JP2000063513A - Dendrimer containing vinyl group - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To reduce the compounding ratio of a low molecular weight compound having a problem in safety or physical properties by using a high molecular weight and low viscosity vinyl group-containing dendrimer in a solventless resin composition. , Which contributes to the improvement of the work environment, and also uses coating methods such as roll coaters and knife coaters that are conventionally used, offset printing, gravure printing, letterpress printing,
Films can be formed by a printing method such as screen printing.Also, in the case of conventional active energy rays such as ultraviolet rays, infrared rays, electron beams, and γ-ray irradiation, particularly in the case of electron beams and γ-ray irradiation, a catalyst or an initiator is used. It is an object of the present invention to provide a low-viscosity, curable vinyl group-containing dendrimer that can be cured without using the same. SOLUTION: A polyfunctional compound (a) obtained by adding an active hydrogen-containing (meth) acrylate compound (b) to a polyamino dendrimer with Michael is reacted with active hydrogen contained in the polyfunctional compound (a). A vinyl group-containing dendrimer obtained by stoichiometrically reacting with a vinyl group-containing compound (c) having a possible functional group.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can be used as a resin for film forming materials such as paints and inks, or as a sealing agent, a molding agent, an adhesive, and a pressure-sensitive adhesive. The present invention relates to a vinyl group-containing dendrimer that can be used as a curing agent or a reactive diluent for a resin composition.
Further, the present invention relates to a vinyl group-containing dendrimer which can be used as a heat- or radiation-curable resin as a printing ink, a paint vehicle, an adhesive, or the like.

[0002]

2. Description of the Related Art Conventionally, paints, adhesives, adhesives, inks,
Resin solutions containing organic solvents have been used as fillers and molding materials. These resin solutions scatter a large amount of organic solvents in the painting, filling and curing / drying steps. With increasing interest in the global environment and the working environment, restrictions on the use of such resin solutions have come to be imposed. As one of the methods, development of resin materials such as water-soluble resin, powder and hot melt has been promoted. A water-based resin composition requires a large amount of heat in order to evaporate water as a dispersion medium, and often contains a small amount of an organic solvent from the viewpoint of improving the coating property, and a problem remains from the viewpoint of waste liquid treatment. There is. In addition, in the case of coating or filling powder or hot melt, it is necessary to introduce new equipment because the method is significantly different from the conventional painting and filling equipment. In order to solve the above problems, high solidification of resin solution,
Improvements have been made to water-soluble resins, and with such efforts, it is considered that the amount of the resin solution used will become more prominent in the future. However, as a fundamental solution, there is no problem of pollution, safety and health, ignition, explosion, etc., it can be widely applied, and coating, development of a solventless liquid resin composition that is easy to fill is strongly desired. There is.

A typical example of the solventless liquid resin composition is a radiation curable resin composition. Conventional radiation-curable resin compositions are composed of low-viscosity monomers such as various acrylate-based monomers, 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 is contained in a large amount, the volume shrinkage upon curing is large, and the cured coating film is fragile. There has been a problem of odor due to residual monomers in the coating film. Therefore, improvements such as reduction in the amount of reactive diluent used and increase in molecular weight have been desired.

Further, in order to improve the mechanical performance of the cured product, it is preferable to blend a polyfunctional reactive diluent, a reactive oligomer, and a high molecular weight resin material, etc., but these materials have a high viscosity or are solid. Therefore, considering the flow characteristics of the composition before curing, a large amount of a reactive diluent needs to be blended, and the blending amount is limited. Therefore, a cured product obtained by curing a conventional solventless liquid resin composition is poor in cured product properties such as hardness, toughness, mechanical properties and chemical resistance, and is practically a solvent-based or water-based resin composition. It was a property far inferior. Radiation-curable resin compositions containing large amounts of high-molecular weight reactive oligomers and resin materials have been developed for the purpose of improving coating film performance, but low-molecular weight reactive dilutions are used to reduce the viscosity to a coatable level. It is difficult to say that environmental improvements have been made due to the use of agents and organic solvents.

Further, in recent years, with the progress of research on polymers having a highly branched structure such as comb-shaped, star-shaped, and dendrimer, dendrimers having a methacrylic group at the end have been studied (Ref. Shi W.et .al., J Appl Polym Sci, 5
9,12,1945 (1996)., Moszner N.et.al., Macromol chem p
hys, 197, 2, 621 (1996). JP-A-8-231864). However, the known compounds have not been able to obtain sufficient curability as a radiation curing material and sufficient adhesion to a substrate. Regarding viscosity, it can be said that it has a low viscosity as compared with a linear compound having the same molecular weight, but the object of obtaining a low-viscosity resin composition by blending in a large amount has not been sufficiently achieved.

[0006]

DISCLOSURE OF THE INVENTION The present invention aims to obtain a solventless resin composition having a sufficient coating film performance and a low viscosity that can be coated, and has a high molecular weight. It is intended to provide a vinyl group-containing dendrimer capable of reducing the compounding ratio of a low molecular weight compound having a problem in safety and performance by using a polyfunctional liquid resin having a low viscosity. Further, the present invention, conventionally used roll coater, coating method such as knife coater, offset printing, gravure printing, letterpress printing, can be formed into a film by a printing method such as screen printing, heating, ultraviolet rays,
Contains vinyl groups that can be cured by conventional triggers such as infrared rays, electron rays, and γ-ray irradiation, and can be cured without the use of catalysts or initiators especially in the case of electron rays and γ-ray irradiation. It provides a dendrimer.

In order to solve the above-mentioned problems, the present inventor has conducted earnest research on the correlation between the structure of various resin systems and the viscosity, and as a result, comb-shaped polymers, and further multi-branched polymers, rather than general linear polymers. By changing the molecular structure of the polymer, it was found that the polymer has a high viscosity and low viscosity, and that many terminal functional groups such as vinyl groups can be introduced into one molecule. Furthermore, they have found a vinyl group-containing dendrimer, which is a new liquid resin that can be cured at a high speed by using a conventional curing method, particularly by using an electron beam as a curing trigger.

[0008]

[Means for Solving the Problems]

That is, the present invention provides a polyamino dendrimer with an active hydrogen-containing (meth) acrylate compound (b).
And a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen contained in the polyfunctional compound (a), in a stoichiometric manner. The present invention relates to a vinyl group-containing dendrimer formed by reacting an equal amount. Further, the present invention relates to the above vinyl group-containing dendrimer, wherein the polyamino dendrimer is a compound represented by the following formula (i) or (ii).

[0010]

[Chemical 2]

The present invention further relates to the above vinyl group-containing dendrimer, wherein the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen is an isocyanate group-containing vinyl compound (c-1). Furthermore, the present invention relates to the vinyl group-containing dendrimer, wherein the chain length of the branch portion introduced with the vinyl group has 9 to 70 atoms. Furthermore, the present invention has a number average molecular weight of 200 to 100,000 and a viscosity of 100,000.
The present invention relates to the above vinyl group-containing dendrimer which is liquid at cps (30 ° C.) or less. Further, the present invention relates to the above-mentioned vinyl group-containing dendrimer which is an active energy ray curable type. Furthermore, the present invention relates to the above vinyl group-containing dendrimer for use in coatings.

The present invention further relates to the above-mentioned vinyl group-containing dendrimer for use in ink. Furthermore, the present invention relates to a cured product obtained by irradiating the above vinyl group-containing dendrimer with an active energy ray.

Generally, the term dendrimer has been used for highly branched and highly ordered multibranched compounds. However, with the recent progress of research on synthetic methods of dendrimers, various multi-branched compounds with low regularity have been developed as new dendrimers for the purpose of simplifying synthetic methods such as development of dendritic compounds by one-step method. The current situation is that no conclusion has been reached regarding the nomenclature. Therefore, in the present invention, a dendrimer refers to a three-dimensionally branched multi-branched compound, and generically refers to a hyper-branched low regularity and a highly regular dendrimer. Such a dendrimer is composed of a core site, a branch site, a branch site, and a terminal site, as shown in FIG. FIG. 1 further shows a model diagram of a minimum unit dendrimer and a standard dendrimer according to the present invention, and the number of branches bonded to the core site, the number of branch sites, the number of branch sites, and the number of terminal sites contained in each dendrimer. .

In the present invention, the core part and the branch part have a structure in which at least three branches are combined, for example, 1
As those composed of atoms, the following formula (2-a),
Examples of (2-b) include those represented by the following formulas (2-c), (2-d), and (2-e) as those composed of a cyclic compound. In addition, equations (2-f) and (2-
The structure and metal atom represented by g) can also be exemplified as the core site and the branch site. In addition, the following general formula (2-h)
The structure represented by (2-k) is an example of a structure corresponding to only the core portion, and the core portion of such a structure can have four or more branches and is preferable. Also, the distinction between the core part and the branch part shall be determined by the structure of the starting material when the dendrimer is synthesized. In the structural formula below, Rx is the carbon number
It is 1 to 12, preferably 1 to 6 alkylene groups.

[0015]

[Chemical 3]

In the present invention, a branch site is a general term for a structural site that connects one core site or a branch site with an adjacent branch site or an end site, and the structure is not particularly limited, but at least four atoms are included. It is assumed to be composed of. Further, the number of branch sites present in one molecule of the dendrimer is at least 5, preferably 7 to 125, and more preferably 9 to 100. Further, in the present invention, the terminal site contained in the vinyl group-containing dendrimer,
Basically, it is a vinyl group represented by the formulas (8-1) to (8-7).

Further, in the case of a dendrimer having a regular regularity, the size thereof is expressed by a concept term of generation. In the present invention, a branched structure starting from the core compound defined above is referred to as a first generation dendrimer, and a structure having a branched structure branched from all the terminal portions of the first generation is referred to as a second generation. FIG. 2 shows a third-generation dendrimer having a core site and an end site to which four branches are bound, and each generation is shown in the figure. This is the definition of generation in the present invention.

In the present invention, the active hydrogen-containing terminal functional group contained in the polyfunctional compound (a) is a reaction site for introducing a vinyl group. In the present invention, the polyfunctional compound (a) contains at least 3, preferably 4 to 64, active hydrogen-containing terminal functional groups in one molecule, and 5 or more active hydrogens derived therefrom, preferably 6 to 12
Contains 8 pieces. Examples of the active hydrogen-containing terminal functional group include organic residues containing active hydrogen shown below. -NH2: primary amino group (3-1) -NHR1: secondary amino group (R1 is an alkyl group having 1 to 3 carbon atoms) (3-2) -COOH: carboxyl group (3-3) -OH: hydroxyl group ( 3-4) -Si (OR) 3-n (OH) n (n = an integer of 1 to 3); hydroxysilyl group (3-5) -P = O (OH) 2: phosphoric acid group (3-6 ) The type of active hydrogen-containing terminal functional group is not particularly limited,
Since the physical properties of the coating film are affected by the structure of the joint, it is basically selected according to the desired physical properties. More vinyl groups can be introduced by using a primary amino group, a hydroxysilyl group, or a phosphoric acid group.

In the present invention, the polyamino dendrimer having an amino group at the terminal is represented by the above formula (i),
The propyleneimine-based dendrimer (WO093 / 14147, which is obtained by repeating the reaction of reacting butylenediamine and acrylonitrile shown in (ii) to reduce the terminal nitrile group to an amine as one step (WO093 / 14147,
US5530092, Japanese Examined Patent Publication No. 7-330631), Michael addition of methyl acrylate to ammonia or ethylenediamine, and reaction of introducing a secondary amino group at the terminal by ester amide exchange reaction are one step, and by repeating the reaction as necessary. The resulting amidoamine-based dendrimer represented by the following structural formula (iv) (WO84 / 02705, JP-B 6-701)
32) or an intermediate product thereof, or the following formula (i ii),
Examples thereof include compounds having a structure represented by (v).

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

The preferred size of the highly ordered dendrimer used in the present invention is not particularly limited, but preferably 1 to 5 generations, more preferably 1 to 3 generations, particularly 1 or 2 generations are used. It is possible to obtain a resin having both preferable viscosity before curing and physical properties after curing. As such 1st generation or 2nd generation dendrimers, DSM
A polyamino dendrimer represented by the above formula (i) or (ii), which is manufactured by a company, is preferable from the viewpoint of easy availability.

Further, in the present invention, the number average molecular weight of the polyfunctional compound (a) used is not particularly limited, but a preferable range of the molecular weight is 30 to 50 as the number average molecular weight.
000, more preferably 50 to 5,000, and if the number average molecular weight is 5,000, especially 50,000 or more, it may be unfavorable in handling because of high viscosity and solid.

The polyfunctional compound (a) used in the present invention is obtained by Michael-adding a polyamino dendrimer having a primary or secondary amino group and an active hydrogen-containing (meth) acrylate compound (b). can get. A vinyl group-containing dendrimer having preferable pre-curing viscosity and cured product characteristics can be obtained.

The above-mentioned active hydrogen-containing (meth) acrylic compound (b) is a (meth) acrylic compound having at least one hydroxyl group, carboxyl group, etc. in the molecule, and is represented by the following formula (4). A hydroxyalkyl (meth) acrylate compound, CH2 = C (R1) COO-R2-OH (4) (In the formula, R1 is a hydrogen atom or CH3, R2 is a carbon number 2
-22, preferably 2-16 alkyl groups are each represented. ) Polyalkylene glycol mono (meth) acrylate compound represented by the following formula (5), CH2 = C (R1) COO (CxH2xO) mH (5) (In the formula, R1 is a hydrogen atom or CH3, x is 1 to 6) , Preferably an integer of 2 to 4, m is 1 to 25, and preferably 4 to
Each represents 16 integers. ) A polylactone mono (meth) acrylate compound represented by the following formula (6), CH2 = C (R1) COOCyH2yO (COCzH2zO) kH (6) (wherein, R1 is a hydrogen atom or CH3, y is 2 to 22,
Preferably, it is an integer of 2 to 16, z is an integer of 2 to 15, preferably 3 to 5, and k is an integer of 1 to 20, preferably 1 to 5, respectively. ) Or, urethane mono (meta) represented by the following formula (7)
It is an acrylate compound.

CH2 = C (R1) COR3O [CONHR4NHOR5O] hH (7) (wherein R1 is a hydrogen atom or CH3, R3 is a carbon atom of 2)
~ 22 alkyl group, R4 is represented by the following formula (3-a) ~ (3-
is an isocyanate residue represented by h), R5 is-(CpH
2pO) q- or a dihydric alcohol residue represented by -CpH2p-, where p is an integer of 1 to 4, q is an integer of 1 to 100, and h is an integer of 1 to 10, respectively. )

[0028]

[Chemical 7]

In the present invention, the chain length of the above-mentioned active hydrogen-containing (meth) acrylic compound (b) has a short chain length when a hard cured product is required, and has flexibility. For the purpose of improving it, a long chain length is preferable.
Within the above range, the bulk viscosity tends to decrease although the molecular weight increases with the extension of the chain length. If the length is longer than the above range, the bulk viscosity of the vinyl group-containing dendrimer may be high, or the vinyl group-containing dendrimer may be solid at room temperature and may have poor curability, which is not preferable.

More specific examples of the hydroxyalkyl (meth) acrylate compound represented by the general formula (4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4
-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and the like.

Examples of the alkylene glycol mono (meth) acrylate compound represented by the general formula (5) include diethylene glycol mono (meth) acrylate,
Triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol Examples include mono (meth) acrylate.

The polylactone mono (meth) acrylate compound represented by the general formula (6) is 2- (meth)
Acryloyloxyethyl hydrogencaprolactonate, 2- (meth) acryloyloxyethyl hydrogendicaprolactonate, 2- (meth) acryloyloxyethyl hydrogen poly (degree of polymerization 3-5)
Examples include caprolactonate and 2- (meth) acryloyloxyethyl-2-hydroxy-6hexanolactonate.

In addition to the compounds represented by the above general formulas (4) to (7), 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- Hydroxy-
There is 3-phenoxypropyl (meth) acrylate,
Glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene oxide modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, ethylene oxide modified trimethylolpropane mono (meth) acrylate are also used. can do.

As the (meth) acrylic compound having a carboxyl group in the molecule, maleic acid, fumaric acid, itaconic acid, citraconic acid, alkyl or alkenyl monoesters of these, 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 , Methacrylic acid and the like can be used.

In the present invention, the blending amount of the active hydrogen-containing acrylic compound (b) is not particularly limited as long as at least one active hydrogen-containing (meth) acrylic compound (b) is added, but polyamino Based on the total active hydrogen derived from the dendrimer system, preferably 10% or more,
More preferably, it is 50% or more. If it is less than this range, it is difficult to obtain a multi-branched structure and it is difficult to sufficiently reflect the characteristics of the component (b).

The above-mentioned method for synthesizing the polyfunctional compound (a) can be carried out according to a conventional method, but when alcohol such as methanol or ethanol is used as a reaction solvent, side reaction is unlikely to occur. When a solvent is used, it is preferably used 1 to 100 times the blending weight of the polyamino dendrimer. Although heating is not particularly required, it is preferable to heat in the range of 30 ° C to 70 ° C when the molecular weight of the polyamino dendrimer or (meth) acrylic compound is large. The reaction time varies depending on the type of amino compound used and the reaction temperature, but is generally 30 minutes to 72 hours, generally 1 day at room temperature and 1 to 10 hours when heated to 50 to 100 ° C. To do.

In the present invention, the vinyl group is introduced in order to make the polyfunctional compound (a) have reactivity and is not particularly limited as long as it has a polymerizable double bond, but the following preferable structures are shown. CH2 = CHCOO-; acrylic group (8-1) CH2 = CH (CH3) COO-; methacrylic group (8-2) CH2 = CH-; vinyl group (8-3) CH2 = CH-CH2-O-; Allyl group (8-4) -CH = CH-; Dienyl group (8-5) CH2 = CH-C6H4-; Phenylvinyl group (8-6) CH2 = CH-O-; Vinyl ether group (8-7) Above Among the vinyl groups, an acrylic group is preferable for UV curing from the viewpoint of reactivity during radiation curing, and a relatively high curability is also shown for a methacrylic group during electron beam curing, 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 ether group is preferable from the viewpoint of improving curability.

In the present invention, the chain length of the branch site having a vinyl group introduced means the first X-CH = CH- (X is a hydrogen atom or an organic group, counted from the bonding atom at the branch site to which the terminal vinyl group is bonded. Residue) The number of atoms bound linearly up to the structure. When a ring structure such as an aromatic ring, a cyclo ring or a hetero ring is contained in the middle, the number of bonds with the ring structure is counted instead of the number of atoms. In the present invention, the chain portion having a vinyl group introduced therein preferably has a chain length of 2 to 100, more preferably 9 to 70.

In the present invention, the vinyl group-containing dendrimer is obtained by introducing a vinyl group into the above polyfunctional compound (a), and basically, the active hydrogen-containing terminal functional group contained in the polyfunctional compound (a) is contained. And a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen. In the present invention, the functional group capable of reacting with active hydrogen is selected depending on the type of the active hydrogen-containing terminal functional group contained in the polyfunctional compound (a). When the functional group is a primary or secondary amino group, an acrylic group, a carboxyl group, a hydroxyl group, an epoxy group is preferable, and when the active hydrogen-containing terminal functional group is a hydroxyl group, an isocyanate group,
An epoxy group, an alkoxysilyl group, a phosphoric acid group, or a carboxyl group is preferable, and when the active hydrogen-containing terminal functional group is a carboxyl group, an epoxy group is preferable. Examples of the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen, which can be used when the terminal of the polyfunctional compound (a) is an amino group, include 2-hydroxy-3-acryloxypropyl methacrylate and the like, an acryloyl group. Other compounds having a vinyl group can be exemplified, but in this case, it may be difficult to obtain sufficient curability as an ultraviolet curable compound because an acrylic group cannot be introduced at the terminal.

Examples of the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen, which can be used when the terminal is a hydroxyl group, include, for example, glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate. , 1-vinyl-3,4-epoxycyclohexane, (3,4-epoxycyclohexyl-5-hydroxyhexanoic carboxylate) (meth) acrylate, epoxycyclohexylmethyl polycaprolactone (meth) acrylate, allyl glycidyl ether,
Terminal epoxy-based vinyl group-containing compounds such as vinylcyclohexyl epoxide, terminal alkoxysilyl-based vinyl group-containing compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxysilane , Acid phosphoxyethyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, acid phosphoxypropyl methacrylate, acid phosphoxyethyl methacrylate,
Examples thereof include a terminal phosphoric acid-based vinyl group-containing compound such as acid phosphoxy polyoxyethylene glycol monomethacrylate and acid phosphoxy polyoxypropylene glycol monomethacrylate.

When the isocyanate group-containing vinyl compound (c-1) having an isocyanate group is used, the active hydrogen-containing terminal functional group of the polyfunctional compound (a) is
It can be used in the case of a hydroxyl group, a carboxyl group, an amino group and the like, and in particular, a combination of a hydroxyl group and an isocyanate group proceeds under mild conditions and can be said to be preferable in consideration of the stability of the terminal vinyl group.

A preferred method of using the above isocyanate group-containing vinyl compound (c-1) is, for example, obtained by Michael-adding an active hydrogen-containing (meth) acrylate compound (a-1) to a polyamino dendrimer. A vinyl group can be introduced by adding the isocyanate group-containing vinyl compound (c-1) to the polyfunctional compound (a).

Examples of the above-mentioned isocyanate group-containing vinyl compound (c-1) include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate,
There are allyl isocyanate, (meth) acryloyl isocyanate (MAI), isopropenyl-α, α-dimethylbenzyl isocyanate (TMI) and the like. In the present invention, a compound obtained by reacting the diisocyanate compound (c-2) and the vinyl compound (c-3) containing a functional group capable of reacting with an isocyanate group in equimolar amounts is also the isocyanate group-containing vinyl compound (c- It can be used as 1).

The above diisocyanate compound (c-2)
Examples include 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolutoluylene diisocyanate, hexamethylene diisocyanate, and 4-methyl-m-diisocyanate. Phenylene, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethyl xylylene diisocyanate, cyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, 2,2,4-
Trimethylhexamethylene diisocyanate, 2,4
4-trimethylhexamethylene diisocyanate, m-
Examples thereof include tetramethyl xylylene diisocyanate, p-tetramethyl xylylene diisocyanate, dimer acid diisocyanate, and the like.

The vinyl compound (c-3) containing a functional group capable of reacting with an isocyanate group used in the present invention includes vinyl compounds having an amino group, a hydroxyl group, a carboxyl group and the like. Those having a carboxyl group are preferable from the viewpoint of reactivity with an isocyanate group. As such a (meth) acrylic compound having a hydroxyl group, of the above compounds, those containing only one hydroxyl group can be used, but those having a relatively low molecular weight are preferable from the viewpoint of reactivity with diisocyanate. , For example, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2
-(Meth) acryloyloxyethyl hydrogencaprolactonate and the like can be mentioned.

In the present invention, the vinyl group-containing dendrimer is a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen contained in the polyfunctional compound (a).
Can be obtained by mixing stoichiometrically the same amount and reacting. For example, when the active hydrogen-containing functional group possessed by the polyfunctional compound (a) is a hydroxyl group and a vinyl group is introduced into the terminal by the isocyanate group-containing vinyl compound (c-1), the synthesis method is carried out according to the conventional method. be able to. Although it can be synthesized in a solvent-free system, if ethyl acetate, methyl ethyl ketone, or the like is used as a reaction solvent, if necessary, temperature control is easy and side reactions do not easily occur. When using a solvent, the NV of the reaction system is preferably 20 to 90%. Further, if necessary, a catalyst used in usual urethane synthesis, for example, tin octylate, 2-
A tin-based catalyst such as tin ethylhexanoate may be added. The preferable addition amount of the catalyst is 1 to 0.01% by weight with respect to the isocyanate group-containing vinyl compound (c-1). The reaction temperature is preferably 30 ° C to 70 ° C. The reaction time varies depending on the dilution ratio with the solvent, the amount of the catalyst, the reaction temperature, etc., but is completed in about 30 minutes to 72 hours.

The vinyl group-containing dendrimer obtained according to the present invention has a number average molecular weight of 200 to 100,000.
Preferably 300 to 50,000, more preferably 400 to
40,000 and 100,000 cps or less, preferably 50,000 to 500 cps, and more preferably 20.
It is a liquid that exhibits a viscosity (30 ° C.) of 000 to 1000 cps. If the molecular weight is lower than this, curing shrinkage becomes severe, which is not preferable. Further, the viscosity is not particularly problematic when it is in a viscosity range capable of forming a film, but if it exceeds the above range, handling such as compounding is inconvenient, and a compounding amount of a low molecular weight compound such as a reactive diluent is large. In addition, it is not preferable in terms of solubility with other components.

The vinyl group-containing dendrimer obtained in the present invention can be used as a curable solventless liquid resin as it is, as a film forming material for paints, inks, etc., a molding material, an adhesive, etc., but it is monofunctional or polyfunctional. By adding and mixing a cross-linking agent such as (meth) acrylic compound, polyisocyanate, melamine, etc., viscosity can be adjusted, film-forming property, and film performance can be adjusted. Further, for the same reason, a curing agent resin such as amino resin or phenol resin may be blended. Further, in order to improve the coating performance, known polyamide resins, cellulose derivatives, vinyl resins, polyolefins, natural rubber derivatives, acrylic resins, epoxy resins, polyesters, general-purpose polymers such as polystyrene, urethane acrylic resins,
A reactive resin having a vinyl group such as an epoxy acrylic resin, an ester acrylic resin, an alkyd resin, a rosin-modified alkyd resin and a linseed oil-modified alkyd resin, a drying oil such as linseed oil, tung oil and soybean oil may be blended.
However, the amount of each of these is preferably 40% by weight.
More preferably, it is 20% by weight or less. Further, water or an organic solvent, a compatibilizer, a surfactant, a lubricant or the like may be added if necessary. The blending amount thereof is preferably 20% by weight, more preferably 10% by weight or less.

The vinyl group-containing dendrimer obtained according to the present invention is appropriately provided with a dye, a coloring agent comprising carbon black, titanium white, phthalocyanine, an azo dye, a pigment such as quinacridone, an Si-based fine particle, an inorganic filler such as mica and calcium carbonate. When added in an amount, it can be used as various printing inks, colored paints and the like. Further, in the case of curing by irradiation with active energy rays, known photopolymerization sensitizers and initiators can be added.

The vinyl group-containing dendrimer of the present invention can be coated or filled on a plate, film or sheet of various metals, plastics, papers, etc. with a roll coater, bar coater, knife coater or the like, and a temperature condition of -5 to 300 ° C. Can be cured underneath. In addition, ink composition using the vinyl group-containing dendrimer of the present invention, the composition for film forming material such as paint, various steel plates, metal plates such as aluminum plate,
Coating methods such as roll coater and knife coater on base materials such as plastic film, paper, plastic film laminated paper, or offset printing, gravure printing,
It is possible to form a film with a film thickness of 0.1 to 500 μm by conventional methods such as printing methods such as letterpress printing and silk screen printing, and to heat or irradiate active energy rays such as electron rays, ultraviolet rays, visible rays, infrared rays, etc. Can be cured by.

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 up to 300 kV is used. An electron beam irradiation device with a low acceleration voltage is more effective for curing a thin film because energy is concentrated on the surface, and is preferable because it causes less damage to a coating film or a substrate. The acceleration voltage in this case is in the range of 30 to 70 kV.
The electron beam irradiation dose (DOSE) is preferably 1
˜1000 kGy, more preferably 5 to 200 kGy. If it is less than this range, it is difficult to obtain a sufficiently cured product, and if it is more than this range, the coating film or the base material is greatly damaged, which is not preferable.

[0052]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. ◎ Structural analysis, number average molecular weight, and viscosity measurement method 1) Structural analysis The structure of the vinyl group-containing dendrimer synthesized here is 1H.
-Confirmed by 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 kinds of vinyl group-containing dendrimers with known structures analyzed by 1H-NMR. Based on GPC
The result measured in was adopted. In addition, the molecular weight distribution (Mw /
For Mn), the value obtained by the same measuring device was adopted. 3) Viscosity: Rheometer (RDS-made by Rheometrics Inc.)
II, RFS-II) Rheometer RDS-II (high viscosity type) manufactured by Rheometrics Co., Ltd. or RFS-II according to the viscosity of the sample.
Steady-state viscosity measured with (low viscosity type) (shift rate = 1 to
The value of 10 / sec) was adopted. ◎ Electron beam irradiation equipment and irradiation conditions 1) Area beam type electron beam irradiation equipment Curetron EBC-200
-20-30 (NISSIN HIGH VOLTAGE) Electron beam acceleration: 200kV DOSE was adjusted by the amount of current in the range of 5-80kGy. 2) MIN-EB (manufactured by AIT) Electron beam acceleration: 60 kV DOSE was adjusted at a belt conveyor speed within a range of 5 to 80 kGy.

The abbreviations of the following compounds used in Examples and Comparative Examples are shown below. 1) Polyfunctional compound DAB4: 8-Cascade; 1,4-Diamin
obbutane [4]; propylamin DAB8: 16-Cascade; 1,4-Dami
nobutane [8]; propramine 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 (Polymerization degree 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 (c-1) MOI: methacryloyloxyethyl isocyanate TMI: dimethyl meta-isopyropenyl benzyl isocyanate and Synthetic product shown in the serial Synthesis Example 1-6

(Synthesis Example 1) Stirrer for equimolar adduct of tolylene diisocyanate (TDI) and 4HBA, nitrogen introducing pipe, temperature sensor, condenser,
And 4HBA: 144 g, ethyl acetate 144 g in a 1000 ml four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution of TDI: 174 g, ethyl acetate:
174 g, tin 2-ethylhexanoate: 0.2 g was added, and the above solution filled in a dropping funnel was added dropwise in 1 hour while heating and stirring in a water bath set at 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

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

(Synthesis Example 3) Stirrer for equimolar addition of TDI and HEA, nitrogen introduction tube, temperature sensor, condenser,
And HEA: 116 g, 120 g of ethyl acetate in a 1000 ml four-neck round bottom flask equipped with a dropping funnel filled with TDI: 174 g, ethyl acetate: 1
74 g, tin 2-ethylhexanoate: 0.2 g,
The above solution filled in a dropping funnel was added dropwise over 1 hour while heating and stirring in a hot water bath set to 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Synthesis Example 4) Stirrer for equimolar adduct of IPDI and HEA, nitrogen introducing pipe, temperature sensor, condenser,
And HEA: 116 g, 120 g of ethyl acetate in a 1000-mL four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution, IPDI: 222 g, ethyl acetate:
220 g of tin 2-ethylhexanoate: 0.2 g was added, and the above solution filled in a dropping funnel was added dropwise over 1 hour while heating and stirring in a water bath set at 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Synthesis Example 5) Stirrer for addition of equimolar adduct of hexamethylene diisocyanate (HMID) and HEA, nitrogen introducing pipe, 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 HMDI: 168 g, ethyl acetate:
170 g of tin 2-ethylhexanoate: 0.2 g was added, and the above solution filled in a dropping funnel was added dropwise over 1 hour while heating and stirring in a water bath set to 50 ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Synthesis Example 6) Stirrer for equimolar adduct of HMID and 4HBA, nitrogen introducing pipe, temperature sensor, condenser,
And 4HBA: 144 g, and ethyl acetate: 170 g, ethyl acetate: 170 g, 2-ethylhexanoic acid tin: 0.2 g was added to a 1000 ml four-neck round bottom flask equipped with a dropping funnel filled with a mixed solution of 140 g of ethyl acetate and 50 g. The above solution filled in a dropping funnel was added dropwise over 1 hour while heating and stirring in a hot water bath set to ° C. The reaction was terminated when the NCO value fell below the theoretical value by the titration method.

(Example 1) DAB 4: 31.6 g, HE in a 1000 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
A: 92.8 g, ethyl acetate: 125 g were mixed, and 75
After refluxing for 3 hours in a hot water bath set at 0 ° C., a part of the sample was sampled and 1 H-NMR was measured. As a result, the proton peak derived from the acrylic group was almost disappeared. Then, the water bath temperature was lowered to 60 ° C., a mixed solution of MOI: 118 g and ethyl acetate: 120 g was added, and after 10 to 30 minutes, tin 2-ethylhexanoate: 0.6 g was added. Three
The heating and stirring were continued for up to 4 hours, and the time when the NCO group characteristic absorption (2270 cm-1) on the IR chart disappeared was defined as the reaction end point. Further, ethyl acetate used as a reaction solvent was removed by an evaporator to obtain a desired vinyl group-containing dendrimer. The 1H-NMR chart of the obtained vinyl group-containing dendrimer is shown in FIG. 3, and its attribution is shown in the following figure. The physical property values are shown in Table 1.

[0061]

[Chemical 8]

Example 2 DAB 4: 31.6 g, 4HB in a 500 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
A: 115 g, ethyl acetate: 63 g, methanol: 30
After mixing g, the mixture was refluxed in a hot water bath set at 75 ° C. for 3 hours, partly sampled, and 1 H-NMR was measured. As a result, a proton peak derived from an acrylic group was almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, and the solvent was distilled off while continuing heating and stirring at 80 ° C in a water bath at atmospheric pressure. Furthermore, a vacuum line was connected from the top of the condenser to 70 ° C. When the ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less in a water bath lowered to, a viscous liquid resin was obtained (yield 9
8%). Therefore, MOI: 11
5 g, ethyl acetate: 260 g were added, and after a further 10 minutes,
Tin 2-ethylhexanoate: 0.6 g was added. The mixture was heated and stirred for 3 hours, and the NCO group characteristic absorption (2
The end point of the reaction was the point at which 270 cm-1) disappeared. Further, ethyl acetate used as a reaction solvent was removed by an evaporator to obtain a desired vinyl group-containing dendrimer. 1H of the obtained vinyl group-containing dendrimer
The NMR chart is shown in FIG. 4 and the attribution is shown in the following figure.
The physical property values are shown in Table 1.

[0063]

[Chemical 9]

(Example 3) DAB 8: 36.65 g, 4H in a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser.
BA: 115 g, ethyl acetate: 65 g, methanol: 3
When 0 g was blended and refluxed in a hot water bath set at 75 ° C. for 3 hours, a part of the sample was sampled and 1 H-NMR was measured. As a result, a proton peak derived from an acrylic group was almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, and the solvent was distilled off while continuing heating and stirring at 80 ° C in a water bath at atmospheric pressure. Furthermore, a vacuum line was connected from the top of the condenser to 70 ° C. When ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less with the water bath lowered to 1, a viscous liquid resin was obtained (yield 97%). Then, MOI: 1
14 g and ethyl acetate: 265 g were added, and 10 minutes later, tin 2-ethylhexanoate: 0.6 g was added. Four
The reaction was terminated when the NCO group characteristic absorption ((2270 cm-1) on the IR chart disappeared, and the ethyl acetate used as a reaction solvent was removed by an evaporator to remove the objective vinyl. A group-containing dendrimer was obtained, the 1H-NMR chart of the obtained vinyl group-containing dendrimer is shown in Fig. 5, and its attribution is shown in the following figure, and the physical properties are shown in Table 1.

[0065]

[Chemical 10]

(Example 4) DAB 4: 31.6 g, PPG in a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser.
6A: 382 g, ethyl acetate: 178 g, methanol:
After 30 g was mixed and refluxed in a hot water bath set at 75 ° C. for 4 hours, a part of the sample was sampled and 1 H-NMR was measured. As a result, a proton peak derived from an acrylic group was almost disappeared. Therefore, a diversion tube was set between the reactor and the condenser, and the solvent was distilled off while continuing heating and stirring at 80 ° C in a water bath at atmospheric pressure. Furthermore, a vacuum line was connected from the top of the condenser to 70 ° C. 40mmHg in hot water bath
When ethyl acetate and methanol were completely distilled off by reducing the pressure to the following, a viscous liquid resin was obtained (yield 98%). Therefore, the MOI:
115 g and ethyl acetate: 530 g were added, and 10 minutes later, tin 2-ethylhexanoate: 0.6 g was added. Three
The mixture was heated and stirred for a period of time, and the time point when the NCO group characteristic absorption (2270 cm-1) on the IR chart disappeared was taken as the reaction end point. Further, ethyl acetate used as a reaction solvent was removed by an evaporator to obtain a desired vinyl group-containing dendrimer. The 1H-NMR chart of the obtained vinyl group-containing dendrimer is shown in FIG. 6, and its attribution is shown in the following figure. The physical property values are shown in Table 1.

[0067]

[Chemical 11]

(Example 5) DAB 4: 31.6 g, 4HB in a 500 ml four-neck round bottom flask equipped with a stirrer, a nitrogen introducing tube, a temperature sensor, and a condenser.
A: 57.5 g, PPG6A: 191 g, ethyl acetate:
After 120 g and 30 g of methanol were mixed and refluxed for 4 hours in a hot water bath set at 75 ° C., a part of the sample was sampled and 1 H-NMR was measured. As a result, the proton peak derived from the acrylic group almost disappeared. . Therefore, a diversion tube was set between the reactor and the condenser, and the solvent was distilled off while continuing heating and stirring at 80 ° C in a water bath at atmospheric pressure. Furthermore, a vacuum line was connected from the top of the condenser to 70 ° C.
When the ethyl acetate and methanol were completely distilled off by reducing the pressure to 40 mmHg or less in the water bath lowered to 2, a viscous liquid resin was obtained (yield 98%). Therefore, MOI: 115 g, ethyl acetate:
395 g was added, and after a further 10 minutes, tin 2-ethylhexanoate: 0.6 g was added. Continue heating and stirring for 3 hours, and
The time when the NCO group characteristic absorption (2270 cm-1) on the R chart disappeared was defined as the reaction end point. Further, ethyl acetate used as a reaction solvent was removed by an evaporator to obtain a desired vinyl group-containing dendrimer. The 1 H-NMR chart of the obtained vinyl group-containing dendrimer is shown in FIG. 7, and its attribution is shown in the following figure. The physical properties are shown in Table 1.
It was shown to.

[0069]

[Chemical 12]

(Examples 6 to 23) In a four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, a dropping funnel, and a condenser, the polyfunctional compound (a) shown in Table 1 and the polyfunctional compound (a) Charge an equivalent amount of ethyl acetate,
The dropping funnel was charged with a solution prepared by diluting the active hydrogen-containing acrylic compound (b) with ethyl acetate to a concentration of 75% by weight. While stirring the inside of the flask, the active hydrogen-containing acrylic compound (b) charged in the dropping funnel was added dropwise.
Except when HEA was used as the active hydrogen-containing acrylic compound (b), the same mole number of methanol as that of the polyfunctional compound (a) was further added into the flask (reaction system). The reaction system was immersed in a hot water bath set at 75 ° C. and refluxed for 4 hours, then partly sampled, 1 H-NMR was measured, and the end point was confirmed by disappearance of a proton peak derived from an acrylic group. Then, a diversion tube was set between the reactor and the condenser, and the solvent was distilled off while continuing heating and stirring at 80 ° C. in a hot water bath under normal pressure. 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 with a water bath lowered to 70 ° C. As a result, a viscous liquid substance (modified polyfunctional compound ( a)) was obtained. Further, the water bath temperature is lowered to 60 ° C., and ethyl acetate is newly added so as to have NV of 50% so that the active hydrogen contained in the modified polyfunctional compound (a) is stoichiometrically equivalent. The isocyanate group-containing vinyl compound (c-1) was added, and further diluted with ethyl acetate so that the concentration of the entire reaction system would be 50%. After a further 10 minutes, tin 2-ethylhexanoate was added to 0.5% by weight of the isocyanate group-containing vinyl compound (c-1).
The mixture was heated and stirred for 3 hours or more as it was, and the time when the NCO group characteristic absorption (2270 cm −1) on the IR chart disappeared was taken as the reaction end point. Further, ethyl acetate used as a reaction solvent was removed by an evaporator to obtain a desired vinyl group-containing dendrimer. The raw material composition at the time of synthesizing the obtained vinyl group-containing dendrimer and the characteristics of the obtained vinyl group-containing dendrimer are shown in Table 1 together. Further, as Comparative Examples 1 to 3, commercially available dipentaerythritol hexaacrylate (DHPA) and ethylene oxide-modified pentaerythritol triacrylate were measured by the same method.
The physical property evaluation results of (TMPT3EO, TMPT6EO) are also shown.

[0071]

[Table 1]

(Examples 24 to 47, Comparative Examples 4 to 6) The vinyl group-containing dendrimers obtained in Examples 1 to 42 were treated with # 6.
4 kinds of films with a bar coater (size of base material for evaluation → thickness; 20 μm, width; 5 cm, length; 20 cm)
It was coated on the surface and irradiated with an electron beam with various DOSEs (5, 20, 40 kGy). Table 2 shows the type of vinyl group-containing dendrimer used and the curing characteristics of the coating film obtained by electron beam irradiation (finger touch test → ×: with tack, △: without tack, but with scratches on nails, ○: without tack No scratches from nails), substrate adhesion (coating film unpeeling rate by cellotape peeling test), and
Solvent resistance (residual ratio obtained from weight change before and after 50 MEK rubbing tests), curl (evaluated by sensory test of substrate film deformation property → ○: no curl, △: edge warped, ×:
The film is rolled up), and the evaluation results of abrasion resistance are shown. In Table 2, as Comparative Examples 4 to 6, commercially available dipentaerythritol hexaacrylate and ethylene oxide-modified pentaerythritol triacrylate (TMPT3EO, T) are used.
The evaluation results of MPT6EO) are also shown.

[0073]

[Table 2]

[0074]

INDUSTRIAL APPLICABILITY By using a multifunctional liquid resin having a high molecular weight and a low viscosity as a solventless curable resin according to the present invention, it can be used in a usual solventless curable resin composition. It contributes to the improvement of the working environment by reducing or eliminating the compounding ratio of low molecular weight compounds that have problems with safety and physical properties, and it has been used in the coating of conventional roll coaters, knife coaters, etc. Method, offset printing, gravure printing, letterpress printing, can be formed into a film by a printing method such as screen printing, can be cured by conventional triggers such as heating, ultraviolet rays, infrared rays, electron beams, γ-ray irradiation, especially electronic The present invention provides a multi-branched compound which can be cured without using a catalyst or an initiator in the case of irradiation with rays or γ rays.

[Brief description of drawings]

Figure 1: Model diagram of dendrimer

[Figure 2] Model diagram of dendrimer

FIG. 3 1H-NMR chart of the vinyl group-containing dendrimer obtained in Example 1.

FIG. 4 1H-NMR chart of the vinyl group-containing dendrimer obtained in Example 2.

FIG. 5: 1H-NMR chart of the vinyl group-containing dendrimer obtained in Example 3.

FIG. 6 1H-NMR chart of the vinyl group-containing dendrimer obtained in Example 4.

FIG. 7: 1H-NMR chart of the vinyl group-containing dendrimer obtained in Example 5.

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

[Procedure amendment]

[Submission date] February 8, 1999 (1999.2.8)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

In the present invention, the core part and the branch part have a structure in which at least three branches are combined, for example, 1
As those composed of atoms, the following formula (2-a),
Examples of (2-b) include those represented by the following formulas (2-c), (2-d), and (2-e) as those composed of a cyclic compound. In addition, the formula (2-f) and the formula (2
The structure and metal atom shown by -g) can also be illustrated as a core part and a branch part . Also distinction core site and the branch site you shall be determined from the structure of the starting material during dendrimer synthesis.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

[0015]

[Chemical 1]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

The above diisocyanate compound (c-2)
The di isocyanate, isophorone diisocyanate, 4,4'-diphenylmethane, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, diisocyanate Santo Ruiren, hexamethylene diisocyanate, 4-methyl -m- phenylene, naphthylene diisocyanate, para Phenylene diisocyanate, tetramethyl xylylene diisocyanate, cyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethyl xylylene diisocyanate Isocyanate, p-tetramethylxylylene diisocyanate, diisocyanate dimer Nate and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/00 C09D 5/00 C 4J043 11/10 11/10 F term (reference) 4J027 AG12 AG23 AG24 AH03 AJ06 BA01 CD08 4J031 BA29 BB01 BB03 BC07 BD12 CD29 4J034 DA01 DA05 DR04 HA01 HA04 HA18 HB11 HC12 HC73 LA23 LA33 QA05 RA07 RA08 4J038 FA241 MA14 PA17 4J039 AD21 AE04 AE08 AE09 AF02 SA07 SA02 SA71 SA62 SA08 SA02 SA71 SA08 SA02 SA71 SA08 SA02 SA07 SA02 SA08 SA02 TA11 TA35 TA38 TA53 TA72 TA78 TA79 UB231 WA06 WA16 ZB03 ZB22

Claims (9)

[Claims] 1. A polyfunctional compound (a) obtained by Michael-adding an active hydrogen-containing (meth) acrylate compound (b) to a polyamino dendrimer, and an active hydrogen contained in the polyfunctional compound (a). A vinyl group-containing dendrimer obtained by reacting a vinyl group-containing compound (c) having a reactive functional group with a stoichiometrically equivalent amount. 2. The vinyl group-containing dendrimer according to claim 1, wherein the polyamino dendrimer is a compound represented by the following formula (i) or (ii). [Chemical 1] 3. The vinyl group-containing dendrimer according to claim 1, wherein the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen is an isocyanate group-containing vinyl compound (c-1). 4. The vinyl group-containing dendrimer according to any one of claims 1 to 3, wherein the branch portion introduced with the vinyl group has a chain length of 9 to 70 atoms. 5. A number average molecular weight of 200 to 100,000,
The vinyl group-containing dendrimer according to any one of claims 1 to 4, which is a liquid having a viscosity of 100,000 cps (30 ° C) or less. 6. The vinyl group-containing dendrimer according to claim 1, which is an active energy ray-curable type. 7. The vinyl group-containing dendrimer according to claim 1, which is used for paints. 8. The vinyl group-containing dendrimer according to claim 1, which is used for ink. 9. A cured product obtained by irradiating the vinyl group-containing dendrimer according to claim 1 with an active energy ray.