JP2970664B2 - Hyperbranched compound and curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention can be used as a resin for film-forming materials such as paints and inks, or as a resin for sealants, molding agents, adhesives, and pressure-sensitive adhesives. It relates to a multi-branched compound which can be used as a curing agent or a reactive diluent for the composition. Further, the present invention relates to a multi-branched compound which can be used as a printing ink, a paint vehicle, an adhesive or the like as a heat / 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. Aqueous resin compositions require a large amount of heat to evaporate water as a dispersion medium, and often contain a small amount of organic solvent in order to further improve coatability, leaving a problem in terms of waste liquid treatment. I have. 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, etc. have been performed.
It is considered that the use amount of the resin solution will tend to decrease more in the future. But the fundamental solution is pollution,
There is a strong demand for the development of a solvent-free liquid resin composition which is free of problems of safety and health, ignition, explosion, etc., can be widely applied, and 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 are prepared from low-viscosity monomers such as various acrylic monomers, and reactive oligomers such as urethane acrylate, epoxy acrylate, or ester acrylate, and, if necessary, other resin components. 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. Also, in order to improve the mechanical performance of the cured product, it is preferable to blend a polyfunctional reactive diluent, a reactive oligomer, and further a high molecular weight resin material, but since these materials are high-viscosity or solid materials, Considering the flow characteristics of the composition before curing, a large amount of a reactive diluent must be blended, and the blending amount is limited. Therefore, the cured product obtained by curing the conventional solventless liquid resin composition has a hardness,
The cured product properties such as toughness, mechanical properties, and chemical resistance were poor and practically far from solvent-based or water-based resin compositions. 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.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a solventless resin composition having a sufficient coating film performance and a low viscosity which can be applied. It is an object of the present invention to provide a multi-branched compound that is made possible by using a low-viscosity polyfunctional liquid resin to reduce the blending ratio of a low-molecular-weight compound having problems in safety and performance. Conventional coating methods such as roll coater and knife coater, offset printing, gravure printing, letterpress printing, screen printing and other printing methods can be used to form films, heating, ultraviolet, infrared, electron beam,
A multi-branched compound and a curable resin 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 and γ-ray irradiation. It provides a composition.

The inventor of the present invention has 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 low viscosity while having a high molecular weight and can be multifunctionalized. In addition, the present inventors have found that the multibranched compound has an active hydrogen-containing functional group at the terminal, and thus exhibits good adhesion to various base materials, particularly to plastic materials which have been considered to be very difficult in radiation curing systems. Furthermore, curing is performed at a higher speed by using a conventional curing method, particularly using an electron beam as a trigger, within a viscosity range in which a film can be formed by a conventional film forming method while containing a large amount of a high molecular weight component. A multi-branched compound that is a new liquid resin that can be used has been found.

[0005]

That is, the present invention relates to a polyamino compound (a) having two or three primary or secondary amino groups in the molecule, and a method of converting an active hydrogen-containing (meth) acrylic compound (b) into a Michael compound. A core compound is added to the core compound, and a vinyl compound (c) having a functional group capable of reacting with active hydrogen is added to the core compound so that active hydrogen other than active hydrogen derived from the vinyl group remains at the terminal. Related to branched compounds.

Further, the present invention relates to the above-mentioned multi-branched compound wherein the polyamino compound (a) has a number average molecular weight of 30 to 1,000. Further, the present invention relates to the above-mentioned multi-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 is characterized in that a vinyl compound (c) having a functional group capable of reacting with active hydrogen is added to at least one of all active hydrogen terminals of the core compound, and the total active hydrogen of the core compound is added. To the above-mentioned multibranched compound obtained by adding a vinyl compound (c) having a functional group capable of reacting with active hydrogen to 95% or less of the compound. Further, the present invention has a number average molecular weight of 200 to 10,000 and a viscosity of 100,000 c.
The present invention relates to the above-mentioned multi-branched compound which is a liquid of not more than ps (30 ° C.). Further, the present invention provides the above-mentioned multibranched compound (A)
The present invention relates to a curable composition comprising 99% by weight and 1 to 95% by weight of a polymerizable unsaturated group-containing compound (B) other than the above.

Further, the present invention relates to the above curable composition wherein the viscosity of the polymerizable unsaturated group-containing compound (B) is 10,000 cps (30 ° C.) or less. Furthermore, the present invention relates to the above curable composition, wherein the polymerizable unsaturated group-containing compound (B) is a (meth) acrylic monomer. Furthermore, the present invention
The present invention relates to the above curable composition which is of a radiation curing type. Further, the present invention relates to a printing ink using the curable composition. Further, the present invention relates to a paint using the curable composition. Further, the present invention relates to a cured product obtained by irradiating the curable composition with radiation.

[0009]

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 multibranched structure, and contains active hydrogen derived from a primary or secondary amino group in the molecule. A compound having a total of three or more,
A linear / branched aliphatic polyamino compound, a cyclic aliphatic polyamino compound, an aliphatic aromatic polyamino compound, an aliphatic aromatic polyaminopolyol compound and the like can be mentioned.

The straight-chain / branched aliphatic amine used in the present invention includes hydrazine compounds such as hydrazine and adipic dihydrazide; ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, diaminooctane, diaminodecane; Examples thereof include diamino compounds represented by the following general formula (1) such as 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, bis (aminomethyl)
-Bicyclo [2,2,1] heptane, methylenebis (furanmethanamine) and the like.

Further, examples of the aliphatic aromatic polyamino compound include meta-xylene diamine and para-xylene diamine. Examples of the aliphatic aromatic polyaminopolyol compound include an ethylene oxide adduct of meta-xylene diamine, a propylene oxide adduct of meta-xylene diamine, an ethylene oxide adduct of para-xylene diamine, and a propylene oxide adduct of para-xylene diamine. Can be.

Of these, the use of a diamino compound generalized by the following formula (1) is preferable from the viewpoint of improving the mechanical properties after curing because the shape of the core compound can be variously changed. _{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
Represents an integer of 0, preferably 1 to 12. ) Represents an alkylene group, a phenylene group or a cycloalkylene group. )

Since these polyamino compounds (a) are starting materials for the core compound, those containing amino groups at a higher density in one molecule are more effective for lowering the viscosity and multifunctionalization of the multi-branched compound. is there. In order to satisfy such an object, a diamino compound having a low molecular weight such as ethylenediamine, tetramethylamine and xylylenediamine, or a compound having three primary or secondary amino groups such as diethylenetriamine is preferable. Further, the number average molecular weight of the polyamino compound (a) used in the present invention is not particularly limited, but a preferable molecular weight range is 30 to 10,000 as a number average molecular weight, more preferably 50 to 5 as a number average molecular weight.
A compound having a number average molecular weight of 500, especially 10
A polyamino compound having a molecular weight of 00 or more may be unfavorable in handling due to high viscosity or solid.

When the polyamino compound (a) contains a primary amino group, the two active hydrogens derived from the amino group and the active hydrogen-containing (meth) acrylic compound (b) are Michael-added to form a multibranched core compound. Is possible. In addition, active hydrogen containing (meta) introduced at the terminal
The active hydrogen derived from the acrylic compound (b) or the unreacted active hydrogen derived from the amino group of the polyamino compound (a) is used in the addition reaction with the vinyl compound (c) having a functional group capable of reacting with the active hydrogen. Functions as a reaction site.

The active hydrogen-containing (meth) acrylic compound (b) of the present invention is a (meth) acrylic compound having an active hydrogen-containing group such as a hydroxyl group or a carboxyl group in the molecule, and one or more active hydrogen-containing compounds in the molecule. Having a hydroxyl group (meta)
Examples of the acrylic compound include a hydroxyalkyl (meth) acrylate compound represented by the following formula (2): CH ₂ ＣC (R ¹ ) COO—R ² —OH (2) (where R ¹ is a hydrogen atom Or CH ₃ and R ² have 2 to 2 carbon atoms
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) wherein 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. )

A polylactone mono (meth) acrylate compound represented by the following formula (4): CH ₂ ＣC (R ¹ ) COOC _y H _2y O (COC _z H _2ZO ) _k H (4) 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^FourIs an isocyanate represented by the following a to h
Anate residue, R^FiveIs-(C_rH_2rO)_q-Or -C _pH
_2pA dihydric alcohol residue represented by-, where r is 1 to 4
, P is an integer of 2 to 22, h is an integer of 1 to 10, and q is
Each represents an integer of 1 to 100. )

[0020]

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In the present invention, the chain length of the active hydrogen-containing (meth) acrylic compound (b) should be short if a hard cured product is required, and it should be flexible. For the purpose of improvement, those having a long chain length are preferred. Within the above range, the bulk viscosity tends to decrease despite an increase in the molecular weight as the chain length increases. If the length is longer than the above range, the bulk viscosity of the multi-branched compound is increased, and the compound is solid at ordinary temperature, and the curability may be poor.

More specifically, examples of the hydroxyalkyl (meth) acrylate compound represented by the general formula (2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxybutyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate.

As the alkylene glycol mono (meth) acrylate compound represented by the general formula (3), for example, diethylene glycol mono (meth) acrylate,
Triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tripropylene glycol (meth) acrylate, dipropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (Meth) acrylate and the like.

The polylactone mono (meth) acrylate compound represented by the general formula (4) is 2- (meth) acrylate
Acryloyloxyethyl hydrogencaprolact
Tonate, 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate, 2- (meth) acryloyloxyethyl hydrogen poly (degree of polymerization: 3 to
5) Caprolactonate, 2- (meth) acryloyloxyethyl-2-hydroxy-6 hexanolactonate and the like.

Further, in addition to the general formulas (2) to (4), 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, Hydroxy-
3-phenoxypropyl (meth) acrylate,
Glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene oxide-modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, and ethylene oxide-modified trimethylolpropane mono (meth) acrylate An active hydrogen-containing (meth) acrylic compound (b) containing a hydroxyl group as described above can also be mentioned.

Examples of the (meth) acrylic compound having a carboxyl group in the molecule include maleic acid, fumaric acid, itaconic acid, citraconic acid, and their alkyl or alkenyl monoesters and 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 And methacrylic acid.

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). The compounding amount of the (meth) acrylic compound (b) is preferably 10% or more, more preferably 50% or more, of the total active hydrogen of the polyamino compound. It is desirable to react with. If the amount is less than this, a multi-branched structure is hardly obtained, and the characteristics of the active hydrogen-containing hydrogen compound (b) component are not sufficiently reflected.

The reaction for obtaining the core compound of the present invention can be basically carried out in accordance with a conventional method. However, 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 amino 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 10 when heated to 50 to 100 ° C.
End within hours.

In the present invention, the vinyl group is introduced into the core compound in order to make it reactive, and is not particularly limited as long as it has a polymerizable double bond, but the preferred structure is shown below. CH ₂ = CHCOO-; acrylic group _{CH 2 = CH (CH 3)} COO-; methacrylic group CH ₂ = CH-; vinyl group _{CH 2 = CH-CH 2 -O-} ; allyl -CH = CH-; dienyl Group CH ₂ ＣＨCH—C ₆ H ₄ —; phenyl vinyl group CH ₂ ＣＨCH—O—; vinyl ether group Among the above vinyl groups, an acrylic group is preferable in UV curing from the viewpoint of reactivity during radiation curing, and an electron beam. At the time of curing, a relatively high curability is exhibited even with a methacryl group, which can be said to be preferable in terms of both reactivity and safety. Further, the combined use of an acrylic group and a vinyl group is also preferable from the viewpoint of improving the reactivity.

In the present invention, the hyperbranched compound is obtained by introducing a vinyl group into the above-mentioned core compound. Basically, an active hydrogen-containing terminal functional group contained in the core compound and a functional group capable of reacting with active hydrogen are contained. It is obtained by reaction with a vinyl group-containing compound (c) having a group. The core compound has an active hydrogen terminal functional group such as a hydroxyl group, a carboxyl group, and an amino group. If the compound has a functional group that can react with these active hydrogen terminal functional groups, a functional group that can react with active hydrogen The vinyl group-containing compound (c) having is not particularly limited.

Examples of the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen include an epoxy group-containing vinyl compound, an alkoxysilyl group-containing vinyl compound, a phosphoric acid group-containing vinyl compound, and an isocyanate group-containing vinyl compound. And the like.

Examples of the epoxy group-containing vinyl compound include glycidyl (meth) acrylate, allyl glycidyl ether, epoxycyclohexylmethyl (meth) acrylate, epoxycyclohexylmethyl polycaprolactone (meth) acrylate, vinylcyclohexyl epoxide, and methylglycidyl methacrylate. Can be.

Examples of the alkoxysilyl group-containing vinyl compound include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane and the like. Can be mentioned.

Examples of the phosphoric acid group-containing vinyl group compound include acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, acid phosphooxypropyl methacrylate, acid phosphooxyethyl acrylate, and acid phosphooxypolyoxyethylene. Glycol monomethacrylate, acid phosphooxy polyoxypropylene glycol monomethacrylate and the like can be mentioned.

When the active hydrogen terminal functional group of the core compound used in the present invention is a hydroxyl group, a vinyl group is introduced into the core compound using an isocyanate group-containing vinyl compound which reacts with the hydroxyl group under mild conditions. This method is desirable in view of the stability of the terminal vinyl group. Examples of the isocyanate group-containing vinyl compound include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate (MAI), and 3-isopropenyl-α, α-dimethylbenzyl isocyanate (TMI). There is. 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 equimolar amount can also be used as the isocyanate group-containing vinyl compound.

As the above 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, 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-tetramethylxylene Range isocyanate, p-tetramethylxylylene diisocyanate, dimer Mention may be made of a diisocyanate.

Examples of the vinyl compound containing a functional group capable of reacting with the isocyanate group include a vinyl compound having an amino group, a hydroxyl group, a carboxyl group and the like.
Those having a hydroxyl group or a carboxyl group are preferred from the viewpoint of reactivity with an isocyanate group. 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. -Hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen caprolactonate, and the like.

The rate of vinyl group introduction in the present invention is not particularly limited as long as at least one is introduced with respect to all active hydrogens present in the core compound.
It is 0 to 95%, more preferably 20 to 80%. If it is less than this, it is not preferable because sufficient curability is not obtained, and if it is more than this, the viscosity of the obtained multibranched compound is increased,
It is not preferable because a decrease in compatibility with other components and a decrease in film properties such as adhesion may be observed. For example, the compounding amount of the isocyanate group-containing vinyl compound (c) is determined based on the amount of unreacted active hydrogen derived from the polyamino compound present in the core compound,
Or an active hydrogen group-containing (meth) acrylic compound (b-
There is no particular limitation as long as it is added to at least one of the active hydrogen groups derived from 1), but it is preferably 10 to 95%, more preferably 20 to 80%.

When the above isocyanate group-containing vinyl compound (c) is added, a catalyst used in ordinary urethane synthesis, for example, a tin catalyst such as tin 2-ethylhexanoate may be added, if necessary. You may. A preferable addition amount of the catalyst is 0.01 to 1% by weight based on the isocyanate group-containing vinyl compound (c).

The hyperbranched compound of the present invention has a number average molecular weight of 200 to 10,000, preferably 300 to 500.
0, more preferably 400 to 4000, and 1000
00 cps or less, preferably 50,000 to 500 cp
s, more preferably a liquid having a viscosity (30 ° C.) of 200,000 to 1000 cps. If the molecular weight is lower than this, curing shrinkage becomes severe, which is not preferable. On the other hand, if the molecular weight is high, the viscosity tends to increase, which is not preferable from the viewpoint of coating properties. If the viscosity exceeds the above range, it is not preferable in terms of solubility with other components and film forming properties.

In the present invention, the hyperbranched compound (A)
Has sufficient coating performance even when used alone, but is mixed with another polymerizable unsaturated group-containing compound (B) for the purpose of adjusting the viscosity and curability of the cured composition, It can also be. In the present invention, the polymerizable unsaturated group-containing compound (B) other than the hyperbranched compound is one in the molecule.
The compound is not particularly limited as long as it has at least two unsaturated double bonds, and examples thereof include (meth) acrylic compounds and vinyl compounds. Among these, from the viewpoint of safety and availability, The use of (meth) acrylic compounds is preferred.

As the (meth) acrylic compound, for example,
Methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenty Nyl (meth) acrylate, (dicyclopentenyl)
Monofunctional (meth) acrylic compounds such as oxy (meth) acrylate,

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-
Octanediol diacrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis [4-{(meth) acryloxydiethoxy} phenyl] propane,
2,2-bis [4-{(meth) acryloxyethoxy}
Phenyl] propane, 2,2-bis [4-{(meth) acryloxypolyethoxy} phenyl] propane, 2,
2-bis [4-{(meth) acryloxydipropoxy} phenyl] propane, 2,2-bis [4-{(meth) acryloxypropoxy} phenyl] propane,
2,2-bis [4-{(meth) acryloxy-polypropoxy} phenyl] propane, tricyclo [5.2.
1.0 ^2,6 ] decanyldi (meth) acrylate
Functional (meth) acrylic compounds,

Trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, ethylene oxide-modified trimethylolpropanetri (meth) acrylate Tri- or more functional (meth) such as dipentaerythritol hexa (meth) acrylate
An acrylic compound can be used.

Further, as the vinyl compound, for example,
Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, vinyl cyclohexyl ether, vinyl-4-hydroxybutyl ether, butanediol-1,4-divinyl ether, vinyl pyrrolidone,
Vinylcaprolactam, vinylcarbazole, vinyl-
Examples thereof include 1-imidazole, divinylethylene urea, N-vinylformamide, N-vinylformalin, allyl glycidyl ether, allyl chloride and the like. Further, a diene compound, a styrene compound, an unsaturated fatty acid compound, or the like may be used.

In the present invention, the hyperbranched compound (A)
The compounding ratio of the polymerizable unsaturated group-containing compound (B) is preferably (A) :( B) = 5: 95 to 99: 1,
The ratio is more preferably from 20:80 to 80:20. If the content of (A) is less than this, the curing properties are remarkably deteriorated, for example, the curing shrinkage becomes severe. Further, the viscosity of the cured product obtained in the present invention is 10 to 50,000 cps (3
0 ° C.) is desirable, and if it is desired to obtain a cured product having a lower viscosity than this, a large amount of the polymerizable unsaturated compound (B) is required, which is not preferable, and those having a higher viscosity are not preferable because of poor coatability.

The hyperbranched compound obtained in the present invention is
As it is, it can be used as a non-solvent liquid resin that can be used as a film-forming material such as paints and inks, as a molding material, as an adhesive, etc. By adding and mixing the agents, the viscosity can be adjusted, and the film forming property and the film 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. In addition, if necessary, solvent, compatibilizer, surfactant or
A lubricant or the like may be added. The amount of these compounds is 20% by weight, preferably 10% by weight or less.

To the curable liquid resin obtained by the present invention, a coloring agent comprising a dye, a pigment such as carbon black, titanium white, phthalocyanine, an azo dye, or quinacridone, or an inorganic filler such as Si-based fine particles, mica, or calcium carbonate is suitably used. By adding it in an appropriate amount, it can be used as various printing inks, colored paints, and the like. In the case of curing by irradiation with a radiation, a known photopolymerization sensitizer or initiator can be added. Further, in order to improve the fluidity of the curable composition, water or an organic solvent may be blended.

The multibranched 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. Can be cured. The composition for a film-forming material using the liquid resin of the present invention is applied to a base material such as various steel plates, metal plates such as aluminum plates, plastic films, papers, and plastic film laminated papers by a coating method such as a roll coater or 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 keV, more preferably 3
An electron beam irradiation device having an acceleration voltage in the range of 0 to 300 kV is used. The use of an electron beam irradiator with a low accelerating voltage is more effective for curing a thin film because energy is more concentrated on the surface of the coating film. The irradiation dose (DOSE) is preferably 1 to 1000 kGy, more preferably 5 to 200 kGy.
Range. 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.

[0051]

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. 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 equipment and irradiation conditions 1) Area beam type electron beam irradiation equipment Curetron EBC-200
-20-30 (Nisshin High Voltage) Electron beam acceleration: 150 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: 50 keV 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-xylene diamine MXDA-EO2: Ethylene oxide-modified meta-xylene diamine (amine / ethylene oxide = 1/2 (m
ol / mol)) MXDA-PO2: propylene oxide-modified meta-xylene diamine (amine / propylene oxide = 1/2)
(Mol / mol)) DETA: diethylenetriamine IPDA: isophoronediamine 2) Active hydrogen-containing (meth) acrylic compound (b) 4HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate PPG6A: polypropylene glycol (polymerization of PPG chain Degree = 6) Acrylate PEG7A: Polyethylene glycol (degree of polymerization of PEG chain = 7) Acrylate PCL2A: 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate (Placcel FA-2 manufactured by Daicel Chemical Industries, Ltd.) SA: 2 -Acryloyloxyethyl ethyl hydrogen succinate 3) isocyanate group-containing vinyl compound MOI: methacryloyloxyethyl isocyanate TMI: 3-isopropenyl-α, α-dimethyl 4) Polymerizable unsaturated group-containing compound (B) PEG9DA: polyethylene glycol diacrylate (Mn = 508, η = 36.2 cps) NODA: 1,9 nonanediol di Acrylate (Mn = 2
68, η = 7.3 cps) TPGDA: tripropylene glycol diacrylate (Mn = 300, η = 12 cps) TMPT3EO: EO-modified trimethylolpropane triacrylate NK ester A-TMPT-3EO (Mn manufactured by Shin-Nakamura Chemical Co., Ltd.)
= 428, η = 50 cps) DPHA: dipentaerythritol hexaacrylate (Mn = 578, η = 5000 cps) In other comparative examples, UV-1700B as a linear urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Shikko UV-1700B ( Mn = 2000, η = 22500 cps) were used.

(Synthesis Example 1) An 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) Equimolar adduct of isophorone diisocyanate (IPDA) 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 (HMDI) 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 HMDI 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.

(Synthesis Example 7) Equimolar adduct of IPDI and PPG6A Stirrer, nitrogen inlet tube, temperature sensor, condenser,
Then, IPDI: 222 g, ethyl acetate: 222 g, tin 2-ethylhexanoate: 0.3 g were mixed in a 1000 ml four-necked round bottom flask equipped with a dropping funnel filled with a mixed solution of 510 g of PPG6A and 510 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 Synthesis of ED / 4HBA / MOI = 1/4/3 (１ ／ mole scale) ED was placed in a 1000 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser. : 20.1 g, 192.2 g of 4HBA, 71 g of ethyl acetate, and 20 g of methanol were mixed, refluxed for 3 hours in a hot water bath set at 75 ° C., then partially sampled, and ¹ H-NMR was measured. As a result, the proton peak derived from the acryl group 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
A viscous liquid resin was obtained (98% yield). Then, the temperature of the hot water bath was lowered to 60 ° C., MOI: 155.15 g and ethyl acetate: 367 g were added, and after 10 to 30 minutes, 2-ethylhexane was added. Tin acid: 0.8 g was added. The heating and stirring were continued for 3 to 4 hours, and the NCO group characteristic absorption (227
The point at which 0 cm ^-1 ) disappeared was regarded as the reaction end point. Further, the target polybranched compound was obtained by removing the solvent from the ethyl acetate used as a reaction solvent by an evaporator. Table 1 shows the physical properties of the obtained hyperbranched compound, and Tables 2 and 3 show the physical properties of the polymerizable composition comprising the hyperbranched compound and the polymerizable unsaturated group-containing compound.

(Example 35) ED / PPG6A / Synthesis Example 4 = Synthesis of 1/3/3 (1/3 mol scale) Four 1000 ml four-necked port equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser In a round bottom flask, ED: 20 g, PPG6A: 510 g, ethyl acetate: 2
07 g and methanol: 20 g were mixed and refluxed in a hot water bath set at 75 ° C. for 6 hours.
^{When 1} H-NMR was measured, the proton peak derived from the 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. 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: 96%). Therefore, hot water temperature 7
While keeping the temperature at 0 ° C., ethyl acetate was newly added so that the NV became 50%, 233 g of Synthesis Example 4 was added, and the mixture was further diluted with ethyl acetate so that the concentration of the whole reaction system became 50%.
After another 10 minutes, 1.1 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.

(Examples 1 to 34 and 34 to 57) Stirring
Equipment, nitrogen inlet, temperature sensor, and condenser
In a four-necked round-bottomed flask equipped with
Compound (a) and an equivalent amount of ethyl acetate,
Ethyl acetate (b) containing silicon-containing (meth) acrylic compound
While stirring the solution diluted to 75% by weight
Was added. When HEA is used as an active hydrogen-containing compound
Except for the case where the amino compound (a)
Ingredients. Hot water set at 75 ° C for the above reaction solution
After refluxing in the bath for 4 hours, a part of the sample was taken,¹H
-Measure the NMR and determine the proton peak derived from the acrylic group.
After confirming the end point of the reaction,
Set a shunt tube in between and heat at 80 ° C hot water bath at normal pressure.
The solvent was distilled off while stirring was continued. Further condenser
Connect a vacuum line from the top and use a hot water bath cooled to 70 ° C.
By reducing the pressure to 0 mmHg or less, ethyl acetate and
Liquid and viscous liquid resin
I got Therefore, with the hot water bath temperature kept at 70 ° C, acetic acid was newly added.
Is added so that the NV becomes 50%.
Group-containing vinyl compound (c) as (meth) acrylic compound
(B) The number of moles was added.
It was diluted with ethyl acetate to 0%. Another 10 minutes
Then, tin 2-ethylhexanoate is added to an isocyanate group-containing
0.5% by weight of the carbonyl compound (c) was added. 3 as it is
Continue to heat and stir for more than an hour, NCO group characteristics of IR chart
Absorption (2270cm ^-1) Disappearance is defined as the reaction end point.
Was. Furthermore, the ethyl acetate used as the reaction solvent was evaporated
Solvent to remove the target multi-branched compound
Obtained. Raw material composition and yield during synthesis of the obtained multi-branched compound
Table 1 also shows the properties of the obtained multibranched compound. Also, the ratio
Active hydrogenation at the end measured by the same method as a comparative example
Hyperbranched compound having no compound (ED / HEA / MOI =
1/4/4, ED / 4HBA / MOI = 1/4/4, E
D / PPG6A / synthetic system 4 = 1/4/4) and commercially available
Linear urethane acrylate: violet UV-1700B,
The evaluation results of and are also shown.

[0062]

[Table 1]

[0063]

(Examples 58 to 83) Curable compositions prepared by using some of the polybranched compounds obtained in Examples 1 to 57 and various compounds containing a polymerizable unsaturated group (B) were prepared.
Table 2 shows the compositions and viscosities of these curable compositions. The curable composition and the multi-branched compound were coated on four kinds of films (size of base material for evaluation → thickness: 20 μm, width: 5 cm, length: 20 cm) with a # 6 bar coater, and various The electron beam was irradiated with DOSE (5, 20, kGy). Table 3 shows the composition of the curable composition used or the type of the hyperbranched compound and the curability of the coating film obtained by electron beam irradiation (touch test → ×: tack present, Δ: no tack but scratched by nail) Yes, ○: No damage due to tackless nails), substrate adhesion (non-peeling rate of coating film by cellophane tape peeling test), solvent resistance (residual rate determined from weight change around 50 MEK rubbing tests), The evaluation results of the wear properties are shown. As a comparative example, a hyperbranched compound having no polar group at the terminal (ED / HEA / MOI = 1/4/4) measured by the same method, and a commercially available linear urethane acrylate: purple light UV-1
The evaluation results of the curable composition using 700B are also shown.

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

According to the present invention, by using a multi-branched compound having a high molecular weight, a low viscosity, and having an active hydrogen-containing site at a terminal as a solvent-free type cured resin, various base materials, particularly, It has become possible to provide a resin and a resin composition exhibiting good adhesion to a plastic substrate, which has been considered to be extremely difficult with a radiation curing system. This contributes to the improvement of the working environment by reducing or eliminating the blending ratio of low-molecular-weight compounds that are problematic in terms of safety and physical properties used in ordinary solvent-free curable compositions. The film can be formed by a coating method such as a roll coater and a knife coater which have been conventionally used, and a printing method such as offset printing, gravure printing, letterpress printing, screen printing, and heating, ultraviolet rays, infrared rays, electron beams, and γ rays. It can be cured by a conventional trigger such as irradiation, especially in the case of electron beam, γ-ray irradiation, etc., and can be cured without using a catalyst or an initiator,
It has become possible to provide a multi-branched compound exhibiting high adhesion to various plastics, which has been considered difficult so far.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 220/36 C08F 220/36 C09D 4/00 C09D 4/00 5/00 5/00 C 11/10 11/10 175/16 175/16 // C09J 4/00 C09J 4/00 175/16 175/16 (72) Inventor Miki Kawashima Examiner, Toyo Ink Manufacturing Co., Ltd. Tsutomu Onodera, 2-3-13-1 Kyobashi, Chuo-ku, Tokyo (56) JP-A-11-140042 (JP, A) JP-A-9-31150 (JP, A) JP-A-8-259660 (JP, A) JP-A-1-33170 (JP, A) JP-A-49 -94736 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C07C 271/00-271/68 C08F 2 / 00-2/60 C08F 12/00-12/36 C08F 212/00-212/36 C08F 20/00-20/70 C08F 220/00-220/70 C09D 1/00-201/10 C09J 1/00- 201/10

Claims (12)

(57) [Claims] 1. A two primary or secondary amino group in the molecule or
Other are polyamino compound having three (a) an active hydrogen-containing (meth) acrylic compound (b) to Michael addition co
And A compound, a vinyl compound having a functional group reactive with an active hydrogen to the core compound (c), vinyl-terminated HajimeYukari
So that active hydrogen other than the original active hydrogen remains
Multi-branched compound made. 2. The hyperbranched compound according to claim 1, wherein the polyamino compound (a) has a number average molecular weight of 30 to 1,000. 3. The multibranched compound according to claim 1, 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. ) 4. A vinyl compound (c) having a functional group capable of reacting with active hydrogen is added to at least one of all active hydrogen terminals of the core compound, and 95% of the total active hydrogen of the core compound is added. The hyperbranched compound according to any one of claims 1 to 3, wherein a vinyl compound (c) having a functional group capable of reacting with active hydrogen is added below. 5. The hyperbranched compound according to claim 1, which is a liquid having a number average molecular weight of 200 to 10,000 and a viscosity of 100,000 cps (30 ° C.) or less. 6. A curable composition comprising 5 to 99% by weight of the multibranched compound (A) according to any one of claims 1 to 5 and 1 to 95% by weight of a compound having a polymerizable unsaturated group (B) other than the above. Composition. 7. A polymerizable unsaturated group-containing compound (B) having a viscosity of 1
The curable composition according to claim 6, which is in a liquid form of 0000 cps (30 ° C) or less. 8. The curable composition according to claim 6, wherein the polymerizable unsaturated group-containing compound (B) is a (meth) acrylic monomer. 9. The curable composition according to claim 6, which is of a radiation-curable type. 10. The method of claim 6 to 9 printing ink obtained by using the hardening composition according to any one. 11. The method of claim 6 to paint made with 9 curable composition according to any. 12. The method of claim 6 to 11 cured product obtained by irradiating the curable composition according to any.