Clay-like composition containing ethylene-α-olefin-nonconjugated polyene copolymer

Abstract

To develop a clay-like composition that can be shaped into a desired article shape by hand or the like at room temperature or lower (40°C or lower).SOLUTION: There is provided a clay-like composition (Y) which comprises: an ethylene / α-olefin / non-conjugated polyene copolymer (S) satisfying the following requirement (i) and having a constituent unit derived from ethylene (A); an α-olefin (B) having 3 to 20 carbon atoms; and a non-conjugated polyene (C) containing two or more partial structure selected in total from the group consisting of the following general formulae (I) and (II) in the molecule; and a filler (X) in a range of 40 to 60 mass% with respect to 100 mass% of the total amount of the copolymer (S) and the filler (X), and satisfies the following requirements (y-1) to (y-3). (i) Weight average molecular weight (Mw) is in the range of 1,000 to 160,000. (y-1) Mooney viscosity ML (1+4) at 100°C is 5 or less. (y-2) Specific gravity is in the range of 1.2 to 0.8. (y-3) Deformable at 23°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a clay-like composition containing an ethylene·α-olefin·non-conjugated polyene copolymer.

Background Art

[0002] Instead of the conventional linear economy of mass production, mass consumption, and mass disposal, the conversion to a circular economy that preserves and maintains the value of products and resources for as long as possible and minimizes waste generation is becoming an important theme of ESG. In addition, as the pursuit of a lifestyle that suits an individual's values progresses, an image of the future is predicted in which the integration of product and service creation is required to realize diverse ways of living.

[0003] For example, as a clay composition having sufficient processability that enables easy processing by hand and suppressed stickiness, a clay composition containing an ethylene·α-olefin copolymer, a polymer wax containing a monomer unit derived from propylene, and a poly·α-olefin has been proposed (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In order to contribute to the above-described future image with materials, the inventors aim to develop a clay-like composition that can be shaped into a desired article shape by hand at room temperature or below (40°C or below).

Means for Solving the Problems

[0006] As a result of diligent research, the inventors have been able to develop a clay-like composition that can be molded into the desired shape of an article by hand or other means at room temperature or below (below 40°C).

[0007] In other words, the present invention provides an ethylene-α-olefin-non-conjugated polyene copolymer (S) that satisfies the following requirement (i), having constituent units derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following general formulas (I) and (II) in the molecule, The present invention relates to a clay-like composition (Y) characterized by containing a filler (X) in an amount of 40 to 60% by mass relative to the total amount of the copolymer (S) and filler (X) (100% by mass), and satisfying the following requirements (y-1) to (y-3). (i) The weight-average molecular weight (Mw) is in the range of 1,000 to 160,000. (y-1) The Mooney viscosity ML(1+4) at 100°C is 5 or less. (y-2) The specific gravity is in the range of 1.2 to 0.8. (y-3) Deformable at 23℃

[0008] [ka] [Effects of the Invention]

[0009] The clay-like composition of the present invention can be molded into the desired shape of an article by hand or other means at room temperature or below (below 40°C), making it suitable as a raw material for clay crafting. Furthermore, it can be molded into any shape without necessarily using specific molds or nozzles. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below. <Ethylene-α-olefin-nonconjugated polyene copolymer (S)> The ethylene-α-olefin-non-conjugated polyene copolymer (S) (hereinafter also simply referred to as "polymer (S)"), which is one of the components contained in the clay-like composition of the present invention, is a copolymer having constituent units derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following general formulas (I) and (II) in its molecule, and having the following requirement (i).

[0011] [ka]

[0012] <Requirement (i)> Requirement (i) specifies that the weight-average molecular weight (Mw) of the copolymer (S) according to the present invention is in the range of 1,000 to 160,000, more preferably in the range of 36,000 to 110,000, and particularly preferably in the range of 43,000 to 100,000.

[0013] The copolymer (S) satisfies requirement (i), making it easy to bring the Mooney viscosity of the clay-like composition containing the copolymer (S) to a range that satisfies requirement (y-1) below, and thus the processability of the clay-like composition is good, which is preferable.

[0014] <α-olefin (B)> Examples of α-olefins (B) having 3 to 20 carbon atoms that constitute the copolymer (S) according to the present invention include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Of these, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene, are preferred, and propylene is particularly preferred. These α-olefins may be used individually or in combination of two or more.

[0015] In other words, the copolymer (S) contains at least one structural unit derived from an α-olefin (B) having 3 to 20 carbon atoms, and may contain two or more structural units derived from α-olefins (B) having 3 to 20 carbon atoms.

[0016] <Non-conjugated polyenes (C)> Examples of non-conjugated polyenes (C) that contain a total of two or more substructures selected from the group consisting of the above general formulas (I) and (II) in the molecule that constitute the copolymer (S) according to the present invention include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, and dicyclopentadiene. Among these, it is preferable that the non-conjugated polyene (C) contains VNB, and more preferably that the non-conjugated polyene (C) is VNB, because it exhibits good reactivity with organic peroxides when the clay-like composition containing the copolymer is used by crosslinking, and the heat resistance of the clay-like composition is easily improved. The non-conjugated polyene (C) may be used alone or in combination of two or more types.

[0017] The copolymer (S) according to the present invention may further contain, in addition to constituent units derived from ethylene (A), α-olefins having 3 to 20 carbon atoms (B), and the non-conjugated polyene (C), constituent units derived from a non-conjugated polyene (D) that contains only one substructure selected from the group consisting of general formulas (I) and (II) in its molecule. The non-conjugated polyene (D) may be used alone or in combination of two or more types.

[0018] Examples of such non-conjugated polyenes (D) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, and 5-(2-ethyl-3-butenyl) Examples include (nyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene. Of these, ENB is preferred.

[0019] If the copolymer (S) contains a constituent unit derived from a non-conjugated polyene (D) that contains only one substructure selected from the group consisting of general formulas (I) and (II) in its molecule, the proportion is not particularly limited as long as it does not impair the objectives of the present invention, but is usually contained in a mass fraction of about 0 to 20% by mass, preferably 0 to 8% by mass, and more preferably 0.01 to 8% by mass (provided that the sum of the mass fractions of (A), (B), (C), and (D) is 100% by mass).

[0020] The copolymer (S) according to the present invention is not particularly limited as long as the clay-like composition containing the copolymer (S) satisfies the requirements (y-1) to (y-3) described later, however, it is preferable that, in addition to requirement (i) above, the following requirements (ii) and (iii) are also satisfied.

[0021] <Requirement (ii)> Requirement (ii) specifies that the molar ratio of ethylene / α-olefin in the copolymer (S) according to the present invention satisfies 40 / 60 to 90 / 10, preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, and even more preferably 55 / 45 to 78 / 22. Using such a copolymer (S) as a component of the clay-like composition of the present invention is preferable because the resulting clay-like composition can be molded at room temperature.

[0022] Furthermore, the amount of ethylene (content of constituent units derived from ethylene (A)) and the amount of α-olefin (content of constituent units derived from α-olefin (B)) in the copolymer (S) are as follows: 13 This can be determined by 13C-NMR.

[0023] <Requirement (iii)> Requirement (iii) specifies that the molecular weight distribution (Mw / Mn) of the copolymer (S), as measured by gel permeation chromatography (GPC), is in the range of 4 to 80. This molecular weight distribution (Mw / Mn) is preferably in the range of 4 to 70, more preferably 5 to 70. When the copolymer (S) according to the present invention satisfies requirement (iii), it contains an appropriate amount of low molecular weight components, resulting in good processability of the clay-like composition containing the copolymer (S).

[0024] The weight-average molecular weight (Mw) and number-average molecular weight of the copolymer (S) can be determined as polystyrene-converted values ​​measured by gel permeation chromatography (GPC). The copolymer (S) according to the present invention preferably further satisfies the following requirements (iv) to (vi).

[0025] <Requirement (iv)> Requirement (iv) specifies that in the copolymer (S) according to the present invention, the mass fraction of constituent units derived from non-conjugated polyene (C) is in the range of 0.07 mass% to 10 mass% of 100 mass% of the copolymer (S) (i.e., out of 100 mass% of the total mass fraction of all constituent units). The mass fraction of constituent units derived from non-conjugated polyene (C) is preferably 0.1 mass% to 8.0 mass%, more preferably 0.5 mass% to 5.0 mass%.

[0026] The copolymer (S) according to the present invention is preferable because, if it satisfies requirement (iv), the clay-like composition containing the copolymer (S) has sufficient hardness and excellent mechanical properties. Furthermore, when the clay-like composition is crosslinked with an organic peroxide, it exhibits a fast crosslinking velocity, which is also preferable. Furthermore, the amount of non-conjugated polyene (C) in the copolymer (S) (the content of constituent units derived from non-conjugated polyene (C)) is, 13 This can be determined by 13C-NMR.

[0027] <Requirement(v)> Requirement (v) specifies that in the copolymer (S) according to the present invention, the weight-average molecular weight (Mw) of the copolymer (S), the mass fraction of constituent units derived from the non-conjugated polyene (C) in the copolymer (S) (mass fraction of (C): mass%), and the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) satisfy the following relation (1). 4.5 ≤ Mw × (C) mass fraction / 100 / (C) molecular weight ≤ 40 … Equation (1)

[0028] When the copolymer (S) according to the present invention satisfies requirement (v), the molded article obtained by crosslinking a clay-like composition containing the copolymer (S) with an organic peroxide exhibits excellent mechanical properties, which is therefore preferable.

[0029] <Requirements (vi)> Requirement (vi) is the complex viscosity η of the copolymer (S) according to the present invention, obtained by linear viscoelasticity measurement (190°C) using a rheometer, at a frequency ω = 0.1 rad / s. * (ω =0.1)(Pa·sec) and the complex viscosity η at a frequency ω = 100 rad / s * (ω =100 )(Pa·sec), and the ratio P(η * (ω =0.1 ) / η * (ω =100 )) and the intrinsic viscosity [η], and the mass fraction of the structural unit derived from the non-conjugated polyene (C) ((mass fraction of (C): mass %) satisfy the following formula (2). P / ([η] 2.9 ) ≤ mass fraction of (C) × 6 … Formula (2)

[0030] Here, the complex viscosity η * (ω =0.1 ) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω =100 ) at a frequency ω = 100 rad / s, and the ratio P(η * (ω =0.1 ) / η * (ω =100 )) represent the frequency dependence of viscosity, and P / ([η] 2.9 ), which corresponds to the left side of formula (2), tends to show a high value when there are many long-chain branches, although it is affected by short-chain branches and molecular weight. Generally, in an ethylene·α-olefin·non-conjugated polyene copolymer, the more the structural unit derived from the non-conjugated polyene is contained, the more the long-chain branches tend to be contained. However, the copolymer (S) is considered to be able to satisfy the above formula (2) because it has fewer long-chain branches than a conventionally known ethylene·α-olefin·non-conjugated polyene copolymer. In the present invention, the P value was obtained from the complex viscosity at 0.1 rad / s and the complex viscosity at 100 rad / s, measured using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under the conditions of 190 °C, a strain of 1.0%, and varying frequencies, by obtaining the ratio (η * ratio). The copolymer (S) preferably satisfies the following formula (2'). P / ([η] 2.9 ) ≤ mass fraction of (C) × 5.7 … Formula (2') The intrinsic viscosity [η] refers to the value measured in decalin at 135°C.

[0031] <Requirement (vii)> Requirement (vii) specifies that the chart obtained by GPC measurement of the copolymer (S) according to the present invention shows two or more peaks, and the area of ​​the peak appearing on the side with the smallest molecular weight is preferably 20% or less of the total peak area. More preferably, the area of ​​the peak appearing on the side with the smallest molecular weight is 2 to 18%, and even more preferably 3 to 16%, of the total peak area.

[0032] If the copolymer (S) satisfies requirement (vii), the molecular weight distribution of the copolymer will exhibit a bimodal or other multimodal nature, containing high molecular weight components and low molecular weight components in appropriate proportions, resulting in good processability of the clay-like composition containing the copolymer (S).

[0033] <Requirement (viii)> The copolymer (S) has a long chain branching number (LCB) per 1000 carbon atoms, obtained using 3D-GPC. 1000C It is preferable that the natural logarithm of the weight-average molecular weight (Mw) [Ln(Mw)] satisfies the following formula (3). LCB 1000C ≤1 - 0.07 × Ln(Mw) …Equation (3) The above formula (3) allows us to determine the upper limit of the long-chain branching content per unit number of carbon atoms in the copolymer (S).

[0034] Such copolymers (S) are preferable because they have a low proportion of long-chain branching, exhibit excellent curing properties when the clay-like composition containing copolymers (S) is crosslinked with organic peroxides, and the molded articles obtained using them have excellent mechanical properties. The copolymer (S) more preferably satisfies the following formula (3'). LCB 1000C ≤1 - 0.071 × Ln(Mw) …Equation (3') Here, Mw and the number of long-chain branches per 1000 carbon atoms (LCB) 1000C) can be determined by structural analysis using 3D-GPC. Specifically, in this specification, it was determined as follows.

[0035] Using a 3D high-temperature GPC system, model PL-GPC220 (manufactured by Polymer Laboratories), the absolute molecular weight distribution was determined, and simultaneously, the intrinsic viscosity was determined using a viscometer. The main measurement conditions were as follows. Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precision Detectors) Bridge-type viscometer PL-BV400 (manufactured by Polymer Laboratories) Column: TSKgel GMHHR-H(S)HT x 2 + TSKgel GMHHR-M(S) x 1 (Each piece has an inner diameter of 7.8mmφ and a length of 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: Ca 1.5 mg / mL Sample filtration: Filtered using a 1.0 μm pore size sintered filter.

[0036] The dn / dc value required to determine the absolute molecular weight was determined for each sample using the dn / dc value of standard polystyrene (molecular weight 190,000), which is 0.053, and the response intensity of a differential refractometer per unit injection mass. The long-chain branching parameter g'i for each eluted component was calculated from equation (v-1) based on the relationship between the intrinsic viscosity obtained from a viscometer and the absolute molecular weight obtained from a light scattering photometer.

[0037]

number

[0038] Furthermore, the average values ​​for each parameter, g', were calculated using the following formulas (v-2), (v-3), and (v-4). Note that the Trendline, assuming only short-chain branching, was determined for each sample.

[0039]

number

[0040] Furthermore, using g'w, we can determine the number of branching points per molecular chain (BrNo) and the number of long-chain branches per 1000 carbon atoms (LCB). 1000C The degree of branching λ per unit molecular weight was calculated. BrNo was calculated using the Zimm-Stockmayer equation (v-5), and LCB was also calculated. 1000C The calculation of λ was performed using equations (v-6) and (v-7). g is the long-chain branching parameter obtained from the radius of inertia Rg, and the following simple correlation is made between it and g' obtained from the intrinsic viscosity.

[0041] g=g' (1 / ε ) ε (structure factor) = 0.5~1.5 (usually 0.75) Although various values ​​have been proposed for ε in the formula depending on the shape of the numerator, the calculations here were performed assuming ε = 1 (i.e., g' = g).

[0042]

number

[0043] Method for producing ethylene-α-olefin-non-conjugated polyene copolymer (S) The ethylene-α-olefin-non-conjugated polyene copolymer (S) according to the present invention is a copolymer obtained by copolymerizing monomers consisting of ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of general formulas (I) and (II) in the molecule, and a non-conjugated polyene (D) optionally containing a total of only one substructure selected from the group consisting of general formulas (I) and (II) in the molecule.

[0044] The copolymer (S) according to the present invention may be prepared by any method as long as it satisfies requirement (i), preferably requirements (ii) and (iii), and furthermore, requirements (iv) to (viii). However, it is preferably obtained by copolymerizing monomers in the presence of a metallocene compound, and more preferably by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound.

[0045] The ethylene-α-olefin-non-conjugated polyene copolymer (S) according to the present invention can be specifically produced, for example, by employing the method of using a metallocene catalyst as described in International Publication No. 2015 / 122495.

[0046] <Filler (X)> Filler (X), one of the components contained in the clay-like composition of the present invention, is a known rubber reinforcing agent used in rubber compositions, and is an inorganic substance commonly referred to as carbon black or an inorganic reinforcing agent.

[0047] Specifically, examples of fillers (X) related to the present invention include Asahi #55G, Asahi #60UG (both manufactured by Asahi Carbon Co., Ltd.), carbon black of Seest (V, SO, 116, 3, 6, 9, SP, TA, etc.) (manufactured by Tokai Carbon Co., Ltd.), carbon blacks surface-treated with silane coupling agents, etc., and silica, activated calcium carbonate, fine talc, fine silicic acid, light calcium carbonate, heavy calcium carbonate, talc, kaolin, clay, etc.

[0048] The filler (X) may be used alone or as a mixture of two or more types. Preferably, the filler (X) used in this invention is carbon black, light calcium carbonate, heavy calcium carbonate, talc, kaolin, clay, etc.

[0049] In addition to the copolymer (S) and filler (X) described above, the clay-like composition of the present invention may contain other components as long as they do not impair the effects of the present invention. These other components may include, for example, at least one selected from organic peroxides, softeners, antioxidants, processing aids, surfactants, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, and thickeners. Furthermore, each additive may be used alone or in combination of two or more.

[0050] <Coloring agents> As colorants, pigments and dyes commonly used as colorants for rubber can be used. The pigments are not particularly limited, and either organic or inorganic pigments can be used. Examples of organic pigments include azo pigments such as azo lake pigments, insoluble monoazo pigments, insoluble disazo pigments, condensed azo pigments, and chelate azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments; dye chelates such as basic dye type chelates and acid dye type chelates; and nitro pigments and nitroso pigments.

[0051] Examples of inorganic pigments include titanium dioxide, iron oxide yellow, iron oxide brown, chromium oxide, Prussian blue, ultramarine, molybdenum red, iron oxide black, lead yellow, complex oxide pigments, and carbon black.

[0052] In particular, considering lightfastness, isoindolinone pigments, quinacridone pigments, condensed azo pigments, phthalocyanine pigments, quinophthalone pigments, anthraquinone pigments, and carbon black are preferred.

[0053] Specific examples of organic pigments include, for example, Pigment Yellow 1 (Color Index (hereinafter referred to as CI) 11680), Pigment Yellow 3 (CI 11710), Pigment Yellow 14 (CI 21095), Pigment Yellow 17 (CI 21105), Pigment Yellow 42 (CI 77492), Pigment Yellow 74 (CI 11741), Pigment Yellow 83 (CI 21108), Pigment Yellow 93 (CI 20710), and Pigment Yellow 98 (CI 11727). ), Pigment Yellow 109 (CI56284), Pigment Yellow 110 (CI56280), Pigment Yellow 128 (CI20037), Pigment Yellow 138 (CI56300), Pigment Yellow 139 (CI56298), Pigment Yellow 147 (CI60645), Pigment Yellow 154 (CI11781), Pigment Yellow 155 (CI-), Pigment Yellow 180 (CI21290), Pigment Yellow 185 (CI56290), Pigment Orange 5 (CI12075), Pigment Orange 13 (CI21110), Pigment Orange 16 (CI21160), Pigment Orange 34 (CI21160), Pigment Orange 43 (CI71105), Pigment Orange 61 (CI11265), Pigment Orange 71 (CI56120), Pigment Red 5 (CI12490), Pigment Red 8 (CI12335), Pigment Red 17 (CI12390), Pigment Red 22 (CI Pigment Red 12315), Pigment Red 48:2 (CI15865:2), Pigment Red 112 (CI12370), Pigment Red 122 (CI73915), Pigment Red 177 (CI65300), Pigment Red 202 (CI73907), Pigment Red 254 (CI56110), Pigment Violet 19 (CI46500), Pigment Violet 23 (CI51319), Pigment Blue 15:1 (CI74160), Pigment Blue 15:3 (CIExamples include Pigment Blue 15:4 (CI74160), Pigment Blue 60 (CI69800), Pigment Green 7 (CI74260), and Pigment Green 36 (CI74265).

[0054] Specific examples of inorganic pigments include, for example, Pigment Yellow 42 (CI77492), Pigment White 6 (CI77891), Pigment Blue 27 (CI77510), Pigment Blue 29 (CI77007), and Pigment Black 7 (CI77266).

[0055] Preferably, examples include Pigment Yellow 74 (CI11741), Pigment Yellow 109 (CI56284), Pigment Yellow 110 (CI56280), Pigment Yellow 128 (CI20037), Pigment Yellow 155 (CI-), Pigment Yellow 180 (CI21290), Pigment Red 122 (CI73915), Pigment Red 202 (CI73907), Pigment Violet 19 (CI46500), Pigment Blue 15:1 (CI74160), Pigment Blue 15:3 (CI74160), Pigment Blue 15:4 (CI74160), Pigment Blue 60 (CI69800), Pigment Black 7 (CI77266), and the like.

[0056] Examples of carbon black include acetylene black, channel black, and furnace black. Specific examples of carbon as described above include "Carbon Black #990", "#970", "#960", "#950", "#650", "#750", "MA600", "#4000", "MA100", "#40", "#32", "#30", "MA230", "#3230", "#3350" (all manufactured by Mitsubishi Chemical Corporation), "MONARCH880", "-1000", "-1300", "-1400", "-460", "-480", "VULCAN-P", "-XC-72", "-9A32", "ELFTEX-8" (all manufactured by Cabot Corporation), "C Examples include "colorBlackFW1", "-2", "-200", "-18", "-S160", "-S170", "SpecialBlack-5", "-6", "-4", "-4A", "Printex-90", "-80", "-60", "-40", "-30", "-3", "-140U", "-140V", "-150T", "-P", "-L6", "-L", "-U", "-V" (all manufactured by Degussa), "Raven-5000ULTRAIII", "-7000", "-5750", "-5250", "-890H", "-790ULTRA", "-C ULTRA", "Conductex-SC ULTRA", and "-975ULTRA" (all manufactured by Colombian).

[0057] <Softener> Examples of softening agents include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymers such as terpene resins, petroleum resins, and coumarone indene resins; ester-based softening agents such as dioctyl phthalate and dioctyl adipate; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub(factis). Of these, petroleum-based softening agents are preferred, and process oil is particularly preferred.

[0058] If the clay-like composition contains a softening agent, the amount of softening agent is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of copolymer (S).

[0059] <Anti-aging agent (stabilizer)> By incorporating an antioxidant (stabilizer) into the clay-like composition of the present invention, the lifespan of the clay-like composition and the various molded articles obtained from the clay-like composition can be extended. Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0060] Examples of anti-aging agents include aromatic 2-amine anti-aging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether anti-aging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate anti-aging agents such as dibutyldithiocarbamate nickel; and sulfur-based anti-aging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0061] When the clay-like composition contains an antioxidant, the amount of antioxidant is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of copolymer (S). When the amount of antioxidant is within the above range, the lifespan of the resulting molded article can be extended.

[0062] <Processing aids> As processing aids, those commonly used in rubber processing can be widely used. Specifically, examples include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, zinc laurate, or esters. Of these, stearic acid is preferred.

[0063] If the copolymer composition contains a processing aid, it can be appropriately blended in an amount of typically 1 to 3 parts by mass per 100 parts by mass of the ethylene copolymer (L). When the amount of processing aid is within the above range, it is preferable because it provides excellent processability such as kneadability, extrusionability, and injection moldability. The processing aid may be a single type or two or more types.

[0064] <Activating agent> Examples of activators include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triaryl merilate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide moduloides; kutadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0065] If the clay-like composition contains an activator, the amount of activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of copolymer (S).

[0066] <Organic peroxide> Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0067] When using organic peroxides, the amount of organic peroxides blended into the copolymer composition is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of copolymer (S). When the amount of organic peroxides blended is within the above range, there is no bloom on the surface of the resulting molded article, and the clay-like composition exhibits excellent crosslinking properties, making it preferable.

[0068] When using organic peroxides as crosslinking agents, it is preferable to use crosslinking aids in combination. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; zinc oxide (e.g., ZnO#1, zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.); magnesium oxide; activated zinc oxide (e.g., zinc oxide such as "META-Z102" (product name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0069] When a crosslinking aid is used, the amount of the crosslinking aid in the clay-like composition is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 6 moles, per mole of organic peroxide.

[0070] <Clay-like composition> The clay-like composition of the present invention comprises the copolymer (S) and the filler (X), wherein the content of filler (X) is in the range of 40 to 60% by mass, preferably 40 to 55% by mass, more preferably 40 to 50% by mass [provided that the total amount of (A) and (X) is 100% by mass], and is a clay-like composition that satisfies the following requirements (y-1) to (y-3).

[0071] <Requirement (y-1)> The Mooney viscosity ML(1+4) at 100°C is 5 or less, preferably 2 to 4. By satisfying this requirement for Mooney viscosity, the material can be easily molded into any shape by hand, and deformation is reduced.

[0072] <Requirement (y-2)> The specific gravity is in the range of 1.2 to 0.8. Because the clay-like composition of the present invention falls within this specific gravity range, it is light and easy to handle. If the composition is too heavy, it will increase the strain on the arm during use, and conversely, if it is too light, the adhesion between it and the mating material will decrease, resulting in reduced grip.

[0073] <Requirement (y-3)> It is deformable at 23°C. In this invention, "deformable" means that it can be easily deformed by hand.

[0074] Method for producing clay-like compositions Examples of methods for producing the clay-like composition of the present invention include mixing each component contained in the clay-like composition using conventionally known kneading machines such as mixers, kneaders, and rolls, as well as continuous kneading machines such as twin-screw extruders, and preparing a solution in which each component contained in the clay-like composition is dissolved or dispersed, and then removing the solvent.

[0075] Uses of clay-like compositions The clay-like composition of the present invention can be molded into any shape at room temperature (40°C or below), and therefore, in addition to clay modeling, it can be used for various applications, such as grips selected from golf club grips, cane grips, toothbrush grips, tableware grips, cleaning tool grips, teacup grips, writing instrument grips, fishing rod grips, door grips, automobile steering wheel grips, and bicycle steering wheel grips; Road or flooring material; Anti-slip strips can be selected from options such as stair anti-slip strips, pool floor anti-slip strips, floor mat anti-slip strips, table anti-slip strips, and anti-slip strips for small items; Cushioning materials selected from wall cushioning materials and L-shaped cushioning materials; Putty can be selected from air conditioner hole filling putty, antenna hole filling putty, wall hole repair putty, flooring repair putty, and rubber part repair putty; Joint filler; door stopper; It can be used for purposes such as [examples of use].

[0076] Depending on the application, the clay-like composition may be crosslinked and molded into any shape suitable for the application, or the clay-like composition may be molded into any shape suitable for the application and then crosslinked. [Examples]

[0077] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples. The copolymer (S) used in the example is shown below.

[0078] <Production of ethylene-propylene-VNB copolymer (S-1)> In the method for producing ethylene-propylene-VNB copolymer described in Example 1 (

[0386] to

[0391] ) of International Publication No. 2019 / 180802, the ethylene-propylene-VNB copolymer (S-1) shown in Table 1 below was produced by adjusting the amount of hydrogen feed.

[0079] [Table 1]

[0080] <Composition of ethylene-propylene-VNB copolymer (S-1)> The mass fraction (mass%) of each constituent unit of copolymer (S-1) is: 13 The copolymer was determined by measurement using 1C-NMR. The measurement was performed using an ECX400P nuclear magnetic resonance spectrometer (JEOL), with a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and 8000 cumulative cycles. 13 The spectrum was obtained by measuring the 1C-NMR spectrum.

[0081] <Iodine value> The iodine value of copolymer (S-1) was determined by titration. Specifically, it was measured using the following method. 0.5 g of copolymer (S-1) was dissolved in 60 ml of carbon tetrachloride, a small amount of Wies' reagent and 20% potassium iodide solution were added, and the mixture was titrated with 0.1 mol / L sodium thiosulfate solution. Near the endpoint, a starch indicator was added, and the mixture was titrated while stirring well until the pale purple color disappeared. The amount of iodine consumed per 100 g of sample was then calculated.

[0082] <Intrinsic viscosity> The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscometer manufactured by Rigosha Co., Ltd., at a temperature of 135°C and using decalin as the measurement solvent.

[0083] <Moony viscosity> Mooney viscosity ML(1+4) at 100°C was measured at 100°C using a Mooney viscometer "SMV-202" (manufactured by Shimadzu Corporation) in accordance with JIS K6300 (1994).

[0084] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)> The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are polystyrene-converted values ​​measured by gel permeation chromatography (GPC). The measurement equipment and conditions are as follows. The molecular weight was calculated using a calibration curve created with commercially available monodisperse polystyrene and based on a conversion method.

[0085] Equipment: Gel permeation chromatograph Alliance GP2000 (Waters Corporation) Analysis equipment: Empower2 (manufactured by Waters Corporation) Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (7.5mm I.D. x 30cm, manufactured by Tosoh Corporation) Column temperature: 140℃, Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer (RI), Flow rate: 1.0mL / min, Injection volume: 400μL, Sampling time interval: 1s, Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation) Molecular weight conversion: EPR conversion using the old method / Calibration method considering viscosity.

[0086] <Low molecular weight components> If the chart obtained by the above GPC measurement showed two or more peaks, the ratio (%) of the area of ​​the peak appearing on the side with the smallest molecular weight to the total peak area was defined as the content of low molecular weight components with a molecular weight of 2000 or less. If the chart obtained by the GPC measurement showed only one peak, the content of low molecular weight components was defined as 0%.

[0087] <complex viscosity η * > Using an Ares viscoelasticity measuring device (manufactured by Rheometric Scientific) as the rheometer, the complex viscosity η was measured at a frequency ω = 0.01 rad / s under conditions of 190°C and 1.0% strain. * ( ω =0.01)Complex viscosity η at frequency ω = 0.1 rad / s * ( ω =0.1) Complex viscosity η at frequency ω = 10 rad / s * ( ω =10) and complex viscosity η at frequency ω = 100 rad / s * ( ω =100) (All units are Pa·sec) were measured. Also, from the obtained results, η * ( ω =0.1) and η * ( ω =100) The ratio of complex viscosity to (η) * The p-value (η) is the ratio. * ( ω =0.1) / η * ( ω =100) ) was calculated.

[0088] < Number of long chain branches per 1000 carbon atoms (LCB) 1000c )> The measurement was performed using the method described above. [Example 1] 100 parts by mass of copolymer (S-1) obtained by the above manufacturing method, 50 parts by mass of kaolin (product name TRANSLINK-37 (manufactured by BASF Japan Ltd.)) and 50 parts by mass of calcium carbonate (product name Shirotsuya CC (manufactured by Shiraishi Kogyo Co., Ltd.)) as fillers (X), 2.5 parts by mass of titanium dioxide (R-820, manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, and 50 parts by mass of paraffin-based oil (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) as a softener were kneaded using a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.) to obtain a clay-like composition (1).

[0089] In the aforementioned kneading process, copolymer (S-1) was kneaded for 1 minute, then titanium dioxide, TRANSLINK-37, Shirotsuka CC, and paraffin-based oil were added and kneaded for 2 minutes. After that, the ram was raised and cleaned, and kneaded for another 2 minutes to obtain clay-like composition (1).

[0090] The clay-like composition (1) was kneaded using an 8-inch roll (manufactured by Nippon Roll Co., Ltd.) with the front roll surface temperature at 50°C, the rear roll surface temperature at 50°C, the front roll rotation speed at 18 rpm, and the rear roll rotation speed at 16 rpm.

[0091] The mixing was performed by turning the clay-like composition (1) three times and rolling it through six times to obtain a sheet with a thickness of 2.2 to 2.5 mm. The physical properties of the obtained clay-like composition were measured using the following method. The results are shown in Table 2.

[0092] <Physical properties of clay-like compositions> [Moony Viscosity ML (1+4) 100℃] The Mooney viscosity (ML(1+4)100℃) at 100℃ was measured in accordance with JIS K6300-1.

[0093] [specific gravity] The measurement was performed in accordance with JIS K6268 "Vulcanized rubber - Density measurement".

[0094] [Deformation at 23℃] The following shapes were manually formed on a stainless steel workbench at room temperature to test the moldability. Spherical (2cm diameter), cube-shaped (2cm square), flat (2cm x 2cm x 2mm thick), string-shaped (3mm diameter x 2cm length) The moldability was evaluated by visually assessing the moldability, retention of the shape, and adhesion of the clay-like composition to the hands.

[0095] [Example 2] A clay-like composition was obtained in the same manner as in Example 1, except that 4 parts by mass of dipyroxide blue (manufactured by Dainichi Seika Co., Ltd.) was added as a coloring agent, in addition to the components used in Example 1. The physical properties of the obtained clay-like composition were measured by the method described above. The results are shown in Table 2.

[0096] [Example 3] A clay-like composition was obtained in the same manner as in Example 1, except that, in addition to the components used in Example 1, 4 parts by mass of PIGMOTEX RED 102 ET (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added as a coloring agent, 50 parts by mass of Vesta BS (trade name: manufactured by Inoue Sekkai Kogyo Co., Ltd.) was added as a dehydrating agent, and 6.8 parts by mass of dicumyl peroxide: DCP-40 (Perkmyl D-40C, manufactured by NOF Corporation) was added as an organic peroxide. The physical properties of the obtained clay-like composition were measured by the method described above. The results are shown in Table 2.

[0097] Furthermore, the crosslinking rate (vulcanization rate) of the clay-like composition containing organic peroxides was measured by the method described below. The results are shown in Table 2. Furthermore, the obtained clay-like composition was pressed using a press molding machine at 170°C for 10 minutes to produce a 2 mm thick cross-linked clay-like composition (A-2) sheet. Hardness tests and tensile tests were performed on the obtained cross-linked clay-like composition (A-2) sheet.

[0098] Furthermore, crosslinking was performed at 170°C for 15 minutes to obtain a crosslinked body (A-3) with a thickness of 12.5 mm and a diameter of 29 mm. The compression set was measured using the crosslinked body (A-3). The physical properties of the obtained crosslinked material were measured using the following method. The evaluation results are shown in Table 2.

[0099] <Physical properties of uncrosslinked clay-like compositions> <Vulcanization rate> Using the clay-like compositions in the examples and comparative examples, the vulcanization rate (tc90) was measured as follows using a measuring device: RPA2000 (manufactured by ALPHA TECHNOLOGIES) under measurement conditions of 170°C and 10 minutes. The torque change obtained under constant temperature and constant shear rate conditions was measured. The time it took to reach a torque that was 90% of the difference between the maximum and minimum torque values ​​was defined as the vulcanization rate (tc90; minutes).

[0100] <Hardness test (Duro-A hardness)> In accordance with JIS K 6253, the hardness (Type A durometer, HA) of the crosslinked sheet was measured using six 2mm thick sheet-like rubber molded products with smooth surfaces, stacked with the flat portions facing each other to a thickness of approximately 12mm. However, test specimens containing foreign matter, air bubbles, or scratches were not used. Furthermore, the dimensions of the measurement surface of the test specimen were such that measurement could be taken with the indenter tip at a distance of 12mm or more from the edge of the test specimen.

[0101] <Tensile Test> In accordance with JIS K 6251, tensile tests were conducted at a measurement temperature of 23°C and a tensile speed of 500 mm / min to measure the breaking strength (TB) [MPa] and elongation at break (EB) [%] of the sheet. Specifically, a dumbbell-shaped test specimen of type 3, as described in JIS K6251 (2001), was prepared by punching out a sheet-like cross-linked molded body. Using this test specimen, a tensile test was conducted at a measurement temperature of 25°C and a tensile speed of 500 mm / min according to the method specified in JIS K6251, and the tensile stress [25% modulus (M25)] when the elongation was 25%, the tensile stress [100% modulus (M100)] when the elongation was 100%, the tensile stress at the breaking point (TB), and the tensile elongation at the breaking point (EB) were measured.

[0102] <Compression set (CS)> In accordance with JIS K 6262, a cross-linked body with a diameter of 29 mm and a height (thickness) of 12.5 mm was used as the test specimen. The specimen was compressed by 25% from its height before loading (12.5 mm), and then heat-treated for 22 hours in a gear oven at 70°C with a spacer. The specimen was then removed, left at room temperature for 30 minutes, and its height was measured. The compression set (%) was then calculated using the following formula. Compression set (%) = {(t0-t1) / (t0-t2)} × 100 t0: Height of the test specimen before testing t1: Height after treating the test specimen under the above conditions and leaving it at room temperature for 30 minutes. t2: Height of the test specimen when mounted on the measuring mold.

[0103] <Effective network chain density> (Crosslink density) After cutting the sheet-like sample into 20mm x 20mm x 2mm pieces, it was immersed in toluene at 37°C for 72 hours in accordance with JIS K 6258 (1993) to induce swelling, and the effective network chain density (crosslinking density) was calculated using the Flory-Rehner formula (B).

[0104]

number

[0105] [Example 4] A clay-like composition was obtained in the same manner as in Example 1, except that 4 parts by mass of PIGMOTEX YELLOW 83 ET (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added as a coloring agent, in addition to the components used in Example 1. The physical properties of the obtained clay-like composition were measured by the method described above. The results are shown in Table 2.

[0106] [Comparative Example 1] A clay-like composition was obtained in the same manner as in Example 1, except that 12.5 parts by mass of NipSeal VN3 (trade name, manufactured by Tosoh Silica Co., Ltd.) was added as silica instead of the calcium carbonate used in Example 1. The physical properties of the obtained clay-like composition were measured by the method described above. The results are shown in Table 2.

[0107] [Comparative Example 2] Except for replacing each component used in Example 1, the procedure was carried out in the same manner as in Example 1, with the addition of 100 parts by mass of copolymer (S-1), 150 parts by mass of carbon black: Asahi 50HG (product name Asahi Carbon Co., Ltd.) as filler (X), 50 parts by mass of paraffinic oil (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) as a softener, and 6.8 parts by mass of dicumyl peroxide: DCP-40 (Perkmyl D-40C, manufactured by NOF Corporation) as an organic peroxide. The physical properties of the obtained clay-like composition, as well as the crosslinking rate and physical properties of the crosslinked material, were measured by the method described above. The results are shown in Table 2.

[0108] [Comparative Example 3] A clay-like composition was obtained by following the same procedure as in Example 1, except that the components used in Example 1 were replaced with copolymer (S-1): 100 parts by mass, carbon black: Asahi 50HG (product name Asahi Carbon Co., Ltd.) as filler (X): 150 parts by mass, and paraffinic oil (PW-32, manufactured by Idemitsu Kosan Co., Ltd.) as a softener: 100 parts by mass. The physical properties of the obtained clay-like composition were measured by the method described above. The results are shown in Table 2.

[0109] [Table 2]

Claims

1. An ethylene-α-olefin-non-conjugated polyene copolymer (S) having constituent units derived from ethylene (A), an α-olefin (B) having 3 to 20 carbon atoms, and a non-conjugated polyene (C) containing a total of two or more substructures selected from the group consisting of the following general formulas (I) and (II) in the molecule, satisfying the following requirement (i), and A clay-like composition (Y) characterized by containing a filler (X) in an amount of 40 to 60% by mass relative to the total amount of the copolymer (S) and filler (X): 100% by mass, and satisfying the following requirements (y-1) to (y-3). (i) The weight-average molecular weight (Mw) is in the range of 1,000 to 160,000. (y-1) Mooney viscosity ML(1+4) at 100°C is 5 or less. (y-2) The specific gravity is in the range of 1.2 to 0.

8. (y-3) It is deformable at 23°C. 【Chemistry 1】

2. The clay-like composition according to claim 1, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (S) satisfies the following requirements (ii) and (iii). (ii) The molar ratio [(A) / (B)] of constituent units derived from ethylene (A) to constituent units derived from α-olefin (B) is in the range of 40 / 60 to 90 / 10; (iii) The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) measured by gel permeation chromatography (GPC) (molecular weight distribution; Mw / Mn) is in the range of 4 to 80;

3. The clay-like composition according to claim 2, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (S) further satisfies the following requirements (iv) to (vi). (iv) The mass fraction of constituent units derived from non-conjugated polyene (C) is 0.07% to 10% by mass of copolymer (S) in 100% by mass; (v) Weight-average molecular weight (Mw), weight fraction of constituent units derived from non-conjugated polyene (C) (weight fraction of (C) (weight%)), and molecular weight of non-conjugated polyene (C) (molecular weight of (C)) The following equation (1) is satisfied: 4.5 ≤ Mw × mass fraction of (C) / 100 / molecular weight of (C) ≤ 40 ... Equation (1) (vi) The ratio P(η*(ω=0.1) / η*(ω=100)) of the complex viscosity η*(ω=0.1) (Pa・sec) at a frequency ω = 0.1 rad / s and the complex viscosity η*(ω=100) (Pa・sec) at a frequency ω = 100 rad / s, obtained by linear viscoelastic measurement (190°C) using a rheometer, the intrinsic viscosity [η], and the mass fraction of the constituent units derived from the non-conjugated polyene (C) (mass fraction of (C)) satisfy the following equation (2): P / ([η]2.9) ≤ (C) × 6 ... Equation (2)

4. A clay-like composition according to any one of claims 1 to 3, wherein the filler (X) is carbon black or an inorganic reinforcing agent.

5. A crosslinked clay-like composition according to any one of claims 1 to 4, characterized in that an ethylene-α-olefin-non-conjugated polyene copolymer (S) is crosslinked.

6. A grip selected from golf club grips, cane grips, toothbrush grips, tableware grips, cleaning tool grips, teacup grips, writing tool grips, fishing rod grips, door grips, automobile steering wheel grips, and bicycle steering wheel grips, comprising the crosslinking body described in claim 5.

7. A road or floor material comprising the bridged body described in claim 5.

8. A non-slip surface selected from a stair non-slip surface, a swimming pool non-slip surface, a floor mat non-slip surface, a table non-slip surface, and a small object non-slip surface, including the crosslinking body described in claim 5.

9. A cushioning material selected from wall cushioning material and L-shaped cushioning material, including the crosslinking body described in claim 5.

10. A putty selected from air conditioner hole filling putty, antenna hole filling putty, wall hole repair putty, flooring repair putty, and rubber parts repair putty, which includes the crosslinking body described in claim 5.

11. A joint filler comprising the crosslinked body described in claim 5.

12. A door stopper comprising the crosslinking body described in claim 5.

13. A method for manufacturing a grip material, characterized by molding a clay-like composition according to any one of claims 1 to 3 into an arbitrary shape at a temperature of 40°C or lower.

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