JPS6011930B2 - Energy beam-curable epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an energy ray-curable epoxy resin composition that absorbs energy rays such as ultraviolet rays, acts as a barrier to energy rays, and at the same time has an antioxidant function.

More specifically, an energy ray-curable epoxy resin composition consisting of paint or ink is applied and cured on the material to act as a stable barrier in the presence of energy rays and at the same time prevent oxidation and protect the material even in the presence of air. The present invention relates to an energy ray-curable epoxy resin composition used for this purpose. Plastics, synthetic rubber, synthetic fibers, printed matter, etc. are degraded by ultraviolet rays and oxygen in the air.

For example, strength decreases, elasticity is lost, electrical properties deteriorate, and furthermore, cracks occur or become discolored, making it unusable. Also, as seen in printed matter, yellowing and discoloration of pigments caused by sunlight, especially ultraviolet rays, are common phenomena, and such quality deterioration is very serious. Currently, methods for preventing such quality deterioration are being researched, and one of the common methods is to add an ultraviolet absorber and an antioxidant to the material in advance.

However, in this method, the absolute amount is large because it is added to the entire amount of the material, and not only is it lost due to sublimation and thermal decomposition during the roll wire of plastics, rubber, etc. There is a lack of effective use of Ultraviolet deterioration and oxidation progress from the surface, so it is desirable that more absorbent be present on the surface.

However, in current embodiments it is not possible to selectively aggregate the absorbent onto the surface. Another method is to dissolve a polymer with UV protection ability in a volatile organic solvent, apply it, and then evaporate the solvent to form a transparent film. However, it is still not sufficient because it has disadvantages such as thermal deterioration of the material due to heating, and it tends to be impractical. on the other hand,
Adding an ultraviolet absorber to an energy beam-curable epoxy resin has not been done in the past because of the idea that it might inhibit the activation of the catalyst. The purpose of the present invention is to basically solve the shortcomings of the current technology, and to create a film-like material by adding ultraviolet absorbers and antioxidants to energy ray-curable epoxy resin, applying it to the material, and curing it under ultraviolet light in a short period of time. It forms and protects the material, and is not affected by material damage due to volatile organic solvents or thermal deterioration, and is effective in preventing ultraviolet rays and oxidation, so it has a remarkable effect on quality protection. bring.

The composition of the present invention contains, as essential components, an epoxy resin membrane, a catalyst precursor (B) that releases a catalyst that causes cationic polymerization of an epoxy resin upon irradiation, an ultraviolet absorber, and an antioxidant. The energy beam curable epoxy resin composition according to the present invention contains a catalyst precursor such as allyl diazonium quartz which releases a catalyst that causes cationic polymerization of the epoxy resin upon irradiation with ultraviolet rays. The Lewis acid generated when the acid onium salt decomposes acts as a cationic polymerization catalyst, and the polymerization type is different from that of conventionally known radical polymerization type vinyl compounds.For example, the curing time by ultraviolet irradiation is longer than that of the radical polymerization type. Vinyl compounds require 20 seconds to several minutes, but the cationically polymerized epoxy resin used in the present invention cures with 0.1 to 5 seconds of irradiation, making it possible to shorten the time considerably. It has excellent properties such as flexibility, adhesion, maneuverability, chemical resistance, flexibility, and abrasion resistance, and since it is used as a solvent-free type, it does not deteriorate the working environment due to solvents. problems,
It completely overcomes all the drawbacks, has great industrial economic value, and is expected to have a wide range of applications.

The epoxy resins used in the present invention are conventionally known aromatic epoxy resins (A-1), alicyclic epoxy resins (A-1), and alicyclic epoxy resins (A-1).
2) and aliphatic epoxy resin (A-3).

Particularly preferable aromatic epixy resins (A-1) are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof, such as bisphenol A Alternatively, examples thereof include glycidyl ether and epoxy novolak resin produced by reacting an alkylene oxide adduct thereof with epichlorohydrin. Particularly preferred as the alicyclic epoxy resin (A-2) are polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring (A-2-1), or compounds containing cyclohexene or cyclobentene rings. There is a cyclohexene oxide or cyclobentene oxide-containing compound (A-2-2) obtained by epoxidation with a suitable oxidizing agent such as hydrogen peroxide or peracid. Polyglycyether (A
A typical example of -2-1) is glycidyl ether produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Further, representative examples of the cyclohexene oxide or cyclobentene oxide containing compound (A-2-2) include those represented by the following formula. Particularly preferred as the aliphatic epoxy resin (A-3) are aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof; a typical example thereof is 1,6-hexanediol. diglycidyl ether of glycerin, triglycidyl ether of glycerin, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, and one or more alkylenes. Oxide (ethylene oxide, propylene oxide)
Examples include polyglycidyl ethers of polyether polyols obtained by adding .

Examples of the catalyst precursor 'B' used in the present invention, which releases a catalyst that causes cationic polymerization of epoxy resin upon irradiation, include onium salts of Lewis acids, and specific examples include aromatic diazonium salts of halides. Rin, that is, the general formula (where MXn, m is tetrafluoroborate, hexac.

rostanate (N), tetrachloropherate (plate),
is a halogen-containing key anion selected from the group consisting of hexafluorophosphate, hexafluoroarsenate (V), hexafluoroantimonate (V) and bismuth (m) chloride, and Y is nitro, halogen, N-morpholino, alkyl, alkoxy, aryl, amino is a substituent selected from the group consisting of arylamino, alkylamino, and arylmercapto groups. m is the number of charges of the halide key anion represented by MXmm, n indicates the number of halogen atoms contained in the Lewis acid produced by decomposition of the above salt. Examples of such compounds include p
-methoxybenzenediazonium hexafluorophosphate, p-nitrobenzenediazonium hexafluorophosphate, o-nitrobenzenediazonium hexafluorophosphate, 2,5-dichlorobenzenediazonium hexafluorophosphate, p-chlorobenzenediazonium hexafluorophosphate, p- N-morpholinophenyl diazonium hexafluorophosphate, 2,5-diethoxy 4-(p-tolyl)
Benzenediazonium hexafluorophosphate, 2
-chloro-4-dimethylamino-5-methoxybenzenediazonium hexafluorophosphate, 2,5-
Diethoxy 4-(p-tolylmercapto)benzenediazonium hexafluorophosphate, 2,5-dimethoxy 4-N-morpholinobenzenediazonium hexafluorophosphate, 2,5-diethoxy-4-ethoxyphenylbenzenediazonium hexafluorophosphate, 2・4,6-Trichlorobenzenediazonium hexafluorophosphate, 2,4,6-tripromobenzenediazonium hexafluorophosphate, 4-nitro-p-toluenediazonium hexafluorophosphate, 2nitro-P-toluenediazonium Hexafluo.

Phosphate, 6-nitro 2,4-xylene diazonium hexafluorophosphate, 4-chloro 2,5
-dimethoxybenzenediazonium hexafluorophosphate, 2,5-dimethoxy-4-morpholinobenzenediazonium hexafluorophosphate "2,5-
Dimethoxy-4'-methyl-4-biphenyldiazonium hexafluorophosphate, 2,4,5-triethoxy-4-biphenyldiazonium hexafluorophosphate, 4-(dimethylamino)-1-1-naphthalenediazonium hexafluorophosphate, p - nitrobenzenediazonium hexafluoroarsenate,
p-N-morpholinophenyldiazonium hexafluoroarsenate, 2,5-dichlorobenzenediazonium hexafluoroarsenate, p-nitrobenzenediazonium hexafluoroantimonate, p-morpholinobenzenediazonium hexafluoroantimonate, 2,4-dichlorobenzene Diazonium hexachloroantimonate, 2,5-dichlorobenzenediazonium hexachloroantimonate, 2,5-dichlorobenzenediazonium hexafluoroantimonate, 2
・4-dichlorobenzenediazonium bismuth chloride, o-nitrobenzenediazonium bismuth chloride, p-N-morpholinobenzenediazonium bismuth chloride, 2,4-dichlorobenzenediazonium tetrachloropherate, p-nitrobenzenediazonium tetrachloroferate, P -N-morpholinobenze, diazonium tetrachloropherate, 2,4-dichlorobenzenediazonium hexachlorostanaate, p-nitrobenzenediazonium hexachlorostanaate, 2,4-dichlorobenzenediazonium tetrafluoroborate, p-nitrobenzenediazonium tetrafluoroborate , 2,5-diethoxy-4-(p-tolylmercapto)benzenediazonium tetrafluoroborate, 2,6-diethoxy-4-(p-tolylmercapto)benzenediazonium tetrafluoroborate, 2,5-dimethoxy-4-(benzoylamino) −
Examples include benzenediazonium tetrafluoroborate and p-anili/phenyldiazonium tetrafluoroporate. The aromatic diazonium salt body of the halide used as the catalyst precursor 'B} in the present invention can be produced by various methods. For example, aryldiazonium hexafluorophosphate is prepared by converting the corresponding aniline into N
OPF6 (This is a mixture of HOI and NaN02 with HPF
6 or a hexafluorophosphate salt), or by adding HPF6 or its salt to other diazonium salts and precipitating the resulting salt. Aromatic diazonium salt armor bodies can also be produced in the same manner.

Furthermore, the aromatic diazonium salts of halides can be produced by other methods, and it goes without saying that the aromatic diazonium salts of halides used in the present invention are not limited in any way by the manufacturing method. . In addition, any onium salt of a Lewis acid that has the ability to initiate cationic polymerization of epoxy resin can be used.
97, No. 51-56885, No. 51-133256, No. 52-30420, and No. 52-3089.

Although the composition of the present invention is not an essential component, it may contain a diluent, such as butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether,
Reactive dilution of epichlorohydrin, styrene oxide, octylene oxide tododecene oxide, butanediol diglycidyl ether, 1,6-hexanediol glycidyl ether, glycerin triglycidyl ether, dibentene dioxide, epoxidized vegetable oil, glycidyl methacrylate, etc. Although non-reactive diluents such as acetone, acetonitrile, butyronitrile, benzonitrile, toluene, xylene, methyl ethyl ketone, cellosolve ether, monochlorobenzene, tetrachloroethane, o-dichlorobenzene, propylene carbonate can be used, reactive diluents can be used. When used, it provides a cured product with preferable physical properties.

The non-reactive diluent exemplified above can also be used as a solvent for uniformly dispersing the catalyst precursor [B' in the composition. Examples of the ultraviolet absorber 'C' used in the present invention include salicylic acid converter (C-1), benzophenone derivative (
C-2), benzotriazole derivative (C-3), acrylic.

Nitrile conductor (C-4), benzoic acid derivative (C-5)
, organometallic key salt (C-6), and the like. Examples of the salicylic acid derivative (C-1) include phenyl salicylate, 4-tert-butylphenyl salicylic acid, p-octylphenyl salicylic acid, and the benzophene plexi conductor (C-2) /・hydroxybenzophenone, 2-hydroxy-4-toxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-
2-carboxybenzophenone, 2-hydroxy-4-methoxy 5-sulfobenzophenone trihydrate, 4-hydroxy-4-n-octoxybenzophenone,
Examples include 2-hydroxy-4-oxybenzylbenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 2,2-dihydroxy-4,4-dimethoxybenzophenone. As the penzotriazole derivative (C-3), 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
21 (2'-hydroxy-3', 5-G-ten-
butylphenyl)-5-chlorobenzotriazole, 2
1 (2'-hydroxy-5-rt-butylphenyl) penzotriazole, 2-(2'-hydroxy-3,5-di-rt-butylphenyl) penzotriazole, 2-(2'-hydroxy-3'-1) rt-butyl-5'-methylphenyl)penzotriazole,
Examples include 2-(2'-hydroxy-3'-61-diisoamyl phenyl)penzotriazole, 2-(2-hydroxy-4'-octoxyphenyl)penzotriazole, and acrylonitrile derivatives (C-4 ) are 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cya/-3,3-diphenyl acrylate, and methyl-Q-cyano-8-methyl-P-(p-methoxyphenyl) acrylate. is exemplified, and examples of the benzoic acid derivative (C-5) include zorcinol-monobenzoate, 2,4'-di-rt-butyl phenyl-3,5-di-rt-butyl-4-hydroxybenzoate and organometallic rust salt (C-6)
Examples include nickel bis-octyl phenyl sulfamide, [2,2'-thiobis(4-ten monooctyl phenolate)]1n-butylamine nickel, ethyl-3'
A nickel salt of 5-di-nert-butyl-4-hydroxybenzyl phosphate is exemplified.

The antioxidant dish used in the present invention includes hindered phenol derivative (D-1), thiodibropionic acid derivative (
D-2) "Phosphite conductor (D-3), etc., and hindered phenol conductor (D-1) is 4.4
-thiobis(6- to rt-31 methylphenol 40
4-butylidenebis(6-tert-butyl-3-methylphenol), 212-thiopis(6-ten-butyl-4-methylphenol), 206-di-butylphenol, 414-methylenebis(6-tert-butylphenol) 4,4'-pis (2,6-di-rt-butylphenol), 404-methylenebis (6
-tert-butyl-o-cresol), 404'-thiobis(6-tert-butyl-o-cresol), 1.
103-tris(5-rt-butyl-4-hydroxy-2-methylphenyl)butane, 2,4,6 tris(3,5-t-butyl-4-hydroxybenzyl)mesitylene, 1,3,5 -Tris (3.5
-G-sasa rt-butyl-4-hyde 0 oxybenzyl)
Isocyanurate, 113-bis (rt to 315-bis)
-butyl-4-hydroxyphenyl)-2,2-bis(2dodecylthioethoxycarbonyl)propane, 116-bis(3,5-dirt-butyl-4-hydroxyphenylacetoxy)hexane, 6-(4-hydroxy-3,5-di-rt-butylanilino)-2,4-bis(n-octylthio), 1,3
・5-triazine, tetrabis[8-(315-Gt
e-Repetyl-4-Hydroxyphenylene).

pionyloxymethyl]methane, n-octadecyl 3
-(4'-hydroxy-3'-large-butyl phenyl) propionate, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphonate, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzyl phosphonate, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzyl phosphonate, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzyl phosphonate, Examples include rt-butylbenzyl phosphonate, etc. Examples of the thiodipropionic acid derivative (D-2) include dilaurylthiodipropionate and distearylthiodipropionate, and examples of the phosphite derivative (D-3). Examples include triphenyl phosphite, trisnonyl phenyl phosphite, diphenyl decyl phosphite, and dicresyl phosphite. The curable composition of the present invention includes, for example, mercury lamp,
By irradiating the composition with ultraviolet rays, visible light, electron beams, etc. emitted from xenon lamps, carbon arc lamps, tungsten filament lamps, etc., catalyst precursors can be added to the composition.
The aromatic diazonium salt of the halide represented by the above general formula, which is included as B', decomposes to form the general formula:
For example, BF3, PF5, F as indicated by MKn.
eC13, AsF5, SbF5, SnC14, BiC1
3, which initiates the polymerization of the epoxy resin and cures the composition.

In this case, the irradiation source used is dependent on the catalyst precursor used {
It must be sufficient to provide sufficient energy to reach a level of B-decomposition, and the wavelength range of the radiation must be selected to provide sufficient energy absorption to stimulate the desired decomposition. The curable composition of the present invention can be used to enhance the photosensitivity of the aromatic diazonium salt of halide contained as the catalyst precursor 'B), such as anthraquinone, 1-chloroanthraquinone, purimulin, acenaphthylene. , naphthalene, anthracene, and stabilizers during transportation and storage, such as 1-vinyl-2-pyrrolidinone polymers, 1-alkyl-2-pyrrolidinone, 1-alkyl-2-pyrrolidinone, Cyclic amides such as 5-one, 1-alkyl-3-pyrrolin-2-one, nitrile compounds such as propionitrile, phthyronitrile, isobutyronitrile, adiponitrile, phenylacetonitrile, benzonitrile, such as N·N-dimethylacetamide, Acyclic amides such as N.N-diethylacetamide, urea derivatives such as 111,3,3-tetramethylurea, 1,1,3,3-tetraoctadecylurea, dimethylsulfoxide, sulfolane, etc. It may also contain a sulfur compound or the like.

The component ratio of the energy beam-curable epoxy resin composition used in the present invention is 0.1 to 2 parts by weight, preferably 0.5 parts by weight, of catalyst precursor [B} to 10 parts by weight of epoxy resin.
~6 parts by weight, the ultraviolet absorber {circle over (2)} is 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight, and the antioxidant [D} is 0.01 to 15 parts by weight, preferably is 0.1~
It is 8 parts by weight.

In the above composition, the epoxy resin ■ is not limited to one type, but may be two or more types (A-1), (A-2>, and (A-3)). Absorbent (q), antioxidant (even if it irritates the skin, there is no problem even if two or more types are used.The energy ray-curable epoxy resin composition obtained by the above combination can be used for example, polyolefin, ABS, polyacetal,
On various plastic molded products such as polyurethane, polyamide, polyvinyl alcohol, polyvinyl chloride, unsaturated polyester, polyvinylidene chloride, epoxy resin, polystyrene, cellulose, printed materials such as natural paper and synthetic paper, and printed materials such as cans. If the coating is applied by other known coating methods such as brush coating, spray coating, dipping coating, roll coater coating, curtain flow coating, etc., it will have the various advantages and characteristics as described above, and the curing time will be reduced. It is possible to obtain a coating film that is extremely short and has the advantages of a solvent-free coating process, and the coating film cured by UV rays has excellent adhesion to various materials, portability, flexibility, abrasion resistance, It not only improves physical properties such as solvent resistance, but also significantly improves film resistance against ultraviolet rays and oxidation, and has extremely great practical value.

The present invention will be specifically illustrated by examples below, but the scope of the present invention is not limited thereby.

Example 1 10 parts by weight of alicyclic epoxy resin CX-201 (epoxy equivalent: 152-156 manufactured by UCC), 2 parts by weight of ultraviolet absorber
1 part by weight of rt-butyl-4-methylphenol was added and dissolved in 2 parts by weight of 1-(2-hydroxy-5-methylphenyl)penzotriazole and the antioxidant 2.6-di, 1 part by weight of curing catalyst was added and mixed, and Mayer (N Hey yeah
r) A film thickness of 5 microns is applied onto a polyvinyl chloride film using a drawbar such as a qd, and a high-pressure mercury lamp (Iwasaki Electric UOII-222 type 80W' 1 willow) is applied at a distance of 8 to 15 skins per minute. The ultraviolet rays were irradiated through the lens at a speed of .

Claims (1)

[Claims] 1 Epoxy resin (A) 100 as an essential component
0.1 to 2 parts by weight of a catalyst precursor (B) that releases a catalyst that causes cationic polymerization of an epoxy resin upon irradiation;
An energy beam-curable epoxy resin composition containing 0.01 to 20 parts by weight of an ultraviolet absorber (C) and 0.01 to 15 parts by weight of an antioxidant (D).