WO2000060964A1

WO2000060964A1 - Flame retardant technical textiles with high visibility features

Info

Publication number: WO2000060964A1
Application number: PCT/FR2000/000941
Authority: WO
Inventors: Pierre Baleix
Original assignee: Conseil Investissement Management Engineering
Priority date: 1999-04-12
Filing date: 2000-04-12
Publication date: 2000-10-19
Also published as: AU3972700A; FR2792011A1; FR2792011B1; EP1176883A1

Abstract

The invention relates to method for providing a fabric with long-lasting highly visible colours or intense shades of white, comprising a specific preparation consisting of two stages wherein one stage involves the re-washing of the initial unbleached colours. The inventive method provides intense, long-lasting and varied colours (yellow, orange, red, fuchsia, bright green). The invention can be used for protective clothing.

Description

"NON-FIRE" TECHNICAL TEXTILES HAVING "HIGH VISIBILITY" CHARACTERISTICS

Technical area

The present invention relates to the technical sector of fabrics or other textiles or other similar supports, based on or comprising fibers or textiles called "technical" "fireproof", and / or capable of protecting against chemical, thermal, biological attack , biochemical, bacteriological, viral and similar aggressions.

More particularly, the invention relates to such fabrics treated so as to exhibit certain coloristic properties such as "whiteness" or "high visibility".

The invention relates to these fabrics, supports, etc., having the properties indicated either "pure" or as a mixture with other textile fibers.

The invention also relates to the process for manufacturing such fabrics, textiles, similar supports (hereinafter "textiles" together and separately), as well as their uses for the protection (in particular, but not limited to) of human beings against assaults mentioned above.

Finally, the invention relates to clothing, coveralls, sets and protective systems consisting of, or comprising, at least one such textile.

The invention relates to all natural and / or synthetic fibers, optionally comprising reinforcements (carbon fibers, metallic fibers, etc.) or fibers providing additional properties (polyamides).

Prior Art

In risky activities, such as the petroleum, oil services, chemicals, nuclear, civil security such as firefighters, airport security and similar activities like public works, etc. which are well known, attempts have been made to develop protective clothing, in particular for human beings, and in particular "fire-resistant" textiles.

Textiles or protective materials can be classified into several categories.

Leather is generally black or dark brown in color, therefore not very visible in an environment of smoke, fog, vapor and the like. It is heavier and bothers and tires the user. It has low resistance to fire, thermal effects (heat shrinkage), and chemical attack. Its maintenance is difficult and its durability is limited.

Fireproof fabrics. 100% cotton or polyester (PE) / cotton blend. Their fire resistance is limited, and decreases over time and washes. Their dimensional stability is average, as well as their resistance to tearing. If they use fluorescent cotton, it exhibits low resistance to light over time. Their resistance to chemical aggressions is low, in particular to acids, and their low durability requires the use of heavy weight textiles.

Modified acrylic fabrics / cotton with fireproofing treatment. Their dimensional stability is limited, their resistance to chemical attack, in particular to acids, is low, their resistance to tearing is medium and to date we can only give them a single visibility color (fluorescent yellow).

Polvamide-lmide / viscose fabrics with fireproofing treatment. Their dimensional stability is limited, they have a low resistance to chemical attack, in particular to acids, which further decreases over time, and their resistance to tearing is medium.

It is often, if not always desirable, and even vital, that the protection, rescue or civil security teams be very visible, this to ensure their own security and the coordination of their efforts.

However, we have seen that the protective materials were very ineffective in terms of "high visibility". The industry has therefore produced fluorescent strips to compensate for this deficiency, but these products generally lack "fire-resistant" characteristics and also have a low resistance. They are therefore only palliatives, certainly very useful but which do not provide an overall solution to the problem of "fire-resistant" materials, and / or resistant to other types of attack, and which must be "highly visible". Furthermore, it was not known in the prior art to apply dye mixtures HV (high visibility) or BL (white) on aramid fibers.

Patent FR 96 08 908 describes a textile combining yarns of different materials knitted in two superimposed layers. The textile has two layers, one of threads of synthetic fibers forming the outer surface, and the other of threads of natural fibers forming the inner surface. The two layers are connected by a connecting wire. Synthetic threads can be dyed in "fluorescent" colors. It is a textile whose texture is not adapted to the problem of the invention. The colors obtained are not comparable in strength, durability or intensity to those obtained according to the invention.

Patent EP 0 573 772 describes a "non-woven" type product comprising thermoplastic fibers (fuses) and a fluorescent layer comprising a fluorescent pigment. The pigment is combined with a resin to obtain a maximum concentration of fluorescent pigment in the vicinity of the external face. Retroreflective patterns are deposited by transfer, then the layers are bonded and the film is removed from the transfer.

Patent EP 0 171 900 describes thermally stable reflective strips, intended to be positioned on a flame retardant garment. The fluorescent coating is combined with retroreflective means. The fluorescent coating can be red or bright yellow. This document therefore teaches a known protective textile (NOMEX ™, Acrylic / cotton, glass fibers, ceramic fibers, etc.) on which a fluorescent thermoplastic layer is deposited then retroreflective thermoplastic strips.

To date, therefore, there is no material resistant by nature to fire, heat (high temperature thermal radiation) and / or other types of attack, which can be treated in "high visibility" and having properties of mechanical and chemical resistance, in particular. In particular, there is no material of this type to date. can include or incorporate several fluorescent colors of "high visibility", allowing to improve both protection and security by "high visibility" of the user. Furthermore, to date there is no process allowing intensive coloring of protective materials with dyes or safety pigments, we do not know to date that lightly dye or pigment these materials, with resistance to limited light.

General description of the invention

The invention provides for the first time a material combining excellent "fire-proof", chemical, mechanical, etc. protection characteristics and "high visibility" characteristics never achieved, all without using palliatives or simple associations of properties as does the prior art.

In addition, the invention provides for the first time a material combining the same protection characteristics as above with a "white" color essential in hospital or nuclear or chemical environment. More specifically, the invention provides a method for incorporating intense safety colors in protective materials.

Finally, these HV or BL properties are durable for the first time. The materials obtained comply in particular with standard EN 471 and the standard OEKOTEX. As will be seen below, the invention applies to known protective materials as well as to any material based on a mixture of synthetic and natural fibers, intrinsically endowed with "fire-retardant" or not properties, including those with base or comprising glass veils (which can replace asbestos), and in general to any flat structure of fabric, textile, non-woven, "mat" type of fibers, and the like, and in particular materials based on aramid fibers (including such fibers).

As will also be seen below, the materials according to the invention also exhibit a remarkable set of properties such as resistance to washing and to multiple washing (resistance to washing), resistance to abrasion or wear, resistance to light, and resistance to pilling ("pilling"), which gives great durability to the "high visibility" properties.

Detailed description of the invention

The invention applies to warp and weft fabrics or to other textile materials (such as certain knitted fabrics, veils, nonwovens, needles, composites) which are made up or not of fire-retardant fibers by nature. Mention will be made, by way of nonlimiting examples, of aramid fibers (meta-aramids or para-aramids in pure or mixed form) such as NOMEX (TM), NOMEX-DELTA / A (TM), NOMEX-DELTA / C (TM) and the like, or NOMEX (TM) -VISCOSE, NOMEX (TM) -KEVLAR (TM) textiles and the like.

These fibers will be transformed into unbleached threads and fabrics (raw weaving output) weighing around 100 to 400 g / m2 and produced in different weaves corresponding to the desired weight for the end use.

The invention allows the use of a varied choice of HV colors such as Yellow Orange Red or Fuschia or Bright Green with very intense tones with high luminescence and lasting.

The invention also makes it possible to obtain a deep and lasting "white" color, much superior to the natural white color, in particular compared to a NOMEX (TM) textile which has not been subjected to the process according to the invention.

This property relating to the "white" color is particularly surprising and interesting.

Treatment process according to the invention from unbleached fabrics or materials

The present invention relates generally to a process for imparting intense HV or BL colors to textiles, in particular "protective" fabrics, characterized in that it comprises a specific preparation in two stages, one of which is rewashing fabrics or materials ecru of departure, the second aiming to eliminate all the residues coming from one or more preceding stages.

Preferably, the treatment sequence consists of:

- classic washing step with detergent, on unbleached fabrics or materials;

- classic bleaching step;

- rewashing or "second preparation" step according to the invention;

- drying;

- Conventionally applying the dye mixture either fluorescent (H V) or titanium oxide Tiθ2 (BL) with a vinyl or acrylic resin or polyurethane and a fluorinated resin and a polymerization catalyst known to those skilled in the art. Preferably: - washing step at 60 ° C

- bleaching of pure aramid tissue or aramid + cellulosic mixture concentration:

- in fluorescent dye mixture (H V): 15 to 20%

- in titanium oxide: 15 to 20% - in vinyl or acrylic resin or polyurethane: 5 to 10%. Preferably:

- removal weight: 20 to 30 g / m2.

Preferably: - last polymerization step at 170-180 ° C, preferably for 30 to 40 s.

Dyes and fluorescent dye mixtures, of all colors, are known to those skilled in the art, although certain colors have never been used in the prior art. Titanium oxide is also known. Those skilled in the art will understand the general scope of the rewashing or "second preparation" treatment and adapt it to different materials, textiles, fabrics, sails, nonwovens, etc. mentioned above, as well as other usual dyes and additives not mentioned.

Without wishing to be bound by a theory, the Applicant considers that the rewashing step or "second preparation" improves the compatibility between the fabric and the HV or BL dye mixtures by eliminating the residues which, it seems, harm this compatibility and have led to the defects and limitations of the prior art.

A person skilled in the art will also be able to envisage applying the general method according to the invention to any textile, including outside "safety" applications, to give the fabric special or more intense and / or more durable colors than those obtained. according to the prior art.

It will be noted that one of the important advantages of the invention is to provide safety clothing which is at the same time effective, durable and comfortable because it is very light.

Test results

Abrasion, heat transmission after flame exposure, flame exposure, "pilling", light fastness, wash fastness, fastness tests were performed. friction and dimensional stability.

The test standards and the results obtained are collated in the table below. The values presented in the Table are averages. The conditions of the tests and the colors are specified in the "Notes": general notes

Suite 1: color HV

Suite 2: BL color test.

BOARD

Weight 300 g / m2 Color: high visibility HV white BL

TABLE (Suite 1)

Other primary indices:

(1) x = 0.4021; y = 0.4971

(2) x = 0.5711; y = 0.3399

(3) x = 0.5387; y = 0.3751

TABLE (Suite 2)

NOTES

(1) Number of cycles until failure. The standard requires a minimum of 40,000.

(2) The standard requires a minimum level B1, i.e. HTI24> 3s and <6s (HTI = Heat Transmission)

(3) The standard requires that no flame develop on the top or side of the sample, that no holes be formed, and that no molten or ignited debris is formed.

(4) This test uses a "pilling box" and covers 3600 revolutions over 10 hours. The scale of results is as follows:

1 Important

2 Significant

3 Moderate

4 Light

5 Draw

(5) NOMEX (TM) III - HV Yellow. 81 hour test.

(6) Fastness to washing at 60 ° C.

The standard requires a result> 3.

(7) The standard requires a result> 4.

(8) 25 washes 60 ° C ± 3 ° C Detergent 1 g / l 1 drying. NOTES (continued) (1)

(1) Martindale test conditions Temp. 20 ± 3 ° C

Relative humidity RH = 65 ± 5% Applied pressure 12 k.Pa Basic textile used: NOMEX (TM) III. Medium on HV Yellow or HV Red dyes

(2) Pretreatment according to EN 531 Average results on NOMEX (TM) III HV yellow textiles 302 g / m2 and NOMEX (TM) III HV red 310 g / m2 for a protective fabric in industry according to EN standard 531.

(3) Pretreatment according to EN 531 NOMEX (TM) III HV yellow or red standard.

(4) NOMEX (TM) NI HV yellow or red Number of washes: 5/60 ° C ± 3 ° C Number of dryings: 1 / drum.

NOTES (continued) (2)

(1) Color BL Tests on NOMEX (TM) III

20 ° C ± 3 ° C HR 65 ± 5% Applied pressure 12 k.Pa

(2) Color BL

No white NOMEX (TM) III pretreatment Weight 258 g / m2.

(3) Color BL - 1 layer structure

Pretreatment (according to standard EN 531).

(4) Color BL

NOMEX (TM) III 5 washes / 60 ± 3 ° C

1 drying (drum).

(6) NOMEX (TM) HV red

The color "spots" and the change in color are determined.

(7) NOMEX (TM) HV red.

NOTES (continued) (3)

(1) Test on NOMEX (TM) III HV red Temp. 20 ± 3 ° C H.R. 65 ± 5%

Applied pressure 12 k.Pa

(2) Test on NOMEX (TM) III HV orange Weight 222 g / m2 No pretreatment according to EN 531.

(3) Test on NOMEX (TM) III HV orange Pretreatment according to EN 531 standard Construction (number of layers): 1.

(4) Test on NOMEX (TM) III HV orange 5 washes / 60 ± 3 ° C 1 drying / (drum).

(1) 'like (1) on HV fuschia or green

(3) 'like (3) on HV fuschia or green

(4 ') like (4) on HV fuschia or green

(2) "like (2) on green HV.

The results presented in the TABLE indicated a remarkable set of properties, and in particular

- good light fastness, which passes the European standard EN 471 even for at least five high visibility colors. - excellent light fastness for the "white" color which is very unexpected on this application.

- very satisfactory washing performance at 60 ° C, allowing great durability of the product.

- for comfort (lightness and ease) remarkable and unknown to this day. We can thus make light fluorescent shirts or jackets. The present invention therefore makes it possible to produce materials, in particular of the textile or similar type, which provide users of clothing or protective systems with a very great improvement in their safety in dangerous operations. Indeed, the invention allows for the first time the incorporation of HV or BL colors in materials having a remarkable set of mechanical properties, resistances etc., the colors being intense and being able to be varied, the whole being resistant to wear and washing, and in the light, and therefore of lasting effectiveness. The invention finds obvious applications in all present or future fields of operations in dangerous, contaminated, smoky areas, etc., in particular:

- petroleum and parapetroleum industry (refineries, offshore or "off-shore" platforms, distribution) - nuclear industry (BL or HV)

- chemical industry (with anti-acid treatment)

- naval industry (ships, shipyards, rescue or towing at sea)

- space and aeronautical industry, and in general all high-tech industries (electronics, ...) (clean rooms)

- security of airports, motorways, rail links, transport of dangerous goods

- civil protection (corps of firefighters, police, gendarmerie, armies, customs) - hospitals, medical, paramedical emergency services, pharmaceutical laboratories (in particular BL)

- chemical industry in general, or biochemical

- safety of racing circuits, rallies, or similar events, and Formula 1 or Rally racing drivers - incorporation or association with other safety elements such as safety shoes for industry, sportswear, marking ski slopes or the like, vehicle safety marking

- equipment or systems comprising delicate materials, for example in robotics: • protection against dust and other contamination (in particular mixtures of NOMEX (TM) fibers or the like with carbon fibers and a polyamide (added anti-static functions) in particular NOMEX (TM) DELAT-A • protection of these materials against fire , thermal radiation, and the like

• the whole being associated according to the invention with signaling of these materials for obtaining intense integrated HV colors and colors which can be varied. A starting material like NOMEX (TM) DELTA-C with fine fibers brings even better comfort and better ease (because it is much lighter), this comfort is also very noticeable with the other NOMEX (TM) III and NOMEX products ( TM) DELAT-A.

Claims

1. - Process for giving a fabric, or textile, or nonwoven (glass veil, fiber mat) or similar material, "high" colors

5 visibility "(HV) or white (BL) characterized in that it includes a rewashing step or" second preparation "with a detergent, after the first washing step.

2. - Method according to claim 1 characterized in that the o sequence of steps is as follows:

- classic washing step with detergent

- classic bleaching step

- rewashing step or "second preparation" with a detergent

- drying - application of the fluorescent dye (HV) or titanium oxide (BL) mixture with a vinyl or acrylic or polyurethane resin and a polymerization catalyst.

3. - Method according to claim 1 or 2 characterized in that it comprises a final step of polymerization at 170 - 180 ° C and for 30 to 40 s.

4. - Method according to any one of claims 1 to 3 characterized in that the starting product is a textile, fabric, non-woven and the like, in the unbleached state.

5. - Method according to any one of claims 1 to 4 characterized in that:

- the washing step is carried out at 60 ° C - the concentration of HV or BL dye mixture is 15 to 20%

- the concentration of resin (s) is 5 to 10%.

6. - Method according to any one of claims 1 to 5 characterized in that the starting material has qualities of safety fabric

- "not fire" and / or - chemical resistance, in particular to acids and / or

- resistance to certain bacteriological or viral or biochemical agents and / or

- resistance to thermal radiation.

7. - Fabrics, textiles, nonwovens, fiber mats, glass veils and the like, characterized in that they have been treated according to a process according to any one of claims 1 to 6.

8. - Fabrics, textiles, nonwovens, fiber mats, glass veils and the like according to claim 7, characterized in that they have colors:

- "high visibility" HV

• fluorescent,. including red (Y = 35), orange (Y = 47), yellow (Y = 78)

. or fuschia, bright green

- intense and long-lasting "white" BL.

9. - Garments characterized in that they consist of, or comprise, a fabric, textile, nonwoven, fiber mat, glass veil or the like, according to claim 7 or 8.

10. - Garments according to claim 9, characterized in that they are based on safety textiles as described in claim 6.

11. - Protection systems for delicate materials, characterized in that they consist of, or comprise, a fabric, textile, nonwoven, fiber mat, glass veil or the like, according to claim 7 or 8.

12. - Method according to any one of claims 1 to 6, fabrics, textiles, nonwovens, fiber mats, glass veils and the like, according to claim 7 or 8, clothing according to claim 10, or protection systems according to claim 11, characterized in that that the base material is, or comprises, based on aramid fibers, NOMEX (TM), in particular NOMEX (TM) III or NOMEX (TM) DELTA-A with carbon fibers and polyamide or NOMEX (TM) DELTA -Confine fine fibers.

13. - Applications of the subjects of claims 1 to 12 in all areas of security such as:

- petroleum / parapetroleum industry

- chemical industry - civil security

- medical, paramedical, hospital, emergency services, laboratories (BL)

- security of airports, equipment and markup of sports equipment, ships, incorporation into other security elements.