JP2000095960A - Polymerizable dye monomer and polymer obtained from the monomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colorant which is excellent in resistances to water, light, solvents, and migration and in safety incorporating a polymerizable colorant monomer having a specified structure into the same. SOLUTION: This colorant contains a polymerizable colorant monomer represented by formula II (e.g. a compd, represented by formula I). 100 pts.wt. this colorant monomer alone or together with 5-100,000 pts.wt. monomer selected from among styrenic compds. and α,β-unsatd. mono- to polycarboxylic acids and their esters, amides, and anhydrides is polymerized to give a (co)polymer. The colorant monomer or (co)polymer is incorporated in an amt. of 1-50 wt.% into an ink for ink jet printers or in an amt. of 1-70 wt.% into a color toner. In formula II, R is H, 1-8C alkyl, hydroxyalkyl, or a group selected from among polymerizable groups represented by formula III (X is 2-4C alkylene); and A is an anion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerizable dye monomer designed to have a desired hue and a polymer obtained from the monomer. More specifically, the present invention relates to a method for absorbing ultraviolet and / or visible wavelengths. The present invention relates to a colorant used for a plastic molded product, a color printer ink, a color copier toner and the like, comprising a polymerizable dye monomer and a polymer obtained from the monomer.

[0002]

2. Description of the Related Art A problem that occurs in a product using a dye as a coloring agent is that light resistance, water resistance, heat resistance, migration resistance, etc. are low and lack reliability and safety. is there. The present invention can provide a coloring agent that can solve the problems of dyes in various applications. The issues for each of the above uses are described below.

(Plastic molded products) Plastics are used in all industrial products, and each is colored according to purposes. Above all, for coloring highly transparent plastics such as polymethyl methacrylate, polystyrene and polycarbonate, dyes which are usually soluble in the plastics are selected so as not to impair the transparency. However, in the plastic colored with the dye, the heat resistance of the dye, in addition to the problem of light resistance, the solvent resistance, the hygiene of the dye extracted and transferred from the low migration resistance, becomes a problem,
Applications were limited.

(Colorants for Inkjet Printers) Among various color printers, color inkjet printers are rapidly becoming popular because they can perform high-quality recording at relatively low cost. Inks for color inkjet printers are mainly composed of water-soluble materials, and water-soluble dyes are often used as pigments.

[0005] Therefore, printed matter printed with ink using a dye has a disadvantage that characters and the like become unclear due to water droplets or the like during storage, and a disadvantage that the color gradually fades due to light. To compensate for these shortcomings, for example,
JP-A-2-29678, JP-A-2-25587
No. 6, JP-A-6-128515 and the like propose a method of suppressing the dye from being washed away by water and improving water resistance by ionic bonding between the dye and an amine or a cationic compound. However, since the mechanism for improving the water resistance is due to salt formation, the storage stability of the ink and the reliability of printing were insufficient, such as precipitation and clogging. JP-A-54-68303 and JP-A-8-60059 propose to increase the light fastness by adding an ultraviolet absorbing material to the ink. Therefore, it was difficult to sufficiently improve the light resistance with the ultraviolet absorber added in a small amount.

(Coloring Agent for Color Toner) In a full-color copying machine, pigments and dyes for toners can be used. A toner using a pigment has high light resistance but low transparency, and the particle size must be extremely small in order to ensure color reproducibility in full-color copying. In order to produce a small diameter toner, a method of sufficiently pulverizing a mixture of a resin for a toner, a dye, and other additives, and a polymerization method, that is, a method in which a resin monomer, a dye, and other additives are added to water. A method of producing a finely divided toner by performing polymerization after mixing, dispersing, and the like has been performed. However, a satisfactory small-diameter color toner has not yet been obtained in terms of productivity, cost, restrictions on usable resins, and the like. On the other hand, a toner using a dye has excellent color reproducibility and excellent image transparency, and is suitable for applications using transmitted light, such as OHP sheets. However, lightfastness is inferior to toners using pigments, and it is difficult to obtain satisfactory characteristics in terms of migration resistance, solvent resistance, safety, and the like.

Accordingly, an object of the present invention is to provide a dye excellent in water resistance, light resistance, solvent resistance, migration resistance, safety and the like.

[0008]

As a result of repeated studies, the present inventors have found that a specific dye monomer or a polymer obtained from the specific dye monomer which is easily synthesized by a conventionally known synthesis method is obtained. It has been found that the above object can be achieved.

The present invention has been made based on the above findings, and provides a polymerizable dye monomer represented by the following general formula (I).

[0010]

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[0011]

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The present invention also provides a polymer obtained from the polymerizable dye monomer.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polymerizable dye monomer of the present invention and a polymer obtained from the monomer will be described in detail.

In the compound represented by the above general formula (I), which is the polymerizable dye monomer of the present invention, the alkyl group having 1 to 8 carbon atoms represented by R includes, for example, methyl, ethyl, Propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl,
Hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, and the like. Examples of the hydroxyalkyl group having 1 to 8 carbon atoms include, for example, a group having a structure in which a hydrogen atom of the above alkyl group is substituted with a hydroxyl group. No. Examples of the alkylene group having 2 to 4 carbon atoms represented by X include ethylene, trimethylene,
Tetramethylene and the like.

In the compound represented by the above general formula (I), which is the polymerizable dye monomer of the present invention, the anion represented by A includes, for example, chlorine anion, bromine anion, iodine anion, Inorganic anions such as halogen anion such as fluorine anion, perchlorate anion, thiocyanate anion, phosphorus hexafluoride anion, antimony hexafluoride anion and boron tetrafluoride anion, benzenesulfonic acid anion, toluenesulfonic acid anion, trifluoromethane Organic sulfonic acid anions such as methanesulfonic acid anion; octyl phosphate anion; organic phosphate anions such as dodecyl phosphate anion; octadecyl phosphate anion; phenyl phosphate anion; and nonylphenyl phosphate anion.

As typical examples of the dye monomer represented by the above general formula (I), the following compound No. 1-4. However, the present invention is not limited at all by the following exemplified compounds. In the following examples, the dye monomer cations without anions are shown.

[0017]

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[0018]

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[0019]

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[0020]

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The polymer of the present invention is obtained from the above-mentioned polymerizable dye monomer. The polymer of the present invention,
In addition to polymerizing the monomer alone, a copolymer of the monomer and a conventionally known monomer can be used. Further, in order to adjust the hue, a copolymer obtained by combining two or more kinds of the polymerizable dye monomers of the present invention can be used. The production of the polymer of the present invention can be easily carried out in water, in an organic solvent or without a solvent using a conventionally known polymerization catalyst.

Well-known monomers used for synthesizing the above-mentioned copolymer which is the polymer of the present invention include styrene compounds and α, β-unsaturated mono- to polycarboxylic acids and their esters, amides and imides. , Or anhydride,
For example, the former includes styrene, α-methylstyrene, hydroxystyrene and the like, and the latter includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, 1-butyne-2,3. ,
Examples of the ester include methyl, ethyl, 2-hydroxyethyl, propyl, butyl, octyl, dodecyl, 2,2,6,6-tetracarboxylic acid of the α, β-unsaturated carboxylic acid. Methyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, 2- [3- (2-benzotriazolyl) -4
And the above-mentioned amides include methylamide, dimethylamide, ethylamide, diethylamide, propylamide, dipropylamide, butylamide, dibutylamide, hexylamide of the above α, β-unsaturated carboxylic acid. Octylamide, phenylamide and the like. Examples of the imide include maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide and N-phenylmaleimide.

When a copolymer is prepared using the dye monomer of the present invention and a well-known monomer, the amount of the well-known monomer is appropriately selected according to the intended use. It is in the range of 5 to 100,000 parts by weight based on 100 parts by weight of the dye monomer of the present invention.

The polymerizable dye monomer of the present invention and the polymer of the present invention obtained from the monomer absorb ultraviolet and / or visible wavelengths and are designed to have a desired hue. It is used for applications such as plastic molded articles, ink for color printers (inkjet printers), and toner for color copiers (color toners). In particular, the dye monomer and polymer of the present invention are preferably used for a dye for ink or a color toner of an ink jet printer.

When the dye monomer or polymer of the present invention is used as a dye or the like for ink or color toner of an ink jet printer, the amount of the dye monomer or polymer varies depending on the application. Usually 1 to 1 in ink
50% by weight, and 1 to 70% by weight in the toner.

[0026]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited at all by the following examples.

Example 1 (Preparation of Cl ^- salt of compound No. 1) 11.46 g of 1-aminonaphthalene was added to N-methyl-2-
The resultant was dissolved in 120 g of pyrrolidone, and 3.74 g of sodium amide was added with stirring at room temperature. Further, 1.20 g of sodium iodide was used as a catalyst, and 2,5-
After adding 0.89 g of di-t-butylhydroquinone, p
13.43 g of -chloromethylstyrene was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 2 hours. Chloroform 2
The mixture was dissolved by adding 00 ml, and washed three times with a separating funnel. The chloroform layer was separated, and the residue obtained by distilling off chloroform was separated and purified by a silica gel column to obtain 11.62 g of p-vinylbenzylnaphthylamine as an intermediate.
(56% yield).

11.62 g of the obtained intermediate, 4,4′-
18.69 g of bis (diethylamino) benzophenone,
As a polymerization inhibitor, 0.53 g of 2,5-di-t-butylhydroquinone and 150 g of toluene were added as solvents,
The mixture was heated to 45 ° C. under a stream of nitrogen to obtain 8.8% phosphorus oxychloride.
3 g was added dropwise over 10 minutes. After completion of the dropwise addition, the temperature was raised to 100 ° C over 1 hour, and the mixture was stirred at 100 ° C for 1 hour. After cooling, toluene was distilled off, and 200 ml of chloroform was added to dissolve the residue. The mixture was washed three times with a separating funnel. The chloroform layer was separated, and the residue obtained by distilling off chloroform was separated and purified by a silica gel column. 1 C
20.11 g (yield 69.6%) of l ^- salt (blue crystal) was obtained. The λmax of the obtained crystal was 601 nm (the solvent was methanol, the same applies hereinafter), and ε (molar extinction coefficient at λmax, the same applies hereinafter) was 6.8 × 10 ⁴ . Also, IR
Was measured, and the following results were obtained as main absorption peaks. 34
00 cm ^-1 , 3200 cm ^-1 , 2950 cm ^-1 , 157
^{0cm -1, 1440cm -1, 1400cm -1} , 1370
^{cm -1, 1340cm -1, 1270cm -1} , 1210c
m ⁻¹ , 1180 cm ⁻¹ , 1150 cm ⁻¹ , 1070 cm
^-1 , 1000 cm ^-1 , 910 cm ^-1 , 820 cm ^-1 , 7
60cm ^-1, 710cm ^-1.

[0029] Example 2 (ClO ₄ compound No.1 ^- production of salt) synthesized Compound No. 5.00 g of a Cl ^- salt of 1, 5.83 g of sodium perchlorate (monohydrate) and 0.09 of 2,5-di-t-butylhydroquinone as a polymerization inhibitor
g was dissolved in 30 g of methanol and reacted at 60 ° C. for 1 hour. After cooling, the mixture was diluted with 200 g of distilled water, and the precipitated crystals were filtered and dried. 1 of ClO ₄ ^- was obtained salt (blue crystals) 4.51 g (81.5% yield). The obtained crystal had λmax of 602 nm and ε of 7.0 × 10 ⁴ . The IR was measured, and the following results were obtained as main absorption peaks. 3320 cm ^-1 , 3070 cm ^-1 , 2950
^{cm -1, 1570cm -1, 1450cm -1} , 1410c
m ^-1 , 1370 cm ^-1 , 1340 cm ^-1 , 1270 cm
^-1 , 1220 cm ^-1 , 1190 cm ^-1 , 1150c
^{m -1, 1070cm -1, 1010cm -1} , 960c
^{m -1, 920cm -1, 880cm -1} , 860cm -1, 8
^{20cm -1, 800cm -1, 760cm -1} , 710cm
^-1 , 620 cm ^-1 .

Example 3 (Preparation of Cl ^- salt of compound No. 2) N-ethyl-N-methacryloylethylaniline 55.9
g, 4-dimethylamino-1-naphthaldehyde19.
9 g and 0.1 g of 4-methoxyphenol as a polymerization inhibitor were dissolved in 500 g of toluene and heated to 45 ° C. After 18.4 g of phosphorus oxychloride was added dropwise thereto over 30 minutes, the temperature was raised to 100 ° C., and the mixture was reacted for 2 hours.
After cooling, washing with water and column purification were carried out in the same manner as in Example 1; 2 Cl ^- salt (blue crystals) 28.8 g
(42.2% yield). The λmax of the obtained crystal is 6
02 nm and ε were 6.2 × 10 ⁴ . The IR was measured, and the following results were obtained as main absorption peaks. 340
^{0cm -1, 2950cm -1, 1710cm -1} , 1580
^{cm -1, 1450cm -1, 1410cm -1} , 1380c
m ^-1 , 1340 cm ^-1 , 1270 cm ^-1 , 1220 cm
^{-1, 1180cm -1, 1160cm -1,} 1070c
^{m -1, 1010cm -1, 920cm -1} , 830cm -1,
760cm ^-1, 710cm ^-1.

[0031] Example 4 (PF ₆ compound No.2 ^- production of salt) synthesized Compound No. 2 -Cl ^- salt of 10.00 g, potassium hexafluorophosphate 13.49 g and 2,5-di-t-butylhydroquinone 0.1 as a polymerization inhibitor
6 g was dissolved in 60 g of methanol and reacted at 60 ° C. for 1 hour. After cooling, the mixture was diluted with 400 g of distilled water, and the precipitated crystals were filtered and dried. 2 PF ₆ ^- salt (blue crystals) 9.64 g (83.1% yield). The obtained crystal had λmax of 603 nm and ε of 6.5 × 10 ⁴ . The IR was measured, and the following results were obtained as main absorption peaks. 3400 cm ^-1 , 2950 cm ^-1 , 171
0 cm ^-1 , 1590 cm ^-1 , 1450 cm ^-1 , 1410
^{cm -1, 1380cm -1, 1340cm -1} , 1270c
^{m -1, 1220cm -1, 1180cm -1} , 1160cm
^{-1, 1070cm -1, 1010cm -1,} 920cm -1,
^{840cm -1, 760cm -1, 710cm -1} , 600c
m ⁻¹ , 550 cm ⁻¹ .

Examples 5 to 10 (Compound Nos. 3 and 4
Production of Cl ⁻ , ClO ₄ ⁻ , and PF ₆ ⁻ Salts of Compound No. Production was carried out in the same manner as in Example 1 or 2, except that the raw materials corresponding to the structural formulas of 3 and 4 were used.
All of the obtained compounds were blue crystals. Table 1 below shows λmax and ε of each compound.

[0033]

[Table 1]

Example 11 (Dye copolymer for color printer) 1 of ClO ₄ ^- salt 30 parts by weight, 13 parts by weight of 2-acrylamido-2-methylpropanesulfonic acid,
46 parts by weight of 2-hydroxyethyl methacrylate, 11 parts by weight of methacrylic acid, and 28% by weight of aqueous ammonia 4
Azobisisobutyronitrile as a polymerization catalyst and 5 parts by weight of methylcellosolve as a solvent.
The reaction was performed at 5 ° C. for 5 hours. The solvent was distilled off to obtain a copolymer (blue solid). The obtained copolymer had a number average molecular weight of 13
300 and a weight average molecular weight of 18,200. Water was added to the copolymer to obtain an aqueous solution A having a solid content of 25% by weight. As Comparative Example 1, Compound No. 1 of ClO ₄ ^- except excluding salt the reaction was carried out in the same conditions,
A colorless copolymer was obtained. Water was added to 70 parts by weight of the colorless copolymer and 30 parts by weight of Direct Blue 199 as a dye to prepare an aqueous solution B having a solid content of 25% by weight.

(Light Resistance Test) 30 parts by weight of glycerin were added to 70 parts by weight of each of the aqueous solutions A and B to prepare inks for ink jet printing. Each ink was printed on plain paper with an ink jet printer to obtain test pieces. After drying, the OD value of the test piece was measured. Next, using a xenon weather resistance tester (Table Sun, manufactured by Suga Test Machine Co., Ltd.),
After standing at 40 ° C. and 15 A / m ² for 24 hours, the OD value was measured again, and the light resistance was compared based on the residual OD ratio.
The results are shown in Table 2 below.

(Water Resistance Test) 30 parts by weight of glycerin were added to 70 parts by weight of each of the aqueous solutions A and B to prepare inks for ink-jet printing. Each ink was printed on plain paper by an ink-jet printer to obtain test pieces. After drying, the OD value of the test piece was measured. Next, the test piece was immersed in water adjusted to 25 ° C. in a thermostatic layer for 5 minutes, and then the OD value was measured.
Water resistance was compared from the remaining OD ratio. The results are shown in Table 2 below.

[0037]

[Table 2]

Example 12 (Dye Copolymer for Color Toner) 22 parts by weight of Cl ^- salt of 1, 1 part by weight of n-butyl methacrylate, 21 parts by weight of benzyl methacrylate and a reactive surfactant Adecaria soap NE-2
0 (manufactured by Asahi Denka Kogyo KK), and 1.5 parts by weight of potassium persulfate as a polymerization initiator.
Emulsion polymerization was carried out at 3 ° C. for 3 hours. The reaction solution was filtered through a 320-mesh sieve to remove coarse particles, thereby obtaining a blue copolymer dispersion C. As Comparative Example 2, the above compound No. 1 Cl
^The reaction was carried out in the same manner as in Example 12 except that Basic Blue 7 was used instead of the salt, to obtain a dispersion D of a blue copolymer.

Dispersions C and D of the blue copolymer were respectively sprayed on a glass substrate, and heated and melted in an oven at 120 ° C. to form a film having a thickness of 0.5 mm. White paper was placed on these films, and after being left in an oven at 60 ° C. for 24 hours while applying a load of 10 g / cm ² , the state of each white paper was observed. Table 3 below shows the results.
Shown in

[0040]

[Table 3]

Example 13 (Colored resin molded product) 2 PF ₆ ^- salt 30 parts by weight of benzoyl peroxide 3 parts by weight were dissolved in 70 parts by weight of methyl methacrylate, bulk polymerization at 60 ° C. was poured to a thickness of 1cm the solution in an aluminum foil cup with a diameter of 5cm Then, a blue resin molded product E was obtained. As Comparative Example 3, the above compound No.
2 PF ₆ ^- but using Solvent Blue 94 instead of the salt is carried out in the same manner as in polymerization to obtain a blue resin molded product F.

Each of the blue resin molded products E and F was immersed in methanol / water = 5/5 (weight ratio), and
After standing for a time, the color of each solution was observed. The results are shown in Table 4 below.

[0043]

[Table 4]

As is apparent from the above examples, when a dye consisting of a polymer obtained from the dye monomer (compound represented by the above formula (I)) of the present invention was used, a conventional dye was used. Compared with the case where [Example 11], it can be seen that the light resistance and water resistance are excellent from [Example 11], the migration resistance is excellent from [Example 12], and the solvent resistance is excellent from [Example 13].

[0045]

The polymerizable dye monomer of the present invention and the polymer of the present invention obtained from the monomer have excellent light resistance, water resistance, migration resistance, solvent resistance and safety. Which is useful as a pigment that replaces conventional dyes.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 11/00 C09D 11/00 (72) Inventor Shoichiro Konishi 5-2-13-1 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. F term (reference) 4J039 AD03 AD09 AD10 AD12 AD13 AD21 AD23 BE02 CA03 CA06 EA35 EA38 EA39 EA43 EA45 GA24 GA34 4J100 AB07P AB15P AL08P AL66P AL67P AM14P BA31P BA32P BC43P BC49P BD15P CA07

Claims (4)

[Claims] 1. A polymerizable dye monomer represented by the following general formula (I). Embedded image Embedded image 2. A polymer obtained from the polymerizable dye monomer according to claim 1. 3. The polymerizable dye monomer according to claim 1, which is used as a dye for an ink or a color toner of an inkjet printer. 4. The polymer according to claim 2, which is used as a dye for an ink or a color toner of an ink jet printer.