JP2000073055A - Reactive oxygen inhibition inhibitor and use thereof - Google Patents

Abstract

(57) Abstract: The present invention provides a reactive oxygen inhibition inhibitor having sufficient film-forming properties and a low viscosity capable of forming a film, and an electron beam even under an oxygen concentration of 500 ppm or more. Hardening
An object of the present invention is to provide a curable composition that can be used. Another object of the present invention is to provide a method for forming a cured film by electron beam irradiation under an oxygen concentration of 500 ppm or more and a cured product. A secondary or tertiary amine structure comprising a core site, a branch site, a branch site, and at least four terminal sites, and a long-chain group or an active hydrogen-containing group as the terminal site; Reactive oxygen inhibition inhibitor comprising vinyl group-containing dendrimer having vinyl group and 5
A curable composition that can be cured by an electron beam even under an oxygen concentration of 00 ppm or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in the effect of suppressing oxygen inhibition, and is capable of forming a coating material such as paints and inks, a sealing agent, a molding agent,
Can be used in a wide range of fields as resin materials such as adhesives and pressure-sensitive adhesives.
The present invention relates to a high-molecular-weight, low-viscosity reactive oxygen inhibition inhibitor capable of obtaining a cured product even under an oxygen concentration of m or more, a curable composition containing the same, a method for forming a cured film using the same, and a cured product. is there.

[0002]

2. Description of the Related Art In recent years, interest in the global environment and work environment has been increasing, and restrictions on the use of organic solvents have been added. As one method, there is no problem of pollution, safety and health, ignition, explosion, etc.
In addition, there is a strong demand for the development of a solventless liquid resin composition that is easy to form and fill. A typical example of the solvent-free liquid curable composition is an active energy ray-curable curable composition. Above all, the electron beam curing system is solvent-free and does not require an initiator, furthermore, the drying time is extremely short compared to the ultraviolet curing system as well as the thermosetting system, Its effectiveness has been acknowledged because it does not require any treatment. However, the conventional electron beam curing system has the following problems: 1) the problem that the apparatus is large and the initial investment is large; and 2) the oxygen concentration is preferably several tens ppm or less, in order to eliminate the inhibition of surface curing caused by the generation of oxygen radicals. However, there is a problem that running cost is required since inerting with an inert gas such as high-purity nitrogen or the like is required to be 200 ppm or less. In addition, in order to obtain a sufficient cured product in the air even in an ultraviolet curing system or a thermosetting system, it is necessary to add a large amount of initiator and sensitizer. Inhibition of curing by oxygen has been studied by various research institutions, and non-reactive additives such as amine compounds and phosphorus compounds have been studied. However, the amount of addition is limited due to the low water resistance and solvent resistance of the cured product, which is extracted after curing, and a sufficient effect of inhibiting curing inhibition is not obtained. In addition, the cationic resin material, which is relatively low in oxygen curing inhibition, is expensive in raw materials, requires an initiator even in an electron beam curing system, and the product lineup is insufficient. Therefore, there is a problem that a wide range of product specifications is not satisfied. Further, since the molecular weight is low in any of the systems, the physical properties of the coating film such as mechanical strength are reduced, and thus, at the present time, both the inhibition of curing and the physical properties of the coating film are not achieved.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a reactive oxygen inhibition inhibitor having a sufficient film performance and a low viscosity capable of forming a film, and an electron beam even under an oxygen concentration of 500 ppm or more. An object is to provide a curable composition that can be cured. In addition, the present invention provides a 500p
An object of the present invention is to provide a method for forming a cured film by electron beam irradiation under an oxygen concentration of pm or more and a cured product.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed a vinyl group-containing dendrimer having a secondary or tertiary amine structure,
It has a high effect of suppressing curing inhibition by oxygen in a radical reaction system, and also has a low viscosity despite being a high molecular weight,
In addition, since a large number of functional groups such as vinyl groups can be introduced into the terminal, it has been found that the fluidity and the physical properties of the cured product are improved while maintaining the curability at an oxygen concentration of 500 ppm or more, leading to the present invention.

That is, the present invention comprises a core site, a branch site, a branch site, and at least four terminal sites, a secondary or tertiary amine structure, and the following general formula (1-1): Or at least one long-chain group selected from the group consisting of (1-3) or the following general formulas (2-1) to (2)
And -5) a reactive oxygen inhibition inhibitor comprising at least one active hydrogen-containing group selected from the group consisting of: and a vinyl group-containing dendrimer containing a vinyl group. ^{_{-C n H 2n R 1 (1-1}} ) - (C x H 2x O) m R 3 (1-2) -C y H 2y O (COC z H 2z O) k R 3 (1-3) ( In the formula, R ¹ is a phenyl group or a hydrogen atom, and n is 4 to 2
An integer of 5, x is an integer of 1 to 6, R ³ is a phenyl group or an alkyl group having 1 to 22 carbon atoms, y is an integer of 2 to 22,
z is an integer of 2 to 15, m is an integer of 1 to 25, k is 1 to 2
Each represents an integer of 0. -NHR ¹ : primary and secondary amino groups (2-1) (wherein, R ¹ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) -COOH: carboxyl group (2-2) -OH : Hydroxyl group (2-3) -Si (OR ⁴ ) _3-n (OH) _n : hydroxysilyl group (2-4) (R4 is a phenyl group or an alkyl group having 1 to 20 carbon atoms, n
= 1 to 3 represent an integer. ) -P = O (OH) ₂ : phosphoric acid group (2-5) Further, in the present invention, the vinyl group-containing dendrimer has at least three active hydrogen-containing functional groups per molecule, and
Reacting a long-chain-group-containing compound (b) having a functional group capable of reacting with active hydrogen with a long-chain-group-containing hyperbranched compound (X), The present invention relates to the above reactive oxygen inhibition inhibitor, which is a compound obtained by reacting with a vinyl group-containing compound (c) having a possible functional group. Further, the present invention provides a method wherein the vinyl group-containing dendrimer is a polyamino dendrimer comprising an active hydrogen-containing (meth) acrylic compound (b-1) or an active hydrogen-containing (meth) acrylic compound (b-1) and A long-chain-group-containing hyperbranched compound (X-1) obtained by Michael addition of a mixture of a non-functional (meth) acrylic compound (b-2) represented by the formula (3) and a functional group capable of reacting with active hydrogen The present invention relates to the above reactive oxygen inhibition inhibitor, which is a compound obtained by reacting a vinyl group-containing compound (c) having a group. CH ₂ ＣC (R ¹ ) COO—R ² (3) (wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is —C _n H
_{2n + 1, - (C x} H 2x O) m R 3 or -C _y H _2y O (CO,
C _z H _2z O) _k R ³ and R ^{3 each} represent a phenyl group or a group having 1 to 2 carbon atoms.
2 is an alkyl group, n is an integer of 4 to 25, x is an integer of 1 to 6, y is an integer of 2 to 22, z is an integer of 2 to 15, and m is 1
And an integer of 1 to 20 and k represents an integer of 1 to 20, respectively. The present invention also relates to the above reactive oxygen inhibition inhibitor, wherein the polyamino dendrimer is a compound represented by the following formula (i) or (ii).

Embedded image In addition, the present invention provides a vinyl group-containing dendrimer having a number average molecular weight of 200 to 100,000 and a viscosity of 100,000 cp.
The present invention relates to the above reactive oxygen inhibition inhibitor, which is a liquid compound having a s (30 ° C.) or lower. The present invention also relates to a curable composition comprising the above-described reactive oxygen inhibition inhibitor (A) and another polymerizable unsaturated group-containing compound (B). Further, in the present invention, the compounding ratio of the reactive oxygen inhibition inhibitor (A) to the other polymerizable unsaturated group-containing compound (B) is 10:90 to 95:
5 (weight ratio). The present invention also relates to the above curable composition, wherein the other polymerizable unsaturated group-containing compound (B) is a (meth) acrylic compound or a vinyl ether compound. In addition, the present invention provides that the other polymerizable unsaturated group-containing compound (B) has a viscosity of 10%.
000 cps (30 ° C.) or less and a number average molecular weight of 200
It relates to the curable composition described above, which is 0 or less. The present invention also relates to the above-mentioned curable composition used for printing ink. The present invention also relates to the above-mentioned curable composition for use in paints. The present invention also relates to the curable composition described above, which is curable by active energy rays. Also, the present invention
The present invention relates to a method for forming a cured film by irradiating the curable composition with an active energy ray under an oxygen concentration of 500 ppm or more. Further, the present invention provides an acceleration voltage of 30 to 100.
The present invention relates to a method for forming the above-mentioned cured film, which is irradiated with a kV electron beam. The present invention also relates to a cured product obtained by the above-described method for forming a film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl group-containing dendrimer of the present invention can be used by itself or a composition containing the same at 500 ppm.
It is a reactive compound having an oxygen hardening inhibition suppressing function of suppressing hardening inhibition by oxygen generated when a radical reaction is caused by heat or active energy rays under the above oxygen concentration.

[0007] In general, the term dendrimer has been used for highly branched, highly ordered, hyperbranched compounds. However, with the progress of research on the synthesis of dendrimers in recent years, various low-ordered multi-branched compounds with the aim of simplifying the synthesis method, such as the development of dendritic compounds by the one-step method, have been developed as new dendrimers. However, there is no conclusion on the nomenclature. Therefore, in the present invention, the dendrimer refers to a three-dimensionally branched hyperbranched compound, and generically refers to a hyper-branched having low regularity and a dendrimer having high regularity. The 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 model diagrams of the minimum unit dendrimer and the standard dendrimer according to the present invention, and shows the number of branches, the number of branch sites, the number of branch sites, and the number of terminal sites bound to the core site contained in each dendrimer. .

In the present invention, the core site and the branch site have a structure in which at least three branches are bonded.
As a compound composed of atoms, the following formula (4-a):
(4-b), and examples of the compound composed of a cyclic compound include compounds represented by the following formulas (4-c), (4-d), and (4-e). Also, (4-f) and (4-f)
The structure and metal atom as shown in g) can also be exemplified as the core site and branch site. The following formulas (4-h) to (4-h)
The structure shown by k) is an example of a structure corresponding to only the core portion, and the core portion of the following structure is preferable because it can have four or more branches. The distinction between the core site and the branch site is determined from the structure of the starting material at the time of dendrimer synthesis. In the following structural formula, Rx is an alkylene group having 1 to 12, preferably 1 to 6 carbon atoms. In the following formulas (4-a) and (4-d), a secondary or tertiary amino group can be introduced into the core structure.

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In the present invention, the term “branch site” is a general term for a component site that connects one core site or branch site to an adjacent branch site or terminal site. The structure is not particularly limited, but at least four atoms are required. It is assumed to be composed of The number of branch sites in one molecule of the dendrimer is at least 5, preferably 7 to 125, and more preferably 9 to 100.

In the present invention, the terminal portion contained in the vinyl group-containing dendrimer is represented by the above formula (1-1)
The long-chain group represented by (1-3), and the following formulas (7-1) to
It is a vinyl group represented by (7-7) or, if necessary, an active hydrogen-containing functional group represented by formulas (2-1) to (2-5).

In general, in the case of a dendrimer having a correct regularity, its size is represented by a conceptual term of generation. In the present invention, a branched structure starting from a core compound as defined above is referred to as a first generation dendrimer, and a structure having a branched structure branched from all terminal sites of the first generation is referred to as a second generation. FIG. 2 shows a third-generation dendrimer having a core site to which four branches are bonded and a terminal site, and each generation is shown in the figure. This is defined as generation in the present invention.

FIG. 2

In the present invention, the long-chain group contained as a terminal portion of the vinyl group-containing dendrimer is effective for achieving both a high molecular weight and a low viscosity while maintaining the curing properties, and improves the compatibility with other components. There is also an effect of causing the above, and is represented by the above formula (1-1), (1-2) or (1-3). In the above formulas (1-1) to (1-3), R1 is a hydrogen atom or a phenyl group, and n is 1 to 25, preferably 4
An integer of ~ 16, x is an integer of 1-6, preferably an integer of 2-4,
R3 is a phenyl group or C1 to C22, preferably 1
To 16 alkyl groups, y is 2 to 22, preferably 2 to 1
An integer of 6, z is an integer of 2 to 15, preferably an integer of 3 to 5, m
Is an integer of 1 to 25, preferably 2 to 16, and k is 1 to 2.
It represents an integer of 0, preferably 1 to 5, and out of this range, it is not preferable because the long-chain group is crystallized, the molecular weight becomes unnecessarily large, and the viscosity increases.

In the present invention, the vinyl group-containing dendrimer is an active hydrogen-containing functional group of the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X) and a vinyl group-containing functional group capable of reacting with active hydrogen. Obtained by reaction with compound (c). The active hydrogen-containing functional group contained in the functional compound (a) or the long-chain group-containing hyperbranched compound (X) is a reaction site for introducing a vinyl group or a long-chain group as needed. Even in the reaction state, it plays a role of improving the performance of the coating film. In the present invention, the polyfunctional compound (a) has at least three active hydrogen-containing functional groups in one molecule.
, Preferably 4 to 64, and 5 or more, preferably 6 to 128 active hydrogens derived therefrom. Examples of the active hydrogen-containing functional group include, for example, organic residues containing active hydrogen represented by the above formulas (2-1) to (2-5). Of these active hydrogen-containing functional groups, primary, secondary amino, hydroxysilyl,
The use of a phosphoric acid group is preferable because it allows hyperbranching, so that more vinyl groups can be introduced into the terminal.

The polyamino dendrimer used in the present invention is a dendrimer having a primary or secondary amino group at a terminal, for example, butylene diamine represented by the above structural formulas (i) and (ii) And acrylonitrile, and the reaction of reducing the terminal nitrile group to amine is defined as one step, and this reaction is repeated to obtain a propyleneimine-based dendrimer (WO09
3/14147, US5530092, JP 7-330631), Michael addition of methyl acrylate to ammonia or ethylenediamine, and furthermore, introduction of a secondary amino group at the terminal by esteramide exchange reaction as one step. Amidoamine-based dendrimers represented by the following structural formula (iv) obtained by repeated reaction (WO84
/ 02705, JP-B-6-70132) or an intermediate product thereof, and a compound having a structure represented by the following structural formulas (iii) or (v). The preferred size of the highly ordered dendrimer used in the present invention is not particularly limited, but is preferably 1 to 5 generations, more preferably 1 to 5 generations.
When dendrimers of the third to third generations, particularly the first or second generations, are used, those having both desirable viscosity before curing and physical properties after curing can be obtained. As the first or second generation polyamino dendrimers, the polyamino dendrimers (i) and (ii) commercialized by DSM are preferred from the viewpoint of easy availability. Further, dendrimers having an amide bond represented by the following formulas (vi) to (xii) can also be used as the polyfunctional compound having a secondary amino group.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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In the present invention, the number average molecular weight of the polyfunctional compound (a) used is not particularly limited, but the preferred molecular weight range is 30 to 5000 as the number average molecular weight.
0, more preferably 50 to 5,000, and when the number average molecular weight is 5,000, especially 50,000 or more, it may be unfavorable in handling due to high viscosity or solid.

In the present invention, the vinyl group-containing dendrimer can be obtained by reacting the polyfunctional compound (a) with a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen. A long-chain-group-containing multibranch obtained by reacting a polyfunctional compound (a) with a long-chain-group-containing compound (b) having a functional group capable of reacting with reactive hydrogen for the purpose of adjusting solubility, physical properties of a coating film, etc. Compound (X) and vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen
Can also be obtained from the reaction with

In the present invention, the long-chain group-containing hyperbranched compound (X) has at least two active hydrogen-containing functional groups,
The number is preferably 3 to 60, and the number of active hydrogens is 2 or more, preferably 2 to 127, and more preferably 4 to 100. In the present invention, the method for synthesizing the long-chain group-containing multibranched compound (X) can be selected depending on the type of the functional group and the type of the target active hydrogen-containing functional group. For example, when the above polyamino-based dendrimer is used as the polyfunctional compound (a), a long-chain-group-containing multibranched compound (X-1) is added by Michael addition of an active hydrogen-containing (meth) acrylic compound (b-1). ) Can be easily synthesized.

In the present invention, the active hydrogen-containing (meth)
Ryl compound (b-1) has a carboxyl group
(Meth) acrylic compound or represented by the following formulas (5-1) to (5-4)
(Meth) acrylic compound having a hydroxyl group
You. CH_Two= C (R¹) COO-R^Two—OH (5-1) In the above formula, R¹Is a hydrogen atom or CH_Three, R^TwoIs carbon number 2
To 22, preferably 2 to 16 alkyl groups, respectively.
You. CH_Two= C (R¹) COO (C_xH_2xO)_mH (5-2) In the above formula, R¹Is a hydrogen atom or CH_Three, X is 1 to 6, good
Preferably an integer of 2 to 4, m is 1 to 25, preferably 4 to
16 integers are shown. CH_Two= C (R¹) COOC_yH_2yO (COC_zH_2zO)_kH (5-3) In the above formula, R¹Is a hydrogen atom or CH_Three, Y is 2 to 22,
Preferably an integer of 2 to 16, z is 2 to 15, preferably
An integer of 3 to 5, k is an integer of 1 to 20, preferably an integer of 1 to 5
Are respectively shown. CH_Two= C (R¹) COR^ThreeO [CONHR^FourNHOR^FiveO]_hH (5-4) In the above formula, R¹Is a hydrogen atom or CH_Three, R^ThreeIs carbon number 2
To 22 alkyl groups, R^FourAre the following formulas (6-a) to (6-
h) an isocyanate residue represented by R^FiveIs-(C _pH_2p
O)_q-Or -C_pH_2p-Dihydric alcohol residue indicated by
Wherein p is an integer of 1-4, and q is an integer of 1-100.
The number and h each represent an integer of 1 to 10.

Embedded image In the present invention, as the chain length of the active hydrogen-containing (meth) acrylic compound (b-1), when a hard cured product is required, a shorter chain length is used, and flexibility is improved. For the purpose of making it long, those having a long chain length are preferable. Within the above range, the bulk viscosity tends to decrease despite an increase in the molecular weight as the chain length increases. When the length is longer than the above range, the bulk viscosity of the vinyl group-containing dendrimer is increased, and the dendrimer is solid at ordinary temperature, and the curability may be poor.

More specifically, for example, the above formula (5-
1) Examples of the hydroxyalkyl (meth) acrylic compound shown include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
Hydroxybutyl (meth) acrylate and the like.

Examples of the polyalkylene glycol mono (meth) acrylic compound represented by the above formula (5-2) include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate and tetraethylene glycol mono ( (Meth) acrylate, tripropylene glycol (meth) acrylate,
Examples include tetrapropylene glycol (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate.

The polylactone mono (meth) acrylic compound represented by the above formula (5-3) includes 2- (meth) acryloyloxyethyl hydrogencaprolactone
2- (meth) acryloyloxyethyl hydrogen dicaprolactate, 2- (meth) acryloyloxyethyl hydrogen poly (degree of polymerization: 3-5)
Examples include caprolactonate and 2- (meth) acryloyloxyethyl-2-hydroxy-6 hexanolactonate.

In addition to the above formulas (5-1) to (5-4), 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate , 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene oxide-modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, ethylene oxide-modified trimethylol Propane mono (meth) acrylate can also be used.

Examples of the (meth) acrylic compound having a carboxyl group include maleic acid, fumaric acid, itaconic acid, citraconic acid, or an alkyl or alkenyl monoester thereof, and β- (meth) acryloxyethyl phthalate. Monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β
-(Meth) acryloxyethyl monoester, β- (meth) acryloxyethyl monosuccinate, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like can be used.

For the purpose of improving the solubility and low viscosity of the vinyl group-containing dendrimer, for example, when the terminal functional group of the polyfunctional compound (a) is a primary amino group or a secondary amino group, the above formula ( Non-functionality (meta) shown in 3)
The acrylic compound (b-2) can be introduced by a Michael addition reaction. In the above (3) wherein, R ¹ represents a hydrogen atom or a methyl group, R ² is _{-C n H 2n + 1, -} (C x H 2x O)
mR ³ or _{-C y H 2y O (COC z} H 2z O) k R 3,,
R ³ is a phenyl group or a group having 1 to 22 carbon atoms, preferably 1
To 16 alkyl groups, n is 4 to 25, preferably 4 to
An integer of 16, x is an integer of 1 to 6, preferably 2 to 4, y
Is an integer of 2 to 22, preferably 2 to 16, and z is 2 to 1.
5, preferably an integer of 3 to 5, m represents an integer of 1 to 25, preferably 2 to 16, and k represents an integer of 1 to 20, preferably 1 to 5. However, it is not preferable because the molecular weight increases more than necessary and the viscosity increases. R1 is preferably a hydrogen atom because it is more effective for improving the reaction efficiency.

More specifically, in the above formula (3), R ²
Alkyl- (meth) acrylic compounds represented by —C _n H _{2n + 1} include methyl methacrylate, ethyl methacrylate, butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate,
Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (Meth) acrylate and the like.

In the above formula (3), R ² _is- (C _x H
_2x O) _m as the alkylene glycol (meth) acrylic compound represented by R ^3, methoxy diethylene glycol (meth) acrylate, main methoxypropane triethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy ethyleneglycol (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n -Pentaxytetraethylene glycol (meta)
Acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol ( (Meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentaxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol ( Meta)
Acrylate, ethoxypolyethylene glycol (meth) acrylate, or phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxytetrapropylene glycol Some include an alkoxy group such as (meth) acrylate and a phenoxy group.

Further, in the above formula (3), R ² is —C _y H _2y O (C
OC _z H _2z O) _k As the polylactone (meth) acrylic compound represented by R ^3, 2- (meth) acryloyloxy phenoxyethyl hydrogen methoxy caproaldehyde Lactobacillus sulfonate, 2- (meth) acrylo yl oxyethyl dihydrogen Methoxy dicaprolactonate, 2- (meth) acryloyloxyethyl hydrogen methoxypoly (degree of polymerization 3 to 5) caprolactonate, 2- (meth) acryloyloxyethyl-2-methoxy-6 hexanolactonate, etc. Can be mentioned.

In the present invention, the active hydrogen-containing (meth) acrylic compound (b-1) and the non-functional (meth) acrylic compound (b) for synthesizing the long-chain group-containing polyfunctional compound (X-1) The blending amount of -2) is not particularly limited as long as one active hydrogen-containing (meth) acrylic compound (b-1) is added, but is preferably based on the total active hydrogen derived from the polyamino dendrimer. Is 10-95
%, More preferably 50 to 90%. If the number is less than this, it is difficult to obtain a multibranched structure, and (b-
In some cases, it is difficult to sufficiently reflect the characteristics of the components (1) and (b-2), which is not preferable. Further, for example, a mixture of an active hydrogen-containing (meth) acrylic compound (b-1) and a non-functional (meth) acrylic compound (b-2) is added to the above polyamino-based dendrimer by Michael addition to thereby obtain a long-chain group-containing compound. The branched compound (X-1) can be obtained efficiently. In this case, the active hydrogen-containing (meth) acrylic compound (b-1) and the non-functional (meth) acrylic compound (b
The mixing ratio with (b-2) varies depending on the total number of active hydrogens derived from the polyamino compound, but preferably (b-1): (b
-2) = 1: 99 to 99: 1, more preferably 20: 8
0 to 95: 5. When the amount of the component (b-2) is too large, it is difficult to obtain a sufficient curability, so that it is not preferable.

The reaction for obtaining the long-chain group-containing polyfunctional compound (X-1) can be carried out according to a conventional method.
When an alcohol such as methanol or ethanol is used as a reaction solvent, side reactions hardly occur. When a solvent is used, 1 to 10 based on the blending weight of the polyamino dendrimer is used.
It is preferable to use 0 times. Heating is not particularly required, but when the molecular weight of the polyamino dendrimer or the (meth) acrylic compound is large, the temperature is 30 ° C to 7 ° C.
It is preferable to heat in the range of 0 ° C. The reaction time varies depending on the type of amino compound to be used and the reaction temperature, and is 30 minutes to 72 hours, generally about one day and night at room temperature,
When the temperature is raised to 50 to 100 ° C., the process is completed within 1 to 10 hours.

In the present invention, the vinyl group is introduced into the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X) in order to make it reactive and has a polymerizable double bond. Although not particularly limited, preferred structures are shown below. CH ₂ = CHCOO-; acryl group _{(7-1) CH 2 = CH (} CH 3) COO-; methacrylic group (7-2) CH ₂ = CH-; vinyl group (7-3) CH ₂ = CH- CH ₂ -O-; allyl (7-4) -CH = CH-; dienyl group _{(7-5) CH 2 = CH-} C 6 H 4 -; phenylvinyl group (7-6) CH ₂ = CH- O-; vinyl ether group (7-7) Among the above vinyl groups, acrylic groups are preferable in UV curing from the viewpoint of reactivity during radiation curing, and methacryl groups exhibit relatively high curability during electron beam curing. It can be said that it is preferable from both aspects of safety and safety.

In the present invention, the chain length of the branch portion into which the vinyl group is introduced means the first X-CH = CH- (X is a hydrogen atom or an organic (Residue) The number of atoms bonded to the linear structure 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 to the ring structure is counted instead of the number of atoms. In the present invention, the preferable chain length of the branch site into which the vinyl group is introduced is 2 to 100, and more preferably 9 to 70.

In the present invention, the vinyl group-containing dendrimer is basically composed of an active hydrogen-containing functional group contained in the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X),
It is obtained by reaction with 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 according to the type of the active hydrogen-containing functional group contained in the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X). For example, when the active hydrogen-containing functional group is a primary or secondary amino group, an acryl group, a carboxyl group, a hydroxyl group, or an epoxy group is preferable.When the active hydrogen-containing 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 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 that can be used when the active hydrogen-containing functional group is an amino group include acryloyl groups such as 2-hydroxy-3-acryloxypropyl methacrylate. Other compounds having a vinyl group can be exemplified, but in this case, since an acrylic group cannot be introduced into the terminal, sufficient curability may not be obtained particularly as an ultraviolet curable compound. Examples of the vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen that can be used when the active hydrogen-containing functional group is a hydroxyl group include glycidyl (meth) acrylate,
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, compound compound containing an epoxy terminal vinyl group such as vinylcyclohexyl epoxide, Vinyltrimethoxysilane,
Alkoxysilyl-terminated vinyl group-containing compounds such as vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxysilane, acid phosphoxyethyl methacrylate, 3-chloro-2-acid phosphopropyl methacrylate Acrylate, acid phosphoxypropyl methacrylate, acid phosphoxyethyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, acid phosphoxypolyoxypropylene glycol monomethacrylate, etc. Can be mentioned.
When an isocyanate group-containing vinyl compound having an isocyanate group (c-1) is used, the above-mentioned active hydrogen-containing functional group can be used in the case of a hydroxyl group, a carboxyl group, an amino group, and the like. Since the combination proceeds under mild conditions, it 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, a method in which a (meth) acrylic compound (b-1) containing an active hydrogen is added to a polyamino dendrimer by Michael addition. A vinyl group can be introduced by subjecting the isocyanate group-containing vinyl compound (c-1) to an addition reaction with the long-chain group-containing hyperbranched compound (X).

Examples of the isocyanate group-containing vinyl compound (c-1) include methacryloyloxyethyl isocyanate (MOI), vinyl isocyanate,
Examples include allyl isocyanate, (meth) acryloyl isocyanate (MAI), and isopropenyl-α, α-dimethylbenzyl isocyanate (TMI). In the present invention, a compound obtained by reacting the diisocyanate compound (c-2) with a vinyl compound (c-3) having a functional group capable of reacting with an isocyanate group in an equimolar amount is also a vinyl compound having an isocyanate group (c- Can be used as 1). The above diisocyanate compound (c
-2) include 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate,
4-methyl-m-phenylene diisocyanate, 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-tetramethylxylylene diisocyanate, p
-Tetramethylxylylene diisocyanate, dimer acid diisocyanate and the like. Examples of the vinyl compound (c-3) having a functional group capable of reacting with an isocyanate group used in the present invention include vinyl compounds having an amino group, a hydroxyl group, a carboxyl group and the like. Is preferred in terms of reactivity with isocyanate groups.
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 preferred from the viewpoint of reactivity with diisocyanate. , For example, 4
-Hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogencaprolactonate, and the like.

The introduction ratio of the vinyl group in the present invention is particularly determined if at least one vinyl group is introduced with respect to all active hydrogens present in the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X). Although not limited, preferably 10 to 9
5%, more preferably 20-80%. If the amount is less than this, it is not preferable because sufficient curability cannot be obtained.If the amount is more than this, the viscosity of the obtained vinyl group-containing dendrimer is increased, the compatibility with other components is reduced, and the film properties such as adhesion are deteriorated. May be undesired. For example, the compounding amount of the isocyanate group-containing vinyl compound (c-1) is
At least 1 to all active hydrogen groups present in the polyfunctional compound (a) or the long-chain group-containing hyperbranched compound (X)
There is no particular limitation as long as they are added, but preferably 10 to
95%, more preferably 20-80%.

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

The vinyl group-containing dendrimer obtained by the present invention has a number average molecular weight of 200 to 100,000,
Preferably from 300 to 50,000, more preferably from 400 to
40,000 or less, preferably 100,000 cps or less, preferably 50,000 to 500 cps, more preferably 2
It is a liquid having a viscosity of 000 to 1000 cps (30 ° C.). If the molecular weight is lower than this, curing shrinkage becomes severe, which is not preferable. In the case where the molecular weight is high, there is no particular problem in the case where the viscosity is within the range where the film can be formed. However, when the molecular weight is higher than the above range, the viscosity increases, which is not preferable in view of the film forming property. On the other hand, if the viscosity exceeds the above range, it is not preferable in terms of solubility with multiple components and film forming properties.

The vinyl group-containing dendrimer is mixed with a polymerizable unsaturated group-containing compound (B) other than the vinyl group-containing dendrimer for the purpose of adjusting the viscosity and curability of the curable composition. I can do it, but
Particularly, examples of the polymerizable unsaturated group-containing compound (B) include acrylic compounds and vinyl ether compounds. Among these, the use of a (meth) acrylic compound is preferred from the standpoint of availability.

In the present invention, the (meth) acrylic compound blended in the composition includes methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) as monofunctional (meth) acrylate compounds. Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, isodecyl (meth) acrylate, n-
Lauryl (meth) acrylate, tridecyl (meth)
Acrylate, n-stearyl (meth) acrylate,
Isostearyl (meth) acrylate, behenyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, n-butoxyethyl (meth) acrylate, 2-phenyl Enoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth) acryloyloxyethyl hydrogen succinate, (meth) acryloyloxypropyl hydrogen phthalate, (meth) acryloyloxypropyl Tetrahydrohydrogen phthalate, (meth) acryloyloxypropyl hexahydrohydrogen phthalate, (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyloxy
-3-acryloyloxypropyl (meth) acrylate,
Mono (2- (meth) acryloyloxyethyl) acid phosphate may be exemplified, but is not limited thereto. Polyfunctional (meth) acrylic compounds include 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate. Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, 3- (meth) acryloyloxyglycerin mono (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta In addition to polyfunctional (meth) acrylic compounds such as (meth) acrylate, urethane acrylic and epoxy Lil, although esters of acrylic or mixtures thereof, and the like as examples, not necessarily limited thereto. Further, when a (meth) acrylic compound having three or more functional groups is used, the reactivity is increased, and the inhibition of curing by oxygen can be further improved.

The vinyl ether compounds to be blended in the present invention include monofunctional vinyl ether compounds such as hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, and the like.
Cyclohexane dimethanol monovinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, and polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol, pentaerythritol Divinyl ether, propylene glycol divinyl ether,
Dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediele divinyl ether, 1,6-hexanediol divinyl ether, glycerol divinyl ether, trimethylolpropane divinyl ether, 1, 4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, hydroquinone divinyl ether, hydroquinone diethoxy divinyl ether, resorcin diethoxy divinyl ether, bisphenol A diethoxy divinyl ether, bisphenol S diethoxy divinyl ether, etc. Divinyl ether compounds, glycerol trivinyl ether, sorbitol Tri- or more functional polyvinyl such as lavinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, ditrimethylolpropane polyvinyl ether, etc. Examples thereof include ether compounds and mixtures thereof, but are not necessarily limited thereto. In addition to the above, examples of the polymerizable unsaturated group-containing compound (B) include vinyl pyrrolidone, vinyl caprolactam, vinyl carbazole, vinyl-1-imidazole, divinyl ethylene urea, N-vinyl formamide, N-vinyl formalin, Allyl glycidyl ether, allyl chloride and the like can be mentioned. Further, a diene compound, a styrene compound, an unsaturated fatty acid compound, or the like may be used.

Among the above polymerizable unsaturated group-containing compounds (B), the reactive diluent for the vinyl group-containing dendrimer is preferably 8.5 to 12.5, more preferably 9.0 to 10.0 as the SP value. It is. Compounds in this range have excellent compatibility with vinyl group-containing dendrimers or general reactive oligomers, and are also regions that can make use of the characteristics of dendrimers that do not easily spread chains.

In the present invention, the mixing ratio of the vinyl group-containing dendrimer (A), which is a reactive oxygen inhibition inhibitor, and the polymerizable unsaturated group-containing compound (B) is determined based on the molecular weight of the vinyl group-containing dendrimer (A). , The number of vinyl groups contained, the number of secondary or tertiary amino structures, the structure of the compound containing a polymerizable unsaturated group (B) to be blended, or the oxygen concentration at the time of curing. ): (B)
= 5: 95-99: 1, more preferably 20: 80-8
0:20. If the amount of the reactive oxygen inhibition inhibitor is smaller than this, it is difficult to obtain a sufficient oxygen inhibition inhibitory effect.

Further, the viscosity of the curable composition obtained in the present invention is desirably from 10 to 50,000 cps (30 ° C.), and the more preferable range is from 20 to 20,000 cps. Inferior and undesirable.

The reactive oxygen inhibition inhibitor of the present invention or the curable composition containing the same may be used for controlling viscosity, forming a film,
To adjust the coating performance, amino resin, phenolic resin, polyamide resin, cellulose derivative, vinyl resin, polyolefin, natural rubber derivative, acrylic resin,
General-purpose resin materials such as epoxy resin, polyester, polystyrene, alkyd resin, rosin-modified alkyd resin, and linseed oil-modified alkyd resin, and drying oils such as linseed oil, tung oil, and soybean oil may be blended. However, the amount of each of these is preferably 60% by weight or less, more preferably 40% by weight or less, based on the total amount of the composition.

Further, if necessary, water, an organic solvent, a compatibilizer, a surfactant, a lubricant and the like may be added. The amount of these components is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the composition. Also,
When the reactive oxygen inhibition inhibitor of the present invention or the curable composition containing the same is cured by ultraviolet light or heat, known initiators, sensitizers, catalysts and the like can be used.
The electron beam-curable composition of the present invention is prepared by adding an appropriate amount of a coloring agent composed of 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. Thus, it can be used as various printing inks and coloring paints.

The reactive oxygen inhibition inhibitor of the present invention and the curable composition containing the same can be used for various metals, plastics, papers,
Coating or filling a plate, sheet or film-like substrate made of ceramic or composite material with a roll coater, bar coater, knife coater, etc., offset printing,
By printing by a printing method such as gravure printing, letterpress printing, silk screen printing, etc., 0.1 to 50
A film can be formed with a film thickness of 0 μm. The hemiacetal ester-based polyfunctional (meth) acrylic compound having a cycloalkane structure filled or formed by the above method and a composition containing the same are heat or an active energy ray such as an electron beam, ultraviolet ray, visible light ray, or infrared ray. Irradiation can cure even under a high oxygen concentration of 500 ppm or more.

In the present invention, the high oxygen concentration of 500 ppm or more includes the concentration range achieved by performing inerting with an inert gas such as nitrogen or argon. The allowable concentration of oxygen that can be cured by active energy rays is determined by the irradiation conditions (trigger type, electron beam as a trigger; acceleration voltage, irradiation dose, etc., when ultraviolet is a trigger; initiator concentration). Depending on the amount of the agent and the type of the other (meth) acrylic monomer or vinyl monomer, it is preferable to cure under the best conditions without being inhibited by oxygen even in air.

When an electron beam is used as a curing trigger in the present invention, it is preferable to use an acceleration voltage in the range of preferably 10 to 1000 kV, more preferably 30 to 300 kV.
One electron beam irradiation device is used. An electron beam irradiator with a low accelerating voltage concentrates energy on the surface, so that electron beam is intensively absorbed on the coating / printing surface where curing is likely to be inhibited by oxygen, and curability can be improved. Therefore, it is effective and preferable for curing a thin film. The acceleration voltage in this case is in the range of 30 to 70 kV. 100kV
When the following low acceleration voltage electron beam irradiation is performed, damage to the coating film and the substrate is small.

The electron beam irradiation dose (DOSE) is
Preferably 1 to 1000 kGy, more preferably 5 to 2 kGy
The range is 00 kGy. If the amount is less than this, it is difficult to obtain a sufficiently cured product, and if it is more than this, damage to a coating film or a substrate is large, which is not preferable.

The film formation in the present invention means a film having a thickness of 0.1 to 500 μm on a substrate made of paper, metal, plastic, ceramics or the like by a method such as printing and painting. Means to form

[0062]

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.構造 Structural analysis, measuring method of number average molecular weight and viscosity 1) Structural analysis: The structure of the vinyl group-containing dendrimer synthesized here was confirmed by ¹ H-NMR. 2) Number average molecular weight: Gel permeation chromatography (TOSOH SC-8020) A calibration curve of gel permeation chromatography (GPC) was independently created from several types of dendrimers having a known structure analyzed by ¹ H-NMR. GP based on this
The result measured in C was adopted. In addition, the molecular weight distribution (Mw
/ Mn) adopted the value obtained with the same measuring instrument. 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 (Nissin High Voltage) Electron beam acceleration; 150 kV Absorbed dose (Dose); The range of 5 to 20 kGy was adjusted by the current amount and the transport speed. 2) MIN-EB (manufactured by AIT) Electron beam acceleration: 50 kV, output: 10 W Absorbed dose (Dose): The range of 5 to 20 kGy was adjusted by the transport speed.

◎ Abbreviations of the following compounds used in Examples and Comparative Examples are described. 1) Polyfunctional compound (a) DAB4: described in structural formula (i) 4-Cascade: 1,4-diaminobuta
ne [4]: propylamine DAB8: described in structural formula (ii) 8-Cascade: 1,4-diaminobuta
ne [4]: (1-azabutylidene) ⁴
propylamine 2) Active hydrogen-containing (meth) acrylic compound (b-1) HEA: 2-hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate PPG6A: Polypropylene glycol (degree of polymerization of PPG chain = 6) acrylate 3) Non-functionality (Meth) acrylic compound (b-2) BA: butyl acrylate EHA: 2-ethylhexyl acrylate LA: lauryl acrylate MPEG9A: methoxy polyethylene glycol (PE
G chain polymerization degree = 9) Acrylate 4) Isocyanate group-containing vinyl compound (c-1) MOI: methacryloyloxyethyl isocyanate and synthetic products shown in Synthesis Examples 1-2 below 5) Polymerizable unsaturated group-containing compound (B) HDDA: 1,6 hexanediol diacrylate (η
= 6.0 cps) TPGDA: tripropylene glycol diacrylate (η = 12 cps) TMPT3EO: ethylene oxide-modified trimethylolpropane triacrylate (η = 50 cps) DPHA: dipentaerythritol hexaacrylate (η = 5000 cps)

(Synthesis Example 1) 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: 0.1 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 HMDI and 4HBA Stirrer, nitrogen inlet tube, temperature sensor, condenser,
And HMDI: 168 g, ethyl acetate: 170 g, tin 2-ethylhexanoate: 0.1 g were blended into 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 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.

Example 1 DAB4 / HEA / LA / M
Synthesis of OI (1/10 mol scale) DAB 4: 32 g, HEA: 23 g, LA: 144 g in a 1000 ml four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser.
Ethyl acetate: blending 199 g, was refluxed for 3 hours at the set hot water bath to 75 ° C., partially sampled, ¹ H-
NMR measurement showed that the proton peak derived from the acryl group had almost disappeared. Therefore, the bath temperature is set to 60
C., and a mixed solution of MOI: 31 g and ethyl acetate: 31 g was added. After 10 to 30 minutes, tin 2-ethylhexanoate: 0.02 g was added. The heating and stirring were continued for 3 to 4 hours, and the NCO group characteristic absorption (2270c
The point at which m- ¹ ) disappeared was regarded as the reaction end point. Further, the target vinyl group-containing dendrimer was obtained by removing the ethyl acetate used as a reaction solvent by an evaporator.

(Example 2) DAB4 / HEA / LA / M
Synthesis of OI (1/10 mole scale) DAB 4: 32 g, HEA: 46 g, LA: 96 g, ethyl acetate: 174 g in a 1000 ml four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser. Was refluxed for 3 hours in a hot water bath set at 75 ° C., and then sampled partially to obtain ¹ H-
When NMR was measured, the proton peak derived from the acryl group had almost disappeared. Therefore, the hot water bath temperature is set to 60 ° C.
, And a mixed solution of MOI: 62 g and ethyl acetate: 62 g was added. After 10 to 30 minutes, tin 2-ethylhexanoate: 0.03 g was added. Continue heating and stirring for 3-4 hours, and absorb the NCO group characteristic absorption (2270c
The point at which m- ¹ ) disappeared was regarded as the reaction end point. Further, the target vinyl group-containing dendrimer was obtained by removing the ethyl acetate used as a reaction solvent by an evaporator.

(Examples 3 to 20) Stirring apparatus, introduction of nitrogen
Four-necked round with tube, temperature sensor and condenser
Polyfunctional compound (a) shown in Table 1 in a bottom flask, equivalent weight
Containing ethyl acetate, containing active hydrogen (meta)
Acrylic compound (b-1), non-functional (meth) acryl
To 50% by weight of ethyl compound (b-2) with ethyl acetate.
The diluted solution was added with stirring. Activated water
Unless HEA was used as the element-containing compound,
Mix the same molar number of methanol as the polyfunctional compound (a)
You. The above reaction solution was placed in a hot water bath set at 75 ° C for 4 hours.
After reflux, sample partly, ¹Measure H-NMR
The reaction is terminated by the proton peak derived from the acrylic group.
After confirming the point, divide the pipe between the reactor and the condenser.
And continue heating and stirring at 80 ° C in a hot water bath at normal pressure.
The solvent was distilled off while shaking. From the top of the condenser
Connect a vacuum line and use a water bath at 70 ° C
g and ethyl acetate and methano
When the solvent was completely distilled off, a viscous liquid resin was obtained.
Therefore, while maintaining the hot water bath temperature at 70 ° C., newly add ethyl acetate
NV is added to 50% and contains isocyanate group
Vinyl compound (c-1) as (meth) acrylic compound
(B-1) and non-functional (meth) acrylic compound
Addition is made by multiplying the total mole number of (b-2) by the yield.
Acetic acid so that the concentration of the entire reaction system becomes 50%.
Diluted with ethyl. After another 10 minutes, 2-ethylhexa
Tin acid isocyanate group-containing vinyl compound (c-1)
0. 5% by weight was added. Heat and stir for 3 hours or more
The stirring was continued, and the NCO-based characteristic absorption of the IR chart (2270
cm ^-1The point at which) disappeared was regarded as the reaction end point. Furthermore, anti
Solvent removal of ethyl acetate used as solvent by evaporator
To obtain the desired vinyl group-containing dendrimer.
Obtained. Synthesis formula of the obtained vinyl group-containing dendrimer and
Table 1 shows the basic characteristics of the obtained compound. Table 2
Is a reactive oxygen inhibition inhibitor of vinyl group-containing dendrimers
Irradiate electron beam under various conditions to evaluate performance,
The result of having evaluated the characteristic of the obtained cured coating film is shown.

[0069]

[Table 1]

[0070]

[Table 2]

The reactive oxygen inhibition inhibitors (A) and the compounds containing various polymerizable unsaturated groups (B) obtained in Examples 1 to 20 are shown in Tables 3-1 and 3-2 in Examples 21 to 45. A curable composition was prepared by blending with the indicated formulation to show the viscosity. Table 3-
1 and 3-2 show the results of irradiating these curable compositions with electron beams under various conditions and evaluating the properties of the obtained cured coating films. Further, as a comparative example, the results of evaluating the curability of the polymerizable unsaturated group-containing compound (B) alone are also shown. (Comparative Examples 1-4) In addition, the evaluation methods of various physical properties shown in Table 2, Table 3-1 and Table 3-2 are described below. ◎ Sample preparation method The film base material described in the table (size of base material for evaluation → thickness: 20 μm, width: 5 cm, length;
20 cm) and irradiated with an electron beam under the conditions described in the table (oxygen concentration, electron beam acceleration voltage, DOSE). ◎ Test method ・ Curability; (Touch test) → ×: Tack, △: No tack but scratches with nails, ○: No damage with no nails ・ Substrate adhesion (coating film by cellophane peel test) Solvent resistance (visual determination of residual coating after 50 MEK rubbing tests) Abrasion resistance (visual determination of surface damage after 50 rubs of cotton cloth) → ×: disappearance of coating, △ : Scratched, ○: no scratching)

[0072]

[Table 3]

[0073]

[0074]

According to the present invention, a film-forming material such as paints and inks, a sealant, a molding agent, and the like, which are excellent in inhibiting oxygen inhibition.
Can be used in a wide range of fields as resin materials such as adhesives and pressure-sensitive adhesives.
Provided is a high-molecular-weight, low-viscosity reactive oxygen inhibition inhibitor capable of obtaining a cured product even under an oxygen concentration of m or more, a curable composition containing the same, a method for forming a cured film using the same, and a cured product. It is a thing. Is provided.

[Brief description of the drawings]

Fig. 1 Model diagram of dendrimer

Fig. 2 Model diagram of dendrimer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C07C 211/14 C07C 211/14 237/10 237/10 F term (reference) 4H006 AA01 AB51 AC52 AC53 BU32 BV53 BV74 4H025 AA31 AA37 AA39 AA63 AA68 4J038 CE051 CG141 CH031 CH041 CH131 CH151 CH161 CH171 CJ001 CR061 GA03 GA09 GA14 GA15 NA02 PC02 PC03 PC08 PC10 4J039 BC34 BC36 BE33 EA04 EA48 FA01 FA02 FA06 GA01 GA02 GA03 4J043SA08 SA62 SA71 SB01 TA02 TA07 TA11 TA31 TA32 TA33 TA35 TA55 TA72 TA79 TB01 TB03 TB04 UA181 UB131 UB231 UB241 WA05 WA16 WA17 WA22 WA25 WA29 ZB03 ZB22 ZB41

Claims (15)

[Claims] 1. A secondary or tertiary amine structure comprising a core site, a branch site, a branch site, and at least four terminal sites, wherein the terminal sites are represented by the following general formulas (1-1) to (1-3). )
At least one long-chain group selected from the group consisting of: or at least one active hydrogen-containing group selected from the group consisting of the following formulas (2-1) to (2-5); and a vinyl group-containing vinyl group A reactive oxygen inhibition inhibitor comprising a dendrimer. ^{_{-C n H 2n R 1 (1-1}} ) - (C x H 2x O) m R 3 (1-2) -C y H 2y O (COC z H 2z O) k R 3 (1-3) ( In the formula, R ¹ is a phenyl group or a hydrogen atom, and n is 4 to 2
An integer of 5, x is an integer of 1 to 6, R ³ is a phenyl group or an alkyl group having 1 to 22 carbon atoms, y is an integer of 2 to 22,
z is an integer of 2 to 15, m is an integer of 1 to 25, k is 1 to 2
Each represents an integer of 0. ) -NHR ¹ : primary and secondary amino groups (2-1) (wherein, R ¹ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.) -COOH: carboxyl group (2-2) -OH : Hydroxyl group (2-3) -Si (OR ⁴ ) _3-n (OH) _n : hydroxysilyl group (2-4) (R4 is a phenyl group or an alkyl group having 1 to 20 carbon atoms, n
= 1 to 3 represent an integer. ) -P = O (OH) ₂ : phosphate group (2-5) 2. A polyfunctional compound (a) having at least three active hydrogen-containing functional groups in one molecule and having five or more active hydrogens can react with active hydrogens. Reacting a long-chain-group-containing hyperbranched compound (X) obtained by reacting a long-chain-group-containing compound (b) having a functional group with a vinyl-group-containing compound (c) having a functional group capable of reacting with active hydrogen; The reactive oxygen inhibition inhibitor according to claim 1, which is a compound comprising: 3. A polyamino dendrimer comprising an active hydrogen-containing (meth) acrylic compound (b-1) or an active hydrogen-containing (meth) acrylic compound (b-1) and a vinyl group-containing dendrimer having the following general formula: A long-chain group-containing hyperbranched compound (X-) obtained by Michael addition of a mixture of the non-functional (meth) acrylic compound (b-2) represented by (3).
The reactive oxygen inhibition inhibitor according to claim 1 or 2, which is a compound obtained by reacting 1) with a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen. CH ₂ ＣC (R ¹ ) COO—R ² (3) (wherein, R ¹ is a hydrogen atom or a methyl group, and R ² is —C _n H
_{2n + 1, - (C x} H 2x O) m R 3 or -C _y H _2y O (CO,
C _z H _2z O) _k R ³ and R ^{3 each} represent a phenyl group or a group having 1 to 2 carbon atoms.
2 is an alkyl group, n is an integer of 4 to 25, x is an integer of 1 to 6, y is an integer of 2 to 22, z is an integer of 2 to 15, and m is 1
And an integer of 1 to 20 and k represents an integer of 1 to 20, respectively. ) 4. The reactive oxygen inhibition inhibitor according to claim 3, wherein the polyamino dendrimer is a compound represented by the following formula (i) or (ii). Embedded image 5. A dendrimer having a vinyl group having a number average molecular weight of 200 to 100,000 and a viscosity of 100,000 cps.
4. A liquid compound having a temperature of (30 ° C.) or lower.
2. The reactive oxygen inhibition inhibitor according to item 1. 6. A curable composition comprising the reactive oxygen inhibition inhibitor (A) according to any one of claims 1 to 5 and another compound (B) containing a polymerizable unsaturated group. 7. The compounding ratio of the reactive oxygen inhibition inhibitor (A) to the other polymerizable unsaturated group-containing compound (B) is 10:90.
7. The curable composition according to claim 6, wherein the ratio is about 95: 5 (weight ratio). 8. The curable composition according to claim 6, wherein the other polymerizable unsaturated group-containing compound (B) is a (meth) acrylic compound or a vinyl ether compound. 9. The curable composition according to claim 6, wherein the other polymerizable unsaturated group-containing compound (B) has a viscosity of 10,000 cps (30 ° C.) or less and a number average molecular weight of 2000 or less. Composition. 10. A printing ink application according to claim 6 to 9.
The curable composition according to claim 1. 11. The curable composition according to claim 6, which is used for coating. 12. An active energy ray-curable composition.
10. The curable composition according to any one of claims 9 to 9. 13. The curable composition according to claim 12, wherein
A method for forming a cured film by irradiating an active energy ray under an oxygen concentration of ppm or more. 14. The method for forming a cured film according to claim 13, wherein an electron beam having an acceleration voltage of 30 to 100 kV is irradiated. 15. A cured product obtained by the method of claim 13 or 14.