JP2023081307A - Composition and film - Google Patents

Abstract

To provide a composition which is excellent in snow slipping properties in both of snow qualities of wet snow and dry snow.SOLUTION: A composition includes a thermoplastic resin A, a polymer B and powder C. The polymer B has a constituent unit represented by formula (1) or formula (2), a moisture content in the powder C that has been processed under a specific processing condition (a) satisfies 1,000-5,000,000 mass ppm when it is measured under a specific measurement condition (b), with respect to 100 pts.mass of the total of the resin A and the polymer B, the content of the resin A is 1-99 pts.mass, the content of the polymer B is 1-99 pts.mass, and the content of the powder C is 0.01-25 pts.mass.SELECTED DRAWING: Figure 1

Description

The present invention relates to compositions and membranes.

In areas with heavy snowfall, snow cover on living environment materials due to snowfall is a problem. For example, collapse of structural members due to increased load due to snow cover, snow damage caused by a large amount of snow falling at once, failure to check road traffic safety indicator boards and devices such as road signs and traffic lights, solar panels decrease in power generation efficiency.

According to a report by Yoshida et al. (Hokkaido Prefectural Research Institute Report 299, 13-17 (2000)), the quality of falling snow is classified into wet snow with high water content and dry snow with low water content. Whether it is wet snow or dry snow is determined by the environmental temperature at which the snow falls. If the surface properties of the snow-covering material are hydrophilic, it is easier to remove (sliding) the snow. ) is described as easy to In this way, since contradictory properties of hydrophilicity and water repellency are required, there are very few reports on the design of surface properties of materials that are effective in sliding various types of snow.

In Patent Document 1, a vinylidene fluoride-based fluororesin is used as a matrix resin, and a ceramic-based inorganic aggregate, organic polymer beads, and fluororesin powder are added, and a topcoat is applied on top of an undercoat film formed on a metal plate. As a paint, a vinylidene fluoride-based fluororesin-coated metal plate having excellent scratch resistance, galling resistance, and snow-slipping properties is described.

In Patent Document 2, a plurality of grooves extending in one direction are arranged on a solid surface to form unevenness at intervals of 2 μm or more and 4 mm or less, and the convex portions of the unevenness are made hydrophilic with a water contact angle of 30° or less. , describes a snow-slippery solid characterized by making recesses water-repellent with a water contact angle of 90° or more, and a technique for producing the same.

JP-A-2000-355671 JP 2003-226867 A

However, it does not require surface processing such as painting, surface cutting, or special post-processing such as texturing, and even if it has a smooth shape, it can be used for both wet and dry snow. There is a demand for materials with excellent properties.

The present invention has been made in view of the above problems. It is an object of the present invention to provide a composition and a film which are excellent in snow sliding properties for both wet snow and dry snow.

式中、Ｒ^１～Ｒ^３は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、又は、アルキル基から選択される。各アルキル基及び各アルコキシ基の内の少なくとも1つの水素原子は、独立にハロゲン原子で置換されていてもよい。
処理条件（ａ）：環境温度８０℃、真空度０．０８ＭＰａの条件に設定した真空乾燥機で粉体Ｃを１７時間乾燥させたのち、環境温度５０℃、環境湿度９５％ＲＨの条件に設定した恒温恒湿機内に粉体Ｃを２４時間保持する。
測定条件（ｂ）：加熱温度１９０℃、保持時間１０分の水分気化条件でカールフィッシャー水分計を用いて測定する。 A composition according to one aspect of the present invention includes a thermoplastic resin A, a polymer B, and a powder C. The polymer B has a structural unit represented by formula (1) or formula (2),
The water content in the powder C treated under the following treatment conditions (a) satisfies 1000 mass ppm to 5000000 mass ppm when measured under the following measurement conditions (b),
With respect to a total of 100 parts by mass of the resin A and the polymer B, the content of the resin A is 1 to 99 parts by mass, and the content of the polymer B is 1 to 99 parts by mass. The content of powder C is 0.01 to 25 parts by mass.

wherein R ¹ to R ³ are each independently selected from a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. At least one hydrogen atom in each alkyl group and each alkoxy group may be independently substituted with a halogen atom.
Processing conditions (a): After drying the powder C for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80°C and a degree of vacuum of 0.08 MPa, conditions of an environmental temperature of 50°C and an environmental humidity of 95% RH were set. The powder C is held for 24 hours in the thermo-hygrostat.
Measurement conditions (b): Measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes.

The median diameter (D50) of the powder C measured by a laser diffraction method can be 0.05 to 30 μm.

The powder C can be silica powder or silicone powder.

A film according to one aspect of the present invention includes resin M and powder C. As shown in FIG. A contact angle of 50 to 90° is measured by dropping a water droplet of 2 μL on the horizontal surface of the film. The surface of the film has a sea region of the resin M and an island region of the powder C,
the ratio of the area of the island region to the total area of the sea region and the island region is 0.01 to 30%;
A film in which the water content in the powder C treated under the following treatment conditions (a) satisfies 1000 mass ppm to 5000000 mass ppm when measured under the following measurement conditions (b).
Processing conditions (a): After drying the powder C for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80°C and a degree of vacuum of 0.08 MPa, conditions of an environmental temperature of 50°C and an environmental humidity of 95% RH were set. The powder C is held for 24 hours in the thermo-hygrostat.
Measurement conditions (b): Measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes.

An article according to one aspect of the present invention has the above-described film on at least a portion of its outer surface.

According to the present invention, there is no need for special post-processing such as painting processing, surface processing such as surface cutting, and texturing processing, and even if it has a smooth shape, it can be used for both wet snow and dry snow. It is possible to obtain a film which is excellent in both quality and snow-sliding properties.

FIG. 1 is an enlarged schematic diagram of the surface of a film according to one embodiment. FIG. 2 is an enlarged schematic diagram of a cross section near the surface of a film according to one embodiment. FIG. 3 is a side view for explaining the tilt angle θ of the film 10. FIG.

Several embodiments of the invention are described in detail below. However, the present invention is not limited to the following embodiments.

(Composition)
The composition of the present embodiment is a composition containing a thermoplastic resin A, a polymer B, and a powder C, and with respect to a total of 100 parts by mass of the resin A and the polymer B, The content of the resin A is 1 to 99 parts by mass, the content of the polymer B is 1 to 99 parts by mass, and the content of the powder C is 0.01 to 25 parts by mass.

(Thermoplastic resin A)
Examples of thermoplastic resins are olefin-based polymers, styrene-based polymers, methacrylic-based resins, acrylic-based resins, ester-based resins, amide-based resins, and vinyl-based polymers. The thermoplastic resin A may be a single resin or a mixture of two or more resins.

<Olefin polymer>
The olefinic polymer of the present invention is a polymer containing 51% by weight or more of structural units derived from an olefin having 2 to 10 carbon atoms (provided that the total amount of the olefinic polymer is 100% by weight). . The olefins having 2 to 10 carbon atoms include, for example, ethylene, 1-propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and the like. May contain seeds.

The olefinic polymer may also contain structural units derived from monomers other than olefins having 2 to 10 carbon atoms. Examples of monomers other than olefins having 2 to 10 carbon atoms include aromatic vinyl monomers such as styrene; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, acrylic Unsaturated carboxylic acid esters such as butyl acid, methyl methacrylate and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene); non-conjugated dienes such as cyclopentadiene and 5-ethylidene-2-norbornene; and propylene.

The olefin polymer may have two or more structural units derived from other monomers.

The olefin-based polymer can be at least one selected from the group consisting of an ethylene-based polymer, a propylene-based polymer, and a butene-based polymer, or a combination of any two or more thereof. may

The ethylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from ethylene, examples of which include ethylene homopolymer, ethylene-1-butene copolymer, and ethylene-1-hexene copolymer. ethylene-1-octene copolymer and ethylene-1-butene-1-hexene copolymer. The ethylene-based copolymer may be a combination of two or more ethylene-based copolymers.

A propylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from propylene, and examples thereof include propylene homopolymers, propylene-ethylene copolymers, and propylene-1-butene copolymers. , propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene It is a copolymer. The propylene-based copolymer may be a combination of two or more propylene-based copolymers. It is preferred that the olefin-based polymer is a propylene-based copolymer.

The butene-based copolymer is a polymer containing 50% by mass or more of structural units derived from 1-butene, examples of which include 1-butene homopolymer, 1-butene-ethylene copolymer, 1- Butene-propylene copolymer, 1-butene-1-hexene copolymer, 1-butene-1-octene copolymer, 1-butene-ethylene-propylene copolymer, 1-butene-ethylene-1-hexene copolymer 1-butene-ethylene-1-octene copolymer, 1-butene-propylene-1-hexene copolymer, and 1-butene-propylene-1-octene copolymer. The butene-based copolymer may be a combination of two or more butene-based copolymers.

<Styrene-based polymer>
A styrenic polymer is a polymer containing 51% by weight or more of constitutional units derived from styrene or a styrene derivative. Examples of styrene derivatives include p-methylstyrene, p-tert-butylstyrene, α-methylstyrene and p-methoxystyrene. The styrene polymer may contain structural units derived from monomers other than styrene or styrene derivatives, such as olefins having 2 to 10 carbon atoms; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; ; unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; vinyl ester compounds such as vinyl acetate; 1,3-butadiene, 2-methyl-1,3- Conjugated dienes such as butadiene (isoprene); non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.

<Methacrylic resin>
A methacrylic resin is a polymer containing 51% by weight or more of structural units derived from a methacrylate ester. (2-ethylhexyl methacrylate) and the like.

<Acrylic resin>
An acrylic resin is a polymer containing 51% by weight or more of structural units derived from an acrylic ester, and examples thereof include poly(methyl acrylate), poly(ethyl acrylate), poly(butyl acrylate), poly (2-ethylhexyl acrylate) and the like.

<Ester-based resin>
An ester resin is a polymer containing 51% by weight or more of structural units derived from an ester of a polyhydric carboxylic acid and a polyhydric alcohol. Examples thereof include polycarbonate, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. , polybutylene naphthalate, and the like.

<Amide resin>
An amide resin is a polymer containing 51% by weight or more of structural units repeating amide bonds. methylene dodecaneamide), poly(p-phenylene terephthalamide), poly(m-phenylene terephthalamide) and the like.

<Vinyl polymer>
The vinyl-based polymer of the present invention is a polymer containing 51% by weight or more of constitutional units derived from a monomer having a vinyl group. Examples thereof include polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, Examples include polyvinylidene chloride.

(Tg of thermoplastic resin A)
The glass transition temperature (Tg) of the thermoplastic resin A is preferably 0° C. or higher, more preferably 50° C. or higher, and even more preferably 80° C. or higher, from the viewpoint of snow sliding properties in wet snow. The higher the glass transition temperature (Tg), the more excellent the snow sliding properties of the composition on wet snow.

The glass transition temperature (Tg) of thermoplastic resin A is a value determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

(MFR of thermoplastic resin A)
The melt mass flow rate (MFR) of thermoplastic resin A measured at a temperature of 190°C or 230°C and a load of 2.16 kgf or 3.80 kgf (37.3 N) is 0.01 g/10 minutes or more. can be 200 g/10 minutes or less. The upper limit of MFR can be 100 g/10 min, 50 g/10 min, 30 g/10 min. The smaller the melt mass flow rate of the thermoplastic resin A, the more excellent the moldability of the composition tends to be.

As a method for producing the thermoplastic resin A, a known polymerization method using a known polymerization catalyst is used.

(Polymer B)
Polymer B of the present invention is a polymer having a structural unit represented by formula (1) or formula (2).

式中、Ｒ^１～Ｒ^３は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、及び、アルキル基から選択される。ハロゲン原子の例は、Ｆ，Ｃｌ，Ｂｒ，Ｉである。

wherein R ¹ to R ³ are each independently selected from hydrogen atoms, halogen atoms, alkoxy groups and alkyl groups. Examples of halogen atoms are F, Cl, Br, I.

The number of carbon atoms in the alkoxy group or alkyl group of R ¹ to R ³ in formulas (1) and (2) is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less. is. The alkyl groups and alkoxy groups of R ¹ to R ³ may be linear, branched or cyclic, but preferably linear. At least one hydrogen atom in each alkyl group and each alkoxy group of R ¹ to R ³ may be independently substituted with a halogen atom such as fluorine. It is preferred that all hydrogen atoms in each alkyl group and each alkoxy group are replaced with halogen atoms such as fluorine.

Polymer B is preferably a polymer containing 51% by weight or more of structural units of formula (1) and/or (2), for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride , tetrafluoroethylene/hexafluoropropylene copolymer, ethylene/tetrafluoroethylene copolymer, ethylene/chlorotrifluoroethylene copolymer, perfluoroalkoxyalkane (e.g. tetrafluoroethylene/perfluoroalkoxyethylene copolymer polymerization), ethylene-tetrafluoroethylene copolymer, and the like.

From the viewpoint of workability, the polymer B is preferably polychlorotrifluoroethylene, polyvinylidene fluoride, or perfluoroalkoxyalkane.

When a vinylidene fluoride-based polymer is used as the polymer B, it may be a resin containing vinylidene fluoride units. A copolymer containing The content of vinylidene fluoride units in the vinylidene fluoride polymer is preferably 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.

Other vinyl monomers copolymerizable with vinylidene fluoride include, for example, fluorinated vinyl monomers such as vinyl fluoride, ethylene tetrafluoride, ethylene trifluorochloride, and propylene hexafluoride; styrene; , ethylene, butadiene, and propylene.

As a method for producing the polymer B, a known polymerization method using a known polymerization catalyst is used.

(Tm of polymer B)
The melting point of polymer B determined by DSC is not particularly limited, but from the viewpoint of processability, it is preferably less than 300°C, more preferably less than 280°C, and even more preferably less than 260°C. be.
The melting point (Tm) of polymer B determined by DSC is the melting temperature of the crystalline phase contained in polymer B. Specifically, in the DSC curve obtained when polymer B is heated, It is the peak top temperature in the endothermic peak on the high temperature side.

In addition, this melting point is measured under the following conditions. (i) About 10 mg of polymer B is heat-treated at 220°C for 5 minutes in a nitrogen atmosphere, and then cooled to 50°C at a cooling rate of 10°C/min. (ii) Next, after keeping the temperature at 50° C. for 1 minute, the temperature is increased from 50° C. to 180° C. at a heating rate of 10° C./min.

(MFR of polymer B)
Polymer B should have a melt mass flow rate (MFR) of 0.01 g/10 minutes or more, measured under conditions of a temperature of 230°C, or a temperature of 190°C or 297°C, and a load of 2.16 kgf or 5.0 kgf. can be 200 g/10 minutes or less. The upper limit of MFR can be 100 g/10 min, 50 g/10 min, 30 g/10 min. The smaller the melt mass flow rate of the polymer B, the more excellent the moldability of the composition tends to be.

As a method for producing the polymer B, a known polymerization method using a known polymerization catalyst is used.

(Powder C)
The powder C in the present invention is preferably a powder that exhibits solid particulate properties even at a temperature of 100°C. Examples of the powder are powders containing one or a plurality of constituent elements selected from the group consisting of metalloid elements, metal elements, halogen elements, and carbon, and preferably powders containing metalloid elements as constituent elements. is the body. These powders may be used alone or in combination of two or more.

<Powder C Containing Metalloid Element as Constituent Element>
The powder C containing a metalloid element as a constituent element is a powder containing at least one metalloid element selected from the group consisting of B, Si, Ge, As, Sb, Te, Po, and At as a constituent element. , preferably a powder containing at least one selected from the group consisting of B and Si, more preferably a powder containing Si.

The powder containing a metalloid element as a constituent element may be a powder of a single metalloid, a powder of a mixture of single metalloids, an oxide or nitride of a metalloid (single type or multiple types). Powders of semimetal compounds such as powders may also be used.

［式（３）中、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシ基、アルキル基である。］ The powder containing a metalloid element as a constituent element is preferably silicon dioxide powder (silica powder).
Further, the powder containing a metalloid element as a constituent element may be a silicone powder. The silicone powder contains structural units represented by formula (3).

[In Formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. ]

The number of carbon atoms in the alkoxy group or alkyl group of R ⁴ and R ⁵ is preferably 1 or more and 15 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less. Alkyl groups and alkyl groups may be linear, branched, or cyclic, but are preferably linear.

<Powder Containing a Metal Element as a Constituent Element>
The powder containing a metal element as a constituent element is a powder containing at least one element selected from the group consisting of Groups 1 to 12 of the periodic table as a constituent element, or a powder containing, as a constituent element, at least one element selected from the group consisting of Groups 1 to 12 of the periodic table. A powder containing at least one element selected from the group consisting of base metal components (Al, etc.) up to Group 16 as a constituent element, preferably at least one selected from the group consisting of Groups 2 to 12. It is a powder containing three elements as constituent elements, and more preferably contains at least one element selected from the group consisting of Mg, Ca, Ti, Fe, Ni, Cu, Zn, Ag, Au, and Os as constituent elements. It is powder.
The powder containing a metal element as a constituent element may be a metal (including alloy) powder or a metal compound powder.
An example of a metal compound powder is a metal oxide powder. An example of metal oxide powder is alumina powder.
Other examples of metal compound powders are metal halide powders. Examples of metal halide powders are metal fluoride powders, metal chloride powders, metal bromide powders, and metal iodide powders, and metal halide powders are metal halide powders containing multiple types of halogen elements. may Specific examples of metal halide powders are copper iodide powder and copper chloride powder.

<Powder Containing Carbon Atom as a Constituent Element>
The powder containing a carbon atom as a constituent element is a powder containing a carbon atom as a constituent element and showing solid properties even at a temperature of 100 ° C., preferably thermosetting resin, diamond, graphite, fullerene, etc. A thermosetting resin is preferred.

These powders C may be porous powders. If the powder is porous, the hygroscopicity of the powder can be easily increased.

(Particle size of powder C: median diameter D50 measured by laser diffraction method)
The median diameter D50 of the powder C may be 30 μm or less, 25 μm or less, or 20 μm or less from the viewpoint of snow sliding properties. If the D50 is too large, the dispersibility is lowered and molding defects tend to occur. The median diameter D50 of the powder C may be 15 μm or less, 13 μm or less, 10 μm or less, 7 μm or less, or 6 μm or less from the viewpoint of snow sliding properties.
The median diameter D50 of the powder C may be 0.05 μm or more, 0.5 μm or more, 1 μm or more, or 2 μm or more from the viewpoint of ease of handling during production. It may be 3 μm or more, and may be 5 μm or more.

The median diameter D50 can be obtained from the particle size value at a cumulative amount of 50% by weight read from the obtained particle size cumulative distribution curve by measuring the weight-based particle size distribution according to JISR1629 using a laser diffraction particle size distribution analyzer. can. Examples of the laser diffraction particle size distribution analyzer include MT-3300EX-II manufactured by Nikkiso Co., Ltd.

(Hygroscopicity of powder C)
After the powder C is treated under the treatment conditions (a) below, the water content of the powder C measured under the measurement conditions (b) below should be 1000 to 5000000 mass ppm. In order to make the powder C exhibit such hygroscopicity (hydrophilicity), the composition of the powder C, the unevenness (porosity) of the surface of the powder C, and the like may be appropriately adjusted.
Processing conditions (a)
First, the powder C is dried for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80° C. and a degree of vacuum of 0.08 MPa. Next, the powder C is left for 24 hours in a thermo-hygrostat set to conditions of an environmental temperature of 50° C. and an environmental humidity of 95% RH.
Measurement conditions (b)
The moisture contained in the powder C treated under the treatment conditions (a) is measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes.

The water content of the powder C measured under the treatment conditions (a) and measurement conditions (b) is preferably 5000 mass ppm to 4500000 mass ppm, more preferably 10000 mass ppm to 4000000 mass ppm. The water content may be 20000 ppm by weight or more, or 50000 ppm by weight or more. The water content of the powder C may be 100000 ppm by mass or more, or may be 200000 ppm by mass or more. The water content of powder C may be 4,000,000 mass ppm or less, 3,000,000 mass ppm or less, 2,000,000 mass ppm or less, 1,000,000 mass ppm or less, and 700,000 mass ppm or less. It may be 500000 mass ppm or less. If the powder C with too low water content is used, it tends to be difficult to improve the snow sliding property of the compact. If the powder C having an excessively high water content is used, the strength of the molded body tends to decrease.

Examples of the method for producing the above powder C include known gas phase methods such as PVD method and CVD method, coprecipitation method, alkoxide method, sol-gel method, hydrothermal synthesis method, polymerization method, spray drying method, freeze drying method, etc. A mechanical method such as a liquid phase method, resin kneading, various pulverizing methods, or a mechanical alloying method may also be used.

<Composition>
In the composition of the present invention, the content of the resin A is 1 to 99 parts by mass with respect to the total of 100 parts by mass of the resin A and the polymer B, and the content of the polymer B is 1 to 99 parts by mass. 99 parts by mass. In the composition, the content of the resin A is preferably 10 to 90 parts by mass, the content of the polymer B is preferably 10 to 90 parts by mass, and the content of the resin A is 10 to 80 parts by mass. It is more preferable that the content of the polymer B is 20 to 90 parts by mass, the content of the resin A is 10 to 70 parts by mass, and the content of the polymer B is It is even more preferable that it is 30 to 90 parts by mass, the content of the resin A is 20 to 70 parts by mass, and the content of the polymer B is 30 to 80 parts by mass. It is even more preferable.

In the composition of the present invention, the content of powder C is 0.01 to 25 parts by mass with respect to a total of 100 parts by mass of resin A and polymer B. In the composition, the content of powder C is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 15 parts by mass. It is even more preferable that the content of the substance C is 0.01 to 10 parts by mass, and it is even more preferable that the content of the powder C is 0.5 to 10 parts by mass. The content of powder C may be 7 parts by mass or less, or may be 5 parts by mass or less.

(Peak number of glass transition temperature)
The number of peaks in the glass transition temperature of the composition of the present invention is preferably unimodal. In other words, the thermoplastic resin A and the polymer B are preferably completely compatible.

The composition may contain additives other than the thermoplastic resin A, the polymer B, and the powder C, if necessary. Additives include stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, inorganic fibers, organic fibers, composite fibers, inorganic whiskers, and fillers. Examples of stabilizers include lubricants, antioxidants, heat stabilizers, light stabilizers, weather stabilizers, metal deactivators, ultraviolet absorbers, light stabilizers, and copper damage inhibitors. Examples of light stabilizers include hindered amine light stabilizers, examples of colorants include titanium oxide, carbon black and organic pigments, examples of metal powders include ferrite, examples of inorganic fibers include glass fibers, Examples of organic fibers include carbon fibers and aramid fibers. Examples of inorganic whiskers include potassium titanate whiskers. Examples of fillers include glass beads, glass balloons, glass flakes, asbestos and mica. , calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice stone, evo powder, cotton flock, cork powder, barium sulfate, fluororesin, cellulose powder, wood powder. Only one kind of additive may be contained, or two or more kinds thereof may be contained. The additive may be contained in the dispersed phase of the thermoplastic resin A, may be contained in the dispersed phase of the polymer B, and the thermoplastic resin A and the polymer B form separate dispersed phases. good too.

(Method for producing composition)
As a method for producing the composition according to the present invention, there is a method of melt-kneading the thermoplastic resin A, the polymer B and the powder C, and a thermoplastic resin in the presence of the thermoplastic resin A, the polymer B and the powder C. A method of polymerizing various monomer components constituting the resin A and the polymer B can be mentioned. From the viewpoint of workability, the method of melt-kneading the thermoplastic resin A, the polymer B and the powder C is preferable.

The melt-kneading described above can be performed by a known method using a known apparatus. For example, the thermoplastic resin A, the polymer B and the powder C are mixed using a mixing device such as a Henschel mixer, a ribbon blender, or a tumble mixer, and then further melted and kneaded, or using a constant feeder. After continuously supplying the thermoplastic resin A, the polymer B, the powder C, and various additives as necessary to obtain a mixture, the mixture is subjected to a uniaxial or biaxial or more A method of melt-kneading using an extruder, a Banbury mixer, a roll kneader, or the like can be mentioned.

The melt-kneading temperature is preferably 80°C or higher, more preferably 100°C to 300°C, more preferably 120°C to 280°C, still more preferably 140°C to 260°C. be.
(action)
According to the composition according to the present embodiment, in addition to the thermoplastic resin A, since it has the polymer B containing a fluorine atom, by melting and molding the composition, a molded article of the composition can be obtained. The powder C having hygroscopicity can be selectively arranged on the surface of the . Therefore, articles such as various films having specific surfaces, which will be described later, can be favorably molded. The surface of the membrane tends to impart snow-sliding properties in both low temperature conditions and high temperature conditions.

(film)
A film according to an embodiment of the present invention is a film containing resin M and powder C,
A contact angle of 50° or more and 90° or less measured by dropping a water droplet of 2 μL on the horizontal surface of the film (standing at an inclination angle θ of 0° with respect to the horizontal plane: see FIG. 3),
The surface of the film has a sea region of the resin M and an island region of the powder C,
the ratio of the area of the island region to the total area of the sea region and the island region is 0.01 to 30%;
The water content in the powder C treated under the following treatment conditions (a) satisfies 1,000 mass ppm to 5,000,000 mass ppm when measured under the following measurement conditions (b).
Processing conditions (a): After drying the powder C for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80°C and a degree of vacuum of 0.08 MPa, conditions of an environmental temperature of 50°C and an environmental humidity of 95% RH were set. The powder C is held for 24 hours in the thermo-hygrostat.
Measurement conditions (b): Measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes.

<Resin M>
The surface of the resin M is not particularly limited as long as it has a hydrophobicity that can provide a contact angle with water within the range described above. Resin M may be a mixture of thermoplastic resin A and polymer B in the composition described above.

<Water contact angle on the film surface>
The contact angle of the film surface is measured by the θ/2 method by dropping a water droplet of 2 μL on the horizontal surface of the film. Contact angle measurements are made at 23°C. A contact angle is measured according to JIS R 3257:1999.
The contact angle of the film surface is preferably 60° or more and 90° or less, more preferably 70° or more and 90° or less, and even more preferably 70° or more and 85° or less.

<Sea-island structure on the membrane surface>
As shown in FIG. 1, the surface of the film 10 has a sea region S of resin M and an island region I of powder C. As shown in FIG. Since the powder C exhibits water absorption as described above, the island region I is a hydrophilic region, and the sea region of the resin M is a hydrophobic region. That is, many hydrophilic island regions I are dispersed in hydrophobic sea regions S on the surface of the film.

As shown in the cross-sectional view of the film in FIG. 2, it is preferable that the powder C protrudes from the resin M on the surface of the film. On the surface, the resin M forms a sea region S, and the powder C forms an island region I.

(Proportion of area of island region I on surface)
The ratio of the area of the island region I to the total of the sea region S and the island region I on the surface of the film is 0.01% or more and 30% or less, preferably 0.05% or more and 15% from the viewpoint of snow sliding. %, more preferably 0.05% or more and 10% or less, and still more preferably 0.05% or more and 5% or less.
The area of the island region I on the surface of the film is calculated based on the image taken from the direction perpendicular to the surface. For example, by elemental analysis such as SEM-EDS, the island region I and the sea region S can be separated and their areas can be obtained.

<Average distance between island regions I>
The average distance between the island regions I on the surface of the film is preferably 5 μm or more and 60 μm or less, more preferably 10 μm or more and 55 μm or less, and even more preferably 15 μm or more and 50 μm or less, from the viewpoint of snow sliding property.
The average distance between island regions I is obtained by finding the shortest distances between adjacent island regions I and arithmetically averaging them.

<Dispersion of distance between island regions I>
On the surface of the film, the degree of dispersion of the distance between the island regions I is preferably 0.450 or more, more preferably 0.500 or more, and even more preferably 0.550 or more. The degree of dispersion of distances between island regions I is defined by the following equation.
Dispersion of distances between island regions=average deviation of distances between island regions/average distance between island regions (4)

<Size of Island Region I>
The average equivalent circle diameter of the island regions can be 0.001 to 30 μm.

<Water absorption amount of powder C>
The water absorption amount of the powder C is as described above.

<Thickness of film>
Although the thickness of the film is not limited, it can be, for example, 1 μm or more. There is no particular upper limit, but it can be 150 mm.

(Method for manufacturing membrane)
The film of the present embodiment can be obtained by melting and molding the above composition. Examples of molding methods are extrusion, compression molding, injection molding. Extrusion methods include, for example, a T-die molding method, a single-layer extrusion molding method by an inflation molding method, a multilayer extrusion molding method by a T-die molding method or a single-layer extrusion molding method by an inflation molding method, and a spinning extrusion method. mentioned. Known methods such as a feed block method and a multi-manifold method can be used as the multilayer extrusion method. Examples of injection molding methods include general injection molding, injection foam molding, supercritical injection foam molding, ultra-high speed injection molding, injection compression molding, gas-assisted injection molding, sandwich molding, and sandwich foam. A molding method, an insert/outsert molding method, and the like can be mentioned.

Extrusion molding and compression molding are preferred as molding methods from the viewpoint of snow-slipping properties.

(Aspect of article using membrane)
The film of the present invention may be used alone, or laminated with other resin members, metal members, paper, leather or the like to form a multi-layer article.

A surface treatment may be applied to the surface of the film of the present invention. Examples of surface treatment methods include embossing, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.

Specific examples of the film of the present invention include transparent optical members, fiber materials, agricultural materials, exterior members, furniture and interior decoration members, house members, toy members, gardening members, automobile members, and packaging materials. Examples of transparent optical members include solar panel members, lens members, and the like. Fiber materials include, for example, clothing fabric members, interior fabric members, and industrial fiber members. Examples include film members, house members, and net members. Exterior members include, for example, carport members, fence members, gate members, gatepost members, post members, cycle port members, deck members, sunroom members, roof members, and terraces. members, handrail members, shade members, awning members, etc. Examples of furniture and interior decoration members include sofa members, table members, chair members, bed members, dresser members, cabinet members, dresser members, etc. Home appliance members include, for example, watch members, mobile phone members, white goods members, and the like. Toy members include, for example, plastic model members, diorama members, video game main body members, and the like. , planter members, vase members, flowerpot members, and the like. Automotive members include, for example, bumper materials and instrument panel materials. Packaging materials include, for example, food packaging materials, fiber packaging materials, and general merchandise. Examples include packaging materials. Further, other uses include, for example, monitor members, office automation (OA) equipment members, medical members, drainage pans, toiletry members, bottles, containers, snow removal product members, and various construction members.

(action)
The surface of the film according to the present embodiment has a predetermined contact angle with water and has water repellency, so it is excellent in snow sliding under dry snow conditions (less than -3 ° C.), and in addition, the resin sea area on the surface Since the island regions I of the hydrophilic powder C are dispersed in the S at a suitable area ratio, the skidability is also excellent under wet snow conditions (-3° C. or higher). If the area ratio of the island region is too high, the hydrophilicity tends to be too strong and the snow-sliding property of dry snow tends to decrease.

Hereinafter, the present invention will be described using examples and comparative examples. The thermoplastic resin A, polymer B, and powder C used in Examples and Comparative Examples are shown below.

(1) Thermoplastic resin A
(A-1) Polymethyl methacrylate (trade name) Sumipex LG (manufactured by Sumitomo Chemical)
MFR (230°C 3.80 kgf (37.3 N)): 10.0 g/10 minutes

(2) Polymer B
(B-1) Polyvinylidene fluoride (trade name) Kureha KF Polymer #1300 (manufactured by Kureha)
MFR (230°C 2.16 kg (21.2 N): 0.2 g/10 minutes

(B-1) Polyvinylidene fluoride (trade name) Solef 460S (manufactured by Solvay Japan)
MFR (230°C 2.16 kg (21.2 N): 0.1 g/10 minutes

(3) Powder C
(C-1) SiO ₂ (silica) powder (trade name) Sunsphere H-51 (manufactured by AGC Si Tech)
Median diameter D50: 5.4 μm
Moisture content: 225350ppm

(C-2) SiO ₂ (silica) powder (trade name) AEROSIL RY200S (manufactured by AEROSIL)
Median diameter D50: 103.1 μm
Moisture content: 380ppm

(C-3) SiO ₂ (silica) powder (trade name) Sunsphere H-31 (manufactured by AGC Si Tech)
Median diameter D50: 3.0 μm
Moisture content: 493330ppm

(C-4) SiO ₂ (silica) powder (trade name) Sunsphere H-121 (manufactured by AGC Si Tech)
Median diameter D50: 12.0 μm
Moisture content: 468980ppm

The physical properties of each thermoplastic resin, each polymer, each component, and composition were measured according to the methods shown below.

(1) Melt mass flow rate (MFR, unit: g/10 minutes)
It was measured according to the method specified in JIS K7210-2014. The measurement temperature was 230° C., and the load was 2.16 kgf or 3.80 kgf.

(2) Median diameter D50 (unit: μm)
A median diameter D50 measured by a laser diffraction method was obtained by the following method. A sample dispersed in ethanol using a homogenizer was measured according to JIS R1629 using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd. "MT-3300EXII"), and the cumulative read from the obtained particle size cumulative distribution curve D50 was obtained from the particle size value of 50% by weight.

(3) Moisture content (unit: ppm)
First, powder C was dried for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80° C. and a degree of vacuum of 0.08 MPa. Next, the powder C was held for 24 hours in a constant temperature and humidity machine set to conditions of an environmental temperature of 50° C. and an environmental humidity of 95% RH. After that, the water content of the powder C was measured using a Karl Fischer moisture meter under the conditions of a heating temperature of 190° C. and a holding time of 10 minutes at the heating temperature to vaporize the moisture.

(4) Contact angle (unit: °)
The contact angle was measured by using DM-501 manufactured by Kyowa Interface Science Co., Ltd. and measuring the contact angle of pure water with respect to the horizontal stationary surface of the film by the θ/2 method. The droplet volume was 2 μL.

(5) SEM-EDS analysis SEM-EDS analysis was performed by coating the surface of the film with osmium with a thickness of 4 nm, and using the osmium-coated sample with JSM-7900F manufactured by JEOL Ltd. at an acceleration voltage of 3.5 kV. , and measured by EDS analysis of the sample surface at an observation magnification of ×1000. The observation area was 1.3 mm ² .
The obtained analysis image was binarized using the image analysis software Azo-kun manufactured by Asahi Engineering Co., Ltd., and the area ratio of the island portion was evaluated from the obtained binarized image. Also, from the binarized image, the shortest distance between the outer peripheries (edge portions) of adjacent island regions was determined, and the arithmetic mean value and degree of dispersion were determined.

(7) Sliding property in wet snow (mm/sec)
On the surface of the film that had been degreased in advance with ethanol to form ^a 150 mm square and left at an angle θ (see FIG. 3) with the horizontal plane at an angle of 19°, a sample of Chubu Corporation Co., Ltd. was applied at an environmental temperature of 15 ° C. Using a shaved ice machine HC-77B for making cube ice, 270 g of artificial snow was snowed from a height of 205 mm for 15 seconds, and the time required for the snow-capped artificial snow to fall between marked lines of 30 mm was measured. .
Snow sliding in wet snow is a snowfall phenomenon that occurs under the condition that wet snow is covered.

(8) Sliding performance in dry snow (°)
On the surface of the film that had been degreased in advance with ethanol to form a 150 mm ^square and left horizontally so that the angle θ (see FIG. 3) made with the horizontal plane was 0°, the film was placed at an environmental temperature of -5 ° C. 250 g of artificial snow that passes through a mesh size of 5.6 mm / 1.66 mm is produced using a shaved ice machine HC-77B manufactured by Co., Ltd., and the angle θ formed with the horizontal surface of the test piece is gradually changed from 0 to 90 °. and measured the angle θ at which the snow started to fall with a goniometer.
Snow sliding in dry snow is a snowfall phenomenon that occurs under the condition that dry snow covers. Excellent for
Note that "snow does not slide down" means "a state in which snow does not slide down even when the angle θ between the test piece and the horizontal plane is 90°".

(Example α1)
20 parts by mass of thermoplastic resin (A-1), 80 parts by mass of polymer (B-1), and 3 parts by mass of powder (C-1) are uniformly mixed, A shaft kneader (KZW15-45MG manufactured by Technobell Co., inner diameter: 15 mm, L/D = 45) was heated and melt-kneaded at a set temperature of 210°C and a screw rotation speed of 500 rpm to obtain a composition. After preheating the resin at a temperature of 210 ° C. for 5 minutes using a compression molding machine (P-37) of Shindo Metal Works, pressurize the composition under the conditions of a temperature of 210 ° C. and a pressure of 10 MPa for 5 minutes, a width of 150 mm, A film was obtained as a molded body having a length of 150 mm and a thickness of 2 mm. The snow-sliding properties of the obtained film on wet snow and on dry snow were evaluated.

(Example α2)
Instead of 80 parts by mass of polymer (B-1), 80 parts by mass of polymer (B-2), and 3 parts by mass of powder (C-1), 3 parts by mass of powder ( The procedure was the same as in Example α1, except that C-3) was used.

(Example α3)
Instead of 80 parts by mass of polymer (B-1), 80 parts by mass of polymer (B-2), and 3 parts by mass of powder (C-1), 3 parts by mass of powder ( The procedure was the same as in Example α1, except that C-4) was used.

(Comparative example α1)
The procedure was the same as in Example α1, except that 1 part by mass of powder (C-2) was used instead of 3 parts by mass of powder (C-1).

(Comparative example α2)
The procedure was the same as in Example α1, except that 3 parts by mass of powder (C-2) was used instead of 3 parts by mass of powder (C-1).

(Comparative example α3)
The procedure of Example α1 was repeated except that 5 parts by mass of powder (C-2) was used instead of 3 parts by mass of powder (C-1).

(Comparative example α4)
The procedure was the same as in Example α1, except that powder C was not added.

(Comparative example α5)
The procedure was the same as in Example α1 except that the polymer B was not added and 100 parts by mass of the thermoplastic resin (A-1) and 5 parts by mass of the powder (C-1) were used.

(Comparative example α6)
The procedure was the same as in Example α1, except that the thermoplastic resin A was not added, and 100 parts by mass of the polymer (B-1) and 5 parts by mass of the powder (C-1) were used.
Table 1 shows the conditions and results.

所定の組成の組成物により、湿雪及び乾雪の両方において滑雪性に優れる成形体が得られることが確認された。

It was confirmed that a composition having a predetermined composition yields a molded article having excellent snow-sliding properties on both wet snow and dry snow.

(Example β1)
20 parts by mass of the thermoplastic resin (A-1), 80 parts by mass of the polymer (B-1), and 3 parts by mass of the powder (C-1) are uniformly mixed and kneaded by a twin screw with an inner diameter of 15 mm. Machine (KZW15-45MG manufactured by Technobel Co., inner diameter: 15 mm, L/D = 45) was heated and melted and kneaded at a set temperature of 210°C and a screw rotation speed of 500 rpm to obtain a composition. After preheating the resin at a temperature of 210 ° C. for 5 minutes using a compression molding machine (P-37) of Shindo Metal Works, pressurize the composition under the conditions of a temperature of 210 ° C. and a pressure of 10 MPa for 5 minutes, a width of 150 mm, A molded body was obtained which was shaped into a film having a length of 150 mm and a thickness of 2 mm. The contact angle of the surface of the film was 81.0°, the area ratio of the hydrophilic island regions of the powder C was 2.3%, and the water content of the powder C (hydrophilic region) was 225350 ppm. Snow sliding in wet snow and dry snow on the surface of this compact was evaluated.

(Comparative example β1)
Example β1 was the same as Example β1, except that the amount of powder C added was increased to 30 parts by mass. The contact angle on the surface of the obtained molded product was 83.8°, and the area ratio of the hydrophilic region was 35%.

Table 2 shows the conditions and results.

It was confirmed that a film having a predetermined surface structure has excellent snow sliding properties on both wet snow and dry snow.

DESCRIPTION OF SYMBOLS 10... Membrane, I... Island area, S... Sea area, M... Resin, C... Powder.

Claims (5)

A composition containing a thermoplastic resin A, a polymer B, and a powder C,
The polymer B has a structural unit represented by formula (1) or formula (2),
The water content in the powder C treated under the following treatment conditions (a) satisfies 1000 mass ppm to 5000000 mass ppm when measured under the following measurement conditions (b),
With respect to a total of 100 parts by mass of the resin A and the polymer B, the content of the resin A is 1 to 99 parts by mass, and the content of the polymer B is 1 to 99 parts by mass. The composition, wherein the content of powder C is 0.01 to 25 parts by mass.

[In the formula, R ¹ to R ³ are each independently selected from a hydrogen atom, a halogen atom, an alkoxy group, or an alkyl group. At least one hydrogen atom in each alkyl group and each alkoxy group may be independently substituted with a halogen atom.
Processing conditions (a): After drying the powder C for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80°C and a degree of vacuum of 0.08 MPa, conditions of an environmental temperature of 50°C and an environmental humidity of 95% RH were set. The powder C is held for 24 hours in the thermo-hygrostat.
Measurement conditions (b): Measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes. The composition according to claim 1, wherein the median diameter D50 of said powder C measured by a laser diffraction method is 0.05 to 30 µm. The composition according to claim 1 or 2, wherein said powder C is silica powder or silicone powder. A film containing resin M and powder C,
The contact angle measured by dropping 2 μL of water droplets on the horizontal surface of the film is 50 to 90°,
The surface of the film has a sea region of the resin M and an island region of the powder C,
the ratio of the area of the island region to the total area of the sea region and the island region is 0.01 to 30%;
A film in which the water content in the powder C treated under the following treatment conditions (a) satisfies 1000 mass ppm to 5000000 mass ppm when measured under the following measurement conditions (b).
Processing conditions (a): After drying the powder C for 17 hours in a vacuum dryer set to conditions of an environmental temperature of 80°C and a degree of vacuum of 0.08 MPa, conditions of an environmental temperature of 50°C and an environmental humidity of 95% RH were set. The powder C is held for 24 hours in the thermo-hygrostat.
Measurement conditions (b): Measured using a Karl Fischer moisture meter under the moisture vaporization conditions of a heating temperature of 190° C. and a holding time of 10 minutes. An article having the film of claim 4 on at least a portion of its outer surface.

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