Coating composition, substrate with coating film, and method for producing coating layer

Abstract

To provide a coating composition exhibiting superior curability at room temperature, the coating composition containing an ethylene-α-olefin-non-conjugated polyene copolymer and a crosslinking agent.SOLUTION: A coating composition containing a specific ethylene-α-olefin-non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y) that is an organohydrogenpolysiloxane represented by a specific formula and having, within one molecule, at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms, a platinum-based catalyst, and a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to coating compositions, coated substrates, and methods for producing coating layers. [Background technology]

[0002] Waterproofing materials are widely used to protect building materials and the like from external factors such as pollutants, water, oil, etc. Known waterproofing materials include coating waterproofing materials containing urethane resins (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2023-59157 Summary of the Invention [Problem to be solved by the invention]

[0004] Although urethane resins can be crosslinked at room temperature, there is room for improvement in weather resistance. Under these circumstances, the present inventors investigated a coating composition containing an ethylene-α-olefin-non-conjugated polyene copolymer and a crosslinking agent. Ethylene-α-olefin-non-conjugated polyene copolymers, such as ethylene-propylene-non-conjugated diene copolymer (EPDM), generally do not contain unsaturated bonds in the main chain of their molecular structure. Therefore, these copolymers have excellent weather resistance and are widely used in a variety of applications.

[0005] However, the present inventors have found that a coating composition containing an ethylene-α-olefin-non-conjugated polyene copolymer and a crosslinking agent may not cure well at room temperature. An object of the present disclosure is to provide a coating composition containing an ethylene-α-olefin-non-conjugated polyene copolymer and a crosslinking agent, which has excellent room temperature curing properties. [Means for solving the problem]

[0006] One aspect of the composition of the present disclosure is an ethylene·α-olefin·non-conjugated polyene copolymer (A) containing a structural unit derived from ethylene [A1], a structural unit derived from an α-olefin having 3 to 20 carbon atoms [A2], and a structural unit derived from a non-conjugated polyene [A3] containing in total two or more of at least one partial structure selected from the group consisting of the following formula (I) and formula (II) in one molecule, a hydrosilyl group-containing compound (Y) which is an organohydropolysiloxane represented by the following formula (Y1) and has at least one silicon atom-bonded aralkyl group and at least two silicon atom-bonded hydrogen atoms in one molecule, a platinum-based catalyst, and a solvent, and is a coating composition.

Effects of the Invention

[0007] The coating composition of the present disclosure contains an ethylene·α-olefin·non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y), and a platinum-based catalyst, and is excellent in room-temperature curability.

Modes for Carrying Out the Invention

[0008] In the present specification, the numerical range n1 to n2 means n1 or more and n2 or less when n1 < n2, and means n2 or more and n1 or less when n1 > n2. In the present specification, when a plurality of lower limit values and upper limit values are described in the description of an element, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also described.

[0009] In the present specification, when the units of the numerical values described before and after "~" indicating a numerical range are the same, the unit of the numerical value described before "~" may be omitted. For example, "50 mol% to 85 mol%" may be described as "50 to 85 mol%".

[0010] In this specification, the amount of each component in a composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to that component are present in the composition.

[0011] In this specification, unless otherwise specified, each component in the composition or each structural unit in the polymer may contain one type or two or more types. In this specification, the term "polymer" may be used without any particular distinction between homopolymers and copolymers. That is, the term "polymer" is used to mean both homopolymers and copolymers.

[0012] [Coating composition] The coating composition of the present disclosure (hereinafter also referred to as the "composition of the present disclosure") contains an ethylene-α-olefin-non-conjugated polyene copolymer (A), a hydrosilyl group-containing compound (Y), a platinum catalyst, and a solvent. Each component will be described below.

[0013] <Ethylene-α-olefin-non-conjugated polyene copolymer (A)> The ethylene-α-olefin-non-conjugated polyene copolymer (A) (hereinafter also referred to as "copolymer (A)") contains structural units derived from ethylene [A1], structural units derived from an α-olefin having 3 to 20 carbon atoms [A2], and structural units derived from a non-conjugated polyene [A3]. The non-conjugated polyene [A3] is a non-conjugated polyene containing a total of two or more partial structures per molecule, each of which is at least one type selected from the group consisting of the following formulas (I) and (II):

[0014] [ka]

[0015] Examples of the α-olefin [A2] having 3 to 20 carbon atoms 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. Among these, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene, are preferred, with propylene being particularly preferred. Such α-olefins are preferred because they are relatively inexpensive in terms of raw material cost, the resulting copolymers exhibit excellent mechanical properties, and crosslinked products having rubber elasticity can be obtained. The α-olefins [A2] may be used alone or in combination of two or more.

[0016] Examples of the non-conjugated polyene [A3] include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, 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 Examples of suitable non-conjugated polyenes include 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and dicyclopentadiene. The non-conjugated polyene [A3] preferably contains VNB, and more preferably is VNB, because it is readily available, the resulting copolymer exhibits good hydrosilyl crosslinkability, and the heat resistance of the composition is likely to be improved. The non-conjugated polyene [A3] may be used alone or in combination of two or more.

[0017] The copolymer (A) may further contain structural units derived from a non-conjugated polyene [A4]. The non-conjugated polyene [A4] is a non-conjugated polyene containing only one partial structure selected from the group consisting of formula (I) and formula (II) per molecule.

[0018] Examples of the non-conjugated polyene [A4] include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(2-methyl-1-propenyl)-2-norbornene. Because of its high availability, ease of controlling the crosslinking rate of the resulting copolymer, and ease of obtaining good mechanical properties, the non-conjugated polyene [A4] preferably contains ENB, and more preferably is ENB. The non-conjugated polyene [A4] may be used alone or in combination of two or more.

[0019] The copolymer (A) may contain at least one structural unit derived from a biomass-derived monomer. Examples of the biomass-derived monomer include biomass-derived ethylene, biomass-derived α-olefins having 3 to 20 carbon atoms, and biomass-derived non-conjugated polyenes. Examples of the biomass-derived α-olefins include biomass-derived propylene. Examples of the biomass-derived non-conjugated polyenes include biomass-derived 5-vinyl-2-norbornene and biomass-derived 5-ethylidene-2-norbornene. The monomers used as raw materials for the copolymer (A) may contain only biomass-derived monomers, only fossil fuel-derived monomers, or both biomass-derived monomers and fossil fuel-derived monomers. The biomass-derived monomers can be obtained by known methods. It is preferable that the copolymer (A) contain structural units derived from biomass-derived monomers from the viewpoint of reducing the environmental impact.

[0020] The copolymer (A) may contain at least one structural unit derived from a chemically recycled monomer. Examples of the chemically recycled monomer include ethylene derived from chemical recycling, an α-olefin having 3 to 20 carbon atoms derived from chemical recycling, and a non-conjugated polyene derived from chemical recycling. The monomers used as raw materials for the copolymer (A) may contain only chemically recycled monomers, only fossil fuel-derived monomers, or both chemically recycled monomers and fossil fuel-derived monomers. The chemically recycled monomers are obtained by known methods. It is preferable that the copolymer (A) contains a structural unit derived from a chemically recycled monomer from the viewpoint of reducing the environmental load (mainly reducing waste).

[0021] Copolymer (A) preferably satisfies the following requirements (i) and (ii): In addition to satisfying requirements (i) and (ii), copolymer (A) preferably satisfies one or more of the following requirements (iii) to (v), more preferably satisfies two or more of the following requirements (iii) to (v), still more preferably satisfies requirements (iii) and (iv), and particularly preferably satisfies all of the following requirements (iii) to (v).

[0022] Requirement (i): When all structural units contained in the copolymer (A) are taken as 100 mol %, the ratio [(A1) / (A2)] of the molar fraction (A1) of structural units derived from ethylene [A1] to the molar fraction (A2) of structural units derived from an α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1. The ratio [(A1) / (A2)] is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 85 / 15, even more preferably 55 / 45 to 80 / 20, still more preferably 55 / 45 to 78 / 22, and particularly preferably 60 / 40 to 75 / 25.

[0023] When the copolymer (A) satisfies the requirement (i), the crosslinked body and coating layer obtained from the composition containing such a copolymer tend to be excellent in rubber elasticity, flexibility and mechanical strength.

[0024] When all structural units contained in the copolymer (A) are taken as 100 mol %, the molar fraction (A1) of structural units derived from ethylene [A1] is preferably 50 to 85 mol %, more preferably 55 to 80 mol %, and even more preferably 60 to 75 mol %.

[0025] Requirement (ii): The mass fraction of the structural unit derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A). The mass fraction of the structural unit derived from the non-conjugated polyene [A3] is preferably 0.1 to 8.0 mass%, more preferably 0.5 to 5.0 mass%, further preferably 0.5 to 3.0 mass%, particularly preferably 0.5 to 2.0 mass%.

[0026] When the copolymer (A) satisfies the requirement (ii), the crosslinked body and the coating layer obtained from the composition containing such a copolymer tend to have sufficient hardness and excellent mechanical properties. When the copolymer (A) satisfies the requirement (ii), the copolymer (A) tends to have excellent hydrosilyl crosslinkability and a high crosslinking rate.

[0027] When the copolymer (A) further contains a structural unit derived from the non-conjugated polyene [A4], the mass fraction of the structural unit is preferably 20 mass% or less, more preferably 8.0 mass% or less, and even more preferably 0.01 to 8.0 mass% in 100 mass% of the copolymer (A).

[0028] The molar fraction (A1) of the structural unit derived from ethylene [A1], the molar fraction (A2) of the structural unit derived from an α-olefin having 3 to 20 carbon atoms [A2], the ratio [(A1) / (A2)], the mass fraction of the structural unit derived from the non-conjugated polyene [A3], and the mass fraction of the structural unit derived from the non-conjugated polyene [A4] were measured using the apparatus and conditions described in the Examples section below. 13It can be calculated by measuring the C-NMR spectrum.

[0029] Requirement (iii): The weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×[A3] mass fraction / 100 / [A3] molecular weight≦80 (1)

[0030] The formula (1) in the requirement (iii) is preferably the following formula (1a). 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦75 (1a) Formula (1) in requirement (iii) is preferably the following formula (1b). 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦70 (1b)

[0031] Requirement (iii) represents the content of structural units derived from the non-conjugated polyene [A3] per weight-average molecular weight (Mw) in the copolymer (A). When the copolymer (A) satisfies requirement (iii), the content of structural units derived from the non-conjugated polyene [A3] in such a copolymer is more appropriate. Therefore, the composition tends to exhibit sufficient hydrosilyl crosslinkability and a high crosslinking rate. Furthermore, the crosslinked body and coating layer formed from the composition tend to have a good balance of mechanical properties and heat aging resistance.

[0032] The weight average molecular weight (Mw) of the copolymer (A) means the weight average molecular weight measured by 3D-gel permeation chromatography (GPC) under the conditions described in the explanation of requirement (v) and in the Examples section below.

[0033] Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency of ω=100 rad / sec* (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ [A3] mass fraction × 6 (2)

[0034] Formula (2) in requirement (iv) is preferably the following formula (2a). P / ([η] 2.9 ) ≦ [A3] mass fraction × 5.7 (2a)

[0035] ratio P(η * (ω=0.1) / η * (ω=100) ) (hereinafter also referred to as "P value") represents the frequency dependence of viscosity. Therefore, P / ([η] 2.9 ) tends to show a high value when there is a lot of long-chain branching, although it is affected by factors such as short-chain branching and molecular weight. Generally, the more structural units derived from non-conjugated polyene an ethylene-α-olefin-non-conjugated polyene copolymer contains, the more long-chain branching it tends to have. However, copolymer (A) has less long-chain branching than conventionally known ethylene-α-olefin-non-conjugated polyene copolymers, and is therefore thought to be able to satisfy formula (2) or (2a).

[0036] The P value is the ratio of the complex viscosity measured at 190°C, 1.0% strain, and 0.1 rad / sec using a viscoelasticity measuring device (e.g., Ares (Rheometric Scientific)) to the complex viscosity measured at 100 rad / sec, with only the measurement frequency changed. The intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0037] The copolymer (A) preferably satisfies the following requirement (v). Requirement (v): The number of long chain branches (LCB) per 1000 carbon atoms obtained using 3D-GPC 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] satisfy the following formula (3). LCB 1000C ≦1-0.07×Ln(Mw) (3)

[0038] Formula (3) is preferably the following formula (3a): LCB 1000C ≦1-0.071×Ln(Mw) (3a) The upper limit of the number of long-chain branches per unit carbon atom in copolymer (A) is determined by formula (3) or (3a). When copolymer (A) satisfies requirement (v), the proportion of long-chain branches contained in such copolymer is low, and therefore the curing characteristics when the composition is crosslinked tend to be excellent, and the crosslinked body and coating layer formed from the composition tend to have excellent heat aging resistance.

[0039] Requirement (v) Mw and number of long chain branches per 1000 carbon atoms (LCB) 1000C ) can be determined by a structural analysis method using 3D-GPC, and specifically, can be determined as follows.

[0040] First, the absolute molecular weight distribution is determined using a GPC device (for example, a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories)), and the intrinsic viscosity is determined using a viscometer. The main measurement conditions are as follows:

[0041] Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (Manufactured by Precision Detectors) Bridge-type viscometer PL-BV400 (Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 + TSKgel GMH HR-M(S) x 1 piece (inner diameter 7.8mmφ x length 300mm per piece) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: ca 1.0 mg / mL Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm

[0042] The dn / dc value required to determine the absolute molecular weight is determined for each sample from the dn / dc value of standard polystyrene (molecular weight 190,000), 0.053, and the response intensity of the differential refractometer per unit injected mass.

[0043] Next, the long chain branching parameter g' for each eluted component was calculated from the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer. i is calculated using the following formula (v-1): In formula (v-1), [η] = KM v , v=0.726. This equation is called the Mark-Houwink-Sakurada equation, where K is the solvent constant and M is the average molecular weight.

[0044]

number

[0045] The average values ​​of g' are calculated from the following formulas (v-2), (v-3), and (v-4). A trendline assuming only short chain branches is determined for each sample.

[0046]

number

[0047] g' w Using these, the number of branching points per molecular chain BrNo, the degree of branching per unit molecular weight λ, and the number of long chain branches per 1000 carbon atoms LCB 1000CTo calculate BrNo, use the following Zimm-Stockmayer formula (v-5): λ and LCB 1000C The following formulas (v-6) and (v-7) are used to calculate g is the long chain branching parameter calculated from the radius of gyration Rg, and there is a simple correlation between g' calculated from the intrinsic viscosity as follows: g=g' (1 / ε) (ε (structure factor) = 0.5 to 1.5) Various values ​​have been proposed for ε in the formula depending on the shape of the molecule. Here, calculations are performed assuming ε = 1 (i.e., g' = g).

[0048]

number

[0049] λ=BrNo / M (v-6) LCB 1000C =λ×14000 (v-7) In formula (v-7), "14000" means a molecular weight equivalent to 1000 methylene (CH2) units.

[0050] The copolymer (A) preferably satisfies the following requirement (vi). Requirement (vi): Complex viscosity η at a frequency ω = 0.01 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.01) (Pa·sec) and the complex viscosity η at a frequency of ω=10 rad / sec * (ω=10) (Pa·sec) and the apparent iodine value derived from the non-conjugated polyene [A3] satisfy the following formula (4). Log[η * (ω=0.01) ] / Log[η * (ω=10) ] ≦ 0.0753 × {apparent iodine value derived from non-conjugated polyene [A3]} + 1.42 (4)

[0051] In formula (4), the left side represents the shear rate dependency, which is an index of the content of long chain branches, and the right side represents an index of the content of non-conjugated polyene [A3] that is not consumed as long chain branches during polymerization. If the copolymer (A) satisfies formula (4), the degree of long chain branching is not too high, which is preferable.

[0052] Complex viscosity η * (ω=0.01) and complex viscosity η * (ω=10) is the complex viscosity η in requirement (iv) * (ω=0.1) and complex viscosity η * (ω=100) Measurements can be performed in the same way except for the measurement frequency. The apparent iodine value derived from the non-conjugated polyene [A3] can be calculated by the following formula: Apparent iodine value derived from [A3] = mass fraction of [A3] × 253.81 / molecular weight of [A3]

[0053] In the copolymer (A), as described above, the non-conjugated polyene [A3] preferably contains VNB, and more preferably is VNB. That is, in the formulas (1) and (2), the "mass fraction of [A3]" is preferably the "mass fraction of structural units derived from VNB."

[0054] As described above, when the copolymer (A) contains structural units derived from ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and a non-conjugated polyene [A4], the mass fraction of the structural units derived from the non-conjugated polyene [A4] is preferably 20 mass% or less (where the total mass fraction of the structural units derived from ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and a non-conjugated polyene [A4] is taken as 100 mass%). In this case, the copolymer (A) preferably satisfies the following requirement (vii).

[0055] Requirement (vii): The weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), the mass fraction of the structural unit derived from the non-conjugated polyene [A4] (mass fraction (mass%) of [A4]), the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]), and the molecular weight of the non-conjugated polyene [A4] (molecular weight of [A4]) satisfy the following formula (5) (where the total of the mass fractions of the structural units derived from ethylene [A1], the α-olefin [A2] having 3 to 20 carbon atoms, the non-conjugated polyene [A3], and the non-conjugated polyene [A4] is 100% by mass). 4.5≦Mw×{(mass fraction of [A3] / 100 / molecular weight of [A3])+(mass fraction of [A4] / 100 / molecular weight of [A4])}≦80 (5) Formula (5) specifies the total content of structural units derived from non-conjugated polyenes ([A3] and [A4]) per weight average molecular weight (Mw) in the copolymer (A).

[0056] The formula (5) in the requirement (vii) is preferably the following formula (5a): 4.5≦Mw×{(mass fraction of [A3] / 100 / molecular weight of [A3])+(mass fraction of [A4] / 100 / molecular weight of [A4])}≦75 (5a)

[0057] When the copolymer (A) containing structural units derived from the non-conjugated polyene [A4] satisfies the requirement (vii), a crosslinked body and a coating layer having excellent mechanical properties and heat aging resistance can be obtained.

[0058] The copolymer (A) preferably satisfies the following requirement (viii). Requirement (viii): The mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass %) of [A3]) and the weight average molecular weight (Mw) of the copolymer (A) satisfy the following formula (6): 6-0.45×Ln(Mw)≦[A3] mass fraction≦10 (6) When the copolymer (A) satisfies the requirement (viii), such a copolymer is preferred because it contains a sufficient amount of structural units derived from the non-conjugated polyene [A3].

[0059] The intrinsic viscosity [η] of the copolymer (A) is preferably 0.1 to 5.0 dL / g, more preferably 0.5 to 5.0 dL / g, still more preferably 0.8 to 4.0 dL / g, and particularly preferably 1.0 to 3.5 dL / g.

[0060] The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 600,000, more preferably 30,000 to 550,000, still more preferably 50,000 to 550,000, and particularly preferably 60,000 to 500,000.

[0061] The intrinsic viscosity [η] and weight average molecular weight (Mw) of the copolymer (A) are preferably both within the above ranges. The intrinsic viscosity [η] of the copolymer (A) can be measured using the apparatus and conditions described in the Examples section. The weight average molecular weight (Mw) of the copolymer (A) can be measured by 3D-GPC using the apparatus and conditions described in the Examples section.

[0062] The copolymer (A) can be obtained, for example, by copolymerizing ethylene [A1], an α-olefin [A2] having 3 to 20 carbon atoms, a non-conjugated polyene [A3], and, if necessary, a non-conjugated polyene [A4]. The copolymer (A) is preferably obtained by copolymerizing the above monomers in the presence of a metallocene compound, and more preferably by copolymerizing the above monomers in the presence of a catalyst system containing a metallocene compound. The copolymer (A) can be produced, for example, by the production method using a metallocene catalyst described in JP 2018-119096 A and WO 2015 / 122495 A.

[0063] The copolymer (A) may be used alone or in combination of two or more. The content of copolymer (A) in the composition of the present disclosure is preferably 10 to 99.9 mass%, more preferably 15 to 99.5 mass%, even more preferably 20 to 99 mass%, and particularly preferably 23 to 98 mass%, based on 100 mass% of the solid content of the composition. In one embodiment, the content of copolymer (A) may be, for example, 30 to 99.5 mass%, 50 to 99 mass%, or 60 to 98 mass%, based on 100 mass% of the solid content of the composition. The solid content of the composition refers to all components excluding the solvent.

[0064] <Hydrosilyl Group-Containing Compound (Y)> The hydrosilyl group-containing compound (Y) (hereinafter also referred to as "compound (Y)") is an organohydrogenpolysiloxane represented by the following formula (Y1): Compound (Y) has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in one molecule.

[0065] [ka]

[0066] The meanings of the symbols in formula (Y1) are as follows: n and p are each independently 0 or a positive number. m is 1 to 20. The sum of n, m, and p is 5 to 50. Multiple R 1 and R 2 are each independently a monovalent alkyl group. 1 are each independently an alkyl group. 2 are each independently an alkyl group. 1 is R 2 In the alkyl group, some of the carbon atom-bonded hydrogen atoms may be substituted with halogen atoms. R a is an aralkyl group. The two R are independently R 1, R 2 , hydrogen atoms, and R a When n=1, at least one of the two R is a hydrogen atom, and when n=0, both of the two R are hydrogen atoms. 1 or R 2 It is preferable that:

[0067] The crosslinked product and coating layer obtained by crosslinking a composition containing copolymer (A) and compound (Y) as a crosslinking agent tend to have little odor and excellent heat aging resistance. In addition, the composition can be handled in air.

[0068] Compound (Y) is an organohydrogenpolysiloxane with a linear structure that has a relatively low degree of siloxane polymerization and has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule.

[0069] In formula (Y1), m is the number of diorganosiloxy units having silicon-bonded aralkyl groups, and is 1 to 20, preferably 2 to 10, more preferably 2 to 8, and even more preferably 3 to 6.

[0070] In formula (Y1), n ​​is the number of organohydrogensiloxy units having silicon-bonded hydrogen atoms. n can be 0 or 1, but when n=1, at least one of the two Rs is a hydrogen atom, and when n=0, both Rs are hydrogen atoms. In other words, the organohydrogenpolysiloxane represented by formula (Y1) has a structure containing at least two silicon-bonded hydrogen atoms per molecule. Note that even if n is a number other than 0 or 1, one or both of the Rs at both ends of the molecular chain can be silicon-bonded hydrogen atoms.

[0071] n is preferably a number other than 0 or 1, and more preferably a number satisfying n≧m. n is preferably 3-10, more preferably 3-9, and even more preferably 5-9.

[0072] In formula (Y1), p is the number of diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms. p may be 0, or may be the number obtained by subtracting the values ​​of n and m from the total degree of polymerization of siloxy units, which is represented by the sum of n, m, and p, as described below. p is preferably 0 to 12, more preferably 0 to 10, even more preferably 0 to 5, and particularly preferably 0 to 2.

[0073] In the organohydrogenpolysiloxane represented by formula (Y1), the diorganosiloxy unit (-[O-Si(R 1 )(R a )]-), organohydrogensiloxy units having silicon-bonded hydrogen atoms (-[O-Si(R 1 )H]-), and diorganosiloxy units that do not contain aralkyl groups or silicon-bonded hydrogen atoms (-[O-Si(R 1 )(R 2 The siloxy units such as (Y1)-) may be arranged in blocks or randomly. That is, the order of arrangement of the siloxy units in formula (Y1) is not particularly limited.

[0074] The compound (Y) has a relatively low degree of siloxane polymerization. In formula (Y1), the sum of the values ​​of n, m, and p is 5 to 50, preferably 5 to 20, and more preferably 5 to 15. In formula (Y1), it is preferable that m is 3 to 6, n is 5 to 9, and p is 0 to 2.

[0075] In formula (Y1), R 1 and R 2 The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group, with a methyl group being particularly preferred.

[0076] In formula (Y1), R aThe number of carbon atoms in the aralkyl group in R is preferably 7 to 20, more preferably 7 to 15. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group. a As R, an aralkyl group containing at least one branching unit represented by -CH(CH3)- in the alkanediyl group between the aryl group such as a phenyl group and the silicon atom is preferred. a As the alkyl group, an aralkyl group represented by —CH2—CH(CH3)—C6H5 is particularly preferred.

[0077] The aralkyl group is a characteristic functional group that confers usefulness as a crosslinking agent to the hydrosilyl group-containing compound (Y). In particular, the presence of an aralkyl group together with a silicon-bonded hydrogen atom in the compound (Y) having n, m, and p within the above ranges tends to significantly improve the physical properties of the resulting crosslinked product. By using the compound (Y) in combination with the copolymer (A), a coating layer with particularly excellent physical properties, such as elongation at break, can be obtained.

[0078] The compound (Y) may be used alone or in combination of two or more. In the composition of the present disclosure, the content of compound (Y) is preferably 0.1 to 100 parts by mass, more preferably 0.3 to 75 parts by mass, even more preferably 0.5 to 50 parts by mass, still more preferably 0.8 to 30 parts by mass, particularly preferably 1 to 20 parts by mass, particularly preferably 2 to 10 parts by mass, and most preferably 2.5 to 5 parts by mass, relative to 100 parts by mass of copolymer (A).

[0079] <Platinum-based catalyst> Platinum catalysts for hydrosilyl crosslinking are widely used in hydrosilylation crosslinking reactions involving the addition of silicon-bonded hydrogen atoms to carbon-carbon double bonds. Platinum catalysts for hydrosilyl crosslinking are addition reaction catalysts, and any catalyst can be used without particular limitation as long as it promotes the addition reaction (hydrosilylation reaction of an alkene) between, for example, an alkenyl group contained in the copolymer (A) and a hydrosilyl group contained in the hydrosilyl group-containing compound (Y).

[0080] Examples of platinum-based catalysts include the fine powder metal platinum catalysts described in U.S. Pat. No. 2,970,150 and the like, the chloroplatinic acid catalysts described in U.S. Pat. No. 2,823,218 and the like, the complex compounds of platinum and hydrocarbons described in U.S. Pat. Nos. 3,159,601 and 159,662 and the like, the complex compounds of chloroplatinic acid and olefins described in U.S. Pat. No. 3,516,946 and the like, and the complex compounds of platinum and vinylsiloxanes described in U.S. Pat. Nos. 3,775,452 and 3,814,780 and the like.

[0081] Specific examples of platinum catalysts include platinum itself (platinum black); platinum complexes such as chloroplatinic acid, platinum-hydrocarbon complexes, platinum-vinylsiloxane complexes, platinum-alcohol complexes, chloroplatinic acid-olefin complexes, and chloroplatinic acid-vinylsiloxane complexes. Among these, platinum-vinylsiloxane complexes are preferred due to their high catalytic activity. Examples of platinum-vinylsiloxane complexes include 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complexes. The platinum-based catalyst may be supported on a carrier such as alumina or silica.

[0082] The platinum catalyst may be used alone or in combination of two or more. In the composition of the present disclosure, the content of the platinum-based catalyst (e.g., platinum complex) is preferably 0.0001 to 1.0 part by mass, more preferably 0.001 to 0.50 part by mass, even more preferably 0.005 to 0.30 parts by mass, and particularly preferably 0.010 to 0.15 part by mass, relative to 100 parts by mass of the copolymer (A). The composition having a platinum-based catalyst content equal to or greater than the lower limit exhibits excellent room-temperature curing properties. The coating layer obtained from the composition having a platinum-based catalyst content equal to or less than the upper limit exhibits excellent physical properties, such as mechanical properties.

[0083] <Solvent> The coating composition of the present disclosure contains a solvent. The solvent can be selected arbitrarily from those that dissolve the above components. Examples of the solvent include organic solvents such as hydrocarbon organic solvents, ester organic solvents, and ketone organic solvents. Examples of the hydrocarbon organic solvents include aliphatic hydrocarbon solvents such as n-hexane, n-heptane, cyclohexane, and decalin; and aromatic hydrocarbon solvents such as toluene, xylene, and tetralin. Examples of the ester organic solvents include ethyl acetate and butyl acetate. Examples of the ketone organic solvents include acetone and methyl ethyl ketone.

[0084] Among these, hydrocarbon organic solvents are preferred because they have excellent solubility for the above components, and at least one selected from the group consisting of cyclohexane, decalin, toluene, xylene, and tetralin is more preferred. For example, the solvent may be toluene or a mixed solvent of toluene and cyclohexane.

[0085] The solvent may be used alone or in combination of two or more. When the entire coating composition of the present disclosure is taken as 100% by mass, the solvent content is preferably 50% by mass or more but less than 100% by mass, more preferably 60 to 98% by mass, even more preferably 70 to 96% by mass, and particularly preferably 75 to 94% by mass. The composition having a solvent content equal to or greater than the lower limit allows the copolymer (A) and other components to dissolve well in the solvent, making it suitable as a coating material. The composition having a solvent content equal to or less than the upper limit exhibits excellent drying properties and room-temperature curing properties.

[0086] <Other ingredients> The composition of the present disclosure may further contain components other than those described above (hereinafter also referred to as "other components"). Examples of other components include antioxidants, fillers, softeners, moisture absorbents, reaction inhibitors, organic peroxides, crosslinking aids, crosslinking accelerators, foaming agents, activators, processing aids, plasticizers, tackifiers, colorants, and polymers other than the copolymer (A). The other components may be used alone or in combination of two or more.

[0087] (anti-aging agent) The compositions of the present disclosure may further contain an anti-aging agent. As the antioxidant, any known antioxidant that can be blended into a general rubber composition can be used, including, for example, phenol-based antioxidants, amine-based antioxidants, and sulfur-based antioxidants.

[0088] The phenolic antioxidant is preferably a hindered phenolic compound, such as 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4,4'-butylidenebis(6-tert-butyl-m-cresol), N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene, and 2,5-di-tert-butylhydroquinone.

[0089] Examples of the amine-based antioxidants include aromatic secondary amine-based antioxidants such as phenylbutylamine, N,N-di-2-naphthyl-p-phenylenediamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 2,2,4-trimethyl-1,2-dihydroquinoline polymers.

[0090] Examples of sulfur-based antioxidants include thioether-based antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0091] The antioxidant may be used alone or in combination of two or more. The case where the composition of the present disclosure contains an antioxidant will be described below: The content of the antioxidant is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 7 parts by mass, still more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of copolymer (A).

[0092] (filler) The composition of the present disclosure may further contain a filler to improve physical properties such as tensile stress at break and tensile elongation at break. Known fillers that can be compounded in general rubber compositions can be used as the filler. Examples of fillers include titanium oxide, carbon black, calcium carbonate (e.g., heavy calcium carbonate, light calcium carbonate), talc, clay, kaolin, silica, and differential silicic acid. Among these, titanium oxide is preferably used.

[0093] The filler may be used alone or in combination of two or more. Cases in which the composition of the present disclosure contains a filler will be described below. In the composition of the present disclosure, the content of the filler is preferably 5 to 300 parts by mass, more preferably 10 to 270 parts by mass, even more preferably 20 to 240 parts by mass, and particularly preferably 30 to 220 parts by mass, relative to 100 parts by mass of copolymer (A). In one embodiment, the content of the filler may be, for example, 10 to 200 parts by mass, 20 to 100 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of copolymer (A).

[0094] (softener) The compositions of the present disclosure may further contain an emollient. The softener may be any known softener that can be incorporated into a typical rubber composition. Examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin, or derivatives thereof; synthetic polymers such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic oils, tall oil, and sub(factice). Among these, petroleum-based softeners and hydrocarbon-based synthetic oils are preferred. Among petroleum-based softeners, process oils are more preferred, with paraffin-based process oils being particularly preferred. The hydrocarbon synthetic oil is preferably an ethylene-α-olefin copolymer such as an ethylene-propylene copolymer, and commercially available products can be used as the copolymer. The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, and even more preferably propylene. Examples of commercially available products include Lucant HC-10, Lucant HC-20, Lucant HC-40, Lucant HC-100, Lucant HC-150, Lucant HC-600, and Lucant HC-2000 (all registered trademarks, manufactured by Mitsui Chemicals, Inc.).

[0095] The softener may be used alone or in combination of two or more kinds. The case where the composition of the present disclosure contains a softener will be described below. The content of the softener is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 10 to 120 parts by mass, per 100 parts by mass of copolymer (A). When the content of the softener is within the above range, a composition can be obtained that has little tack and is excellent in processability, heat aging resistance, mechanical properties, etc. When the composition of the present disclosure contains a softener, the softener is usually incorporated into the rubber component. Therefore, in calculating the solid content and the rubber fraction described below, the softener corresponds to the components other than the solvent in the coating composition.

[0096] (moisture absorbent) The compositions of the present disclosure may further contain a moisture absorbent. Examples of moisture absorbents include calcium oxide, silica gel, sodium sulfate, molecular sieves, zeolite, and white carbon. Of these, calcium oxide is preferred.

[0097] The moisture absorbent may be used alone or in combination of two or more kinds. The case where the composition of the present disclosure contains a moisture absorbent will be described below: The content of the moisture absorbent is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of copolymer (A).

[0098] (Reaction inhibitor) The reaction inhibitor is a compound that has the function of suppressing the crosslinking reaction (hydrosilylation reaction of an alkene) between, for example, an alkenyl group contained in the copolymer (A) and a hydrosilyl group contained in the hydrosilyl group-containing compound (Y). The composition containing the reaction inhibitor tends to have stable processability during kneading and molding.

[0099] Examples of the reaction inhibitor include benzotriazole; acrylonitrile; acetylene alcohols such as 1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1-ethynyl-1-cyclohexanol, and 3,5-dimethyl-1-hexyn-3-ol; N,N-diallylacetate; amide compounds such as N,N-diallylbenzamide, N,N,N',N'-tetraallyl-o-phthalic acid diamide, N,N,N',N'-tetraallyl-m-phthalic acid diamide, and N,N,N',N'-tetraallyl-p-phthalic acid diamide; and others, sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, and tetramethyltetravinylcyclotetrasiloxane. Among these compounds, acetylene alcohols such as 1-ethynyl-1-cyclohexanol are preferred.

[0100] The reaction inhibitor may be used alone or in combination of two or more. From the viewpoint of room temperature curability, the composition of the present disclosure preferably does not contain a reaction inhibitor. When a reaction inhibitor is blended, the content of the reaction inhibitor in the composition of the present disclosure is preferably 1.0 part by mass or less, more preferably 0.5 part by mass or less, per 100 parts by mass of copolymer (A) so as not to interfere with crosslinking at room temperature.

[0101] <Preparation of Composition> The composition of the present disclosure can be prepared, for example, by mixing the copolymer (A), the hydrosilyl group-containing compound (Y), the platinum catalyst, and the solvent, and, if necessary, the other components described above.

[0102] The composition of the present disclosure can be produced, for example, by a method comprising the steps of: (1) dissolving the copolymer (A) in a solvent to prepare a solution; and (2) adding the hydrosilyl group-containing compound (Y) and a platinum catalyst to the solution.

[0103] In step (1), the above-mentioned other components may be added as necessary. In step (1), for example, the copolymer (A) and, if necessary, the other components may be masticated or kneaded, and the resulting masticated or kneaded product may be mixed with a solvent. Note that the solution may contain components that are insoluble or have low solubility in the solvent, such as a filler, and such a case is also referred to as a "solution."

[0104] In step (1), the components may be masticated or kneaded using a kneading device such as a Banbury mixer, a kneader, or an internal mixer. The mastication or kneading temperature in step (1) is preferably 80 to 170°C, more preferably 110 to 170°C, and even more preferably 130 to 170°C. The mastication or kneading time in step (1) is preferably 1 to 10 minutes, and more preferably 2 to 8 minutes.

[0105] The temperature for preparing the solution in step (1) is preferably 0 to 100°C, more preferably 5 to 50°C, and even more preferably 10 to 40°C, and may be, for example, 40°C or lower, or 30°C or lower. The solution obtained in step (1) may be stirred as needed.

[0106] In step (2), the hydrosilyl group-containing compound (Y) and a platinum catalyst are added to the solution obtained in step (1). In step (2), the above-mentioned other components may be added as necessary. The temperature of the solution in step (2) is preferably 0 to 100° C., more preferably 5 to 50° C., and even more preferably 10 to 40° C., and may be, for example, 40° C. or lower, or 30° C. or lower. It is preferable to carry out step (2) while maintaining the temperature of the solution within the above range. The coating composition obtained in step (2) may be stirred as needed.

[0107] When at least one selected from the group consisting of an antioxidant, a filler, a softener, an activator, a processing aid, a plasticizer, a tackifier, a colorant, and a polymer other than the copolymer (A) is added as another component, it is preferable to add it before the above kneading. When at least one selected from the group consisting of a moisture absorbent, a reaction inhibitor, an organic peroxide, a crosslinking aid, a crosslinking accelerator, and a foaming agent is added, it is preferable to add it after the above kneading.

[0108] The coating composition of the present disclosure can be cured (crosslinked) at room temperature, i.e., has excellent room temperature curability (room temperature crosslinkability). Furthermore, the coating layer formed from the coating composition of the present disclosure has excellent weather resistance because it is a crosslinked system of copolymer (A) and compound (Y). Conventional waterproof coating materials containing urethane-based resins do not have sufficient weather resistance and may require the provision of a top coat layer on the layer formed from the waterproof coating material. However, when the coating composition of the present disclosure is used as a waterproof coating material, the provision of such a top coat layer is not necessarily required. However, the present disclosure does not in any way preclude the provision of a top coat layer on the coating layer. The coating composition of the present disclosure can be used as a substitute for waterproof coating materials containing urethane-based resins. The coating layer formed from the coating composition of the present disclosure may be used as a top coat layer provided on a conventionally known coating film. As described above, the coating layer has excellent weather resistance.

[0109] [Application] The coating composition of the present disclosure can be used, for example, as a protective or modifying material for a substrate, a material for imparting aesthetic appearance to a substrate, an adhesive between a substrate and other materials, a sealant, or a waterproof coating material, or a combination of two or more selected from the group consisting of these.

[0110] The coating composition of the present disclosure is suitable, for example, as a waterproof coating material or a covering material for building materials or structures. By using the coating composition of the present disclosure, for example, a highly reliable coating layer (e.g., a waterproof layer) can be formed. The composition can be used, for example, in both new construction and renovation work.

[0111] While heat is required to crosslink ethylene-α-olefin-non-conjugated polyene copolymers with sulfur or organic peroxides, the coating composition of the present disclosure can be cured at room temperature, making it possible to coat areas that cannot be heated. Therefore, the coating composition of the present disclosure is particularly suitable as a waterproof coating material.

[0112] A coating layer can be formed from the composition of the present disclosure. The coating layer can be produced, for example, by a method including the above-mentioned step (1), the above-mentioned step (2), and the step (3) of volatilizing at least a portion of the solvent contained in the coating composition obtained in the above-mentioned step (2) from the coating composition.

[0113] The coated substrate of the present disclosure includes a substrate and a coating layer formed from the coating composition of the present disclosure. The coating layer is provided on the substrate. The coated substrate may have a primer layer between the substrate and the coating layer that exhibits adhesion to both the substrate and the coating layer.

[0114] The coated substrate of the present disclosure can be produced, for example, by a method comprising step (I) of applying the coating composition of the present disclosure to a substrate, and step (II) of curing the applied composition to form a coating layer on the substrate.

[0115] In step (I), the coating composition can be applied to the substrate by, for example, applying it with a trowel, spatula, roller or brush, spraying, or dipping. The amount of the composition applied can be adjusted by the application method, the number of applications, the content of the solvent in the composition, the thickness of the coating layer, etc.

[0116] In step (3) and step (II), the curing conditions (crosslinking conditions) of the coating composition are not particularly limited. The curing temperature is preferably 0 to 100°C, more preferably 5 to 50°C, and even more preferably 10 to 40°C. The curing temperature may be, for example, 40°C or lower, or may be 30°C or lower. The coating composition can be dried and cured (crosslinked) at room temperature. The curing time is preferably 0.5 to 50 hours, more preferably 1 to 40 hours, and even more preferably 1 to 30 hours. In the above steps, at least a portion of the solvent is removed by volatilization from the coating composition.

[0117] In steps (3) and (II), the curing conditions for the coating composition are not limited to the above, and may be, for example, higher than 100°C and not higher than 200°C for 10 seconds to 2 hours, or 120 to 180°C for 20 seconds to 30 minutes.

[0118] Examples of the substrate include walls or floors of buildings such as houses or buildings (specifically, verandas, roofs, corridors, rooftops, and stands in the buildings); and silicone rubber molded products. Examples of the silicone rubber contained in the silicone rubber molded products include addition-curable silicone rubber, peroxide-curable silicone rubber, condensation-curable silicone rubber, and ultraviolet-curable silicone rubber.

[0119] Examples of materials for the substrate include mortar, concrete, ALC, plywood, stone, glass, porcelain tile, iron, aluminum, stainless steel, galvanized iron plate, copper plate, FRP, epoxy resin, vinyl chloride, lead, and EPDM rubber sheet.

[0120] The thickness of the coating layer formed from the coating composition of the present disclosure is preferably 20 to 4000 μm, more preferably 100 to 4000 μm, even more preferably 150 to 3000 μm, and particularly preferably 150 to 2000 μm.

[0121] An example of a coated substrate of the present disclosure is a fuel cell separator having a separator substrate, a silicone rubber layer formed on one or both surfaces of the separator substrate, and a coating layer formed from the coating composition of the present disclosure on the surface of the silicone rubber layer opposite to the surface that contacts the separator substrate.

[0122] Metals used as separator substrates include, for example, aluminum, iron, copper, zinc, nickel, stainless steel, brass, and titanium. The thickness of the silicone rubber layer is preferably 50 to 5000 μm, more preferably 100 to 3000 μm, and the thickness of the coating layer is preferably 20 to 4000 μm, more preferably 150 to 3000 μm.

[0123] [Example of situation] The present disclosure relates to, for example, the following [1] to

[10] . [1] An ethylene-α-olefin-non-conjugated polyene copolymer (A) comprising: a structural unit derived from ethylene [A1]; a structural unit derived from an α-olefin [A2] having 3 to 20 carbon atoms; and a structural unit derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures selected from the group consisting of the following formulas (I) and (II): a hydrosilyl group-containing compound (Y) which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule; A platinum-based catalyst; a solvent; A coating composition comprising: [ka] [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , hydrogen atoms, and R a -[O-Si(R 1 )(R a )]-, -[O-Si(R 1 )H]- and -[O-Si(R 1 )(R 2 The structural units of n=1, n=2, and n=3 may be arranged in a block fashion or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms. [2] The coating composition according to [1], wherein the content of the solvent is 50% by mass or more and less than 100% by mass when the entire coating composition is taken as 100% by mass. [3] The coating composition according to [1] or [2], wherein the solvent comprises a hydrocarbon organic solvent. [4] The coating composition according to any one of [1] to [3] above, wherein the copolymer (A) satisfies the following requirements (i) and (ii): Requirement (i): the ratio [(A1) / (A2)] of the molar fraction (A1) of the structural units derived from the ethylene [A1] to the molar fraction (A2) of the structural units derived from the α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of the structural units derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A). [5] The coating composition according to any one of [1] to [4], wherein the weight average molecular weight (Mw) of the copolymer (A) measured by 3D-GPC in terms of polystyrene is 10,000 to 600,000. [6] The coating composition according to [4] or [5], wherein the copolymer (A) satisfies the following requirements (iii) and (iv): Requirement (iii): the weight-average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×[A3] mass fraction / 100 / [A3] molecular weight≦80 (1) Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / s obtained by linear viscoelasticity measurement (190 ° C) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency of ω=100 rad / sec * (ω=100) (Pa·sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ [A3] mass fraction × 6 (2) [7] The coating composition according to any one of [1] to [6] above, which is used as a protective or modifier for a substrate, a material for imparting aesthetic appearance to a substrate, an adhesive for connecting a substrate with other materials, a sealant, or a waterproof coating material, or a combination of two or more selected from the group consisting of these. [8] A coated substrate comprising a substrate and a coating layer formed from the coating composition according to any one of [1] to [7], wherein the coating layer is provided on the substrate. [9] A step (1) of dissolving an ethylene-α-olefin-non-conjugated polyene copolymer (A) containing structural units derived from ethylene [A1], structural units derived from an α-olefin [A2] having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures selected from the group consisting of the following formulas (I) and (II), in a solvent to prepare a solution; a step (2) of obtaining a coating composition by adding a hydrosilyl group-containing compound (Y), which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule, and a platinum catalyst to the solution; (3) a step of volatilizing at least a portion of the solvent from the coating composition; A method for producing a coating layer, comprising: [ka] [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , hydrogen atoms, and R a -[O-Si(R 1 )(R a )]-, -[O-Si(R 1 )H]- and -[O-Si(R 1 )(R 2 The structural units of n=1, n=2, and n=3 may be arranged in a block fashion or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

[10] The method for producing a coating layer according to [9], wherein the step (3) is carried out at 30°C or lower. [Example]

[0124] The composition of the present disclosure will be described in more detail below based on examples, but the composition of the present disclosure is not limited to these examples.

[0125] [Physical properties of copolymer (A)] The physical properties of the copolymer (A) were measured as follows.

[0126] <Composition of Copolymer (A)> The content of each structural unit in the copolymer (A) is: 13 The C-NMR spectrum of copolymer (A) was calculated using an ECX400P nuclear magnetic resonance spectrometer (manufactured by JEOL Ltd.) under the conditions of a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000. 13 C-NMR spectrum was measured.

[0127] <Intrinsic viscosity> The intrinsic viscosity [η] of the copolymer (A) was measured using a fully automatic intrinsic viscometer (manufactured by Rigo Co., Ltd.) under the conditions of a temperature of 135° C. and a measurement solvent of decalin.

[0128] <3D-GPC conditions> The weight average molecular weight (Mw) and the number of long chain branches per 1000 carbon atoms (LCB) of copolymer (A) 1000C ) is a value determined by a structural analysis method using 3D-GPC. Specifically, the absolute molecular weight distribution was determined using a 3D-high temperature GPC device PL-GPC220 (manufactured by Polymer Laboratories), and the intrinsic viscosity was determined simultaneously using a viscometer. The main measurement conditions were as described above. The number of long chain branches (LCB) per 1000 carbon atoms 1000C ) was calculated using the method described above.

[0129] <Complex viscosity η * > The rheometer used was a viscoelasticity measuring device, Ares (manufactured by Rheometric Scientific), and the complex viscosity η was measured at a frequency of ω = 0.1 rad / s under the conditions of 190°C and 1.0% strain. * (ω=0.1) , and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) From the results obtained, η * (ω=0.1) and η * (ω=100) The P value (η * (ω=0.1) / η * (ω=100) ) was calculated.

[0130] [Production Example 1: Production of Ethylene-Propylene-VNB Copolymer (A-1)] A 300-liter polymerization reactor was continuously fed with purified dehydrated hexane solvent at 25.4 L / hr through line 1, triisobutylaluminum (TiBA) at 20 mmol / hr, (C6H5)3CB(C6F5)4 at 0.075 mmol / hr, and di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride at 0.015 mmol / hr through line 2. Ethylene, propylene, hydrogen, and VNB were simultaneously fed at 4.7 kg / hr, 4.3 kg / hr, 220 L / hr, and 240 g / hr, respectively, through separate lines. The polymerization was carried out at a temperature of 110°C, a total pressure of 1.7 MPaG, and a residence time of 40 minutes. Thus, ethylene-propylene-VNB copolymer (A-1) was obtained.

[0131] [Table 1]

[0132] [Production Example 2: Production of Compound (Y-1)] A reactor was charged with 536 g of methylhydrogenpolysiloxane represented by the following formula (Y1b) and heated to 40°C while stirring under a nitrogen flow. 0.4 g of a toluene solution of platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex (Pt concentration 0.3 wt%) was added, and 265 g of α-methylstyrene was added dropwise while maintaining the reaction temperature at 40 to 90°C.

[0133] After the dropwise addition, stirring was continued for 2 hours at 85°C, and then 0.5 g of the reaction solution was sampled and confirmed to be about 36% by alkali decomposition gas generation method (remaining Si-H groups were decomposed with an ethanol / aqueous solution of KOH, and the reaction rate of Si-H groups was calculated from the volume of generated hydrogen gas). The reaction solution was then heated to 135°C under reduced pressure for 2 hours to distill off low boiling points, yielding 673 g of compound (Y-1).

[0134] The obtained compound (Y-1) is 29 The compound (Y-1) was confirmed to be a compound represented by the following formula (Y1a) by Si-NMR. The viscosity of the obtained compound (Y-1) was measured at 25°C using an Ubbelohde viscometer according to JIS Z8803:2011. 2 / s.

[0135] [ka]

[0136] The raw materials used in the examples are listed below. EPDM1: Ethylene-propylene-ENB copolymer (trade name: Mitsui EPT™ X-4010M (Mitsui Chemicals, Inc.)), ML(1+4)100°C (ASTM D1646): 8, ethylene content (ASTM D3900): 54% by mass, ENB content (ASTM D6047): 7.6% by mass, [η]: 1.03 dL / g, specific gravity: 0.87 Antioxidant: Amine-ketone antioxidant (Nocrac 224, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., 2,2,4-trimethyl-1,2-dihydroquinoline polymer) Filler: Ishihara Sangyo Kaisha, Ltd., R-820, titanium oxide Softener 1: Ethylene-propylene copolymer (Product name: Lucant HC-2000 (Mitsui Chemicals, Inc.)) Softener 2: Ethylene-propylene copolymer (Product name: Lucant HC-40 (Mitsui Chemicals, Inc.)) Softener 3: Paraffin-based process oil (Product name: Diana Process Oil PW-32 (Idemitsu Kosan Co., Ltd.) Peroxide: Nouryon Chemical Co., Ltd., DCP-40C, containing dicumyl peroxide Platinum catalyst: NE Chemcat, 3% Pt-VTS-IPA solution, catalyst solution containing approximately 10% by mass of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane platinum complex

[0137] [Example 1] The ethylene-propylene-VNB copolymer (A-1) obtained in Production Example 1 was dissolved in toluene to obtain a solution. Then, 3 parts by mass of compound (Y-1) as a crosslinking agent was added to the solution per 100 parts by mass of copolymer (A-1), and the mixture was stirred for 5 minutes using a mechanical stirrer. Next, 0.8 parts by mass of a platinum-based catalyst (the catalyst solution described above) was added, and the mixture was stirred for 5 minutes. In this way, a coating composition was prepared. The toluene content of the resulting coating composition was 90% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 10% by mass.

[0138] [Example 2] In the first stage, 100 parts by mass of the ethylene-propylene-VNB copolymer (A-1) obtained in Production Example 1 was masticated for 1 minute using a BB-4 Banbury mixer (Kobe Steel, Ltd.), to which 40 parts by mass of a filler (R-820) and 1 part by mass of an antioxidant (Nocrac 224) were then added and kneaded for 2 minutes at 140°C. The ram was then raised and cleaned, and kneading was continued for another 1 minute. The kneaded product was then discharged at approximately 150°C to obtain the first-stage compound. Next, in the second step, the mixture obtained in the first step was mixed with toluene to obtain a solution. Then, 3 parts by mass of compound (Y-1) as a crosslinking agent was added to the above solution relative to 100 parts by mass of copolymer (A-1), and the mixture was stirred for 5 minutes using a mechanical stirrer. Then, 0.8 parts by mass of a platinum-based catalyst (the above catalyst solution) was added, and the mixture was stirred for 5 minutes. A coating composition was prepared in this manner. The toluene content of the resulting coating composition was 90% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 10% by mass.

[0139] [Example 3] A coating composition was prepared in the same manner as in Example 2, except that the above blend was mixed with toluene so that the final rubber fraction would be 20% by mass. The toluene content of the resulting coating composition was 80% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 20% by mass.

[0140] [Example 4] A coating composition was prepared in the same manner as in Example 2, except that the above blend was mixed with a mixed solvent of toluene:cyclohexane = 50:50 (mass ratio). The total content of toluene and cyclohexane in the obtained coating composition was 90 mass%, and the total content of components other than toluene and cyclohexane (i.e., rubber fraction) was 10 mass%.

[0141] [Example 5] A coating composition was prepared in the same manner as in Example 2, except that the amount of filler blended in the first stage was 160 parts by mass and the blend was mixed with toluene so that the final rubber fraction would be 30% by mass. The toluene content of the resulting coating composition was 70% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 30% by mass.

[0142] [Example 6] A coating composition was prepared in the same manner as in Example 5, except that the above blend was mixed with toluene so that the final rubber fraction would be 45% by mass. The toluene content of the resulting coating composition was 55% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 45% by mass.

[0143] [Example 7] A coating composition was prepared in the same manner as in Example 6, except that the amount of filler blended in the first stage was 200 parts by mass, and 100 parts by mass of softener 1 was blended in the first stage. The toluene content of the obtained coating composition was 55% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 45% by mass.

[0144] [Example 8] A coating composition was prepared in the same manner as in Example 7, except that in the first step, Softener 2 was used instead of Softener 1. The toluene content of the obtained coating composition was 55 mass %, and the total content of components other than toluene (i.e., rubber fraction) was 45 mass %.

[0145] [Example 9] A coating composition was prepared in the same manner as in Example 7, except that in the first step, Softener 3 was used instead of Softener 1. The toluene content of the obtained coating composition was 55 mass %, and the total content of components other than toluene (i.e., rubber fraction) was 45 mass %.

[0146] [Comparative Example 1] A coating composition was prepared in the same manner as in Example 2, except that EPDM1 was used instead of copolymer (A-1), and 6.8 parts by mass of peroxide (DCP-40C) was added as a crosslinking agent instead of compound (Y-1) and a platinum catalyst. The toluene content of the resulting coating composition was 90% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 10% by mass.

[0147] Comparative Example 2 A coating composition was prepared in the same manner as in Example 2, except that 6.8 parts by mass of peroxide (DCP-40C) was added as a crosslinking agent instead of compound (Y-1) and the platinum-based catalyst. The toluene content of the resulting coating composition was 90% by mass, and the total content of components other than toluene (i.e., rubber fraction) was 10% by mass.

[0148] Comparative Example 3 A coating composition was prepared in the same manner as in Example 2, except that EPDM1 was used instead of copolymer (A-1). The toluene content of the obtained coating composition was 90 mass %, and the total content of components other than toluene (i.e., rubber fraction) was 10 mass %.

[0149] [Curing property evaluation method] 50 g of the coating composition prepared above was poured onto a glass petri dish, and after leaving it to stand at room temperature (23°C) for 24 hours, curability was evaluated. The curability was evaluated by whether the sample stuck to the bottom of the glass petri dish returned to its original state when removed. Hardening: Elongation returns to normal Does not harden: stretch does not return to its original state

[0150] [Table 2]

Claims

1. an ethylene / α-olefin / non-conjugated polyene copolymer (A) comprising: a structural unit derived from ethylene [A1]; a structural unit derived from an α-olefin [A2] having 3 to 20 carbon atoms; and a structural unit derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures selected from the group consisting of the following formulas (I) and (II); a hydrosilyl group-containing compound (Y), which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule; A platinum-based catalyst; a solvent; A coating composition comprising: 【Chemistry 1】 [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , a hydrogen atom, and R a is selected from the group consisting of —[O—Si(R 1 ) (R a )]-,-[O-Si(R 1 )H]- and -[O-Si(R 1 ) (R 2 ) )]- may be arranged in a block form or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

2. 2. The coating composition according to claim 1, wherein the content of the solvent is 50% by mass or more and less than 100% by mass when the entire coating composition is taken as 100% by mass.

3. The coating composition according to claim 1 , wherein the solvent comprises a hydrocarbon organic solvent.

4. 2. The coating composition according to claim 1, wherein the copolymer (A) satisfies the following requirements (i) and (ii): Requirement (i): the ratio [(A1) / (A2)] of the molar fraction (A1) of the structural units derived from the ethylene [A1] to the molar fraction (A2) of the structural units derived from the α-olefin [A2] having 3 to 20 carbon atoms is 40 / 60 to 99.9 / 0.1; Requirement (ii): The mass fraction of the structural units derived from the non-conjugated polyene [A3] is 0.07 to 10 mass % in 100 mass % of the copolymer (A).

5. 2. The coating composition according to claim 1, wherein the copolymer (A) has a weight average molecular weight (Mw) of 10,000 to 600,000 in terms of polystyrene as measured by 3D-GPC.

6. The coating composition according to claim 4, wherein the copolymer (A) satisfies the following requirements (iii) and (iv): Requirement (iii): the weight average molecular weight (Mw) of the copolymer (A), the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]), and the molecular weight of the non-conjugated polyene [A3] (molecular weight of [A3]) satisfy the following formula (1): 4.5≦Mw×mass fraction of [A3] / 100 / molecular weight of [A3]≦80 (1) Requirement (iv): Complex viscosity η at a frequency ω = 0.1 rad / sec obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer * (ω=0.1) (Pa·sec) and the complex viscosity η at a frequency ω = 100 rad / sec * (ω=100) (Pa sec) and the ratio P(η * (ω=0.1) / η * (ω=100) ), the intrinsic viscosity [η] (dL / g), and the mass fraction of the structural unit derived from the non-conjugated polyene [A3] (mass fraction (mass%) of [A3]) satisfy the following formula (2): P / ([η] 2.9 ) ≦ mass fraction of [A3] × 6 (2)

7. The coating composition according to any one of claims 1 to 6, which is used as any one of a protective material or modifier for a substrate, a material for imparting beauty to a substrate, an adhesive between a substrate and other materials, a sealant, and a waterproof coating material, or a combination of two or more selected from the group consisting of these.

8. A substrate and a coating layer formed from the coating composition according to any one of claims 1 to 6, A coated substrate, wherein the coating layer is provided on the substrate.

9. a step (1) of dissolving an ethylene / α-olefin / non-conjugated polyene copolymer (A) containing structural units derived from ethylene [A1], structural units derived from an α-olefin [A2] having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene [A3] containing, in one molecule, two or more partial structures in total, each of which is at least one type selected from the group consisting of the following formulas (I) and (II), in a solvent to prepare a solution; a step (2) of adding a hydrosilyl group-containing compound (Y), which is an organohydrogenpolysiloxane represented by the following formula (Y1) and which has at least one silicon-bonded aralkyl group and at least two silicon-bonded hydrogen atoms in each molecule, and a platinum-based catalyst to the solution to obtain a coating composition; (3) a step of volatilizing at least a portion of the solvent from the coating composition; A method for producing a coating layer, comprising: 【Chemistry 2】 [In formula (Y1), n ​​and p each independently represent 0 or a positive number, m represents 1 to 20, the sum of n, m, and p represents 5 to 50, and a plurality of R 1 and R 2 are each independently a monovalent alkyl group, and R a is an aralkyl group, and two R are each independently R 1 , R 2 , a hydrogen atom, and R a is selected from the group consisting of —[O—Si(R 1 ) (R a )]-,-[O-Si(R 1 )H]- and -[O-Si(R 1 ) (R 2 ) )]- may be arranged in a block form or randomly, provided that when n=1, at least one of the two R's is a hydrogen atom, and when n=0, both of the two R's are hydrogen atoms.

10. The method for producing a coating layer according to claim 9, wherein the step (3) is carried out at 30°C or lower.

Images