JP3090047B2 - Non-aqueous active energy ray-curable resin composition that can be washed with water - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous active energy ray-curable resin composition which can be washed with water . Of the present invention
The active energy ray-curable resin composition can be used as an active ingredient of various coatings for plastic films, various coatings such as woodwork paints, printing inks, and adhesives.

[0002]

2. Description of the Related Art Active energy ray-curable resin compositions are
In general, it contains a reactive oligomer and a reactive diluent, and is excellent in safety because it does not contain a solvent, and has excellent characteristics in terms of productivity and energy saving because of its excellent curability. Be recognized.

However, since the active energy ray-curable resin composition is generally insoluble in water, when the resin composition is subjected to various uses, the resin composition adheres to a coating machine such as a roll coater or peripheral equipment. When washing the object, it was necessary to use a solvent. That is, despite the fact that a general active energy ray-curable resin composition is characterized by not using a solvent as described above, a solvent is used for cleaning what has adhered to a coating machine or a peripheral device. Therefore, it was not sufficient in terms of safety such as fire hazard, air pollution and working environment.

In recent years, various water-soluble active energy ray-curable resin compositions and emulsion type active energy ray-curable resin compositions have been developed. When these resin compositions are used, they can be washed with water even when they adhere to a coating machine or peripheral equipment. However, the reactive oligomer used in the water-soluble active energy ray-curable resin composition requires the introduction of a hydrophilic functional group such as a carboxylate into the resin, so that the structure of the resin is limited and various applications are required. However, there is a problem that it is difficult to sufficiently cope with the problem and the water resistance is poor. Further, the emulsion type active energy ray-curable resin composition has a problem that a drying step is required after coating, and further, solvent resistance is poor.

[0005]

SUMMARY OF THE INVENTION The present invention provides an active energy having basic performances such as water resistance and solvent resistance and capable of being washed with water even when applied to a coating machine or peripheral equipment. An object is to provide a line-curable resin composition.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, an active energy containing a predetermined amount of a specific polyurethane (meth) acrylate shown below as a reactive oligomer. The linear curable resin composition has basic properties such as water resistance and solvent resistance, and the water-insoluble reactive diluent in the resin composition due to the self-emulsifying property of the specific polyurethane (meth) acrylate. Even when such components are present, it has been found that the entire resin composition is emulsified at the time of washing with water, and that washing with water can be performed efficiently, and the present invention has been completed.

That is, the present invention provides (A) a (meth) acrylate ester having at least one hydroxyl group in a molecule, and (B) three or more reactive isocyanate groups in a molecule.
Organic polyisocyanates having the above and (C) a general formula
_{(1): H- (OCH 2} CH 2) in _n -OR (wherein, R
Represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 3 to 25
Is shown. Polyurethane obtained by reacting a polyethylene glycol represented by) (meth) acrylate 20
-99% by weight, reactive diluent 1-80% by weight, reactive oligomer 0-70% by weight, and photopolymerization initiator 0-10
The present invention relates to a water-washable non-aqueous active energy ray-curable resin composition containing 1% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION A (meth) acrylic ester containing at least one hydroxyl group in the molecule as the component (A) (here, (meth) acrylic ester is an acrylic ester or a methacrylic ester) Hereinafter, (meth) has the same meaning.) Means various compounds having at least one hydroxyl group and at least one (meth) acryloyl group in a molecule. Specific examples thereof include 2-hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ε-caprolactone condensation of 2-hydroxyalkyl (meth) acrylate Polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; 4-hydroxybutyl (meth) acrylate, 2-hydroxyphenoxypropyl (meth) acrylate, pentaerythritol Tri (meth) acrylate and the like. These compounds can be used alone or in combination. As the component (A), polyol polyacrylates such as polyepoxy (meth) acrylate can be used, but when these are used, the viscosity of the obtained polyurethane (meth) acrylate is obtained. Therefore, these polyol polyacrylates are preferably used in combination with the various (meth) acrylates exemplified above.

The organic polyisocyanate (B) has three reactive isocyanate groups in the molecule.
Those having the above are preferred. Specific examples thereof include, for example, 1,6-hexane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate,
Trimers having an isocyanuric acid structure obtained from various diisocyanates such as diphenylmethane diisocyanate, and a prepolymer obtained by reacting the diisocyanates with a polyhydric alcohol such as trimethylolpropane,
And so on. It should be noted that the purpose and action and effect of the present invention are not
Unless removed, two or more isocyanate groups in the molecule
Is converted into the above-mentioned reactive isocyanate in the molecule.
Combined use with organic polyisocyanates having three or more groups
You can do it.

The component (C) has the general formula (1): H- (OC
H ₂ CH ₂ ) _n —OR (wherein R is an alkyl having 1 to 4 carbon atoms )
And n represents an integer of 3 to 25. )
Polyethylene glycols. The polyethylene
Glycols are obtained from polyurethane (meth) acryl
For the rate, basic performance such as water resistance and solvent resistance,
Provides a good balance between water washability and self-emulsification
be able to. In addition, even if a polypropylene glycol containing at least one hydroxyl group is used instead of the component (C), the water washing property is not sufficient because there is no self-emulsifying property.

The polyurethane (meth) acrylate of the present invention is obtained by reacting the above components (A), (B) and (C). The use ratio of each component is 10 to 80% by weight, preferably 10 to 70% by weight of component (A), 10 to 80% by weight, preferably 10 to 70% by weight of component (B), and 10% by weight of component (C). ~ 80
%, Preferably 20 to 70% by weight. The amounts of the components (A) and (B) used are determined in consideration of the crosslinking density and the like of the obtained polyurethane (meth) acrylate, and the component (C) is used for the obtained polyurethane (meth) acrylate. Was determined in consideration of the water washability and the water resistance of the cured film. When the amount of the component (C) is less than 10% by weight, the water washability is insufficient. When the amount is more than 80% by weight, the curing becomes insufficient or insufficient due to a decrease in the crosslink density. However, the water resistance of the cured film tends to decrease.

The method for producing the polyurethane (meth) acrylate of the present invention is not particularly limited, and the component (A),
The component (B) and the component (C) are reacted at the above-mentioned usage ratio. The reaction may be carried out in a lump, or the component (A) and the component (B) may be reacted, and then the component (C) may be reacted. The reaction temperature is usually about 40 to 100 ° C, preferably 60 to 80 ° C, and the total reaction time is about 4 to 12 hours. The completion of the reaction can be easily confirmed by quantifying the disappearance of the isocyanate residue by IR.
In the urethanization reaction, a known urethanization catalyst such as stannous octylate is preferably used to promote the reaction. In order to prevent polymerization of the component (A) during the urethanization reaction, a polymerization inhibitor such as hydroquinone, methoxyphenol, or phenothiazine is used in an amount of about 10 to 5000 ppm, preferably 50 to 2 ppm, based on the reaction system.
It is better to use 000 ppm or to perform air sealing.

The active energy-curable resin composition of the present invention contains 20 to 99% by weight of the polyurethane (meth) acrylate obtained above and 1 to 80% by weight of a reactive diluent. When the proportion of the polyurethane (meth) acrylate in the composition is less than 20% by weight, it is difficult to emulsify the entire resin composition even if the polyurethane (meth) acrylate is self-emulsified, Poor cleaning performance.

Examples of the reactive diluent include various ones. For example, water-soluble ones such as N-vinylpyrrolidone, hexaethylene glycol di (meth) acrylate, acryloyl morpholine, and tripropylene glycol di (meth) Acrylate, 1,6-hexanedi (meth) acrylate, bisphenol A poly (number of repetitions: about 1 to 4) ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane mono or poly (repeating unit) About 1-3) Water-insoluble such as ethoxytriacrylate, pentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, etc. The and the like.

Further, in the present invention, an active energy ray-curable resin composition comprising the polyurethane (meth) acrylate and the reactive diluent to which a reactive oligomer other than the above, a photopolymerization initiator, and an additive are added. It can be used as an object.

Examples of the reactive oligomer include various polyester acrylates, epoxy acrylates, and polyurethane acrylates other than those described above. The usage ratio is 0 to 70% by weight in the active energy ray-curable resin composition.

The photopolymerization initiator is unnecessary when an electron beam or the like is used as the active energy ray, but is required when curing with ultraviolet rays. As the photopolymerization initiator, various known ones such as Darocure 1173, Irgacure 651, Irgacure 184, Irgacure 907 (all manufactured by Ciba Geigy), benzophenone and the like can be used. The usage ratio is 0 to 10% by weight or less in the active energy ray-curable resin composition.

As the additives, antifoaming agents, leveling agents, etc., and depending on the intended use, pigments, silicon compounds, etc. can be selected and used according to the purpose. The usage ratio is within a range that does not deviate from the original purpose.

[0019]

The water-washable non-aqueous active energy ray-curable resin composition of the present invention can be cured by a curing reaction.
Ri, the the solvent-free polyurethane (meth) acrylate
Since it exhibits a certain degree of water resistance and solvent resistance, it can be applied to various uses. Moreover, if the state of the active energy ray curable resin composition, coating machine, even when adhered to the peripheral devices, it can be easily washed with water, a safe, a significant improvement in the working environment It can be achieved. In particular, even when the active energy ray-curable resin of the present invention contains a water-insoluble reactive diluent which has conventionally been difficult to wash with water,
According to the fat composition, it is possible to maintain water detergency, so that the effect
Has a great advantage .

[0020]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, “parts” and “%” are based on weight unless otherwise specified.

Production Example 1 (Production of polyurethane acrylate a) In a flask equipped with a stirrer, a thermometer, an air blowing tube and a reflux condenser, 145.4 parts of (A) hydroxypropyl acrylate and (B) hexamethylene diisocyanate were added. 330.8 parts of a monomer (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate HX"), 0.7 part of 4-methoxyphenol, and a polymerization inhibitor (manufactured by Wako Pure Chemical Industries, Ltd., trade name "Q-1301") )) 0.007 parts were charged. Subsequently, 0.14 parts of stannous octoate was charged into the system while air blowing and stirring were performed, the temperature in the system was increased to 75 to 80 ° C., and the temperature was maintained for 1.5 hours, and then (C) polyethylene glycol monomethyl ether (Toho Chemical Industry) 223.7 parts of “Methoxy PEG # 400” (trade name, manufactured by Co., Ltd.) was added, and the mixture was further kept warm for 2 hours to obtain polyurethane acrylate a.

Production Example 2 (Production of polyurethane acrylate b) In Production Example 1, 309.1 parts of pentaerythritol triacrylate as the component (A), 233.2 parts of "Coronate HX" as the component (B), and the component (C) The reaction was carried out in the same manner as in Production Example 1 except that 157.7 parts of "methoxy PEG # 400" was used to obtain polyurethane acrylate b.

Production Example 3 (Production of polyurethane acrylate c) In Production Example 1, 98.3 parts of hydroxypropyl acrylate was used as the component (A), 223.6 parts of "Coronate HX" was used as the component (B), and component (C) was used. Polyethylene glycol monomethyl ether (Toho Chemical Industry Co., Ltd.)
The reaction was carried out in the same manner as in Production Example 1 except that 378.1 parts of methoxy PEG # 1000 (trade name, manufactured by Toshiba Corporation) was used to obtain a polyurethane acrylate c.

Production Example 4 (Production of polyurethane acrylate d) In the same flask as in Production Example 1, (A) 485.1 parts of pentaerythritol triacrylate, (B) 214.9 parts of "Coronate HX", 4-methoxyphenol 0.7
And 0.007 part of the polymerization inhibitor "Q-1301". Then, while performing air blowing and stirring, 0.14 part of stannous octoate was charged and the system was charged with 75 to 80 parts.
C. and kept for 1.5 hours to obtain polyurethane acrylate d.

Production Example 5 (Production of polyurethane acrylate e) Polyester diol (co-condensate of adipic acid and 1,4-butanediol,
(Weight average molecular weight: 500) 265.0 parts, isophorone diisocyanate 271.0 parts, 2-hydroxyethyl acrylate 160.0 parts, 4-methoxyphenol 0.
7 parts were charged, and the temperature was raised to 75 ° C. over 1.5 hours.
After incubating at 5-80 ° C for 1 hour, stannous octoate 0.1
By charging 4 parts and further keeping the temperature for 1 hour, a polyurethane acrylate e was obtained.

Production Example 6 (Production of polyurethane acrylate f) In Production Example 5, 355.9 parts of polypropylene glycol (weight average molecular weight 700), 226.1 parts of isophorone diisocyanate, 118.0 parts of 2-hydroxyethyl acrylate, and Except that 0.3 part of methoxyphenol was charged, the reaction was carried out in the same manner as in Production Example 5 to obtain polyurethane acrylate f.

Examples 1-4, Comparative Examples 1-4 (Preparation of active energy ray-curable resin compositions) Predetermined amounts of polyurethane acrylates a-f shown in Table 1, various reactive diluents, and photopolymerization initiators 3 parts of Irgacure 184 (manufactured by Ciba-Geigy) were mixed to prepare a varnish (active energy ray-curable resin composition). The following performance evaluation was performed on the prepared varnish. Table 2 shows the evaluation results.

(Evaluation of Performance) (1) Water Washability After applying the roll coater using the above varnish, the roll coater was washed with water to confirm the washability. ：: good, △: slightly poor, ×: varnish remains. (2) Water resistance The above-mentioned varnish is applied on a glass plate at a film thickness of 20 μm.
Irradiation with ultraviolet light from a high-pressure mercury lamp of 0 W / cm (100 m
j / cm ² ) to cure the varnish. Water was dropped on the surface of the cured film, covered with a watch glass, and allowed to stand at room temperature for 24 hours to observe changes in appearance. ：: no change, △: slightly swelling, ×: whitening, cracking. (3) Chemical Resistance In the evaluation of water resistance, the same evaluation was performed using toluene instead of water. ：: no change, △: slightly swelling, ×: whitening, cracking.

[0029]

[Table 1]

In the table, DTMTPA: ditrimethylolpropane tetraacrylate, Bs-750: bisphenol A ethylene oxide-modified diacrylate (manufactured by Arakawa Chemical Industries, Ltd.), and TPGDA: tripropylene glycol diacrylate are shown.

[0031]

[Table 2]

Continuation of the front page (56) References JP-A-54-160494 (JP, A) JP-A-6-287260 (JP, A) JP-A-3-166212 (JP, A) JP-A-2-292315 (JP) JP-A-2-34620 (JP, A) JP-A-4-20514 (JP, A) JP-A-8-134156 (JP, A) JP-A-5-301935 (JP, A) 5-117361 (JP, A) JP-A-6-9739 (JP, A) JP-A-6-240186 (JP, A) JP-A-8-208783 (JP, A) JP-A-63-251459 (JP, A A) JP-A-63-317515 (JP, A) JP-B-48-41708 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299 / 00-299/08 C08F 2/00-2/60 C08G 18/00-18/87

Claims (2)

(57) [Claims] (1) (A) (meth) acrylic ester containing at least one hydroxyl group in the molecule , (B) intramolecular
An organic polyisocyanate having three or more isocyanate groups reactive with a compound represented by the general formula (1): H- (O
CH ₂ CH ₂ ) _n -OR (wherein, R represents an alkyl group having 1 to 4 carbon atoms )
And n represents an integer of 3 to 25. )
20 to 99% by weight of a polyurethane (meth) acrylate obtained by reacting polyethylene glycols, 1 to 80% by weight of a reactive diluent, 0 to 70% of a reactive oligomer
A water-washable, non-aqueous active energy ray-curable resin composition containing 0 to 10% by weight of a photopolymerization initiator. 2. The use ratio of each component of the polyurethane (meth) acrylate is 10 to 80% by weight of the component (A),
The water-washable non-aqueous active energy ray-curable resin composition according to claim 1, which is 10 to 80% by weight of the component (B) and 10 to 80% by weight of the component (C).