Hook-and-loop fastener and method for manufacturing same

Abstract

Provided is a hook-and-loop fastener exhibiting excellent flame retardancy and excellent engagement force. The hook-and-loop fastener has a base part and an engagement element part on at least one surface of the base part. The base part and the engagement element part contain a resin and at least one compound selected from the group consisting of a phosphorus-based compound and a halogen-based compound. When a mapping image of secondary ions derived from the phosphorus-based compound or the halogen-based compound in a cross-section of the engagement element part is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the ratio EI / ES of the spectral intensity EI in a region at a depth of 45‒55% from the surface of the engagement element part in the center of gravity direction to the spectral intensity ES in a region at a depth of 0‒10%, is 0.16‒0.90.

Description

Hook-and-loop fastener and its manufacturing method Related Applications

[0001] This application claims priority from Japanese Patent Application No. 2024-020673, filed on February 14, 2024, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a surface fastener having a base material and engaging elements on at least one surface of the base material, and a method for manufacturing the same.

[0003] In recent years, hook-and-loop fasteners have been used as various attachment means in a wide range of fields, including vehicles such as automobiles, airplanes, and trains, special clothing such as fire-resistant clothing, firefighting clothing, and high-temperature work clothing, and industrial materials such as heat insulating materials and building materials. Hook-and-loop fasteners used in these fields are required to have a high level of flame retardancy.

[0004] To make products such as hook-and-loop fasteners flame-retardant, several methods are available: molding using resins containing flame retardants, molding using resins with flame-retardant monomers incorporated into the molecular chain, or applying flame retardants to the surface of molded products through post-processing. The molding method, such as spinning, using resins containing flame retardants involves problems such as poor moldability, such as foaming caused by the flame retardant decomposing and volatilizing when molding at high temperatures, which significantly reduces physical properties, and breaking of fibers due to foaming when spinning at high speeds, making stable production impossible. Another problem is that the inclusion of flame retardants inside the fasteners changes the hardness of the engaging elements, such as the loops and hooks, of the hook-and-loop fasteners, reducing their engaging force.

[0005] Furthermore, in the method of molding using a resin that incorporates a flame-retardant monomer into its molecular chain, the introduction of the flame-retardant monomer skeleton into the molecular chain inhibits the crystallization of the resin, which causes a change in the hardness of the engaging element and a decrease in the engaging force, which is a problem.

[0006] On the other hand, as a method for adding a flame retardant in a post-processing step, there is a method in which the flame retardant is applied to the surface of a molded product together with a binder. As another method, for example, Patent Document 1 (JP 2001-295175 A) describes a fiber treatment agent in which a flame retardant is contained in a supercritical fluid or a similar fluid, and describes a method in which the flame retardant is absorbed into the fibers of a fiber structure using the supercritical fluid or a similar fluid.

[0007] Japanese Patent Application Laid-Open No. 2001-295175

[0008] However, the method of applying a flame retardant together with a binder has the problem that the adhesion of the flame retardant to the surface of the engaging element portion of the hook-and-loop fastener causes a decrease in the engaging force. Therefore, in the past, the flame retardant was attached only to the base material by applying a back coat resin containing the flame retardant to the base material, but there was room for further improvement in the flame retardancy of the hook-and-loop fastener as a whole.

[0009] Furthermore, Patent Document 1 primarily targets fabrics such as flame-retardant curtains as fiber structures, and although it describes preventing the texture of fabrics from hardening, it does not mention hook-and-loop fasteners as fiber structures. In particular, hook-and-loop fasteners, unlike simple fabrics, require repeated engagement and disengagement between the engaging elements by utilizing the deformability and hardness of the multiple male and female engaging elements that stand in a base material, and therefore require a different mechanism of action from the improvement in the texture of fabrics described in Patent Document 1. Therefore, it was unclear how the flame retardancy and engaging force would be affected if such a technology were to cause the hook-and-loop fastener to absorb the flame retardant.

[0010] SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hook-and-loop fastener that has both high flame retardancy and high engaging force.

[0011] Another object of the present invention is to provide a method for manufacturing a hook-and-loop fastener that improves flame retardancy and maintains or improves engagement force.

[0012] In a hook-and-loop fastener, in order for male engaging elements to repeatedly engage and disengage with female engaging elements, good deformability is required for the male engaging elements and female engaging elements. The inventors of the present invention have intensively investigated a method for improving the flame retardancy not only of the base material but also of the engaging element portions. As a result, they have found that by treating a hook-and-loop fastener made of resin with a supercritical fluid containing at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds, it is possible to impregnate the phosphorus-based compound and / or halogen-based compound into not only the base material but also the engaging element portions, thereby improving the flame retardancy. As a result of further research, a mapping image of secondary ions derived from phosphorus-based compounds or halogen-based compounds in a cross section of the engaging element portions was analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), and it was found that the spectral intensity E Ｓ Spectral intensity E in the region of 45-55% depth Ｉ The ratio E Ｉ / E Ｓ The inventors have found that a hook-and-loop fastener having a specific range of α, β and β not only has excellent flame retardancy, but also maintains or improves the engagement force compared to a hook-and-loop fastener before the introduction of a phosphorus-based compound and / or a halogen-based compound into the engagement element portion, and have completed the present invention.

[0013] That is, the present invention can be configured in the following aspects: [Aspect 1] A hook-and-loop fastener having a base material and an engaging element portion on at least one surface thereof, wherein the base material and the engaging element portion contain a resin and at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds, and when a mapping image of secondary ions derived from the phosphorus-based compound or halogen-based compound in a cross section of the engaging element portion is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), a spectral intensity E Ｓ Spectral intensity E in the region of 45-55% depth Ｉ The ratio E Ｉ / E ＳA surface fastener according to Aspect 1, wherein when a mapping image of secondary ions derived from the phosphorus-based compound or the halogen-based compound in a cross section of the substrate is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the spectral intensity B Ｓ Spectral intensity B in the depth range of 45 to 55% Ｉ Ratio B Ｉ / B Ｓis 0.29 to 0.90 (preferably 0.32 to 0.88, more preferably 0.36 to 0.85, and even more preferably 0.40 to 0.80). [Aspect 3] The hook-and-loop fastener according to aspect 1 or 2, wherein the phosphorus content is 0.05 to 1.20 wt % (preferably 0.10 to 1.00 wt %, and more preferably 0.20 to 0.80 wt %). [Aspect 4] The hook-and-loop fastener according to any one of aspects 1 to 3, wherein the impregnation rate of the phosphorus element is 0.05 to 0.25 wt % (preferably 0.08 to 0.23 wt %, and more preferably 0.11 to 0.20 wt %). [Aspect 5] The hook-and-loop fastener according to any one of aspects 1 to 4, wherein the resin is at least one resin selected from the group consisting of polyester-based resins, polyolefin-based resins, and polyamide-based resins. [Aspect 6] The hook-and-loop fastener according to any one of Aspects 1 to 5, wherein the substrate and engaging element portions contain the phosphorus-based compound, and the phosphorus-based compound is a phosphate ester-based compound. [Aspect 7] The hook-and-loop fastener according to any one of Aspects 1 to 6, wherein the decomposition temperature of the compound is within a range of the decomposition temperature of the resin −200°C to the decomposition temperature of the resin +100°C. [Aspect 8] The hook-and-loop fastener according to any one of Aspects 1 to 7, wherein the bending stiffness when bent 15° with a bending stiffness tester is 800 to 1500 g (preferably 900 to 1300 g, more preferably 1000 to 1200 g). [Aspect 9] A method for producing the hook-and-loop fastener according to any one of Aspects 1 to 8, comprising a supercritical fluid treatment step of treating a hook-and-loop fastener made of resin, having a substrate and engaging element portions on at least one surface thereof, with a supercritical fluid containing at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds. [Aspect 10] A method for producing a hook-and-loop fastener according to Aspect 9, wherein in the supercritical fluid treatment step, the supercritical fluid is supercritical carbon dioxide and the treatment temperature is 80 to 170°C (preferably 90 to 160°C, more preferably 100 to 150°C).[Aspect 11] A method for producing a hook-and-loop fastener according to aspect 9 or 10, wherein the treatment pressure in the supercritical fluid treatment step is 10 to 50 MPa (preferably 13 to 40 MPa, more preferably 15 to 30 MPa).

[0014] As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms, including "at least one," unless the content clearly dictates otherwise. As used herein, the terms "and / or," "at least one," and "one or more" include any and all combinations of the associated listed items.

[0015] It should be noted that any combination of at least two elements disclosed in the claims and / or the specification and / or the drawings is included in the present invention, and in particular any combination of two or more of the claims set forth in the claims is included in the present invention.

[0016] The hook-and-loop fastener of the present invention has excellent flame retardancy and engaging force. Furthermore, the method for manufacturing the hook-and-loop fastener of the present invention can improve flame retardancy while maintaining or improving engaging force.

[0017] The present invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are merely for illustration and explanation purposes and should not be used to define the scope of the present invention. The scope of the present invention is defined by the appended claims. In the accompanying drawings, the same reference numerals in multiple drawings indicate the same parts. The drawings are not necessarily drawn to scale and are exaggerated to illustrate the principles of the present invention. This is a mapping image of secondary ions derived from a phosphorus-based compound in a cross section of an engagement element portion of Example 6. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a male engagement element. This is a schematic cross-sectional view showing an embodiment of a female engagement element. This is a schematic cross-sectional view showing an embodiment of a cross section perpendicular to the protruding direction of the engagement element portion. This is a partially enlarged view of FIG. 4A. 1 is a schematic cross-sectional view showing one embodiment of a cross section perpendicular to the protruding direction of an engaging element portion; FIG. 2 is a schematic cross-sectional view showing one embodiment of a woven surface fastener; FIG. 3 is a schematic cross-sectional view showing one embodiment of a molded surface fastener;

[0018] [Hook-and-loop fastener] The hook-and-loop fastener is not particularly limited as long as it has a base material and engaging elements on at least one surface thereof. The hook-and-loop fastener can be repeatedly attached and detached on the surface by utilizing the mechanical engagement and detachment of male engaging elements and female engaging elements. Typical examples of the hook-and-loop fastener include woven and knitted fabric hook-and-loop fasteners and molded hook-and-loop fasteners. Examples of the woven and knitted fabric hook-and-loop fasteners include woven and knitted fabric hook-and-loop fasteners whose base material is a woven or knitted fabric base fabric made of yarns (warp and weft in the case of woven fabrics) and engaging element yarns. Examples of the molded hook-and-loop fasteners include molded hook-and-loop fasteners whose base material is a substrate formed by extrusion molding or injection molding of resin.

[0019] The hook-and-loop fastener may have a large number of male engaging elements and / or female engaging elements as engaging element portions on at least one surface of the base material. For example, the hook-and-loop fastener may be a male hook-and-loop fastener having a large number of male engaging elements on one surface of the base material, a female hook-and-loop fastener having female engaging elements on one surface of the base material, a mixed hook-and-loop fastener having both male engaging elements and female engaging elements on one surface of the base material, a double-sided hook-and-loop fastener having male engaging elements on one surface of the base material and female engaging elements on the other surface, or a double-sided mixed hook-and-loop fastener having both male engaging elements and female engaging elements on both surfaces of the base material.

[0020] The male engaging elements are not particularly limited as long as they are known male engaging elements that can engage with female engaging elements, and examples thereof include male engaging elements 12 having shapes such as the hook-shaped cross section shown in Fig. 2A, the approximate Y-shaped cross section shown in Fig. 2B, the umbrella-shaped cross section shown in Fig. 2C, the approximate T-shaped cross section shown in Fig. 2D, the mushroom-shaped cross section shown in Fig. 2E, the arrowhead-shaped cross section shown in Fig. 2F, the double-step arrowhead-shaped cross section shown in Fig. 2G, and the wavy cross section shown in Fig. 2H. Note that Figs. 2A to 2H are schematic cross-sectional views showing various embodiments of male engaging elements, and show male hook-and-loop fasteners 10 having male engaging elements 12 of each shape on one surface of the base material 11. The shape of the multiple male engaging elements in the hook-and-loop fastener may be a single shape, or may be a combination of multiple shapes.

[0021] The female engaging element is not particularly limited as long as it is a known female engaging element that can engage with a male engaging element, and examples thereof include the loop-shaped female engaging element 22 shown in Fig. 3, and may also be a female engaging element that has been subjected to a napping process to have a napped finish (brushed finish). Fig. 3 is a schematic cross-sectional view showing one embodiment of a female engaging element, and shows a female hook-and-loop fastener 20 having a female engaging element 22 on one surface of a base material portion 21.

[0022] The engaging element needs to be deformable when engaging, and elastic enough to return to its original shape to complete the engagement, and also needs to be deformable when disengaging, and elastic enough to return to its original shape after disengagement to engage again.

[0023] Therefore, in the case of a male engaging element, the engaging element may have a narrowest width in a cross section perpendicular to the protruding direction from the base portion of 40 μm or more, preferably 40 to 500 μm, more preferably 50 to 300 μm, and even more preferably 60 to 200 μm. The upper limit of the width can be set appropriately depending on the shape of the engaging element, but from the viewpoint of flame retardancy (burning time, dripping burning time), it may preferably be 1000 μm or less.

[0024] In the case of a woven or knitted fabric surface fastener, the yarn forming the woven or knitted fabric may be a monofilament or a multifilament, and in the case of a multifilament, the number of filaments may be 2 to 50. Furthermore, in the case of a multifilament, the single fiber fineness of the yarn may be 2 to 80 dtex, and in the case of a monofilament, the single fiber fineness may be 100 to 500 dtex.

[0025] In order to fix the threads that make up the woven or knitted fabric base fabric, particularly the threads for the engaging elements, to the base material, the woven or knitted fabric hook-and-loop fastener may be fabricated by applying a urethane or acrylic adhesive resin (back coat resin) to the base material to form a back coat resin layer, thereby fixing the threads for the engaging elements, or the threads that make up the woven or knitted fabric base fabric may include heat-fusible fibers (binder fibers), and the threads for the engaging elements may be fixed by heat fusion.

[0026] The thickness of the substrate may be 70 μm or more. In the case of a woven or knitted fabric surface fastener, the thickness of the base fabric may be 80 to 250 μm, and in the case of a molded surface fastener, the thickness of the substrate may be 0.1 to 2 mm.

[0027] The substrate and engaging element portions of the hook-and-loop fastener contain a resin and at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds. Hereinafter, a hook-and-loop fastener whose substrate and engaging element portions contain at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds may be referred to as a flame-retardant hook-and-loop fastener.

[0028] The resin may be a thermoplastic resin or a thermosetting resin. Examples of thermosetting resins include epoxy resins, unsaturated polyester resins, thermosetting polyimide resins, bismaleimide resins, phenolic resins, melamine resins, and thermosetting polyurethane resins. The resin is preferably a thermoplastic resin, and examples thereof include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid; polyamide resins such as aliphatic polyamides (e.g., polyamide 6, polyamide 66, polyamide 11, and polyamide 12), semi-aromatic polyamides, and wholly aromatic polyamides; polyolefin resins such as polyethylene and polypropylene; polyvinyl chloride resins; styrene resins; acrylic resins such as polyacrylic acid, polymethacrylic acid, polyacrylic acid esters, and polymethacrylic acid esters; polyvinyl acetate; polyurethane resins; polycarbonate resins; polyphenylene sulfide resins; polyetherimide resins; polyarylate resins; cellulose resins; and thermoplastic elastomers. These resins may be used alone or in combination. The thermoplastic elastomer is a copolymer composed of a hard segment and a soft segment, and specific examples thereof include styrene-based elastomers, olefin-based elastomers, vinyl chloride-based elastomers, urethane-based elastomers, ester-based elastomers, and amide-based elastomers, depending on the type of hard segment. Among these thermoplastic resins, at least one resin selected from the group consisting of polyester-based resins, polyolefin-based resins, and polyamide-based resins may be used.

[0029] As for the resin, as will be described later, a resin that easily swells in relation to the solubility of the supercritical fluid is preferred from the viewpoint of impregnating the phosphorus-based compound and / or halogen-based compound. For example, the solubility parameter δ (SP value) of the resin is 12.0 to 26.0 (MPa). ０．５ Preferably, it is 13.0 to 24.0 (MPa). ０．５ , more preferably 15.0 to 22.0 (MPa) ０．５In this specification, the solubility parameter δ refers to the solubility parameter defined by the square root of the cohesive energy density proposed by Hildebrand. The resin having the above SP value may preferably be at least one resin selected from the group consisting of polyester-based resins and polyolefin-based resins.

[0030] The phosphorus-based compounds and halogen-based compounds are compounds containing phosphorus and halogen, respectively, which are flame-retardant elements, and can act as flame retardants when contained in a resin. These compounds can be appropriately selected depending on the type of resin to exert a flame-retardant effect, and two or more types may be contained in combination. These compounds may also be compounds containing both phosphorus and halogen, in which case they are considered to be phosphorus-based compounds in this specification.

[0031] Among these compounds, halogen-based compounds can exhibit flame retardancy by capturing OH radicals that promote combustion reactions, diluting the oxygen concentration in the gas phase, and blocking oxygen, and are generally known to have a higher flame retardancy effect than phosphorus-based compounds. However, in the present invention, as will be described later, these compounds are impregnated and distributed to a predetermined depth in the engaging element portion, so that even phosphorus-based compounds that exhibit flame retardancy by blocking oxygen and insulating by forming a carbonized layer through a dehydration carbonization reaction can exhibit a sufficiently high flame retardancy effect.

[0032] As the phosphorus-based compound, phosphorus-based flame retardants having a high flame retardant effect are preferred, and examples thereof include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, cresyl di-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tris(2-ethylhexyl)phosphate, resorcinol bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), resorcinol bis(di-2,6-xylenyl phosphate), tris(chloroethyl)phosphate, tris(chloropropyl)phosphate, Examples of suitable phosphate compounds include phosphate ester compounds such as tris(dichloropropyl)phosphate, tris(dibromoneopentyl)phosphate, tris(dichloropropyl)phosphate, and tris(tribromoneopentyl)phosphate; phosphate ester amide compounds; phosphonate compounds such as dimethylmethylphosphonate, dimethylvinylphosphonate, diethylvinylphosphonate, and diphenylvinylphosphonate; metal phosphinate compounds such as metal diethylphosphinate; phosphazene compounds; red phosphorus; phosphate compounds such as ammonium phosphate, guanidine phosphate, guanylurea phosphate, and melamine phosphate; and polyphosphate compounds such as ammonium polyphosphate and melamine polyphosphate. Among these, phosphate ester compounds are preferred, and from the viewpoint of eliminating the generation of halides, non-halogen phosphate ester compounds are more preferred.

[0033] Examples of halogen-based compounds include chlorine-based compounds such as chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene, chlorendic acid, and chlorendic acid anhydride; decabromodiphenyl ether, octabromodiphenyl ether, bis(tribromophenoxy)ethane, bis(pentabromodiphenyl)ethylene, tris(tribromophenoxy)triazine, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), tetrabromobisphenol A-bis(2,3-dibromopropyl ether), tetrabromobisphenol A-bis(allyl ether), tetrabromobisphenol A-epoxy oligomer, and tetrabromobisphenol A-carbon and bromine-based compounds such as brominated ester oligomer, tetrabromobisphenol S, tetrabromobisphenol S-bis(2,3-dibromopropyl ether), ethylenebistetrabromophthalimide, tris(dibromopropyl)isocyanurate, hexabromocyclododecane, octabromotrimethylphenylindane, tribromoneopentyl alcohol, dibromoneopentyl glycol, dibromocresyl glycidyl ether, tetrabromophthalate, tetrabromophthalate diol, hexabromobenzene, tribromophenol, dibromophenol, dibromocresol, tribromophenyl allyl ether, brominated polystyrene, brominated polyphenylene ether, and polypentabromobenzyl acrylate. Of these, bromine-based compounds are preferred.

[0034] The flame-retardant hook-and-loop fastener may contain various additives other than the above-mentioned resin and phosphorus-based compound and / or halogen-based compound, as long as the effects of the present invention are not impaired, and may further contain a compound containing a flame-retardant element other than the phosphorus-based compound and / or halogen-based compound as a flame retardant. For example, the flame retardant may contain a combination of the phosphorus-based compound and / or halogen-based compound with at least one flame retardant selected from the group consisting of silicon-based flame retardants and nitrogen-based flame retardants.

[0035] Examples of silicon-based flame retardants include silicone compounds.

[0036] Examples of nitrogen-based flame retardants include guanidine-based compounds such as guanidine sulfamate; triazine-based compounds such as melamine sulfate, melamine cyanurate, melam, and melem; hindered amine-based compounds; and azoalkane-based compounds.

[0037] The decomposition temperature of the phosphorus-based compound and / or halogen-based compound is preferably within a range of the decomposition temperature of the resin −200° C. to the decomposition temperature of the resin +100° C. These compounds exhibit flame retardant effects by radical trapping, diluting the oxygen concentration in the gas phase, carbonizing the resin, etc., but from the perspective of preventing resin decomposition, the flame retardant effect can be more efficiently exhibited when the decomposition temperature of these compounds is closer to the decomposition temperature of the resin. In this specification, the decomposition temperature is a value measured by the method described in the Examples below.

[0038] When a mapping image of secondary ions derived from phosphorus-based compounds or halogen-based compounds in a cross section of the engaging element portion is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the surface of the engaging element portion has a spectral intensity E Ｓ Spectral intensity E in the region of 45-55% depth Ｉ The ratio E Ｉ / E Ｓ is 0.16 to 0.90.

[0039] The flame-retardant hook-and-loop fastener contains at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds not only in the base material but also in the engaging element material, and the phosphorus-based compounds are impregnated and distributed to a predetermined depth in the threads and molded articles constituting the engaging element material, so that the flame-retardant action of the phosphorus-based compounds and / or halogen-based compounds results in excellent flame retardancy for the entire hook-and-loop fastener. Furthermore, the phosphorus-based compounds and / or halogen-based compounds are not merely held in the gaps between the threads constituting the base material and the engaging element material or deposited on the surface of the threads and molded articles, but are impregnated into the interior of the threads and molded articles made of resin, so that physical detachment of the phosphorus-based compounds and / or halogen-based compounds can be suppressed, resulting in excellent durability. Furthermore, the distribution of the phosphorus-based compounds and / or halogen-based compounds in the engaging element material has a gradient distribution that decreases from the surface to the interior, and the spectral intensity E in the region (surface region) from the surface to a depth of 0 to 10% from the surface toward the center of gravity is Ｓ and the spectral intensity E in the region of 45-55% depth from the surface toward the center of gravity (internal region) Ｉ Relative to E Ｉ / E Ｓ When the amount of the impregnation is within a specific range, the engaging force can be maintained or improved, possibly because the resin is impregnated to such an extent that the physical properties of the resin itself are not deteriorated, or because the engaging force is strengthened by the phosphorus-based compound and / or the halogen-based compound.

[0040] Spectral intensity E Ｓ and E Ｉ indicates the amount of phosphorus-based compounds or halogen-based compounds present in the surface region and the internal region of the engaging element portion, respectively, and the ratio of the spectral intensities E Ｉ / E Ｓ is an index that indicates the extent to which phosphorus-based compounds or halogen-based compounds are present in the internal region of the engaging element portion compared to the surface region thereof, that is, the extent to which phosphorus-based compounds or halogen-based compounds are impregnated and distributed in the depth direction from the surface of the engaging element portion. Ｉ / E ＳIf the ratio E of the spectral intensities is too large, the phosphorus-based compound or the halogen-based compound is impregnated too much inside, which changes the physical properties such as strength and hardness that the resin forming the engaging element portion originally has, and the engaging force tends to decrease. Ｉ / E Ｓ If the ratio E of the spectral intensities at the engaging element portion of the hook-and-loop fastener is too small, the phosphorus-based compound or the halogen-based compound is unevenly distributed on the surface and does not penetrate deep into the material, resulting in a large distance between the resin and the flame retardant, and thus the flame retardancy tends not to be sufficiently improved. Ｉ / E Ｓ For example, in the case of a male engaging element, the ratio E Ｉ / E Ｓ may be 0.18 to 0.80, preferably 0.23 to 0.75, and more preferably 0.35 to 0.70. In the case of a female engaging element, the ratio E Ｉ / E Ｓ may be 0.30 to 0.88, preferably 0.35 to 0.85, and more preferably 0.40 to 0.80.

[0041] Time-of-flight secondary ion mass spectrometry (TOF-SIMS) is a technique in which a solid sample is irradiated with an ion beam (primary ions), and ions (secondary ions) emitted when some of the molecules constituting the surface are ionized are mass-separated by utilizing the difference in their flight times. For a given secondary ion, it is possible to perform a mapping analysis that shows the strength of the ion intensity as an in-plane distribution. By performing a mapping analysis of secondary ions derived from phosphorus-based compounds or halogen-based compounds on the cross section of the engagement element portion by TOF-SIMS, it is possible to grasp the state of impregnation of the engagement element portion with phosphorus-based compounds or halogen-based compounds. For example, FIG. 1 shows secondary ions (PO ) derived from phosphorus-based compounds on the cross section of the engagement element portion of Example 6. ３ －) is shown. In the mapping image, bright areas indicate a high abundance of secondary ions, while dark areas indicate a low abundance of secondary ions.

[0042] In this specification, the cross section of the engaging element portion measured by TOF-SIMS basically refers to a cross section perpendicular to the protruding direction of the engaging element protruding from the substrate portion, at a position where the height from the base is 1 / 3 of the height of the engaging element portion (the distance from the base to the apex). For example, in the case of the male engaging element 12 having each cross-sectional shape shown in Figures 2A to 2H, the distance from the base 12a to the apex 12b of the male engaging element 12 is defined as height h, and the cross section cut along line A-A at a position of height h x 1 / 3 from the base 12a can be the measurement point. However, when the engaging element is composed of a monofilament (engaging element thread) having a substantially uniform thread diameter in the longitudinal direction, such as the hook-shaped cross section shown in Figure 2A, the measurement point may be the cross section of the engaging element thread protruding from the substrate portion (e.g., line A-A in Figure 2A), or the cross section of the engaging element thread at the cross section of the substrate portion (e.g., line B-B in Figure 2A).

[0043] Furthermore, when the engaging element is composed of a multifilament (thread for the engaging element), such as the loop-shaped female engaging element 22 shown in Fig. 3, the measurement point may be the cross section of the thread for the engaging element protruding from the substrate, i.e., the cross section perpendicular to the protruding direction at a position where the height from the base is 1 / 3 of the height of the engaging element portion (for example, line A-A in Fig. 3), but from the viewpoint of making it easier to obtain a clear cross-sectional shape by cutting, the measurement point may also be the cross section of the thread for the engaging element at the cross section of the substrate (for example, line B-B in Fig. 3). Furthermore, when the thread for the engaging element is composed of a multifilament, the cross section of a single fiber in the multifilament is the measurement point, and voids between the single fibers are not included in the measurement point.

[0044] Mapping analysis (imaging analysis) of secondary ions derived from phosphorus-based compounds or halogen-based compounds is performed on the measurement cross section of the engaging element portion by TOF-SIMS to obtain a mapping image. The brightness of the mapping is calculated for the obtained mapping image using image analysis software. The average value of the brightness of the mapping in each of the two-dimensional regions of the region from 0 to 10% depth and the region from 45 to 55% depth from the surface of the engaging element portion toward the center of gravity is defined as the spectral intensity E Ｓ and E Ｉ The ratio of the spectral intensities in the engaging element portion E Ｉ / E Ｓ More specifically, the ratio E of the spectral intensities in the engaging element portion can be calculated. Ｉ / E Ｓ is a value measured by the method described in the Examples below, and the analytical method will be described in detail below.

[0045] In this specification, the "surface" of the engaging element portion refers to the contour portion of the measured cross section of the engaging element portion. This contour portion can be determined by a mapping image of secondary ions derived from the resin, phosphorus-based compounds, or halogen-based compounds, and is the outermost portion where the mapping of secondary ions derived from the resin, phosphorus-based compounds, or halogen-based compounds is observed with high brightness. Furthermore, the "center of gravity" of the engaging element portion refers to the center of gravity determined from the shape of the measured cross section of the engaging element portion. The "direction from the surface to the center of gravity" refers to the direction along the line passing through the center of gravity that is the shortest distance connecting a point on one surface to a point on the other surface. The "0-10% depth" region is a surface region represented by a rectangular region with a center line that is 0-10% away from a point on one surface, when the distance between a point on one surface and a point on the other surface is 100%. The "45-55% depth" region is an internal region represented by a rectangular region with a center line that is 45-55% away from a point on one surface. Here, since the detection of mapping brightness in a linear one-dimensional region may be insufficient, in order to grasp the abundance of phosphorus-based compounds or halogen-based compounds through sufficient detection, a rectangular two-dimensional region is targeted, including the region perpendicular to the line. The rectangular region has the line passing through the center of gravity as its center line and includes the perpendicular direction of the line. The width of the rectangle representing the perpendicular direction of the line is set to a range of 20% of the distance between a point on one surface of the line and a point on the other surface, i.e., a range of ±10% in the perpendicular direction from the center line. Note that if the resolution of the analysis software does not allow for an exact 20%, the analysis range is set as the range closest to 20%. Furthermore, if the contour of the measured cross section is curved, such as a circle, the region from 0 to 10% depth is set so that the entire region is encompassed within the contour in order to compare the surface region and the internal region with the same area as the ratio of spectral intensity. For example, if the contour of the measured cross section is circular, the center line is set to a line passing through the center of gravity, and a rectangular region is set so that it is inscribed in the circle.

[0046] For example, Figures 4A and 4C are schematic cross-sectional views showing various embodiments of the measurement cross section 30 of the engaging element portion. As shown in Figure 4A, when the measurement cross section 30 of the engaging element portion is circular (e.g., Figures 2A, 2E, and 3), a rectangle 32 (indicated by a dashed line in Figure 4A) having a predetermined width is drawn, with the shortest straight line 31 (indicated by a dotted line in Figure 4A) passing through points 31a and 31b on the surface and the center of gravity 31c as its center line. Here, the rectangle 32 is drawn so as to be inscribed in the circular measurement cross section 30. That is, as shown in Figure 4B, which is a partially enlarged view of the periphery of point 31a on the surface in Figure 4A, the rectangle 32 is drawn so that its vertex does not pass through point 31a on the surface and is tangent to the measurement cross section 30, and the same applies to the side of point 31b on the surface. Then, with respect to the linear distance in the long side direction of the rectangle 32, a two-dimensional region 33 whose distance from one short side is 0 to 10% is defined as a region with a depth of 0 to 10%, and a two-dimensional region 34 whose distance from one short side is 45 to 55% is defined as a region with a depth of 45 to 55%.

[0047] Furthermore, as shown in FIG. 4C , when the measurement cross section 30 of the engaging element portion is rectangular (for example, FIGS. 2B to 2D and 2F to 2H ), a rectangle 32 (indicated by a dashed line in FIG. 4C ) having a predetermined width is drawn with the shortest straight line 31 (indicated by a dotted line in FIG. 4C ) passing through points 31 a, 31 b on the surface and the center of gravity 31 c as its center line, and a two-dimensional region 33 that is 0 to 10% of the linear distance from point 31 a on the surface to point 31 b on the surface is defined as a region with a depth of 0 to 10%, and a two-dimensional region 34 that is 45 to 55% of the linear distance from point 31 a on the surface is defined as a region with a depth of 45 to 55%.

[0048] From the viewpoint of improving flame retardancy, it is preferable that the hook-and-loop fastener is impregnated with a phosphorus-based compound or a halogen-based compound and distributed to a predetermined depth in the base material as well as the engaging element portion. For example, when a mapping image of secondary ions derived from the phosphorus-based compound or the halogen-based compound in the cross section of the base material is analyzed by TOF-SIMS, the spectral intensity B Ｓ Spectral intensity B in the depth range of 45 to 55% Ｉ Ratio B Ｉ / B ＳThe spectral intensity B may be 0.29 to 0.90, preferably 0.32 to 0.88, more preferably 0.36 to 0.85, and even more preferably 0.40 to 0.80. Ｉ and B Ｓ indicates the amount of phosphorus-based compounds or halogen-based compounds present in the surface region and the internal region of the substrate, respectively, and the ratio of the spectral intensities B Ｉ / B Ｓ is an index that indicates the extent to which phosphorus-based compounds or halogen-based compounds are present in the inner region of the substrate compared to the surface region, i.e., the extent to which phosphorus-based compounds or halogen-based compounds are impregnated and distributed in the depth direction from the surface of the substrate. Ｉ / B Ｓ If the ratio B of the spectral intensities is too large, the phosphorus-based compound or the halogen-based compound is impregnated too much into the interior of the substrate, which changes the physical properties such as strength and hardness that the resin forming the substrate originally has, and the flexibility tends to be poor. Ｉ / B Ｓ If the value is too small, the phosphorus-based compound or halogen-based compound tends to be unevenly distributed on the surface and not fully impregnated into the interior, which may result in insufficient improvement in flame retardancy.

[0049] In this specification, the cross section of the substrate portion measured by TOF-SIMS, in the case of a woven or knitted fabric surface fastener, refers to the cross section of the thickest thread among the threads (excluding the threads for the engaging elements; in the case of a woven or knitted fabric, this refers to the warp and weft threads) that make up the substrate portion (woven or knitted fabric base fabric). For example, FIG. 5 is a schematic cross section showing one embodiment of a woven fabric surface fastener, showing a woven fabric surface fastener 40 having a substrate portion 41 made up of warp threads 41a and weft threads 41b, and an engaging element portion 42 made up of threads for engaging elements. In the woven fabric surface fastener 40 shown in FIG. 5, a thick thread is selected from the warp threads 41a and weft threads 41b that make up the substrate portion 41, and its cross section is taken as the measurement point 43. In FIG. 5, the warp thread 41a, whose cross section is perpendicular to the longitudinal direction, is shown as the measurement point 43, but if the weft thread 41b is thicker, the cross section perpendicular to the longitudinal direction of the weft thread 41b is taken as the measurement point. In Figure 5, the yarns constituting the substrate 41 are warp yarns 41a and weft yarns 41b. However, if there is another yarn constituting the substrate (e.g., a heat-fusible fiber, etc.) and that yarn is the thickest, the measurement point is a cross section perpendicular to the longitudinal direction of that yarn. Note that, for example, if the heat-fusible fiber is a multifilament and each filament is fused to form a monofilament, it is treated as a single fiber. Also, in Figure 5, to simplify the explanation of the measurement method, both the warp yarns 41a and the weft yarns 41b constituting the substrate 41 are illustrated as monofilaments. However, if the yarns constituting the substrate are multifilaments, the measurement point is the cross section of the thickest single fiber in the multifilament, and voids between the single fibers are not included in the measurement point.

[0050] In the case of a molded surface fastener, the cross section of the substrate portion measured by TOF-SIMS refers to a cross section at a location where the engaging elements do not protrude in a cross section perpendicular to the surface direction of the substrate portion (substrate). For example, Fig. 6 is a schematic cross section showing one embodiment of a molded surface fastener, showing a molded surface fastener 50 having a substrate portion 51 and engaging elements 52. In the molded surface fastener 50 shown in Fig. 6, the measurement location 53 is a location where the engaging elements 52 do not protrude in a cross section perpendicular to the surface direction of the substrate portion 51.

[0051] In the measurement cross section of the substrate, a mapping analysis (imaging analysis) of secondary ions derived from a phosphorus-based compound or a halogen-based compound is performed by TOF-SIMS in the same manner as in the measurement and analysis method of the engaging element portion described above, and the brightness of the mapping is calculated for the obtained mapping image using image analysis software. Then, the average value of the brightness of the mapping in each of the two-dimensional regions of the region from 0 to 10% depth and the region from 45 to 55% depth from the surface of the substrate toward the center of gravity is calculated as the spectral intensity B Ｓ and the spectral intensity B in the region of 45 to 55% depth Ｉ The ratio of the spectral intensities in the substrate part B Ｉ / B Ｓ can be calculated.

[0052] In the case of a woven or knitted fabric surface fastener, the above-described method for measuring and analyzing the engaging element portion can be applied. For example, since the measurement point 43 of the woven or knitted fabric surface fastener 40 in Fig. 5 has a circular yarn cross section, as shown in Fig. 4A, a rectangle (dashed line) having a predetermined width and centered on a straight line in the diameter direction passing through a point on the surface and the center of gravity 44 is drawn inscribed in the yarn cross section shape, and the average brightness of the mapping is calculated as the spectral intensity B Ｓ and B Ｉ The ratio of the spectral intensities B Ｉ / B Ｓ can be calculated.

[0053] In the case of a molded surface fastener, the center of gravity of the substrate portion does not have to be the center of gravity of a shape including the entire surface of the substrate portion, and the center of a straight line in the thickness direction of a selected measurement cross section may be set as the center of gravity of the substrate portion. For example, in the molded surface fastener 50 of Figure 6, an arbitrary location on the substrate portion 51 where the engaging element portions 52 do not protrude is selected as the measurement location 53, a rectangle (dashed line) of a predetermined width is drawn with the straight line in the thickness direction as its center line, and the center 54 of this straight line is set as the center of gravity of the substrate portion. Then, similar to the above-mentioned method for analyzing the engaging element portions, the average value of the brightness of the mapping is calculated as the spectral intensity B Ｓ and B Ｉ The ratio of the spectral intensities B Ｉ / B Ｓ can be calculated.

[0054] In this specification, the spectral intensity ratio of secondary ions analyzed by TOF-SIMS is calculated as the spectral intensity ratio of the same secondary ion. That is, the spectral intensity E in the region of 0 to 10% depth from the surface of the engaging element portion toward the center of gravity is Ｓ , the spectral intensity E in the region of 45 to 55% depth from the surface of the engaging element portion toward the center of gravity Ｉ , the spectral intensity B in the region of 0 to 10% depth from the surface of the substrate toward the center of gravity Ｓ , and the spectral intensity B in the region of 45 to 55% depth from the surface of the substrate toward the center of gravity Ｉ In the case where a plurality of types of phosphorus-based compounds and / or halogen-based compounds are contained, it is sufficient that the spectral intensity of secondary ions derived from at least one type of phosphorus-based compound or halogen-based compound satisfies the above range.

[0055] When the hook-and-loop fastener contains a phosphorus-based compound in the substrate portion and the engaging element portion, the phosphorus content may be 0.05 to 1.20 wt%, preferably 0.10 to 1.00 wt%, and more preferably 0.20 to 0.80 wt%, from the viewpoint of achieving both flame retardancy and engaging force. In this specification, the phosphorus content represents the ratio of the weight of phosphorus contained in the hook-and-loop fastener to the weight of the entire hook-and-loop fastener (i.e., the weight of phosphorus including not only phosphorus derived from phosphorus-based compounds impregnated inside the resin, but also phosphorus derived from phosphorus-based compounds that are not impregnated inside the resin but are merely attached to the surface), and is a value measured by the method described in the Examples below.

[0056] When the hook-and-loop fastener contains a phosphorus-based compound in the base material and the engaging element, from the viewpoint of achieving both flame retardancy and engaging force as well as excellent flexibility, the phosphorus impregnation rate may be 0.05 to 0.25 wt %, preferably 0.08 to 0.23 wt %, and more preferably 0.11 to 0.20 wt %. In this specification, the phosphorus impregnation rate represents the ratio of the weight of phosphorus firmly impregnated inside the hook-and-loop fastener to the weight of the entire hook-and-loop fastener. To measure the phosphorus impregnation rate, the hook-and-loop fastener is treated with a good solvent that can dissolve 10 g / L or more of the phosphorus-based compound contained in the hook-and-loop fastener, the phosphorus-based compound adhering to the surface is removed, and the hook-and-loop fastener with the phosphorus-based compound remaining inside is used as a measurement sample, and the weight ratio of the phosphorus element can be measured by ICP atomic emission spectroscopy.

[0057] When the hook-and-loop fastener contains a halogen-based compound in the substrate portion and the engaging element portion, the content of the halogen element may be 0.05 to 10.0 wt%, preferably 0.10 to 8.00 wt%, and more preferably 0.20 to 5.00 wt%, from the viewpoint of achieving both flame retardancy and engaging force. In this specification, the content of the halogen element represents the ratio of the weight of the halogen element contained in the hook-and-loop fastener to the weight of the entire hook-and-loop fastener (i.e., the weight of the halogen element including not only the halogen element derived from the halogen-based compound impregnated inside the resin but also the halogen element derived from the halogen-based compound that is not impregnated inside the resin but is merely attached to the surface), and is a value measured by the method described in the Examples below.

[0058] When the hook-and-loop fastener contains a halogen-based compound in the base material and the engaging element, from the viewpoint of achieving both flame retardancy and engaging force as well as excellent flexibility, the halogen impregnation rate may be 0.05 to 2.00 wt %, preferably 0.08 to 1.50 wt %, and more preferably 0.11 to 1.20 wt %. In this specification, the halogen impregnation rate represents the ratio of the weight of the halogen element firmly impregnated inside the hook-and-loop fastener to the weight of the entire hook-and-loop fastener. To measure the halogen impregnation rate, the hook-and-loop fastener is treated with a good solvent that can dissolve 10 g / L or more of the halogen-based compound contained in the hook-and-loop fastener, the halogen-based compound adhering to the surface is removed, and the hook-and-loop fastener with the halogen-based compound remaining inside is used as a measurement sample, and the weight ratio of the halogen element can be measured by ICP atomic emission spectroscopy.

[0059] In order to maintain the engagement force, it is preferable that the hook-and-loop fastener has hardness even when impregnated with a phosphorus-based compound and / or a halogen-based compound, but if it is too hard, flexibility will be impaired. For example, the hook-and-loop fastener may have a bending stiffness of 800 g to 1500 g, preferably 900 g to 1300 g, and more preferably 1000 g to 1200 g, as measured by a bending stiffness tester. The bending stiffness is a value measured by the method described in the examples below.

[0060] The hook-and-loop fastener has excellent flame retardancy, and for example, the burning time in a burning test may be 15 seconds or less, preferably 10 seconds or less, and more preferably 5 seconds or less. Also, the burning time of a drop in a burning test may be 5 seconds or less, preferably 3 seconds or less, and more preferably 1 second or less. The burning time of a drop in a burning test and the burning time of a drop are values ​​measured by the methods described in the Examples below.

[0061] [Method for manufacturing a hook-and-loop fastener] A method for manufacturing a hook-and-loop fastener includes a step of treating a hook-and-loop fastener made of resin and having a base material and engaging element portions on at least one surface thereof, using a supercritical fluid containing at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds.

[0062] In the above-mentioned manufacturing method, a surface fastener made of a resin (hereinafter sometimes referred to as a "precursor surface fastener") is treated with a supercritical fluid containing at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds, thereby allowing the compound to be impregnated not only into the substrate portion but also into the engaging element portion, thereby improving the flame retardancy of the precursor surface fastener. A supercritical fluid is a fluid that is in a state of temperature and pressure above its critical point, in which the liquid and gas are indistinguishable, and has high solubility like a liquid and high diffusibility like a gas. When the precursor surface fastener is treated with a supercritical fluid in which a phosphorus-based compound and / or a halogen-based compound is dissolved or dispersed, the supercritical fluid penetrates the resin that makes up the precursor surface fastener and swells the resin, allowing the phosphorus-based compound and / or halogen-based compound contained in the supercritical fluid to diffuse into the resin.

[0063] In addition, in such a production method, it is possible to impart flame retardancy by post-processing, and in particular, by adjusting various conditions (for example, temperature, pressure, time, etc.), it is possible to achieve the above-mentioned spectral intensity ratio E Ｉ / E ＳAfter the engaging element portion is impregnated with a phosphorus-based compound and / or a halogen-based compound so that the value falls within a specific range, the engaging force of the precursor surface fastener can be maintained or improved without decreasing. Therefore, in the production of the precursor surface fastener, it is possible to design the type and shape of the resin so as to provide the desired engaging force without considering the decrease in engaging force in post-processing. With the above-mentioned production method, the phosphorus-based compound and / or halogen-based compound can be impregnated in accordance with the shape of the engaging element portion, so that it can be used for precursor surface fasteners of various shapes.

[0064] The precursor surface fastener has a base material and engaging elements on at least one surface thereof, and is made of resin. As described above, the precursor surface fastener may be either a woven or knitted fabric surface fastener or a molded surface fastener. These surface fasteners can be produced by known or conventional methods.

[0065] For example, a woven surface fastener can be obtained by weaving threads for engaging elements together with warp and weft threads in the warp direction to form a woven fabric having a woven base fabric and a plurality of loop engaging elements erected on its surface, and then heating the woven fabric to fuse the heat-fusible fibers contained as weft threads to fix the bases of the loop engaging elements to the woven base fabric, and if the loop engaging elements are formed from multifilaments, a female surface fastener can be obtained.Also, if the loop engaging elements are formed from monofilaments, a male surface fastener can be obtained by appropriately cutting the sides of the loop engaging elements to form male engaging elements.

[0066] Molded hook-and-loop fasteners can also be obtained by extrusion molding or injection molding. In extrusion molding, resin is first extruded from a nozzle having slits with the same cross-sectional shape as the substrate and the engaging elements present on its surface, to obtain a tape-like material having ridges for engaging elements on its surface. Subsequently, slits are made in the engaging element ridges in the tape width direction, and the tape is stretched to widen the slits, turning the ridges into a row of engaging elements, thereby obtaining a hook-and-loop fastener. In injection molding, molten resin is poured onto the surface of a mold with many cavities in the shape of the desired engaging elements, allowed to solidify, and then the resin sheet is peeled off from the mold to obtain a hook-and-loop fastener.

[0067] Examples of supercritical fluids used in the above production method include carbon dioxide, nitrous oxide, ethane, propane, ethylene, ammonia, nitrogen, helium, argon, etc. Of these, carbon dioxide is preferably used because the conditions for bringing it to a supercritical state are relatively mild (critical temperature 31.1°C, critical pressure 7.38 MPa) and it is highly safe from an environmental standpoint.

[0068] The resin constituting the precursor surface fastener can be any of the above-mentioned resins. As the resin, a resin that easily swells in relation to the solubility of the supercritical fluid is preferred from the viewpoint of impregnating the phosphorus-based compound and / or halogen-based compound. For example, when supercritical carbon dioxide is used, the solubility parameter δ (SP value) of the resin is 12.0 to 26.0 (MPa). ０．５ Preferably, it is 13.0 to 24.0 (MPa). ０．５ , more preferably 15.0 to 22.0 (MPa) ０．５ may be.

[0069] The resin used in the present invention preferably has the above SP value, in that it can easily impregnate male engaging elements having a thick fiber diameter that is normally difficult to impregnate, and thick engaging elements and base material portions of molded surface fasteners that are even more difficult to impregnate, and more preferably has an SP value of 13.0 to 24.0 (MPa). ０．５ , more preferably 15.0 to 22.0 (MPa) ０．５ The SP value of the resin is 12.0 (MPa) ０．５If the SP value of the resin is 26.0 (MPa) or more, excessive swelling of the resin due to supercritical carbon dioxide can be prevented, and excessive impregnation of the flame retardant can be prevented, which is preferable in that deterioration of mechanical properties such as engagement force can be prevented. ０．５ If the temperature is below this range, swelling of the resin in supercritical carbon dioxide becomes appropriate, and it is possible to combine the flame retardant and the resin without reducing the engaging force, which is preferable.

[0070] It is known that the density and polarity of supercritical carbon dioxide change depending on the temperature and pressure. Based on the SP value of supercritical carbon dioxide of 10.3 when the processing temperature is 100°C and the processing pressure is 25 MPa, the difference in SP value between the resin constituting the engaging element of the hook-and-loop fastener and supercritical carbon dioxide is 15.0 (MPa) in terms of improving the above effect. ０．５ Preferably, it is less than or equal to 13.0 (MPa). ０．５ The following is the result.

[0071] A specific example of the resin is polyethylene (SP value: 16.4 (MPa) ０．５ ), polypropylene (SP value: 17.0 (MPa) ０．５ Polyolefin resins such as polyethylene terephthalate (SP value: 21.8 (MPa) ０．５ ), polybutylene terephthalate (SP value: 20.5 (MPa) ０．５ ), polyethylene naphthalate (SP value: 20.6 (MPa) ０．５ Polyester resins such as polymethyl methacrylate (SP value: 18.8 (MPa) ０．５ acrylic resins such as polyvinyl acetate (SP value: 19.2 (MPa) ０．５ ), nitrocellulose (SP value: 20.5 (MPa) ０．５ The difference in SP value between these resins and supercritical carbon dioxide is as follows: polyethylene: 6.1 (MPa) ０．５ , Polypropylene: 6.7 (MPa) ０．５ , polyethylene terephthalate: 11.5 (MPa) ０．５ , Polybutylene terephthalate: 10.2 (MPa) ０．５ , polyethylene naphthalate: 10.3 (MPa) ０．５, polymethyl methacrylate: 8.5 (MPa) ０．５ , polyvinyl acetate: 8.9 (MPa) ０．５ , nitrocellulose: 10.2 (MPa) ０．５ Nylon 6: 17.4 (MPa) ０．５ It can be said that the affinity is higher than that of hydrophilic resins such as

[0072] In particular, when the male engaging element is made of a resin whose difference in SP value with respect to supercritical carbon dioxide is within the above range, even if the narrowest width in the cross section perpendicular to the protruding direction from the base material portion (the cut length along line A-A in Figures 2A to 2H) is about 40 to 1000 μm, the effect of the treatment with supercritical carbon dioxide becomes significant, and the above-mentioned spectral intensity ratio E Ｉ / E Ｓ It is possible to adjust the spectral intensity ratio E Ｉ / E Ｓ From the viewpoint of adjusting the width, the narrowest width in a cross section perpendicular to the direction of protrusion of the male engaging element from the base portion may be preferably 40 to 500 μm, more preferably 50 μm to 300 μm, and even more preferably 60 to 200 μm.

[0073] Furthermore, even if the thickness of the substrate portion (the cut length along the line B-B in FIG. 2A and FIG. 3) is about 70 to 1000 μm, it is suitable for the treatment effect with supercritical carbon dioxide, and the above-mentioned spectral intensity ratio B Ｉ / B Ｓ It is possible to adjust the spectral intensity ratio B to be within a specific range. Ｉ / B Ｓ From the viewpoint of adjusting the thickness, in the case of a woven or knitted surface fastener, the thickness of the base fabric is preferably 80 to 250 μm, and in the case of a molded surface fastener, the thickness of the substrate is preferably 100 to 500 μm.

[0074] The phosphorus-based compound and / or halogen-based compound can be any of the various phosphorus-based compounds and / or halogen-based compounds described above. Treatment with a supercritical fluid can be carried out at relatively low temperatures depending on the type of supercritical fluid, making it possible to impregnate phosphorus-based compounds and / or halogen-based compounds with low decomposition temperatures, which are difficult to incorporate using a manufacturing method that involves molding a resin composition obtained by mixing a resin and a flame retardant. For example, not only phosphorus-based compounds and / or halogen-based compounds with a decomposition temperature of 300°C or higher, but also phosphorus-based compounds and / or halogen-based compounds with a low decomposition temperature of approximately 50 to 300°C can be impregnated into the hook-and-loop fastener, allowing for a wide selection of phosphorus-based compounds and / or halogen-based compounds.

[0075] The solubility of the supercritical fluid can be changed by changing the temperature and pressure, and the conditions can be set depending on the resin, phosphorus-based compound, and / or halogen-based compound that make up the precursor surface fastener. Depending on the type of supercritical fluid, the conditions may be, for example, a processing temperature of 20 to 300°C and a processing pressure of 5 to 50 MPa.

[0076] For example, the treatment temperature may be equal to or higher than the critical temperature as long as it does not impair the effects of the present invention. When supercritical carbon dioxide is used, the treatment can be carried out under relatively low temperature conditions, so the treatment temperature may be 31° C. or higher. However, if the supercritical carbon dioxide is diffused into the resin, the spectral intensity ratio E Ｉ / E Ｓ From the viewpoint of adjusting the temperature, the temperature may be preferably 80 to 170°C, more preferably 90 to 160°C, and even more preferably 100 to 150°C.

[0077] The treatment pressure may be equal to or higher than the critical pressure as long as it does not impair the effects of the present invention. When supercritical carbon dioxide is used, the treatment pressure may be 7.38 MPa or higher. However, when a phosphorus-based compound and / or a halogen-based compound is dissolved and impregnated into the precursor surface fastener, the spectral intensity ratio E Ｉ / E ＳFrom the viewpoint of adjusting the temperature, the treatment pressure may be preferably 10 MPa or more, more preferably 13 MPa or more, and even more preferably 15 MPa or more. The upper limit of the treatment pressure is not particularly limited, but may be, for example, 50 MPa or less, preferably 40 MPa or less, and more preferably 30 MPa or less.

[0078] In order to impregnate the precursor surface fastener with the phosphorus-based compound and / or halogen-based compound in a specific distribution, the treatment time with the supercritical fluid may be 10 to 300 minutes, preferably 15 to 240 minutes, and more preferably 30 to 180 minutes.

[0079] The treatment with the supercritical fluid can be carried out by placing the precursor surface fastener in a pressure-resistant container, sealing it, introducing a medium such as carbon dioxide through a pipe attached to the pressure-resistant container, heating and pressurizing it to a supercritical state, dissolving or dispersing a phosphorus-based compound and / or a halogen-based compound in the supercritical fluid, and treating the precursor surface fastener in the pressure-resistant container. The phosphorus-based compound and / or the halogen-based compound may be prepared together with the precursor surface fastener in the pressure-resistant container, in which case the phosphorus-based compound and / or the halogen-based compound may be dissolved or dispersed in the supercritical fluid in the pressure-resistant container and then the precursor surface fastener may be treated. Alternatively, the phosphorus-based compound and / or the halogen-based compound may be prepared in a container separate from the pressure-resistant container containing the precursor surface fastener. In this case, a supercritical fluid containing the phosphorus-based compound and / or the halogen-based compound may be formed in the separate container and then introduced into the pressure-resistant container.

[0080] In the treatment with the supercritical fluid, the precursor surface fastener may be wound into a roll so as to leave a space between the substrate portions to the extent that the engaging element portions are not crushed. In this case, the engaging element portions act as spacers, making it easier for the supercritical fluid to penetrate, so that the phosphorus-based compound and / or halogen-based compound can be sufficiently impregnated even in a short treatment time of, for example, 10 to 60 minutes.

[0081] In terms of adjusting the impregnation of the precursor surface fastener with the phosphorus-based compound and / or halogen-based compound, the weight of the phosphorus-based compound and / or halogen-based compound prepared in the treatment with the supercritical fluid may be 1 to 25% of the weight of the precursor surface fastener.

[0082] The hook-and-loop fastener may have a flame retardant loading rate of 0.5 to 20 wt %. Furthermore, when the engaging element portion is impregnated with a phosphorus-based compound and / or a halogen-based compound in a specific relationship as described above, excellent flame retardancy is achieved even with a small amount of flame retardant. Therefore, the loading rate may be low, preferably 1 to 10 wt %, more preferably 2 to 9 wt %, even more preferably 3 to 8 wt %, and most preferably 5 to 8 wt %. Here, the flame retardant includes not only phosphorus-based flame retardants and halogen-based flame retardants as described above, but also silicon-based flame retardants and nitrogen-based flame retardants. In this specification, the flame retardant loading rate is a value measured by the method described in the Examples section below.

[0083] Because of their excellent flame retardancy, flame-retardant hook-and-loop fasteners can be used in a wide range of fields, including vehicles such as automobiles, aircraft, and trains, special clothing such as fire-resistant clothing, firefighting clothing, and high-temperature work clothing, and industrial materials such as heat insulating materials and building materials. For example, they can be used as covering materials for vehicle seats, interior materials such as ceiling materials, wall materials, and flooring materials, fastening materials for curtains and carpets, fasteners for special clothing, fastening materials for heat insulating materials and high-temperature gas filters, and fastening materials for building interiors, furniture, and other interior decor.

[0084] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by these examples. In the following examples and comparative examples, various physical properties were measured by the following methods.

[0085] (Measurement of cross-sectional length of engaging element and substrate) The cross sections of the engaging element portion and the substrate portion were exposed using a razor, and observed using a digital microscope (manufactured by Keyence Corporation, "VHX-8000"), and the cross-sectional length of each engaging element portion taken along line A-A in FIGS. 2A and 3 and the cross-sectional length of the substrate portion taken along line B-B in FIGS. 2A and 3 were measured using the measurement function.

[0086] (Flame Retardant Decomposition Temperature) Approximately 10 mg of the flame retardant used in the Examples and Comparative Examples was sampled and measured for weight change when heated from 40°C to 500°C at a rate of 10°C / min using a differential thermal and thermogravimetric simultaneous analyzer (TG-DTA; manufactured by Rigaku Corporation, "Thermo Plus-EV02") under a nitrogen atmosphere at a flow rate of 50 mL / min. The temperature at which the weight decreased by 10% from the initial weight (approximately 10 mg) was measured as the flame retardant decomposition temperature. Furthermore, when measuring the decomposition temperature of the flame retardant impregnated into the hook-and-loop fastener, 300 mL of ethanol was placed in a 500 mL beaker and heated to 75°C. After adding 1 g of the hook-and-loop fastener sample, the mixture was stirred for 60 minutes to extract the flame retardant. The resulting solution was air-dried to remove the ethanol, yielding a flame retardant. The resulting flame retardant was used to measure the decomposition temperature of the flame retardant using the method described above.

[0087] (Resin decomposition temperature) The hook-and-loop fastener before impregnation with the flame retardant was crushed with scissors in a polyethylene bag, and about 10 mg of the crushed sample was sampled, and the change in weight was measured using a simultaneous differential thermal and thermogravimetric analyzer (TG-DTA; manufactured by Rigaku Corporation, "Thermo Plus-EV02") in a nitrogen atmosphere at a flow rate of 40 mL / min while the temperature was raised from 40°C to 500°C at a rate of 10°C / min. The temperature at which the weight had decreased by 10% from the initial weight (about 10 mg) was measured as the decomposition temperature of the hook-and-loop fastener.

[0088] (TOF-SIMS) Each of the hook and loop fastener samples obtained in the examples and comparative examples was embedded in epoxy resin, and a microtome was used to cut out measurement cross sections of the substrate portion and the engaging element portion to prepare measurement samples. In the case of a hook (male) hook and loop fastener, the measurement cross section of the engaging element portion was cut along line A-A in FIG. 2A, and the measurement cross section of the substrate portion was cut along line B-B in FIG. 2A. In the case of a loop (female) hook and loop fastener, the measurement cross section of the engaging element portion was cut along line A-A in FIG. 3, and the measurement cross section of the substrate portion was cut along line B-B in FIG. 3. The obtained measurement samples were analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS) under the following conditions to measure PO as secondary ions. ３ － or Br －In the obtained mapping image, PO ３ － or Br － The areas where PO is abundant are brightly colored. ３ － or Br － Areas where the amount is low are shown dark. Measurement device: ION-TOF, "TOF-SIMS 5" Primary ion source: Bi ３ ＋＋ Primary ion acceleration voltage: 10 keV Primary ion current: 0.2 pA Primary ion pulse frequency: 10 kHz Measurement mode: Burst Alignment mode Measurement range: 500 x 500 μm (256 x 256 pix) Number of integrations: 32 scans

[0089] The obtained mapping image was converted into a grayscale image, which was then analyzed using the image analysis software "ImageJ." ３ － or Br － The high-brightness contour portion of the mapping was provisionally considered to be the surface, and a rectangle was drawn with a center line that was the shortest distance from a point on one surface through the center of gravity to a point on the other surface, and a brightness profile was plotted along the long side of the rectangle. First, in order to clearly determine the contour portion (surface) from the brightness plot, the range along the long side of the rectangle was set to include the epoxy resin portion. Although the brightness of the epoxy resin portion in the profile should be set to 0, slight brightness may be detected near the interface with the engaging element portion due to halation. Therefore, the outermost portion where a brightness of 70% of the maximum detected brightness was detected was defined as the surface of the engaging element portion, and this outermost portion was connected by a line to form the outer periphery. Next, a rectangle was drawn so as to inscribe the determined outer periphery, and a brightness profile along the long side of the rectangle was plotted. The average brightness values ​​in the regions 0-10% and 45-55% away from the surface were calculated as the spectral intensity E Ｓ and E Ｉ and the spectral intensity ratio E Ｉ / E ＳSimilarly, for the measured cross section of the substrate, the average brightness values ​​in the regions at distances of 0 to 10% and 45 to 55% from the surface were calculated as the spectral intensity B Ｓ and B Ｉ and the spectral intensity ratio B Ｉ / B Ｓ was calculated.

[0090] (Flame retardant support rate) The flame retardant support rate was calculated from the weight of the untreated hook-and-loop fastener before the flame retardant was applied and the weight of the hook-and-loop fastener after the flame retardant treatment using the following formula: Flame retardant support rate (wt %) = ([weight of treated hook-and-loop fastener] - [weight of untreated hook-and-loop fastener]) / [weight of untreated hook-and-loop fastener] x 100

[0091] (Phosphorus or Bromine Element Content) Each hook-and-loop fastener sample obtained in the Examples and Comparative Examples was cut to a predetermined size, its weight was measured, and the sample was weighed into a quartz decomposition vessel (volume: 80 mL). Nitric acid, hydrochloric acid, and sulfuric acid were added, and the sample was subjected to microwave decomposition using an automatic microwave decomposition apparatus (manufactured by CEM, "Discover SP-D80"). After microwave decomposition, the sample was diluted to 100 mL with ultrapure water and filtered through a filtration filter (pore size: 0.45 μm). The phosphorus or bromine element content (wt%) contained in the hook-and-loop fastener was measured using an ICP optical emission spectrometer (manufactured by Thermo Fisher Scientific, "iCAP6500Duo"). Three samples were measured for each hook-and-loop fastener sample, and the average value was calculated.

[0092] (Phosphorus or Bromine Impregnation Rate) 7.5 g of each hook-and-loop fastener sample obtained in the Examples and Comparative Examples and 150 mL of ethanol were placed in a 500 mL beaker and stirred at 100 rpm at room temperature for 30 minutes. The hook-and-loop fastener sample was then removed and air-dried for 24 hours to remove the phosphorus compounds from the surface of the hook-and-loop fastener sample. The phosphorus content (wt%) of the obtained hook-and-loop fastener sample was measured using the same method as the above-mentioned method for measuring the phosphorus content, and this was taken as the phosphorus impregnation rate. Three hook-and-loop fastener samples were measured, and the average value was calculated. For Example 11 and Comparative Example 10, chloroform was used instead of ethanol to remove the halogen compounds, and the bromine impregnation rate was measured.

[0093] (Bending Stiffness) Each hook-and-loop fastener sample obtained in the Examples and Comparative Examples was cut into a length of 4 cm and a width of 3 cm to prepare a sample piece. The lengthwise direction was the MD direction, and the widthwise direction was the CD direction. Using a bending stiffness tester (manufactured by Kumagai Riki Kogyo Co., Ltd., "2048-BF"), the load (g) was measured when the sample was bent 15° in the lengthwise direction. The load was measured for three sample pieces, and the average value was calculated as the bending stiffness (g).

[0094] (Flame Retardancy) The flame retardancy of each hook-and-loop fastener sample obtained in the Examples and Comparative Examples was evaluated with reference to the aircraft combustion test (14 CFR PART 25 Sec25.853(a)). Specifically, using a combustion tester, the hook-and-loop fastener sample was attached to a U-shaped jig so that the exposed surface was 5.08 cm x 20 cm in size, and the sample was held vertically and exposed to a flame from a hand burner from below for 12 seconds, and the burning state was observed. The time (s) from when the burner was removed until the flame self-extinguished and the burning time (s) of the dripped material were measured. The measurement was performed three times, and the average value was calculated for each.

[0095] (Engagement strength) Peel strength and shear strength were measured with reference to JIS L 3416-2000. When the hook fastener sample of each of the examples and comparative examples was a hook fastener, a loop fastener (manufactured by Kuraray Fastening Co., Ltd., "B2790Y.00") was used as the mating fastener, and when the hook fastener sample was a loop fastener, a hook fastener (manufactured by Kuraray Fastening Co., Ltd., "A8693Y.71") was used to prepare engagement samples.

[0096] The peel strength was measured as the peel strength (N / cm) per 1 cm width by peeling the engaging sample using an autograph (manufactured by Shimadzu Corporation) equipped with a tensile test jig under the following conditions: tensile speed: 300 mm / min, load cell: 5 kg, tape peeling: 50 mm. For each hook-and-loop fastener sample, three engaging samples were measured, and the average value was calculated.

[0097] The shear strength was measured by pulling the engaged sample in the shear direction using an autograph (manufactured by Shimadzu Corporation) equipped with a tensile test jig under the following conditions: tensile speed: 300 mm / min, load cell: 1000 N, tape peeling: 50 mm, and the tensile shear strength per unit area (N / cm ２ For each surface fastener sample, measurements were made using three engaged samples, and the average value was calculated.

[0098] [Example 1] A 50 mL stainless steel pressure vessel (manufactured by JASCO Corporation) was charged with a 10 cm x 20 cm cut polyethylene terephthalate (PET) woven hook surface fastener (manufactured by Kuraray Fastening Co., Ltd., "A8693Y.71") and glass filter paper (manufactured by ADVANTEC Corporation, "GA-100") impregnated with 20 wt% triphenyl phosphate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) relative to the weight of the surface fastener. The oven (manufactured by GL Sciences Inc.) containing the pressure vessel was heated to 100 ° C., and then liquid carbon dioxide was pumped into the pressure vessel using a liquid pump (manufactured by JASCO Corporation) to pressurize it to 18 MPa, bringing the pressure vessel into a supercritical state. After 60 minutes of treatment, the carbon dioxide in the pressure vessel was discharged and the surface fastener in the pressure vessel was removed.

[0099] Example 2 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment time was changed to 180 minutes, to obtain a hook-and-loop fastener.

[0100] Example 3 A surface fastener was obtained by carrying out supercritical fluid treatment in the same manner as in Example 1, except that the treatment pressure was set to 25 MPa.

[0101] Example 4 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment pressure was 25 MPa and the treatment time was 180 minutes, to obtain a hook-and-loop fastener.

[0102] Example 5 A surface fastener was obtained by carrying out supercritical fluid treatment in the same manner as in Example 1, except that the treatment temperature was 120° C. and the treatment pressure was 25 MPa.

[0103] Example 6 A surface fastener was obtained by carrying out supercritical fluid treatment in the same manner as in Example 1, except that the treatment pressure was set to 29 MPa.

[0104] Example 7 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment temperature was 120° C. and the treatment pressure was 29 MPa, to obtain a hook-and-loop fastener.

[0105] Example 8 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment temperature was 150° C. and the treatment pressure was 29 MPa, to obtain a hook-and-loop fastener.

[0106] [Example 9] A hook-and-loop fastener was obtained by supercritical fluid treatment in the same manner as in Example 1, except that the hook-and-loop fastener used in the supercritical fluid treatment was changed to a PET woven loop hook-and-loop fastener (manufactured by Kuraray Fastening Co., Ltd., "B2790Y.00") and the treatment pressure was changed to 29 MPa.

[0107] [Example 10] A hook-and-loop fastener was obtained by supercritical fluid treatment in the same manner as in Example 1, except that the hook-and-loop fastener used in the supercritical fluid treatment was changed to a PET woven loop hook-and-loop fastener (manufactured by Kuraray Fastening Co., Ltd., "B2790Y.00"), the treatment temperature was changed to 150°C, and the treatment pressure was changed to 29 MPa.

[0108] Example 11 A hook-and-loop fastener was obtained by carrying out supercritical fluid treatment in the same manner as in Example 3, except that the flame retardant was changed to hexabromobenzene.

[0109] [Example 12] A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the surface fastener used in the supercritical fluid treatment was changed to a molded hook surface fastener made of polybutylene terephthalate (PBT) (manufactured by Kuraray Fastening Co., Ltd., "W02711"), to obtain a surface fastener.

[0110] [Example 13] A supercritical fluid treatment was carried out in the same manner as in Example 3, except that the surface fastener used in the supercritical fluid treatment was changed to a PBT molded hook surface fastener (manufactured by Kuraray Fastening Co., Ltd., "W02711"), to obtain a surface fastener.

[0111] [Example 14] A hook-and-loop fastener was obtained by supercritical fluid treatment in the same manner as in Example 3, except that the hook-and-loop fastener used in the supercritical fluid treatment was changed to a molded hook-and-loop fastener made of polypropylene (PP) (manufactured by Kuraray Fastening Co., Ltd., "W02110").

[0112] Comparative Example 1 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment temperature was 40° C. and the treatment pressure was 10 MPa, to obtain a hook-and-loop fastener.

[0113] Comparative Example 2 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment temperature was set to 70° C., to obtain a hook-and-loop fastener.

[0114] Comparative Example 3 A supercritical fluid treatment was carried out in the same manner as in Example 1, except that the treatment temperature was 180° C. and the treatment pressure was 29 MPa, to obtain a hook-and-loop fastener.

[0115] Comparative Example 4 A PET woven hook surface fastener (manufactured by Kuraray Fastening Co., Ltd., "A8693Y.71") was subjected to various evaluations without any treatment.

[0116] Comparative Example 5 A PET woven hook surface fastener (Kuraray Fastening Co., Ltd., "A8693Y.71") was back-coated. Specifically, an aqueous polyurethane resin solution consisting of 30 wt% triphenyl phosphate (Fujifilm Wako Pure Chemical Industries, Ltd.), 30 wt% polyurethane resin (Dainippon Ink and Chemicals, Inc., "Bondic 1612NS"), and 40 wt% water was applied to the back surface (the surface not having hooks) of the surface fastener. The surface was then dried at 100°C for 5 minutes and aged at 80°C for 9 hours, resulting in a solids adhesion rate of 35 g / m. ２ The hook-and-loop fastener was obtained.

[0117] [Comparative Example 6] A polyurethane resin aqueous solution was applied to a PET woven hook surface fastener in an amount 1.5 times that of Comparative Example 5, dried at 100°C for 5 minutes, and aged at 80°C for 9 hours, after which the solid adhesion rate was 45 g / m ２ A hook-and-loop fastener was produced in the same manner as in Comparative Example 5, except that the thickness was adjusted to be as follows:

[0118] Comparative Example 7 Various evaluations were carried out on a PBT woven loop surface fastener (manufactured by Kuraray Fastening Co., Ltd., "B2790Y.00") without any treatment.

[0119] Comparative Example 8 A PBT woven loop hook-and-loop fastener (manufactured by Kuraray Fastening Co., Ltd., "B2790Y.00") was back-coated. Specifically, an aqueous polyurethane resin solution consisting of 30 wt% triphenyl phosphate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 30 wt% polyurethane resin (manufactured by Dainippon Ink and Chemicals, Inc., "Bondic 1612NS"), and 40 wt% water was applied to the back surface (the side not having the loops) of the hook-and-loop fastener. The back surface was then dried at 100°C for 5 minutes and aged at 80°C for 9 hours, resulting in a solids adhesion rate of 45 g / m. ２ The hook-and-loop fastener was obtained.

[0120] [Comparative Example 9] A polyurethane resin aqueous solution was applied to a PBT woven loop hook-and-loop fastener in twice the amount of that in Comparative Example 8, dried at 100°C for 5 minutes, and aged at 80°C for 9 hours, after which the solid adhesion rate was 60 g / m ２ A hook-and-loop fastener was produced in the same manner as in Comparative Example 8, except that the thickness was adjusted to be as follows:

[0121] Comparative Example 10 A hook-and-loop fastener was obtained by carrying out supercritical fluid treatment in the same manner as in Example 1, except that the flame retardant was changed to tetrabromobisphenol A and the treatment pressure was changed to 29 MPa.

[0122] [Comparative Example 11] A supercritical fluid treatment was carried out in the same manner as in Comparative Example 1, except that the surface fastener used in the supercritical fluid treatment was changed to a PBT molded hook surface fastener (manufactured by Kuraray Fastening Co., Ltd., "W02711"), to obtain a surface fastener.

[0123] [Comparative Example 12] A supercritical fluid treatment was carried out in the same manner as in Comparative Example 2, except that the surface fastener used in the supercritical fluid treatment was changed to a PBT molded hook surface fastener (manufactured by Kuraray Fastening Co., Ltd., "W02711"), and a surface fastener was obtained.

[0124] [Comparative Example 13] A supercritical fluid treatment was carried out in the same manner as in Example 3, except that the surface fastener used in the supercritical fluid treatment was changed to a molded hook surface fastener made of nylon 6 (Ny6) (manufactured by Kuraray Fastening Co., Ltd., "W02510"), to obtain a surface fastener.

[0125] The manufacturing conditions for the hook-and-loop fasteners of Examples 1 to 14 are shown in Table 1, the evaluation results of the hook-and-loop fasteners obtained in Examples 1 to 14 are shown in Table 2, the manufacturing conditions for the hook-and-loop fasteners of Comparative Examples 1 to 13 are shown in Table 3, and the evaluation results of the hook-and-loop fasteners obtained in Comparative Examples 1 to 13 are shown in Table 4.

[0126]

[0127]

[0128]

[0129]

[0130] As shown in Table 2, the woven surface fasteners of Examples 1 to 11 have a spectral intensity ratio E Ｉ / E Ｓ Since the flame retardancy is in a specific range, not only is the flame retardancy excellent, but the engaging force is equal to or greater than that of the untreated Comparative Examples 4 and 7.

[0131] On the other hand, as shown in Table 4, the woven surface fasteners of Comparative Examples 1 and 2 have a spectral intensity ratio E Ｉ / E Ｓ Since the impregnation temperature was small and the phosphorus-based compound was not sufficiently impregnated into the inner region, the flame retardancy was improved compared to the untreated Comparative Example 4, but the flame retardancy was not sufficient.

[0132] The woven surface fastener of Comparative Example 3 has a spectral intensity ratio E Ｉ / E Ｓ Since the amount of the phosphorus-based compound is excessively impregnated, the engaging force is lower than that of the untreated Comparative Example 4.

[0133] The woven surface fasteners of Comparative Examples 5, 6, 8, and 9 were coated with a backcoat resin containing the same phosphorus-based compound as in Examples 1 to 10, but the resin did not penetrate the interior of the material and was only attached to the surface, so they did not exhibit sufficient flame retardancy. In addition, because the backcoat resin was attached to the surface of the engaging element portion, the engaging force was reduced compared to the untreated Comparative Examples 4 and 7.

[0134] In the woven surface fastener of Comparative Example 10, it was difficult to incorporate the flame retardant into the fiber due to the supercritical fluid treatment conditions of the flame retardant, its solubility in the fluid, molecular size, etc., and the ratio E Ｉ / E Ｓ is small, so it does not exhibit sufficient flame retardancy.

[0135] Furthermore, as shown in Table 2, the molded surface fasteners of Examples 12 to 14 have a spectral intensity ratio E Ｉ / E Ｓ is in a specific range, the composition not only has excellent flame retardancy but also excellent engaging force.

[0136] On the other hand, as shown in Table 4, the molded surface fasteners of Comparative Examples 11 to 13 have a spectral intensity ratio E Ｉ / E Ｓ Since the thickness is small and the phosphorus compound is not sufficiently impregnated in the inner region, sufficient flame retardancy is not exhibited.

[0137] The hook-and-loop fastener can be used in vehicles such as automobiles, airplanes, and trains, special clothing such as fire-resistant clothing, firefighting clothing, and high-temperature work clothing, and industrial materials such as heat insulating materials and building materials.

[0138] As described above, the preferred embodiment of the present invention has been described, but various additions, modifications, or deletions can be made without departing from the spirit of the present invention, and such additions, modifications, or deletions are also included within the scope of the present invention.

[0139] 10... Male hook-and-loop fastener 20... Female hook-and-loop fastener 11, 21, 41, 51... Base material portion 12, 22, 42, 52... Engaging element portion 12a, 22a... Base portion of engaging element portion 12b, 22b... Top portion of engaging element portion h... Height of engaging element portion 30... Cross section of engaging element portion 31... Straight line connecting point on surface and center of gravity 31a, 31b... Points on surface 31c, 44, 54... Center of gravity 32... Rectangular region 33... Region 0 to 10% deep from surface 34... Region 45 to 55% deep from surface 40... Woven hook-and-loop fastener 41a... Warp thread 41b... Weft thread 43, 53... Measurement point 50... Molded hook-and-loop fastener

Claims

1. A hook-and-loop fastener having a base material and an engaging element on at least one surface thereof, wherein the base material and the engaging element contain a resin and at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds, and when a mapping image of secondary ions derived from the phosphorus-based compound or halogen-based compound in a cross section of the engaging element is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the spectral intensity E in the region of 0 to 10% depth from the surface of the engaging element toward the center of gravity is Ｓ Spectral intensity E in the region of 45-55% depth Ｉ The ratio E Ｉ / E Ｓ A hook-and-loop fastener having a viscosity of 0.16 to 0.

90.

2. The hook-and-loop fastener according to claim 1, wherein when a mapping image of secondary ions derived from the phosphorus-based compound or halogen-based compound in a cross section of the substrate is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the spectral intensity B in the region of 0 to 10% depth from the surface of the substrate toward the center of gravity is Ｓ Spectral intensity B in the depth range of 45 to 55% Ｉ Ratio B Ｉ / B Ｓ A hook-and-loop fastener having a viscosity of 0.29 to 0.

90.

3. A hook-and-loop fastener according to claim 1 or 2, wherein the phosphorus content is 0.05 to 1.20 wt %.

4. A hook-and-loop fastener according to claim 1 or 2, wherein the impregnation rate of the phosphorus element is 0.05 to 0.25 wt %.

5. A hook-and-loop fastener according to claim 1 or 2, wherein the resin is at least one resin selected from the group consisting of polyester-based resins, polyolefin-based resins, and polyamide-based resins.

6. A hook-and-loop fastener according to claim 1 or 2, wherein the base material and the engaging element contain the phosphorus-based compound, and the phosphorus-based compound is a phosphate ester-based compound.

7. A hook-and-loop fastener according to claim 1 or 2, wherein the decomposition temperature of said compound is within the range of the decomposition temperature of said resin minus 200°C to the decomposition temperature of said resin plus 100°C.

8. A hook-and-loop fastener according to claim 1 or 2, which has a bending stiffness of 800 to 1500 g when bent at 15° using a bending stiffness tester.

9. A method for producing a hook-and-loop fastener according to claim 1 or 2, comprising a supercritical fluid treatment step in which a hook-and-loop fastener made of resin, having a base material and engaging element portions on at least one surface thereof, is treated with a supercritical fluid containing at least one compound selected from the group consisting of phosphorus-based compounds and halogen-based compounds.

10. A method for producing a hook-and-loop fastener according to claim 9, wherein in the supercritical fluid treatment step, the supercritical fluid is supercritical carbon dioxide and the treatment temperature is 80 to 170°C.

11. A method for producing a hook-and-loop fastener according to claim 10, wherein the processing pressure in the supercritical fluid processing step is 10 to 50 MPa.

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