RU1819274C - Latexes of copolymers of butylacrylate and di-n-substituted acrylamide - Google Patents

Abstract

Usage: components of photographic materials. SUMMARY OF THE INVENTION: Latexes of copolymers of butyl acrylate and di-M-substituted acrylamide of the general formula {scn m -CH2-CR——————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————— Where with,, CH3, p .98-0.85,, 02-0.15, with a glass transition temperature of 45-50 ° C, containing water and particles of a copolymer with a diameter of 0.05-0.2 microns in the following ratio of components, wt.%: Copolymer of butyl acrylate and di-M-substituted acrylamide 5-15, water 85-95.4 tab.

Description

The invention relates to the chemistry of high molecular weight compounds, namely to products of the copolymerization of alkyl esters of acrylic acid and surfactant monomers (PAMs) of the anionic type, which can be used to convert various substances, including photochemicals, into colloidal state.

Narrowly dispersed colloids of hydrophobic compounds with a particle size of less than 0.3 microns and not containing polluting substances are necessary to obtain high-quality color film materials representing loaded latex systems in which a hydrophobic substance is adsorbed on the particles. To obtain a loaded latex, a hydrophobic substance is dissolved in a volatile

a water-miscible solvent, polymer latex was added to the solution, after which the solvent was removed in vacuo. Loadable latexes obtained by emulsion copolymerization of, for example, butyl acrylate, N-Na-sulfoalkyl acrylamide and acetoacetoethoxyethyl acrylate have the disadvantage that they are contaminated with the emulsifier used in their synthesis. The use of such latexes in film materials leads to a decrease in color images. In addition, analog latexes are not sufficiently loaded with photochemicals. This leads to the need to introduce excessive polymer ballast into the materials, to thicken the layers and. as a result, deterioration in the sharpness characteristics of photographic materials.

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In this connection, the task of creating impurities was determined from elemental analysis of latexes with an increased degree of load-films obtained from latex, washed containers and not containing polluting water and dried in vacuum. In accordance with this task. From the available data it was not necessary, we synthesized latexes, including 5 that can be contained latexes, water and particles (0.05-0.2 microns in diameter) do not have aggregative stability, a large copolymer of the general formula for loading hydrophobic photochemicals .

Stability of loaded latex zavi /,. % sieves from the forces of association of load molecules and

 CHj-CH% 1 of the Yupolymer, which, in turn, is determined by the CONHCHj SOjNal structure of both the polymer and the (CH2) 3OCC10H2 loaded substance. Finding

the optimum load of a latex with one or another substance requires experimental 2-4; K N, CH3: 98-0.85; , 02-15 research and search for somo-0.15 (with a glass transition temperature of -45- rooms for the synthesis of polymer latex. 50 ° C) at a content of components of a high loading color-forming latex, wt.%: With our components of the claimed latex copolymer 5-15, water 95-80. Allows reducing the thickness of blue by 20%. The optimal concentration of latexes is 20 sensitive and is 35% green-sensitive in the range of 5-15%. As with higher, body layers.

in such a way, at lower concentrations, a greater load is formed of the declared less rainfall or coagulum in the process of tex near F-absorbers or mixtures thereof

loading of latex with photochemicals allows either to reduce the thickness of light-monomer units of PAM, providing 25 protective layers (by 50%) by reducing

aggregative stability of the latex content of polymer ballast in them and

particles due to the presence in them, the presence of the material, or at the same thickness, should improve the sharpness characteristics of the ionic groups

to twist in the copolymer in the amount of corresponding layers; increase by 12-17% the protective properties of their mass fraction from 0.02 to 0.15. 30 tons of films.

At, 02, the charge density in the copolymer. The latex loading ability is not sufficient to stabilize the load; it is determined taking into account the particles released after the nanowires, and at item 0.15, the hydrophilic loading of the sediments increases, while for determining

the presence and swelling of the copolymer, so that the amount of photochemicals dropped out also leads to coagulation of latexes using the spectrophotometry method.

The synthesis and use of latexes (including synN-γ-decipoxypropyl-N-Na-sulfoal-tez monomers) is illustrated by examples,

kilacrylamides are synthesized by interactions. PRI me R 1. Synthesis of N-y-decyloxy by N-y-decyloxypropylamine sropyl-L-g4a sulfobutyl acrylamide.

2-hydroxyethanesulfonic acid or with alcohol sul-0a) To a solution of 21.5 g (0.1 mol) with N-γ-decitones followed by acylation of hydroxypropylamine in 30 ml of benzene in a stream

of the resulting amines with acryloyl chloride. Nitrogen was added 13.6 g (0.1 mol) of 1,4-butane. When used for the acylation of meta-sultone. The mixture is maintained at room temperature, the same able temperature during the day, then 2

obtained M-y-decyloxypropyl-M-Ma-sul - 45 hours heated at a bath temperature of 60 phoalkyl methacrylamides. These monomers are 65 ° C. After cooling, the mixture is separated

are new compounds. product recrystallized from metaLatex is prepared by the emulsion-nola-dried method. Yield 21.7 g (62%); PMR 5 ppm.

polymerization of butyl acrylate and N-у-СОС1з: NH2 6.65 (broad), -CH2-O-3.4, -CH2-N

decyloxypropyl-M-Ma-sulfoalkyl acryl-50 and СН2-5Оз 2.9 (broad), CH2C-0-1.7 (broad),

and methacrylamide in water in the presence of per-CHg-C 1.27, -CH3 0.87.

potassium sulfate. Latex copolymers under-b) To a solution of 7.0 g (0.02 mol), N-γ is sufficiently soluble in conventional loxypropyl-HF-sulfobutylamine and 0.8 g

solvents to determine their NaOH molecule in 45 ml of a mixture of tetrahydrofuran and

l masses. In order to characterize the coproduct (2: 1), at the same time slowly, by addition, we determined that an aqueous solution of 2.4 g NaOH and 3.62 g

glass them by the method of thermochemical (0.04 mol) acryloyl chloride at a temperature The found temperatures are t-re 5-10 ° C. The mixture is incubated for

e in the range of -50 - -45 ° C. The composition is latex-hour, then heated at a bath temperature of 60 ° C for 40 minutes, after which tetrahydrofuran and water are distilled off in vacuo, the residue is extracted with chloroform. After distillation of chloroform in vacuo, the product is recrystallized from ethanol. Yield 4.77 g (56%), PMR d ppm. СОС1з: СН2 5.3-5.8, -CH2-О and -CH2-N 3.4 (br), -CH2-S03 3.0 (br). -CH2CX 1.7 (. O, S). -CH2- 1.26 (m).

Example 2. Similarly, N-y-decyloxy propi-1M-Ma-sulfobutylmeth-acrylamide is obtained. Methacryloyl chloride is used as an acylating agent. The PMR spectrum differs from the spectrum shown in Example 1 by the presence of an additional signal from the CH3 group d ppm. 1.87 and a signal from protons at a double bond of 5.05 (d).

L / M 3. Synthesis of N-y-decyloxy-propyl-M-Ma-sulfoethyl acrylamide

a) A mixture of 164.5 g (0.75 mol) of N-y-decyloxypropylamine, 56 g (0.375 mol) of sodium 2-hydroxyethanesulfonate and 0.28 g of a 47% NaOH solution is stirred in an autoclave at a temperature of 190 -198 ° C for 5 hours. The reaction mass is cooled and extracted twice with acetone. The residue was dissolved with 400 ml of water, acidified to pH 1-2, the precipitated sulfonic acid was filtered off, washed with water and dissolved in ethanol. The pH of the solution was adjusted to 11.5, the solvent was distilled off, the residue was dried to constant weight. Yield 44 g (34%), nitrogen content of the secondary amino group 3.98 (subtract).

b) To a solution of 44 g (0.125 mol) of N-y-decyloxypropyl-M-sulfoethyl amine and 16.5 g (0.136 mol) of triethylamine, 17.4 g (0.163 mol) of methacryloyl chloride are added with stirring . The mass was held for 2 hours. Then 62.5 g of a 10% methanol solution of NaOH were added and the solvent was removed in vacuo. The residue was dissolved in ethanol, the mixture was filtered and the solvent was again removed in vacuo, after which the product was dried in vacuo. Yield 51.1 g (97%). Bromine number 36.0 (subtract 36.6). PMR dm.d. CH2 5.01 (d), -OCHa 3.65 (broad). -CH2N -CH2S03 3.34 (broad). CH3-, 87 (s), -CH2- 1.27, -CH3 0.87 (t).

LYMER A. By analogy with Example 3-6), synthesis is carried out using acryloyl chloride. The yield of N-y-decyloxypropyl-M-Na-sulfoethyl acrylamide is 87%.

The PMR spectrum of the monomer differs from that given in Example 3 b) by the absence of a signal in the region of 1.87 ppm. and a signal from protons at a double bond of 5.3-5.8 ppm. (t).

PRI me R 5. According to the method of example 1 receive N-y-decyloxypropyl-M-No.-sulfopropylacrylamide, using in the first

the stage of synthesis of propansultone. Product yield, counting on the starting amine, 42%. The PMR spectrum of the product differs from that given in Example 1 with a lower signal intensity in the region of 1.7 ppm

PRI me R 6. Latexes of copolymers of butyl acrylate and N-y-decyloxypropyl-M-Na-sulfobutyl acrylamide. To a mixture of 1 g of M-y-decyloxypropyl-M-Ma-sulfobutylacrylamide, 100-400 ml of distilled water and 20.0 g of butyl acrylate, after heating for several minutes at 65-70 ° C in a stream of nitrogen, solution 0 is added. 1 g of potassium persulfate in 2 ml of water. The reaction mixture was stirred at 58 ° C for 3 hours, after which unreacted butyl acrylate was removed by blowing air. Get 104-415 ml of 5-20% latex (yield 99.0%) with an average particle size of 0.1 microns. The glass transition temperature of the copolymer is -50 ° C. The content of PAM units in the copolymer corresponds to 05 (p, 95) according to elemental analysis (% S 0.35; calculated .0.38). Similarly, copolymer latexes are obtained with a PAM unit content corresponding to 02: 0.15 (p, 98; 0.5) with the downloads of this monomer respectively 0.4; 3.0 g (elemental analysis data;% S, 0.11 and 1.02, respectively; 0.15 and 1.12 calculated). The glass transition temperature of the copolymers is -50 and -45 ° C; the average particle size of the latex is 0.15 and 0.05 microns.

Example. Latexes of copolymers of butyl acrylate and N-y-decyloxypropyl-N-Na-sulfobutylmethacrylamide are prepared according to the procedure for Example 6; in this case, copolymers with a ratio of butyl acrylate and PAM of 0.98: 0.02; 0.95: 0.05; 0.85: 0.15 (data of elemental analysis% S resp. 0.13; 0.33; 1.04, calculated-0.14; 0.36; 1.09).

Example 3. Latexes of N-y-decyloxypropyl-N-Na-sulfoethyl acrylate and methacrylamide butyl acrylate copolymers are prepared analogously to the latexes of Example 6. Copolymers containing PAM units corresponding to n2, 02; 0.05; 0.15 (n, respectively, 0.98; 0.95; 0.85), according to elemental analysis, contain% S; 0.13; 0.37; 1.14 and 0.13; 0.35; 1.08, respectively (calculated 0.16; 0.39; 1.16 and 0.15; 0.38; 1.12). The particle size of the latex is 0.05-0.2 microns. The glass transition temperature of the copolymer is -45- -50 ° C.

PRI me R 9. Latexes of copolymers of butyl acrylate and N-y-decyloxypropyl-M-Na-sulfopropyl acryl- and methacrylamide obtained similarly to the latexes of example 6. Copolymers containing PAM units P2-0.02; 0.05; 0.15 (, 98; 0.95: 0.85) in

elemental analysis data have% S 0.14; 0.36; 1.09 and 0.13; 0.33; 1.08, respectively, calculated; 0.15; 0.38; 1.12 and 0.15: 0.36: 1.09.

PRI me R 10. The definition of loaded ™ latex yellow color-forming component. To a solution of 4.5 g of a yellow color-forming component (CSC) of 2-chloro-5-y- (2,4-ditretamylphenoxy-butyrylamino) -anilide a-M-benzylhydantoyl-3-yl-pivaloyloacetic acid in 80 ml of a mixture of acetone and methanol (1: 1), 7.5 ml of 20% or 30 ml of 5% latexes were added with stirring, after which the organic solvents were removed in vacuo and the colloids were left for one day at room temperature. When a precipitate is present in the loaded latex, it is separated, dried, extracted with alcohol, and the content of the components is determined using spectrophotometry. Sensitized bromosilver emulsion, tanning agent and stabilizer are added to the loaded latexes, after which the composition is applied to the substrates so that the same amount of CTC and Ad are per unit area. After drying the samples, the thickness of the resulting films was determined. Characteristics of the samples are given in table 1.

For loading, 5-20% latexes with a content of PAM units in the copolymer of 0.02 0.05 and 0.15 were used. Moreover, it was found that the difference in the loaded ™ of latex s, 02-0.15, is within the experimental error. Latexes of copolymers in which PAM contains a residue of acrylic acid or methacrylic are not distinguished by loading.

The latex of the copolymer (1) of butyl acrylate, acetoacetoxyethyl acrylate and Na-salt of 2-acrylamido-2-methylpropanesulfonic acid (in the ratio 85: 5: 10) obtained in accordance with the analogue was used as the loaded latex of the analogue.

Thus, the use of latexes of a copolymer of butyl acrylate and N-y-decyloxypropyl-M-Ma-sulfoalkyl acryl (or methacryl -) amide allows reducing the thickness of the photo layer by 20% due to the reduction of the polymer ballast introduced with the component and due to the absence of a non-polymerizable emulsifier reduces the dark veil of the image by 33%.

.Examples and. Determination of latex loading by the magenta color-forming component. To a solution of 4.5 g of purple CTC (1- / 2,4,6-trichlorophenyl / -3- 3- / 2,4-ditretamylphenoxyacetylamino / benzoylamino-pyrazolone-5) in 80 ml of a mixture of acetone-methanol (1: 1) with stirring 10 ml of latex with a concentration of 15% are added, after which the solvents are removed in

vacuum. The colloidal systems are filtered, the precipitates are separated, dried, extracted with ethanol and the content of the components is determined by spectrophotometry. A sensitized halogen-silver emulsion is added to the loaded latexes, a tanning agent, a stabilizer, and the composition are poured onto substrates, so that the component deposition and AO are the same for all samples. After drying the samples, the thickness of the obtained films is determined. For loading, the latexes of Examples 6-9 were used, containing copolymers with pap values from 0.02 to 0.15. It was found that the loading of such latexes is close in magnitude, regardless of whether PAM contains a residue of acrylic or methacrylic acid, the data are shown in Table 2.

As an analogue, the same latex was used as with Example 10.

Thus, with the help of latexes of copolymers of butyl acrylate and M-u-decyloxypropyl-M-Na-sulfoalkyl acry (or methacryl -) amides, the value of the dark veil can be reduced by 33% and 35%

reduce the thickness of the photo.

PRI me R 12. Loading latex

2-hydroxy-4-H-octyloxybenzophenone (UV absorber A), To a solution of 4.1 g of 2-hydroxy-4-noctyloxybenzophenone in 70 ml of a mixture

acetone-methanol (1: 1) 10 ml of 14% or 28 ml of 5% latex are added. After that, the organic solvents are removed in vacuo and the mixture is filtered. In the case when the precipitate is separated, it is extracted

alcohol, and the amount of loaded UV absorber is determined using spectrophotometry.

For the preparation of samples of light-protective films, the claimed

latex copolymers with a concentration of from 5 to 20% obtained in examples 6-8. These latexes have the same (within the limits of experimental errors) loading of the UV absorber A. In the quality of latex, the same latex was used as in Example 10. 10 ml of a 6% solution of gelatin in water was added to the loaded latexes and the compositions are applied to samples of a single-layer photo material with a purple image, taking into account that the same amount of UV absorber should be contained in a unit area. Moreover, depending on the loaded ™ latex, the copolymer-UV absorber ratio changes, and at the same time, the thickness of the films obtained with their use.

After drying, the samples are irradiated with a xenon lamp at an illumination of 200,000 lux for 48 hours, and% fading is determined by changing the initial dye absorption density. We have found that the light-shielding effect of films containing equal amounts of a UV absorber is the same. The data obtained are given in table.3.

Thus, the use of inventive latexes makes it possible to obtain films with the same light-shielding effect, but of a smaller thickness than in the case of using the latex analogue.

Example 13. Loading latexes with a mixture of UV absorbers. For loading, mixtures of (5: 1) 2-hydroxy-4-H-octyloxybenzophenone (A) with 2- {2-hydroxy-5-methylphenyl) -6-benzotriazole (B) and with 5-chloro-2- {2 -oxy-5-methyl-3) -tertbutylphenyl) benzotriazole (B).

To a solution of 1.17 g of UV absorber A and 0.23 g of B (C) in 60 ml of a 1: 1 acetone-methanol mixture was added 10 ml of 14% latex, after which the organic solvents were distilled off in vacuo. The resulting colloids are filtered, 10 ml of a 6% aqueous solution of gelatin is added and applied to the same areas of the plates with a yellow image obtained using a yellow CTC.

As a latex analogue, a latex based on a copolymer of (P) butyl acrylate and a Na-salt of acrylamidomethyl propanesulfonic acid, used in Example 14 to load it with a UV absorber, was used. .

A reduced loading of latexes leads to the loss of coagulum UV absorbers, reduces the protective properties of films, and increases the percentage of fading of a color image.

Samples were irradiated with a xenon lamp at 200,000 lux for 48 hours. The test results are shown in Table 4.

As can be seen from the table, the use of the inventive latexes makes it possible to obtain films with the same light-protective effect from the same amounts of ingredients. Thus, the inventive latexes have increased loading, which makes it possible to reduce the thickness of the blue-sensitive layer of color photographic material by 20%, the green-sensitive layer by 35%, and the light-protective layers by 50%, which in turn improves the sharpness characteristics of film photos. Film materials obtained using new latexes in photosensitive layers have a reduced (by 33%) level of the dark veil of color images.

FORMULA AND SECTION

Latexes of copolymers of butyl acrylate and di-M-substituted acrylamide of the formula

; B

 tON- (CH2VSOjNa ICH2) 3OC1DH71

where, R-H. CHz; 98-0.85; , 02- 0.15, having a glass transition temperature of -45-50 ° C, containing water and copolymer particles with a diameter of 0.05-0.2 μm, with the following content of components in latex, wt%: Copolymer of butyl acrylate and di-M-substituted acrylamide 5-15, Water 85-95.

Table 1

table 2

Table 3

Table 4