Functional fabrics and their uses

Abstract

To provide a functional fabric having functions such as pollution-preventing and antivibration properties, while maintaining a tactile feeling that a base fabric originally has without losing flexibility (suppleness and stiffness).SOLUTION: A functional fabric comprises a base fabric (Y) and a functional membrane (X) containing a 4-methyl-1-pentene-based copolymer (A) that meets the following requirements (a) to (d): (a) the copolymer comprises 65-93 mol% of a component unit (i) derived from 4-methyl-1-pentene and 7-35 mol% of a component unit (ii) derived from a 2-4C α-olefin; (b) extreme viscosity [η], measured in decalin at 135°C, is 0.5-5.0 dl / g; (c) a melting point (Tm), measured by differential scanning calorimetry, is less than 200°C or substantially unobservable; (d) density is 820-850 kg / m3; and (e) molecular weight distribution (Mw / Mn), a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), is 1.0-3.5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a functional fabric containing a 4-methyl-1-pentene copolymer and uses thereof. [Background technology]

[0002] Conventionally, in the fields of clothing, daily necessities, medical products, automobile parts, and the like, attempts have been made to enhance the stain-resistant function by imparting water-repellent, oil-repellent, and the like to synthetic or natural fiber fabrics, and in particular, fluorine-based polymers (Patent Document 1) and urethane resins (Patent Document 2) have been used as water-repellent materials.

[0003] For example, Patent Document 1 discloses a synthetic fiber fabric in which a copolymer coating consisting of a fluorine-containing polymer monomer, a fluorine-free comonomer, and a crosslinking agent is formed between the fabric and a fluorine-containing polymer.

[0004] Patent Document 2 discloses a method for producing a coated fabric, which comprises applying a coating resin solution made of a synthetic polymer mainly composed of polyurethane resin or polyamino acid urethane resin to a polyester fiber fabric dyed with a disperse dye to form a coating film, and then crosslinking the film with an electron beam.

[0005] In addition to water repellency, attempts have been made to impart vibration-damping properties to materials such as artificial leather and synthetic leather. For example, Patent Documents 3 and 4 describe that specific styrene-based thermoplastic elastomer (TPS) compositions can be used for applications such as synthetic leather and artificial leather with vibration-damping properties. Patent Document 4 also describes that compositions in which TPS or the like is blended with a specific polyurethane-based elastomer (TPU) with vibration-damping properties can be used for artificial leather and synthetic leather.

[0006] On the other hand, 4-methyl-1-pentene copolymers are superior to polyethylene and polypropylene in heat resistance, transparency, electrical properties, etc., and are widely used in a variety of applications, particularly known as industrial release films, capacitor films, etc. Furthermore, by adjusting the molecular weight and composition of 4-methyl-1-pentene copolymers to lower their melting point, they are able to maintain heat resistance and release properties while improving solubility in solvents, and their application to industrial films has been disclosed (see Patent Documents 5 and 6). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 60-39482 [Patent Document 2] Japanese Patent Application Publication No. 7-11586 [Patent Document 3] Patent No. 5236417 [Patent Document 4] Patent No. 4184178 [Patent Document 5] Patent No. 5840064 [Patent Document 6] Japanese Patent Application Publication No. 2017-132251 Summary of the Invention [Problem to be solved by the invention]

[0008] As mentioned above, various methods for imparting functionality to base fabrics have been disclosed, but it has been difficult to impart contamination prevention and vibration-damping properties to base fabrics while maintaining the original feel of the base fabric. Furthermore, fluorine-based materials have become environmentally hazardous, such as the emission of fluorine-based gases when disposed of, so there has been a demand for olefin-based materials with a low environmental impact. Furthermore, coating base fabrics or laminating them with base fabrics can cause problems such as loss of stiffness and flexibility, whitening when bent, and stickiness if made too flexible. Therefore, there is a need for a material that can provide a good fit without losing flexibility (flexibility and stiffness) and improve the non-stick properties of the outermost layer.

[0009] The object of the present invention is to provide a functional fabric that has been endowed with functions such as stain prevention and vibration damping properties while maintaining the original feel of the base fabric without losing its softness (suppleness and stiffness). [Means for solving the problem]

[0010] In view of the above circumstances, the present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that the above-mentioned problems can be solved by impregnating or laminating a functional film containing a specific 4-methyl-1-pentene copolymer into a base fabric, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [8].

[0011] [1] A functional fabric comprising a base fabric (Y) and a functional film (X) containing a 4-methyl-1-pentene copolymer (A) that satisfies the following requirements (a) to (d): (a) a copolymer containing 65 to 93 mol % of structural units (i) derived from 4-methyl-1-pentene and 7 to 35 mol % of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (provided that the total of structural units (i) and structural units (ii) is 100 mol %); (b) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g; (c) a melting point (Tm) of less than 200°C or substantially no melting point as measured by differential scanning calorimetry (DSC); (d) Density is 820 to 850 kg / m 3 is; (e) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC), is 1.0 to 3.5.

[0012] [2] The 4-methyl-1-pentene copolymer (A) has at least one functional group selected from the group consisting of an active hydrogen-containing functional group, an acid anhydride group, and an epoxy group. The functional fabric according to [1].

[0013] [3] The functional fabric according to item [1] or [2], wherein the base fabric (Y) is selected from woven fabrics and nonwoven fabrics made of natural fibers or synthetic fibers.

[0014] [4] The functional film (X) contains the 4-methyl-1-pentene copolymer (A) and a solvent (B) having a relative dielectric constant of 5 or less at 25 ° C., and the content of the solvent (B) is 0.001 to 0.5 mass% relative to 100 mass% of the functional film (X). The functional fabric according to any one of items [1] to [3].

[0015] [5] A method for producing the functional fabric according to any one of items [1] to [4], comprising: a first step of applying a coating agent containing the 4-methyl-1-pentene copolymer (A) and a solvent (B) having a relative dielectric constant of 5 or less at 25°C to the base fabric (Y); and a second step of drying the base fabric (Y) to which the coating agent has been applied, thereby forming the functional film (X).

[0016] [6] A method for producing the functional fabric according to any one of items [1] to [3], comprising a step of laminating a functional film (X) containing the 4-methyl-1-pentene copolymer (A) onto the base fabric (Y).

[0017] [7] Clothing material comprising the functional fabric according to any one of items [1] to [4]. [8] Outdoor equipment comprising the functional fabric described in any one of items [1] to [4]. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a functional fabric that retains the mold releasability, water repellency, and vibration damping properties that are characteristic of 4-methyl-1-pentene copolymers, and does not impair the texture or flexibility of the base fabric. DETAILED DESCRIPTION OF THE INVENTION

[0019] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be practiced with appropriate modifications within the scope of the object of the present invention. In this specification, the terms "polymer" and "(co)polymer" are used to include homopolymers and copolymers unless otherwise specified.

[0020] The functional fabric according to the present invention is characterized by comprising a base fabric (Y) and a functional film (X) containing a 4-methyl-1-pentene copolymer (A) described below. In one embodiment of the functional fabric according to the present invention, the functional film (X) preferably contains a solvent (B) having a relative dielectric constant of 5 or less at 25°C, and the content of the solvent (B) is preferably 0.001 to 0.5% by mass relative to 100% by mass of the functional film (X).

[0021] [Base fabric (Y)] As the base fabric (Y) used in the functional fabric of the present invention, any sheet-like fibrous substrate having a suitable thickness, a firm feel, and a soft texture can be used, and various fibrous substrates made of woven or nonwoven fabrics made of natural or synthetic fibers, artificial leather, synthetic leather, natural leather, etc. are preferably used.

[0022] The woven or nonwoven fabric made of the above-mentioned natural or synthetic fibers (hereinafter also referred to as "fibrous materials") is not particularly limited, and conventionally known fabrics can be used. Examples of the fibrous materials include natural fibers such as cotton, linen, silk, and wool; regenerated fibers such as rayon and cupra; and synthetic fibers such as polyester, nylon, acrylic, polyurethane, polypropylene, polyethylene, poly-4-methyl-1-pentene, and polyvinyl chloride. Examples of woven fabrics include woven fabrics and knitted fabrics made from the above-mentioned fibrous materials. Examples of nonwoven fabrics include those made by entangling the above-mentioned fibrous materials into a web by chemical methods, mechanical methods, or a combination thereof.

[0023] Specific embodiments of the fibrous substrate include fibrous sheets such as entangled nonwoven sheets and knitted / woven sheets formed using ultrafine fibers or bundles thereof, special porous fibers, ordinary synthetic fibers, semi-synthetic fibers, natural fibers, inorganic fibers, etc.

[0024] Among the above-mentioned fibrous base materials, a fibrous sheet formed using ultrafine fibers or bundles of ultrafine fibers is preferably used, and the single fiber fineness of the ultrafine fibers constituting the fibrous sheet is preferably 0.5 dtex or less, and more preferably 0.1 dtex or less.

[0025] When the fibrous substrate is made of ultrafine fiber bundles, the total fineness of the ultrafine fiber bundles is preferably 0.5 to 10 dtex in terms of the feel of the functional fabric, etc. The ultrafine fibers constituting the fibrous substrate are preferably made of polyester fibers and / or polyamide fibers in terms of the strength, feel, cost, etc. of the resulting functional fabric.

[0026] The base fabric (Y) used in the present invention may have a coating layer of a surface treatment agent formed on the surface of the base fabric (Y) in order to improve adhesion with the 4-methyl-1-pentene copolymer (A) described below, and in this case, the thickness of the coating layer is preferably 5 μm or less. If the thickness of the coating layer is too thick, it becomes difficult to obtain a functional fabric having a soft and unified feel.

[0027] The thickness of the woven or nonwoven fabric made of the natural or synthetic fibers is preferably 20 μm to 3000 μm, more preferably 20 μm to 1500 μm, and even more preferably 50 μm to 1000 μm, in terms of ease of handling.

[0028] [4-methyl-1-pentene copolymer (A)] The 4-methyl-1-pentene copolymer (A) used in the present invention satisfies all of the following requirements (a) to (e).

[0029] <Requirement (a)> The 4-methyl-1-pentene copolymer (A) is a copolymer containing 65 to 93 mol % of structural units (i) derived from 4-methyl-1-pentene and 7 to 35 mol % of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (provided that the total of structural units (i) and structural units (ii) is 100 mol %).

[0030] The above requirement (a) stipulates that the 4-methyl-1-pentene copolymer (A) has a specific ratio of structural units (i) derived from 4-methyl-1-pentene and structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms.

[0031] In this specification, a structural unit derived from an α-olefin refers to a structural unit corresponding to an α-olefin, i.e., a structural unit represented by -CH-CHR- (where R is a hydrogen atom or an alkyl group). The same can be said for the structural unit (i) derived from 4-methyl-1-pentene, and refers to a structural unit corresponding to 4-methyl-1-pentene (i.e., a structural unit represented by -CH-CH(-CHCH(CH))-).

[0032] In the 4-methyl-1-pentene copolymer (A), the lower limit of the amount of the structural unit (i) is 65 mol%, preferably 67 mol%, more preferably 68 mol%, and the upper limit of the amount of the structural unit (i) is 93 mol%, preferably 91 mol%, more preferably 90 mol%.

[0033] In the 4-methyl-1-pentene copolymer (A), when the amount of the structural unit (i) is equal to or greater than the lower limit, flexibility and water repellency are easily achieved. On the other hand, when the amount of the structural unit (i) is equal to or less than the upper limit, the melting point (described later) increases, resulting in a stiff feeling and a hard base fabric.

[0034] Therefore, in the 4-methyl-1-pentene copolymer (A), the upper limit for the amount of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms is 35 mol%, preferably 33 mol%, and more preferably 32 mol%, and the lower limit for the amount of structural units (ii) is 7 mol%, preferably 9 mol%, and more preferably 10 mol%.

[0035] The content (mol %) of each structural unit constituting the 4-methyl-1-pentene copolymer (A) is: 13 The measurement is carried out by C-NMR. Details of the measurement method are as described in the Examples below.

[0036] Thus, the 4-methyl-1-pentene copolymer (A) used in the present invention contains an α-olefin having 2 to 4 carbon atoms as the α-olefin. The structural unit (ii) may be derived from one of these α-olefins, or from two or more α-olefins. When the structural unit (ii) is derived from one α-olefin, it is preferably propylene.

[0037] <Requirement (b)> The 4-methyl-1-pentene copolymer (A) has an intrinsic viscosity [η] measured in decalin at 135° C. in the range of 0.5 to 5.0 dl / g.

[0038] The intrinsic viscosity [η] is preferably 1.0 to 4.0 dL / g, more preferably 1.2 to 3.5 dL / g. As will be described later, the molecular weight can be controlled by using hydrogen in combination during polymerization, and a wide range of molecular weights can be obtained, from low to high, and the intrinsic viscosity [η] can be adjusted to fall within the above range. Details of the measurement method are as described in the Examples below.

[0039] <Requirement (c)> The 4-methyl-1-pentene copolymer (A) has a melting point (Tm) of less than 200° C. or substantially no melting point as measured by differential scanning calorimetry (DSC).

[0040] The melting point (Tm) is preferably 160°C or lower or not substantially observable, more preferably 150°C or lower or not substantially observable, particularly preferably 150°C or lower. Note that "not substantially observable melting point" means that the heat of fusion ΔH(Tm) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially observable, being 0 J / g. "not substantially observable heat of fusion ΔH(Tm)" means that no peak is observed in DSC measurement.

[0041] The lower limit of the melting point (Tm) observed is preferably 110°C, more preferably 120°C, and even more preferably 125°C.

[0042] By satisfying these requirements, the functional fabric of the present invention can have high water repellency and flexibility, and the stiff feeling is reduced.

[0043] <Requirement (d)> The density of the 4-methyl-1-pentene copolymer (A) is 820 to 850 kg / m 3 is.

[0044] The density is preferably 825 to 850 kg / m 3 , more preferably 830 to 850 kg / m 3The details of the measurement method are as described in the Examples below. The density of the 4-methyl-1-pentene copolymer (A) can be appropriately changed by changing the comonomer composition ratio of the 4-methyl-1-pentene-α-olefin copolymer. The 4-methyl-1-pentene copolymer (A) having a density within the above range is advantageous because it has good transparency and mold releasability.

[0045] <Requirement (e)> The 4-methyl-1-pentene copolymer (A) has a molecular weight distribution (Mw / Mn), which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC), in the range of 1.0 to 3.5.

[0046] The molecular weight distribution (Mw / Mn) is preferably 1.2 to 3.0, more preferably 1.5 to 2.8. When the molecular weight distribution (Mw / Mn) is within the above range, the influence of low molecular weight and low stereoregular polymers resulting from the composition distribution is small, and the mechanical strength of the obtained molded product (film, etc.) is less likely to decrease, which is preferable.

[0047] The 4-methyl-1-pentene copolymer (A) preferably satisfies one or more, more preferably all, of the following requirements (f) to (g):

[0048] <Requirement (f)> The 4-methyl-1-pentene copolymer (A) has a weight average molecular weight (Mw) of preferably 1,000 to 1,000,000, more preferably 5,000 to 800,000, and even more preferably 10,000 to 500,000, as calculated in terms of polystyrene, as measured by gel permeation chromatography (GPC). Details of the measurement method are as described in the examples below.

[0049] <Requirement(g)> The melt mass flow rate (MFR; according to ASTM D1238, temperature 230°C, load 2.16 kg) of the 4-methyl-1-pentene copolymer (A) is preferably in the range of 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and even more preferably 1.0 to 30 g / 10 min.

[0050] When the melt mass flow rate (MFR) of the 4-methyl-1-pentene copolymer (A) is within the above range, good dispersibility is obtained, and the molecular weight of the resin is not too low, so that sufficient mechanical strength can be obtained as a molded product (film, etc.), which is preferable.

[0051] In another preferred embodiment, the 4-methyl-1-pentene copolymer (A) has one or more functional groups selected from the group consisting of an active hydrogen-containing group, an acid anhydride group, and an epoxy group. These functional groups are preferably contained in the 4-methyl-1-pentene copolymer (A) in an amount of 0.1 to 10.0 equivalents. The introduction (modification) of these functional groups into the copolymer (A) can be carried out by known methods, and is not particularly limited.

[0052] By introducing a functional group into the 4-methyl-1-pentene copolymer (A), it is possible to impart adhesion to a base fabric (Y) having a polar group, such as natural fibers, polyester, acrylic, polyamide, etc., and to obtain a functional fabric in which the functional film (X) does not peel off when bent.

[0053] <Method for producing 4-methyl-1-pentene copolymer (A)> The method for producing the 4-methyl-1-pentene copolymer (A) is not particularly limited. For example, the copolymer can be produced by polymerizing 4-methyl-1-pentene and the above-mentioned α-olefin having 2 to 4 carbon atoms in the presence of an appropriate polymerization catalyst such as a magnesium-supported titanium catalyst or a metallocene catalyst.

[0054] Suitable polymerization catalysts that can be used here include conventionally known catalysts, such as magnesium-supported titanium catalysts and metallocene catalysts described in International Publication Nos. 01 / 53369, 01 / 27124, JP-A-3-193796, JP-A-2-41303, JP-A-2011 / 055803, and JP-A-2014 / 050817. Polymerization can be carried out by a method appropriately selected from liquid-phase polymerization methods including solution polymerization and suspension polymerization, and gas-phase polymerization methods.

[0055] In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent constituting the liquid phase. Examples of the inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof.

[0056] Furthermore, in the liquid phase polymerization method, bulk polymerization can also be performed using the monomer corresponding to the structural unit (i) derived from the aforementioned 4-methyl-1-pentene (i.e., 4-methyl-1-pentene) or the monomer corresponding to the structural unit (ii) derived from the aforementioned α-olefin having 2 to 4 carbon atoms (i.e., the aforementioned α-olefin having 2 to 4 carbon atoms) itself as a solvent.

[0057] Furthermore, by copolymerizing the above-mentioned 4-methyl-1-pentene with the above-mentioned α-olefin having 2 to 4 carbon atoms in a stepwise manner, it is also possible to appropriately control the composition distribution of the 4-methyl-1-pentene structural units (i) and the α-olefin structural units (ii) constituting the 4-methyl-1-pentene-α-olefin copolymer (A).

[0058] The polymerization temperature is preferably −50 to 200° C., more preferably 0 to 100° C., and further preferably 20 to 100° C. The polymerization pressure is preferably normal pressure to 10 MPa gauge pressure, and more preferably normal pressure to 5 MPa gauge pressure.

[0059] During polymerization, hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the resulting polymer. The appropriate amount of hydrogen to be added is about 0.001 to 100 nL per 1 kg of the total amount of the 4-methyl-1-pentene and the α-olefin having 2 to 4 carbon atoms.

[0060] [Solvent (B)] The solvent (B) is not particularly limited as long as it is a liquid substance having a relative dielectric constant of 5 or less at 25°C and capable of dissolving at least a portion of the 4-methyl-1-pentene copolymer (A). Examples of the solvent (B) include aliphatic hydrocarbon solvents such as n-hexane, n-heptane, n-octane, naphthenic solvents, and isoparaffinic solvents, and aromatic solvents.

[0061] The naphthenic solvent is a compound containing a structure derived from naphthene in one molecule, and specific examples thereof include cyclohexane, methylcyclohexane, ethylcyclohexane, and Exxol D (registered trademark, manufactured by ExxonMobil Corporation).

[0062] The isoparaffinic solvent is a compound containing a structure derived from isoparaffin in one molecule, and specific examples thereof include IP Solvent (registered trademark, manufactured by Idemitsu Kosan Co., Ltd.), Shellsol (registered trademark, manufactured by Shell Chemical Co., Ltd.), and Isopar (registered trademark, manufactured by ExxonMobil Corporation).

[0063] The aromatic solvent is a compound containing a structure derived from an aromatic group such as a benzene ring in one molecule. Specific examples thereof include toluene, xylene, Solvesso (registered trademark, manufactured by ExxonMobil Corporation), Ipsol (registered trademark, manufactured by Idemitsu Kosan Co., Ltd.), mineral spirits, etc.

[0064] The 4-methyl-1-pentene copolymer (A) is uniformly spread by adding a solvent (B) having a relative dielectric constant of 5 or less at 25° C. to the 4-methyl-1-pentene copolymer (A). Therefore, by impregnating a base fabric (Y) with a coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) and drying it, the surface smoothness and uniformity of the functional fabric tend to be improved.

[0065] The boiling point of the solvent (B) is preferably 10 to 300° C., more preferably 20 to 250° C., and even more preferably 70 to 200° C. If the boiling point is within this range, a good balance between handleability and production efficiency when producing functional fabrics can be achieved.

[0066] In addition to the above aliphatic hydrocarbon solvents and aromatic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, isophorone, γ-butyrolactone, etc. The amount of the ketone solvent used is preferably 0.5 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass, assuming the total amount of the solvent to be 100% by mass.

[0067] [Additives] The 4-methyl-1-pentene copolymer (A) may be modified in various ways by adding secondary additives. Specific examples of secondary additives include, but are not limited to, plasticizers, ultraviolet absorbers, infrared absorbers, fluorescent brighteners, release agents, antibacterial agents, nucleating agents, heat stabilizers, antioxidants, slip agents, antistatic agents, color inhibitors, conditioners, matting agents, defoaming agents, preservatives, gelling agents, latex, fillers, inks, colorants, dyes, pigments, and fragrances. These secondary additives may be used alone or in combination.

[0068] Examples of the plasticizer include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetylricinoleate, etc.), aliphatic dialkoxy esters (adipic acid-propylene glycol polyester, etc.), aliphatic tricarboxylic acid esters (triethyl citrate, etc.), phosphate triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

[0069] Examples of the release agent include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters of fatty acids (C4-30) (hardened castor oil, etc.), glycol esters of fatty acids, and liquid paraffin.

[0070] Examples of heat resistance stabilizers include phenol-based (2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, etc.), polycyclic phenol-based (2,2'-methylenebis(4-methyl-6-t-butylphenol), other methylene-bridged polycyclic phenols, etc.), phosphorus-based (tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate, tris(2,4-di-t-butylphenyl)phosphite, etc.), and amine-based (N,N-diisopropyl-p-phenylenediamine, etc.).

[0071] Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ones.

[0072] Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodines.

[0073] Examples of surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Nonionic surfactants include polyethylene glycol-based nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-based nonionic surfactants such as polyethylene oxide, glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol or sorbitan fatty acid esters, polyhydric alcohol alkyl ethers, and alkanolamine fatty amides. Examples of anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids; sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-based amphoteric surfactants such as higher alkylaminopropionates; and betaine-based amphoteric surfactants such as higher alkyldimethyl betaines and higher alkyldimethyl hydroxyethyl betaines.

[0074] Examples of the antistatic agent include the above-mentioned surfactants, fatty acid esters, and polymeric antistatic agents. Examples of the fatty acid esters include esters of stearic acid and oleic acid, and examples of the polymeric antistatic agents include polyether ester amides.

[0075] Examples of pigments include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lakes, thioindigo, phthalocyanines, anthraquinones). Examples of dyes include azos, anthraquinones, triphenylmethanes, etc. The amount of these pigments and dyes added is not particularly limited, but is usually 5 parts by mass or less, preferably 0.1 to 3 parts by mass, in total, per 100 parts by mass of the copolymer (A).

[0076] Examples of slip agents include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher fatty acid salts (such as calcium stearate), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearamide and erucamide).

[0077] The amount of each of the above-mentioned various additives to be added is not particularly limited depending on the intended use as long as the object of the present invention is not impaired. However, it is preferable that each of the additives is added in an amount of 0.01 to 30 parts by mass relative to the 4-methyl-1-pentene-α-olefin polymer (A).

[0078] [Method of manufacturing functional fabrics] The method for producing the functional fabric of the present invention is not particularly limited, but for example, a method of impregnating the base fabric (Y) with a coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) and then drying the coating agent; a method comprising a step of laminating a functional film (X) containing the 4-methyl-1-pentene copolymer (A) onto the base fabric (Y). More specifically, 1) A method comprising a first step (hereinafter also referred to as the "coating step") of applying a coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) to the base fabric (Y), and a second step (hereinafter also referred to as the "drying step") of drying the base fabric (Y) to which the coating agent has been applied to form a functional film (X); 2) A method in which a film (functional film (X)) containing the 4-methyl-1-pentene copolymer (A) is extrusion laminated onto the base fabric (Y) under heat melting using a monolayer extrusion film forming machine or a coextrusion film forming machine, and the film is molded with a cooling roll. 3) A method in which a film (functional film (X)) is formed using a resin composition containing the 4-methyl-1-pentene copolymer (A) using an extrusion film forming machine or a co-extrusion film forming machine, and then the film is laminated onto the base fabric (Y) under heat and pressure using a hot roll or a hot press machine; 4) A method of forming a functional film (X) by laminating a resin composition containing the 4-methyl-1-pentene copolymer (A) onto the base fabric (Y) while melting the resin composition using a calender-type heating roll. Alternatively, two or more of these methods 1) to 4) may be used in combination, etc. Among these, the above methods 1) and 3) are preferred.

[0079] In the above methods (for example, methods 2) to 4)), an embossing roll having a textured pattern may be used on the cooling roll or the heating roll in order to impart designability and / or non-stickiness to the functional film (X) containing the 4-methyl-1-pentene copolymer (A).

[0080] In the method 1) above, a functional fabric can be produced in which a functional film (X) is formed on the surface and / or inside the vicinity of the surface of the base fabric (Y) by heating to a temperature close to the boiling point of the solvent (B) in the drying step to remove the solvent to a certain extent. When the functional film (X) is formed inside the vicinity of the surface of the base fabric (Y), the functional film (X) may be formed interspersed among the fibers constituting the base fabric (Y).

[0081] The method for applying the coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) is not particularly limited, and examples thereof include application using a brush or paintbrush, spraying, screen printing, flow coating, spin coating, and dipping, as well as application to a roll or a flat plate using a bar coater, a T-die, a T-die with a bar, a doctor knife, a roll coater, a die coater, or the like.

[0082] In the present invention, "removal of the solvent" does not mean only complete removal of the solvent, but also removal of the solvent to an extent that the material can be molded. Specifically, when the entire functional film (X) formed using the coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) is taken as 100% by mass, the solvent (B) is removed until the solvent (B) is approximately 0.001 to 0.5% by mass. When the content of the solvent (B) is within the above range, the original flexibility of the base fabric (Y) can be maintained.

[0083] The method for removing the solvent is not particularly limited, and the mixture may be left to dry, but is generally removed by heating and drying at 30 to 220°C. To prevent thermal degradation or thermal decomposition of the 4-methyl-1-pentene copolymer (A), it is preferable to remove the solvent at a temperature equal to or lower than the melting point (Tm) of the 4-methyl-1-pentene copolymer (A). If the drying temperature is too low, the drying time will be long, which may result in a decrease in productivity, whereas if the drying temperature is too high, problems such as foaming and deterioration may occur.

[0084] In the drying step, the temperature may be increased in two or more stages or continuously to prevent foaming and dry in a short time. Furthermore, the amount of solvent remaining in the coating layer can be reduced by immersing the coating layer in a solvent in which the copolymer (A) is poorly soluble, such as water, methanol, ethanol, acetone, or methylene chloride, or by exposing the coating layer to the vapor of the solvent. The amount of solvent remaining in the coating layer after drying is preferably 0.5% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.01% by mass or less.

[0085] When the functional film (X) containing the 4-methyl-1-pentene copolymer (A) is molded by extrusion or the like, the 4-methyl-1-pentene copolymer (A) needs to be heated to a temperature above its melting point (Tm) to melt it. However, when the functional film (X) is formed using the coating agent, it can be formed at a temperature lower than the melting point (Tm), so that the amount of decomposition products due to thermal degradation of the copolymer (A) is reduced, and the mold releasability and water repellency may be improved.

[0086] Examples of the decomposition products include low molecular weight components such as dimers to pentamers of the monomer components constituting the copolymer (A), which are obtained by decomposing a 4-methyl-1-pentene-based copolymer (A) at a high temperature, and the above-mentioned additives, such as plasticizers, ultraviolet absorbers, infrared absorbers, fluorescent brighteners, mold release agents, antibacterial agents, nucleating agents, heat stabilizers, antioxidants, slip agents, antistatic agents, anti-coloring agents, regulators, matting agents, defoaming agents, preservatives, gelling agents, latexes, fillers, inks, colorants, dyes, pigments, fragrances, and a part of the components decomposed by oxidation.

[0087] [Adhesion-improving resin] When it is necessary to increase the adhesion or bonding strength between the functional film (X) and the base fabric (Y) in the composition or coating agent containing the 4-methyl-1-pentene-based copolymer (A), for example, a) a thermoplastic adhesive resin, b) a resin having an adhesive component, or c) a component obtained by graft-modifying the copolymer (A) with a polar compound (hereinafter also referred to as "graft-modified copolymer (A')") can be further blended within a range not impairing the object of the present invention. In particular, an embodiment in which the composition or the coating agent contains a resin (C) which is any one of the resins a) to c) having a functional group selected from the group consisting of an active hydrogen-containing functional group, an acid anhydride group, and an epoxy group is preferable.

[0088] <a) Thermoplastic adhesive resin> Examples of the thermoplastic adhesive resin (hereinafter also referred to as "adhesive resin (a)") include known thermoplastic adhesives. However, it is preferable to use those selected from polyolefins into which polar functional groups are introduced, ionomer resins, and copolymers of ethylene or monomers containing ethylene and glycidyl methacrylate. Examples of the polyolefin into which polar functional groups are introduced include commercially available thermoplastic resin "Admer" (registered trademark) (manufactured by Mitsui Chemicals, Inc.) and polyolefin-based adhesive resin "Modic" (manufactured by Mitsubishi Chemical Corporation). Similarly, in the form of a liquid dissolved or dispersed in a solvent, there are liquid polyolefin-based adhesives "Unistol" (registered trademark) (manufactured by Mitsui Chemicals, Inc.) and chlorinated polyolefin varnish "Super Kron" (manufactured by Nippon Paper Industries Co., Ltd.). The addition amount of the adhesive resin (a) is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, based on 100% by mass of the copolymer (A).

[0089] <b) Resin having a tackifying component> The resin having the tackifying component (hereinafter also referred to as "resin (b)") is not particularly limited as long as it is a resin having adhesiveness. For example, it includes thermoplastic resins having a melting point (Tm) of less than 110°C measured by DSC and conventionally known thermoplastic elastomers. Specifically, polyolefin-based thermoplastic resins or polyolefin-based thermoplastic elastomers are preferable. Specific examples of polyolefin-based thermoplastic resins or polyolefin-based thermoplastic elastomers include ethylene-based polymers, propylene-based copolymers, and butene-based copolymers. More specifically, copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, copolymers of ethylene and α-olefins having 3 to 20 carbon atoms and cyclic olefins, ethylene-based copolymers having various vinyl compounds such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters as comonomers, copolymers of propylene and α-olefins having 4 to 20 carbon atoms, copolymers of propylene and α-olefins having 4 to 20 carbon atoms and cyclic olefins, and ethylene-based copolymers having various vinyl compounds such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters as comonomers, etc. can be mentioned.

[0090] Thermoplastic elastomers also include polystyrene elastomers. Examples of polystyrene elastomers include block copolymers (SBS) of polystyrene blocks that form the hard portion (crystalline portion) and diene monomer blocks that form the soft portion, hydrogenated styrene-butadiene-styrene block copolymers (HSBR), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-isobutylene-styrene copolymers (SIBS), and styrene-isobutylene copolymers (SIB). Polystyrene elastomers can be used alone or in combination of two or more types.

[0091] Styrene-ethylene-propylene-styrene block copolymers are obtained by hydrogenating styrene-isoprene-styrene block copolymers (SIS). Specific examples of SIS include those commercially available from JSR Corporation under the trade name JSR SIS (registered trademark), Kuraray Co., Ltd. under the trade name Hybler (registered trademark), and Shell Corporation under the trade name Kraton D (registered trademark).

[0092] A specific example of SEPS is commercially available under the trade name Septon (registered trademark) from Kuraray Co., Ltd. A specific example of SIBS is commercially available under the trade name Sibustar (registered trademark) from Kaneka Corporation.

[0093] Furthermore, as an example of a thermoplastic resin or thermoplastic elastomer, an elastomer made of an olefin-based block copolymer can also be used. Examples of elastomers made of a polyolefin-based block copolymer include block copolymers of a polyolefin block that forms a highly crystalline polymer such as polypropylene, which serves as the hard portion, and an amorphous monomer copolymer that serves as the soft portion. Specific examples include an olefin (crystalline)-ethylene-butylene-olefin block copolymer and a polypropylene-polyolefin (amorphous)-polypropylene block copolymer. Specific examples include those commercially available from JSR Corporation under the trade name DYNARON. The amount of resin (b) added is preferably 0 to 50% by mass, more preferably 0.1 to 20% by mass, relative to 100% by mass of the 4-methyl-1-pentene copolymer (A).

[0094] c) Graft-modified copolymer (A') When the 4-methyl-1-pentene copolymer (A) is mixed with a polar resin, it is preferable to use the graft-modified copolymer (A').

[0095] Examples of polar compounds used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof, vinyl ester compounds, vinyl chloride, vinyl group-containing organosilicon compounds, carbodiimide compounds, etc. Among these, unsaturated carboxylic acids or derivatives thereof and vinyl group-containing organosilicon compounds are particularly preferred.

[0096] Examples of unsaturated carboxylic acids or their derivatives include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having a carboxylic acid group with alkyl alcohols, and unsaturated compounds having one or more carboxylic acid anhydride groups. Examples of unsaturated groups include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. These compounds can be conventionally known compounds, and are not particularly limited. Specific examples include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and Nadic Acid (registered trademark) (endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof, such as acid halides, amides, imides, anhydrides, and esters. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. These unsaturated carboxylic acids and / or their derivatives can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, Nadic acid (registered trademark), or their acid anhydrides are particularly preferred.

[0097] As the vinyl group-containing organosilicon compound, conventionally known compounds can be used without any particular limitation, but specific examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxysilane), γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethylethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethylethoxysilane, 3-methacryloxypropyl ... Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like can be used. Preferred examples include γ-glycidoxypropyltripyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, and more preferred examples include vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, which have small steric hindrance and high graft modification efficiency.

[0098] The graft-modified copolymer (A') can be obtained by grafting the polar compound in an amount of usually 1 to 100 parts by mass, preferably 5 to 80 parts by mass, with respect to 100 parts by mass of the 4-methyl-1-pentene copolymer (A). This graft reaction is usually carried out in the presence of a radical initiator.

[0099] Examples of radical initiators used in graft polymerization include organic peroxides and azo compounds. The radical initiator can be directly mixed with the 4-methyl-1-pentene copolymer (A) and the polar compound, or can be dissolved in a small amount of organic solvent before use. Any organic solvent can be used as the radical initiator, without any particular limitations, as long as it can dissolve the radical initiator.

[0100] Furthermore, when a polar compound is grafted onto the 4-methyl-1-pentene copolymer (A), a reducing substance may be used, which may increase the amount of the polar compound grafted.

[0101] The graft modification reaction of the 4-methyl-1-pentene copolymer (A) with a polar compound can be carried out by a conventionally known method, for example, by dissolving the 4-methyl-1-pentene copolymer (A) in an organic solvent, adding a polar compound and a radical initiator to the solution, and reacting at a temperature of 70 to 200°C, preferably 80 to 190°C, for 0.5 to 15 hours, preferably 1 to 10 hours.

[0102] Alternatively, the 4-methyl-1-pentene copolymer (A) can be reacted with a polar compound without a solvent using an extruder, etc. This reaction is preferably carried out at a temperature usually higher than the melting point (Tm) of the 4-methyl-1-pentene copolymer (A), specifically at 160 to 290°C, for usually 0.5 to 10 minutes.

[0103] The modification amount (graft amount of polar compound) of the graft-modified copolymer (A') obtained in this manner is usually 0.1 to 50 mass%, preferably 0.2 to 30 mass%, and more preferably 0.2 to 10 mass%, relative to 100 mass% of the 4-methyl-1-pentene copolymer (A) that has been subjected to the graft modification reaction.

[0104] [Complex] The functional fabric of the present invention can be used for various purposes as a composite by combining it with other components. That is, the composite according to this embodiment includes a component that is provided on at least one surface of the functional fabric and is different from the functional fabric.

[0105] The functional fabric of the present invention has an excellent balance of performances such as releasability, water repellency, and flexibility (reduced stiffness), and therefore the same effect can be achieved even when it is composited with a material different from the functional fabric. In other words, the composite of the present invention has an excellent balance of performances such as releasability, water repellency, flexibility, and vibration damping.

[0106] Various known methods can be applied as a method for forming the composite of the present invention. For example, the composite can be produced by thermocompression bonding or welding the functional fabric and a member different from the functional fabric, as needed, using a press or the like. Alternatively, the composite can be produced by forming a functional film (X) on the surface of the base fabric (Y) or inside the vicinity of the surface of the composite substrate obtained by thermocompression bonding or welding the base fabric (Y) and a member different from the base fabric (Y) using a press or the like, as needed, in the same manner as in the above-mentioned method for producing the functional fabric.

[0107] A composite can also be produced by applying an adhesive between the functional fabric and a member different from the functional fabric and bonding them via the adhesive. A composite can also be produced by applying an adhesive between the base fabric (Y) and a member different from the base fabric (Y) and bonding them via the adhesive, and then forming a functional film (X) on the surface of the base fabric (Y) side or inside the vicinity of the surface in the same manner as in the above-mentioned method for producing a functional fabric.

[0108] As the adhesive, an SBR-based solvent adhesive or a hot melt adhesive made of EVA, petroleum resin, or a mixture of EVA and petroleum resin can be suitably used.

[0109] The material different from the functional fabric or the material different from the base fabric (Y) is not particularly limited, and examples thereof include fur, metal, carbon material, rubber, thermoplastic elastomer, thermoplastic resin, thermosetting resin, polymer foam, mesh structure (warp knitted fiber, double Russell mesh, three-dimensional spring structure, etc.), fiber reinforced plastic, paper, wood, glass, stone, ceramic, etc. These materials may be used alone or in combination of two or more.

[0110] [Application] The functional fabrics and composites of the present invention have characteristics such as mold release properties, water repellency, stress relaxation properties, and vibration damping properties due to the 4-methyl-1-pentene copolymer (A). Furthermore, by impregnating or laminating a functional film (X) containing the 4-methyl-1-pentene copolymer (A) into a base fabric (Y) such as a woven or nonwoven fabric made of natural or synthetic fibers, it is possible to achieve both flexibility and water repellency, as well as strength when sewn and design properties, which were difficult to achieve with conventional 4-methyl-1-pentene copolymer (A) alone, and the fabrics and composites can be used in a variety of applications.

[0111] The functional fabric and composite of the present invention can be used for conventionally known applications such as clothing materials, medical materials, sanitary materials, food packaging materials, fishing materials, agricultural and forestry materials, civil engineering and construction materials, shoe materials, sports materials, leisure materials, and industrial materials. For example, clothing materials include innerwear such as underwear, socks, shirts, briefs, trunks, shorts, camisoles, spats, bras, tights, and belly warmers; outerwear such as T-shirts, sweaters, coats, jackets, jumpers, pants, skirts, zippers, buttons, hats, and gloves; and sportswear such as training wear, ski wear, swimwear, leotards, and supports. Medical supplies include surgical sheets, medical wear, blood absorbers, drug absorbers, medical tape, bandages, and compresses. Hygiene supplies include diapers, incontinence pads, sanitary products, maternity pads, breast pads, mask strings, eye patch strings, and wound dressings. Fishing materials include seaweed nets, purse seine nets, and aquaculture nets. Agriculture and forestry supplies include: Examples of construction materials include insect nets, windbreak nets, shading nets, weed prevention nets, bird prevention nets, cucumber nets, flower nets, etc.; civil engineering and construction materials include water retention sheets, condensation prevention sheets, greening sheets, seedling raising sheets, vegetation nets, sandbag nets, etc.; shoe materials include shoe uppers, shoelaces, and sports; leisure materials include sports nets, shoe uppers, and insect nets for golf, baseball, tennis, table tennis, volleyball, badminton, soccer, handball, basketball, hockey, ice hockey, water polo, etc.; industrial materials include hats, hand towels, car wash supplies, toys, etc.; and outdoor materials include tents, fly sheets, camping chairs, raincoats, backpacks, cloth buckets, etc.

[0112] The functional fabric of the present invention is particularly preferably used as a material for clothing and outdoor use, and has the characteristics of being lightweight and not generating harmful gases when disposed of, while exhibiting similar release and water repellency compared to conventionally used fluorine-based and silicone-based coating agents. [Example]

[0113] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. The methods for measuring the physical properties of the polymer, the materials used, the methods for preparing test pieces, and the evaluation methods used in the examples and comparative examples are as follows.

[0114] [Physical property measurement method] <Content of structural units> The 4-methyl-1-pentene and α-olefin contents in the polymer were quantified using the following equipment and conditions: 13 The α-olefin content measured by C-NMR is based on the results. However, the α-olefin content measured by this method does not include the content of 4-methyl-1-pentene.

[0115] Using a JEOL ECP500 nuclear magnetic resonance spectrometer, the sample was analyzed using a mixed solvent of orthodichlorobenzene / deuterated benzene (80 / 20% by volume), a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120°C, and observation nuclei. 13 The measurement was performed using C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7 μs (45° pulse), the repetition time was 5.5 s, the number of accumulations was more than 10,000, and 27.50 ppm was used as the reference value for the chemical shift. 13 The composition of 4-methyl-1-pentene·α-olefin was quantified by C-NMR spectroscopy.

[0116] <Intrinsic viscosity> This value was measured in decalin at 135°C using an Ubbelohde viscometer. Approximately 20 mg of the polymer powder, pellets, or resin mass was collected and dissolved in 15 mL of decalin. The specific viscosity ηsp of the resulting decalin solution was measured in an oil bath heated to 135°C. This decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity ηsp was measured in the same manner. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to zero was used to calculate the limiting viscosity [η] (see the formula below). [η]=lim(ηsp / C) (C→0)

[0117] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)> Molecular weights were measured by gel permeation chromatography (GPC). Specifically, a Waters ALC / GPC150-Cplus liquid chromatograph (integrated with a differential refractometer detector) was used, and two Tosoh GMH6-HT and two Tosoh GMH6-HTL separation columns were connected in series. The mobile phase consisted of o-dichlorobenzene and 0.025% by mass dibutylhydroxytoluene (Takeda Pharmaceutical Co., Ltd.) as the antioxidant. The mobile phase was run at 1.0 mL / min, the sample concentration was 15 mg / 10 mL, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. Standard polystyrenes with weight-average molecular weights (MW) of 1,000 to 4,000,000, manufactured by Tosoh, were used.

[0118] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn value) were calculated by analyzing the obtained chromatogram using a calibration curve prepared by a known method using a standard polystyrene sample. The measurement time per sample was 60 minutes.

[0119] <Melting point (Tm)> The melting point (Tm) of the polymer was measured by differential scanning calorimetry (DSC) using a DSC220C device manufactured by Seiko Instruments Inc. Specifically, 7 to 12 mg of the copolymer obtained in the following synthesis example was sealed in an aluminum pan and heated from room temperature to 200°C at 10°C / min. The copolymer was then held at 250°C for 5 minutes to completely melt, and then cooled to -50°C at 10°C / min. After leaving the sample at -50°C for 5 minutes, the sample was heated again to 250°C at 10°C / min. The peak temperature during this second heating was taken as the melting point (Tm).

[0120] <density> Measurement was carried out using a density gradient tube in accordance with JIS K7112.

[0121] <Melt mass-flow rate (MFR)> According to ASTM D1238, copolymers (A-1) to (A-3) were measured at a temperature of 230°C and a load of 2.16 kgf, and copolymer (cA-4) was measured at 260°C and a load of 5.0 kgf.

[0122] <Storage stability> In preparing a coating agent containing a 4-methyl-1-pentene copolymer and a solvent, the 4-methyl-1-pentene copolymer and the solvent were placed in a container equipped with a stirrer, and the composition was prepared by stirring at 200 rpm for 1 hour at 80°C, and then stored at room temperature for 24 hours. After the storage, the composition was evaluated as follows: if it was transparent when visually observed under visible light, it was marked with a circle; if it appeared cloudy but exhibited fluidity, it was marked with a triangle; and if it was cloudy and exhibited no fluidity, it was marked with an x.

[0123] <Film coatability> When functional fabrics were prepared using a coating agent containing a 4-methyl-1-pentene copolymer and a solvent, the film coatability was evaluated as follows. The coating agent containing a 4-methyl-1-pentene copolymer and a solvent was stored at room temperature for 24 hours. It was then applied to a base fabric (Y) at 25°C and spread evenly with an applicator. It was then dried at 25°C for 30 minutes and then at 80°C for 1 hour. When a functional fabric with a functional film was obtained, the appearance of the functional fabric on the functional film side was visually inspected. If irregularities not due to the base fabric were found, they were evaluated as "x" (unclear) due to undissolved particles. If there were no irregularities or uneven thickness, they were evaluated as "o."

[0124] <Tackiness> The tackiness of the functional fabric was evaluated as follows: When the surface of the obtained functional fabric on the functional film side was pressed with a finger, if the 4-methyl-1-pentene copolymer component was visibly adhered to the finger, it was evaluated as having tackiness (△), and if no component remained on the finger, it was evaluated as not having tackiness (◯).

[0125] <Flexibility> The functional fabric was cut into pieces measuring 100mm x 50mm, and 10 monitors were asked to freely bend, roll, and deform it with their hands, and evaluate its flexibility (suppleness, stiffness) on a four-point scale. An average score of rank 2 or lower was considered acceptable. Rank 1: Good flexibility Rank 2: A little lacking in flexibility Rank 3: Rough feeling Rank 4: Significant roughness

[0126] <Water contact angle measurement> Using the DropMaster500 image processing, solid-liquid interface analysis system, the contact angle value when a water droplet was dropped onto the obtained functional fabric was measured. The larger the contact angle value, the higher the releasability for highly polar materials.

[0127] <Critical interfacial tension> Critical interfacial tension measurements were performed using a DropMaster 500 image processing solid-liquid interface analysis system. The contact angle of the functional fabric obtained in the examples was measured at 23°C and 50% humidity using a mixture for wetting tension reagents (manufactured by Wako Pure Chemical Industries, Ltd.) as the test liquid. The critical interfacial tension was calculated based on this. The smaller the critical interfacial tension, the higher the releasability for highly polar materials.

[0128] <Solvent content, decomposition product content> The content of solvent and copolymer decomposition products in the film was measured with reference to the test methods described in JP 2011-88352 A, JP 2007-224311 A, etc. Specifically, a 50 μm thick film was cut into 20 × 2 mm strips, and 10 mg of each was precisely weighed and heated at 180 °C for 30 minutes under a helium stream. The gas components evolved during heating were collected using a dynamic headspace method and measured using a thermal desorption GC / MS spectrometer (HP6890 / HP5975, manufactured by Agilent Technologies). The obtained MS spectrum was then converted to a quantitative value using decane as a standard sample. Peaks derived from the solvent were taken as the amount of solvent, and peaks not derived from the solvent were taken as the amount of decomposition products.

[0129] [Synthesis of 4-methyl-1-pentene copolymer] <Synthesis of 4-methyl-1-pentene copolymer (A-1)> A 1.5-liter stainless steel autoclave equipped with a stirrer and thoroughly purged with nitrogen was charged with 300 ml of normal hexane (dried over activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the stirrer was turned on.

[0130] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.19 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of pre-prepared methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was pressure-charged into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the autoclave's internal temperature was adjusted to 60°C. Sixty minutes after the start of polymerization, 5 ml of methanol was pressure-charged into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Then, acetone was poured into the reaction solution while stirring.

[0131] The resulting powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The amount of the resulting copolymer (A-1) was 44.0 g, and the 4-methyl-1-pentene content in the polymer was 84.1 mol% and the propylene content was 15.9 mol%. The physical properties of the resulting copolymer (A-1) are shown in Table 1.

[0132] <Synthesis of 4-methyl-1-pentene copolymer (A-2)> A 1.5-liter stainless steel autoclave equipped with a stirrer and thoroughly purged with nitrogen was charged with 300 ml of normal hexane (dried over activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene at 23° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the stirrer was turned on.

[0133] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.16 MPa (gauge pressure). Subsequently, 0.34 ml of a previously prepared toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was pressure-charged into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C. Sixty minutes after the start of polymerization, 5 ml of methanol was pressure-charged into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

[0134] The resulting powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The resulting copolymer (A-2) weighed 36.3 g, and the 4-methyl-1-pentene content in the polymer was 86.2 mol% and the propylene content was 13.8 mol%. The physical properties of the resulting copolymer (A-2) are shown in Table 1.

[0135] <Synthesis of 4-methyl-1-pentene copolymer (A-3)> A 1.5-liter stainless steel autoclave equipped with a stirring blade and thoroughly purged with nitrogen was charged with 750 ml of 4-methyl-1-pentene at 23° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the stirrer was turned on.

[0136] Next, the autoclave was heated to an internal temperature of 60°C and pressurized with propylene to a total pressure of 0.13 MPa (gauge pressure). Subsequently, 0.34 ml of a toluene solution containing 1 mmol of pre-prepared methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was pressure-charged into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the autoclave's internal temperature was adjusted to 60°C. Sixty minutes after the start of polymerization, 5 ml of methanol was pressure-charged into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Then, acetone was poured into the reaction solution while stirring.

[0137] The resulting powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The weight of the resulting 4-methyl-1-pentene-α-olefin copolymer (A-3) was 36.9 g, and the 4-methyl-1-pentene content in the polymer was 72.5 mol % and the propylene content was 27.5 mol %. The physical properties of the resulting copolymer (A-3) are shown in Table 1.

[0138] <Synthesis of 4-methyl-1-pentene copolymer (cA-4)> A 1.5-liter stainless steel autoclave equipped with a stirring blade and thoroughly purged with nitrogen was charged with 750 ml of 4-methyl-1-pentene at 23° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was then charged into the autoclave, and the stirrer was turned on.

[0139] Next, the autoclave was heated to an internal temperature of 60°C, pressurized with propylene to a total pressure of 0.11 MPa (gauge pressure), and 50 ml of hydrogen was added as a chain transfer agent. Subsequently, 0.34 ml of a previously prepared toluene solution containing 1 mmol of methylaluminoxane (calculated as Al) and 0.01 mmol of diphenylmethylene(1-ethyl-3-t-butyl-cyclopentadienyl)(2,7-di-t-butyl-fluorenyl)zirconium dichloride was pressure-injected into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the internal temperature of the autoclave was adjusted to 60°C. Twenty minutes after the start of polymerization, 5 ml of methanol was pressure-injected into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

[0140] The resulting powdery polymer containing the solvent was dried at 130°C under reduced pressure for 12 hours. The resulting 4-methyl-1-pentene-α-olefin copolymer (cA-4) weighed 31.2 g, and the 4-methyl-1-pentene content in the polymer was 99 mol% and the propylene content was 1 mol%. The physical properties of the resulting copolymer (cA-4) are shown in Table 1.

[0141] [Table 1]

[0142] [Base fabric] <Base fabric (Y-1)> Made with 30 count yarn containing 50% cotton, 40% nylon, and 10% spandex, with a basis weight of 82 g / m 2 , density 0.4g / cm 3 The plain woven fabric was used as the base fabric (Y-1). <Base fabric (Y-2)> A fabric was circularly knitted at 60 gauge using 60 count yarn containing 65% polyester and 35% rayon to form a base fabric (Y-2).

[0143] [Example 1] To 100 parts by weight of 4-methyl-1-pentene copolymer (A-1), 0.1 parts by weight of tris(2,4-di-t-butylphenyl)phosphite and 0.1 parts by weight of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate were added as heat stabilizers. Toluene (Wako Pure Chemical Industries, Ltd.) was added to a solids concentration of 5% by weight, and the mixture was stirred at 200 rpm at 40°C for 1 hour to prepare a coating agent containing 4-methyl-1-pentene copolymer (A-1). This coating agent was applied to a base fabric (Y-1) at 25°C, spread evenly with an applicator, and then dried at 25°C for 30 minutes and then at 80°C for 1 hour to obtain a functional fabric. The physical properties of the resulting functional fabric were measured and the results are shown in Table 2.

[0144] [Example 2] The same procedure as in Example 1 was carried out, except that the 4-methyl-1-pentene copolymer (A-2) was used instead of the 4-methyl-1-pentene copolymer (A-1), and the resulting coating agent was applied to a base fabric (Y-1) to obtain a functional fabric. The physical properties of the obtained functional fabric were measured, and the results are shown in Table 2.

[0145] [ Reference Example 1 ] The same procedure as in Example 1 was carried out except that the 4-methyl-1-pentene copolymer (A-3) was used instead of the 4-methyl-1-pentene copolymer (A-1), and the resulting coating agent was applied to a base fabric (Y-1) to obtain a functional fabric. The physical properties of the obtained functional fabric were measured, and the results are shown in Table 2.

[0146] [ See Example 2 ] Pellets were prepared by adding 0.1 parts by weight of tris(2,4-di-t-butylphenyl)phosphite and 0.1 parts by weight of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as heat stabilizers to 99.8 parts by weight of 4-methyl-1-pentene copolymer (A-2). The pellets were then fed into a 250mm die-width T-die molding machine equipped with a 30mmφ single-screw extruder. The resin pellets were fed from the resin feed hopper and melted through the cylinder of the single-screw extruder, which was set at 240°C. The extrusion molding was then carried out at a die temperature of 240°C to obtain a 30µm thick film. This film was then laminated onto a base fabric (Y-1) and heat-sealed in a heat press at 0.2 MPa and 150°C for 30 seconds to obtain a functional fabric. The physical properties of the resulting functional fabric were measured and the results are shown in Table 2.

[0147] [Comparative Example 1] The same procedure as in Example 1 was carried out except that 4-methyl-1-pentene copolymer (cA-4) was used instead of 4-methyl-1-pentene copolymer (A-1). However, since the copolymer was insoluble in solvents and had poor storage stability, no functional fabric was obtained.

[0148] Comparative Example 2 The film was obtained using a single-screw extruder set at 270°C, except that 4-methyl-1-pentene copolymer (cA-4) was used instead of 4-methyl-1-pentene copolymer (A-2). See Example 2 The same procedure as in 1. was carried out to obtain a functional fabric. The physical properties of the obtained functional fabric were measured and the results are shown in Table 2.

[0149] [Table 2] [Industrial Applicability]

[0150] The functional fabric of the present invention has excellent functions such as water repellency and vibration damping while maintaining the original feel of the base fabric without losing its flexibility (suppleness and stiffness), making it effective for clothing materials, outdoor products, artificial leather, synthetic leather, etc. Furthermore, since it does not contain fluorine or silicone, it also has an excellent environmentally friendly effect.

Claims

1. The present invention comprises a base fabric (Y) and a functional film (X) containing a 4-methyl-1-pentene copolymer (A) that satisfies the following requirements (a) to (e): A functional fabric characterized in that the functional film (X) contains the 4-methyl-1-pentene copolymer (A) and a solvent (B) having a relative dielectric constant of 5 or less at 25°C, and the content of the solvent (B) is 0.001 to 0.5 mass% with respect to 100 mass% of the functional film (X): (a) A copolymer containing 65 to 93 mol% of structural units (i) derived from 4-methyl-1-pentene and 7 to 35 mol% of structural units (ii) derived from an α-olefin having 2 to 4 carbon atoms (provided that the total of structural units (i) and structural units (ii) is 100 mol%); (b) the intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl / g; (c) a melting point (Tm) measured by differential scanning calorimetry (DSC) of 110°C or higher and lower than 200°C; (d) Density is 820 to 850 kg / m 3 is; (e) The molecular weight distribution (Mw / Mn), which is the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) as measured by gel permeation chromatography (GPC), is 1.0 to 3.

5.

2. The 4-methyl-1-pentene copolymer (A) has at least one functional group selected from the group consisting of an active hydrogen-containing functional group, an acid anhydride group, and an epoxy group. Functional fabric according to claim 1.

3. The functional fabric according to claim 1 or 2, wherein the base fabric (Y) is selected from woven fabrics and nonwoven fabrics made of natural fibers or synthetic fibers.

4. A method for producing the functional fabric according to any one of claims 1 to 3, The method for producing a functional fabric includes: a first step of applying a coating agent containing the 4-methyl-1-pentene copolymer (A) and a solvent (B) having a relative dielectric constant of 5 or less at 25°C to the base fabric (Y); and a second step of drying the base fabric (Y) to which the coating agent has been applied, thereby forming the functional film (X).

5. A clothing material comprising the functional fabric according to any one of claims 1 to 3.

6. An outdoor material comprising the functional fabric according to any one of claims 1 to 3.

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