JP2001048906A - Material curable with active energy rays and top coating agent for decorative paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material curable by active energy rays imparting a dried coated film excellent in physical properties, especially resistance to solvents while the coated film is free from tackiness, useful for a top coating agent for decorative paper by including a specific acrylate and a specific polymer. SOLUTION: This material includes (A) an acrylate having one carboxyl and one or more acryloyls in the molecule and (B) a polymer having amino group units in the molecule. The prefereble ratio of the component B is 20-3,000 pts.wt. per 100 pts.wt. of the component A. The material preferably includes (C) and acrylate including two or more acryloyls and no carboxyl in the molecule, (D) a photopolymerization initiator and (E) a solvent. The preferable ratio of the component C is 20-3,000 pts.wt. per 100 pts.wt. of the component A. The preferably component B is a compound having amino group units and organopolysiloxane units in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an active energy ray-curable material and a topcoat agent for decorative paper.

[0002]

2. Description of the Related Art For example, in a decorative paper in which a printing layer is formed on the surface of a paper base material, a top coat layer as a transparent layer is provided on the surface of the printing layer. Although a thermosetting material is known as such a top coat agent, an active energy ray-curable material is attracting attention from the viewpoint of productivity and physical properties,
Are being considered.

[0003] The above-mentioned active energy ray-curable material is prepared as a paint containing a solvent and a polymerizable monomer not only for use as a topcoat agent for decorative paper but also for various uses. Then, after the application, the coating is dried, and the obtained dried coating is converted into a cured coating by irradiation with active energy rays. The above-mentioned curing is superior in productivity to thermal curing, and the resulting cured coating film has excellent hardness.

[0004] By the way, in using an active energy ray-curable material, it is important that the dried coating film has no tackiness from the viewpoint of handleability. As a method of imparting non-tackiness to a dry coating film, T
A method in which a polymer having a high g is used in combination is conceivable. According to this method, non-tackiness appropriate for the combined amount of the polymer is provided.

[0005]

However, in the case of an active energy ray-curable material simply using a polymer as described above, the physical properties of the cured coating film are deteriorated, and specifically, the solvent resistance is deteriorated. There is a problem. The present invention has been made in view of such circumstances, and an object of the present invention is to provide an active energy ray-curable material and a cosmetic which are excellent in physical properties (especially solvent resistance) of a cured coating film while the dried coating film has no tackiness. An object of the present invention is to provide a paper topcoat agent.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that the above object can be achieved by using a combination of an active energy ray-curable (polymerizable) monomer and a specific polymer. Were found to be able to be easily achieved, and the present invention was completed.

That is, a first gist of the present invention is to provide a polymer (B) having an amino group unit in a molecule together with an acrylate (A) having one carboxyl group and one or more acryloyl groups in the molecule. The active energy ray-curable material is characterized by containing

A second aspect of the present invention resides in a topcoat agent for decorative paper comprising the above-mentioned active energy ray-curable material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The active energy ray-curable material of the present invention comprises an acrylate (A) having one carboxyl group and one or more acryloyl groups in the molecule as an active energy ray-curable (polymerizable) monomer. An acrylate containing, as a non-tackiness imparting agent, a polymer (B) having an amino group unit in the molecule and, if necessary, two or more acryloyl groups having no carboxyl group in the molecule ( C).

First, the basic component of the active energy ray-curable material of the present invention, that is, the acrylate (A) having one carboxyl group and one or more acryloyl groups in the molecule will be described. Examples of such an acrylate (A) include, in addition to (meth) acrylic acid, a reaction product of a hydroxyl group-containing polyfunctional acrylate and an acid anhydride. Specific examples thereof include, for example, (meth) acrylic acid, Pentaerythritol triacrylate succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, dipentaerythritol pentaacrylate maleate monoester,
Examples include pentaerythritol triacrylate phthalate monoester, dipentaerythritol pentaacrylate phthalate monoester, pentaerythritol triacrylate tetrahydrophthalate monoester, and dipentaerythritol pentaacrylate tetrahydrophthalate monoester. Among them, pentaerythritol triacrylate succinic acid monoester is preferably used.

Next, the component functioning as a non-tackiness imparting agent, that is, the polymer (B) having an amino group unit in the molecule will be described. As such a polymer (B), for example, a polymer of a (meth) acrylic acid ester of an amino alcohol may be mentioned. Examples of the acrylic acid include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth).
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, etc. And especially N, N
-Dimethylaminoethyl (meth) acrylate is preferably used.

The polymerization of the (meth) acrylic acid ester of amino alcohol can be carried out according to a known polymerization method using a radical polymerization initiator such as azobisisobutyronitrile in the presence of a solvent such as ethyl acetate. In the present invention, a polymerizable monomer having an organopolysiloxane unit and another polymerizable monomer can be used as a copolymer component in the above polymerization.

Examples of the polymerizable monomer having an organopolysiloxane unit include an organopolysiloxane compound having one radically polymerizable group in one molecule. Examples of the radical polymerizable group include a (meth) acryloyl group and a styryl group, and a (meth) acryloyl group is particularly preferable. Further, the organopolysiloxane unit is preferably represented by the following general formula.

[0014]

Embedded image

In the above formula, R ¹ and R ² represent a methyl group or a phenyl group which may be the same or different from each other, and n represents an integer of 5 or more, preferably an integer of 5-300. . The polymerizable monomer having an organopolysiloxane unit as described above has an effect of improving non-tack property by silicone.

Examples of the other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. A) alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate and tridecyl (meth) acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate , Styrene, methylstyrene and the like. The polymerizable monomer as described above has an effect of increasing the Tg of the polymer (B) and thereby improving the non-tack property.

In the present invention, the polymer (B) includes:
Those having an organopolysiloxane unit together with an amino group unit in the molecule are preferably used. When preparing the polymer (B) having an organopolysiloxane unit together with an amino group unit in the molecule, the polymerizable monomer having the organopolysiloxane unit with respect to the (meth) acrylate (a1) of the amino alcohol is used. The use ratio of the body (a2) is usually 1/50 as a molar ratio of a2 / a1.
00 to 1/25, preferably 1/3000 to 1/100
It is said. Further, the other polymerizable monomer (a3)
Is usually 1 to 5 as a3 / a1 molar ratio.
0, preferably 3 to 30. And the number average molecular weight of the polymer (B) is usually 400 to 60,000,
Preferably, it is 1,000 to 30,000.

Next, the acrylate (C) having an optional component, that is, two or more acryloyl groups having no carboxyl group in the molecule will be described. Examples of such acrylate (C) include trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate and the like. Among these,
Dipentaerythritol hexaacrylate is preferably used.

The active energy ray-curable material of the present invention comprises:
The acrylate (A) and the polymer (B) are contained as essential components. That is, the polymer (B) imparts non-tackiness to the dried coating film by suppressing the tackiness induced in the case of the dried coating film of the acrylate (A) alone according to the amount used. At this time, the cured coating film after irradiation with active energy rays crosslinks the polymer (B) by the interaction (salt-forming action) between the carboxyl group of the acrylate (A) and the amino group of the polymer (B). Incorporates into the structure and exhibits excellent solvent resistance and hardness.

Polymer (B) to acrylate (A)
Is appropriately determined depending on the desired non-tack property. The number of carboxyl groups in the acrylate (A) used is appropriately determined in consideration of the interaction between the carboxyl group and the amino group (salt-forming action). Although the ratio of the polymer (B) to 100 parts by weight of the acrylate (A) cannot be uniquely determined as described above, it is usually 30 to 3000 parts by weight, preferably 50 to 2 parts by weight.
000 parts by weight. When the use ratio of the polymer (B) is less than the above range, the effect of imparting non-tackiness to the dried coating film tends to be insufficient, and when the use ratio of the polymer (B) is larger than the above range, The inherent properties of the active energy ray-curable material, such as the hardness of the cured coating film, tend to decrease.

The active energy ray-curable material of the present invention comprises:
The above acrylate (C), that is, an acrylate having two or more acryloyl groups having no carboxyl group in the molecule, is contained as an optional component. Acrylate (C) has the effect of increasing the crosslink density and increasing the hardness of the cured coating film due to its polyfunctionality. The ratio of the acrylate (C) to 100 parts by weight of the acrylate (A) is usually 20 to 3000 parts by weight, preferably 40 to 25 parts by weight.
00 parts by weight.

Usually, the active energy ray-curable material of the present invention contains a photopolymerization initiator and a solvent.

Examples of the photopolymerization initiator include, for example, 2,2-
Diethoxyacetophenone, 2,2-dimethoxy-2-
Phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, p, p'-
Bisdiethylaminobenzophenone, Michler's ketone,
Benzoin methyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzophenone, methylbenzoyl formate, 2,2-diethoxyacetophenone, 4-N, N'-dimethylacetophenone,
-Methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2--4-diethylthioxanthone, oligo [2-hydroxy-2-methyl-1-
[4- (1-methylvinyl) phenyl] propanone and the like. The amount of the photopolymerization initiator used is usually 0.1 to 1 based on the total amount of the acrylates (A) and (C).
0% by weight.

Examples of the solvent include hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone. The amount of the solvent to be used is generally 30 to 80% by weight based on the total solids constituting the active energy ray-curable material of the present invention. The viscosity measured at 25 ° C. of the active energy ray-curable material of the present invention containing the solvent thus prepared is preferably 100 to 200 mPa · s from the viewpoint of workability of coating and the like. The viscosity can be measured using a B-type viscometer (manufactured by Tokimec).

The active energy ray-curable material of the present invention comprises
It is used by being applied to the surface of a printed layer of decorative paper formed by forming a printed layer on the surface of a paper base, and the surface of other objects to be coated.
Then, after the application, the coating is dried, and the obtained dried coating is converted into a cured coating by irradiation with active energy rays.

As a coating method, spray coating, dip coating, roll coater coating, flow coater coating, spin coater coating and the like are appropriately employed depending on the shape of the object to be coated. The coating thickness is usually 1 to 15 μm, preferably 3 to 15 μm as the thickness of the dried coating film after removing the solvent from the viewpoint of the physical properties of the coating film. Examples of the active energy rays applied to the dried coating film include ultraviolet rays, electron beams, and radiation, and practically, ultraviolet rays are applied.
Xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, carbon arc lamps,
A tungsten lamp or the like is used. The radiation dose is usually 50 to 2,000 mJ / cm ² , preferably 100 to
It is 1,000 mJ / cm ² .

[0027]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

<Synthesis of Polymer (B)>

Synthesis Example 1 In a reactor equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 120 g of ethyl acetate, 108 g of methyl methacrylate and 12 g of dimethylaminoethyl methacrylate were added.
g, azobisisobutyronitrile 0.16 g,
The temperature inside the reactor was raised to 80 ° C. under a nitrogen stream, and a polymerization reaction was carried out at the same temperature for 2 hours. Subsequently, 0.16 g of azobisisobutyronitrile and 60 g of ethyl acetate were added, and
For 2 hours. Further, subsequently, 0.32 g of azobisisobutyronitrile and 100 g of ethyl acetate were added, and the mixture was reacted at 80 ° C. for 4 hours. Then, the polymer (B
1) was obtained.

Synthesis Example 2 In the same reactor as in Synthesis Example 1, 80 g of ethyl acetate, 64 g of methyl methacrylate, 16 g of dimethylaminoethyl methacrylate, and 0.10 g of azobisisobutyronitrile.
Was heated to 80 ° C. under a nitrogen stream, and a polymerization reaction was carried out at the same temperature for 2 hours. Subsequently, 0.10 g of azobisisobutyronitrile and 40 g of ethyl acetate were added and reacted at 80 ° C. for 2 hours. Further, 0.21 g of azobisisobutyronitrile and ethyl acetate 6
6.7 g was added and reacted at 80 ° C. for 4 hours. Then, a polymer (B2) was obtained.

Synthesis Example 3 Synthesis Example 1 was the same as Synthesis Example 1 except that the charged amount of methyl methacrylate was changed to 106.8 g, and 1.2 g of methacryloylpolysiloxane (“FM-0725” manufactured by Chisso) was additionally charged. A polymerization reaction was carried out in the same manner as in the above to obtain a polymer (B3).

Synthesis Example 4 Synthesis Example 2 was the same as Synthesis Example 2 except that the charged amount of methyl methacrylate was changed to 63.2 g, and 0.8 g of methacryloylpolysiloxane (“FM-0725” manufactured by Chisso) was additionally charged. A polymerization reaction was carried out in the same manner as in the above to obtain a polymer (B4).

Synthesis Example 5 In Synthesis Example 1, the charged amounts of methyl methacrylate and dimethylaminoethyl methacrylate were 58.
The polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 8 g and 60 g, and 1.2 g of methacryloylpolysiloxane (“FM-0725” manufactured by Chisso) was additionally added, to obtain a polymer (B5).

Synthesis Example 6 Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount of methyl methacrylate was changed to 96 g and that 12 g of methacryloylpolysiloxane (“FM-0725” manufactured by Chisso) was additionally added. After the reaction, the polymer (B
6) was obtained.

Synthesis Example 7 A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that the charge of methyl methacrylate was changed to 120 g and the charge of dimethylaminoethyl methacrylate was stopped. Obtained.

Examples 1 to 14 and Comparative Examples 1 to 2 Polymers (B1) having an amino group unit in the molecule described above
(B7) an acrylate (A) having one carboxyl group and one or more acryloyl groups in the molecule shown in Table 1 below, and an acrylate having two or more acryloyl groups having no carboxyl group in the molecule (C), a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone: "IRG184" manufactured by CIBA-GEIGY) and an organic solvent (ethyl acetate) were blended in the proportions shown in Table 2, and the present invention and comparative control were used. Energy curable material for use in the preparation of

[0037]

<Acrylate (A)> “TO-756”: pentaerythritol triacrylate succinate monoester (manufactured by Toa Gosei) “TO-1382”: dipentaerythritol pentaacrylate succinate monoester (manufactured by Toa Gosei) <Acrylate (C)> “DPHA”: dipentaerythritol hexaacrylate “PETA”: pentaerythritol triacrylate “TMPTA”: trimethylolpropane triacrylate

Each of the above-mentioned active energy ray-curable materials was applied to a 100 μm-thick polyethylene terephthalate film (“T600E100” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) using a bar coater so that the dried coating film became 8 μm. The resultant was dried by heating at ℃ for 3 minutes. Then, using a high-pressure mercury lamp with an output of 120 W / cm, under the light source 15c
From the position of m, the above-mentioned coating films were irradiated with ultraviolet rays of 600 mJ / cm ² . Then, the following tests (1) to (3) were performed, and the results are shown in Table 3.

(1) Tack test: The tackiness of the dried coating film before ultraviolet irradiation was evaluated in three stages (（: no tack, Δ: slight tack, ×: tack).

(2) Measurement of pencil hardness: JIS-K540
0 Based on the “pencil scratch test”, the cured coating film after irradiation with ultraviolet rays is evaluated.

(3) Solvent resistance test: The cured coating film after irradiation with ultraviolet rays was rubbed by reciprocating 100 times with a methyl ethyl ketone impregnated cotton cloth. Then, the appearance of the cured coating film was evaluated in three stages (（:
No change, Δ: extremely thin whitening, ×: whitening).

[0042]

[Table 2]

[0043]

[Table 3]

Example 15 A polymer (B3) was obtained in the same manner as in Synthesis Example 3;
Subsequently, the inside of the reactor was switched to an air stream at the same temperature,
83.5 g of ethyl acetate, 0.52 g of hydroquinone monomethyl ether, pentaerythritol triacrylate succinic acid monoester (“TO-75” manufactured by Toagosei Co., Ltd.)
6 ") 35.8 g was added and stirred and mixed for 30 minutes to obtain an active energy ray-curable material.

The above active energy ray curable material 100
g, a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone: “IRG18” manufactured by CIBA-GEIGY)
4 ") 0.9 g was blended and the same evaluation as in Example 1 was carried out. As a result, tackiness: ○ and solvent resistance: △.

Example 16 A polymer (B3) was obtained in the same manner as in Synthesis Example 3;
Subsequently, the inside of the reactor was switched to an air stream at the same temperature,
447.1 g of ethyl acetate, 1.04 g of hydroquinone monomethyl ether, pentaerythritol triacrylate succinate monoester (“TO-75” manufactured by Toagosei Co., Ltd.)
6)) 35.8 g and 155.8 g of dipentaerythritol hexaacrylate were added, and mixed by stirring for 30 minutes.
An active energy ray-curable material was obtained.

The above active energy ray curable material 100
g, a photopolymerization initiator (1-hydroxycyclohexyl phenyl ketone: “IRG18” manufactured by CIBA-GEIGY)
4 ") 0.9 g was blended, and the same evaluation as in Example 1 was performed. As a result, tackiness: ： and solvent resistance: ○.

[0048]

According to the present invention as described above, an active energy ray-curable material and a topcoat agent for decorative paper, which are excellent in physical properties (especially solvent resistance) of a cured coating film even though the dried coating film is non-tacky. Is provided.

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Claims (8)

[Claims] 1. An activity comprising an acrylate (A) having one carboxyl group and one or more acryloyl groups in the molecule and a polymer (B) having an amino group unit in the molecule. Energy ray curable material. 2. The active energy ray-curable material according to claim 1, wherein the polymer (B) has an organopolysiloxane unit together with an amino group unit in the molecule. 3. The active energy ray-curable material according to claim 1, which contains an acrylate (C) having at least two acryloyl groups having no carboxyl group in the molecule. 4. The active energy ray-curable material according to claim 1, which contains a photopolymerization initiator. 5. The active energy ray-curable material according to claim 1, further comprising a solvent. 6. The active energy ray-curable material according to claim 1, wherein the ratio of the polymer (B) to 100 parts by weight of the acrylate (A) is 30 to 3000 parts by weight. 7. The active energy ray-curable material according to claim 1, wherein the ratio of the acrylate (C) to the acrylate (A) is 20 to 3000 parts by weight. 8. A topcoat agent for decorative paper comprising the active energy ray-curable material according to claim 1.