Biocidal textile support

Abstract

The biocidal textile support includes bronopol in the dry state present on the surface of the support and having a contact biocidal action, the bronopol being linked to the support by a photo-crosslinkable or photo-polymerizable binder, and its use as an element of a device for protecting against biological risks. A biocidal suit or garment and a mask, preferably antibacterial or antiviral, including such a biocidal support, are also described.

Claims

1. A biocidal textile support consisting of: a textile support selected from the group consisting of a woven, a knit, a non-woven, a rope and a braid; bronopol; and a photo-crosslinked or photo-polymerized binder; wherein bronopol is present in the dry condition at the surface of the support and having a biocidal contact action, wherein bronopol is bound to the support with a photo-crosslinked or photo-polymerized binder.

2. The biocidal support according to claim 1, wherein bronopol is present on the support in an amount from 0.01 to 50 g per m.sup.2 of support.

3. The biocidal support according to claim 1, wherein bronopol in the dry condition is present inside the support and has a biocidal contact action.

4. The biocidal support according to claim 3, wherein bronopol is present inside the support in a mass ratio (bronopol/support) ranging from 1/5,000 to 1.

5. The biocidal support according to claim 1, wherein the binder comprises a material selected from the group consisting of vinyl compound, acrylic compound, polyurethane compound, amine and silicon material, wherein said material is photo-crosslinked or photo-polymerized.

6. The biocidal support according to claim 5, wherein the binder comprises a material selected from the group consisting of aliphatic acrylate, heteroaliphatic acrylate, urethane acrylate and ether acrylate, wherein said material is photo-crosslinked or photo-polymerized.

7. The biocidal support according to claim 5, wherein the binder comprises a material selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate and dipropylene glycol diacrylate, wherein said material is photo-crosslinkable or photo-polymerizable.

8. The biocidal support according to claim 1, wherein bronopol is impregnated or sprayed or applied with a printing paste on or in the support.

9. Biocidal clothing or suit or mask or personal protective equipment, comprising a support according to claim 1.

10. A method for manufacturing a biocidal textile support according to claim 1 comprising the following steps: i) either soaking the support in a bath comprising a composition comprising bronopol and a binder or mixture of binders; ii) or spraying the support with a composition comprising bronopol and a binder or mixture of binders; iii) or printing the support with a composition comprising bronopol and a binder or a mixture of binders iv) optionally padding the support from the preceding step; v) drying the support from the preceding step; vi) photo-polymerizing or photo-crosslinking of the support-dried composition complex.

11. The method according to claim 10, wherein the photo-crosslinkable or photo-polymerizable binder is activated by ionizing radiations of the gamma type, X-rays or ultraviolet rays.

12. The method according to claim 11, wherein the photo-crosslinkable or photo-polymerizable binder is activated by ultraviolet radiations in the presence of a photo-initiator.

13. The method according to claim 10, wherein the binder comprises a material selected from the group consisting of vinyl compound, acrylic compound, polyurethane compound, amine and silicone material, wherein said material is photo-crosslinkable or photo-polymerizable.

14. The method according to claim 13, wherein the binder comprises a material selected from the group consisting of aliphatic acrylate, urethane acrylate and ether acrylate, which material is photo-crosslinkable or photo-polymerizable.

15. The method according to claim 14, wherein the binder comprises a material selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate, and dipropylene glycol diacrylate, wherein said material is photo-crosslinkable or photo-polymerizable.

Description

EXAMPLE 1

(1) A textile support of the fabric type is impregnated by padding with a solution for the mass composition is the following:

(2) TABLE-US-00001 1/10 diluted bronopol: .sup.5 g Ultraphil TG: 0.5 g Invadine PBN 0.5 g Water: 94 g

(3) The textile support is then dried at 160 C. for 3 minutes.

(4) The bactericidal activity of the thereby treated textile was evaluated against Bacillus cereus, according to the indications of the JIS Z 2801:2000 standard.

(5) Experimental Conditions: reference strain: Bacillus cereus CIP 105151 preparation of the textile support: the support is sterilely cut out into portions of 4 cm4 cm. Control support: Petri dish. The supports are inoculated with 400 l of a bacterial suspension so as to obtain about 10.sup.5 CFU/support, and left as such during incubation (24 h). Solutions: the bacterial suspensions were prepared with the Nutrient Broth solution diluted to 1/250. The recovery solution is the SCDLP solution recommended by the standard. The subsequent dilutions were carried out in PBS (Sigma). Media: gelose trypcase soja (Biomrieux)
Deposit on the supports: 0.84.10.sup.5 CFUs
The contact time is 24 hours.
Results:

(6) TABLE-US-00002 Tested sample CFU Control at T0 Petri dish 1.03 .Math. 10.sup.5 Control at T24 h Petri dish 1.93 .Math. 10.sup.4 Test at T24 h Treated fabric <10

EXAMPLE 2

(7) A non-woven textile support is impregnated by padding with a solution for which the mass composition is the following:

(8) TABLE-US-00003 Bronopol: 2.5 g Invadine PBN: 0.5 g Water: 197 g

(9) The non-woven is then dried at 100 C. for 3 minutes.

(10) The bactericidal activity of the thereby treated textile was evaluated against Staphylococcus aureus, according to the indications of the JIS Z 2801:2000 standard.

(11) Experimental Conditions: reference strain: Staphylococcus aureus ATCC 33591 Preparation of the textile support: the support is sterilely cut out into portions of 4 cm4 cm. Control support: Petri dish. The supports are inoculated with 400 l of a bacterial suspension so as to obtain about 10.sup.5 CFU/support. Solutions: the suspensions were prepared with Nutrient Broth solution diluted to 1/500. The recovery solution is the SCDLP solution recommended by the standard. The subsequent dilutions were carried out in PBS (Gibco). Media: gelose trypcase soja (Biomrieux) Contact time: 24 h
Deposit on the supports: 1.4.10.sup.5 CFU
The contact time is 24 hours.
Results:

(12) TABLE-US-00004 Tested sample CFU Control at T0 Petri dish 1.6 .Math. 10.sup.5 Control at T24 h Petri dish .sup.2 .Math. 10.sup.4 Test at T24 h Treated fabric <10

EXAMPLE 3

(13) A non-woven textile support is impregnated by padding according to the procedure of Example 2.

(14) The bactericidal activity of the thereby treated textile was evaluated against Acinetobacter baumanii, according to the indications JIS Z 2801:2000 standard under the same experimental conditions as described in Example 2.

(15) The reference strain: Acinetobacter baumanii mR

(16) Deposit on the supports: 1.6.10.sup.5 CFU

(17) The contact time is 24 hours.

(18) Results:

(19) TABLE-US-00005 Tested sample CFU Control at T0 Petri dish 1.5 .Math. 10.sup.5 Control at T24 h Petri dish 1.5 .Math. 10.sup.7 Test at T24 h Treated fabric <10

(20) It is observed that the textile treated according to Examples 1, 2 and 3 have bactericidal activity towards the bacterial strains Bacillus cereus, Staphylococcus aureus and Acinetobacter baumanii.

EXAMPLE 4

(21) A non-woven textile support treated according to Example 2 is also subject to an evaluation of its antiviral activity against the H1N1 virus, the Adenovirus type 3 and the Parainfluenza type 3 virus according to the indications of the JIS Z 2801:2000 standard.

(22) Experimental Conditions: Reference viral strain: H1N1 ATCC VR-1520 Reference viral strain: Adenovirus type 3 ATCC VR-847 Reference viral strain: Parainfluenza type 3 ATCC VR-93 Preparation of the textile support a) the support is sterilely cut out into portions of 4 cm4 cm. Control support: a Petri dish in glass. b) Preparation of the viral suspension

(23) The estimation of the number of infectious units, i.e. the viral titre is determined by the SPAERMAN-KRBER method by calculating the negative logarithm of the 50% limited point (log DICT.sub.50).

(24) The titration technique is the one indicated in the NF EN 14476+A1 standard (January 2007).

(25) The titre of the viral suspension is adjusted between 5.0 log DICT.sub.50 and 7.5 log DICT.sub.50 in an EMEM culture medium with 2% SCS (Adenovirus of type 3 and Parainfluenza virus of type 3) and EMEM with 0.125% of BSA (H1N1) from a parent viral suspension according to the recommendations of the JIS Z 2801:2000 standard.

(26) TABLE-US-00006 Parent viral Adjusted viral suspension suspension Viral suspension titre Ig DICT.sub.50 titre Ig DICT.sub.50 H1N1 9.5 7.1 Adenovirus of type 3 9.3 7.3 Parainfluenza virus of type 3 9.4 7.6 c) Putting into contact viruses/supports The supports are inoculated with 400 l of the viral suspension adjusted in the preceding step. The viral suspension is covered with a glass slide, according to the recommendations of the JIS Z 2801:2000 standard.

(27) Test Conditions: contact temperature: 361 C. contact time: 24 hours

(28) Calculation of the reduction logarithm R
R=log DICT.sub.50 Testlog DICT.sub.50 Control 24 hours.

(29) The treatment of the support meets the requirement of the JIS Z 2801:2000 standard if R2 lg.

(30) Results:

(31) TABLE-US-00007 Control log Dict.sub.50 Test log Dict.sub.50 R H1N1 4.6 0.9 3.7 Adenovirus of type 3 6.3 2.5 3.8 Parainfluenza virus of type 3 5.9 3.8 2.1
Conclusion: under the conditions of the test and according to the JIS Z 2801 standard (version of 2000), the tested textile has a virucidal activity (reduction log (R)2 log) towards the H1N1 virus, the Adenovirus of type 3 and the Parainfluenza of type 3 after 24 h of contact at 36 C.1 C.

EXAMPLE 5

(32) A textile is printed with rotary cylinders with a printing paste for which the mass composition is the following:

(33) TABLE-US-00008 Pigment printing paste: 1,000 g Colouring agent: 28 g Bronopol: 20 g Dipropylene glycol diacrylate: 100 g

(34) The textile is then dried and polymerized for 30 seconds at 180 C., and then subject to gamma radiations.

(35) The bactericidal activity of the thereby treated textile was evaluated against Bacillus cereus, according to the indications of the JIS Z 2801:2000 standard.

(36) Experimental Conditions: reference strain: Bacillus cereus CIP 105151 Preparation of the textile support: the support is sterilely cut into portions of 4 cm4 cm. Control support: Petri dish. The supports are inoculated with 400 l of bacterial suspension so as to obtain about 10.sup.5 CFU/support. Solutions: the bacterial suspensions were prepared with the Nutrient Broth solution diluted to 1/250. The recovery solution is the SCDLP solution recommended by the standard. The subsequent dilutions are carried out in PBS (Gibco). Media: gelose trypcase soja (Biomrieux)

(37) Deposit on the supports: 1.11.10.sup.5 CFU The contact time is 24 hours.
Results:

(38) TABLE-US-00009 Tested sample CFU Control at T0 Petri dish 1.3 .Math. 10.sup.5 Control at T24 h Petri dish 7.3 .Math. 10.sup.5 Test at T24 h Treated fabric <10

EXAMPLE 6

(39) A textile support is impregnated with rotary cylinders with a reactive printing paste, for which the mass composition is the following:

(40) TABLE-US-00010 Aqueous neutral printing paste: 800 g Reactive colouring agent: 80 g Bronopol: 20 g Dipropylene glycol diacrylate: 100 g Benzophenone: 10 g.

(41) The textile is dried as one ream at 150 C. for 3 minutes, and then photo-polymerized under a UV insulator, and is then introduced into a vapourizer at 102 C. for 10 min.

(42) The obtained textile is rinsed with clear water, and then washed in boiling water for 3 min and rinsed with warm water.

(43) The washed textile is then dried as a ream at 150 C. for 3 minutes.

(44) The obtained textile is designated as a treated and fixed textile.

(45) A control support of the 100% cotton type is prepared.

(46) The printing paste deposited on the reference textile support has the following mass composition:

(47) TABLE-US-00011 Aqueous neutral printing paste: 800 g Reactive colouring agent: 80 g Bronopol: 20 g.

(48) The control textile is dried as a ream at 150 C. for 3 minutes and is introduced into a vapourizer at 102 C. for 10 minutes.

(49) The obtained textile is rinsed with clear water, and then washed in boiling water for 3 min and rinsed with warm water.

(50) The washed textile is then dried as a ream at 150 C. for 3 minutes.

(51) The obtained control textile is called a treated and non-fixed textile.

(52) The bactericidal activity of the treated and fixed textile, of the treated and non-fixed textile were evaluated against Bacillus cereus, according to the indications of the JIS Z 2801:2000 standard under the same experimental conditions as described in Example 1.

(53) Reference strain: Bacillus cereus CIP 105151

(54) Deposit on the supports: about 10.sup.5 CFU

(55) The contact time is 24 hours

(56) Results:

(57) TABLE-US-00012 Tested sample CFU Test at T24 h Treated and non-fixed textile 1.1 .Math. 10.sup.3 Test at T24 h Treated and fixed textile <10

(58) Conclusion: The treated and fixed textile support has bactericidal activity at T24 h unlike the treated and non-fixed textile support. The bronopol bound by photo-polymerization to the treated and fixed textile support is further present after the washing step on the treated and fixed textile support while the unbound bronopol by photo-polymerization to the treated and non-fixed textile support was leached during the washing step.

EXAMPLE 7

(59) A textile support of the 100% cotton fabric type prepared according to the experimental procedure of Example 6 is subject to gentle washing at 60 C. The thereby obtained textile is called a treated, fixed and washed textile.

(60) A textile support textile of the 100% cotton fabric type prepared according to the experimental procedure of Example 6 is taken as a control textile support. The thereby obtained textile is called a treated and fixed textile.

(61) The bactericidal activity of the treated, fixed and washed textile and of the treated and fixed textile were evaluated against Bacillus cereus, under the indications of the JIS Z 2801:2000 standard under the same experimental conditions as described in Example 1.

(62) Reference strain: Bacillus cereus CIP 105151

(63) Deposit on the supports: 1.11.10.sup.5 CFU

(64) The contact time is 24 hours

(65) Results:

(66) TABLE-US-00013 Tested sample CFU Test at T24 h Treated and fixed textile <10 Test at T24 h Treated, fixed and washed textile <10
Conclusion: The bronopol bound by photo-polymerization to the treated, fixed and washed textile support remains present after gentle washing at 60 C. The treated, fixed and washed textile support retains a bactericidal activity at T24 h similar to that of the treated and fixed control textile support.

EXAMPLE 8

(67) Rapidity of action of bronopol at various concentrations impregnated on various textile supports, against Bacillus cereus

(68) Two textile supports of the polyester/cotton type are impregnated by padding with a solution (1) and a solution (2) respectively.

(69) Six textile supports of the polyester/polyamide type are impregnated by padding with a solution (2), (3), (4) and (5), respectively.

(70) The polyester-cotton textile supports impregnated with the solutions (1) and (2) are respectively called treated polyester/cotton textiles (1) and (2).

(71) The polyester/polyamide textile supports impregnated with the solutions (2), (3), (4) and (5) are respectively called treated polyester/polyamide textiles (2), (3), (4), (4A), (5) and (5A).

(72) The solutions (1), (2), (3), (4) and (5) have the mass composition:

(73) TABLE-US-00014 Solution (1): Solution (2): Bronopol: 1 g Bronopol: 2 g Invadine PBN: 1 g Invadine PBN: 1 g Ultraphil TG: 1 g Ultraphil TG: 1 g Water: 197 g Water: 196 g Solution (3): Solution (4): Bronopol: 3 g Bronopol: 4 g Invadine PBN: 1 g Invadine PBN: 1 g Ultraphil TG: 1 g Ultraphil TG: 1 g Water: 195 g Water: 196 g Solution (5): Bronopol: 10 g Invadine PBN: 1 g Ultraphil TG: 1 g Water: 195 g

(74) The polyester-cotton textile supports were then dried at 160 C. for 2 minutes and the polyester/polyamide textile supports are then dried at 160 C. for 1 minute.

(75) The entrainment rate of the treated polyester/cotton textiles (1) and (2) is 60%.

(76) The entrainment rate of the polyester/cotton textiles is: 126% for the treated polyester/polyamide textile (2), 128% for the treated polyester/polyamide textile (3), 116% for the treated polyester/polyamide textile (4), 127% for the treated polyester/polyamide textile (4A), 116% for the treated polyester/polyamide textile (5).

(77) The bactericidal activity of the treated polyester/cotton textiles (1) and (2) and of the treated polyester/polyamide textiles (2), (3), (4), (4A), (5) and (5A) was evaluated against Bacillus cereus, according to the indications of the JIS Z 2801:2000 standard under the same experimental conditions described in Example 1.

(78) Reference strain: Bacillus cereus CIP 105151

(79) Deposit on the treated polyester/cotton textile supports (1) and (2): 0.64.10.sup.5 CFU

(80) Deposit on the treated polyester/polyamide textile supports (4) and (5): 0.41.10.sup.5 CFU

(81) Deposit on the treated polyester/polyamide textile supports (2), (3), (4A) and (5A): 0.62.10.sup.5 CFU

(82) The contact time is 30 minutes

(83) Results:

(84) TABLE-US-00015 Tested sample CFU Test at T0 Treated polyester/cotton textiles (1) and 0.78 .Math. 10.sup.5 (2) Test at T30 min Treated polyester/cotton textile (1) 10 Test at T30 min Treated polyester/cotton textile (2) <10 Test at T0 Treated polyester/polyamide textiles (4) 0.53 .Math. 10.sup.5 and (5) Test at T30 min Treated polyester/polyamide textile (4) <10 Test at T30 min Treated polyester/polyamide textile (5) <10 Test at T0 Treated polyester/polyamide textiles 0.72 .Math. 10.sup.5 (2), (3), (4A) and (5A) Test at T30 min Treated polyester/polyamide textile (2) <10 Test at T30 min Treated polyester/polyamide textile (3) <10 Test at T30 min Treated polyester/polyamide textile (4A) <10 Test at T30 min Treated polyester/polyamide textile (5A) <10

(85) It is observed that the treated polyester/cotton textiles (1) and (2) and the treated polyester/polyamide textiles (2), (3), (4), (4A), (5) and (5A) have rapid bactericidal activity since in 30 minutes, the bacterial strain Bacillus cereus is destroyed.

(86) It is also observed that regardless of the entrainment rate and of the amount of bronopol impregnated in these fabrics, these fabrics retain an efficient and fast bactericidal activity.