JPH02124909A - Preparation of colored vinyl polymer - Google Patents

Abstract

PURPOSE:To prepare the title polymer with little change in hue during polymn. by reacting a vinyl polymerizable monomer with a polymerizable dyestuff which is a reaction product of a dyestuff of a specified formula and a specified compd. in the presence of a polymn. catalyst. CONSTITUTION:A colored vinyl polymer, wherein the color change of the product before and after polymn. is within + or -3nm in terms of the absorption spectra, is prepd. by reacting 100 pts.wt. vinyl polymerizable monomer (A) with 0.1-99.9 pts.wt. polymerizable dyestuff (B) obtd. by reacting a dyestuff of formula I, II, III, IV, V or VI [wherein R1 and R2 are each H or formula VII (wherein R3 is NH, OH, formula VIII or IX; R4 is H, an alkyl, a cycloalkyl or allyl; n and m are each 1-5; X and Y are different from each other and each OH or -NHR2] with a compd. selected from methacryloyl chloride, methacryloyl isocyanate and isocyanatoethyl methacrylate, in the presence of a polymn. catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing colored vinyl polymers used in paints and the like.

(Prior Art and its Problems) Efforts have been made to introduce dyes into polymer skeletons from the viewpoint of coloring stability and uniformity. For example, JP-A-61-
In Japanese Patent No. 203107, a complex of ethylenically unsaturated sulfonic acid and a basic dye is used as a polymerizable dye and copolymerized with a polymerizable monomer to obtain a colored polymer. However, the dyes used in this method have poor solubility in typical organic solvents.

European Polymer Journal (Eur.

Polym, J, Vol, 23. No.8. PP617-
622 (1987) discloses a method of introducing a methacryloyl group into an alkyl group-introduced arethraquinone dye and copolymerizing it with other copolymerizable monomers. According to this method, solubility in solvents is improved, and solvents such as water and alcohol can also be used. however,
This dye changes its hue under the influence of the polymerization initiator,
Designing colored polymers is difficult.

(Means for Solving the Problems) In order to obtain a colored polymer with no change in hue, the inventors of the present invention introduced a polymerizable vinyl group into a dye having a specific chemical formula using a specific compound. It was found that almost no change in hue was observed when radical copolymerization was carried out using

That is, the present invention provides (A) 100 parts by weight of a vinyl polymerizable monomer, and (B) a compound of the formula [wherein R2 and R1 are the same or different, hydrogen or a formula (provided that R8 is -NH1, - (CH,)mNH,, -〇[1 or -(CHt)a+OH.

R4 is hydrogen, an alkyl group, a cycloalkyl group, or an allyl group, n is an integer of 1 to 5,
m represents an integer of 1 to 5. ), X and Y are different, −
Indicates OH or -NHR1. ] and the pigment represented by
Polymerizable dye O obtained by reaction with a compound selected from the group consisting of methacryloyl chloride, methacryloyl isocyanate and isocyanatoethyl methacrylate
01 to 99.9 parts by weight are reacted in the presence of a polymerization catalyst, and the color change between the product before and after polymerization is within ±3 nm in the absorption spectrum. provide.

The dyes used in the present invention are represented by the above six general formulas. These dyes can be obtained by known methods. In general formula (1), -diaminoanthraquinone and 2-hydroxy-3bromotoluene can be reacted in the presence of sodium acetate and copper. Others can be obtained by similar reactions. Similarly to (1) above, dyes of general formulas (2) and (5) can also be used, for example, (2)
(5) is obtained by using 1-aminoanthraquinone as a starting material, and (5) is obtained by using 1,5-dihydroxy-4,8-diaminoanthraquinone as a starting material.

Among the dyes of general formula (3), R1 is obtained by reacting 1-nitroanthraquinone and 2-hydroxy-4-isobutylthiophenol in the presence of KOH.

(4) using 1,5-dinitroanthraquinone (3
) can be obtained by a reaction similar to

The reaction between dyes (1)-(6) and methacryloyl chloride is
For example, the reaction proceeds by dissolving the dyes (1)-(6'') in a solvent other than alcohol, preferably a dehydrated solvent, and then adding a methacryloyl chloride compound in the presence of a tertiary amine. Known tertiary amines such as triethylamine, benzyldimethylamine, and diazabicyclooctadecane can be used as the tertiary amine. Also, the quaternary ammonium salt produced by dehydrochlorination is easily filtered out. The reaction between 1)-(6) and methacryloyl isocyanate or isocyanatoethyl methacrylate is easier and proceeds by adding these compounds to the dye solution.

The above compounds are selected depending on the copolymerization monomer, solvent, etc. when synthesizing the colored polymer. For example, when using a nonpolar monomer such as styrene, methacryloyl chloride is used to increase the compatibility with the styrene monomer, and when using a polar monomer such as methyl methacrylate, methacrylic acid, or acrylamide, methacryloyl isocyanate or isocyanate is used for the same reason. Natoethyl methacrylate is usually used, but is not limited thereto.

Vinyl polymerizable monomers used in polymerization can be broadly classified into the following groups.

Alkyl acrylate or methacrylate: for example methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

Hydroxyl group-containing monomers, such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2
-Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, methalyl alcohol, etc.

Polymerizable amides; for example, acrylamide, methacrylic acid amide, etc.

Polymerizable nitrile; for example, acrylonitrile, methacrylate trile, etc.

Glycidyl (meth)acrylate.

Styrenic compounds; for example, styrene, vinyltoluene, etc.

α-Olefin: For example, ethylene, propylene, etc.

Vinyl compounds: for example vinyl acetate, vinyl propionate, etc.

Diene compounds: for example butadiene, isoprene, etc.

Carboxyl group-containing monomers: for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, monobutyl maleate, etc.

Phosphate group-containing monomers: for example, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, 3-chloro-2-acid phosphooxypropyl methacrylate, etc.

Sulfonic acid group-containing monomer; for example, 2-acrylamide,
2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, etc.

Nitrogen-containing alkyl acrylate or methacrylate;
For example, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc.

In addition to the above-mentioned polymerizable monomers, a polyethylene monomer may be blended to adjust the glass transition temperature and molecular weight of the obtained polymer (Japanese Patent Application No. 277067/1982). These polyethylene monomers are usually 0% of the total monomers.
~50% by weight, but may be used in excess of 50% by weight.

Polymerization is usually carried out using a polymerization initiator. As the polymerization initiator, ordinary ones may be used.

In particular, for solution polymerization, dispersion polymerization, etc., peroxides such as benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl peroxy 2-ethylhexanoate, azobisisobutyronitrile, 2.2′-azobis(2,4-dimethylvaleronitrile), 2.2′-azobis(4-methoxy-2,4-
There are azo compounds such as dimethylvaleronitrile) and dimethyl 2.2°-azobisisobutyrate. 1 of these
It is used either as a species or as a mixture of two or more species. The amount used is usually 0.1 to 10%, preferably 0.2 to 7% based on the total monomers.
Selected within a range of %. The initiator used in emulsion polymerization is selected from those having a positive or negative charge. As a polymerization initiator that imparts a positive charge, an azo amidine compound is used, such as 2.2°-azobis(2-amidinopropane) dihydrochloride, 2.2′-azobis(N,N”
-dimethyleneisobutyramidine), 2.2°-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, and the like. Examples of the polymerization initiator that imparts a negative charge include azo carboxylic acid-containing compounds such as 4.4'-azobis (4-cyanopentanoic acid) and persulfates such as potassium persulfate and ammonium persulfate. These are usually water-soluble initiators and are used dissolved in water. The amount to be used may be determined depending on the desired charging type, but is usually selected in the range of 0.1 to 10% based on the total monomer. Conventionally, when performing radical polymerization in the presence of a dye, it has been impossible to use a peroxide-based polymerization initiator with strong oxidizing power because the polymerization initiator causes structural changes and hue changes in the dye. Therefore, there are disadvantages in that there are major restrictions on the solubility and half-life of the polymerization initiator, and it is difficult to prepare grafted polymers. This places significant constraints on polymer design. On the other hand, since the dye of the present invention has solved these problems, it has a wide selection range of polymerization initiators, and can be applied to a wide range of material designs and a wide variety of manufacturing processes. In particular, it has the great advantage of eliminating the poor light resistance characteristic of azo initiators and facilitating grafting.

Although there are no particular limitations on the method for producing the desired colored polymer, the reaction proceeds by radical copolymerization reaction. For example, solution polymerization, emulsion polymerization, aqueous dispersion polymerization, non-aqueous dispersion polymerization,
Examples include bulk polymerization, and in cases other than solution polymerization and bulk polymerization, the polymer produced is spherical or solid. As the filter solvent, dispersant, emulsifier, etc. used in the polymerization, known ones can be used. Typical examples of solvents that can be used include aromatic hydrocarbons such as xylene and toluene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, cellosolves such as methyl cellosolve and butyl cellosolve, and alcohols such as ethanol and isopropyl alcohol. It will be done. Examples of dispersants include polyvinyl alcohol,
Examples include partially saponified polyvinyl alcohol, gelatin, celluloses, and tribasic calcium phosphate. The polymerization temperature is usually preferably 40 to 160°C. During polymerization, the polymerizable dye is used in a desired amount depending on the intended use, and is used in an amount of O01 to 99.9 parts by weight per 100 parts by weight of the vinyl polymerizable monomer.

(Effects of the Invention) According to the present invention, there is provided a method for producing a colored vinyl polymer in which the hue of the dye hardly changes during polymerization, for example, the change in absorption spectrum is within the range of ±3 nm. When the method of the present invention is used, the range of selection of polymerization initiators, which are thought to be the cause of discoloration, is expanded, and the degree of freedom in polymer design is increased. The colored vinyl polymer obtained in the present invention is suitable for paints, toner inks, medical polymers, diagnostic drug carriers, biosensors, optical sensors, molding resins, and the like.

(Example) Examples will be described below. The invention is not limited to these examples. All reactions were carried out using a 2Q round bottom flask equipped with a reflux tube, a temperature controller, a nitrogen inlet, a raw material inlet, and an inclined paddle type stirring blade.

Example 1 (Synthesis of polymerizable dye) Yellow dye 1009! , 4 Dioxane 13009 Triethylamine 47.059 (1.5 equivalents) The above components were charged into a reactor. A dropping funnel was set in the raw material inlet, and methacryloyl chloride 39°129 (1.1 equivalents) and 1.4 dioxane 1609 were charged and added dropwise over about 60 minutes at room temperature. The reaction was followed by thin layer chromatography, and after the reaction was completed, 10×N methanol was added to consume unreacted methacryloyl chloride. The generated quaternary ammonium salt was removed by filtering the reaction mixture, and the solvent was removed from the solution by evaporation. The remaining solid matter was recrystallized with methanol and filtered and dried to obtain a polymerizable dye (the structure shown below). The structure is IR,
Confirmed by NMR, mass spectrum, and liquid chromatography. The yield was 92%. The absorption wavelength peak in the absorption spectrum was 42In-.

The reaction was carried out in the same manner as in Example 1.

Example 9 Butyl acetate 1609 xylene
1209 styrene
9009n-butyl methacrylate 26
09 Polymerizable dye of Example 1 1209 The above ingredients were charged into a reactor and the temperature was set at 75°C. Attach a dropping funnel to the raw material inlet, charge 10 g of azobisisobutyronitrile and xylene 409, and add about 12 g of
It was dropped in 0 minutes.

After the dropwise addition was completed, the reaction was continued for an additional 6 hours. The solvent was then removed under reduced pressure, and the mixture was crushed after cooling.

When a part of the polymer was taken and the absorption spectrum was measured, there was no change in the absorption wavelength. The molecular weight determined by GPC was Mw: 69,000 and Mn: 24,000.

Example 10 Distilled water 8009PVA-2
17 (Clary) 89 PVA-205 (Clary) 29 Perex 0T-P (Kao) 0.29 Potassium iodide 0.049 The above components were charged into a reactor, and the temperature was set at 70°C. Next, styrene 28092 ethylhexyl acrylate 80g Polymerizable dye of Example 3
409 Lauroyl peroxide 16
g of the mixed solution was added and polymerization was continued for 8 hours. After removing unreacted monomers by steam distillation, the mixture was filtered and dried.

When a part of the polymer was taken and the absorption spectrum was measured, there was no change in the absorption wavelength. The molecular weight determined by GPC was Mw: 61,700 and Mn: 20,400.

Example 11 The same procedure as Example 1O was carried out except that the polymerizable dye used in Example 4 was used.

When a part of the polymer was taken and the absorption spectrum was measured, there was no change in the absorption wavelength. Moreover, the molecular weight according to Gpc is My; 57700. Mn: 18,500.

The polymer obtained according to Example 9, toS 11 was suitable for toner use.

Example 12 Distilled water 12009 Perex C8
(Kao) 14.49 poise 520 (Kao'
) 0.249 copper sulfate
0.249 potassium persulfate
12.09 Styrene 3009 Charge the above ingredients into a reactor, set the temperature to 50°C, and
Polymerization was continued for 18 hours at 70"C. 4
Aggregates were removed through a 00 mesh sieve and purified by ultrafiltration. When the particle size was measured using a Coulter counter, the average particle size was 4.1 μm, and the coefficient of variation was 4.5%.
Met. Next, the following components were charged into the reaction vessel.

The above latex 1009 (solid content 20g
) Distilled water 12009 Perex TR
(Kao) 0.249 Perex 0T-P (Kao) 2.409PV
A-203 (Clary) 3.209PVA
-217 (Clari) 0.21 Potassium iodide 0.06ir Add a mixture of styrene 10.09 benzoyl peroxide 0.69,
Stirring was continued at room temperature for 4 hours. Next, the polymerizable dye of Example 5: 16.09 diisopropenylbenzene 32.09 styrene
Add 82.09 and heat at 75°C for 3 hours.
Polymerization was carried out at ℃ for 4 hours. When the particle size was measured using a Coulter counter, the average particle size was 8.1 μm, and the coefficient of variation was 5.0.
%Met. When the reflection spectrum of this gel particle was measured, there was no change in color tone.

Example 13 Isopropanol 720g distilled water
80gRPC-L (Japan Soda)
109PVAc-X-7830 (Kuraray) 10g
Charge the above ingredients into a reactor, set the temperature to 80°C, and add styrene 14092 ethyl hequinyl acrylate 40g Polymerizable dye of Example 2
209 Benzoyl peroxide 2,09V
-40 (Wako Tsumugi Pharmaceutical Co., Ltd.) 12.09 was added and polymerized at 85°C for 24 hours. When the particle size was measured using a Coulter counter, the average particle size was 5.4 μm and the coefficient of variation was 8.2%. This latex was purified by dialysis and then filtered and dried.

When a part of the polymer was taken and the absorption spectrum was measured, there was no change in the absorption wavelength. Moreover, the molecular weight by GPC is Mw; 156 Q O, Mn;? It was 700.

Example 14 The same procedure as Example 13 was carried out except that Example 6 was used as the polymerizable dye.

When a part of the polymer was taken and the absorption spectrum was measured, there was no change in the absorption wavelength. Moreover, the molecular weight by GPC was Mw: 13900 and Mn: 6700. When the particle size was measured using a Coulter counter, the average particle size was 5.1 μm, and the coefficient of variation was 9.2%.

The particles of Examples 13.14 are suitable for use as toners.

Example 15 12 g of distilled water 11009 cetylpyridinium chloride was poured into a reactor,
Set the temperature to 60℃, and add distilled water 1009V-50 (
Wako Tsumugi Pharmaceutical) 2.09 was added.

At the same time as adding methyl methacrylate 40g ethyl acrylate 409 styrene
609 Polymerizable dye of ethylene glycol dimethacrylate 209 Example 5 40
The mixed solution of No. 9 was added dropwise from the dropping funnel over about 60 minutes, and the mixture was polymerized for a total of 6 hours. When the particle size was measured using a scanning electron microscope, the average particle size was 0.15 μm. When the reflection spectrum of this gel particle was measured, there was no change in color tone.

These colored gel particles are extremely effective as inks, colorants, etc.

Comparative example 1 Polymerization was carried out in the same manner as in Example 13 using the following dyes.

While the absorption wavelength peak of the dye was 512 nm,
The absorption wavelength peak of the produced polymer was 460 nm, and the hue changed from red to orange.

Comparative example 2 Polymerization was carried out in the same manner as in Example 13 using the following dyes.

While the absorption wavelength peak of the dye was 646 nm,
The absorption wavelength peak of the produced polymer was 540 nm, and the hue changed from blue to purple.

Comparative example 3 Polymerization was carried out in the same manner as in Example 13 using the following dyes.

While the absorption wavelength peak of CH3 dye was 432 nm,
The absorption wavelength peak of the produced polymer is 406nn+,
The yellow color has almost disappeared.

Example 16 Isopropanol 330g distilled water
Charge 16g of 70g polyvinylpyrrolidone into the reactor,
The temperature was set at 60°C.

Here, styrene 70g 2-ethylhexyl methacrylate 20g lauroyl peroxide 2. OgV-601 (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.) 6.5g Dye of Example 7
10 g of the mixed solution was added and polymerization was continued for 24 hours. As a result, yellow resin particles with an average particle diameter of 5.2 μl and a coefficient of variation of 13.2% were obtained. There was no change in the absorption spectrum.

Example 17 t-butanol 85g methanol 315g human O 7
°+1 pill cellulose
4.0 g (RPC-L manufactured by Nihon Budatsu) and 6.0 g (X-0945 manufactured by Kuraray) of partially saponified polyvinyl acetate were charged into a reactor, and the temperature was set at 60°C.

Here, styrene 65g (butyl acrylate) 20g dioctanoyl peroxide 8.5g dye from Example 8
15 g of the mixture was added and polymerization was continued for 24 hours. As a result, red particles with a narrow particle size distribution and an average particle diameter of 8.2 μl and a coefficient of variation of 9.4% were obtained. There was no change in the absorption spectrum.

The colored particles of Examples 16 and 17 are suitable for use as color toners.

Patent applicant: Nippon Paint Co., Ltd.

Claims (1)

[Claims] 1. (A) 100 parts by weight of vinyl polymerizable monomer, and (B) formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(6) [In the formula, R_1 and R_2 are the same or different, hydrogen or formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_3 is -NH_2, -(CH_2)_mNH
_2, -OH or -(CH_2)_mOH, R_4 is hydrogen, alkyl group, cycloalkyl group or allyl group,
n represents an integer of 1 to 5, and m represents an integer of 1 to 5. ), X and Y independently represent -OH or -NHR_2. ]
0.1 to 99.9 parts by weight of a polymerizable dye obtained by reacting a dye represented by the formula with a compound selected from the group consisting of methacryloyl chloride, methacryloyl isocyanate, and isocyanatoethyl methacrylate in the presence of a polymerization catalyst. A method for producing a colored vinyl polymer, characterized in that the color change between the product before and after polymerization is within ±3 nm in the absorption spectrum.