 carbon atoms The alkyl group, n is an integer of 1 to 3, and m is an integer of 1 to 25.) 2. The aqueous resin composition according to claim 1, wherein the polyamino compound (a) is a diamino compound represented by the following formula (2). _{H 2 N-CH 2 -R-} CH 2 -NH 2 (2) ( wherein, R is a direct bond, -C _r H _2r - _(r is from 1 to 20
Indicates an integer. ), A phenylene group or a cycloalkylene group. ) 3. The aqueous resin composition according to claim 1, wherein the water-soluble unsaturated group-containing compound (B) has a viscosity of 1 to 10000 cps (30 ° C.) or less. 4. The aqueous resin composition according to claim 1, wherein the liquid multibranched compound (A) has a number average molecular weight of 200 to 10,000 and a viscosity of 100,000 cps (30 ° C.) or less. 5. A film-forming material comprising the aqueous resin composition according to claim 1.