JPH082922B2 - Coloring and curable composition by energy rays - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a novel composition exhibiting color developability and curability by an energy ray which is polymerized and / or cross-linked by an energy ray such as ultraviolet ray, and at the same time is colored by an energy ray. Is.

<Prior art> Resin curing technology using energy rays such as ultraviolet rays is
(1) Curing speed is extremely fast and energy consumption is low,
(2) The area occupied by the device is small, (3) it is easy to start and stop, and (4) it can be used without using a solvent, so it saves energy and resources because of less pollution of living organisms and the environment due to solvent volatilization. Applications are being developed in various fields against the backdrop of social demands such as environmental protection, and for example, paints, printing inks, printing plate materials, etching resists for printed circuit boards, solder resists, marking inks, adhesives. , It is being put to practical use in the fields of anticorrosion repair tapes and technology for immobilizing microorganisms.

Most of these applications are based on unsaturated polyester or acrylic-based carbon-carbon bond radical polymerization. The radical polymerization has a drawback that the reaction is inhibited by the presence of oxygen in the air, and a resin curing technique based on cationic polymerization, which does not have this problem, has been actively studied in recent years, and some have been put into practical use.

However, conventional energy ray curable resins do not change the color tone or develop chromatic color due to the curing reaction, so 1) the degree of curing cannot be visually judged,
It is based on indirect evaluation such as powder adhesion, pencil hardness, and number of scratches due to solvent friction. 2) It is difficult to apply to fields requiring decoration and fashionability because of its limited use. It had a problem such as.

<Problems to be Solved by the Invention> The present invention is to improve the above-mentioned drawbacks of conventional energy ray-curable resins, and develops a color by energy rays so that the degree of curability can be easily determined. It is intended to provide a novel energy ray coloring and curable composition having a function.

<Means for Solving Problems> The present inventor has proposed an energy ray-polymerizable resin composition containing a cation-polymerizable organic compound and an activator that generates an active species that cures the cation-polymerizable organic compound by irradiation with energy rays. As a result of the investigation of the product, a composition containing three components, in which an aromatic halonium salt, an aromatic onium salt of a Group VIa element, or the like is used as an activator, and an electron-donating color organic compound is further added as a new constituent component It has been found that the present invention can be achieved by a product.

That is, the present invention comprises a cationically polymerizable organic compound, an activator that produces an active species that cures the cationically polymerizable organic compound by irradiation with energy rays, and an electron-donating color-developing organic compound that develops color by the action of the activator. Is a curable composition that is colored by energy rays and characterized by:

First, the materials constituting the curable composition for color development by energy rays of the present invention will be described.

Examples of the cationically polymerizable organic compound used in the present invention include organic compounds such as epoxy compounds, vinyl ethers, heterocyclic vinyl compounds, styrenes, cyclic ethers, lactones, vinyl arenes, alicyclic vinyl compounds, and cienes. Is mentioned. These compounds may be used as oligomers or polymers as long as they have a reactive group that causes a reaction such as polymerization or crosslinking depending on the active species.

As the epoxy compound, conventionally known aromatic epoxy resins, alicyclic epoxy resins, epoxy polymers such as aliphatic epoxy resins and epoxy prepolymers, 3,4-
Epoxycyclohexyl-3 ', 4'-epoxycyclohexanecarboxylate, 7-oxabicyclo [4,1,
0] -3-heptyl-7-oxabicyclo [4,1,0] heptanecarboxylate and an ester of an epoxidized cycloalkanecarboxylic acid with an epoxidized cyclic alcohol,
Bis [(3,4-epoxy-6-methylcyclohexyl)]
Substituted epoxycycloalkylmethanol such as methyl-7-oxabicyclo [4,1,0] -3-heptyl) methyl] adipate and an ester of a dibasic acid, 1,4-bis-
There are bis (epoxyalkyl) ethers of glycols such as (2,3-epoxypropoxy) butane, glycidyl octyl ether, glycidyl alkyl ether such as glycidyl decyl ether, and the like.

Examples of vinyl ethers include monovinyl ethers such as methyl vinyl ether, isopropyl vinyl ether, 2-ethylhexyl vinyl ether and vinyl-2-methoxyethyl ether, ethylene glycol divinyl ether, propanediol divinyl ether, 1-methylpropanediol divinyl ether, diethylene glycol divinyl ether. , Triethylene glycol divinyl ether, butanediol divinyl ether, 1,
4-cyclohexanediol divinyl ether, 1,2,3-
There are polyfunctional vinyl ethers such as propane trivinyl ether and trimethylolpropane trivinyl ether.

As the heterocyclic vinyl compound, 2-vinylpyridine, 4
-Vinylpyridine, N-vinyl-2-pyrrolidone, N-
Examples include vinylcarbazole and N-vinyl-3,6-dibromocarbazole.

Styrenes include styrene, 4-methylstyrene,
There is α-methylstyrene. Examples of the cyclic ether include oxetane, 3,3-bis (chloromethyl) oxetane, tetrahydrofuran and tetrahydropyran.

Examples of lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, and δ-valerolactone. Vinyl allenes include 4-vinyl biphenyl and the like. Examples of the alicyclic vinyl compound include vinylcyclohexene. Examples of dienes include isobutylene, butadiene, isoprene and the like.

Examples of the activator used in the present invention include aromatic halonium salts and aromatic onium salts of Group VIa elements, and two or more of these compounds, which may be the same or different, may be used in combination.

The aromatic halonium salt is represented by the following general formula (I).

[R ¹ R ² X] ⁺ Y ⁻ (I) In the formula, R ¹ and R ² represent an unsubstituted or substituted monovalent aryl group, and R ¹ and R ² may be the same. R ¹ and R ² may combine with each other to form a ring with X. X represents a halogen atom such as I, Br or Cl. The Y ^- is ClO ₄ ^-, BF ₄ ^{-,
_{PF 6 -, AsF 6 -,}} SbF 6 -, SnCl 6 -, SbCl 6 - represents the like anions.

Specific examples of the aromatic halonium salt represented by the formula (I) are shown below.

Specific examples of aromatic onium salts of Group VIa elements are shown below.

Examples of the electron-donating color-forming organic compound used in the present invention include arylamines, heterocyclic amines, N-vinyl compounds, triphenylmethanephthalides, fluoranes,
Phenothiazines, indolyl phthalides, leuco auramines, rhodamine lactams, rhodamine lactones, indolines, triarylmethanes, azaphthalides, pyrazolines, and the like. Can be used in combination of one or more. Next, specific examples are crystal violet lactone,
Malachite green lactone, Michler's hydrol,
3-diethylamino-7-chlorofluorane, 3-dimethylamino-6-methoxyfluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylaminobenzo-a-fluorane, 3-diethylamino-6-
Aminofluorane, 3,6-dimethoxyfluorane, 3-
Diethylamino-7-dibenzylaminofluoran, 3
-Diethylamino-6-methyl-7-chlorofluorane, 3-N-methyl-Nn-propylamino-6-methyl-7-anilinofluorane, 3-N-ethyl-N-
Isopentylamino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2- (fluorophenylamino) -6-di-n
-Butylaminofluorane, 3- (N-2-tetrahydrofurfuryl) -N-ethylamino-6-methyl-7
-Anilinofluorane, N- (2,3-dichlorophenyl) -leuco auramine, N-benzoyl auramine,
N-phenyl auramine, rhodamine B lactone, 2-
(Phenyliminoethanedilidene) -3,3'-dimethylindoline, p-nitrobenzylleucomethylene blue, benzoylleucomethylene blue, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, 3,7
-Bisdimethylamino-10- (4'-aminobenzoyl) phenothiazine, 3,7-bisdimethylamino-10-
(4'-Pyrrolidinobenzoyl) phenothiazine, 3,7
-Bisdimethylamino-10- [4'-bis (4 ", 4"-
Dimethylaminophenyl) methylaminobenzoyl] phenothiazine, bis (4-diethylamino-2-methylphenyl) phenylmethane, tris (4-diethylamino-2-methylphenyl) methane, bis (4-diethylamino-2-fluorophenyl) phenylmethane , Bis (4-diethylamino-2-methoxyphenyl) phenylmethane, bis (4-diethylamino-2-methylphenyl) (4-diethylaminophenyl) methane, bis (4-diethylamino-2-methylphenyl) (4-carboxy Phenyl) methane, bis (4-dibenzylamino-2-methylphenyl) phenylmethane, bis (4-
Dibenzylamino-2-methylphenyl) (4-dibenzylaminophenyl) methane, bis [4-di [p-tolyl) amino-2-methylphenyl] phenylmethane, N
-Butyl-3 [bis {4- (N-methylanilino) phenyl} methyl] carbazole, 1,3,5-triphenyl-2
-Pyrarizone, 1-phenyl-3,5 di-p-tolyl-2
-Pyrazoline, 1-phenyl-3,5-bis (p-methoxyphenyl) -2-pyrazoline, 1-phenyl-3-styryl-5-phenyl-2-pyrazoline, 1-phenyl-3- (p-methoxystyryl) ) -5- (p-Methoxyphenyl) -2-pyrazoline, 1-phenyl-3- (p
-Dimethylaminostyryl) -5 (p-dimethylaminophenyl-2-pyrazoline, 1-phenyl-3- (p-
Diethylaminostyryl) -5- (p-diethylaminophenyl) -2-pyrazoline, and the like.

The energy ray-curable and curable composition of the present invention has an activator of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, and an electron-donating color-developing organic compound to 100 parts by weight of a cationically polymerizable organic compound. 0.1 to 50 parts by weight of compound, preferably
It is obtained by mixing at a ratio of 0.5 to 30 parts by weight. Here, for example, a commercially available blender is used for mixing,
Any method can be applied. Here, the optimum blending amount of the activator and the electron-donating color-developing organic compound is the nature of the cationically polymerizable organic compound used, the amount of energy ray irradiation, the desired color density, the desired curing conditions, etc. (time, temperature ) Etc. Also, such compositions are typically 100,00 at 25 ° C.
Although it is a liquid having a viscosity of 0 centipoise or less, the compatibility and composition of a cationically polymerizable organic compound with an activator and an electron-donating color-forming organic compound in order to carry out a reaction with an active species more quickly. To increase the uniformity of
Nitromethane, acetonitrile, benzene, toluene,
It may be dissolved in an organic solvent such as ethyl acetate to form a uniform mixture. When the cationically polymerizable organic compound is a solid, a solvent is used in the same manner as described above, or the three components are mixed together by a method such as dry kneading or melt mixing with the activator and the electron donative color developing organic compound. It is preferable to improve the uniformity of.

The composition of the present invention obtained as described above can be cured by irradiating with energy rays after being applied to various objects to be coated or molded into an arbitrary form such as a film. In this case, it is usually 0.5 although it depends on the intensity of energy rays, the type and shape of the composition, etc.
Even a slightly thick paint, etc., can be cured in tens of minutes for about 10 seconds to 10 seconds. The appropriate energy ray that can be used in the composition of the present invention may be any one as long as it has energy that induces decomposition of the activator, but is preferably a high / low pressure mercury lamp, a metal halide lamp, a xenon lamp, 200n obtained from germicidal lamps, laser light, etc.
Electromagnetic energy or electron beam having a wavelength of m to 700 nm,
Examples include high energy rays such as X-rays and radiation.

The composition of the present invention may further include pigments, fillers, antistatic agents, flame retardants, anti-gelling agents, flow control agents, surfactants, and ultraviolet absorbing agents that are inactive depending on the application within a range that does not impair color development and curing. Agents and the like may be mixed.

The energy ray coloring and curable composition of the present invention can be applied to materials such as metal, rubber, plastic, film, paper, wood, glass, cloth, ceramics, concrete and molded members. Specific applications include protective, decorative and insulating paints and coatings, printing inks, plate-making materials, adhesives, photoresists, sealants, embedding comparands, stationery, writing instruments, ornaments, toys, It can be used for a wide range of other purposes.

<Function> The activator in the energy ray-curable and curable composition of the present invention produces active species such as free radicals, Lewis acids and Bronsted acids upon irradiation with energy rays. By the action of this active species, the cationically polymerizable organic compound undergoes a polymerization reaction to produce a cured product. In parallel with this polymerization reaction, the active species generated by irradiation with energy rays undergo a color reaction with an electron-donating color-developing organic compound to generate a colored product. Therefore, in the energy ray-curable and curable composition of the present invention, the color reaction and the curing reaction are simultaneously performed by the irradiation of the energy ray, and the cured state can be easily evaluated from the colored state. Further, the coloring species can be any color such as red, peach, orange, yellow, green, violet, brown, and black by selecting an electron-donating color-forming organic compound.

<Examples> Next, the present invention will be described with reference to Examples, but these do not limit the scope of the present invention. The parts in the examples are parts by weight.

Example 1 The above mixture was stirred and dissolved to prepare a uniform mixture, which was coated on an aluminum plate to obtain a coating film having a wet thickness of 15 μm. Ultraviolet irradiation was carried out using an ultraviolet curing device (manufactured by Eye Graphic Co., Ltd.) equipped with a 1.5 KW high-pressure mercury lamp, and the curing and coloring state was evaluated. The cured state was evaluated by the presence or absence of surface tack by the finger touch method. as a result,
The coating film was cured by irradiation energy of 6,000 J / m ² , and the coating film developed a clear black color.

Examples 2 to 7 Samples were prepared according to the procedure of Example 1 except that the activators shown in Table 1 were used, and the energy required for curing and the color developability were evaluated. The results are shown in Table 1.

Example 8 A sample was prepared according to the procedure of Example 1 except that the compounds shown in Table 2 were used as the electron-donating color-developing organic compound in Example 1, and the energy required for curing and the color development were evaluated. went. Table 2 shows the results.

Example 13 The above mixture was stirred and dissolved to prepare a uniform mixture, which was coated on an aluminum plate to obtain a coating film having a wet thickness of 18 μm. The sample was evaluated for cure and color development according to the same procedure as in Example 1. As a result, curing was performed by irradiation energy of 3,500 J / m ² , and the cured coating film developed a clear black color.

Example 14 A sample was prepared according to the procedure of Example 1 using the uniform coating solution obtained by mixing and dissolving in the above formulation, and the curability and the color developability were evaluated. As a result, the coating film was cured by irradiation energy of 2,000 J / m ² , and the coating film developed a clear black color.

Example 15 All components were stirred and dissolved in the above formulation to obtain a uniform coating liquid.
This ink was filled in the pen body of the fiber pen. Writing on a plastic film with this pen resulted in an invisible latent image. Next, when this latent image portion was irradiated with sunlight for 30 seconds, the latent image portion was cured and developed a red color. The coating liquid was suitable as an ink for fiber pens without any problems in terms of characteristics.

Example 16 All the components in the above blended amounts were mixed and dissolved to obtain a uniform solution. Offset printing was performed using this ink, and then line speed of 10 under 4 high pressure mercury lamps that required output of 11.2KW.
Passed at m / min. As a result, the printed portion was cured and developed a blue color. The solution was suitable as an offset printing ink without any problem in terms of characteristics.

Example 17 All the above components were mixed and dissolved to obtain a uniform solution. This solution was coated on a PET film with a roll to a thickness of 7 μm and then irradiated with sunlight. The coating was initially colorless and tacky, but upon irradiation for 120 minutes developed a blue color and cured. It was found that the coating film thus obtained had good adhesion to a plastic film and was useful as a colorable and curable coating material by energy rays.

Example 18 A uniform coating solution obtained by stirring and dissolving all the above components was applied onto an aluminum plate to obtain a coating film having a wet thickness of 20 μm.

Next, using the ultraviolet curing device of Example 1, the amount of ultraviolet irradiation was changed, and the color-developed state and cured state of the coating film were evaluated. The results are shown in Table 3. From this result, it was possible to evaluate the cured state based on the color development state of the coating film.

<Effects of the Invention> The color-forming and curable composition with energy rays of the present invention is one which develops color simultaneously with curing, crosslinking or polymerization by irradiation with energy rays such as ultraviolet rays, and is excellent in curability and color-forming property, Moreover, it is rich in color development and can be used as a useful material in a wide range of fields.

That is, the energy ray coloring and curable composition of the present invention is a protective, decorative and insulating coating and coating film,
It can be applied to a wide range of applications such as printing inks, plate-making materials, adhesives, photoresists, sealants, embedding compounds, stationery, writing instruments, decorations and toys.

Further, the curability of the color-curable and curable composition according to the present invention can be evaluated based on the color-developed state.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C08G 59/68 NLE C08K 5/00 KAJ C09D 5/00 PNV C09K 3/00 Y

Claims (1)

[Claims] 1. A cation-polymerizable organic compound, an activator which produces an active species which cures the cation-polymerizable organic compound upon irradiation with energy rays, and an electron-donating color-developing organic compound which develops a color by the action of the activator. An energy ray-curable and curable composition characterized by: