JPH05295012A - Radiation-curable resin composition and its cured molded product - Google Patents

Abstract

PURPOSE:To provide the radiation-curable resin composition containing a specific compound as a free acid, readily cured with UV rays, electron beams, etc., and giving black cured molded products having excellent visible light-shielding abilities. CONSTITUTION:The radiation-curable resin composition comprises (A) a radiation-curable resin, e.g. a compound having one or more of ethylenic unsaturated groups (e.g. epoxydiacrylate), (B) a compound of formula I and/or a component of formula II (sodium, an alkylamine, an alkanolamine, etc., are used for the counter ion for forming the salts of the compound of formula I and/or the compound of formula II) as a free acid in an amount of 0.005-90wt.% (in the resin composition), if necessary, a photopolymerization initiator (e.g. an acetophenone compound or a sulfur compound), a photosensitizer (e.g. triethanolamine), etc. For example, the resin composition is coated on a support such as paper, plastic sheet or synthetic paper and subsequently irradiated with UV rays, electron beams, etc., to form a black cured film having an excellent visible light-shielding ability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation curable resin composition which can be easily cured by ultraviolet rays, electron beams and the like to obtain a cured film having an excellent visible light shielding ability, and a cured molded product thereof.

[0002]

2. Description of the Related Art Conventionally, filters used to prevent noise from remote control switches for televisions, video cameras, etc., and filters for cutting visible light, such as various light-shielding films, are molded products of thermoplastic or thermosetting resin. And made from film. As a material for imparting optical characteristics to these molded products, it is general to use carbon black as a pigment and an oil-soluble disperse dye as a dye. recent years,
As a molding material, a radiation-curable resin material that can be easily cured and molded by ultraviolet rays or electron beams has been widely used. These materials are economically extremely useful because they are easy to process, but on the other hand, the above-mentioned oil-soluble dyes are decomposed by the influence of radicals generated during curing, and UV curable resins using photopolymerization initiators. In the current situation, however, it is difficult to produce a material that uses a radiation curable resin as a material, such as carbon black that inhibits curing, and that has a function of cutting the visible light region.

[0003]

There is a demand for a radiation curable resin composition which can be produced by a simple manufacturing method and gives a cured molded article having an excellent function of cutting visible light.

[0004]

The inventors of the present invention have earnestly studied to improve the above-mentioned problems, and as a result, the present invention has been achieved. That is, the present invention

(1) A radiation-curable resin composition containing a compound represented by the following formula (1) and / or (2) as a free acid (the same applies hereinafter)

[0006]

[Chemical 3]

[0007]

[Chemical 4]

(2) The radiation curable resin composition according to item (1), wherein the radiation curable resin according to item (1) is a compound having one or more ethylenically unsaturated groups. (3) A cured molded article obtained by curing the radiation curable resin composition according to the above (1) is provided.

The present invention will be described in detail. The compounds of the above formulas (1) and (2) used in the present invention can be used alone or in any mixing ratio. The mixing ratio of the compounds (total amount) in the radiation curable resin composition of the present invention is 0.005 to 90% (% by weight). still,
In formulas (1) and (2), cations such as sodium, potassium, lithium, alkylamines and alkanolamines are selected as counterions for forming salts.

When the resin composition of the present invention is used as an ultraviolet curable resin composition, a photopolymerization initiator which initiates or accelerates the photopolymerization reaction is added to the composition. Needless to say, the above photopolymerization initiator is not necessary when the resin composition of the present invention is used as an electron beam curable composition (usually used as a printing ink and paint). The radiation curable resin used in the present invention is preferably an ultraviolet curable resin or an electron beam curable resin, examples of which include the following prepolymers and monomers.

As the prepolymer, urethane (meth) is used.
Acrylate, epoxy (meth) acrylate, saturated polyester / styrene, polyethylene (meth) acrylate, polyether (meth) acrylate, silicon (meth) acrylate, polybutadiene (meth) acrylate, polystyrylethyl (meth) acrylate, polyamide (meth) Acrylate etc. are mentioned. As the monomer, as the monofunctional ethylenically unsaturated group-containing compound, 2-ethylhexyl acrylate, 2-hydroxypropyl (meth) acrylate, ethyl carbitol acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di-ethyl Cyclopentanyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxy-3phenoxypropyl (meth) acrylate, diethylene glycol (2-ethylhexyl) ether (meth) ) Acrylate, phenyl glycidyl ether (meth) acrylate, acryloylmorpholine and the like, and as the bifunctional ethylenically unsaturated group-containing compound, 1,6- Alkylene glycol di (meth) acrylates such as xanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene di (meth) acrylate, tri Polyoxyalkylene glycol di (meth) such as propylene di (meth) acrylate and polypropylene glycol di (meth) acrylate
Epoxy di (meth) s such as acrylates, di (meth) acrylates of alkylene oxide adducts of bisphenol A or hydrogenated bisphenol A, ethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) acrylate An acrylate etc. can be mentioned.

When the resin composition of the present invention is photopolymerized by irradiation with ultraviolet rays or the like, it is preferable to use a photopolymerization initiator that absorbs light energy and generates radicals. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler's ketones, benzyl, benzoin alkyl ether, benzyl dimethyl ketal, carbonyl compounds such as benzoyl benzoate, thioxanthones, and sulfur compounds such as tetramethylthylium mosulfite. And so on.
These can be used alone or in combination of two or more. Further, such a photopolymerization initiator is, for example,
Amine-based compounds such as triethanolamine, P-dimethylaminobenzoic acid isoamyl ester, N, N-diethyl-P-aminobenzonitrile, etc., phosphorus compounds such as tri-n-butylphosphine, chlorine compounds such as hexachloroethane, etc. The photosensitizers can be used alone or in combination of two or more. The mixing ratio of the photopolymerization initiator and the photosensitizer is 100 parts by weight of the resin composition,
1 to 25 parts by weight is preferable. If the amount is less than this, the polymerization reaction does not sufficiently occur even when irradiated with ultraviolet rays, and the physical properties of the film are lacking. If it is too large, no particularly beneficial effect can be obtained.

In addition to the above-mentioned components, the resin composition of the present invention includes a defoaming agent, a leveling agent, a light stabilizer (eg, hindered amine), an antioxidant, a polymerization inhibitor, an antistatic agent, and a metal soap such as zinc stearate. Further, fillers such as ultrafine particles of calcium carbonate and ultrafine particles of colloidal silica can be used together. The resin composition of the present invention can also be used as a water-soluble emulsion by a known method using various emulsifiers.

As a method for producing the radiation-curable resin composition of the present invention, the constituent resin components are first mixed and dissolved, and then the compound of formula (1) and / or formula (2) is added, A method of dispersing by using a dispersing machine such as a roll mill of two rolls and three rolls, a bead mill such as a sand grinder, an attritor, or the like, after mixing and adjusting resin components and the like, the formula (1) and / or the formula Examples of the method include a method in which the compound (2) is dissolved in a solvent such as an alcohol or a ketone, and then added and mixed, and then the solvent is removed by heating or the like, but the method is not limited to these and is generally known. It can be produced by a method.

As a method for producing a black cured molded article for shielding visible light using the resin composition of the present invention, the resin composition of the present invention is coated on a support such as paper, plastic sheet, synthetic paper or the like with a bar. After coating by a general coating method such as coater, spin coater, roll coater, spray coating, dipping, gravure printing, screen printing,
It can be obtained by irradiating an ultraviolet ray, an electron beam or the like to cure. The thickness of the film can be arbitrarily changed according to the purpose of blocking visible light.

In order to cure the resin composition of the present invention with an electron beam, it is preferable to use an electron beam accelerator capable of irradiating energy of 100 to 5000 eV, for example. Further, in order to cure the resin composition of the present invention with ultraviolet rays, an ultraviolet irradiation device equipped with, for example, a xenon lamp, a high pressure mercury lamp, or a metal halide lamp as a light source is used. When using a high-pressure mercury lamp, 80-120
It can be cured by irradiating it with ultraviolet rays from a lamp having a light amount of W / cm.

Needless to say, the resin composition and the molded product of the present invention show extremely excellent optical characteristics and are useful as the above-mentioned visible light cut filter, but in addition, for example, infrared reading is possible. It is also extremely useful for applications such as anti-counterfeiting bar codes in which the bar code is invisible under visible light by being applied onto various bar codes.

[0018]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the part in an Example shows a weight part.

Example 1 200 parts of Kayarad R-114 (bis A type manufactured by Nippon Kayaku Co., epoxy acrylate prepolymer), Kayarad DPHA (acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) 45
0 part, Kayarad R-551 (Nippon Kayaku Co., Ltd. acrylate monomer) 200 parts, Irgacure 907 (Ciba-Geigy polymerization initiator) 45 parts, Kayacure DETX
5 parts of -S (polymerization initiator manufactured by Nippon Kayaku Co., Ltd.) is dissolved and mixed in a 5 liter planetary mixer at 80 ° C for 1 hour, and then cooled to room temperature. Then the compound of formula (1) (Na salt)
After adding 200 parts and mixing for 1 hour, the mixture was kneaded with a two-roll mill to obtain a black resin composition A of the present invention.

Example 2 Except that the compound of formula (1) was changed to the compound of formula (2),
The same operation as in Example 1 was performed to obtain a black resin composition B of the present invention.

Example 3 600 parts of Kayarad UX-6101 (urethane prepolymer manufactured by Nippon Kayaku Co., Ltd.), 100 parts of Kayarad R-561 (acrylate monomer manufactured by Nippon Kayaku Co., Ltd.), Kayarad R-
128 (Nippon Kayaku Co., Ltd. acrylate monomer) 300
Parts, 45 parts of Irgacure 907 (polymerization initiator manufactured by Ciba-Geigy) and 5 parts of Kayacure DETX-S (polymerization initiator manufactured by Nippon Kayaku Co., Ltd.) were dissolved and mixed in a 5 liter planetary mixer at 80 ° C. for 1 hour. Cool to 40 ° C. Then, 100 parts of the compound of formula (1) and 100 parts of the compound of formula (2) were added and mixed for 1 hour, followed by kneading with a three-roll to obtain a black resin composition C of the present invention.

Reference Example 1 The same as Example 1 except that the compound of the formula (1) was changed to the oil-soluble dye Kayaset Black 151 (H) (disazo dye manufactured by Nippon Kayaku Co., Ltd.). Was performed to obtain a black resin composition D.

Reference Example 2 In Example (3), a total amount of 200 parts of the compounds of the formulas (1) and (2) was changed to carbon black (MA manufactured by Mitsubishi Kasei Co., Ltd.).
-100) The same procedure as in Example 3 was carried out except that the amount was changed to 200 parts to obtain a resin composition E.

Reference Example 3 In Example (3), 200 parts of the total amount of the compounds of the formulas (1) and (2) was used as an oil-soluble dye Kayaset Blue K-.
FL (Nippon Kayaku Co., Ltd. metal-containing copper phthalocyanine complex salt dye)
Except for changing the amount to 200 parts, the same operation as in Example 3 was carried out to obtain a blue resin composition F.

Examples 4 to 6 The resin compositions A, B and C obtained in Examples 1 to 3 were coated with corona discharge on white PET so that a film thickness of 20 μm was obtained by using a bar coater. Coating, and then using an ultraviolet irradiation device (GS ASE-20: made by Nippon Battery Co., Ltd.) equipped with a high pressure mercury lamp of 80 W / cm, curing speed 5 m
/ Min to perform curing to obtain black cured moldings. The evaluation results of the curing performance are shown in Table 1.

Reference Examples 4 to 6 Resin compositions D, E, and F obtained in Reference Examples 1 to 3 above
About white PET that has been subjected to corona discharge treatment by screen printing to a film thickness of 30 microns,
Ultraviolet irradiation device equipped with 80 W / cm high pressure mercury lamp (G
SASE-20: manufactured by Nippon Battery Co., Ltd.), but a good cured product could not be obtained. The evaluation results of the curing performance are shown in Table 1.

Table 1 Resin Composition Curability * Change in color tone A 1 pass, no change, no change, B 1 pass, no change, C no change, C 1 pass, no change, D 5 pass, no change, no change E 5 Does not cure even with pass No change at all F 1 Pass cures significantly, fading

* Hue Change Between Resin Composition (Before Curing) and Cured Product As is clear from the results in Table 1, the resin composition of the present invention has excellent curability and the hue change before and after curing. There is no.

[0029]

EFFECTS OF THE INVENTION A black cured molded product having no obstacle during curing and excellent in light shielding performance was obtained.

Claims (3)

[Claims] 1. A radiation curable resin composition comprising a compound represented by the following formula (1) and / or (2) as a free acid. [Chemical 1] [Chemical 2] 2. The radiation curable resin composition according to claim 1, wherein the radiation curable resin according to claim 1 is a compound having at least one ethylenically unsaturated group. 3. A cured molded article obtained by curing the radiation curable resin composition according to claim 1.