Compositions, coatings and laminates

Abstract

To provide a coating layer that can be made further thinner and has improved slipperiness and wear resistance, a composition suitable for a coating capable of forming the coating layer, and a laminate comprising the coating layer.SOLUTION: A composition comprises ultra-high-molecular-weight olefinic polymer particulates (A) satisfying the following requirements (i)-(iii) and a solvent dispersible resin (B): (i) an intrinsic viscosity [η] of 5-50 dl / g as measured in a 135°C decalin solvent; (ii) an average particle size d50 of 3-45 μm in a mass-based particle size distribution by the Coulter counter method; (iii) 50 mass% or more of the particulates passable through a mesh sieve with an opening of 45 μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compositions, coatings and laminates. [Background technology]

[0002] Conventionally, coating materials have been used for the purpose of protecting surfaces in a variety of applications, and coatings containing resin components such as urethane resins and acrylic resins are used in a wide range of applications, including various industrial machines, automobiles, building materials, and home appliances. In particular, coatings used on parts that come into contact with and slide on rubber, plastics, metals, cloth, paper, glass, etc. are required to have excellent sliding properties and abrasion resistance, and, depending on the application, a design-oriented texture (for example, a matte texture) is also required (see, for example, Patent Document 1).

[0003] From the perspective of improving sliding properties and wear resistance, Patent Document 2 discloses a technique of adding polytetrafluoroethylene (PTFE) and a scaly solid lubricant to a coating material. By using the method of Patent Document 2, the coefficient of friction of the coating film is certainly reduced, and improvements in scratch resistance and wear resistance are observed. However, because the interfacial adhesion between the coating film and polytetrafluoroethylene is weak, wear resistance is still unsatisfactory, and there is room for improvement.

[0004] With the aim of further improving wear resistance, Patent Document 3 discloses a lubricating coating containing ultra-high molecular weight polyethylene particles and a water-soluble urethane resin, and a paint for forming said coating. Also, Patent Document 4 discloses a paint composition containing ultra-high molecular weight polyethylene particles and a plate-like or scale-like compound with the aim of forming a dry lubricating coating that is non-adhesive and has excellent low friction properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-146681 [Patent Document 2] Japanese Patent Application Publication No. 9-111179 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-12480 [Patent Document 4] Japanese Patent Application Publication No. 2020-109170 Summary of the Invention [Problem to be solved by the invention]

[0006] In the coatings field, there is a demand for thinner coating films and improved slipperiness (sliding properties) and abrasion resistance. Furthermore, depending on the application or purpose, there may be a demand for coating films with greater durability, a smooth feel, or a matte texture.

[0007] An object of the present invention is to provide a coating film that can be further thinned and has excellent slip properties and abrasion resistance, a composition suitable for a paint capable of forming the coating film, and a laminate having the coating film. From another perspective, an object of the present invention is to provide a coating film that has durability, a smooth feel, and / or a matte texture, a composition suitable for a paint capable of forming the coating film, and a laminate having the coating film. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that by using a composition containing specific ultra-high molecular weight olefin polymer particles, it is possible to further reduce the thickness of a coating film and form a coating film having excellent slip properties and abrasion resistance. They have also found that it is possible to form a coating film having durability, a smooth feel, and / or a matte texture.

[0009] That is, the present invention includes the following aspects [1] to

[11] . [1] A composition containing ultra-high molecular weight olefin polymer fine particles (A) and a solvent-dispersible resin (B) that satisfy the following requirements (i) to (iii): (i) The intrinsic viscosity [η] measured in decalin solvent at 135°C is in the range of 5 to 50 dl / g; (ii) The average particle diameter d50 in the mass-based particle size distribution measured by the Coulter Counter method is in the range of 3 to 45 μm; (iii) 50% by mass or more passes through a 45 μm mesh sieve.

[0010] [2] The composition according to item [1], wherein the average particle diameter d50 of the ultra-high molecular weight olefin polymer fine particles (A) is in the range of 3 to 10 μm. [3] The composition according to item [1] or [2], wherein the ultra-high molecular weight olefin polymer fine particles (A) are ethylene polymer fine particles.

[0011] [4] The composition according to any one of items [1] to [3], wherein the solvent-dispersible resin (B) is at least one resin selected from the group consisting of urethane resin, acrylic resin, acrylic urethane resin, epoxy resin, polyester resin, phenolic resin, silicone resin, and polyamideimide resin.

[0012] [5] The composition according to any one of items [1] to [4], wherein the content of the ultra-high molecular weight olefin polymer fine particles (A) is in the range of 0.5 to 100 parts by mass per 100 parts by mass of the solvent-dispersible resin (B).

[0013] [6] The composition according to any one of items [1] to [5], further comprising a solvent. [7] The composition according to item [6], wherein the solvent is at least one selected from the group consisting of water, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, and alcohols. [8] The composition according to item [6] or [7], which is a paint.

[0014] [9] A coating film formed from the composition according to any one of items [1] to [8].

[10] The coating film according to item [9], wherein at least a portion of the ultra-high molecular weight olefin polymer fine particles (A) is present on the surface of the coating film.

[11] A laminate comprising a substrate and the coating film according to item [9] or

[10] . [Effects of the Invention]

[0015] The present invention provides a coating film that can be further thinned and has excellent slip properties and abrasion resistance, a composition suitable for a paint capable of forming the coating film, and a laminate having the coating film.It also provides a coating film that has durability, a smooth feel, and / or a matte texture, a composition suitable for a paint capable of forming the coating film, and a laminate having the coating film. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a graph plotting gloss values ​​versus particle content ratios of laminates produced in Examples and Comparative Examples. [Figure 2] 1 is a graph plotting the dynamic friction coefficient versus the particle content of the laminates produced in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described in detail below. [Composition] The composition of the present invention contains ultra-high molecular weight olefin polymer fine particles (A) that satisfy the requirements (i) to (iii) described below, and a solvent-dispersible resin (B). The composition of the present invention may further contain a solvent.

[0018] <Ultra-high molecular weight olefin polymer particles (A)> The ultra-high molecular weight olefin polymer fine particles (A) (hereinafter also referred to as "fine particles (A)") satisfy the following requirements (i) to (iii), and preferably further satisfy requirement (iv).

[0019] Requirement (i): The intrinsic viscosity [η] measured in decalin solvent at 135°C is in the range of 5 to 50 dl / g. The intrinsic viscosity [η] of the fine particles (A) is in the range of 5 to 50 dL / g, preferably 5 to 40 dL / g, more preferably 5 to 30 dL / g, even more preferably 5 to 20 dL / g, and particularly preferably 5 to 15 dL / g. When the intrinsic viscosity is in the above range, a coating film excellent in abrasion resistance, self-lubrication, and sliding properties can be formed, which is preferable.

[0020] Requirement (ii): The average particle diameter d50 in the mass-based particle size distribution according to the Coulter counter method is in the range of 3 to 45 μm. The average particle diameter d50 of the microparticles (A) is the value at which the integrated value of the particle shape distribution is 50 mass% when measured by the mass-based particle size distribution method using a Coulter counter, and the average particle diameter d50 is in the range of 3 to 45 μm, preferably 3 to 30 μm, more preferably 3 to 20 μm, even more preferably 3 to 10 μm, still more preferably 3 to 9 μm, and particularly preferably 3 to 8 μm.

[0021] When the average particle diameter d50 of the fine particles (A) is within the above range, a coating film with a matte texture can be obtained, and it is also preferable in that the surface can be easily made smooth even when the coating film is thin.

[0022] Requirement (iii): 50% by mass or more passes through a 45 μm mesh sieve. The fine particles (A) are those that pass through a 45 μm mesh sieve (JIS Z 8801 #325) using a vibrating sieve or an ultrasonic vibrating sieve, with 50% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 99% by mass or more.

[0023] Requirement (iv): 95% by mass or more passes through a 25 μm mesh sieve. The fine particles (A) are preferably those that pass through a 25 μm mesh sieve (JIS Z 8801 #500) using a vibrating sieve or ultrasonic vibrating sieve, with 95% by mass or more, more preferably 99% by mass or more, even more preferably 99.97% by mass or more, and particularly preferably 99.99% by mass or more passing through the sieve.

[0024] A passing amount of 50% by mass or more means that the amount of coarse particles present is small. When the amount of coarse particles is small, the ultra-high molecular weight olefin polymer (particles) efficiently contributes to improving slip properties and abrasion resistance, which is considered preferable. Furthermore, when the amount of coarse particles is small, the coating film surface where the particles are present tends to be less prone to unevenness. As a result, a composition containing particles in the above range is considered preferable because it is more likely to form a coating film with a smooth feel and / or a matte texture.

[0025] In the present invention, the ultra-high molecular weight olefin polymer refers to a homopolymer such as polyethylene, polypropylene, poly-1-butene, or poly-4-methyl-1-pentene, or a copolymer of ethylene with a small amount of other α-olefin, such as propylene, 1-butene, 1-hexene, 1-octene, or 4-methyl-1-pentene, but is preferably an ethylene polymer, and particularly preferably an ethylene homopolymer.

[0026] The melt flow rate (MFR) of the fine particles (A) is preferably less than 1.0 g / 10 min, more preferably 0.01 g / 10 min or more and less than 1.0 g / 10 min, and even more preferably 0.01 to 0.5 g / 10 min. The MFR is measured according to JIS K7210 at 190°C and a test load of 21.6 kg.

[0027] The content of the fine particles (A) in the composition of the present invention is preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 1.5 to 30 parts by mass, particularly preferably 2 to 25 parts by mass, and most preferably 3 to 20 parts by mass, relative to 100 parts by mass of the solvent-dispersible resin (B) described below.

[0028] Furthermore, the content of the fine particles (A) in the composition of the present invention is preferably in the range of 0.1 to 50 mass%, more preferably 0.5 to 40 mass%, even more preferably 1 to 30 mass%, still more preferably 1.5 to 25 mass%, particularly preferably 2 to 20 mass%, and most preferably 3.5 to 20 mass%, when the total of the fine particles (A) and the solvent-dispersible resin (B) is 100 mass%.

[0029] When the content of the fine particles (A) is within the above-mentioned range, it is preferable in that it is easy to obtain effects such as slipperiness, abrasion resistance, smooth touch, and / or matte texture, and it is also possible to maintain high applicability of the coating material.

[0030] The method for producing the fine particles (A) is not particularly limited as long as the fine particles (A) satisfy the above requirements (i) to (iii), and they can be produced, for example, by the methods disclosed in the following documents: (1) WO 2006 / 054696, (2) WO 2008 / 013144, (3) WO 2009 / 011231, (4) WO 2010 / 074073, and (5) JP 2012-131959 A.

[0031] <Solvent-dispersible resin (B)> The solvent-dispersible resin (B) (hereinafter simply referred to as "resin (B)") used in the present invention is not particularly limited, and resins known for use in paints can be used. Examples include urethane resins, acrylic resins, acrylic urethane resins, epoxy resins, polyester resins, phenolic resins, silicone resins, and polyamide-imide resins. Among these, urethane resins, acrylic resins, and acrylic urethane resins are more preferred because of their good slip properties and abrasion resistance and high adhesion to various substrates. Resin (B) may be used alone or in combination of two or more.

[0032] In this specification, the term "solvent dispersible" means that at least a part of the resin (B) is dispersible in a solvent, and includes "water dispersion."

[0033] The urethane resin may have a carboxyl group, a sulfonyl group, and an ethylene oxide group in the molecule. Examples of components used to introduce these atomic groups include 2,2-dimethylol lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, polyethylene glycol, a polyaddition product of ethylene oxide and propylene oxide, and a polymer of ethylene glycol and an active hydrogen compound.

[0034] Examples of methods for producing urethane resins include the following: For example, a polyfunctional isocyanate compound or a compound having an active hydrogen group capable of reacting with an isocyanate group is reacted in an equivalent ratio such that the isocyanate group is in excess, or in an equivalent ratio such that the active hydrogen group is in excess, in the presence or absence of a suitable organic solvent, to produce a resin having a urethane bond in the molecule.

[0035] The acrylic resin can be obtained by polymerizing a mixture of unsaturated monomers selected from hydroxyl group-containing unsaturated monomers, acid group-containing unsaturated monomers, and other unsaturated monomers. Examples of hydroxyl group-containing unsaturated monomers include hydroxyethyl (meth)acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, PLACCEL FM1 (ε-caprolactone-modified hydroxyethyl methacrylate, manufactured by Daicel Chemical Industries, Ltd.), polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. Examples of acid group-containing unsaturated monomers include carboxylic acids such as (meth)acrylic acid, itaconic acid, crotonic acid, and maleic acid. Other unsaturated monomers include, for example, ester group-containing acrylic monomers such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, and lauryl (meth)acrylic acid; vinyl alcohol ester monomers of vinyl alcohol and carboxylic acids such as acetic acid and propionic acid; unsaturated hydrocarbon monomers such as styrene, α-methylstyrene, vinylnaphthalene, butadiene, and isoprene; nitrile monomers such as (meth)acrylonitrile; and (meth)acrylamide monomers such as (meth)acrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, and diacetoneacrylamide.

[0036] The content of resin (B) in the composition of the present invention is preferably 50 to 99.9 mass%, more preferably 60 to 99.5 mass%, even more preferably 70 to 99 mass%, still more preferably 75 to 98.5 mass%, particularly preferably 80 to 98 mass%, and most preferably 80 to 96.5 mass%, when the total of the fine particles (A) and resin (B) is taken as 100 mass%. A content of resin (B) within the above range is preferred in that high coatability can be maintained when the composition of the present invention is used as a coating material.

[0037] <Solvent> The solvent that may be used in the present invention is not particularly limited as long as it can disperse at least a part of the resin (B), but examples thereof include water, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, and alcohols, and may be used alone or in combination of two or more. Among these, water and alcohols are preferred, and water is particularly preferred from the viewpoint of recent global environmental protection and occupational safety and health, such as the impact on the human body from inhaling solvents.

[0038] The content of resin (B) dispersed in the solvent is not particularly limited as long as it does not impair the effects of the present invention, but is preferably in the range of 5 to 70 mass%, more preferably 10 to 60 mass%, and even more preferably 15 to 50 mass%, when the total amount of resin (B) and solvent is taken as 100 mass%. If the content of resin (B) dispersed in the solvent is within the above range, it is preferable because resin (B) can be applied more efficiently when the composition of the present invention is used as a coating material.

[0039] <Other ingredients> The composition of the present invention may contain other components, such as known paint additives, to the extent that the effects of the present invention are not impaired. Specific examples are described below.

[0040] The composition of the present invention may contain an acid-modified polyolefin compound and / or a fatty acid compound to stabilize the solvent dispersion of the above-mentioned fine particles (A) etc., and may further contain an ionomer resin and / or a low-molecular-weight olefin polymer, if necessary, to impart blocking resistance to the coating.

[0041] The composition of the present invention may further contain, as necessary, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an antifoaming agent, a filler, a leveling agent, and the like.

[0042] <Method for preparing the composition> The method for preparing the composition of the present invention is not particularly limited as long as the above-mentioned components can be mixed, and the composition can be prepared by a known method, for example, by adding the above-mentioned fine particles (A) to an aqueous urethane resin or acrylic dispersion prepared by a known method.

[0043] Another method is to add the fine particles (A) to a polyurethane dispersion obtained by dispersing in water a polyurethane resin obtained by reacting an isocyanate-terminated prepolymer obtained by reacting at least a diisocyanate, a diol, and an active hydrogen group-containing compound containing a hydrophilic group with a chain extender containing a polyamine.

[0044] [paint] The composition of the present invention can be used as a coating material, and the coating film formed from the coating material can be used in a wide range of applications, including various industrial machines, automobiles, building materials, home appliances, and office automation equipment.

[0045] It is preferred that at least a portion of the fine particles (A) be present on the surface of a coating film formed from the composition of the present invention, which will provide excellent sliding properties and abrasion resistance as well as a matte texture when the coating film is formed on a portion that comes into contact with and slides against, for example, rubber, plastic, metal, cloth, paper, glass, etc.

[0046] [Laminate] The laminate of the present invention includes a substrate and a coating film formed using the composition of the present invention. Here, the laminate of the present invention may consist of the substrate and the coating film, or may further include a third layer in addition to the substrate and the coating film.

[0047] The substrate is not particularly limited, but examples thereof include ethylene propylene diene copolymer (EPDM) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, polyvinyl chloride (PVC) resin, polycarbonate (PC) resin, and metal.

[0048] EPDM resins are used in a wide range of applications, including interior and exterior materials for automobiles, building materials, office equipment materials, and everyday life.

[0049] ABS resin is suitable for automotive materials and is widely used as a building material, home appliance material, office equipment material, and automotive material. Here, the ABS resin may be in the form of a polymer alloy combined with PC and other components.

[0050] PVC resin is suitable for construction materials such as gutters and interior window sashes, and is widely used as an interior material for automobiles and as a construction material. PC resin is suitable for roofing and is widely used as a building material.

[0051] <Laminate structure and uses> In an exemplary embodiment of the present invention, the laminate of the present invention further comprises a primer layer between the substrate and the coating film as the third layer to further improve adhesion between the substrate and the coating film. This primer layer is a layer made of a primer, and examples of such primers include components commonly used as primers in the field to which the present invention pertains, such as acid-modified polyolefins. This acid-modified polyolefin may be a commercially available product, such as Unistol P-501 (trade name) manufactured by Mitsui Chemicals.

[0052] The laminate of the present invention can be obtained by forming the coating film on the surface of the substrate, for example, by a production method including a step (S-1) of applying the composition of the present invention to the surface of the substrate, and a step (S-2) of drying the composition after the step (S-1).

[0053] Here, the application in the step (S-1) can be carried out by a method generally used in the field to which the present invention belongs, and known means such as application using a brush or paintbrush, spraying, screen printing, flow coating, spin coating, dipping, or a bar coater, T-die, bar-equipped T-die, doctor knife, roll coating, die coating, etc. In this step (S-1), the fine particles (A) do not need to completely maintain the shape they had before application, but they exist as particles.

[0054] The step (S-1) may be carried out, for example, in a manner including a step (S-1a) of forming a primer layer on the surface of the substrate and a step (S-1b) of applying the composition of the present invention to the surface of the primer layer.

[0055] Meanwhile, in step (S-2), the composition is dried to remove the solvent that constituted the composition. As a result, the components of the composition other than the solvent, such as the fine particles (A), are fixed on the substrate, forming the coating film. The specific conditions for drying the composition may be appropriately set depending on the components that constitute the composition, such as the fine particles (A), and the resin that constitutes the substrate. For example, the composition is dried at a temperature of 23 to 200°C, preferably 23 to 110°C, for 10 to 180 minutes, preferably 30 to 120 minutes.

[0056] The laminate of the present invention as described above can be suitably used in applications requiring high abrasion resistance, excellent sliding properties (slipperiness), and a matte appearance, such as automobile and other vehicle parts, home appliances and office equipment, daily necessities, and building materials.

[0057] For example, suitable applications of the laminate using ABS resin as the substrate include vehicle parts such as automobile parts, home appliances and office automation equipment. Suitable applications of the laminate using PVC resin as the substrate include everyday items such as clothing accessories; wallpaper, sheets for flooring and other building materials; and water pipes.

[0058] Suitable applications of the laminate using PC resin as the substrate include building materials such as resin windows and roofing materials, and glass substitutes such as optical members such as lenses and covers.

[0059] Suitable applications for laminates using EPDM resin as the substrate include automobile part materials such as weather strips, glass run channels, vibration-proof and vibration-damping rubber, as well as office equipment materials such as rubber rolls. [Example]

[0060] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples in any way. The methods for measuring various physical properties are as follows.

[0061] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of the microparticles was measured at 135°C by dissolving the microparticles in decalin. <Average particle diameter d50> The average particle diameter d50 was calculated from the mass-based particle size distribution by the Coulter counter method using a precision particle size distribution measuring device (Multisizer Three, manufactured by Beckman).

[0062] <Percentage of particles that pass through a 45 μm mesh sieve> The proportion of particles passing through a 45 μm mesh sieve was determined by measuring the mass of particles passing through a 45 μm mesh sieve (JIS Z 8801 #325).

[0063] <Percentage of particles that pass through a 25 μm mesh sieve> The proportion of particles passing through a 25 μm mesh sieve was determined by measuring the mass of particles passing through a 25 μm mesh sieve (JIS Z 8801 #500).

[0064] [Ultra-high molecular weight polyethylene particles (A-1)] <Synthesis Example 1> (Preparation of magnesium-containing microparticles (a)) A xylene slurry of magnesium-containing microparticles (a) was prepared according to the method described in Synthesis Example 1 of WO 2006 / 054696, adjusting the operating conditions by using xylene instead of toluene. The magnesium concentration of the prepared magnesium-containing microparticle (a) slurry was 0.23 mmol / mL and the aluminum concentration was 0.026 mmol / mL.

[0065] <Synthesis Example 2> (Synthesis of solid catalyst component (b)) A 200 mL glass reactor purged with nitrogen was charged with 69.4 mL of xylene and, under stirring, charged with 30.6 mL of the xylene slurry of the magnesium-containing microparticles (a) prepared in Synthesis Example 1 above (7.05 mmol in terms of magnesium atoms). Next, 33.6 mg of the transition metal compound (c) of the following formula (1) (0.0391 mmol in terms of zirconium atoms) was charged and reacted at room temperature for 1 hour. The reaction mixture was then filtered, washed three times with 500 mL of xylene and twice with 500 mL of decane, filtered, and then 120 mL of decane was added to prepare a decane slurry of the solid catalyst component (b). A portion of the resulting slurry of the solid catalyst component (b) was sampled and its concentration was measured; the zirconium concentration was 0.000307 mmol / mL and the magnesium concentration was 0.0576 mmol / mL. [ka]

[0066] <Synthesis Example 3> (Synthesis of ultra-high molecular weight polyethylene particles) A 1 L stainless steel autoclave was charged with 500 mL of heptane and thoroughly purged with nitrogen. Ethylene was passed through the autoclave at room temperature at 0.4 NL / min for 15 minutes to saturate the liquid and gas phases. The autoclave was then heated to 65°C, and 1.25 mL of a decane solution of triethylaluminum (1.0 mmol / mL in terms of aluminum atoms) and 13.4 mL of solid catalyst component (b) (0.16 mmol in terms of magnesium atoms) were added while ethylene was still flowing through at 0.4 NL / min. The mixture was stirred for 5 minutes while maintaining the temperature. Then, 6 mL of a toluene solution (15 mg / mL) of Emulgen 108 (Kao Corporation) was added. The ethylene flow was stopped, 1 mL of hydrogen was added, and the autoclave was then heated to 70°C. Ethylene was then added at a rate of 0.1 NL / min until the pressure reached 0.35 MPaG. After reaching 0.35 MPaG, polymerization was continued while maintaining the temperature and pressure until the ethylene feed rate reached 56 NL. The autoclave was then cooled, and the ethylene was depressurized. The resulting slurry containing white solids was filtered, washed with heptane, and dried under reduced pressure at 80°C for 10 hours, yielding 69.5 g of ultra-high molecular weight polyethylene microparticles (A-1).

[0067] The physical properties of the obtained ultra-high molecular weight polyethylene fine particles (A-1) (hereinafter also referred to as "fine particles (A-1)") were as follows. ·Intrinsic viscosity [η]=10.8dl / g MFR (190°C, 21.6 kg load) = 0.030 g / 10 min ·Average particle diameter d50=6.2μm 45μm mesh sieve passing rate = 100% by mass 25μm mesh sieve passing rate = 100% by mass

[0068] [Ultra-high molecular weight polyethylene particles (A-2)] "Mipelon (registered trademark) PM-200" (hereinafter also referred to as "fine particles (A-2)") manufactured by Mitsui Chemicals, Inc. was used. The physical properties were as follows. ·Intrinsic viscosity [η]=13.0dl / g MFR (190°C, 21.6 kg load) = 0.020 g / 10 min ·Average particle diameter d50=12.0μm 45μm mesh sieve passing rate = 100% by mass 25μm mesh sieve penetration rate = 99.95% by mass

[0069] [PTFE particles (C-1)] "Dyneon (registered trademark) TF-9205" (average particle diameter d50 = 9.0 μm) manufactured by 3M Japan Ltd. was used.

[0070] [PTFE particles (C-2)] "Lublon (registered trademark) L5" (average particle size d50 = 6.0 μm) manufactured by Daikin Industries, Ltd. was used.

[0071] [Water dispersible resin (B-1)] A polyurethane water dispersion ("Takelac W-6010" manufactured by Mitsui Chemicals; solid content concentration: 30% by mass) was used.

[0072] [Example 1] <Preparation of aqueous coating composition> 0.19 g of the microparticles (A-1) obtained in Synthesis Example 3, 50 g of water-dispersible resin (B-1) (Mitsui Chemicals "Takelac W-6010"; solids concentration 30% by mass), and 3% by mass of surfactant (Evonik "Dynol 604") based on 100% by mass of the microparticles (A-1) were added, and the mixture was stirred at room temperature for 5 minutes using a rotation-revolution type stirring / defoaming mixer (Thinky "ARE-310") to obtain aqueous coating composition (X-1). The content of the microparticles (A-1) was 1.25% by mass when the total solids were taken as 100% by mass.

[0073] <Preparation of laminate> The aqueous coating composition (X-1) obtained above was applied to an EPDM substrate (thickness: 3 mm) that had been previously coated with a primer (MonotaRO's Adhesion Primer Multi-Aerosol Type), and dried for 30 minutes in an atmosphere at 70°C to obtain a laminate with a coating film of 7 μm thickness formed on the substrate.

[0074] [Examples 2 to 5] The aqueous coating composition was prepared and the laminate was fabricated in the same manner as in Example 1, except that the blending ratio of the microparticles (A-1) in the aqueous coating composition (X-1) to the total solid content was changed to the blending ratio shown in Table 1.

[0075] [Example 6] An aqueous coating composition (X-2) was prepared in the same manner as in Example 1, except that the fine particles (A-2) were used instead of the fine particles (A-1).

[0076] <Preparation of laminate> A laminate was produced in the same manner as in Example 1, except that the aqueous coating composition (X-2) was used instead of the aqueous coating composition (X-1).

[0077] [Examples 7 to 10] The aqueous coating composition was prepared and the laminate was fabricated in the same manner as in Example 6, except that the blending ratio of the microparticles (A-2) in the aqueous coating composition (X-2) to the total solid content was changed to the blending ratio shown in Table 1.

[0078] [Comparative Example 1] An aqueous coating composition (X-3) was prepared in the same manner as in Example 1, except that PTFE particles (C-1) were used instead of the fine particles (A-1).

[0079] <Preparation of laminate> A laminate was produced in the same manner as in Example 1, except that the aqueous coating composition (X-3) was used instead of the aqueous coating composition (X-1).

[0080] [Comparative Examples 2 to 5] The aqueous coating composition was prepared and the laminate was fabricated in the same manner as in Comparative Example 1, except that the blending ratio of the PTFE particles (C-1) in the aqueous coating composition (X-3) to the total solids content was changed to the blending ratio shown in Table 2.

[0081] Comparative Example 6 An aqueous coating composition (X-4) was prepared in the same manner as in Comparative Example 1, except that the PTFE particles (C-2) were used instead of the PTFE particles (C-1).

[0082] <Preparation of laminate> A laminate was produced in the same manner as in Comparative Example 1, except that the aqueous coating composition (X-4) was used instead of the aqueous coating composition (X-3).

[0083] [Comparative Examples 7 to 10] The aqueous coating composition was prepared and the laminate was fabricated in the same manner as in Comparative Example 6, except that the blending ratio of the PTFE particles (C-2) in the aqueous coating composition (X-4) to the total solid content was changed to the blending ratio shown in Table 2.

[0084] [Comparative Example 11] A laminate was prepared in the same manner as in Example 1, except that only the water-dispersible resin (B-1) ("Takelac W-6010" manufactured by Mitsui Chemicals; solid content concentration 30% by mass) was applied to a primer-coated EPDM substrate.

[0085] [Laminate evaluation] The obtained laminate was evaluated by the following methods. The evaluation results are shown in Tables 1 and 2. The evaluation results of gloss value and dynamic friction coefficient are also shown in the graphs of Figures 1 and 2, respectively.

[0086] <Gross value> The gloss value of the laminate was measured by applying a gloss meter (Horiba, Ltd. Gloss Checker IG-320, incident angle 60°, receiving angle 60°) to the surface of the laminate. The lower the gloss value obtained, the better the matte effect (matte texture).

[0087] <Dynamic friction coefficient> Using a Gakushin abrasion tester (manufactured by Shinto Scientific Co., Ltd.), the surface of the laminate (5 mm wide, 3 mm thick) was brought into contact with a glass plate (30 mm x 30 mm x 6 mm thick) and the dynamic friction coefficient was measured from 1 to 5,000 reciprocations, and the average value was calculated. The test conditions were load: 200 g, speed: 150 mm / sec, stroke: 80 mm, and measurement environment temperature: 23°C. The lower the dynamic friction coefficient value obtained, the better the slipperiness and abrasion resistance.

[0088] <Durability test> Using a Gakushin abrasion tester (manufactured by Shinto Scientific Co., Ltd.), the surface of the laminate (5 mm wide, 3 mm thick) was brought into contact with a glass plate (30 mm x 30 mm x 6 mm thick) and measurements were taken from 1 to 20,000 reciprocations, with slippage confirmed every 5,000 reciprocations. An "x" in the "slip failure" column indicates that the glass plate bounced off the laminate surface. When poor slippage made it difficult to perform the Gakushin abrasion test, the measurement was deemed impossible. The test conditions were a load of 200 g, a speed of 150 mm / sec, a stroke of 80 mm, and a measurement environment temperature of 23°C. In Tables 1 and 2, "-" indicates that the evaluation was not performed.

[0089] <Root mean square height of surface Sq> The root mean square height Sq of the surface of the resulting laminate was measured using a laser microscope (Olympus Corporation, LEXT OLS4000) under the following measurement conditions: objective lens: 20x, film measurement area: 1.22 mm x 1.22 mm.

[0090] [Table 1]

[0091] [Table 2]

[0092] As is clear from the above results, when the particle content is the same, Examples using fine particles (A) and Comparative Examples using PTFE particles are superior in slip properties, abrasion resistance, and matting effect. Furthermore, Examples 1 to 5 using fine particles (A-1) have higher effects (especially matting effect) than Examples 6 to 10 using fine particles (A-2).

Claims

1. A composition containing ultra-high molecular weight olefin polymer fine particles (A) and a solvent-dispersible resin (B) that satisfy the following requirements (i) to (iii): (i) The intrinsic viscosity [η] measured in decalin solvent at 135°C is in the range of 5 to 50 dl / g; (ii) The average particle diameter d50 in the mass-based particle size distribution determined by the Coulter Counter method is in the range of 3 to 9 μm; (iii) 50% by mass or more passes through a 45 μm mesh sieve.

2. The composition according to claim 1, wherein the ultra-high molecular weight olefin polymer fine particles (A) further satisfy the following requirement (iv): (iv) 99.97% by mass or more passes through a 25 μm mesh sieve.

3. The composition according to claim 1 or 2, wherein the ultra-high molecular weight olefin polymer fine particles (A) are ethylene polymer fine particles.

4. The composition according to any one of claims 1 to 3, wherein the solvent-dispersible resin (B) is at least one resin selected from the group consisting of a urethane resin, an acrylic resin, an acrylic urethane resin, an epoxy resin, a polyester resin, a phenolic resin, a silicone resin, and a polyamide-imide resin.

5. The composition according to any one of claims 1 to 4, wherein the content of the ultra-high molecular weight olefin polymer fine particles (A) is in the range of 0.5 to 100 parts by mass per 100 parts by mass of the solvent-dispersible resin (B).

6. The composition according to any one of claims 1 to 5, further comprising a solvent.

7. 7. The composition according to claim 6, wherein the solvent is at least one selected from the group consisting of water, aliphatic hydrocarbons, aromatic hydrocarbons, ketones, esters, and alcohols.

8. The composition according to claim 6 or 7, which is a paint.

9. A coating film formed from the composition according to any one of claims 1 to 8.

10. The coating film according to claim 9, wherein at least a portion of the ultra-high molecular weight olefin polymer fine particles (A) is present on the surface of the coating film.

11. A laminate comprising a substrate and the coating film according to claim 9 or 10.

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