JPS5933302A - Production of suspended colored polymer - Google Patents

Abstract

PURPOSE:To obtain a clear, stable suspended polymer, by emulsion-polymerizing an ethylenically unsaturated monomer and an oil-soluble dye or an oil-soluble pigment in water in the presence of an emulsifier. CONSTITUTION:An ethylenically unsaturated monomer and an oil-soluble dye or pigment stable to free radicals are dispersed with agitation in water in the presence of an emulsifier to form finely emulsified monomer drops, which are there emulsion-polymerized. The oil-soluble dyes stable to free radicals which can be used particularly suitably include monoazo types other than complex salts, azo dyes containing one -N=N-, and pigments used as colorants for synthetic resins. The oil-soluble dye or pigment is specially selected because it can be dissolved in the monomer, and these can be polymerized within emulsifier micelles at once. Examples of the emulsifiers include preferably anionic emulsifiers and anionic emulsifier-based emulsifier mixtures.

Description

DETAILED DESCRIPTION OF THE INVENTION In emulsion polymerizing ethylenically unsaturated monomers in water, the present invention performs a polymerization reaction by adding an oil-soluble dye or oil-soluble pigment that is dissolved in the monomer and is stable to radicals. The present invention relates to a method for obtaining bright and stable colored polymers. The emulsion polymerization mechanism of ethylenically unsaturated monomers is W,
D, Harkins (7J, Am, chem,
SOc,, 6? , 142B (1947)], the radicals generated by the decomposition of the initiator in water act on the monomer slightly dissolved in water and the trace amount of monomer present in the emulsifier micelles, resulting in activation. Points are formed, polymerization begins, and the oil droplet-shaped monomer is absorbed into the micelles through the aqueous phase.
It was reported that the monomer gradually enlarged and polymerization continued, and eventually the monomer disappeared and changed to polymer particles, and since then, these have remained unchanged to this day.Sm:ht, h-FiwarWW, V,
Sm1-t, h and R.

LL Bwart HJ, phys, ahθtu,
16.592 (11B)], the solubility of the monomer in the dispersion medium, or emulsifier-free polymerization, but the polymerization mechanism remains consistent. It is common knowledge that the substance of emulsion polymerization is transferred to the micellar phase through the dispersion medium. Therefore, in conventional methods, even if dyes or pigments soluble in monomers are added, only the monomers can pass through the aqueous phase, and dye and pigment molecules cannot migrate into suspended particles and remain unreacted. The polymer particles are colorless and cannot be colored as before. Methods for coloring after polymerization include dropping oil-soluble dyes into suspended polymers or adding emulsified dyes and stirring, and dyeing from the outside, which takes a long time, but these methods are complicated and expensive. It has not been put to practical use because it cannot be dyed with high density. Also recently, P. Durl) in et al.
, P. Dur-bin et al. :r, AI) 1) 1.
Polymer 5cj-, 27,703 (197
9) ``J uses a combination of a strong stirring mechanism and a surfactant to pre-emulsify the monomer to create extremely fine particles, and the body temperature of the monomer directly captures and polymerizes the initiator radicals. However, the type of emulsifier and polymerization method are extremely unclear.The present inventor has arrived at the present invention as a result of intensive research with the aim of obtaining a bright and stable colored polymer in suspension. .

That is, in the present invention, an ethylenically unsaturated monomer and a radically stable oil-soluble 1fL dye or oil-soluble pigment are dispersed and stirred in water in the presence of an emulsifier to form a fine emulsified monomer (to form a body temperature) and undergo emulsion polymerization. The present invention provides a method for producing a suspended colored polymer characterized by the following.

The present invention will be explained in more detail below.

The radically stable oil-soluble dyes used in the present invention include Sudan orange (R, A, S, F), Pater yellow, J-naphthol orange, Sudan red (B, A,
8. Azo dyes such as F) and monoazo dyes other than metal complex salts, triphenylmethane dyes which are derivatives of triphenylcarbinol, tsukurein dyes which are derivatives of triphenyl-lumethane, anthraquinone dyes, azine dyes, etc. Thread dyes, thiazine dyes, etc. can be exemplified, and further examples of oil-soluble pigments include organic pigments such as carbon fiber azo yarn, monoazo type, vat dye type, thioindigo type, and azo lake type. Particularly preferred are monoazo dyes other than complex salts, azo dyes having -N=N-1, and pigments used as synthetic resin colorants.

In the present invention, an oil-soluble dye or pigment is particularly used as the dye or pigment. , an ionic surfactant as an emulsifier is usually used, but polyvinyl alcohol lfEl. Polymer dispersants such as fibrous 1st conductors and secondary powder derivatives can also be used as emulsifiers in the present invention. Preferred are anionic and anionic mixed emulsifiers, particularly preferred are fatty acid amide ether sulfate polyethylene glycol alkylphenyl ether/
A mixture of L' yarn with a nonionic activator is used.

As an ethylenically unsaturated monomer, 1 is methyl acrylate;
77971 degree ethyl, acrylic acid butyl ρ, acrylic acid 2
- Esters of acrylic acid and methacrylic A/acids such as ethylhexyl, methyl methacrylate, ethyl methacrylate, butymu methacrylate; vinyl aromatic compounds such as styrene, vinyltoluene; halogens such as vinyl chloride, vinyl bromide, etc. Vinylidene/L/; vinylidene halides such as vinylidene chloride and vinylidene fluoride; vinyl acetate,
Vinyl NTE Iv such as vinyl propionate; monoolefins or conjugated diolefins such as ethylene and butadiene; and vinyl cyanides such as acrylonitrile may be used alone or in a mixture of two or more thereof. Radical initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide are used to initiate polymerization, and if necessary, reducing agents such as sodium thiosulfate, sodium bisulfite, and sodium ascorbate are used in combination. It will be done. In addition, a combination of α,α1-azobinuisoptiμamidinopropane hydrochloride or the like with a cationic monomer or a cationic emulsifier can also be used as an initiator that is expected to generate a cationic radical fragment. Emulsion polymerization by radiation or light without using an initiator is also possible. In addition to the above, additives used in normal emulsion polymerization such as plasticizers, solvents, polymerization degree lowering agents, and sensitive groups for crosslinking may also be added. Emulsion polymerization is carried out by stirring with light and adding an initiator, or single emulsion polymerization is carried out with strong stirring.

Further, ordinary polymerization methods such as batch polymerization, divisional polymerization, and additional polymerization can also be employed. Furthermore, with a particularly preferred combination of strong emulsifiers, a stable target product can be obtained by emulsion polymerization using conventional stirring or shaking. Radical-unstable coloring agents are called induction polymers (nauotlon).
Perlod, ) is long, and the double bond part of the colorant disappears due to the reaction with radicals, and in many cases, the color change of the colorant makes it impossible to achieve the purpose of obtaining a brightly colored polymer.

In the case of radically stable dyes, even if a large amount of coloring agent is added to the monomer, almost no inductor damage is observed.
The target product can be obtained in high yield.

The particle size of suspension polymers is relatively small and is often 0.5μ or less, but when an anionic emulsifier is used, the particle size is 0.1μ or less.
The following homogeneous particles are obtained. Further, when the suspension was salted out, it was separated into a colored polymer precipitate and a colorless and transparent dispersion medium, and it was found that the added oil-soluble colorant was completely contained in the polymer.

The obtained suspension polymer is in a dispersed state and can be used as a raw material suspension for easily distinguishable diagnostic reagents, or as a pigment or vehicle for paints and pigments. It is also used in combination with water-soluble dyes and pigments to create paints with high color density. Furthermore, it can be used as a molding material by breaking the suspended state.

Typical examples will be described below.

Example 1 100 parts of styrene and 70 parts of Sudan Orange, an azo dye
04 (products of companies B, A, S, F) were added to 875 parts of water, and 2.5 parts of polyethylene glyco-μ nonylphenylphene%luete/L/(Neuken EA50) was added as a nonionic emulsifier. As an anionic emulsifier, fatty acid amide ether sulfonic acid sodium amide C3)4
・Add 5 parts to the dissolved liquid and add it to a Gomoku glass polymerization pot (24
) was heated while stirring with a propeller type stirrer at 19 rpm. Next, when the water temperature reached 70" (E), stirred for 5 minutes at 10.00 rpm with a homomixer, and after confirming that the monomer was sufficiently emulsified, 113 Qr, p, m,
While rotating at \, a solution prepared by dissolving 0.5 parts of an initiator (ammonium persulfate) in 25 parts of water was added all at once, and emulsion polymerization was carried out at 75°C in a nitrogen stream for 3 hours. The obtained turbid polymer has a polymerization rate of 80% or more and beautiful red fine particles (particle size 0.
07 to 0.11μ). When a 10% aluminum sulfate aqueous solution was added to the same suspension, coagulation occurred and the mixture was separated into water, a colorless and transparent dispersion medium, and μ-colored resin. This revealed that the dye was completely contained in the polymer.

Example 2 7 t/100 parts of ethyl acrylic acid, Ai, Disbirds Yellow 51, (Cibaset, Brilliant Yellow 4ji)
(Ciba, Geigy products), 1 part of sodium alkylbenzeneulfonate as an anion activator,
2 parts of oleic acid amide ether sulfide, as a nonionic activator, were added to a solution of polyoxyethylene (14) apkyl ether yv Z parts' dissolved in 875 parts of deionized water in a five-mole separable flask containing 2 p.
Rotates at rpm up to ＼70゛C! +It was warm. then 0
．． An aqueous initiator solution prepared by dissolving 5 parts of potassium persulfate in 25 parts of water was added all at once, and emulsion polymerization was carried out at 75°C in a nitrogen atmosphere for 3 hours. As a result, a suspension polymerization solution of polyacrylic acid ethyl μ was colored yellow ( A particle size of around 0.15μ) was obtained.

Example 3 To 200 parts of vinyl acetate monomer, add C, I, % A-z, B/l/-3 (Ceriton, Fastp) V-F, F, 7-lv (B, A, S, F One part of the product was dissolved to make a liquid. Average degree of polymerization 500 in deionized water,
Two parts of polyvinyl alcohol with a degree of saponification of 85% and two parts of stearic acid amide ether μphonic acid soda were dissolved in 1B to prepare an ill solution.

Mix the above two liquids (11%) and mix with a homomixer to 600%
After emulsifying for another 5 minutes at Or, P, and M, the mixture was placed in a glass polymerization pot No. 21, and heated at 2000 r and P using a homomixer.
The temperature was raised to 70°C while rotating at 100 m, and 710 parts of 2% ammonium persulfate was added to carry out a polymerization reaction at 75'C in a nitrogen stream. Disperse well with ultrasonic waves, then continuously add the monomer emulsion on one side and the aqueous initiator solution on the other side over a period of 1 hour, and stir after dropping the monomer. Speed f 500 r,
The temperature was lowered to p and m, and heating was continued for an additional 2 hours to complete the polymerization reaction. The obtained polyvinyl acetate suspension had a viscosity of 22
It exhibited a beautiful dark blue color at 000np.

Example 4 80 parts of styrene monomer and 0.3 part of C.I. Pigment Yellow 23 (Helio, Fast Yellow 3 G.L.) were dispersed in 80 parts of styrene monomer and vinyltoluene monomer to prepare a first solution and deionized. 1III& was prepared by dissolving 2 parts of lauric acid jetanolamide and 2 parts of ether sulfate in 875 parts of water. These two solutions and the ill solution were mixed and stirred with ultrasonic waves for 5 minutes to emulsify and disperse, and then gently stirred with ultrasonic waves in a glass polymerization pot. OXxu'
Emulsion polymerization was carried out for 2 hours and 30 minutes under r-ray irradiation at r/hr.

As a result, a yellow suspension polymer was obtained with a polymerization rate of 80% or more.

patent applicant Polymer Research Institute Co., Ltd. agent (6a2o) Patent attorney Kanji Ida

Claims (1)

[Claims] ■ It is characterized by dispersing and stirring an ethylenically unsaturated monomer and a radically stable oil-soluble dye or oil-soluble pigment in water in the presence of an emulsifier to create fine emulsified monomer cylinders and emulsion polymerization. A method for producing a colored polymer suspension.