SU765312A1 - Composition for producing photomaterial polymeric layer - Google Patents

Description

with 0.2 g mol of ethyl alcohol in an environment of dry ether at 10-15 ° C. The precipitated crystals of compound 1a are separated; washed with ether and dried under vacuum to constant weight. Yield 90-95%, m.p. 121-123 ° C. Found: C 35.54; H 6.04; N 10.15; R 11.10, CgHiiOiNjP. Moll. 268. Calculated,%: C 35.82; H 6.34; N 10.45; R 11.57, Compound 1a in an amount of 0.3 g is dissolved in 5 ml of ethyl alcohol and introduced into 100 g of a 6% aqueous solution of PVA with stirring at a temperature of 40-50 0. The mixture is stirred for 30 minutes at The following composition is obtained at the same temperature, parts by weight: PVA6 Tanning agent (compound 1a) 0.3 (5% from in PVA ca.) Ethyl alcohol4 Water94 From a composition of this composition, a measuring layer is poured onto a polyethylene terephthalate substrate, which is dried 35–40 ° C, and then for 30 min. Exposed to temperature 8 (f C. Physical and mechanical properties of polymers A layer based on PVA containing 5% of Compound 1a by weight of PVA is shown in Table 1. APPENDIX 2. Compound 1a in an amount of 0.6 g is dissolved in 5 ml of ethanol and introduced with stirring in 100 g of a 6% aqueous solution of PVA heated to 40-50 ° C. After stirring for 30 minutes, the composition is obtained following the composition of the brush, parts by weight: Tanning agent (compound 1a) 0.6 (10% by weight of PVA) Ethyl alcohol Water Further manufacture of the polymer layer 1FODEALY analogously to example 1. Example 2. Compound 1a in an amount of 0.9 g is dissolved in 7.5 ml of ethanol and the input T with stirring in 100 g of a 6% -note aqueous solution of PVA heated to 40-50 ° C. After stirring for 30 minutes, a composition of the following composition is obtained, parts by weight: Tanning agent (compound 1a) 0.9 (15% by weight of PVA) Ethyl alcohol Water The manufacture of the polymer layer is carried out as in Example 1. The physicomechanical properties of the polymer layer Based on PVA containing 15% of Compound 1a, see Table. 1. P P m e R 4. Ethyl bis- (carbfenoxyamido) phosphate (compound 16 of the general formula 1, where lR C2H5O;) is obtained by reacting 0.1 g-mol of ethyl diisocyanate phosphate with 0.2 g-mol of phenol in medium dry ether or. benzene in the presence of 1-2 drops of triethylamine. The precipitated crystals of compound 1b are separated, washed with a solvent and dried in vacuum to constant weight. Yield 90-95%, T.PL. 116-118 ° C. Found,%: C 52.52; H 4.84; N 8.04; R 8.90. . Mol.v. 364. Calculated,%: C 52.74; H 4.67; N 7.69; R 8.52. Compound 16 in an amount of 0.4 g is dissolved in 7.5 ml of ethanol and introduced into 100 g of a 6% aqueous solution of PVA with stirring at a temperature of 40-50 ° C. After stirring for 30 minutes, a composition of the following composition is obtained, parts by weight: PVS6 Tanning agent (compound 16) 0.4 (6.7% by weight of PVA) Eg-silt alcohol 6 94 Further production of the polymer layer is carried out analogously to example i. The physicomechanical properties of a polymer layer based on PVA containing 6.7% of compound 16 are presented in Table 1. PRIMERE 5. (“-Diethylphosphone - /,) 3-dichdor) -vinyl-bis- (k arbethoxyamido) phosphate (compound 1c of the general formula 1, where R CjHs; K -0-C-PCO -) (OC, Hv) -g) is prepared by the interaction of 0.1 g-mol (α-diethylphosphone- / 3-dichloro ) -viiyl diisocyanate phosphate with 0.2 g-mol of ethyl alcohol in the medium of dry ether at 15-20 ° C. The precipitated crystals are separated, dried under vacuum to constant weight. The product yield 90-95%, So pl. 104-106 ° C. Found,%: C 30.81; H 4.45; N 6.08; R 12.94. CijHjjOgNjPzCb MOL.B. 471. Vitschlenr,%: C 30.57; H 4.67; N 5.94; R 13.16. Compound 1c in an amount of 0.8 g of piacTBO was poured into 7.5 ml of ethyl alcohol and introduced into 100 g of a 6% aqueous solution of PVA heated to 40-45 ° C. After stirring for 30 minutes at the same temperature, a composition of the following composition is obtained, parts by weight: Tanning agent (compound 1c) 0.8 (13.3% by weight of PVA) Ethyl alcohol6 5 Water94 The manufacture of the polymer layer was carried out according to the procedure described in example 1. The physicomechanical properties of a polymer layer based on PVA containing 13.3% of compound 1a are presented) in Table. 1. Example 6. Phenyl-6is- (carboxethoxy-amido -phosfg.t (compound 1t} from the general formula 1, where R I C2H5) is obtained by the interaction of 0.1 g-mol of phenylphosphonic acid diisocyanate with 0.2 g-mol of ethyl in dry ether at 15–20 ° C, the precipitated crystals are separated, washed with ether, and reduced to constant weight in vacuo, 73% yield, mp 138-140 ° C. 8.84. ССН;, Mol.v 3 Calculated,%: N 8.86. Compound 1g in an amount of 0.6 g is dissolved in 5 ml of ethyl alcohol and injected with stirring into 100 g of 5.8% PVA solution heated to 40-50 ° C. After stirring in t For 30 minutes, a composition of the following composition is obtained, parts by weight: PVS5.8 Tanning agent (compound 1g) 0.6 (10.3% by weight of PVA) Ethyl alcohol4 Water94.2 From the composition of this composition, a polymeric terephthalate layer is poured onto the polyethylene terephthalate substrate, which dried at 35-40 ° C, and then exposed to a temperature of 80 ° C for 30 minutes. The physicomechanical properties of the polymer layer containing 10.3% of compound 1g by weight of PVA are presented in Table. 2. An example. Phenyl-bis- (carbphenoxyamido) phosphate (compound 1d of the general formula 1, where R CsH50;) is obtained by reacting 0.1 g-mol of phenyl diisocyan phosphate with 0.2 g-mol of phenol in the medium of dry ether or benzene in the presence of 1- 2 drops of triethylamine. The precipitated crystals 1d are rinsed with solvent and dried in vacuum to constant weight. Exit 86% L. of pl. 129-130 ° C. Found: N: 6.72.C2oH, 7N206P.Mon.B. 412 Calculated,%: 1M 6.79. Compound 1d in an amount of 0.8 g is dissolved in 7.5 ml of ethyl alcohol and introduced into 100 g of a 6.2% aqueous solution of PVA, heated to 40-45 ° C. After stirring for 30 minutes at the same temperature, a composition of the following composition is obtained, parts by weight: PVS6.2 Tanning agent (compound 1d) 0.8 (12.9% by weight of PVA) Ethyl alcohol6 Water .93.8. The manufacture of the polymer layer is carried out according to the procedure described in Example 6. The physicomechanical properties of the polymer layer based on PVA, containing 12.9% of compound 1d by weight of PVA, are presented in Table. 2. PRI mme R 8. Methyl-bis- (carbethoxyamido) phosphonate (compound 1e of the general formula 1, where,) is obtained by reacting 0.1 g-mol of methylphosphonic acid diisocyanate with 0.2 g-mol of ethyl alcohol in the medium of dry ether at 10-15C. The precipitated crystals are separated and dried under vacuum to constant weight. Yield 99%, T.Sh1. 96-98 ° C. Found,%: Р 13,10.С, а, 5М2О $ R.Mol.v.238 Calculated,%: Р 13.04. Compound 1e in an amount of 0.4 g is dissolved in 7.5 ml of ethyl alcohol and introduced into 100 g of a 6% aqueous solution of PVA with stirring and at a temperature of 40-50 ° C. After stirring for 30 minutes, a composition of the following composition is obtained, parts by weight: PVS6 Tanning agent (compound 1e) 0.4 (6.7 by weight of PVA) Ethyl alcohol 6 Water94. From the composition of this composition, a polyethylene terephthalate base is poured on a polymeric II layer, which is dried at 35–40 ° C, and then exposed to a temperature of 90 ° C for 30 minutes. The physicomechanical properties of a polymeric layer based on PVA containing 6.7 % of compound 1e by weight of PVA are presented in Table. 2. Example 9: Methyl bis (carbofenoxy amido) phosphonate (compound 1g from general formula 1, where R CH 3, R CeHs) is obtained by reacting 0.1 gmol methylphosphonic acid diisocyanate with 0.2 g -mole phenol in the medium of dry ether in the presence of 1-2 drops of triethylamine. The precipitated crystals are separated and dried in vacuo to constant weight. Yield 90%, TP. 145-146 ° C. Found,%: P 9.31, CisHjjNaOsP. Mol.v.334. Calculated,%: P 9.26. Compound 1g in an amount of 0.9 g is dissolved in 7.5 ml of ethyl alcohol and introduced with stirring in 100 g of a 6% aqueous solution of PVA heated to 40-50 ° C. After stirring for 30 minutes, a composition of the composition is obtained, parts by weight: PVA6 Tanning agent (compound 1g) 0.9 (15% by weight of PVA) Ethyl alcohol6 Water94 Manufacturing nonHMqjHoro layer is carried out in Example 8. Physical and mechanical properties of the polymer layer Based on PVA containing b5% of Compound 1g, see Table 2, Example 10. A phenyl-burg (carbztoxiamide) phosphonate (Compound 1c of the general formula 1, where R CgHs. and CjHj) is obtained by the interaction 0.03 g-mol diisocyanta of phenylphosphonic acid with 0.066 g-mol of ethyl alcohol in a dry ether environment. The precipitated crystals are washed with a pact bolt and dried in vacuum to a constant weight,. Yield 76%, Tll. 137-139 ° C. Found,%: C 47.98; H 5.96; N 9.15; R 10.02. CiaHiTNaOgP. Mol.v.300. Calculated,%: C 48.00; H 5.67;,. N, 9.55; R 10.33. X, Compound 1z in an amount of 0.8 g was dissolved in 7.5 ml of ethyl alcohol and introduced into 100 g of a 6.0% PY aqueous solution heated to 40-45 ° C. After stirring for 30 minutes at the same temperature, a composition of the following composition is obtained, parts by weight: PVS6R Tanning agent 1: 0.8 (13.3% by weight of PVA) Ethyl alcohol 6 Water 94.0. 8 The manufacture of the polymer layer was carried out according to the procedure given in example 8. Physical and mechanical properties of the polymer {PVO based on PVA, containing 13.3 compounds 1h from the weight of PVA, are presented in Table 2. As can be seen from Table 1, PVA-based polymer layers made from the proposed compositions containing compounds of general formula I as a tanning agent have significantly less on: reabilitability in water and alkali aqueous solutions (1, 5j5 times) and higher temperature melting (by 3-10 ° С) compared to a polymer layer without a tanning agent and a polymer layer containing: our famous tanning agent is a mixture of formaldehyde and urea (a polymer layer based on PVA without a tanning agent and a layer containing a mixture of formaldehyde and urea as a tanning agent outcast Lebanon procedure opisanyoy in Example 1). The proposed tanning agents for the polymer layer based on PVA are available compounds and are obtained in high yield by reacting organophosphorus diisocyanates with alcohols or phenols. The manufacture of a polymeric composition based on PVA with the suggestion of tanning agents of formula 1, as well as a polymer layer does not require additional equipment. The tanning process is completed in 30 minutes and does not require long-term storage of the material to achieve the necessary physical and mechanical properties, such as swelling and melting temperature. Table 1

Based on PVA without tanning agent Based on PVA containing a mixture of formaldehyde and urea (US Patent 2481676)

Based on PVA, containing 5 wt.% 1A (example I)

Based on PVA, containing 10 wt.% 1A (example 2)

Based on PVA, containing 15 wt.% 1a (Example 3)

Based on PVA, containing 6.7 wt.% 16 (example 4)

Based on PVA, containing 13A wt.% 1c (example 5)

322

35

53

233

58

125

66

60

64

62

55

17

58

Claims (1)

110 claims Composition for producing a polymer layer of photographic materials, consisting of polyvinyl alcohol, tanning agent and water, characterized in that, in order to improve the physicomechanical properties of the polymer layer, it contains, as a tanning agent, a compound of the formula - P (IN-SOOH ) ,, where R is alkyl, aryl, hydroxyalkyl, hydroxyaryl or a radical of the general formula -OC-PtOXOROo Table 2 25 30 35 where alkyl; R-alkyl or aryl, and as their solvent ethyl alcohol in the following ratio of components, parts by weight: Polyvinyl alcohol5.8-6.2 Dubitel0.3-0.9 Ethyl alcohol4.0-6.0 Water 94.2- 93.8. Sources of information taken into account in the examination 1. US patent N 2481676, class 96-111, publ. 1949.