JP3353677B2 - Hyperbranched compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention can be used as a film-forming material such as paints and inks, or as a resin for sealing agents, molding agents, adhesives and pressure-sensitive adhesives. The present invention relates to a method for producing a branched compound that can be used as a curing agent or a reactive diluent for a resin composition. Furthermore, the present invention relates to a method for producing a branched compound that can be used as a printing ink, a vehicle for a paint, an adhesive, or the like as a heat or radiation curable resin.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used for fillers and molding materials. These resin solutions scatter a large amount of organic solvent in the coating, filling and curing / drying steps. With increasing interest in the global and working environments, restrictions on the use of such resin solutions have been added. As one of the methods, development of resin materials such as water-soluble resin, powder, and hot melt has been promoted, but an aqueous resin composition requires a large amount of heat to evaporate water as a dispersion medium, Further, it often contains a small amount of organic solvent for the purpose of improving the coating property, and there is still a problem in terms of waste liquid treatment. Further, in the case of coating and filling of powder or hot melt, a new equipment has to be introduced because the method of coating and filling is greatly different from the conventional coating and filling equipment. 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 the use amount of the resin solution is more likely to decrease in the future due to such efforts. However, as a fundamental solution, there has been a strong demand for the development of a solventless liquid resin composition that can be widely applied without problems of pollution, safety and health, ignition, explosion, etc., and that can be easily applied and filled. I have.

A typical example of a solventless liquid resin composition is a radiation-curable resin composition. Conventional radiation-curable resin compositions are prepared from low-viscosity monomers such as various acrylate monomers, and reactive oligomers such as urethane acrylate, epoxy acrylate, or ester acrylate, and other resin components as necessary. It is configured. The low-viscosity monomer is mainly used as a reactive diluent for the purpose of controlling the viscosity of the composition, but if it contains a large amount thereof, the volume shrinkage during curing is large, and the cured coating film is fragile, and Odors and the like due to residual monomers in the coating film have been regarded as a problem. Therefore, improvements such as reduction of the amount of the reactive diluent used and increase in the molecular weight have been desired.

[0004] In order to improve the mechanical performance of the cured product, it is preferable to blend a polyfunctional reactive diluent, a reactive oligomer, and a high-molecular-weight resin material. considering the flow properties before curing composition because it is, the required result the amount thereof is blended in a large amount of the reactive dilution agent has been limited. Therefore, the cured product obtained by curing the conventional solventless liquid resin composition has poor cured product properties such as hardness, toughness, mechanical properties, and chemical resistance, and is practically a solvent-based or water-based resin composition. It was a property far below. Radiation-curable resin compositions containing a large amount of high-molecular-weight reactive oligomers and resin materials have also been developed with the aim of improving coating performance. It is difficult to say that environmental improvements have been made because of the use of chemicals and organic solvents.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a solvent-free resin composition having sufficient coating properties and a low viscosity capable of being applied, and having a relatively high molecular weight. The present invention provides a method for producing a branched compound, which makes it possible to reduce the blending ratio of a low-molecular-weight compound having problems in safety and performance by using a polyfunctional liquid resin having a low viscosity while being low. is there. Further, the present invention can form a film by a coating method such as conventionally used roll coater and knife coater, and a printing method such as offset printing, gravure printing, letterpress printing, screen printing, and heating, ultraviolet, infrared, and electron beam. Provided is a method for producing a branched compound that can be cured by a conventional trigger such as γ-ray irradiation or the like, and can be cured without using a catalyst or an initiator particularly in the case of electron beam or γ-ray irradiation. Is what you do.

The present inventors have conducted intensive studies on the correlation between the structure and viscosity of various resin systems in order to solve the above-mentioned problems. As a result, general linear polymers were replaced with comb-shaped polymers, and moreover multi-branched polymers. By changing the molecular structure of the polymer, it has been found that the polymer has a high molecular weight, a low viscosity, and a large number of functional groups such as vinyl groups can be introduced. In addition, it has been found that by having a urethane bond in the molecule as a branched compound, it exhibits good adhesion to various base materials, especially to plastic materials which have been extremely difficult in radiation curing systems. Furthermore, a new liquid that can be cured at a high speed by using a conventional curing method, especially using an electron beam as a curing trigger, even though it has a high molecular weight and is within the viscosity range that can be formed by the conventional film forming method. A method for producing a branched compound as a resin has been found.

That is, the present invention relates to a polyamino compound (a) having two or three primary or secondary amino groups in the molecule and having three or more active hydrogens derived from the primary or secondary amino groups in the molecule. To a core compound having a branched structure by Michael addition of an active hydrogen-containing (meth) acrylic compound (b), wherein the core compound has an isocyanate stoichiometrically equivalent to the active hydrogen contained in the core compound. The present invention relates to a method for producing a branched compound in which a group-containing vinyl compound (c) is added and reacted.

Further, the present invention relates to a method for producing the above branched compound, wherein the polyamino compound (a) is a diamino compound represented by the following formula (1). _{H 2 N-CH 2 -R-} CH 2 -NH 2 (1) ( wherein, R is a direct bond, -C _n H _2n - _(n is from 1 to 20
Represents an integer. ), A phenylene group or a cycloalkylene group. )

Further, the present invention relates to a method for producing the above-mentioned branched compound, wherein the active hydrogen-containing (meth) acrylic compound (b) is at least one of the following formulas (2) to (5). CH ₂ ＣC (R ¹ ) COO—R ² —OH (2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is carbon number 2)
To 22 alkylene groups. ^{_{) CH 2 = C (R 1}} ) COO (C x H 2X O) m H (3) ( wherein, R ¹ represents a hydrogen atom or CH _3, x is an integer from 1 to 6, m is 1 to 25 integer representing _{each.) CH 2 = C (R} 1) COOC y H 2y O (COC z H 2Z O) k H (4) ( wherein, R ¹ represents a hydrogen atom or CH _3, y is an integer of 2 to 22 , z represents an integer of 2 to 15, k is an integer from 1 to 20, _{respectively.) CH 2 = C (R} 1) COR 3 O (CONHR 4 NHOR 5 O) h H (5) ( in the formula, R ¹ Is a hydrogen atom or CH ₃ , and R ³ is C 2
To 22 and R ⁴ are represented by the following formulas (6-a) to (6)
Isocyanate residue represented by -h), R ⁵ is - (C _r
H _2r O) _q - (r is an integer of 1 to 4, q is an integer of 1 to 20) or _{-C p H 2p -.. (} P is an integer of 1 to 20) the divalent represented by Alcohol residue, h is 1 to 10
Represents an integer. )

[0010]

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Further, the present invention relates to a method for producing the above-mentioned branched compound, wherein the polyamino compound (a) has an average molecular weight of 30 to 5,000.

[0012]

[0013]

[0014]

Further, the present invention provides a method wherein the branched compound has a number average molecular weight of 200 to 10,000 and a viscosity of 100,000 cps (3
0 ° C.) or lower.

The polyamino compound (a) used in the present invention is used as a starting material for forming the compound into a branched structure, has two or three primary or secondary amino groups in the molecule, and has a total of 3 More than one primary amine or 2
Is a compound having active hydrogen derived from a secondary amine.
Examples thereof include a branched aliphatic polyamino compound, a cycloaliphatic polyamino compound, and an aliphatic aromatic polyamino compound.

Examples of the above-mentioned linear / branched aliphatic polyamino compound used in the present invention include hydrazine compounds such as hydrazine and adipic dihydrazide, ethylenediamine, propanediamine, butanediamine, propanediamine, pentanediamine, hexanediamine. Examples thereof include diamino compounds represented by the following general formula (1) such as diaminooctane, diaminodecane, and diaminododecane; and 2,5-dimethyl-2,5 hexamethylenediamine, polyoxypropylenediamine, and diethylenetriamine.

The cyclic aliphatic polyamino compounds include 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, m-xylenediamine, polycyclohexylpolyamine, bis (aminomethyl) -bicyclo [2,2,1] heptane, methylenebis (furanmethaneamine) and the like. Examples of the aliphatic aromatic polyamino compound include meta-xylene diamine and para-xylene diamine.

Of these, the use of a diamino compound generalized by the following formula (1) can change the shape of the core compound in various ways, and is preferable from the viewpoint of improving mechanical properties after curing. _{H 2 N-CH 2 -R-} CH 2 -NH 2 (1) ( wherein, R is a direct bond, -C _n H _2n - _(n is 1-2
0, preferably an integer of 1 to 10), a phenylene group or a cycloalkylene group. )

In the present invention, the polyamino compound (a)
Since is a starting material for a core compound, it is more effective to contain a higher density of amino groups in one molecule for lowering the viscosity and / or multifunctionalizing the branched compound. In order to satisfy this purpose, it is preferable to use a low-molecular-weight diamine such as ethylenediamine.

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
The polyamino compound having a number average molecular weight of 5,000, especially 50,000 or more is preferably 50,000, more preferably 50,000 to 5,000.

In the present invention, in the active hydrogen-containing (meth) acrylic compound (b), the active hydrogen derived from the amino group of the polyamino compound (a) undergoes a Michael addition reaction to the (meth) acryloyl group, and the core compound is branched. Is done. Also,
The obtained active hydrogen derived from the active hydrogen-containing (meth) acrylic compound (b) at the terminal of the core compound functions as a reaction site in the addition reaction with the isocyanate group-containing vinyl compound (c).

The active hydrogen-containing (meth) acrylic compound (b) of the present invention is a (meth) acrylic compound having an active hydrogen derived from a hydroxyl group, a carboxyl group or the like in the molecule. As the (meth) acrylic compound having a hydroxyl group in the molecule, for example, a hydroxyalkyl (meth) acrylate compound represented by the following formula (2): CH ₂ ＣC (R ¹ ) COO—R ² —OH (2) (Wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is
22, preferably 2 to 16 alkyl groups respectively. )

A polyalkylene glycol mono (meth) acrylate compound represented by the following formula (3): CH ₂ ＣC (R ¹ ) COO (C _x H _2X O) _m H (3) (where R ¹ is A hydrogen atom or CH ₃ , x is an integer of 1 to 6, preferably 2 to 4, m is 1 to 25, preferably 4 to 1;
6 represents an integer. )

The polycaprolactone mono (meth) acrylate compound represented by the following formula _{(4), CH 2 = C} (R 1) COOC y H 2y O (COC z H 2Z O) k H (4) ( in the formula, R ¹ is a hydrogen atom or CH ₃ , y is an integer of 2 to 22, preferably 2 to 16, z is 2 to 15, preferably 3
And k represents an integer of 1 to 20, preferably 1 to 5. )

The urethane mono (meth) represented by the following formula (5)
TA) acrylate compounds, CH_Two= C (R¹) COR^ThreeO [CONHR^FourNHOR^FiveO]_hH (5) (where R¹Is a hydrogen atom or CH_Three, R^ThreeHas 2 to 2 carbon atoms
22 alkyl groups, R^FourAre represented by the following formulas (6-a) to (6-
h) an isocyanate residue represented by R^FiveIs-(C_rH _2r
O)_q-Or -C_pH_2p-Dihydric alcohol residue indicated by
A group, where r is an integer of 1 to 4, p is an integer of 1 to 20, q is
H represents an integer of 1 to 20, and h represents an integer of 1 to 10, respectively.
You. )

[0027]

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More specifically, the hydroxyalkyl (meth) acrylate compounds represented by the general formula (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and the like,

As the alkylene glycol mono (meth) acrylate compound represented by the general formula (3), for example, diethylene glycol mono (meth) acrylate,
Triethylene croaker call mono (meth) acrylate, Te <br/> tiger propylene glycol (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, Such as polytetramethylene glycol mono (meth) acrylate,

As the polycaprolactone mono (meth) acrylate compound represented by the general formula (4),
(Meth) acryloyloxyethyl hydrogen hydrogen caprolactonate, 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate, 2- (meth)
Acryloyloxyethyl hydrogen poly (degree of polymerization: 3 to 5) caprolactone, 2- (meth) acryloyloxyethyl-2-hydroxy-6 hexanolactonate, and the like.

Further, in addition to the general formulas (2) to (5), 2- (meth) acryloyloxyethyl-2-
Hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, modified with ethylene oxide (Meth) acrylic compounds containing two or more hydroxyl groups such as pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and ethylene oxide-modified trimethylolpropane mono (meth) acrylate also contain active hydrogen (meth) )
It can be mentioned as the acrylic compound (b).

The (meth) acrylic compounds having a carboxyl group in the molecule include 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 and the like can be mentioned.

In the present invention, the core compound is obtained by Michael addition of the active hydrogen-containing (meth) acrylic compound (b) to the polyamino compound (a). In the present invention, it is preferably 10% or more, more preferably 50% or more, based on the total active hydrogen of the polyamino compound.
% Or more is preferably reacted with the active hydrogen-containing (meth) acrylic compound (b). If the amount is less than this, a branched structure is hardly obtained, and the characteristics of the active hydrogen-containing (meth) acrylic compound (b) component are not sufficiently reflected.

The reaction for obtaining the core compound of the present invention can be basically performed according to a conventional method, but when an alcohol such as methanol or ethanol is used as a reaction solvent, a side reaction hardly occurs. When using a solvent, it is preferable to use 1 to 100 times the compounding weight of the polyamino compound (a). Heating is not particularly necessary, but when the polyamino compound (a) or the active hydrogen-containing (meth) acrylic compound (b) has a large molecular weight, heating may be performed in the range of 30 ° C to 70 ° C. preferable. The reaction time varies depending on the type of the polyamino compound to be used and the reaction temperature, but it is 30 minutes to 72 hours, generally about one day and night at room temperature, and 1 to 50 to 100 ° C when heated.
It ends within 10 hours.

In the present invention, the isocyanate group-containing vinyl compound (c) is combined with active hydrogen derived from the unreacted amino group of the polyamino compound (a) or active hydrogen contained in the active hydrogen-containing (meth) acrylic compound (b). It is used to introduce a polymerizable vinyl group into the terminal of the core compound by a reaction with an isocyanate group. Examples of the isocyanate group-containing vinyl compound (c) include methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, and 3-isopropenyl α, α-dimethyl isocyanate.

In the present invention, a compound obtained by reacting a diisocyanate compound with a vinyl compound having a functional group capable of reacting with an isocyanate group in an equal amount can also be used as the isocyanate group-containing vinyl compound (c). . As such a diisocyanate compound,
1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate,
Xylylene diisocyanate, 2,4-diisocyanate tolylene, diisocyanate toluene, 2,4-diisocyanate toluene, diisocyanate hexamethylene, diisocyanate-4-methyl-m-phenylene, naphthylene diisocyanate, paraphenylene diisocyanate,
Tetramethyl xylylene diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, 2, 2,
4-trimethylhexamethylene diisocyanate, 2,
4,4-trimethylhexamethylene diisocyanate,
Examples thereof include m-tetramethylxylylene diisocyanate, p-tetramethyl xylylene diisocyanate, dimer acid diisocyanate, and the like.

The vinyl compound having a functional group capable of reacting with an isocyanate group used in the present invention includes a vinyl compound having an amino group, a hydroxyl group, a carboxyl group and the like. Those are preferred from the viewpoint of reactivity with isocyanate groups. As the (meth) acrylic compound having a hydroxyl group, among the above compounds, those containing only one hydroxyl group can be used, but those having a relatively low molecular weight are preferred from the viewpoint of reactivity with diisocyanate. −
Examples thereof include hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2- (meth) acryloyloxyethyl hydrogencaprolactonate.

In the present invention, the branched compound is obtained by adding and reacting an isocyanate group-containing compound (c) in an amount equal to the amount of active hydrogen in the core compound. Here, the active hydrogen in the core compound refers to the active hydrogen derived from the unreacted amino group present in the core compound and the active hydrogen group-containing (meth) acrylic compound (b) terminal added to the polyamino compound. Shows both hydrogen.

Further, in the present invention, the branched compound is obtained by adding an isocyanate group-containing vinyl compound (c) to a solution for synthesizing the core compound. At that time, a catalyst used in ordinary urethane synthesis, for example, a tin-based catalyst such as tin octylate and tin 2-ethylhexanoate may be added as needed. A preferable addition amount of the catalyst is 1 to 0.01% by weight based on the isocyanate group-containing vinyl compound (c).

The branched compound obtained by the present invention has a number average molecular weight of 200 to 100,000, preferably 3
00 to 50,000, more preferably 400 to 5,000, and 100000 cps or less, preferably 50,000 to
500 cps, more preferably 20000 to 1000 c
It is a liquid having a viscosity of ps (30 ° C.). If the molecular weight is lower than this, curing shrinkage becomes severe, which is not preferable. In the case where the molecular weight is high, there is no particular problem in the case where the viscosity is within the range where the film can be formed. However, when the molecular weight is higher than the above range, the viscosity increases, which is not preferable in view of coatability.
If the viscosity exceeds the above range, it is not preferable in terms of solubility with other components and film forming properties.

The branched compound obtained in the present invention can be used as it is as a curable non-solvent liquid resin as a film-forming material such as paints, inks, molding materials, adhesives, etc. By adding and adding a cross-linking agent such as a (meth) acrylic monomer, polyisocyanate, or melamine, the viscosity can be adjusted, and the film forming property and the coating performance can be adjusted. For the same reason, a curing agent resin such as an amino resin or a phenol resin may be blended. In addition, in order to improve the coating performance, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, polyesters, polystyrenes and other general-purpose polymers, urethane acrylic resins, epoxy acrylic resins, alkyds A reactive resin having a vinyl group such as a resin, a rosin-modified alkyd resin, and a linseed oil-modified alkyd resin, and a drying oil such as linseed oil, tung oil, and soybean oil may be blended. However, the amount of each of these is preferably 4
0% by weight, more preferably 20% by weight or less. Further, a solvent, a compatibilizer, a surfactant, a lubricant and the like may be added as necessary. The amount of these compounds is 20% by weight, preferably 10% by weight or less.

The branched compounds obtained according to the present invention include dyes, carbon black, titanium white, phthalocyanine,
Colorants composed of pigments such as azo dyes and quinacridone and Si
By adding an appropriate amount of inorganic fillers such as fine particles, mica, calcium carbonate and the like, it can be used as various printing inks and coloring paints. In the case of curing by irradiation with a radiation, a known photopolymerization sensitizer or initiator can be added. Further, water or an organic solvent may be blended in order to improve the fluidity of the composition containing the branched compound.

The branched compound of the present invention can be coated or filled on various metals, plastics, papers, and other plates, films, and sheets with a roll coater, bar coater, knife coater, or the like, at a temperature of -5 to 300 ° C. It can be cured. The composition for a film-forming material using the branched compound of the present invention is applied to a base material such as various steel plates, a metal plate such as an aluminum plate, a plastic film, a paper, and a plastic film laminated paper by a coating method such as a roll coater and a knife coater. Or, by a conventional method such as offset printing, gravure printing, letterpress printing, silk screen printing or the like, a film having a thickness of 0.1 to 500 μm can be formed, and heating or electron beam, ultraviolet light, visible light, infrared light, etc. By irradiating the radiation.

When curing by electron beam irradiation,
Preferably 10 to 1000 kV, more preferably 30
An electron beam irradiation device having an acceleration voltage in the range of ~ 300 kV is used. The irradiation dose (DOSE) is preferably 1 to
The range is 1000 kGy , more preferably 5 to 200 kGy . If the amount is less than this, it is difficult to obtain a sufficiently cured product, and if it is more than this, damage to a coating film or a substrate is large, which is not preferable.

[0045]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. ◎ Structural analysis, measuring method of number average molecular weight and viscosity 1) Structural analysis The structure of the multibranched compound synthesized here was confirmed by ¹ H-NMR. 2) Number average molecular weight: Gel permeation chromatography (Tosoh SC-8020) A calibration curve for gel permeation chromatography (GPC) was independently prepared from several types of hyperbranched compounds having a known structure analyzed by ¹ H-NMR. The result measured by GPC based on the above was adopted. As the molecular weight distribution (Mw / Mn), a value obtained by using the same measuring instrument was adopted. 3) Viscosity: rheometer (Rheometrics: RDS-)
II, RFS-II) Rheometer RDS-II (high viscosity type) or RFS-II manufactured by Rheometrics Co., Ltd. according to the viscosity of the sample.
(Low viscosity type) steady viscosity (shear speed = 1 ~
10 / sec).

Electron Beam Irradiation Apparatus and Irradiation Conditions 1) Area Beam Type Electron Beam Irradiation Apparatus Curetron EBC-200
-20-30 (Nissin High Voltage) Electron beam accelerating voltage: 200 kV DOSE was adjusted in the range of 5-80 kGy by the amount of current. 2) MIN-EB (manufactured by AIT) Electron beam acceleration voltage: 60 kV DOSE was adjusted at a belt conveyor speed in the range of 5 to 80 kGy .

◎ Abbreviations of the following compounds used in Examples and Comparative Examples are described. 1) Polyamino compound (a) ED: ethylenediamine MXDA: meta-xylylenediamine DETA: diethylenetriamine 2) Active hydrogen-containing (meth) acrylic compound (b) 4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate PPG6A: polypropylene Glycol (degree of polymerization of PPG chain = 6) acrylate PEG7A: Polyethylene glycol (degree of polymerization of PEG chain = 7) acrylate PCL2A: 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate (Placcel FA manufactured by Daicel Chemical Industries, Ltd.) -2) SA: 2-acryloyloxyethyl hydrogen succinate 3) Isocyanate group-containing vinyl monomer (c) MOI: methacryloyloxyethyl isocyanate and Synthetic products shown in the following Synthesis Examples 1 to 6

(Synthesis Example 1) Equimolar adduct of tolylene diisocyanate (TDI) and 4HBA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And 4HBA in a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of 144 g and 144 g of ethyl acetate, TDI: 174 g, ethyl acetate:
174 g and tin 2-ethylhexanoate: 0.2 g were mixed, and the above 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 titration.

(Synthesis Example 2) Isophorone diisocyanate (IPD I )
Equimolar adduct of and 4HBA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And 4HBA: 144 g, ethyl acetate: 144 g, and a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of IPDI: 222 g, ethyl acetate: 220 g, tin 2-ethylhexanoate: 0.2 g, and 50 The above solution filled in the dropping funnel was added dropwise over 1 hour while heating and stirring in a hot water bath set at 0 ° C. The reaction was terminated when the NCO value fell below the theoretical value by titration.

(Synthesis Example 3) Equimolar adduct of TDI and HEA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And HEA: 116 g, ethyl acetate: 120 g in a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of TDI: 174 g, ethyl acetate: 1
74 g, tin 2-ethylhexanoate: 0.2 g,
The solution filled in the dropping funnel was added dropwise over 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 titration.

(Synthesis Example 4) Equimolar adduct of IPDI and HEA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And HEA: 116 g, ethyl acetate: 120 g in a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of ethyl acetate: ethyl acetate:
220 g of tin 2-ethylhexanoate: 0.2 g was mixed, and the above solution filled in the dropping funnel was added dropwise over 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 titration.

(Synthesis Example 5) Equimolar adduct of hexamethylene diisocyanate (HMID) and HEA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And HEA: 116 g and ethyl acetate 120 g in a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of ethyl acetate: 168 g, ethyl acetate:
170 g of tin 2-ethylhexanoate: 0.2 g was mixed, and the solution filled in the dropping funnel was added dropwise over 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 titration.

(Synthesis Example 6) Equimolar adduct of HMID and 4HBA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And HMDI: 168 g, ethyl acetate: 170 g, tin 2-ethylhexanoate: 0.2 g were mixed in a 1000 ml four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution of 144 g of 4HBA and 140 g of ethyl acetate. The above solution filled in the dropping funnel was added dropwise over 1 hour while heating and stirring in a hot water bath set at 0 ° C. The reaction was terminated when the NCO value fell below the theoretical value by titration.

Example 1 ED: 20 g, 4HBA: 19 in a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
After mixing 2 g, 70 g of ethyl acetate and 20 g of methanol and refluxing in a hot water bath set at 75 ° C. for 3 hours, a portion was sampled, and ¹ H-NMR was measured. Had almost disappeared. So, we set a diversion tube between the reactor and the condenser,
The solvent was distilled off while continuing heating and stirring at normal pressure in a water bath at 80 ° C. Further, a vacuum line was connected from the upper part of the condenser, and the pressure was reduced to 40 mmHg or less in a water bath lowered to 70 ° C., so that ethyl acetate was removed. When methanol and methanol were completely distilled off, a viscous liquid resin was obtained (yield: 99%).
Therefore, the water bath temperature was lowered to 60 ° C., and ethyl acetate: 400
g, MOI: 195 g, and 10 minutes later, tin 2-ethylhexanoate: 1 g. Heating and stirring were continued for 3 hours, and the end point was confirmed on the IR chart. Further, ethyl acetate used as a reaction solvent was desolvated by an evaporator to obtain a target multibranched compound. The ¹ H-NMR chart of the obtained hyperbranched compound is shown in FIG. Table 1 shows various physical property values of the obtained hyperbranched compound.

[0055]

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Example 2 ED: 20 g, PPG6A in a 2000 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
649 g, ethyl acetate: 290 g, methanol: 20 g
Was refluxed in a hot water bath set at 75 ° C. for 5 hours, and then partially sampled, and ¹ H-NMR was measured. As a result, a proton peak derived from an acryl group had almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, the solvent was distilled off while continuing to heat and stir at normal pressure in a water bath at 80 ° C., and a vacuum line was connected from the top of the condenser to 70 ° C. Ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less in a hot water bath lowered to give a viscous liquid resin (yield 98).
%). Therefore, while maintaining the hot water bath temperature at 70 ° C., ethyl acetate: 8
60 g and an MOI of 190 g were sequentially added, and 10 minutes later, tin 2-ethylhexanoate: 1 g was added. Heating and stirring were continued for 3 hours, and the end point was confirmed on the IR chart. Further, ethyl acetate used as a reaction solvent was desolvated by an evaporator to obtain a target multibranched compound.
The ¹ H-NMR chart of the obtained hyperbranched compound is shown in FIG. Table 1 shows various physical property values of the obtained hyperbranched compound.

[0057]

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Example 3 A 2000 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was charged with 20 g of ED and 20 g of PPG6A.
325 g, 4HBA: 96 g, ethyl acetate: 189 g,
After mixing 20 g of methanol and refluxing for 5 hours in a hot water bath set at 75 ° C., a part of the sample was sampled, and ¹ H-N
When the MR was measured, the proton peak derived from the acrylic group had almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, the solvent was distilled off while continuing to heat and stir at normal pressure in a water bath at 80 ° C., and a vacuum line was connected from the top of the condenser to 70 ° C. When the pressure was reduced to 40 mmHg or less in a hot water bath, ethyl acetate and methanol were completely distilled off to obtain a viscous liquid resin (yield 98%). Therefore, with the water bath temperature kept at 70 ° C., 630 g of ethyl acetate and 190 g of MOI were sequentially added, and 10 minutes later, 1 g of tin 2-ethylhexanoate was added. Heating and stirring were continued for 3 hours, and the end point was confirmed on the IR chart. Further, ethyl acetate used as a reaction solvent was desolvated by an evaporator to obtain a target multibranched compound. The ¹ H-NMR chart of the obtained hyperbranched compound is shown in FIG. Table 1 shows various physical property values of the obtained hyperbranched compound.

[0059]

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Examples 4 to 24 A four-necked round-bottomed flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was mixed with the polyamino compound (a) shown in Table 1 and an equivalent amount of ethyl acetate. Then, a solution prepared by diluting the active hydrogen-containing (meth) acrylic compound (b) to 75% by weight with ethyl acetate was added thereto with stirring. HEA as an active hydrogen-containing compound
Is used, except that the same molar number of methanol as the polyamino compound (a) is further added. 75 of the above reaction solution
After refluxing for 4 hours in a hot water bath set to ° C., a portion was sampled, ¹ H-NMR was measured, and the end point of the reaction was confirmed by the proton peak derived from the acrylic group. A diversion tube was set, and the solvent was distilled off while heating and stirring at normal pressure in a water bath at 80 ° C. Further, a vacuum line was connected from the top of the condenser, and ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less in a hot water bath lowered to 70 ° C.
A viscous liquid resin (core compound) was obtained. Therefore, lowering the water bath temperature 60 ° C., newly added so that the ethyl acetate to NV50%, such that the active hydrogen equivalent of the core compound is added an isocyanate group-containing vinyl monomer (c),
Further, the reaction system was diluted with ethyl acetate so that the concentration of the whole reaction system became 50%. After a further 10 minutes, tin 2-ethylhexanoate was added to 0.5% of the isocyanate group-containing vinyl monomer (c).
% By weight. Continue heating and stirring for at least 3 hours,
The point at which the characteristic absorption of the NCO group (2270 cm ^-1 ) in the IR chart disappeared was regarded as the reaction end point. Further, ethyl acetate used as a reaction solvent was desolvated by an evaporator to obtain a target multibranched compound. Table 1 shows the raw material composition at the time of synthesis of the obtained hyperbranched compound and the characteristics of the obtained hyperbranched compound. In addition, evaluation results of commercially available dipentaerythritol hexaacrylate (DHPA) and ethylene oxide-modified pentaerythritol triacrylate (TMPT3EO, TMPT6EO) measured by the same method as Comparative Examples 1 to 3 are also shown.

[0061]

[Table 1]

[0062]

(Examples 25 to 48) The multibranched compound obtained in Examples 1 to 24 was treated with a # 6 bar coater in four kinds of films (size → thickness of base material for evaluation; 20 μm, width;
5cm, length; 20cm)
(5, 20, 40 kGy) was irradiated with an electron beam. Table 2
In addition, the type of hyperbranched compound used and the curing characteristics of the coating film obtained by electron beam irradiation (touch test → ×: tack, △:
With no tack but with scratches on nails, ○: No damage due to no tacks on nails, substrate adhesion (non-peeling rate of coating film by cellophane tape peeling test), and solvent resistance (from weight change around 50 MEK rubbing tests) The obtained residual ratio), curl properties (evaluated by a sensory test of substrate film deformability → ○: no curl, Δ: degree of warpage, ×: film rolls), abrasion resistance evaluation results . Table 2 also shows the evaluation results of commercially available dipentaerythritol hexaacrylate and ethylene oxide-modified pentaerythritol triacrylate (TMPT3EO, TMPT6EO) as Comparative Examples 4 to 6.

[0064]

[Table 2]

[0065]

[0066]

According to the present invention, by using a polyfunctional liquid resin having a high viscosity and a low viscosity as a solvent-free curable resin according to the present invention, it can be used in ordinary solvent-free curable resin compositions. By reducing or eliminating the compounding ratio of low-molecular-weight compounds, which have problems in safety and physical properties, it contributes to the improvement of the working environment, and the coating of conventionally used roll coaters, knife coaters, etc. It can be formed by a printing method such as a processing method, offset printing, gravure printing, letterpress printing, screen printing, etc., and can be cured by conventional triggers such as heating, ultraviolet rays, infrared rays, electron beams, γ-ray irradiation, etc. An object of the present invention is to provide a multi-branched compound which can be cured without using a catalyst or an initiator in the case of irradiation with gamma rays or γ rays.

[Brief description of the drawings]

¹ H-NM of Figure 1 multi-branched compound obtained in Example 1
R chart

FIG. 2 shows ¹ H-NM of a hyperbranched compound obtained in Example 2.
R chart

FIG. 3 shows ¹ H-NM of the hyperbranched compound obtained in Example 3.
R chart

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 101/12 C08L 101/12 C09D 5/00 C09D 5/00 C 179/02 179/02 C09J 179/02 C09J 179/02 ( 72) Inventor Toru Kurihashi 2-13-13 Kyobashi, Chuo-ku, Tokyo Toyo Ink Manufacturing Co., Ltd. (56) References JP-A-11-193315 (JP, A) JP-A-11-193317 (JP, A) JP-A-11-193321 (JP, A) JP-A-11-193325 (JP, A) Table 11-11-510840 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 269/04 C08G 73/02

Claims (5)

(57) [Claims] 1. A polyamino compound (a) having two or three primary or secondary amino groups in the molecule and having three or more active hydrogens derived from the primary or secondary amino groups in the molecule, A hydrogen-containing (meth) acrylic compound (b) is Michael-added to a core compound having a branched structure, and the isocyanate group-containing vinyl stoichiometrically equivalent to the active hydrogen contained in the core material is added to the core compound. A method for producing a branched compound in which the compound (c) is added and reacted. 2. The polyamino compound (a) has the following formula (1)
The method for producing a branched compound according to claim 1, which is a diamino compound represented by the formula: H ₂ N—CH ₂ —R—CH ₂ —NH ₂ (1) (wherein, R is a direct bond, —C _n H _2n — (n represents an integer of 1 to 20), a phenylene group or a cycloalkyl group. Represents an alkylene group.) 3. The method for producing a branched compound according to claim 1, wherein the active hydrogen-containing (meth) acrylic compound (b) is at least one of the following formulas (2) to (5). CH ₂ CC (R ¹ ) COO—R ² —OH (2) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ² is a carbon number of ² to 22)
Each represents an alkylene group. ^{_{) CH 2 = C (R 1}} ) COO (C X H 2X O) m H (3) ( wherein, R ¹ represents a hydrogen atom or CH _3, x is an integer of 1 to 6, m
Represents an integer of 1 to 25, respectively. ) CH ₂ CC (R ¹ ) COOC _y H _2y O (COC _z H _2z O) _k H (4) (wherein, R ¹ is a hydrogen atom or CH ₃ , y is an integer of 2 to 22,
z represents an integer of 2 to 15, and k represents an integer of 1 to 20, respectively. ) CH ₂ CC (R ¹ ) CO R ³ O (CONH R ⁴ NHO R ⁵ O) _h H (5) (wherein, R ¹ is a hydrogen atom or CH ₃ , and R ³ is a carbon number of 2 to 22)
Alkylene group, an isocyanate residue R ⁴ is represented by the following formula (6-a) ~ (6 -h), R 5 is _{- (C r H 2r O)} q - (r
Represents an integer of 1 to 4, and q represents an integer of 1 to 20. ) Or -C _p H _2p -. _(P dihydric alcohol residue represented by representing) an integer of 1 to 20, h represents an integer of 1 to 10, respectively. ) 4. The method for producing a branched compound according to claim 1, wherein the polyamino compound (a) has an average molecular weight of 30 to 5,000. 5. A compound having a number average molecular weight of 200 to 10000,
It is a liquid having a viscosity of 10,000 cps (30 ° C.) or less.
Item 5. The method for producing a branched compound according to any one of Items 1 to 4.