Protective sleeve and method of manufacturing a protective sleeve

Abstract

Provided are a protective sleeve in which abrasion of the filaments at the time of cutting is small and heat resistance is excellent, and a method for manufacturing the protective sleeve. The protective sleeve of the present invention is a protective sleeve including: a braided sleeve composed of filaments of fibers including at least one of inorganic fibers and organic fibers, and a resin binder that bonds the filaments in the braided sleeve to each other, the resin binder including a fluorine-containing polymer, the content of fluorine atoms in the fluorine-containing polymer being 50 mass% or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a protective sleeve and a method for manufacturing a protective sleeve. BACKGROUND

[0002] In automobiles, electric appliances, and the like, a wire harness having a wire bundle formed of a plurality of electric wires and a connector connected to an end portion of the wire bundle is sometimes used. In order to protect and bundle the wire bundle constituting such a wire harness, the wire bundle is sometimes arranged in a cylindrical protective sleeve.

[0003] A protective sleeve in which a braided sleeve in which filaments of glass fiber or the like are braided into a cylindrical shape is fixed by a silicone-based varnish is disclosed in Patent Literature 1.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open No. 2012-031527 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] The protective sleeve is sometimes cut and used, and thus it is required that the abrasion of the filaments in the cut portion be small. In addition, the protective sleeve is also required to have excellent heat resistance.

[0009] The present inventors and the like evaluated the protective sleeve described in Patent Literature 1, and as a result, found that the abrasion of the filaments in the cut portion could be suppressed, but there was room for improvement in the heat resistance.

[0010] The present application has been achieved in order to solve the above-described problems, and it is an object of the present application to provide a protective sleeve in which the abrasion of the filaments at the time of cutting is small and the heat resistance is excellent, and a method for manufacturing the protective sleeve.

[0011] MEANS FOR SOLVING THE PROBLEMS

[0012] The present inventors and the like have intensively studied the above-described problems, and as a result, found that if a protective sleeve including a braided sleeve and a resin binder that binds the filaments in the braided sleeve to each other, and the braided sleeve is composed of filaments including at least one of inorganic fibers and organic fibers, and the resin binder contains a fluorine-containing polymer, and the content of fluorine atoms in the fluorine-containing polymer is 50% by mass or less, the desired effects are obtained, and the present application has been achieved.

[0013] That is, the present inventors and the like found that the above-described problems can be solved by the following configuration.

[0014] [1] A protective sleeve including: a braided sleeve, and a resin binder that binds the filaments in the braided sleeve to each other,

[0015] The aforementioned braided sleeve is composed of filaments of fibers including at least one of inorganic fibers and organic fibers,

[0016] The aforementioned resin binder contains a fluorine-containing polymer, and the content of fluorine atoms in the aforementioned fluorine-containing polymer is 50 mass% or less.

[0017] [2] The protective sleeve according to [1], wherein the content of fluorine atoms in the aforementioned fluorine-containing polymer is 5 mass% or more.

[0018] [3] The protective sleeve according to [1] or [2], wherein the number average molecular weight of the aforementioned fluorine-containing polymer is 10,000 to 200,000.

[0019] [4] The protective sleeve according to any one of [1] to [3], wherein the aforementioned fluorine-containing polymer does not have a crosslinked structure.

[0020] [5] The protective sleeve according to any one of [1] to [4], wherein the aforementioned fluorine-containing polymer contains a unit based on a monomer having a reactive group and not having a fluorine atom, the monomer having a reactive group and not having a fluorine atom being at least one selected from the group consisting of a vinyl ether, an allyl ether, a vinyl ester, and an allyl ester.

[0021] [6] The protective sleeve according to any one of [1] to [5], wherein the aforementioned fluorine-containing polymer has a hydroxyl group.

[0022] [7] The protective sleeve according to [6], wherein the aforementioned fluorine-containing polymer having a hydroxyl group contains a unit based on a monomer having a hydroxyl group and not having a fluorine atom, the monomer having a hydroxyl group and not having a fluorine atom being at least one selected from the group consisting of a vinyl ether and an allyl ether.

[0023] [8] The protective sleeve according to any one of [1] to [5], wherein the aforementioned fluorine-containing polymer has a hydroxyl group and a polyoxyalkylene group.

[0024] [9] The protective sleeve according to [8], wherein the aforementioned fluorine-containing polymer having a hydroxyl group and a polyoxyalkylene group contains a unit based on a monomer having a hydroxyl group and a polyoxyalkylene group and not having a fluorine atom, the monomer having a hydroxyl group and a polyoxyalkylene group and not having a fluorine atom being at least one selected from the group consisting of a vinyl ether and an allyl ether.

[0025]

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

[0026]

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

[10] , wherein the fluorine-containing polymer contains units based on a monomer having no fluorine atom and no reactive group, the monomer having no fluorine atom and no reactive group being at least one selected from the group consisting of a vinyl ether and a vinyl ester.

[0027]

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

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

[0028]

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

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

[0029]

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

[13] , wherein,

[0030] a coating containing a resin binder and a liquid medium is attached to a braided sleeve, the resin binder containing a fluorine-containing polymer, to obtain the protective sleeve.

[0031] Effects of the Invention

[0032] According to the present application, it is possible to provide a protective sleeve in which the wire is less abraded at the time of cutting, which is excellent in heat resistance, and a method for manufacturing the protective sleeve. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 A perspective view schematically showing one mode of the protective sleeve of the present application. DETAILED DESCRIPTION

[0034] The terms in the present application are explained below.

[0035] The unit in the polymer refers to the collective term of an atomic group based on one molecule of the monomer directly formed by polymerization of the monomer and an atomic group obtained by chemical conversion of a part of the atomic group. The content (mol%) of each unit with respect to the total units contained in the polymer can be calculated by analyzing the polymer according to nuclear magnetic resonance spectroscopy, or can be determined from the amount of the ingredient used when the polymer is manufactured.

[0036] "(Meth)acrylic acid" is the collective term of "acrylic acid" and "methacrylic acid", and "(Meth)acrylate" is the collective term of "acrylate" and "methacrylate".

[0037] Hydrolyzable silyl group refers to a group that can form a silanol group by a hydrolysis reaction.

[0038] The acid value and the hydroxyl value are values determined according to the method of JIS K 0070-3 (1992).

[0039] The glass transition temperature (Tg) is the midpoint glass transition temperature of the polymer determined by differential scanning calorimetry (DSC) method.

[0040] The minimum film formation temperature (MFT) is the lowest temperature at which a uniform coating film without cracks is formed when the fluorine-containing polymer is dried, and can be determined, for example, using a film formation temperature measuring device, Model IMC-1535 (manufactured by Iyumei Mfg. Co., Ltd.).

[0041] The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values determined by gel permeation chromatography using polystyrene as a standard material.

[0042] The content of fluorine atoms in the fluorine-containing polymer refers to the ratio (%) of the mass of fluorine atoms with respect to the total mass of the fluorine-containing polymer, and can be determined according to nuclear magnetic resonance (NMR) analysis.

[0043] The 60-degree specular gloss is a value determined according to the method of JIS K 5600-4-7 using a variable-angle gloss meter (trade name "UGV-6P", entrance angle 60 degrees, manufactured by Suga Test Instruments Co., Ltd.).

[0044] The protective sleeve (hereinafter, also referred to as the present protective sleeve) of the present application is a protective sleeve including: a braided sleeve composed of filaments of fibers including at least one of inorganic fibers and organic fibers, and a resin binder that bonds the filaments in the braided sleeve to each other, the resin binder including a fluorine-containing polymer, the content of fluorine atoms in the fluorine-containing polymer being 50% by mass or less.

[0045] The present protective sleeve has less abrasion of the filaments at the time of cutting and also has excellent heat resistance. The reason therefor is not necessarily clear, but is considered as follows.

[0046] It is presumed that the fluorine-containing polymer contained in the resin binder that constitutes the present protective sleeve has improved heat resistance due to the inclusion of fluorine atoms. It is also presumed that by making the content of fluorine atoms in the fluorine-containing polymer 50% by mass or less, the function as a binder for bonding the filaments to each other is sufficiently exerted, and the abrasion of the filaments at the time of cutting is suppressed.

[0047] Figure 1 A perspective view schematically showing one mode of the protective sleeve of the present application is shown. As shown in the drawing, 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 filaments 2a. Figure 1

[0048] ​The structure of the protective sleeve 10 is cylindrical so that it can cover a wire bundle formed of a plurality of electric wires.

[0049] For the protective sleeve 10, from the aspect of improvement in work efficiency when covering the wire bundle, an opening portion (not shown) can be provided along the length direction of the protective sleeve 10.

[0050] The resin adhesive 1 functions to fix the filaments 2a constituting the braided sleeve 2 in a state of being bonded to each other. The resin adhesive 1 is present in the protective sleeve 10 in the form of a resin film containing a fluorine-containing polymer.

[0051] The fluorine-containing polymer is a polymer containing a unit having a fluorine atom, and from the aspect of heat resistance of the protective sleeve, a polymer containing a fluoroolefin-based unit (hereinafter, also referred to as unit Al) is preferable.

[0052] The fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with a fluorine atom. One or more hydrogen atoms not substituted with a fluorine atom in the fluoroolefin can be substituted with a chlorine atom. The carbon number of the fluoroolefin is preferably 2 to 6, particularly preferably 2 to 4.

[0053] As the fluorine-containing polymer containing the unit Al, a homopolymer of a fluoroolefin, a copolymer of two or more kinds of fluoroolefins, a copolymer of a fluoroolefin and a monomer other than a fluoroolefin, and the like can be given.

[0054] From the aspect that the adhesion of the resin adhesive 1 to the braided sleeve 2 is more excellent, the fluorine-containing polymer is preferably a copolymer, particularly preferably a copolymer of a fluoroolefin and a monomer other than a fluoroolefin.

[0055] As the fluoroolefin, CF2=CF2, CF2=CFCl, CF2=CHF, CH2=CF2, CF2=CFCF3, CF3-CH=CHF, CF3-CF=CH2, and the like can be given. As the fluoroolefin, from the aspects of heat resistance of the protective sleeve 10 and polymerizability with a monomer other than a fluoroolefin, CF2=CF2 and CF2=CFCl are more preferable, and CF2=CFCl is particularly preferable. Two or more kinds of fluoroolefins can be used in combination.

[0056] For the content of the unit Al, from the aspects of heat resistance of the protective sleeve 10 and adhesion of the resin adhesive 1 to the braided sleeve 2 being more excellent, relative to the total units contained in the fluorine-containing polymer, 20 to 70 mol%, more preferably 30 to 60 mol%, particularly preferably 45 to 55 mol% is preferable.

[0057] As the unit other than the unit Al, a unit based on a monomer not having a fluorine atom (hereinafter, also referred to as a non-fluorine unit) is preferable from the viewpoint of the adhesion of the resin binder 1 to the braided sleeve 2 for the fluorine-containing polymer.

[0058] In the case where the fluorine-containing polymer contains the unit A2, the fluorine-containing polymer can be in a state where at least a part of the reactive group in the unit A2 is reacted with other components (for example, a curing agent and the like), or can be in a state where it is not reacted with other components, but is preferably in a state where it is not reacted with other components. That is, the fluorine-containing polymer in the resin binder 1 can be present in a state where it has a crosslinked structure based on a curing agent, or can be present in a state where it does not have a crosslinked structure, but is preferably present in a state where it does not have a crosslinked structure from the viewpoint of the softness of the protective sleeve 10, and the viewpoint of further reducing the abrasion of the wire when rubbing the cut surface of the protective sleeve 10.

[0059] The unit A2 can be a unit based on a monomer having a reactive group (hereinafter, also referred to as a monomer A2), or can be a unit obtained by converting the group to a different reactive group in a fluorine-containing polymer containing a unit having a reactive group. As the latter unit, a unit obtained by reacting a fluorine-containing polymer containing a unit having a hydroxyl group with a polycarboxylic acid, an acid anhydride thereof, or the like, and converting at least a part of the hydroxyl group to a carboxyl group can be given.

[0060] As the reactive group, a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group, a carboxyl group, and the like can be given. Note that the sulfo group and the carboxyl group can be ionized to -SO3 - or -COO - , or can be chlorinated to -SO3 - Na + or -COO - Na + , and the like.

[0061] As the monomer A2, an unsaturated alcohol such as allyl alcohol, an unsaturated carboxylic acid such as (meth)acrylic acid, and a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, a (meth)acrylate, and the like having a reactive group can be given. As the monomer A2, a vinyl ether, a vinyl ester, an allyl ether, and an allyl ester having a reactive group are preferable.

[0062] As the unit A2, a hydroxyl group or a carboxyl group is preferable as the reactive group from the viewpoint of the adhesion of the resin binder 1 to the braided sleeve 2, and a hydroxyl group is particularly preferable as the reactive group.

[0063] As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0064] As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred. 1 -Z 1 As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0065] X 1 As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0066] As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0067] Z 1 As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0068] As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group, a vinyl ester having a hydroxyl group, an allyl ether having a hydroxyl group, an allyl ester having a hydroxyl group, a (meth)acrylate having a hydroxyl group, and the like can be given. As the monomer A2 having a hydroxyl group, a vinyl ether having a hydroxyl group and an allyl ether having a hydroxyl group are preferred.

[0069] As the polyoxyalkylene group, a polyoxyalkylene group in which an oxyethylene group is predominant is preferred. As the oxyalkylene group other than the oxyethylene group, an oxypropylene group, a 1,2-oxybutylene group, a 1,4-oxybutylene group, and the like can be given, and an oxypropylene group is preferred. The ratio of the oxyethylene group to the total of the 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., a polyoxyethylene group).

[0070] Further, the number of the oxyalkylene groups in the polyoxyalkylene group is preferably 4 or more, more preferably 6 to 40, and particularly preferably 8 to 24.

[0071] In the case where two or more kinds of monomers A2 having a hydroxyl group are used, at least one of the monomers A2 preferably has a polyoxyalkylene group having a hydroxyl group. That is, in this case, the unit A2 preferably includes a unit based on a monomer having a polyoxyalkylene group having a hydroxyl group. The ratio of the content of the unit based on a monomer having a polyoxyalkylene group having a hydroxyl group to the content of the unit A2 in the fluorine-containing polymer (content of the unit based on a monomer having a polyoxyalkylene group having a hydroxyl group / content of the unit A2) is preferably 0.01 to 1.0, more preferably 0.03 to 0.50, in terms of a molar ratio.

[0072] As a specific example of the monomer A2 having a hydroxyl group, CH2=CHO-CH2-cycloC6H 10- CH2OH, CH2=CHCH2O-CH2-cycloC6H 10 -CH2OH, CH2=CHO-CH2-cycloC6H10-CH2-(OCH2CH2) n OH, CH2=CHOCH2CH2OH, CH2=CHOCH2CH2(OCH2CH2) n OH, CH2=CHCH2OCH2CH2OH, CH2=CHCH2OCH2CH2(OCH2CH2) n OH, CH2=CHOCH2CH2CH2CH2OH, and CH2=CHCH2OCH2CH2CH2CH2OH.

[0073] Note that "-cycloC6H 10 -" represents a cyclohexylene group, and "-cycloC6H 10 -" is usually 1,4-. n represents an integer of 8 to 24.

[0074] As the monomer A2 having a carboxyl group, an unsaturated carboxylic acid such as (meth)acrylic acid, a monomer obtained by reacting a hydroxyl group of a monomer having a hydroxyl group with a carboxylic anhydride, and the like can be given.

[0075] As a specific example of the monomer A2 having a carboxyl group, CH2=CHCOOH, CH(CH3)=CHCOOH, CH2=C(CH3)COOH, HOOCCH=CHCOOH, CH2=CH(CH2) n11 COOH (wherein n11 represents an integer of 1 to 10), CH2=CHO(CH2) n12 OC(O)CH2CH2COOH (wherein n12 represents an integer of 1 to 10).

[0076] Two or more kinds of monomers A2 can be used in combination.

[0077] The content of the unit A2 in the fluorine-containing polymer is preferably 0.1 to 35 mol%, more preferably 0.1 to 10 mol%, and particularly preferably 0.2 to 5 mol%, relative to the total units contained in the fluorine-containing polymer, from the viewpoint of the heat resistance of the protective sleeve 10 and the adhesion of the resin binder 1 to the braided sleeve 2.

[0078] The fluorine-containing polymer can contain a unit (hereinafter, also referred to as unit A3) having no reactive group as a non-fluorine unit. The unit A3 is preferably a unit based on a monomer (hereinafter, also referred to as monomer A3) selected from the group consisting of a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, and a (meth)acrylic acid ester.

[0079] As the monomer A3, a vinyl ether and a vinyl ester are preferred from the viewpoint of copolymerizability with a fluoroolefin and the heat resistance of the fluorine-containing polymer.

[0080] Specific examples of the monomer A3 include ethyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, cyclohexylmethyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl neonaonate (HEXION Co., Ltd., trade name: VeoVa 9), vinyl neodecanoate (HEXION Co., Ltd., trade name: VeoVa 10), vinyl versatate, vinyl benzoate, vinyl t-butylbenzoate, t-butyl (meth)acrylate, and benzyl (meth)acrylate.

[0081] Two or more kinds of the monomer A3 can be used in combination.

[0082] In the case where the fluorine-containing polymer contains the unit A3, the content of the unit A3 is preferably 5 to 60 mol%, and particularly preferably 10 to 50 mol%, relative to the total units contained in the fluorine-containing polymer, from the viewpoint of the heat resistance of the protective sleeve 10 and the adhesion of the resin binder 1 to the braided sleeve 2.

[0083] The fluorine-containing polymer is preferably a copolymer containing the unit Al, the unit A2, and the unit A3, and more preferably a copolymer sequentially containing 20 to 70 mol%, 0.1 to 35 mol%, and 5 to 60 mol% of the unit Al, the unit A2, and the unit A3, and particularly preferably a copolymer sequentially containing 30 to 60 mol%, 0.1 to 10 mol%, and 10 to 50 mol% of the unit Al, the unit A2, and the unit A3, relative to the total units contained in the fluorine-containing polymer.

[0084] The fluorine-containing polymer can be compounded with a polymer not having a fluorine atom (hereinafter, also referred to as a non-fluorine polymer). The compounding refers to further seed polymerizing a monomer not having a fluorine atom on the surface of a core portion formed of the above-described homopolymer of a fluorine-containing olefin, the copolymer of two or more kinds of fluorine-containing olefins, or the copolymer of a fluorine-containing olefin and a monomer other than a fluorine-containing olefin to form a shell portion, thereby constructing a core-shell structure. The core portion and the shell portion can have a chemical bond.

[0085] As the fluorine-containing polymer constituting the core portion, the copolymer of two or more kinds of fluorine-containing olefins is preferred.

[0086] As the copolymer of two or more kinds of fluorine-containing olefins, the copolymer of CH2=CF2 and CF2=CF2, the copolymer of CH2=CF2 and CF2=CFCF3, the copolymer of CH2=CF2 and CF2=CFCl, the copolymer of CH2=CF2 and CF2=CF2 and CF2=CFCl, the copolymer of CH2=CF2 and CF2=CF2 and CF2=CFCF3, the copolymer of CF2=CF2 and CF2=CFCF3, and the like can be given, and from the aspects of heat resistance and affinity with the shell portion, the copolymer of CH2=CF2 and CF2=CF2 is preferred.

[0087] As the non-fluorine polymer constituting the shell portion, a polymer containing a (meth)acrylate-based unit is preferred.

[0088] As the (meth)acrylate, alkyl (meth)acrylate, aryl (meth)acrylate, and the like can be given. As specific examples of the (meth)acrylate, 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, phenyl (meth)acrylate can be given. From the aspect of heat resistance, at least one selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate is preferred as the (meth)acrylate.

[0089] Two or more kinds of (meth)acrylates can be used in combination. The (meth)acrylate can have a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, and the like.

[0090] In the case where the fluorine-containing polymer and the non-fluorine polymer are compounded to construct a core-shell structure, the ratio of the mass of the fluorine-containing polymer of the core portion to the mass of the non-fluorine polymer of the shell portion (mass of the core portion / mass of the shell portion) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, and particularly preferably 30 / 70 to 70 / 30.

[0091] From the viewpoint of the blocking resistance of the resin binder 1, the Tg of the fluorine-containing polymer is preferably 0 to 120°C, particularly preferably 10 to 70°C.

[0092] From the viewpoint of the blocking resistance of the resin binder 1, the MFT of the fluorine-containing polymer is preferably 0 to 100°C, particularly preferably 10 to 60°C.

[0093] From the viewpoints of the strength and the processability, the Mn of the fluorine-containing polymer is preferably 10,000 to 200,000, more preferably 20,000 to 100,000, particularly preferably 30,000 to 60,000.

[0094] In the case where the fluorine-containing polymer has a hydroxyl group, from the viewpoints of the heat resistance and the adhesion, the hydroxyl value of the fluorine-containing polymer is preferably 1 to 150 mgKOH / g, more preferably 5 to 100 mgKOH / g, particularly preferably 40 to 60 mgKOH / g.

[0095] In the case where the fluorine-containing polymer has a carboxyl group, from the viewpoints of the stability of the binder and the adhesion, the acid value of the fluorine-containing polymer is preferably 1 to 30 mgKOH / g, particularly preferably 1 to 10 mgKOH / g.

[0096] The content of the fluorine atom in the fluorine-containing polymer is 50% by mass or less, and from the viewpoint of less abrasion of the wire at the time of cutting the protective sleeve 10, it is preferably 40% by mass or less, particularly preferably 30% by mass or less.

[0097] The lower limit of the content of the fluorine atom in the fluorine-containing polymer is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 25% by mass or more, from the viewpoint of more excellent heat resistance of the protective sleeve 10.

[0098] In the case where the protective sleeve 10 is used for the protection of the wire harness in the wire harness of an automobile or an electric product, from the viewpoint of being able to suppress the deterioration of the components constituting the automobile or the electric product, the content of the silicon atom in the fluorine-containing polymer is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 0% by mass.

[0099] The content of the silicon atom in the fluorine-containing polymer can be measured by fluorescent X-ray analysis.

[0100] As the method for producing the fluorine-containing polymer, solution polymerization, emulsion polymerization, suspension polymerization, and the like can be given. From the viewpoint of more excellent effects of the present application, the fluorine-containing polymer is preferably produced in a state of being dispersed in a liquid medium in which water is a main component in the form of particles. By "water being a main component", it means that the liquid medium contains 90% by mass or more of water. Therefore, the fluorine-containing polymer is preferably produced by causing each monomer to polymerize in the presence of water and a polymerization initiator.

[0101] As the fluorine-containing polymer, commercially available products can be used, and as specific examples, "LUMIFLON" series (manufactured by AGC Corporation), "Fluon" series (manufactured by AGC Corporation), "Kynar" series (manufactured by Arkema Inc.), "ZEFFLE" series (manufactured by DAIKIN INDUSTRIES, LTD.), "Eterflon" series (manufactured by Eternal), and "Zendura" series (manufactured by Honeywell) can be given.

[0102] Two or more kinds of fluorine-containing polymers can also be used in combination.

[0103] The resin binder 1 can contain a resin other than the above-described fluorine-containing polymer (hereinafter, also referred to as other resin). As specific examples of the other resin, (meth)acrylic resin, polyurethane resin, epoxy resin, and polyester resin can be given.

[0104] The resin binder 1 is preferably substantially free of silicone-based resin. Thereby, it is possible to suppress the deterioration of the member to which the protective sleeve 10 is applied due to the silicone-based oligomer generated when the silicone resin is exposed to high temperature. By substantially free of silicone-based resin, it means that the content of the silicone resin is 0.1% by mass or less with respect to the total mass of the resin binder 1.

[0105] The content of the fluorine-containing polymer in the resin binder 1 is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass with respect to the total mass of the resin binder 1. When the content of the resin binder 1 is within the above-described range, it is possible to balance the heat resistance of the protective sleeve 10 and the reduction of the abrasion of the wire at the time of cutting at a high level.

[0106] When the resin binder 1 contains the other resin, the content of the other resin is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30% by mass or more and less than 50% by mass with respect to the total mass of the resin binder 1.

[0107] The content of the resin binder 1 is preferably 20 to 300% by mass, more preferably 50 to 200% by mass, and particularly preferably 70 to 150% by mass with respect to the total mass of the braided sleeve 2. When the content of the resin binder 1 is within the above-described range, it is possible to balance the heat resistance of the protective sleeve 10 and the reduction of the abrasion of the wire at the time of cutting at a high level.

[0108] The resin binder 1 can further contain an additive. The additive is a component that is present by being dispersed in the resin binder 1.

[0109] As specific examples of the additives, curing agents, curing catalysts, colorants (dyes, organic pigments, inorganic pigments, luster pigments using metals or mica, etc.), ultraviolet absorbers, light stabilizers, leveling agents, surface adjusting agents, degassing agents, heat stabilizers, thickening agents, dispersants, surfactants, antistatic agents, rust-preventive agents, stain-preventive agents, low-stain treatment agents, plasticizers can be given.

[0110] In the case where 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, relative to 100 parts by mass of the resin binder 1.

[0111] The braided sleeve 2 is a sleeve composed of the filaments 2a.

[0112] The shape of the braided sleeve 2 is only required to be a cylindrical shape so that it can accommodate a wire harness or the like, and as shown in FIG. 1, it can be a circular cylinder or a square cylinder. Figure 1

[0113] The braided sleeve 2 can be a sleeve obtained by braiding the filaments 2a into a cylindrical shape, or a sleeve obtained by forming a planar cloth (for example, a woven fabric, a knitted fabric) composed of the braided filaments 2a into a cylindrical shape.

[0114] The braided sleeve 2 can be composed of the filaments 2a having the same material, or can be composed of two or more kinds of filaments 2a having different materials from each other.

[0115] The filament 2a contains a fiber of at least one of an inorganic fiber and an organic fiber. The filament 2a can be a filament composed of only an inorganic fiber, a filament composed of only an organic fiber, or a filament containing an inorganic fiber and an organic fiber, but is preferably a filament composed of only an inorganic fiber.

[0116] As the inorganic fiber, glass fiber, carbon fiber, alumina fiber, silica fiber, alumina-silica fiber can be given.

[0117] As the organic fiber, polyester fiber (for example, polyethylene naphthalate fiber, polyethylene terephthalate fiber), polyphenylene sulfide fiber, aramid fiber, nylon fiber, polyether sulfone fiber, polyether ketone fiber, tetrafluoroethylene fiber can be given.

[0118] Among them, from the aspect of heat resistance, the filament 2a is preferably a filament formed of glass fiber.

[0119] The filament 2a can be a single filament or a multifilament.

[0120] The fiber diameter of the filament 2a is not particularly limited and can be appropriately selected depending on the use of the protective sleeve 10.

[0121] ​The mass ratio of the braided sleeve 2 in the protective sleeve 10 with respect to the total mass of the protective sleeve 10 is preferably 20 to 80 mass%, more preferably 30 to 70 mass%, particularly preferably 40 to 60 mass%.

[0122] The 60-degree specular gloss of the protective sleeve 10 is preferably 50 to 100, more preferably 60 to 100, particularly preferably 70 to 100. In the case where the 60-degree specular gloss is in the above range, the color development at the time of coloring the protective sleeve 10 is excellent. As a result, even if a plurality of protective sleeves 10 are used at the same time, it is possible to easily distinguish one from another.

[0123] The 60-degree specular gloss of the protective sleeve 10 can be easily adjusted to the above range by using the above-mentioned fluorine-containing polymer.

[0124] The protective sleeve 10 is suitable as a protective sleeve for a wire harness having an electric wire harness formed of a plurality of electric wires and a connector connected to the end portion of the electric wire harness, for example, used for an automobile member, an electrical machine product.

[0125] The method for producing the protective sleeve of the present application can be exemplified by a method of causing a coating material containing a resin binder and a liquid medium to adhere to a braided sleeve and drying, the resin binder including a fluorine-containing polymer. Thereby, the protective sleeve of the present application is obtained.

[0126] The liquid medium contained in the coating material functions as a dispersion medium for dispersing the resin binder in the coating material, and is a component that is evaporated and removed at the time of drying the coating material. The coating material is caused to include the liquid medium, whereby the resin binder is uniformly adhered to the braided sleeve.

[0127] As the liquid medium, water and an organic solvent can be exemplified, and water is preferably included.

[0128] The resin binder and the fluorine-containing polymer contained in the coating material are as described above.

[0129] The content of the liquid medium with respect to the total mass of the coating material is preferably 30 to 70 mass%, particularly preferably 40 to 60 mass%.

[0130] The content of the resin binder with respect to the total mass of the coating material is preferably 30 to 70 mass%, particularly preferably 40 to 60 mass%.

[0131] The content of the fluorine-containing polymer with respect to the total mass of the coating material is preferably 20 to 70 mass%, particularly preferably 20 to 60 mass%.

[0132] In the case where the coating material includes another resin, the content of the other resin with respect to the total mass of the coating material is preferably 10 to 50 mass%, more preferably 10 to 30 mass%, particularly preferably 10 to 20 mass%.

[0133] In the case where the coating material contains an additive, the content of the additive is preferably 1 to 30% by mass, particularly preferably 1 to 10% by mass, relative to the total mass of the coating material.

[0134] The coating material is one which does not substantially generate a cyclic siloxane compound when heated at 200°C for 10 minutes. Thus, the protective sleeve 10 can suppress deterioration of a member to which the protective sleeve 10 is applied even in the case where the protective sleeve 10 is used at a high temperature.

[0135] By "substantially not generating a cyclic siloxane compound" is meant that the content of a cyclic siloxane compound generated when the coating material is heated at 200°C for 10 minutes is less than 300 μg, more preferably less than 10 μg, per 1 g of the coating material.

[0136] As the cyclic siloxane compound, a compound derived from the above-mentioned silicone resin can be given, and for example, octamethylcyclotetrasiloxane can be given.

[0137] The amount of generation of the cyclic siloxane compound can be measured by the method described in the Examples below.

[0138] As a specific example of a method of attaching the coating material to the braided sleeve, a spray coating method, a blade coating method, a flow coating method, a bar coating method, a spin coating method, a dip coating method, a screen printing method, a gravure printing method, a die coating method, an inkjet method, a curtain coating method, a method using a brush, a doctor blade can be given.

[0139] Among them, a method in which the coating material is easily impregnated into the braided sleeve is preferred, and a dip coating method is particularly preferred.

[0140] The liquid medium in the coating material attached to the braided sleeve is preferably removed by drying. Thus, a film of a resin binder (a film containing a fluorine-containing polymer) is formed.

[0141] The drying temperature is preferably 50 to 180°C, and the drying time is preferably 30 minutes to 5 hours.

[0142] The present protective sleeve contains a braided sleeve and a resin binder which bonds the wires in the braided sleeve to each other. The resin binder can be contained in at least a part of the braided sleeve. That is, the resin binder can be attached to at least a part of the braided sleeve. For example, the present protective sleeve contains a mode in which the resin binder is attached to only the inner side or only the outer side of the braided sleeve, or a part thereof; a mode in which the entire braided sleeve is impregnated with the resin binder.

[0143] Examples

[0144] The present application is explained in detail below using examples. Examples 1 and 4 are examples, and Examples 2 and 3 are comparative examples. However, the present application is not limited to these examples. Note that the compounding amounts of the respective components in the tables described below are indicated on a mass basis.

[0145] [Abbreviations]

[0146] CTFE: chlorotrifluoroethylene

[0147] EVE: ethyl vinyl ether

[0148] CHVE: cyclohexyl vinyl ether

[0149] CHMVE: cyclohexyl methyl vinyl ether

[0150] CM-15EOVE: CH2=CHOCH2-cycloC6H 10 -CH2O(CH2CH2O) n H (n = 15)

[0151] [Example of production of aqueous dispersion]

[0152] Ion exchange water 103 g, surfactant 1 (5.2 g) (Newcol 2320, NIPPON NYUKAZAI CO., LTD. trade name), surfactant 2 (0.01 g) (SLS, Nikko Chemicals Co., Ltd. trade name), potassium carbonate (0.155 g) were put in, and under stirring, CTFE (56 g), EVE (27 g), CHVE (1.2 g), CHMVE (16 g), CM-15EOVE (2.7 g) were introduced into a high-pressure vessel which had been vacuum degassed. Then, an aqueous ammonium persulfate solution (1.4 g) having a concentration of 0.5 mass% was introduced into the high-pressure vessel, and after polymerization for 24 hours, the solution in the high-pressure vessel was filtered to obtain an aqueous dispersion L1 containing particles of fluorine-containing polymer P1 having an average particle diameter of 150 nm (fluorine-containing polymer concentration: 50 mass%).

[0153] The fluorine-containing polymer P1 is a polymer containing, in the order, 50 mol%, 38.5 mol%, 1 mol%, 10 mol%, 0.5 mol% of CTFE-based units, EVE-based units, CHVE-based units, CHMVE-based units, and CM-15EOVE-based units, relative to the total monomer units contained in the fluorine-containing polymer P1 (hydroxyl value: 54 mgKOH / g, content of fluorine atoms in the polymer: 27 mass%, Mn: about 50000).

[0154] [Example 1]

[0155] To 100 parts by mass of the aqueous dispersion L1, 7.5 parts by mass of a film-forming aid (Texanol, trade name of Eastman Chemical Company), 0.5 parts by mass of a thickening agent (RHEOLATE 288, trade name of Elementis PLC) were added and mixed to disperse, to obtain a coating C1.

[0156] Next, the braided sleeve of glass fiber was impregnated with the coating C1. After removing the coating that was attached in excess with a brush, heat drying was performed at 150°C for 1 hour to obtain a protective sleeve in which the braided sleeve was fixed with the resin binder in the coating C1.

[0157] [Example 2]

[0158] To 100 parts by mass of DAI-EL Latex GL213RA (manufactured by Daikin Industries, Ltd.) (content of fluorine atoms in the polymer: more than 50 mass%) as an aqueous dispersion of a fluorine-containing elastomer, 5 parts by mass of GL-200RB as a curing agent was added to obtain a coating C2. Using the coating C2 instead of the coating C1, a protective sleeve in which the braided sleeve was fixed with the resin binder in the coating C2 was obtained in the same manner as in Example 1.

[0159] [Example 3]

[0160] Using silicone varnish TSR117 (manufactured by Momentive Performance Materials Inc.) (content of fluorine atoms in the polymer: 0 mass%) as a coating C3 instead of the coating C1, a protective sleeve in which the braided sleeve was fixed with the resin binder in the coating C3 was obtained in the same manner as in Example 1.

[0161] [Example 4]

[0162] To 100 parts by mass of the aqueous dispersion L1, 7.5 parts by mass of a film-forming aid (Texanol, trade name of Eastman Chemical Company), 0.5 parts by mass of a thickening agent (RHEOLATE 288, trade name of Elementis PLC), and 10 parts by mass of a curing agent (Bayhydur 3100, trade name of Covestro) were added and mixed to disperse, to obtain a coating C4.

[0163] Using the coating C4 instead of the coating C1, a protective sleeve in which the braided sleeve was fixed with the resin binder in the coating C4 was obtained in the same manner as in Example 1.

[0164] For the protective sleeves of each example obtained, the following evaluations were performed.

[0165] [Resistance to abrasion]

[0166] Cut the protective sleeve with a cutter and check for wear on the glass fibers in the cut section.

[0167] S: No wear

[0168] A: There is no wear during cutting, but wear will occur if friction is applied.

[0169] B: Wear and tear

[0170] [Heat resistance]

[0171] The protective sleeves obtained in each case were immersed in the test lubricating oil (IRM903, trade name of JAPAN SUN OIL COMPANY, LTD.) at 150°C for 2000 hours. The appearance of the sleeves after immersion was observed.

[0172] A: No swelling

[0173] B: Swelling is visible, but weak.

[0174] C: Obvious swelling is visible.

[0175] [Decomposition product inhibition effect]

[0176] The coatings obtained in each example were heated at 200°C for 10 minutes, and the cyclic siloxanes (octamethylcyclotetrasiloxane) produced were quantified by thermal desorption (ATD)-GC / MS.

[0177] A: The amount of cyclic siloxanes produced is less than 10 μg / g

[0178] B: Cyclic siloxane production is above 10 μg / g and below 300 μg / g

[0179] C: Cyclic siloxane production is above 300 μg / g

[0180] [60-degree mirror finish]

[0181] The 60-degree specular gloss of the surface of the protective sleeves obtained in each example was determined 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 gloss meter (trade name "UGV-6P", incident reflection angle 60 degrees, manufactured by Suga Test Instruments Co., Ltd.).

[0182] A: A 60-degree mirror finish has a gloss level of 50 or higher.

[0183] B: 60-degree mirror gloss level is less than 50.

[0184] The results are shown in Table 1.

[0185] [Table 1]

[0186] Example 1 Example 2 Example 3 Example 4 Wear resistance S B S A Heat resistance A A C B Decomposition inhibitor effect A A C A 60-degree specular gloss A B A A

[0187] As shown in Table 1, it can be confirmed that the abrasion of the wire at the time of cutting of the protective sleeve is small, and the heat resistance is excellent (Example 1, Example 4).

[0188] Note that the specification, claims, abstract, and drawings of Japanese Patent Application No. 2021-040395 filed on March 12, 2021 are hereby incorporated by reference in their entirety into the present specification as a disclosure of the present application.

[0189] Explanation of Reference Signs

[0190] 1 Resin Binder

[0191] 2 Braided Sleeve

[0192] 2a Wire

[0193] 10 Protective Sleeve

Claims

1. A protective sleeve comprising: a braided sleeve, and a resin binder that bonds filaments in the braided sleeve to each other, the braided sleeve is composed of filaments of fibers including at least one of inorganic fibers and organic fibers, the resin binder includes a fluorine-containing polymer, a content of fluorine atoms in the fluorine-containing polymer is 5 mass% or more and 50 mass% or less, the fluorine-containing polymer includes a unit based on a monomer having a reactive group and not having a fluorine atom and a unit based on a monomer not having a fluorine atom and a reactive group.

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

3. The protective sleeve of claim 1 or 2, wherein, the fluorine-containing polymer does not have a crosslinked structure.

4. The protective sleeve of claim 1 or 2, wherein, the monomer having a reactive group and not having a fluorine atom is at least one selected from the group consisting of a vinyl ether, an allyl ether, a vinyl ester, and an allyl ester.

5. The protective sleeve of claim 1 or 2, wherein, the fluorine-containing polymer has a hydroxyl group.

6. The protective sleeve of claim 5, wherein, the fluorine-containing polymer having a hydroxyl group contains a unit based on a monomer having a hydroxyl group and not having a fluorine atom, the monomer having a hydroxyl group and not having a fluorine atom being at least one selected from the group consisting of a vinyl ether and an allyl ether.

7. The protective sleeve of claim 1 or 2, wherein, the fluorine-containing polymer has a hydroxyl group and a polyoxyalkylene group.

8. The protective sleeve of claim 7, wherein, the fluorine-containing polymer having a hydroxyl group and a polyoxyalkylene group contains a unit based on a monomer having a hydroxyl group and a polyoxyalkylene group and not having a fluorine atom, the monomer having a hydroxyl group and a polyoxyalkylene group and not having a fluorine atom being at least one selected from the group consisting of a vinyl ether and an allyl ether.

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

10. The protective sleeve of claim 1 or 2, wherein, the monomer not having a fluorine atom and a reactive group is at least one selected from the group consisting of a vinyl ether and a vinyl ester.

11. The protective sleeve of claim 1 or 2, wherein, a content of the fluorine-containing polymer is 30 to 100 mass% with respect to a total mass of the resin binder.

12. The protective sleeve of claim 1 or 2, wherein, a 60-degree specular gloss of the protective sleeve is 50 or more.

13. A method for manufacturing a protective sleeve according to any one of claims 1 to 12, wherein, a coating material containing a resin binder and a liquid medium, the resin binder including a fluorine-containing polymer, is attached to a braided sleeve to obtain the protective sleeve.

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