CN108601410B

CN108601410B - Improved thermal protective clothing

Info

Publication number: CN108601410B
Application number: CN201680078859.1A
Authority: CN
Inventors: 黎学东; 张丽艳
Original assignee: DuPont Safety and Construction Inc
Current assignee: DuPont Safety and Construction Inc
Priority date: 2016-01-13
Filing date: 2016-01-13
Publication date: 2021-06-29
Anticipated expiration: 2036-01-13
Also published as: CN108601410A; WO2017120800A1

Abstract

The invention relates to a thermal protective garment comprising, in order from the outside to the inside: (a) an outer shell layer; (b) a moisture barrier; (c) a thermal insulation layer; and (d) a comfort liner; wherein the heat insulating layer (c) is a nonwoven fabric comprising 45 to 95 wt% of an infusible short fiber and 5 to 55 wt% of a heat-fixable short fiber, the heat insulating layer (c) having protrusions and/or depressions formed by hot pressing using a mold or roll having a three-dimensional pattern.

Description

Improved thermal protective clothing

Technical Field

The present invention relates to protective garments having improved thermal protection while being lightweight.

Background

Some occupations require workers to be exposed to high temperatures and flames. To avoid injury during work in such situations, personnel such as firefighters may wear protective clothing made of special fire-resistant materials. The protective garment may be a variety of articles of apparel, including work wear, pants, or jackets. For example, firefighters often wear protective clothing commonly referred to as firefighter turnout gear. Such protective garments typically comprise four layers of material, from the outside to the inside, an outer shell, a moisture barrier, an insulation layer and a comfort liner. The outer shell layer is typically a woven fabric made of flame resistant fibers and serves not only to resist flames, but also to protect the wearer from abrasion. A moisture barrier, which is also fire retardant, is also provided to prevent water infiltration from the fire-fighting environment and to saturate the protective garment. The thermal barrier layer is also flame retardant and provides most of the thermal protection. Typically, the insulation layer is a non-woven layer composed of flame retardant fibers. The comfort liner is a woven fabric, also typically composed of flame retardant fibers.

Such protective garments comprising four layers have sufficient thermal protection, but are relatively heavy. Bulky garments can pose a risk of fatigue and heatstroke to the wearer when the garment is worn in a high temperature environment. In addition, it is common for firefighters to perspire heavily in fighting fires due to the heat of the environment and the effort the firefighter has to perform its duties. This sweat is typically absorbed into the comfort liner and insulation layer to keep the firefighter dry. If a significant amount of perspiration is absorbed into the comfort liner and insulation layer, the weight of the garment, which is already quite heavy, may increase significantly. As mentioned above, this increased weight may lead to heat stress and general fatigue.

Therefore, there is a need to provide protective garments having sufficient thermal protection and materials that are as light as possible.

Summary of The Invention

The invention provides a thermal protective garment, which comprises the following components from the outside to the inside in sequence:

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

the outer shell layer is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, polysulfonamide homopolymer, polysulfonamide copolymer, Polybenzimidazole (PBI), acrylonitrile copolymer, flame retardant viscose, flame retardant cotton or mixtures thereof; the basis weight of the woven fabric is about 150-250g/m²；

The moisture barrier is a film made of Polytetrafluoroethylene (PTFE), Polyurethane (PU) or a mixture thereof; and the film has a thickness of about 10-100 μm and about 20-50g/m²Basis weight of (c);

the thermal insulation layer comprises about 45-95 wt% of non-fusible short fibers and about 5-55 wt% of heat-settable short fiberstap fiber), and said nonwoven having protrusions and/or depressions with a basis weight of about 50-200g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, polysulfonamide homopolymer, polysulfonamide copolymer, polybenzimidazole, acrylonitrile copolymer, flame retardant viscose, flame retardant cotton or mixtures thereof; the comfort pad has a thickness of about 100-²The combined basis weight of (a).

The invention also provides a method for preparing the heat insulation layer of the heat protection suit, which comprises the following steps:

i. providing a substantially flat nonwoven fabric comprising about 45-95 wt% of non-fusible staple fibers and about 5-55 wt% of heat-settable staple fibers;

hot pressing the nonwoven of step (i) at a temperature above the highest glass transition temperature (Tg) of the heat-settable staple fibers using a mold or roll having a three-dimensional pattern at a pressure of about 0.1 to 2MPa for about 0.1 to 5 minutes.

Brief Description of Drawings

FIG. 1A shows a cross-sectional view of one embodiment of the thermal protective garment 100 of the present invention having the following layer structure: (a) an outer shell 11, (b) a moisture barrier 12, (c) an insulating layer 13, and (d) a comfort liner 14, wherein the insulating layer 13 has protrusions 131 that contact the comfort liner 14.

FIG. 1B shows a cross-sectional view of one embodiment of the thermal protective garment 100 of the present invention having the following layer structure: (a) an outer shell 11, (b) a moisture barrier 12, (c) an insulation layer 13, and (d) a comfort liner 14, wherein the insulation layer 13 has a recess 132 in contact with the moisture barrier 12.

Fig. 1C shows a cross-sectional view of one embodiment of the thermal protective garment 100 of the present invention having the following layer structure: a) an outer shell 11, (b) a moisture barrier 12, (c) an insulating layer 13, and (d) a comfort liner 14, wherein the insulating layer 13 has protrusions 131 that contact the comfort liner 14 and recesses 132 that contact the moisture barrier 12.

Fig. 2 a shows a perspective view of the insulating layer 13 in an embodiment of the thermal protective garment of the invention, wherein the protrusions 131 are present on said insulating layer 13 in the form of a spherical cap array.

Fig. 2B shows a perspective view of the insulating layer 13 in one embodiment of the thermal protective garment of the present invention, wherein the protrusions 131 are present on said insulating layer 13 in the form of a spherical cap array and the indentations 132 are present on the insulating layer 13 in the form of a spherical cap array.

Fig. 3 shows a perspective view of the insulating layer 13 in an embodiment of the thermal protective garment of the invention, wherein the recesses 132 are present in the form of a cross-grid array on the insulating layer 13.

Detailed Description

All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference for all purposes as if fully set forth herein, if not otherwise indicated.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated.

As used herein, the term "manufactured" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The transitional phrase "consisting of" excludes any unspecified elements, steps, or components. If in the claims, such phrase would conclude the requirement to contain materials other than those stated, except for impurities normally associated therewith. If the phrase "consisting of" appears in a clause of the subject matter of the claims, rather than immediately following the preamble, it is intended to limit only that stated in that clause; other factors are not excluded from the overall claims.

The transitional phrase "consisting essentially of" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements other than those literally discussed, provided such other materials, steps, features, components, or elements do not materially affect the basic and novel characteristics of the claimed invention. The term "consisting essentially of" is intermediate between "comprising" and "consisting of.

The term "comprising" is intended to include embodiments encompassed by the term "consisting essentially of and" consisting of. Similarly, the term "consisting essentially of is intended to include embodiments encompassed by the term" consisting of.

When an amount, concentration, or other value or parameter is given as either a range, preferred range or an upper range preference value and a lower range preference value, this is to be understood as specifically disclosing any pair of any and all ranges formed from any upper range preference value and any lower range preference value, regardless of whether ranges are separately disclosed. For example, when a range of "1-5" is recited, the range should be interpreted to include the ranges "1-4", "1-3", "1-2", "1-2 and 4-5", "1-3 and 5", and the like. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

When the term "about" is used to describe a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.

Furthermore, unless expressly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or". For example, condition a "or" B satisfies any one of the following: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or now), and both a and B are true (or present).

"mole%" or "mole%" refers to mole percent.

In describing and/or claiming the present invention, the term "homopolymer" refers to a polymer derived from the polymerization of a species of repeating units. For example, the term "poly (p-phenylene terephthalamide) homopolymer" refers to a polymer consisting essentially of one repeat unit of p-phenylene terephthalamide.

As used herein, the term "copolymer" refers to a polymer comprising copolymerized units resulting from the copolymerization of two or more comonomers.

As used herein, the term "fiber" is defined as a relatively flexible, elongate body having a high ratio of length to width of a cross-section perpendicular to the length. The fiber cross-section may be any shape, such as round, flat or rectangular, but is typically round. The fiber cross-section may be solid or hollow, preferably solid. The terms "filament" or "continuous filament" are used interchangeably herein with the term "fiber". A single fiber may be formed from only one filament or multiple filaments. Fibers formed from only one filament are referred to herein as "single-filament" fibers or "monofilsant" fibers, and fibers formed from multiple filaments are referred to herein as "multifilament" fibers.

As used herein, the term "yarn" is defined as a single strand consisting of a plurality of fibers. The diameter of a fiber is generally characterized by a linear density, referred to as "denier" or "dtex"; "denier" is the weight in grams of 9000 meters of fiber and "dtex" is the weight in grams of 10,000 meters of fiber.

The embodiments of the invention as described in the summary of the invention, including any other embodiments described herein, may be combined in any manner, and the description of the variables in the embodiments relates not only to the composite laminate of the invention, but also to the articles made therefrom.

The present invention is described in detail below.

The thermal protective garment 100 of the present invention comprises, in order: (a) an outer shell layer 11, (b) a moisture barrier layer 12, (c) an insulation layer 13, and (d) a comfort liner 14; wherein the insulation layer 13 has protrusions 131 in contact with the comfort liner 14 and/or recesses 132 in contact with the moisture barrier 12, as shown in fig. 1 a, 1B and 1C.

Outer shell layer

In the present invention, the outer shell layer is typically a woven fabric made of flame resistant fibers, not only for flame resistance, but also for protecting the wearer from abrasion.

Woven fabrics used as the outer shell layer may include fibers made from poly (p-phenylene terephthalamide) homopolymers, poly (p-phenylene terephthalamide) copolymers, poly (m-phenylene isophthalamide) homopolymers, poly (m-phenylene isophthalamide) copolymers, polysulfonamide homopolymers, polysulfonamide copolymers, Polybenzimidazole (PBI), acrylonitrile copolymers, flame retardant viscose, flame retardant cotton, or mixtures thereof.

In one embodiment, the outer shell layer is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, or mixtures thereof.

In another embodiment, the outer shell layer is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, PBI, or mixtures thereof.

In yet another embodiment, the outer shell layer is a woven fabric comprising fibers made of flame retardant cotton.

Poly (p-phenylene terephthalamide) homopolymer is obtained from the equimolar polymerization of p-phenylene diamine (PPD) and terephthaloyl chloride (TCl). Also, poly (p-phenylene terephthalamide) copolymers are obtained by incorporating up to 10 mole percent of other diamines into the p-phenylene diamine and up to 10 mole percent of other diacid chlorides into the terephthaloyl chloride, provided that the other diamines and diacid chlorides have no reactive groups that interfere with the polymerization reaction. Examples of diamines other than p-phenylenediamine include, but are not limited to, m-phenylenediamine or 3,4 '-diaminodiphenyl ether (3,4' -DAPE). Examples of diacid chlorides other than terephthaloyl chloride include, but are not limited to, isophthaloyl chloride, 2, 6-naphthaloyl chloride, chloroterephthaloyl chloride, or dichloroterephthaloyl chloride.

As used herein, the term "para-aramid" refers to poly (p-phenylene terephthalamide) homopolymers and copolymers.

Poly (metaphenylene isophthalamide) homopolymer was obtained by equimolar polymerization of metaphenylene diamine and isophthaloyl chloride. Also, poly (m-phenylene isophthalamide) copolymers are obtained by incorporating up to 10 mole percent of other diamines into the m-phenylene diamine and up to 10 mole percent of other diacid chlorides into the isophthaloyl chloride, provided that the other diamines and diacid chlorides have no reactive groups which interfere with the polymerization reaction. Examples of diamines other than m-phenylenediamine include, but are not limited to, p-phenylenediamine or 3,4' -diaminodiphenyl ether. Examples of diacid chlorides other than isophthaloyl chloride include, but are not limited to, terephthaloyl chloride, 2, 6-naphthaloyl chloride, chloroterephthaloyl chloride, or dichloroterephthaloyl chloride.

As used herein, the term "meta-aramid" refers to poly (metaphenylene isophthalamide) homopolymers and copolymers.

Polysulfonamide homopolymers can be obtained from the equimolar polymerization of a diamine such as 4,4 '-diaminodiphenyl sulfone (p-DDS) or 3,3' -diaminodiphenyl sulfone (m-DDS) and a diacid chloride such as terephthaloyl chloride or isophthaloyl chloride.

Polysulfonamide copolymers include, for example, copolymers derived from diamines such as p-DDS and mixtures of terephthaloyl chloride with other diacid chlorides such as isophthaloyl chloride; and copolymers derived from diacid chlorides such as terephthaloyl chloride and mixtures of diamines such as p-DDS, m-DDS, and up to 10 mole percent of other diamines such as p-phenylenediamine or m-phenylenediamine.

Preferably, the polysulfonamide copolymers are prepared from p-DDS, m-DDS and terephthaloyl chloride in a molar ratio of 3:1: 4.

As used herein, the term "PSA" refers to polysulfonamide homopolymers and copolymers.

Polybenzimidazole (PBI) is a polymer containing benzimidazole moieties. The most common mode of PBI synthesis is the direct condensation of bis-ortho-diamines (i.e. tetraamines) and dicarboxylic acids or their acid derivatives.

As used herein, the term "acrylonitrile copolymer" refers to "modified polyacrylonitrile" containing from 35 to 85 weight percent acrylonitrile units; "modified polyacrylonitrile" is synonymous with "modified polyacrylonitrile (modacrylic)". The modified polyacrylonitrile polymer is an acrylonitrile copolymer obtained by polymerizing acrylonitrile with other materials such as vinyl chloride, vinylidene chloride or vinyl bromide. For example, poly (acrylonitrile-co-vinyl chloride) is a copolymer between acrylonitrile and vinyl chloride. Although modacrylic fiber burns when exposed directly to a flame, it does not melt or drip and self-extinguishes when the flame is removed.

The flame-retardant viscose or cotton is obtained by incorporating a flame retardant, such as a nitrogen-containing flame retardant or a phosphorus flame retardant, into viscose or cotton fibers by mixing, coating or grafting. The flame retardancy of these flame retardant fibers is due primarily to the char-forming nature thereof, which prevents combustion of the materials made therefrom.

The above-mentioned polymer or copolymer can be spun into a fiber by solution spinning using a solution of the polymer or copolymer in a polymerization solvent or other solvent for the polymer or copolymer. Fiber spinning can be accomplished by dry spinning, wet spinning, or dry-jet wet spinning (also known as air-gap spinning) through a multi-orifice spinneret to form a multifilament fiber, as is known in the art. The spun multifilament fibers can then be treated as desired using conventional techniques to neutralize, wash, dry or heat treat the fibers to produce stable and useful fibers. Exemplary dry, wet and dry jet wet spinning processes are disclosed in U.S. patent nos.3,063,966; 3,227,793, respectively; 3,287,324; 3,414,645, respectively; 3,869,430; 3,869,429; 3,767,756 and 5,667,743. Methods of making aromatic polyamide fibers are disclosed in U.S. patent nos.4,172,938, 3,869,429, 3,819,587, 3,673,143, 3,354,127 and 3,094,511. Chinese patent publication No. 1389604a discloses a specific method of making PSA fibers or copolymers containing sulfone amine monomers. Fibers made of flame retardant viscose or cotton can be made by solution spinning; the flame retardant chemicals are injected before spinning or are treated on the surface of the viscose or cotton fibers.

Aramid fibers are commercially available, for example from Teijin (Japan)

And

of Unitika

Of DuPont

And

of Akzo

Of Kolon Industries, Inc (Korea)

SVM of Russian Kamensk Volokno JSC^TMAnd RUSAR^TMARMOS of Russian JSC Chim Volokno^TMAnd the like. The PSA fiber may be TANLON available from Shanghai Tianlong fiber Limited company (China)^TMAre commercially available. However, the aramid fiber is not limited to these products. PBI fibers are available from PBI Performance Products inc

Are commercially available. Modified polyacrylonitrile fibers are available from Kaneka Corporation as Kanecaron^TMAre commercially available. The flame retardant viscose fiber may be blended from Lenzing group by Lenzing

Are commercially available. The flame-retardant cotton fiber is commercially available from Shenzhen Usprotec flame-retardant application Co.

Woven fabrics suitable for use in the outer shell layer have a plurality of warp yarns extending longitudinally in the machine direction and a plurality of weft yarns extending substantially perpendicular to the warp yarns (i.e., in the cross-machine direction), wherein each yarn comprising the plurality of fibers preferably has a linear density of from about 220 dtex to about 3,300 dtex, more preferably from about 440 dtex to about 2,640 dtex, and most preferably from about 1,100 dtex to about 2,200 dtex. Any weave structure may be used, such as plain, twill, satin, basket (basketweave), and the like. There is no particular requirement for the tightness of the fabric; however, tight weaving is preferred, except to avoid particularly tight weaving to avoid damage to the yarn fibers from tight weaving. Woven fabrics suitable for the outer shell layer include 17 x 17 counts, 20 x 20 counts, or 34 x 34 counts per square inch.

Woven fabrics for use as the outer shell layer are commercially available, for example, from Ibena Shanghai Technical Textiles co

PBI Matrix from PBI Performance Products Inc. of IIIA^TMAnd the like.

In one embodiment, the woven fabric used as the outer shell layer has a basis weight of about 150-250g/m²Or about 180-²。

Moisture barrier

In the present invention, the moisture barrier is provided to prevent water from the fire-fighting environment from penetrating and saturating the clothing, and to allow moisture such as water vapor of sweat to pass through.

The moisture barrier of the present invention may be a film comprising or made of Polytetrafluoroethylene (PTFE), Polyurethane (PU) or mixtures thereof.

The membrane used as the moisture barrier may have micropores that allow water vapor to pass through but block penetration of a liquid (e.g., liquid water), wherein the pores range in size from about 0.01 μm to about 10 μm, or from about 0.1 μm to about 8 μm; the porosity (i.e., the percentage of open space in the volume of the microporous membrane) is from about 50% to about 99%, or from about 70% to about 95%.

In one embodiment, the moisture barrier is a film comprising or made from PTFE having a thickness of about 20 to 50 μm and a basis weight of about 20 to 50g/m²。

Such membranes are commercially available, for example from Ningbo Dentik Fluor Material Co., Ltd

W.L.Gore&Of Associates, Inc

Or

And the like.

Thermal insulation layer

In the present invention, the thermal insulation layer is a nonwoven fabric comprising about 45 to 95 wt% of non-fusible short fibers and about 5 to 55 wt% of heat-settable short fibers, the nonwoven fabric having protrusions and/or depressions.

As used herein, the term "infusible staple fibers" refers to fibers that do not melt prior to decomposition, and the term "heat-settable staple fibers" refers to fibers that have a melting point of from about 70 ℃ to about 350 ℃ or from about 100 ℃ to about 280 ℃ and a glass transition temperature (Tg) of from about 40 ℃ to about 160 ℃ or from about 50 ℃ to about 110 ℃. Tg can be determined by Differential Scanning Calorimetry (DSC) according to ASTM D3418.

Representative non-fusible short fibers useful in the practice of the present invention include fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, or mixtures thereof. Representative heat-settable staple fibers useful in the practice of the present invention include fibers made from polyesters such as polyethylene terephthalate (PET), polyamides such as polyamide 66, polyphenylene sulfide (PPS), or blends thereof.

The above described non-fusible staple fibers are commercially available, for example from DuPont

And

the heat-fixable short fibers described above are also commercially available, for example from Nanya Plastics Corporation

Polyester fiber, Invista Co

Polyester fiber, Toray Industries Inc

PPS fibers and polyamide 66 fibers of Invista co.

The non-meltable staple fibers and heat-settable staple fibers used herein each independently have a linear density of from about 0.5 dtex to about 10 dtex or a diameter of from about 1 μm to about 50 μm, and a length of from about 5mm to about 100 mm.

In one embodiment, the nonwoven fabric used as the thermal insulating layer comprises about 45 to 95 weight percent infusible staple fibers and about 5 to 55 weight percent heat-settable staple fibers; or about 50 to 90 weight percent non-fusible short fibers and about 10 to 50 weight percent heat-settable short fibers; or about 55 to 85 weight percent non-fusible short fibers and about 15 to 45 weight percent heat-settable short fibers.

In another embodiment, the nonwoven fabric used as the thermal barrier layer comprises from about 45 to about 95 weight percent of non-fusible staple fibers made of poly (p-phenylene terephthalamide) homopolymer and from about 5 to about 55 weight percent of heat-settable staple fibers made of polyester, polyamide, PPS, or mixtures thereof.

In one embodiment, the basis weight of the nonwoven fabric used as the thermal insulating layer is from about 50 to 200g/m²And a thickness of about 0.5mm to about 20 mm.

The nonwoven fabric used as the heat insulating layer has protrusions and/or depressions on its surface. Assuming that one looks at the thermal protective garment of the present invention from a side view, if the protrusions are in contact with the comfort liner, they are considered "protrusions"; whereas if the protrusions are in contact with the moisture barrier they are considered "depressions". The number of protrusions and/or depressions is from about 40 to about 1000 per square meter, or from about 70 to about 700 per square meter, or from about 100 to about 400 per square meter. Each projection and/or depression being separated from an adjacent projection and/or depression, wherein the projection has a height, measured from the substantially flat surface portion of the nonwoven fabric to the highest point of the projection, of about 1-10 mm; similarly, the depressions have a depth of about 1-10mm measured from the substantially flat surface portion of the nonwoven fabric to the lowest point of depression.

The protrusions and/or depressions of the nonwoven fabric used as the thermal insulation layer are present in the form of an array of spherical caps, parallel channels, alternating blocks, waves, crosses, stars, capsules, or patterns.

As used herein, the term "spherical cap" is a portion of a sphere cut by a plane. If the plane passes through the center of the sphere such that the height of the spherical cap is equal to the radius of the sphere, the spherical cap is referred to as a hemisphere.

In one embodiment, the protrusions and/or depressions of the non-woven fabric used as the thermal insulation layer are spherical caps, and each of the spherical caps has a height of about 1 to 10mm and is spaced from an adjacent spherical cap by about 1 to 50mm, as shown in fig. 2 a and 2B.

In another embodiment, the protrusions and/or depressions of the nonwoven fabric used as the thermal insulating layer are an array of cruciform shapes, and each cruciform shape has a length of about 1 to 50mm, a width of about 1 to 15mm, and a height/depth of about 1 to 10mm, as shown in fig. 3.

In another embodiment, the protrusions and/or depressions of the nonwoven fabric used as the thermal insulation layer are an array of capsules, and each capsule has a height of about 1-10mm, and a distance from an adjacent capsule of about 1-50 mm.

Methods of making the nonwoven fabric for use as the thermal barrier layer are well known in the art. For example, non-meltable staple fibers are first mixed with heat-settable staple fibers, and then the staple fiber mixture is subjected to water-punching (water-pressing) by thermocompression bonding, needle punching, or under a suitable pressure to bond the staple fibers to each other.

The protrusions and/or depressions of the nonwoven fabric used as the thermal insulating layer may be prepared by hot pressing a substantially flat nonwoven fabric in a mold or roll having a three-dimensional pattern at a suitable pressure and a temperature above the highest glass transition temperature (Tg) of the heat-fixable fibers (when there is more than one heat-fixable fiber).

In one embodiment, the nonwoven fabric used as the thermal insulating layer is prepared by a process comprising the steps of:

i. providing a substantially flat nonwoven fabric comprising about 45-95 wt% non-fusible staple fibers and about 5-55 wt% heat-settable staple fibers;

hot pressing the nonwoven fabric of step (i) at a temperature above the highest Tg of the heat-fixable fiber using a mold or roll having a three-dimensional pattern at a pressure of about 0.1 to 2MPa or about 0.2 to 1MPa for about 0.1 to 5 minutes.

Comfortable lining

The comfort liner is at least one layer of a woven or knitted fabric comprising a blend of poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, polysulfonamide homopolymer, polysulfonamide copolymer, polybenzimidazole, propane, or mixtures thereofFibers made of an olefinic nitrile copolymer, flame retardant viscose, flame retardant cotton or mixtures thereof; the comfort liner has an average of about 100-²The combined basis weight of (a).

In one embodiment, the comfort liner is a woven fabric comprising fibers made from poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, flame retardant viscose or mixtures thereof.

In another embodiment, the comfort liner is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, acrylonitrile copolymer, or mixtures thereof;

woven fabrics for use as the comfort liner are commercially available, for example TV120 from Ibena Textile Shanghai co.

Preparation of the thermal protective clothing

The thermal protective garment 100 of the present invention comprises, in order: (a) an outer shell 11, (B) a moisture barrier 12, (C) an insulating layer 13, and (d) a comfort liner 14, as shown in Aa of fig. 1, B of fig. 1, and C of fig. 1.

As used herein to describe the structure of the thermal protective garment, "/" is used to separate each individual layer from adjacent layers therein. Thus, the structure of the thermal protective garment of the present invention can be expressed as a/b/c/d.

There is no particular limitation on the method for preparing the thermal protective garment of the present invention, which may be any conventionally known method in the art. For example, the method may comprise arranging (a) an outer shell, (b) a moisture barrier, (c) an insulation layer, and (d) a comfort liner in the order a/b/c/d to form an assembly, wherein the protrusions may be present on a surface of the insulation layer in contact with the moisture barrier, or on another surface of the insulation layer in contact with the comfort liner, or on both surfaces, and then sewing or quilting the assembly to obtain a thermal protective garment.

As previously mentioned, there is a need to provide adequate thermal protection for firefighters, using as little heat as possibleThe protective clothing can reduce the burden of the fire fighters. According to NFPA 1971: method for constructing a public cloth in Standard on Protective Assembly for Structural Fire protection, 2000 edition, the Thermal Protective Performance (TPP) of the thermal Protective garment of the present invention was evaluated by the thermal conductivity of the thermal Protective garment when exposed to flash conditions, in "cal/cm²"record. To eliminate the basis weight Factor for thermal protection, Fabric Failure Factor (FFF) values can be used for comparison by using TPP values (cal/cm)²) Divided by the basis weight of the garment (g/m)²) And (4) obtaining. FFF values allow for objective comparisons of thermal protective materials on the same basis. High FFF values indicate high thermal protection per weight.

The object of providing a thermal protective garment with sufficient thermal protection and as light as possible is achieved by providing a patterned insulating layer with surface protrusions and/or depressions forming air gaps which trap air between the insulating layer and the adjacent layers, i.e. the moisture barrier and the comfort liner. When the thermal barrier layer is provided, the air gaps trap air to provide enhanced thermal barrier effect. Since there is no material in these air gaps, improved thermal protection can be provided with less material and therefore less weight. The FFF value of the heat protective garment of the present invention is improved by 10% or more, preferably 15% or more, more preferably 20% or more, as compared with the heat protective garment having the same nonwoven fabric as the heat insulating layer but without the protrusions and/or depressions. As a result, the patterned thermal barrier layer and the thermal protective garment made therefrom as a whole can be made lighter without reducing thermal protective performance, or can be made better without increasing overall basis weight.

It is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent without further elaboration. Thus, the following examples are to be construed as merely illustrative, and not limitative of the disclosure in any way whatsoever.

Examples

The abbreviation "E" stands for "examples" and "CE" for "comparative examples", followed by a number indicating in which example the thermal protective garment was prepared. These examples and comparative examples were prepared and tested in a similar manner.

Material

Outer shell layer (a 1): a woven fabric comprising about 93% by weight meta-aramid fibers, about 5% by weight para-aramid fibers, and about 2% by weight antistatic fibers, supplied by Ibena Shanghai Technical Textiles co

IIIA, basis weight of about 208g/m²。

Outer shell layer (a 2): a woven fabric comprising spun yarns of about 60 weight percent Polybenzimidazole (PBI) staple fiber and about 40 weight percent para-aramid fiber supplied by PBI Performance Products inc^TMBasis weight of about 210g/m²。

Outer shell layer (a 3): a woven fabric comprising flame Retardant cotton fibers provided by the Shenzhen Uprotec Fire Retardant Application co.ltd. having a basis weight of about 180g/m²。

Moisture barrier (b 1): porous PTFE membrane, available from Ningbo Dentik Fluor Material Co., Ltd., trade name

Having a basis weight of about 22g/m²。

Infusible short fiber (f 1): staple fibers made from poly (p-phenylene terephthalamide) homopolymer, available from DuPont under the trade name DuPont

The staple fibers had an average length of about 51mm, an average diameter of about 12 μm, and a linear density of about 1.5 denier (1.65 dtex).

Heat-fixable short fiber (f 2): staple fibers produced from PET with a Tg of 68 ℃ obtained from Nanya Plastic Co, under the trade name Nanya

The staple fibers had an average length of about 51mm and a linear density of about 4 denier (4.4 dtex).

Heat-fixable short fiber (f 3): staple fibers produced from PPS having a Tg of 90 ℃, obtained from DuPont. The staple fibers had an average length of about 51mm and a linear density of about 1.5 denier (1.65 dtex).

Heat-fixable short fiber (f 4): staple fibers produced from polyamide 66 having a Tg of 90 ℃ obtained from Ibena Textile Shanghai co. The staple fibers had an average length of about 51mm and a linear density of 1.5 denier (1.65 dtex).

Comfort liner (d 1): a woven fabric comprising a yarn consisting of about 50% by weight meta-aramid fiber and about 50% by weight flame-retardant viscose fiber, obtained from Ibena Textile Shanghai Co. China, having a basis weight of about 120g/m²。

Comfort liner (d 2): a woven fabric comprising a yarn consisting of about 65 weight percent modacrylic fiber, about 25 weight percent para-aramid fiber, and about 10 weight percent meta-aramid fiber obtained from Ibena Textile Shanghai Co²。

Preparation of thermal protective clothing Components of E1-E3 and CE1-CE10

Step A. preparing a nonwoven fabric for use as the thermal insulating layer (c)

The non-fusible staple fibers and the heat-settable staple fibers are mixed in a specific weight ratio to obtain about 2kg of a fiber mixture, and the fiber mixture is thermally or hydraulically entangled to obtain a substantially flat nonwoven fabric having a thickness of about 0.7-1.0mm, cut into 15cm x 15cm squares.

In E1-E13, each nonwoven fabric was put into a steel mold (composed of two 35 cm. times.35 cm. times.1.5 cm stainless steel plates having a three-dimensional pattern) and hot-pressed at a temperature higher than Tg of the heat-fixable fiber under a pressure of about 0.1 to 2MPa for about 0.1 to 5 minutes to obtain an insulating layer, i.e., a nonwoven fabric having protrusions and/or depressions. After hot pressing, the mould is removed from the hot press, the insulation layer is removed from the mould and cooled to ambient temperature. The weight ratio of non-fusible staple fibers and heat-settable staple fibers, the method of making the nonwoven fabric, the hot pressing temperature, the hot pressing pressure, the shape and size of the protrusions, the number of protrusions per square meter and the basis weight of the nonwoven fabric for the thermal insulating layer are all reported in tables 1-6.

Step B, preparing the thermal protective clothing assembly

For each thermal protective garment component, (a) an outer shell, (b) a moisture barrier, (c) a thermal insulation layer, and (d) a comfort liner are arranged in a/b/c/d order and then sewn or quilted together to form various garment component samples as set forth in tables 1-6. Hereinafter, the "thermal protective garment assembly" will be simply referred to as "TPG assembly".

Test method

Basis weight: the basis weight of each TPG assembly sample was determined by dividing the weight of the TPG assembly by the surface area of the TPG assembly. The results are reported in tables 1-6.

TPP: the TPP value for each TPG module sample is according to NFPA 1971: measured by the method published by the structural fire protection association standard (version 2000). The results are reported in tables 1-6.

FFF: the FFF value for each TPG assembly sample was calculated by dividing the TPP value by the basis weight of the sample. The results are reported in tables 1-6.

Improvement in FFF (Δ F): the percentage improvement in FFF was calculated by the following formula:

ΔF％＝[(FFF_n-FFF₀)/FFF₀]x 100

wherein FFF₀Is the FFF value of the reference example; and

FFF_nis the FFF value of the comparative example.

TABLE 1

"# a" indicates that the comparative example is a reference example for calculating the FFF improvement of CE2, and "# a" indicates that the comparative example is a reference example for calculating the FFF improvement of E1.

“H^b"denotes the height of the spherical cap protrusion; "D^b"denotes the diameter of the spherical cap protuberance.

From the results of table 1, the following is apparent.

Comparing the TPP and FFF data for CE2 and CE1, it can be seen that the thermal insulation layer of the TPG module of CE2 is heavier (14.5% heavier than the thermal insulation layer CE 1), the TPP is increased by 27.9%, and the FFF is increased by 11.8% compared to the TPG module of CE 1. This result demonstrates the well-known trend that the introduction of a thicker thermal barrier layer (and thus a heavier thermal barrier layer) can significantly improve TPP, however, it provides only some FFF improvement (about 12%) when considering the increased basis weight.

Comparing the TPP and FFF data of CE3 and E1, it can be seen that the TPP of the TPG module of E1 with an insulating layer with protrusions on the nonwoven fabric is increased by 45.9% and the FFF is increased by 46.2% compared to the garment module of CE3 with the same nonwoven fabric as the insulating layer but without the protrusions on the surface. The significant TPP and FFF improvements provided by the E1 thermal protective garment assembly of the present invention are significantly attributable to the presence of protrusions on the surface of the thermal insulating layer.

TABLE 2

". a" indicates that CE4 is a reference example for calculating the FFF improvement of E2-E4.

“H^b"indicates the height of the spherical crown protrusion," D^b"denotes the diameter of the spherical cap protuberance.

“L^c"denotes the length of a cross-like projection," W^c"represents the width of a cross-shaped protrusion, and" H^c"indicates the height of a cross-like protrusion.

From the results of table 2, the following is apparent.

Comparing the FFF data of CE4 and E2-E4, it can be seen that surprisingly, the FFF values of the TPG assembly of E2-E4 with thermal insulation layer having protrusions on the nonwoven fabric are significantly improved by 38.5% -45.8% compared to the CE4 garment assembly. Comparing the FFF data of E2 with E3, it can be seen that the FFF value is higher for the TPG assembly of E2 with more protruding insulation layers of the same shape and spherical cap size on the nonwoven fabric than for the TPG assembly of E3.

TABLE 3

". a" indicates that CE5 is a reference example for calculating the improvement in FFF.

From the results of table 3, the following is apparent.

Comparing the FFF data of CE5 and E5-E6, it can be seen that surprisingly, the FFF values of the TPG module of E5 with the thermal barrier layer having protrusions on the nonwoven fabric and the TPG module of E6 having protrusions and depressions on the nonwoven fabric were significantly increased by 28.6% and 17.6%, respectively, compared to the TPG module of CE 5.

In one embodiment of the present invention, the thermal protective garment comprises, in order from the outside to the inside:

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein

The outer shell layer is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, or mixtures thereof, having a basis weight of about 150-250g/m²；

The moisture barrier is a film comprising or made of PTFE, having a thickness of about 10-100 μm and a basis weight of about 20-50g/m²；

The partitionThe thermal layer is a nonwoven fabric comprising about 65 to 95 weight percent non-fusible staple fibers made of poly (p-phenylene terephthalamide) homopolymer and about 5 to 35 weight percent heat-settable staple fibers made of PET; the nonwoven fabric has about 50-350 protrusions and/or depressions in the form of an array of spherical caps, crosses, or capsules having a basis weight of about 50-150g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising fibers made of poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, flame retardant viscose or a mixture thereof; the basis weight of the comfort liner is about 100-²。

TABLE 4

". a" indicates that CE6 is a reference example for calculating the FFF improvement of E7-E8. "# a" indicates that CE7 is a reference example for calculating the FFF improvement of E9-E10.

“H^b"denotes the height of the spherical cap protrusion; "D^b"denotes the diameter of the spherical mold used to make the spherical cap protrusion.

From the results of table 4, the following is apparent.

Comparing the FFF data of CE6 and E7-E8, it can be seen that surprisingly, the FFF of the TPG module of E7-E8 with an insulation layer having protrusions on the nonwoven fabric is significantly increased by 22.8% -24.4% compared to the TPG module of CE 6.

Comparing the FFF data of CE7 and E9-E10, it can be seen that surprisingly, the FFF of the TPG assembly of E9-E10 with an insulating layer having protrusions on the nonwoven fabric is significantly increased by 36.4% -37.3% compared to the garment assembly of CE 7.

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

The insulation layer is a nonwoven fabric comprising about 45-85 wt% of non-fusible staple fiber made of poly (p-phenylene terephthalamide) homopolymer and about 15-55 wt% of heat-settable staple fiber made of PPS; the nonwoven fabric has at least about 50, or 70, or 100 protrusions and/or depressions per square meter in the form of a spherical cap array having a basis weight of about 50-150g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising fibers made of poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, flame retardant viscose or a mixture thereof; the comfort liner has a combined basis weight of about 100-200g/m²。

TABLE 5

"+" indicates that CE8 is a reference example for calculating the FFF improvement of E11.

From the results of table 5, the following is apparent.

Comparing the FFF data of CE8 and E11, it can be seen that the FFF of the TPG module of E11 with a thermal barrier layer having protrusions on the nonwoven fabric is significantly increased by 52.4% compared to the garment module of CE 8.

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

The thermal insulating layer is a nonwoven fabric comprising about 65-95 wt% of non-fusible staple fibers made of poly (p-phenylene terephthalamide) homopolymer and about 5-35 wt% of heat-settable staple fibers made of polyamide 66; the nonwoven fabric has at least about 50, or 70, or 100 protrusions and/or depressions per square meter in the form of a spherical cap array having a basis weight of about 50-150g/m²(ii) a And

TABLE 6

"# a" indicates that CE9 is a reference example for calculating the FFF improvement of E12, and "# a" indicates that CE10 is a reference example for calculating the FFF improvement of E13.

“L^b"denotes the length of a cross-like projection," W^b"represents the width of a cross-shaped protrusion, and" H^b"indicates the height of a cross-like protrusion.

From the results of table 6, the following is apparent.

Comparing the FFF data of CE9 and E12, it can be seen that the FFF of the TPG assembly of E12 with the raised (i.e., recessed) thermal barrier layer in contact with the moisture barrier layer is significantly increased by 42.3% compared to the garment assembly of CE 9. Comparing the FFF data of CE10 and E13, it can be seen that the FFF of the TPG module of E13 with the raised (i.e., recessed) thermal barrier layer in contact with the moisture barrier layer (b) is significantly increased by 30.5% compared to the TPG module of CE 10.

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

the outer shell layer is a woven fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, polybenzimidazole, or mixtures thereof, having a basis weight of about 150-250g/m²；

The thermal insulating layer is a nonwoven fabric comprising about 65-95 wt% of non-fusible staple fibers made of poly (p-phenylene terephthalamide) homopolymer and about 5-35 wt% of heat-settable staple fibers made of PET; the nonwoven fabric has at least about 50, or 70, or 100 protrusions and/or depressions in the form of a crisscross array having a basis weight of about 50 to 150g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising a blend of poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide)Phenylenediamine) copolymer, flame-retardant viscose or mixtures thereof; the comfort liner has a combined basis weight of about 100-200g/m²。

In another embodiment of the present invention, the thermal protective suit comprises, in order from the outside to the inside:

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

the outer shell layer is a woven fabric comprising fibers made of flame-retardant cotton having a basis weight of about 150-250g/m²；

The thermal insulating layer is a nonwoven fabric comprising about 65-95 wt% of non-fusible staple fibers made of poly (p-phenylene terephthalamide) homopolymer and about 5-35 wt% of heat-settable staple fibers made of PET; the nonwoven fabric has at least about 50, or 70, or 100 protrusions and/or depressions in the form of a crisscross array having a basis weight of about 50 to 200g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, acrylonitrile copolymer, or mixtures thereof; the comfort liner has a combined basis weight of about 100-200g/m²。

While the invention has been illustrated and described in typical embodiments, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. Accordingly, modifications and equivalents of the invention herein disclosed may occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the invention as defined by the following claims.

Claims

1. A thermal protective garment, comprising, in order from the outside to the inside:

(a) an outer shell layer;

(b) a moisture barrier;

(c) a thermal insulation layer; and

(d) a comfort liner;

wherein,

the outer shell layer is a woven fabric comprising fibers made from: poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, polysulfonamide homopolymer, polysulfonamide copolymer, polybenzimidazole, acrylonitrile copolymer, flame retardant viscose, flame retardant cotton or mixtures thereof; the basis weight of the woven fabric is 150-250g/m²；

The moisture barrier is a film made of polytetrafluoroethylene, polyurethane or a mixture thereof; and the film has a thickness of 10 to 100 μm and a thickness of 20 to 50g/m²Basis weight of (c);

the heat-insulating layer is a nonwoven fabric comprising 45-95 wt% of an infusible short fiber and 5-55 wt% of a heat-fixable short fiber, and the nonwoven fabric has protrusions and/or depressions having a height and/or depth of 1-10mm and a basis weight of 50-200g/m²(ii) a And

the comfort liner is at least one layer of a woven or knitted fabric comprising fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, polysulfonamide homopolymer, polysulfonamide copolymer, polybenzimidazole, acrylonitrile copolymer, flame retardant viscose, flame retardant cotton or mixtures thereof; the comfort liner has a thickness of 100-²A combined basis weight of;

wherein the thermal insulation layer is prepared by a method comprising the steps of:

i. providing a substantially flat nonwoven fabric comprising 45 to 95 weight percent infusible staple fibers and 5 to 55 weight percent heat-settable staple fibers;

hot pressing the nonwoven fabric of step (i) at a temperature above the highest glass transition temperature of the heat-fixable fibers at a pressure of 0.1 to 2MPa for 0.1 to 5 minutes using a mold or roll having a three-dimensional pattern.

2. The thermal protective garment of claim 1, wherein the non-fusible staple fibers comprising said thermal insulating layer comprise fibers made from poly (p-phenylene terephthalamide) homopolymer, poly (p-phenylene terephthalamide) copolymer, poly (m-phenylene isophthalamide) homopolymer, poly (m-phenylene isophthalamide) copolymer, or mixtures thereof.

3. The thermal protective garment of claim 1, wherein the heat-settable staple fibers comprising said thermal insulating layer are made of polyester, polyamide, polyphenylene sulfide or mixtures thereof.

4. The thermal protective garment of claim 1, wherein said substantially flat nonwoven fabric is made by a thermal bonding, needle punching or hydroentangling process.

5. The thermal protective garment of claim 1, wherein said insulating layer has a thickness of 0.5 to 20mm and a number of protrusions and/or depressions per square meter of 40 to 1000 measured from said substantially flat surface portion of said nonwoven fabric.

6. The thermal protective garment of claim 5, wherein the protrusions and/or depressions of the thermal insulating layer are present in the form of an array of spherical caps, parallel channels, alternating blocks, waves, crosses, stars, capsules, or a floral pattern.

7. The thermal protective garment of claim 6, wherein said protrusions and/or depressions are an array of spherical caps and each spherical cap has a height and/or depth of 1-10mm and a distance from an adjacent spherical cap of 1-50 mm.

8. The thermal protective garment of claim 6, wherein said protrusions and/or depressions are an array of crosses, and each cross has a length of 1 to 50mm, a width of 1 to 15mm, and a height and/or depth of 1 to 10 mm.

9. The thermal protective garment of claim 1, having a fabric failure factor increased by 10% or more as compared to a thermal protective garment having a thermal insulating layer without protrusions and/or depressions on the nonwoven fabric, wherein the fabric failure factor is determined by dividing the thermal protective properties measured according to the method of NFPA 1971 by the basis weight of the fabric.