JP7777460B2 - Functional fabrics and their uses - Google Patents

Description

The present invention relates to a functional fabric containing a 4-methyl-1-pentene copolymer and its uses.

In the fields of clothing, daily necessities, medical products, automotive parts, and the like, attempts have been made to enhance stain resistance by imparting water-repellent, oil-repellent, and other properties to synthetic or natural fiber fabrics, with fluorine-based polymers (Patent Document 1) and urethane resins (Patent Document 2) being used in particular as water-repellent materials.

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 the fluorine-containing polymer.

Patent Document 2 discloses a method for producing coated fabrics, which involves applying a coating resin solution made of a synthetic polymer primarily 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.

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. Furthermore, Patent Document 4 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.

On the other hand, 4-methyl-1-pentene copolymers have superior heat resistance, transparency, and electrical properties compared to polyethylene and polypropylene, and are widely used in a variety of applications, particularly industrial release films and capacitor films. Furthermore, adjusting the molecular weight and composition of 4-methyl-1-pentene copolymers to lower their melting point allows them to maintain heat resistance and release properties while improving solubility in solvents, leading to their application in industrial films (see Patent Documents 5 and 6).

Japanese Unexamined Patent Publication No. 60-39482 Japanese Unexamined Patent Publication No. 7-11586 Patent No. 5236417 Patent No. 4184178 Patent No. 5840064 Japanese Patent Application Laid-Open No. 2017-132251

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

The objective of this invention is to provide a functional fabric that has stain-resistant and vibration-damping properties while maintaining the original feel of the base fabric without losing its flexibility (suppleness and stiffness).

In light of the above-mentioned circumstances, the inventors conducted extensive research to solve the aforementioned problems. As a result, they discovered that the above-mentioned problems could be solved by impregnating or laminating a functional film containing a specific 4-methyl-1-pentene copolymer into a base fabric, leading to the completion of the present invention. In other words, the present invention relates to, for example, the following [1] to [8].

[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 (Tm) as measured by differential scanning calorimetry (DSC);
(d) density is 820 to 850 kg/m ³ ;
(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 functional fabric described in [1], wherein 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.

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

[4] The functional fabric described in any one of items [1] to [3], wherein 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% by mass relative to 100% by mass of the functional film (X).

[5] A method for producing the functional fabric described in 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 to form the functional film (X).

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

[7] Clothing materials comprising the functional fabric according to any one of items [1] to [4].
[8] Outdoor equipment comprising the functional fabric according to any one of items [1] to [4].

The present invention makes it possible to provide a functional fabric that retains the mold releasability, water repellency, and vibration damping properties characteristic of 4-methyl-1-pentene copolymers, without impairing the texture or flexibility of the base fabric.

Specific embodiments of the present invention are 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 invention. In this specification, the terms "polymer" and "(co)polymer" are used to encompass homopolymers and copolymers unless otherwise specified.

The functional fabric of 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. Furthermore, in one embodiment of the functional fabric of 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).

[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.

The woven or nonwoven fabrics made from the above-mentioned natural or synthetic fibers (hereinafter also referred to as "fibrous materials") are 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, poly4-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 using chemical methods, mechanical methods, or a combination thereof.

Specific examples of fibrous substrates include fibrous sheets such as entangled nonwoven sheets and knitted/woven sheets formed using ultrafine fibers or bundles of such fibers, special porous fibers, ordinary synthetic fibers, semi-synthetic fibers, natural fibers, inorganic fibers, etc.

Among the fibrous substrates listed above, fibrous sheets formed using ultrafine fibers or bundles of ultrafine fibers are preferably used, and the single fiber fineness of the ultrafine fibers that make up the fibrous sheet is preferably 0.5 dtex or less, and more preferably 0.1 dtex or less.

When the fibrous base material is formed from ultrafine fiber bundles, it is preferable that the total fineness of the ultrafine fiber bundles be 0.5 to 10 dtex in terms of the feel of the functional fabric. Furthermore, it is preferable that the ultrafine fibers that make up the fibrous base material are formed from polyester-based fibers and/or polyamide-based fibers in terms of the strength, feel, cost, etc. of the resulting functional fabric.

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

The thickness of the woven or nonwoven fabric made from the above-mentioned 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, for ease of handling.

[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):

<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 %).

The above requirement (a) stipulates that the 4-methyl-1-pentene copolymer (A) contains 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.

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 _-CH2- 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 _-CH2- CH( _-CH2CH ( _CH3 ) ₂ )-).

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

When the amount of structural unit (i) in the 4-methyl-1-pentene copolymer (A) is equal to or greater than the above-mentioned lower limit, flexibility and water repellency are easily achieved. On the other hand, when the amount of structural unit (i) is equal to or less than the above-mentioned upper limit, the melting point (described below) increases, resulting in a stiff, bulky feel and a stiff base fabric.

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%.

The content (mol %) of each structural unit constituting the 4-methyl-1-pentene copolymer (A) is measured by ¹³ C-NMR, and the details of the measurement method are as described in the Examples below.

As such, 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.

<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.

The intrinsic viscosity [η] is preferably 1.0 to 4.0 dl/g, more preferably 1.2 to 3.5 dl/g. As described below, the use of hydrogen during polymerization can control the molecular weight, allowing for a wide range of molecular weights from low to high, and adjusting the intrinsic viscosity [η] within the above range. Details of the measurement method are as described in the Examples below.

<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).

The melting point (Tm) is preferably 160°C or lower, or is not substantially observable, more preferably 150°C or lower, or is not substantially observable, and particularly preferably 150°C or lower. "Substantially not 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. "Substantially not observable heat of fusion ΔH (Tm)" means that no peak is observed in DSC measurement.

The lower limit at which the melting point (Tm) is observed is preferably 110°C, more preferably 120°C, and even more preferably 125°C.

By meeting these requirements, the functional fabric of the present invention can have high water repellency and flexibility, and the stiffness is reduced.

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

The density is preferably 825 to 850 kg/m ³ , more preferably 830 to 850 kg/m ³ . 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.

<Requirement (e)>
The 4-methyl-1-pentene copolymer (A) has a 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), in the range of 1.0 to 3.5.

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

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

<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.

<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.

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, resulting in sufficient mechanical strength for a molded product (film, etc.), which is preferable.

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

By introducing functional groups into the 4-methyl-1-pentene copolymer (A), it is possible to impart adhesion to a base fabric (Y) having polar groups, 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.

<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.

Preferably, 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.

In liquid-phase polymerization, an inert hydrocarbon solvent can be used as the solvent that constitutes the liquid phase. Examples of such inert hydrocarbons 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, as well as mixtures thereof.

In addition, in liquid phase polymerization, 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 the solvent.

In addition, by copolymerizing the above-mentioned 4-methyl-1-pentene with the above-mentioned α-olefin having 2 to 4 carbon atoms in stages, 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) of the α-olefin having 2 to 4 carbon atoms that constitute the 4-methyl-1-pentene/α-olefin copolymer (A).

The polymerization temperature is preferably -50 to 200°C, more preferably 0 to 100°C, and even more preferably 20 to 100°C. The polymerization pressure is preferably atmospheric pressure to 10 MPa gauge pressure, and more preferably atmospheric pressure to 5 MPa gauge pressure.

Hydrogen may be added during polymerization to control the molecular weight and polymerization activity of the resulting polymer. The appropriate amount of hydrogen to be added is approximately 0.001 to 100 NL per 1 kg of the total amount of 4-methyl-1-pentene and the α-olefin having 2 to 4 carbon atoms.

[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.

The naphthenic solvent is a compound containing a structure derived from naphthene within one molecule. Specific examples include cyclohexane, methylcyclohexane, ethylcyclohexane, and Exxol D (registered trademark, manufactured by ExxonMobil Corporation).

The isoparaffin solvent is a compound containing a structure derived from isoparaffin within one molecule. Specific examples include IP Solvent (registered trademark, manufactured by Idemitsu Kosan Co., Ltd.), Shellsol (registered trademark, manufactured by Shell), and Isopar (registered trademark, manufactured by ExxonMobil Corporation).

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

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), the 4-methyl-1-pentene copolymer (A) spreads uniformly. Therefore, by impregnating a base fabric (Y) with a coating agent containing the 4-methyl-1-pentene copolymer (A) and solvent (B) and drying it, the surface smoothness and uniformity of the functional fabric tend to be improved.

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. A boiling point within this range provides a good balance between handleability and manufacturing efficiency when producing functional fabrics.

In addition to the aliphatic hydrocarbon solvents and aromatic solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, isophorone, and gamma-butyrolactone may also be included. The amount of this 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 solvent content to be 100% by mass.

[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, coloring inhibitors, adjusters, matting agents, antifoaming agents, preservatives, gelling agents, latex, fillers, inks, colorants, dyes, pigments, and fragrances. These secondary additives may be used alone or in combination.

Plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methyl acetylricinoleate), aliphatic dialkoxy esters (such as adipic acid-propylene glycol polyester), aliphatic tricarboxylic acid esters (such as triethyl citrate), phosphate triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

Mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4-30) (such as hydrogenated castor oil), glycol esters of fatty acids, and liquid paraffin.

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.).

Examples of UV absorbers include benzotriazoles, benzophenones, salicylic acid, and acrylates.

Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodines.

Surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Nonionic surfactants include polyethylene glycol-type 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-type 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. 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. Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates; and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines.

Antistatic agents include the above-mentioned surfactants, fatty acid esters, and polymeric antistatic agents. Fatty acid esters include esters of stearic acid and oleic acid, and polymeric antistatic agents include polyether ester amides.

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

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).

The amount of each of the above additives added is not particularly limited and can be determined depending on the application as long as it does not impair the objectives of the present invention. However, it is preferable that each additive be added in an amount of 0.01 to 30 parts by mass relative to the 4-methyl-1-pentene/α-olefin polymer (A).

[Method of manufacturing functional fabric]
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 drying the resulting coating agent;
and a method including a step of laminating a functional film (X) containing the 4-methyl-1-pentene copolymer (A) on the base fabric (Y).
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) by using an extrusion film forming machine or a co-extrusion film forming machine, and then the film is laminated onto the base fabric (Y) by using a hot roll or a hot press machine under heat and pressure;
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 the methods 1) to 4) may be used in combination. Among these, the above methods 1) and 3) are preferred.

In the above methods (e.g., methods 2) to 4), an embossing roll having an uneven pattern on the cooling roll or heating roll may be used to impart designability and/or non-adhesiveness to the functional film (X) containing the 4-methyl-1-pentene copolymer (A).

In the above method 1), 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 some of the solvent. 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 that make up the base fabric (Y).

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

In the present invention, "removing the solvent" does not mean only completely removing the solvent, but also removing the solvent to the extent that it remains moldable. Specifically, when the entire functional film (X) formed using a coating agent containing the 4-methyl-1-pentene copolymer (A) and the solvent (B) is taken as 100% by mass, it refers to removing the solvent (B) until the solvent (B) is approximately 0.001 to 0.5% by mass. When the content of the solvent (B) is within this range, the original flexibility of the base fabric (Y) can be maintained.

There are no particular limitations on the method for removing the solvent; although it may be dried by leaving it to stand, it is generally removed by heating and drying at 30 to 220°C. Furthermore, 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 below 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 reduce productivity, while if the drying temperature is too high, problems such as foaming and deterioration may occur.

In the drying process, the temperature may be increased in two or more stages or continuously to prevent foaming and dry in a short time. Furthermore, after the drying process, the amount of solvent remaining in the coating layer can be reduced by immersing the coating layer in a solvent in which copolymer (A) is poorly soluble, such as water, methanol, ethanol, acetone, or methylene chloride, or by exposing the coating layer to a vapor atmosphere 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.

When molding the functional film (X) containing the 4-methyl-1-pentene copolymer (A) using a method such as extrusion, the 4-methyl-1-pentene copolymer (A) must be heated to a temperature above its melting point (Tm) to melt it. However, when forming the functional film (X) using the above coating agent, it can be formed at a temperature below the melting point (Tm), which reduces the amount of decomposition products due to thermal degradation of the copolymer (A), and may result in improved mold releasability and water repellency.

Examples of the decomposition products include low-molecular-weight components such as dimers to pentamers of the monomer components that make up 4-methyl-1-pentene copolymer (A), which are obtained by decomposing the copolymer (A) at high temperatures; and the additives mentioned above, such as 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, antifoaming agents, preservatives, gelling agents, latex, fillers, inks, colorants, dyes, pigments, fragrances, and some of the oxidatively decomposed components.

[Adhesion improving resin]
When it is necessary to increase the adhesive strength between the functional film (X) and the base fabric (Y), the composition or coating agent containing the 4-methyl-1-pentene copolymer (A) may further contain, within the scope of the present invention, for example, a) a thermoplastic adhesive resin, b) a resin having a pressure-sensitive 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')". In particular, it is preferable that the composition or coating agent contains a resin (C) that is any one of the resins a) to c) above having a functional group selected from the group consisting of an active hydrogen-containing functional group, an acid anhydride group, and an epoxy group.

<a) Thermoplastic adhesive resin>
Examples of the thermoplastic adhesive resin (hereinafter also referred to as "adhesive resin (a)") include known thermoplastic adhesives, but it is preferable to use one selected from polyolefins having polar functional groups introduced therein, ionomer resins, and copolymers of ethylene or ethylene-containing monomers with glycidyl methacrylate. Examples of polyolefins having polar functional groups introduced therein include commercially available thermoplastic resins such as "ADMER" (registered trademark) (manufactured by Mitsui Chemicals, Inc.) and polyolefin adhesive resins such as "MODIC" (manufactured by Mitsubishi Chemical Corporation). Similarly, examples of liquid forms dissolved or dispersed in a solvent include liquid polyolefin adhesives ("UNISTOR" (registered trademark) manufactured by Mitsui Chemicals, Inc.) and chlorinated polyolefin varnishes such as "SUPERCLONG" (manufactured by Nippon Paper Industries Co., Ltd.). The amount of adhesive resin (a) added is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, based on 100% by mass of copolymer (A).

<b) Resin containing adhesive component>
The resin having the adhesive component (hereinafter also referred to as "resin (b)") is not particularly limited as long as it is an adhesive resin, but examples thereof include thermoplastic resins having a melting point (Tm) of less than 110°C as measured by DSC, and conventionally known thermoplastic elastomers. Specifically, polyolefin-based thermoplastic resins or polyolefin-based thermoplastic elastomers are preferred. Specific examples of polyolefin-based thermoplastic resins or polyolefin-based thermoplastic elastomers include ethylene-based polymers, propylene-based copolymers, and butene-based copolymers. More specific examples include copolymers of ethylene and an α-olefin having 3 to 20 carbon atoms, copolymers of ethylene and an α-olefin having 3 to 20 carbon atoms and a cyclic olefin, ethylene-based copolymers having various vinyl compounds as comonomers such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters, copolymers of propylene and an α-olefin having 4 to 20 carbon atoms, copolymers of propylene and an α-olefin having 4 to 20 carbon atoms and a cyclic olefin, and ethylene-based copolymers having various vinyl compounds as comonomers such as styrene, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid esters.

Another example of a thermoplastic elastomer is a polystyrene-based elastomer. Examples of polystyrene-based elastomers include block copolymers (SBS) of a polystyrene block that forms the hard portion (crystalline portion) and a diene monomer block that forms 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-based elastomers can be used alone or in combination of two or more types.

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).

A specific example of SEPS is one sold by Kuraray Co., Ltd. under the trade name Septon (registered trademark). A specific example of SIBS is one sold by Kaneka Corporation under the trade name Sibustar (registered trademark).

Furthermore, as an example of a thermoplastic resin or thermoplastic elastomer, an elastomer made from an olefin-based block copolymer can also be used. Examples of elastomers made from 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, which 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, based on 100% by mass of the 4-methyl-1-pentene copolymer (A).

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').

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, and carbodiimide compounds. Of these, unsaturated carboxylic acids or derivatives thereof and vinyl group-containing organosilicon compounds are particularly preferred.

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 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 derivatives thereof can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, with maleic acid, Nadic acid (registered trademark), or their acid anhydrides being particularly preferred.

Conventional vinyl group-containing organosilicon compounds can be used, and there are no particular restrictions. 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, and 3-methacryloxypropylmethyldimethylsilane. 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 are γ-glycidoxypropyltripyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, and more preferred are vinyltriethoxysilane, vinyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane, which have little steric hindrance and high graft modification efficiency.

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

The radical initiator used in graft polymerization may be an organic peroxide or an azo compound. The radical initiator may be directly mixed with the 4-methyl-1-pentene copolymer (A) and the polar compound, or may be dissolved in a small amount of organic solvent before use. There are no particular restrictions on the organic solvent, as long as it is capable of dissolving the radical initiator.

In addition, a reducing substance may be used when grafting a polar compound onto the 4-methyl-1-pentene copolymer (A). Using a reducing substance may increase the amount of polar compound grafted.

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, one method involves 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.

Alternatively, the 4-methyl-1-pentene copolymer (A) can be reacted with a polar compound without a solvent using an extruder or the like. This reaction is typically carried out at a temperature above the melting point (Tm) of the 4-methyl-1-pentene copolymer (A), specifically at 160 to 290°C, for a period of typically 0.5 to 10 minutes.

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

[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.

The functional fabric of the present invention has an excellent balance of performance characteristics including mold releasability, water repellency, and flexibility (reduced stiffness), so the same effects are achieved even when composited with a component different from the functional fabric. In other words, the composite of the present invention has an excellent balance of performance characteristics including mold releasability, water repellency, flexibility, and vibration damping.

A variety of known methods can be used to form the composite of the present invention. For example, a composite can be produced by heat-pressing or welding the functional fabric and a member different from the functional fabric, as needed, using a press or the like. Alternatively, a composite can be produced by heat-pressing or welding the base fabric (Y) and a member different from the base fabric (Y), as needed, using a press or the like, to form a functional film (X) on the surface of the base fabric (Y) or inside the vicinity of the surface of the composite substrate, in the same manner as the above-described method for producing the functional fabric.

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. Alternatively, a composite can 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 the functional fabric manufacturing method described above.

Suitable adhesives for use include SBR-based solvent adhesives and hot-melt adhesives made from EVA, petroleum resin, or a mixture of EVA and petroleum resin.

The material different from the functional fabric or the material different from the base fabric (Y) is not particularly limited, but examples 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 types.

[Application]
The functional fabric and composite of the present invention have characteristics such as mold releasability, water repellency, stress relaxation and vibration damping 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 or on a base fabric (Y) such as a woven fabric or nonwoven fabric made of natural or synthetic fibers, it becomes possible to achieve both flexibility and water repellency, and to impart strength and designability when sewn, which were difficult to achieve with conventional 4-methyl-1-pentene copolymer (A) alone, and the fabric and composite can be deployed in a variety of applications.

The functional fabrics and composites 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; and agriculture and forestry supplies include medical supplies such as surgical sheets, medical wear, blood absorbers, drug absorbers, medical tape, bandages, and compresses. Examples of construction materials include insect nets, windbreak nets, shading nets, weed prevention nets, bird prevention nets, cucumber nets, and flower nets; civil engineering and construction materials include water retention sheets, condensation prevention sheets, greening sheets, seedling raising sheets, vegetation nets, and sandbag nets; 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, and water polo; industrial materials include hats, towels, car wash supplies, and toys; and outdoor materials include tents, flysheets, camping chairs, raincoats, backpacks, and cloth buckets.

The functional fabric of the present invention is particularly preferably used as clothing material and outdoor material, 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.

The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples. The methods for measuring the physical properties of the polymer, the materials used, the methods for preparing test specimens, and the evaluation methods used in the examples and comparative examples are as follows.

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

Measurements were performed using a JEOL ECP500 nuclear magnetic resonance spectrometer using a mixed solvent of ortho-dichlorobenzene and deuterated benzene (80/20% by volume), a sample concentration of 55 mg/0.6 mL, a measurement temperature of 120°C, an observation nucleus of ^13C (125 MHz), a sequence of single pulse proton decoupling, a pulse width of 4.7 μsec (45° pulse), a repetition time of 5.5 sec, an accumulation count of 10,000 or more, and a chemical shift reference value of 27.50 ppm. The composition of 4-methyl-1-pentene-α-olefin was quantified from the obtained ^13C -NMR spectrum.

<Intrinsic viscosity>
This is a value 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. After diluting the decalin solution with 5 mL of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to zero was calculated as the limiting viscosity [η] (see the formula below).
[η]=lim(ηsp/C) (C→0)

<Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn)>
The molecular weight was measured by gel permeation chromatography (GPC). Specifically, a Waters ALC/GPC150-Cplus model (integrated with a differential refractometer detector) was used as a liquid chromatograph, and two GMH6-HT and two GMH6-HTL columns (manufactured by Tosoh Corporation) were used as separation columns connected in series. o-Dichlorobenzene was used as the mobile phase medium, and 0.025% by mass of dibutylhydroxytoluene (manufactured by Takeda Pharmaceutical Co., Ltd.) was used as the antioxidant. The mobile phase medium was moved at 1.0 mL/min, the sample concentration was 15 mg/10 mL, the sample injection amount was 500 μL, and a differential refractometer was used as the detector. As the standard polystyrene, a standard polystyrene manufactured by Tosoh Corporation with a weight average molecular weight (Mw) of 1,000 or more and 4,000,000 or less was used.

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

<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 sample was then held at 250°C for 5 minutes to completely melt the copolymer, 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 in this second heating was taken as the melting point (Tm).

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

<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.

<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 stirred at 200 rpm for 1 hour at 80°C to prepare a composition, which was then stored at room temperature for 24 hours. After storage, the composition was evaluated as follows: ○ if it was transparent when visually observed under visible light; △ if it appeared cloudy but exhibited fluidity; and × if it was cloudy and exhibited no fluidity.

<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, then dried at 25°C for 30 minutes and then at 80°C for 1 hour. When a functional fabric having a functional film was obtained as a result of this, the appearance of the functional fabric on the functional film side was visually confirmed. If there were any irregularities not due to the base fabric, they were evaluated as "X" as they were lumps due to undissolved residue, and if there were no irregularities or unevenness in thickness, they were evaluated as "O."

<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 (◯).

<Flexibility>
The functional fabric was cut into a size of 100 mm x 50 mm, and ten monitors were asked to freely bend and roll the fabric by hand to deform it, and the flexibility (suppleness, stiffness) was evaluated on a four-point scale, with an average score of rank 2 or lower being considered acceptable.
Rank 1: Good flexibility Rank 2: Slightly lacking flexibility Rank 3: Feels stiff Rank 4: Feels very stiff

<Water contact angle measurement>
Using the DropMaster 500 image processing solid-liquid interface analysis system, the contact angle of a water droplet dropped onto the functional fabric was measured. The larger the contact angle, the higher the releasability for highly polar materials.

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

<Solvent content, decomposition product content>
The content of solvent and copolymer decomposition products contained 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 generated during the heating were collected using a dynamic headspace method and measured using a thermal desorption GC/MS spectrometer (HP6890/HP5975, manufactured by Agilent Technologies). Next, the obtained MS spectrum was converted to a quantitative value using decane as a standard sample, and the peaks derived from the solvent were taken as the amount of solvent, and the peaks not derived from the solvent were taken as the amount of decomposition products.

[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 stirring blade and thoroughly purged with nitrogen was charged with 300 ml of normal hexane (dried with 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 charged into the autoclave, and the stirrer was turned on.

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-fed 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-fed into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Subsequently, acetone was poured into the reaction solution with stirring.

The resulting powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The amount of copolymer (A-1) obtained 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.

<Synthesis of 4-methyl-1-pentene copolymer (A-2)>
A 1.5-liter stainless steel autoclave equipped with a stirring blade 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 charged into the autoclave, and the stirrer was turned on.

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-fed 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-fed 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.

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.

<Synthesis of 4-methyl-1-pentene copolymer (A-3)>
A 1.5-liter SUS 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 charged into the autoclave, and the stirrer was turned on.

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-fed 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-fed into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. Subsequently, acetone was poured into the reaction solution with stirring.

The resulting powdery polymer containing the solvent was dried at 100°C under reduced pressure for 12 hours. The amount of 4-methyl-1-pentene/α-olefin copolymer (A-3) obtained 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.

<Synthesis of 4-methyl-1-pentene copolymer (cA-4)>
A 1.5-liter SUS 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 charged into the autoclave, and the stirrer was turned on.

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.

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.

[Base fabric]
<Base fabric (Y-1)>
A plain woven fabric having a basis weight of 82 g/m ² and a density of 0.4 g/cm ³ was prepared using 30 count yarn containing 50% cotton, 40% nylon, and 10% spandex, and was used as 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, and used as base fabric (Y-2).

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

[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 resulting functional fabric were measured, and the results are shown in Table 2.

[ 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.

[ Reference example 2 ]
To 99.8 parts by mass of 4-methyl-1-pentene copolymer (A-2), 0.1 parts by mass of tris(2,4-di-t-butylphenyl)phosphite and 0.1 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate were added as heat stabilizers to produce pellets. 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 set at 240°C. The extrusion molding was performed at a die temperature of 240°C through the T-die to obtain a 30μm thick film. This film was 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 results of measuring various physical properties of the resulting functional fabric are shown in Table 2.

[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, a functional fabric could not be obtained.

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

The functional fabric of the present invention has excellent water repellency, vibration damping, and other properties 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, and more. Furthermore, since it does not contain fluorine or silicone, it also has an excellent environmentally friendly effect.

Claims (6)

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 ;
(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. The functional fabric according to claim 1, wherein 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 claim 1 or 2, wherein the base fabric (Y) is selected from woven fabrics and nonwoven fabrics made of natural or synthetic fibers. A method for producing the functional fabric according to any one of claims 1 to 3 , comprising:
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). A clothing material comprising the functional fabric according to any one of claims 1 to 3 . An outdoor material comprising the functional fabric according to any one of claims 1 to 3 .