Protective sleeve and method for manufacturing the same

Abstract

The present invention provides a protection sleeve which has little fraying when cut and which is excellent in heat resistance, and a method for producing such a protection sleeve.　A protection sleeve according to the present invention comprises a braided sleeve and a resin binder for bonding threads in the braided sleeve together, wherein: the braided sleeve is constituted by threads containing inorganic fibers and / or organic fibers; the resin binder contains a fluorine-containing polymer; and the fluorine atom content in the fluorine-containing polymer is 50 mass% or less.

Description

[Technical Field]

[0001] The present invention relates to a protective sleeve and a method for manufacturing the protective sleeve. [Background technology]

[0002] Wire harnesses having a bundle of electric wires and a connector connected to the end of the bundle are often used in automobiles, electrical appliances, etc. To protect and bundle the electric wires constituting such wire harnesses, the bundle is sometimes placed in a cylindrical protective sleeve. Patent Document 1 discloses a protective sleeve in which a braided sleeve made by braiding threads such as glass fibers into a cylindrical shape is fixed with a silicone-based varnish. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-031527 Summary of the Invention [Problem to be solved by the invention]

[0004] Since the protective sleeve may be cut before use, it is required that the fraying of the threads at the cut portion is minimal. The protective sleeve is also required to have excellent heat resistance. The present inventors evaluated the protective sleeve described in Patent Document 1 and found that although it can prevent fraying of the thread at the cut portion, there is room for improvement in heat resistance.

[0005] An object of the present invention is to provide a protective sleeve that has excellent heat resistance and produces little fraying of threads when cut, and a method for manufacturing the protective sleeve. [Means for solving the problem]

[0006] As a result of extensive research into the above-mentioned problems, the present inventors have found that the desired effects can be obtained when the protective sleeve comprises a braided sleeve and a resin binder that binds the yarns in the braided sleeve together, wherein the braided sleeve is composed of yarns containing at least one of inorganic fibers and organic fibers, the resin binder contains a fluorine-containing polymer, and the fluorine atom content in the fluorine-containing polymer is 50 mass% or less, thereby completing the present invention.

[0007] That is, the inventors have found that the above problems can be solved by the following configuration. [1] A protective sleeve comprising a braided sleeve and a resin binder that binds the threads in the braided sleeve together, wherein the braided sleeve is made of threads that contain at least one of inorganic fibers and organic fibers, the resin binder contains a fluorine-containing polymer, and the fluorine atom content in the fluorine-containing polymer is 50 mass% or less. [2] The protective sleeve according to [1], wherein the fluorine atom content in the fluorine-containing polymer is 5% by mass or more. [3] The protective sleeve of [1] or [2], wherein the number average molecular weight of the fluorine-containing polymer is 10,000 to 200,000. [4] The protective sleeve according to any one of [1] to [3], wherein the fluorine-containing polymer does not have a crosslinked structure.

[0008] [5] The protective sleeve according to any one of [1] to [4], wherein the fluorine-containing polymer has units based on at least one monomer selected from the group consisting of vinyl ether, allyl ether, vinyl ester, and allyl ester, which has a reactive group but does not have a fluorine atom. [6] The protective sleeve according to any one of [1] to [5], wherein the fluorine-containing polymer has a hydroxyl group. [7] The protective sleeve according to [6], wherein the fluorine-containing polymer having a hydroxyl group has units based on at least one monomer selected from the group consisting of vinyl ethers and allyl ethers, which has a hydroxyl group but no fluorine atom. [8] The protective sleeve according to any one of [1] to [5], wherein the fluorine-containing polymer has a hydroxyl group and a polyoxyalkylene group. [9] The protective sleeve according to [8], wherein the fluorine-containing polymer having a hydroxyl group and a polyoxyalkylene group has units based on at least one monomer selected from the group consisting of vinyl ethers and allyl ethers, which has a hydroxyl group and a polyoxyalkylene group but does not have a fluorine atom.

[10] The protective sleeve of [8] or [9], wherein the polyoxyalkylene group is a polyoxyethylene group.

[0009]

[11] The protective sleeve according to any one of [1] to

[10] , wherein the fluorine-containing polymer has units based on at least one monomer selected from the group consisting of vinyl ethers and vinyl esters, which does not have a fluorine atom or a reactive group.

[12] The protective sleeve of any one of [1] to

[11] , wherein the content of the fluorine-containing polymer is 30 to 100% by mass based on the total mass of the resin binder.

[13] The protective sleeve according to any one of [1] to

[12] , wherein the protective sleeve has a 60-degree specular gloss of 50 or more.

[14] A method for producing a protective sleeve according to any one of [1] to

[13] , A method for producing a protective sleeve, comprising applying a coating material containing a resin binder containing a fluorine-containing polymer and a liquid medium to a braided sleeve to obtain the protective sleeve. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a protective sleeve that has excellent heat resistance and causes little fraying of threads when cut, and a method for manufacturing such a protective sleeve. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a perspective view schematically illustrating one embodiment of a protective sleeve of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The terms used in the present invention are explained below. The term "unit" in a polymer refers collectively to an atomic group based on one molecule of the monomer formed directly by polymerization of the monomer, and an atomic group obtained by chemically converting a portion of the atomic group. The content (mol %) of each unit relative to the total units contained in the polymer can be determined by analyzing the polymer by nuclear magnetic resonance spectroscopy, and can also be determined from the amounts of components used in producing the polymer. "(Meth)acrylic" is a general term for "acrylic" and "methacrylic", and "(meth)acrylate" is a general term for "acrylate" and "methacrylate". The hydrolyzable silyl group means a group that can undergo a hydrolysis reaction to form a silanol group.

[0013] The acid value and hydroxyl value are values ​​measured according to the method of JIS K 0070-3 (1992). Glass transition temperature (Tg) is the midpoint glass transition temperature of a polymer as measured by differential scanning calorimetry (DSC) method. The minimum film formation temperature (MFT) is the lowest temperature at which a crack-free, uniform coating film is formed when a fluoropolymer is dried, and can be measured, for example, using a film formation temperature measuring device, Model IMC-1535 (manufactured by Imoto Machinery Co., Ltd.). The number average molecular weight (Mn) and weight average molecular weight (Mw) are values ​​measured by gel permeation chromatography using polystyrene as a standard substance.

[0014] The content of fluorine atoms in a fluorine-containing polymer means the proportion (%) of the mass of fluorine atoms to the total mass of the fluorine-containing polymer, and can be measured by nuclear magnetic resonance (NMR) analysis. The 60-degree specular gloss is a value measured according to the method of JIS K 5600-4-7 using a variable-angle glossmeter (product name "UGV-6P", incident / reflecting angle 60 degrees, manufactured by Suga Test Instruments Co., Ltd.).

[0015] The protective sleeve of the present invention (hereinafter also referred to as the present protective sleeve) comprises a braided sleeve and a resin binder that binds the threads in the braided sleeve together, wherein the braided sleeve is composed of threads that contain at least one of inorganic fibers and organic fibers, the resin binder contains a fluorine-containing polymer, and the fluorine atom content in the fluorine-containing polymer is 50 mass% or less. This protective sleeve has less fraying of the threads when cut and has excellent heat resistance. The reason for this is not entirely clear, but is thought to be as follows. The fluorine-containing polymer contained in the resin binder that constitutes this protective sleeve contains fluorine atoms, which is thought to have improved heat resistance. Also, since the fluorine atom content of the fluorine-containing polymer is 50 mass% or less, it is thought to be able to fully function as a binder to bind the yarns together, thereby preventing fraying of the yarns when cut.

[0016] Fig. 1 is a perspective view schematically illustrating one embodiment of the protective sleeve of the present invention. As shown in Fig. 1, the protective sleeve 10 has a resin binder 1 and a braided sleeve 2 contained in the resin binder 1. The braided sleeve 2 is composed of threads 2a.

[0017] The protective sleeve 10 has a cylindrical structure so that it can cover a wire bundle made up of a plurality of electric wires. The protective sleeve 10 may have an opening (not shown) provided along the longitudinal direction of the protective sleeve 10 in order to improve the efficiency of work when covering the wire bundle.

[0018] The resin binder 1 serves to bind and fix the threads 2a that make up the braided sleeve 2. The resin binder 1 exists in the protective sleeve 10 as a resin film containing a fluorine-containing polymer. The fluorine-containing polymer is a polymer containing units having fluorine atoms, and from the viewpoint of the heat resistance of the present protective sleeve, it is preferably a polymer containing units based on fluoroolefin (hereinafter also referred to as units A1). Fluoroolefins are olefins in which one or more hydrogen atoms have been substituted with fluorine atoms. In the fluoroolefins, one or more hydrogen atoms that are not substituted with fluorine atoms may be substituted with chlorine atoms. The number of carbon atoms in the fluoroolefins is preferably 2 to 6, and particularly preferably 2 to 4.

[0019] Examples of the fluorine-containing polymer containing the unit A1 include a homopolymer of a fluoroolefin, a copolymer of two or more kinds of fluoroolefins, and a copolymer of a fluoroolefin and a monomer other than a fluoroolefin. The fluorine-containing polymer is preferably a copolymer, and particularly preferably a copolymer of a fluoroolefin and a monomer other than a fluoroolefin, in order to provide better adhesion between the resin binder 1 and the braided sleeve 2.

[0020] Examples of fluoroolefins include CF2=CF2, CF2=CFCl, CF2=CHF, CH2=CF2, CF2=CFCF3, CF3-CH=CHF, and CF3-CF=CH2. As the fluoroolefin, CF2=CF2 and CF2=CFCl are more preferred, and CF2=CFCl is particularly preferred, from the standpoint of the heat resistance of the protective sleeve 10 and polymerizability with monomers other than fluoroolefins. Two or more types of fluoroolefins may be used in combination.

[0021] The content of units A1 is preferably 20 to 70 mol %, more preferably 30 to 60 mol %, and particularly preferably 45 to 55 mol %, based on the total units contained in the fluoropolymer, in order to improve the heat resistance of the protective sleeve 10 and the adhesion between the resin binder 1 and the braided sleeve 2.

[0022] The fluorine-containing polymer preferably contains, as units other than the units A1, units based on a monomer that does not have a fluorine atom (hereinafter also referred to as non-fluorine units), from the viewpoint of adhesion between the resin binder 1 and the braided sleeve 2. The non-fluorine units preferably contain units having a reactive group (hereinafter also referred to as units A2). When the fluorine-containing polymer contains units A2, the fluorine-containing polymer may have at least a part of the reactive groups in units A2 in a state where they have reacted with other components (for example, a curing agent, etc.), or in a state where they have not reacted with other components, but it is preferable that they have the reactive groups in a state where they have not reacted with other components. In other words, the fluorine-containing polymer in resin binder 1 may be present in a state where it has a crosslinked structure due to the curing agent, or may be present in a state where it has no crosslinked structure, but it is preferable that it is present in a state where it has no crosslinked structure from the viewpoint of the flexibility of protection sleeve 10 and the viewpoint of further reducing fraying of threads when the cut surface of protection sleeve 10 is rubbed.

[0023] The unit A2 may be a unit based on a monomer having a reactive group (hereinafter also referred to as monomer A2), or may be a unit obtained by converting a group having a reactive group in a fluoropolymer containing a unit having the reactive group into a different reactive group. Examples of the latter unit include a unit obtained by reacting a fluoropolymer containing a unit having a hydroxyl group with a polycarboxylic acid or its acid anhydride or the like to convert at least a part of the hydroxyl groups into carboxy groups. Examples of reactive groups include hydroxyl groups, amino groups, epoxy groups, oxetanyl groups, hydrolyzable silyl groups, sulfo groups, and carboxy groups. Note that sulfo groups and carboxy groups can be ionized to form -SO3 - or -COO - It may be chlorided to -SO3 - Na + or -COO - Na + It may be the same as above. Examples of the monomer A2 include unsaturated alcohols such as allyl alcohol, unsaturated carboxylic acids such as (meth)acrylic acid, and vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth)acrylic acid esters, etc., which have a reactive group. Preferred examples of the monomer A2 include vinyl ethers, vinyl esters, allyl ethers, and allyl esters, which have a reactive group.

[0024] From the viewpoint of adhesion between the resin binder 1 and the braided sleeve 2, the unit A2 preferably has a hydroxyl group or a carboxyl group as a reactive group, and particularly preferably has a hydroxyl group. Examples of the monomer A2 having a hydroxyl group include vinyl ethers, vinyl esters, allyl ethers, allyl esters, (meth)acrylic esters, etc. Preferred examples of the monomer A2 having a hydroxyl group include vinyl ethers having a hydroxyl group and allyl ethers having a hydroxyl group.

[0025] The hydroxyl group-containing monomer A2 is a monomer represented by the formula X 1 -Z 1 Preferred are monomers represented by the following formula: X 1 is CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO- or CH2=CHCHO-, preferably CH2=CHO- or CH2=CHCHO-. Z 1 is a monovalent organic group having 2 to 42 carbon atoms and a hydroxyl group. The organic group may be linear or branched. In addition, the organic group may be composed of a ring structure or may include a ring structure. Preferred examples of the organic group include an alkyl group having 2 to 6 carbon atoms and a hydroxyl group, an alkyl group having a hydroxyl group and a cycloalkylene group having 6 to 8 carbon atoms, a polyoxyalkylene group having a hydroxyl group, an alkyl group having 2 to 6 carbon atoms bonded to a polyoxyalkylene group having a hydroxyl group, and an alkyl group having a cycloalkylene group having 6 to 8 carbon atoms bonded to a polyoxyalkylene group having a hydroxyl group.

[0026] The polyoxyalkylene group is preferably a polyoxyalkylene group mainly composed of oxyethylene groups. Examples of oxyalkylene groups other than oxyethylene groups include oxyalkylene groups having 3 to 6 carbon atoms, such as oxypropylene groups, 1,2-oxybutylene groups, and 1,4-oxybutylene groups, with oxypropylene groups being preferred. The proportion of oxyethylene groups to all oxyalkylene groups in the polyoxyalkylene group is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 100 mol% (i.e., polyoxyethylene groups). The number of oxyalkylene groups in the polyoxyalkylene group is preferably 4 or more, more preferably 6 to 40, and particularly preferably 8 to 24.

[0027] When two or more types of monomers A2 having a hydroxyl group are used in combination, it is preferable that at least one of the monomers A2 is a monomer having a polyoxyalkylene group having a hydroxyl group. That is, in this case, the units A2 preferably contain units based on a monomer having a polyoxyalkylene group having a hydroxyl group. The ratio of the content of units based on a monomer having a polyoxyalkylene group having a hydroxyl group to the content of units A2 in the fluorine-containing polymer (content of units based on monomer having a polyoxyalkylene group having a hydroxyl group / content of units A2) is preferably 0.01 to 1.0, more preferably 0.03 to 0.50, in molar ratio.

[0028] Specific examples of the monomer A2 having a hydroxyl group include CH2=CHO-CH2-cycloCH 10 -CH2OH, CH2=CHCH2O-CH2-cycloC6H 10 -CH2OH, CH2=CHO-CH2-cycloCH 10 -CH2-(OCH2CH2) n OH, CH2=CHOCH2CH2OH, CH2=CHOCH2CH2(OCH2CH2) n OH, CH2=CHCH2OCH2CH2OH, CH2=CHCH2OCH2CH2(OCH2CH2) nOH, CH2=CHOCH2CH2CH2CH2OH, and CH2=CHCH2OCH2CH2CH2CH2OH. In addition, "-cycloCH 10 "-" represents a cyclohexylene group, and "-cycloCH 10 The bonding site of "-" is usually 1,4-. n represents an integer of 8 to 24.

[0029] Examples of the monomer A2 having a carboxy group include unsaturated carboxylic acids such as (meth)acrylic acid, and monomers obtained by reacting the hydroxyl group of a monomer having a hydroxyl group with a carboxylic acid anhydride. Specific examples of the monomer A2 having a carboxy group include CH2=CHCOOH, CH(CH3)=CHCOOH, CH2=C(CH3)COOH, HOOCCH=CHCOOH, CH2=CH(CH2) n11 Monomers represented by COOH (where n11 represents an integer of 1 to 10), CH2=CHO(CH2) n12 Examples include a monomer represented by OC(O)CH2CH2COOH (where n12 represents an integer of 1 to 10).

[0030] Two or more types of monomer A2 may be used in combination. The content of units A2 in the fluoropolymer is preferably 0.1 to 35 mol %, more preferably 0.1 to 10 mol %, and particularly preferably 0.2 to 5 mol %, based on the total units contained in the fluoropolymer, in order to improve the heat resistance of the protective sleeve 10 and the adhesion between the resin binder 1 and the braided sleeve 2.

[0031] The fluorine-containing polymer may contain, as a non-fluorine-containing unit, a unit having no reactive group (hereinafter also referred to as unit A3). The unit A3 is preferably a unit based on a monomer selected from vinyl ether, vinyl ester, allyl ether, allyl ester, and (meth)acrylic acid ester (hereinafter also referred to as monomer A3). As the monomer A3, vinyl ethers and vinyl esters are preferred from the viewpoints of copolymerizability with fluoroolefins and heat resistance of the fluorine-containing polymer.

[0032] Specific examples of monomer A3 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl neononanoate (HEXION trade name Veova 9), vinyl neodecanoate (HEXION trade name Veova 10), vinyl versatate, vinyl benzoate, vinyl tert-butylbenzoate, tert-butyl (meth)acrylate, and benzyl (meth)acrylate. Two or more types of monomer A3 may be used in combination. When the fluoropolymer contains units A3, the content of units A3 is preferably 5 to 60 mol %, particularly preferably 10 to 50 mol %, of all units contained in the fluoropolymer, from the viewpoint of improving the heat resistance of the protective sleeve 10 and the adhesion between the resin binder 1 and the braided sleeve 2.

[0033] The fluorine-containing polymer is preferably a copolymer containing units A1, units A2 and units A3, more preferably a copolymer containing units A1, units A2 and units A3 in the stated order of 20 to 70 mol%, 0.1 to 35 mol% and 5 to 60 mol% of the units A1, units A2 and units A3, based on all units contained in the fluorine-containing polymer, and particularly preferably a copolymer containing units A1, units A2 and units A3 in the stated order of 30 to 60 mol%, 0.1 to 10 mol% and 10 to 50 mol%.

[0034] The fluorine-containing polymer may be composited with a polymer that does not have a fluorine atom (hereinafter also referred to as a non-fluorine polymer). Composite means that a core part made of the above-mentioned fluoroolefin homopolymer, copolymer of two or more fluoroolefins, or copolymer of fluoroolefin and a monomer other than fluoroolefin is further subjected to seed polymerization of a monomer that does not have a fluorine atom to form a shell part, thereby constructing a core-shell structure. The core part and the shell part may be chemically bonded.

[0035] The fluorine-containing polymer constituting the core portion is preferably a copolymer of two or more kinds of fluoroolefins. Examples of copolymers of two or more types of fluoroolefins include copolymers of CH2=CF2 and CF2=CF2, copolymers of CH2=CF2 and CF2=CFCF3, copolymers of CH2=CF2 and CF2=CFCl, copolymers of CH2=CF2, CF2=CF2 and CF2=CFCl, copolymers of CH2=CF2, CF2=CF2 and CF2=CFCF3, and copolymers of CF2=CF2 and CF2=CFCF3, and the like, and from the viewpoints of heat resistance and affinity with the shell portion, the copolymer of CH2=CF2 and CF2=CF2 is preferred.

[0036] The non-fluorine-containing polymer constituting the shell is preferably a polymer containing a unit based on a (meth)acrylic acid ester. Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters and (meth)acrylic acid aryl esters. Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate. From the viewpoint of heat resistance, the (meth)acrylic acid ester is preferably at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Two or more (meth)acrylic acid esters may be used in combination. The (meth)acrylic acid ester may have a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an oxetanyl group, or a hydrolyzable silyl group.

[0037] When the fluorine-containing polymer is composited with a non-fluorine-containing polymer to form a core-shell structure, the ratio of the mass of the fluorine-containing polymer in the core part to the mass of the non-fluorine-containing polymer in the shell part (mass of the core part / mass of the shell part) is preferably from 10 / 90 to 90 / 10, more preferably from 20 / 80 to 80 / 20, and particularly preferably from 30 / 70 to 70 / 30.

[0038] The Tg of the fluoropolymer is preferably from 0 to 120°C, particularly preferably from 10 to 70°C, from the viewpoint of the blocking resistance of the resin binder 1. The MFT of the fluoropolymer is preferably from 0 to 100°C, particularly preferably from 10 to 60°C, from the viewpoint of the blocking resistance of the resin binder 1. The Mn of the fluoropolymer is preferably from 10,000 to 200,000, more preferably from 20,000 to 100,000, particularly preferably from 30,000 to 60,000, in view of excellent strength and processability.

[0039] When the fluoropolymer has hydroxyl groups, the hydroxyl value of the fluoropolymer is preferably from 1 to 150 mgKOH / g, more preferably from 5 to 100 mgKOH / g, particularly preferably from 40 to 60 mgKOH / g, from the viewpoint of heat resistance and adhesiveness. When the fluoropolymer has a carboxy group, the acid value of the fluoropolymer is preferably from 1 to 30 mgKOH / g, particularly preferably from 1 to 10 mgKOH / g, from the viewpoint of the stability and adhesiveness of the binder.

[0040] The fluorine atom content in the fluorine-containing polymer is 50% by mass or less, preferably 40% by mass or less, particularly preferably 30% by mass or less, since this reduces fraying of the threads when the protective sleeve 10 is cut. The lower limit of the fluorine atom content in the fluorine-containing polymer is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 25% by mass or more, in order to provide better heat resistance to the protective sleeve 10.

[0041] When the protective sleeve 10 is used to protect a wire bundle in a wire harness of an automobile or an electrical product, the content of silicon atoms in the fluorine-containing polymer is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass, in order to suppress deterioration of the parts that make up the automobile or electrical product. The silicon atom content in the fluorine-containing polymer can be measured by fluorescent X-ray analysis.

[0042] Methods for producing a fluoropolymer include solution polymerization, emulsion polymerization, suspension polymerization, etc. In order to achieve better effects of the present invention, the fluoropolymer is preferably produced in a particulate dispersed state in a liquid medium containing water as the main component. "Containing water as the main component" means that the liquid medium contains 90% by mass or more of water. Therefore, the fluoropolymer is preferably produced by polymerizing each monomer in the presence of water and a polymerization initiator.

[0043] As the fluorine-containing polymer, commercially available products may be used, and specific examples include the "Lumiflon" series (manufactured by AGC), the "Fluon" series (manufactured by AGC), the "Kynar" series (manufactured by Arkema), the "Zeffle" series (manufactured by Daikin Industries, Ltd.), the "Eterflon" series (manufactured by Eternal), and the "Zendura" series (manufactured by Honeywell). Two or more types of fluorine-containing polymers may be used in combination.

[0044] The resin binder 1 may contain a resin other than the above-mentioned fluorine-containing polymer (hereinafter also referred to as other resin). Specific examples of other resins include (meth)acrylic resin, urethane resin, epoxy resin, and polyester resin. It is preferable that the resin binder 1 is substantially free of silicone resin. This can prevent the silicone oligomers generated when the silicone resin is exposed to high temperatures from deteriorating the component to which the protective sleeve 10 is applied. "Substantially free of silicone resin" means that the content of silicone resin is 0.1% by mass or less relative to the total mass of the resin binder 1.

[0045] The content of the fluorine-containing polymer in the resin binder 1 is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and particularly preferably 70 to 100 mass %, relative to the total mass of the resin binder 1. When the content of the resin binder 1 is within the above range, the heat resistance of the protective sleeve 10 can be improved and the fraying of the threads when cut can be reduced at a high level.

[0046] When the resin binder 1 contains other resins, the content of the other resins relative to the total mass of the resin binder 1 is preferably 10 to 70 mass %, more preferably 20 to 60 mass %, and particularly preferably 30 mass % or more and less than 50 mass %.

[0047] The content of resin binder 1 is preferably 20 to 300 mass %, more preferably 50 to 200 mass %, and particularly preferably 70 to 150 mass %, relative to the total mass of braided sleeve 2. When the content of resin binder 1 is within the above range, it is possible to achieve a high level of both heat resistance of protective sleeve 10 and reduced fraying of the threads when cut.

[0048] The resin binder 1 may contain an additive. The additive is a component that is present in the resin binder 1 in a dispersed state. Specific examples of additives include curing agents, curing catalysts, colorants (dyes, organic pigments, inorganic pigments, luster pigments using metals or mica, etc.), ultraviolet absorbers, light stabilizers, leveling agents, surface conditioners, degassing agents, heat stabilizers, thickeners, dispersants, surfactants, antistatic agents, rust inhibitors, antifouling agents, low-staining treatment agents, and plasticizers.

[0049] When the resin binder 1 contains an additive, the content of the additive is preferably 1 to 30 parts by mass, particularly preferably 3 to 15 parts by mass, per 100 parts by mass of the resin binder 1.

[0050] The braided sleeve 2 is a sleeve made of threads 2a. The braided sleeve 2 may have any shape as long as it is tubular so as to be able to accommodate a bundle of electric wires or the like, and may be cylindrical as shown in FIG. 1 or may be rectangular. The braided sleeve 2 may be a sleeve obtained by braiding thread 2a into a tubular shape, or may be a sleeve obtained by forming a flat cloth-like material (e.g., woven fabric, knitted fabric) made by braiding thread 2a into a tubular shape. The braided sleeve 2 may be made of threads 2a made of the same material, or may be made of two or more types of threads 2a made of different materials.

[0051] The yarn 2a contains at least one of inorganic fibers and organic fibers. The yarn 2a may be made of only inorganic fibers, may be made of only organic fibers, or may be made of both inorganic and organic fibers, but is preferably made of only inorganic fibers. Examples of inorganic fibers include glass fibers, carbon fibers, alumina fibers, silica fibers, and alumina-silica fibers. Examples of organic fibers include polyester fibers (for example, polyethylene naphthalate fibers, polyethylene terephthalate fibers), polyphenylene sulfide fibers, aramid fibers, nylon fibers, polyethersulfone fibers, polyetherketone fibers, and tetrafluoroethylene fibers. Among these, the threads 2a are preferably made of glass fibers from the viewpoint of heat resistance. The thread 2a may be a monofilament or a multifilament. The fiber diameter of the thread 2a is not particularly limited and may be appropriately selected depending on the application of the protection sleeve 10.

[0052] The mass proportion of the braided sleeve 2 in the protective sleeve 10 is preferably 20 to 80 mass %, more preferably 30 to 70 mass %, and particularly preferably 40 to 60 mass %, relative to the total mass of the protective sleeve 10.

[0053] The 60-degree specular gloss of the protective sleeve 10 is preferably 50 to 100, more preferably 60 to 100, and particularly preferably 70 to 100. When the 60-degree specular gloss is within this range, the protective sleeve 10 exhibits excellent color development when colored. As a result, even when multiple protective sleeves 10 are used at the same time, they can be easily distinguished from one another. The 60-degree specular gloss of the protection sleeve 10 can be easily adjusted to fall within the above range by using the above-mentioned fluorine-containing polymer.

[0054] The protective sleeve 10 is suitable as a protective sleeve for a wire bundle included in a wire harness. A wire harness includes a wire bundle consisting of a plurality of electric wires and a connector connected to an end of the wire bundle, and is used, for example, in automotive components and electrical products.

[0055] The protective sleeve can be produced by applying a coating material containing a resin binder containing a fluorine-containing polymer and a liquid medium to a braided sleeve and then drying the coating material.

[0056] The liquid medium contained in the paint acts as a dispersion medium to disperse the resin binder in the paint and is a component that evaporates and is removed when the paint dries. The liquid medium contained in the paint allows the resin binder to adhere uniformly to the braided sleeve. The liquid medium includes water and organic solvents, and preferably contains water.

[0057] The resin binder and the fluorine-containing polymer contained in the coating material are as described above.

[0058] The content of the liquid medium is preferably 30 to 70 mass %, particularly preferably 40 to 60 mass %, based on the total mass of the coating material. The content of the resin binder is preferably 30 to 70 mass %, particularly preferably 40 to 60 mass %, based on the total mass of the coating material. The content of the fluorine-containing polymer is preferably from 20 to 70 mass %, particularly preferably from 20 to 60 mass %, based on the total mass of the coating material. When the coating material contains other resins, the content of the other resins is preferably 10 to 50 mass %, more preferably 10 to 30 mass %, and particularly preferably 10 to 20 mass %, relative to the total mass of the coating material. When the coating material contains an additive, the content of the additive is preferably 1 to 30 mass %, particularly preferably 1 to 10 mass %, relative to the total mass of the coating material.

[0059] The paint is preferably one that does not substantially generate cyclic siloxane compounds when heated at 200° C. for 10 minutes, which can prevent deterioration of the component to which the protective sleeve 10 is applied, even when the protective sleeve 10 is used at high temperatures. "Substantially no cyclic siloxane compounds are generated" means that the content of cyclic siloxane compounds generated when the paint is heated at 200°C for 10 minutes is less than 300 μg, and more preferably less than 10 μg, per 1 g of paint. Examples of the cyclic siloxane compound include compounds derived from the above-mentioned silicone resins, such as octamethylcyclotetrasiloxane. The amount of cyclic siloxane compound generated can be measured by the method described in the Examples section below.

[0060] Specific examples of methods for applying paint to a braided sleeve include spray coating, squeegee coating, flow coating, bar coating, spin coating, dip coating, screen printing, gravure printing, die coating, inkjet printing, curtain coating, and methods using a brush or spatula. Among these, it is preferable to use a method that allows the coating material to easily penetrate into the braided sleeve, and the dip coating method is particularly preferable.

[0061] The liquid medium in the coating material adhering to the braided sleeve is preferably removed by drying, thereby forming a coating of the resin binder (a film containing a fluorine-containing polymer). The drying temperature is preferably 50 to 180° C., and the drying time is preferably 30 minutes to 5 hours.

[0062] The protective sleeve includes a braided sleeve and a resin binder that binds the threads in the braided sleeve together. The resin binder may be contained in at least a portion of the braided sleeve. In other words, the resin binder may be attached to at least a portion of the braided sleeve. For example, the protective sleeve may include a configuration in which the resin binder is attached only to the inside or outside of the braided sleeve, or only to a portion thereof, or a configuration in which the entire braided sleeve is impregnated with the resin binder. [Example]

[0063] The present invention will be described in detail below with reference to examples. Examples 1 and 4 are working examples, and Examples 2 and 3 are comparative examples. However, the present invention is not limited to these examples. The blending amounts of each component in the tables below are based on mass.

[0064] [Abbreviation] CTFE: Chlorotrifluoroethylene EVE: Ethyl vinyl ether CHVE: Cyclohexyl vinyl ether CHMVE: Cyclohexyl methyl vinyl ether CM-15EOVE:CH2=CHOCH2-cycloCH 10 -CH2O(CH2CH2O) n H(n=15)

[0065] [Example of production of aqueous dispersion] 103 g of ion-exchanged water, surfactant 1 (5.2 g) (Newcol 2320, Nippon Nyukazai Co., Ltd. product name), surfactant 2 (0.01 g) (SLS, Nikko Chemicals Co., Ltd. product name), and potassium carbonate (0.155 g) were charged into an autoclave that had been vacuum-degassed. CTFE (56 g), EVE (27 g), CHVE (1.2 g), CHMVE (16 g), and CM-15EOVE (2.7 g) were then introduced into the autoclave with stirring. Next, 1.4 g of a 0.5% by mass aqueous solution of ammonium persulfate was introduced into the autoclave. After polymerization for 24 hours, the solution in the autoclave was filtered to obtain an aqueous dispersion L1 (fluoropolymer concentration: 50% by mass) containing particles of fluoropolymer P1 with an average particle size of 150 nm. The fluoropolymer P1 was a polymer containing 50 mol%, 38.5 mol%, 1 mol%, 10 mol% and 0.5 mol% of units based on CTFE, units based on EVE, units based on CHVE, units based on CHMVE and units based on CM-15EOVE, respectively, relative to all monomer units contained in the fluoropolymer P1 (hydroxyl value: 54 mg KOH / g, content of fluorine atoms in the polymer: 27 mass%, Mn: approximately 50,000).

[0066] [Example 1] To 100 parts by mass of aqueous dispersion L1, 7.5 parts by mass of a film-forming aid (Texanol, Eastman Chemical Company trade name) and 0.5 parts by mass of a thickener (RHEOLATE 288, Elementis Corporation trade name) were added, mixed, and dispersed to obtain paint C1. Next, the braided glass fiber sleeve was impregnated with the paint C1. After removing excess paint with a brush, it was dried at 150°C for 1 hour to obtain a protective sleeve in which the braided sleeve was fixed by the resin binder in the paint C1.

[0067] [Example 2] Five parts by mass of GL-200RB as a curing agent was added to 100 parts by mass of Dai-el Latex GL213RA (manufactured by Daikin Corporation), an aqueous dispersion of a fluorine-containing elastomer (fluorine atom content in the polymer: over 50% by mass), to obtain paint C2. A protective sleeve in which the braided sleeve was fixed by the resin binder in paint C2 was obtained in the same manner as in Example 1, except that paint C2 was used instead of paint C1.

[0068] [Example 3] A protective sleeve was obtained in which the braided sleeve was fixed by the resin binder in paint C3 in the same manner as in Example 1, except that silicone varnish TSR117 (manufactured by Momentive Performance Materials) (fluorine atom content in the polymer: 0 mass%) was used as paint C3 instead of paint C1.

[0069] [Example 4] To 100 parts by mass of aqueous dispersion L1, 7.5 parts by mass of a film-forming agent (Texanol, trade name of Eastman Chemical Co.), 0.5 parts by mass of a thickener (RHEOLATE 288, trade name of Elementis Co.), and 10 parts by mass of a curing agent (Bayhydur 3100, trade name of Covestro Co.) were added, mixed, and dispersed to obtain paint C4. A protective sleeve in which the braided sleeve was fixed by the resin binder in the paint C4 was obtained in the same manner as in Example 1, except that the paint C4 was used instead of the paint C1.

[0070] The protective sleeves obtained in each example were evaluated as follows.

[0071] [Fray resistance] The protective sleeve was cut with a cutter, and the presence or absence of fraying of the glass fibers at the cut portion was confirmed. S: No fraying A: No fraying when cut, but fraying occurs when friction is applied B: Frayed

[0072] [Heat resistance] The protective sleeve obtained in each example was immersed in a test lubricating oil (IRM903, trade name of Japan San Oil Co., Ltd.) at 150° C. for 2,000 hours, and the appearance of the sleeve after immersion was observed. A: No swelling B: Swelling is observed but slight C: Obvious swelling is observed

[0073] [Decomposition inhibitor effect] The paint obtained in each example was heated at 200°C for 10 minutes, and the cyclic siloxane (octamethylcyclotetrasiloxane) generated was quantified by thermal desorption (ATD)-GC / MS. A: The amount of cyclic siloxane generated is less than 10 μg / g B: The amount of cyclic siloxane generated is 10 μg / g or more and less than 300 μg / g. C: The amount of cyclic siloxane generated is 300 μg / g or more.

[0074] [60 degree specular gloss] The 60-degree specular gloss of the surface of the protective sleeve obtained in each example was measured according to JIS K 5600-4-7 and evaluated according to the following criteria: The 60-degree specular gloss was measured using a variable-angle glossmeter (product name "UGV-6P", incident / reflecting angle 60 degrees, manufactured by Suga Test Instruments Co., Ltd.). A: 60 degree specular gloss is 50 or more B: 60 degree specular gloss is less than 50

[0075] The results are shown in Table 1.

[0076] [Table 1]

[0077] As shown in Table 1, this protective sleeve showed little fraying of the threads when cut, demonstrating excellent heat resistance (Example 1, Example 4). The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2021-040395, filed on March 12, 2021, are hereby incorporated by reference as the disclosure of the specification of the present invention. [Explanation of symbols]

[0078] 1. Resin binder 2 braided sleeves 2a Thread 10 Protective Sleeve

Claims

1. A protective sleeve comprising a braided sleeve and a resin binder that binds threads in the braided sleeve together, the braided sleeve is made of yarn containing at least one of inorganic fibers and organic fibers, the resin binder contains a fluorine-containing polymer, and the content of fluorine atoms in the fluorine-containing polymer is 25 to 30% by mass; the fluorine-containing polymer comprises a unit based on a fluoroolefin, a unit based on a monomer having no fluorine atom and a reactive group, and a unit having no fluorine atom and no reactive group, the content of units based on the fluoroolefin is 30 to 60 mol %, the content of units based on a monomer having no fluorine atom and a reactive group is 0.1 to 10 mol %, and the content of units having no fluorine atom and no reactive group is 10 to 50 mol %, based on all units contained in the fluorine-containing polymer; A protective sleeve, wherein the content of the fluorine-containing polymer is 70 to 100% by mass based on the total mass of the resin binder.

2. 2. The protective sleeve according to claim 1, wherein the number average molecular weight of the fluorine-containing polymer is 10,000 to 200,000.

3. 3. The protective sleeve according to claim 1, wherein the fluorine-containing polymer does not have a crosslinked structure.

4. A protective sleeve described in any one of claims 1 to 3, wherein the unit based on a monomer having no fluorine atoms and a reactive group is a unit based on at least one monomer having a reactive group and no fluorine atoms selected from the group consisting of vinyl ethers, allyl ethers, vinyl esters and allyl esters.

5. A protective sleeve described in any one of claims 1 to 4, wherein the unit based on a monomer that does not have a fluorine atom and has a reactive group has a hydroxyl group.

6. A protective sleeve as described in claim 5, wherein the unit based on a monomer that does not have a fluorine atom and has a reactive group is a unit based on at least one monomer that has a hydroxyl group and does not have a fluorine atom and is selected from the group consisting of vinyl ethers and allyl ethers.

7. A protective sleeve described in any one of claims 1 to 4, wherein the unit based on a monomer that does not have a fluorine atom and has a reactive group has a hydroxyl group and a polyoxyalkylene group.

8. A protective sleeve as described in Claim 7, wherein the unit based on a monomer that does not have a fluorine atom and has a reactive group is a unit based on at least one monomer selected from the group consisting of vinyl ethers and allyl ethers, which has a hydroxyl group and a polyoxyalkylene group and does not have a fluorine atom.

9. 9. The protective sleeve of claim 7 or 8, wherein the polyoxyalkylene group is a polyoxyethylene group.

10. A protective sleeve described in any one of claims 1 to 9, wherein the unit not having a fluorine atom and a reactive group is a unit based on at least one monomer selected from the group consisting of vinyl ethers and vinyl esters, which does not have a fluorine atom and a reactive group.

11. The protective sleeve according to any one of claims 1 to 10, wherein the protective sleeve has a 60-degree specular gloss of 50 or more.

12. A method for manufacturing a protective sleeve according to any one of claims 1 to 11, A method for producing a protective sleeve, comprising applying a coating material containing a resin binder containing a fluorine-containing polymer and a liquid medium to a braided sleeve to obtain the protective sleeve.

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