Roofing components

Abstract

Provided is a roof member having good adhesiveness of a top layer thereof.　This roof member comprises a substrate, a polyurethane layer disposed on the substrate, and a top layer disposed on the polyurethane layer. At least a portion of the polyurethane layer is formed of a polyurethane foam layer, and the top layer includes a fluorine-containing polymer.

Description

Technical Field

[0001] The present invention relates to a roof member.

Background Art

[0002] As a method for repairing a roof, there is a method of forming a layer containing a resin on a base material of the roof. Patent Document 1 discloses a construction structure for forming a heat-insulating foam layer, a reinforcing waterproof layer, and a surface layer on a base material such as a predetermined roof.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] For the roof member as described above, it is preferable that the adhesion of each layer is good. As a result of the inventors' examination of the construction structure described in Patent Document 1, it was found that the adhesion of the surface layer (top layer) is not sufficient. Therefore, an object of the present invention is to provide a roof member having good adhesion of the top layer.

Means for Solving the Problems

[0005] As a result of intensive studies, the inventors have found that the problems can be solved by the following configuration. [1] A roof member having a base material, a polyurethane layer disposed on the base material, and a top layer disposed on the polyurethane layer, wherein at least a part of the polyurethane layer is composed of a foamed polyurethane layer, and the top layer contains a fluorine-containing polymer. [2] The roof member according to [1], wherein the fluorine-containing polymer has units based on one or more monomers selected from the group consisting of vinyl ether and vinyl ester. [3] The roofing member according to [1] or [2], wherein the fluorine atom content in the fluorine-containing polymer is 1 to 80% by mass. [4] Any of the roof members from [1] to [3], wherein the glass transition temperature of the fluorine-containing polymer is 100°C or less. [5] A roof member of any of [1] to [4] having a crosslinked structure in the fluorine-containing polymer.

[0006] [6] A roof member according to any of [1] to [5], wherein the fluorine-containing polymer is a fluorine-containing polymer having polar crosslinkable groups, or a crosslinked product of a fluorine-containing polymer having polar crosslinkable groups. [7] The roof member of [6] wherein the fluorine-containing polymer having polar crosslinkable groups is a fluorine-containing polymer having hydroxyl groups. [8] The roofing member of [7], wherein the hydroxyl value of the fluorine-containing polymer having hydroxyl groups is 20 to 100 mg KOH / g. [9] Any of the roof members from [1] to [8], wherein the glass transition temperature of the top layer is 100°C or less.

[10] The roof member of any of [1] to [9], wherein the top layer further comprises a pigment.

[11] Any of the roof members from [1] to

[10] , wherein the growth rate of the top layer is 1.0% or more.

[0007]

[12] A roofing member of any of [1] to

[11] , wherein the base material is slate.

[13] A roof member according to any of [1] to

[12] , wherein the polyurethane layer comprises, from the substrate side, a foamed polyurethane layer and a non-foamed polyurethane layer in that order.

[14] Any of the roof members from [1] to

[13] , wherein the ratio of the thickness of the top layer to the foamed polyurethane layer is 0.00001 to 1.0. [Effects of the Invention]

[0008] According to the present invention, a roofing member with good adhesion of the top layer can be provided. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic side view showing an example of a roofing member of the present invention. [Modes for carrying out the invention]

[0010] The meanings of the terms used in this invention are as follows: (Meth)acrylate is a general term for acrylate and methacrylate. Similarly, (meth)acrylic acid is a general term for acrylic acid and methacrylic acid. Furthermore, (meth)acrylic resin refers to a resin composed mainly of polymers based on (meth)acrylate units. In polymers, a unit is a general term for atomic groups formed directly by the polymerization of monomers, based on a single monomer molecule, and atomic groups obtained by chemically transforming a portion of the above atomic group after polymerization. The content (mol%) of each unit relative to the total number of units in the polymer is determined by analyzing the polymer using nuclear magnetic resonance spectroscopy (NMR). The hydroxyl value is a value measured according to the method of JIS K 0070-3 (1992). The glass transition temperature (Tg) of the top layer is the temperature at which the maximum tanδ (loss tangent) value is observed, measured using DMA (dynamic viscoelasticity measurement). The glass transition temperature (Tg) is the value of the intermediate glass transition temperature measured by differential scanning calorimetry (DSC). The number-average molecular weight (Mn) is a value measured by gel permeation chromatography using polystyrene as the standard substance.

[0011] The thickness of the roofing material is measured using an eddy current thickness gauge. For example, the EDY-5000 manufactured by Sanko Electronics Co., Ltd. can be used as an eddy current thickness gauge. The thickness of each layer in the roofing material is measured by observing the cross-section of the roofing material using a scanning electron microscope equipped with an energy-dispersive X-ray analyzer. The mass of solids in a composition refers to the mass remaining after removing the solvent from the composition, if the composition contains a solvent. Components other than the solvent in the composition are considered solids, even if their liquid state is one. The mass of solids in a composition is determined by heating 1 g of the composition at 130°C for 20 minutes.

[0012] The roofing member of the present invention (hereinafter also referred to as "this roofing member") comprises a base material, a polyurethane layer disposed on the base material, and a top layer disposed on the polyurethane layer, wherein at least a portion of the polyurethane layer is composed of a foamed polyurethane layer, and the top layer contains a fluorine-containing polymer. The mechanism by which the top layer of a roof component with such a structure adheres well is not entirely clear, but it is thought to be as follows. In other words, the top layer of this roofing component contains a fluorine-containing polymer. This top layer has good adhesion to the polyurethane layer, and it is believed that the adhesion of the top layer is improved.

[0013] First, I will explain the structure of the main roof components, referring to the drawings. Figure 1 is a schematic side view showing the layer structure of a roof member 10 (this roof member), which is one embodiment of the present invention. The roof member 10 has a base material 12, a foamed polyurethane layer 14, a non-foamed polyurethane layer 16, and a top layer 18, with each layer arranged in this order. In Figure 1, the foamed polyurethane layer 14 and the non-foamed polyurethane layer 16 together form a polyurethane layer 20. Figure 1 shows a configuration in which the polyurethane layer 20 has both a foamed polyurethane layer 14 and a non-foamed polyurethane layer 16, but the non-foamed polyurethane layer 16 may be omitted. In other words, the foamed polyurethane layer 14 may be the polyurethane layer 20 itself. The roof member 10 may have other layers, as long as it does not contradict the spirit of the present invention.

[0014] The following provides a detailed description of each component that makes up this roof structure.

[0015] This roofing component has a base material. The base material may be a non-metallic material (such as slate, roof tiles, concrete, waterproof resin sheets, or wood) or a metallic material. In particular, slate is preferred as the base material from the standpoint of weather resistance of the roofing material. The thickness of the base material is preferably 0.5 to 50 mm, and particularly preferably 1 to 20 mm.

[0016] This roofing component has a polyurethane layer. The polyurethane layer is composed of at least a portion of a foamed polyurethane layer. The foamed polyurethane layer refers to a layer containing foamed polyurethane. From the viewpoint of the thermal insulation properties of the roofing material, the thickness of the foamed polyurethane layer is preferably 0.5 to 50 mm, and particularly preferably 1 to 20 mm. Examples of foamed polyurethanes include foamed polyurethanes formed by the reaction and curing of a foamed polyurethane raw material mixture containing a polyol, which is a compound having two or more hydroxyl groups (e.g., 2 to 10), a polyisocyanate and / or an isocyanate-terminated polyurethane prepolymer, and a blowing agent. As the polyol, polyether polyols and polyester polyols are preferred, with polyether polyols being particularly preferred. The hydroxyl value of the polyol is preferably 300 to 800 mg KOH / g. The number of hydroxyl groups of the polyol is preferably 3 to 8. Examples of polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, the polyisocyanate described as a curing agent in composition (f) described later, and polymers and modified forms of these polyisocyanates. Tolylene diisocyanate and diphenylmethane diisocyanate are preferred as polyisocyanates. An isocyanate-terminated polyurethane prepolymer is a prepolymer having isocyanate groups, obtained by reacting a polyol with an excess equivalent amount of polyisocyanate. Examples of blowing agents include water, low-boiling point fluorinated hydrocarbons, and low-boiling point hydrocarbons, with water alone or water in combination with other blowing agents being particularly preferred. The foamed polyurethane raw material mixture described above may contain components other than those listed above. Examples of other components include catalysts, crosslinking agents, chain extenders, flame retardants, fillers, and reinforcing fibers. The foamed polyurethane layer is preferably formed by mixing raw material components immediately before application to form a foamed polyurethane raw material mixture, applying the foamed polyurethane raw material mixture to a substrate, and foaming and curing the foamed polyurethane raw material mixture on the substrate. The foamed polyurethane raw material mixture is preferably formed by mixing a first component containing a polyol or foaming agent and a second component containing a polyisocyanate immediately before application. Application methods include, for example, application methods using a spray, applicator, die coater, bar coater, roll coater, comma coater, etc., with the use of a spray being preferred. In particular, the use of a spray that mixes the first and second components and sprays them is preferred.

[0017] The polyurethane layer may also preferably have a non-foamed polyurethane layer. The non-foamed polyurethane layer refers to a layer containing non-foamed polyurethane. From the viewpoint of waterproofing the roofing material, the thickness of the non-foamed polyurethane layer is preferably 1 to 10,000 μm, and particularly preferably 10 to 1,000 μm. The non-foamed polyurethane layer may be located on the substrate side relative to the foamed polyurethane layer, or on the opposite side of the substrate relative to the foamed polyurethane layer. In particular, it is preferable that the polyurethane layer has a foamed polyurethane layer and a non-foamed polyurethane layer in that order from the substrate side. Examples of non-foaming polyurethane layers include layers formed by the reaction of a non-foaming polyurethane raw material mixture containing a compound having two or more hydroxyl groups (e.g., 2 to 10) and a polyisocyanate and / or isocyanate-terminated polyurethane prepolymer, and which does not contain a foaming agent such as water. Examples of polyols include polyether polyols, polyester polyols, and hydroxyl group-containing vinyl polymers, with polyether polyols being particularly preferred. The hydroxyl value of the polyol is preferably 50 to 800 mg KOH / g. Examples of polyisocyanates include the polyisocyanates mentioned above as raw materials for foamed polyurethane foam, and blocked polyisocyanates obtained by blocking the isocyanate groups thereof with a blocking agent. The above-mentioned non-foaming polyurethane raw material mixture may contain other components listed as raw materials for the foamed polyurethane foam, and may also contain a solvent. The non-foaming polyurethane layer is preferably formed by applying a non-foaming polyurethane raw material mixture to the surface on which the non-foaming polyurethane layer is to be formed, and then curing the non-foaming polyurethane raw material mixture on the surface. When a blocked polyisocyanate is used, after the coating film of the non-foaming polyurethane raw material mixture is formed, the coating film is heated to deblockize and cure it. Application methods include, for example, sprays, applicators, die coaters, bar coaters, roll coaters, comma coaters, roller brushes, brushes, and spatulas.

[0018] This roofing component has a top layer placed on top of the aforementioned polyurethane layer. The thickness of the top layer is preferably 1 to 1,000 μm, and particularly preferably 10 to 100 μm, from the viewpoint of the weather resistance of the roofing material. The top layer may be directly laminated on the foamed polyurethane layer described above, or it may be directly laminated on the non-foamed polyurethane layer described above. Furthermore, the ratio of the thickness of the top layer to the foamed polyurethane layer (thickness of the top layer / thickness of the foamed polyurethane layer) is preferably 0.00001 to 1.0, more preferably 0.0001 to 0.1, and particularly preferably 0.001 to 0.01. If the thickness ratio is within the above range, the performance of the roofing material will be maintained for a longer period of time.

[0019] The top layer's Tg is preferably 0°C or higher, more preferably 15°C or higher, and particularly preferably 20°C or higher. The above Tg is preferably 100°C or lower, more preferably 75°C or lower, even more preferably 55°C or lower, and particularly preferably 45°C or lower. If the top layer's Tg is within the above range, the top layer exhibits excellent flexibility, allows for easy adjustment of elongation, and provides excellent adhesion. Furthermore, it offers excellent water resistance, maintaining its appearance and adhesion even after water resistance testing.

[0020] The top layer is preferably flexible, and its elongation rate is preferably 1.0% or more, more preferably 2.0% or more, and particularly preferably 3.0% or more. The above elongation rate is preferably 100.0% or less, more preferably 50.0% or less, and particularly preferably 10.0% or less. If the elongation rate of the top layer is within the above range, the adhesion with the polyurethane layer will be further improved.

[0021] The top layer contains a fluorine-containing polymer. The above-mentioned fluorine-containing polymer may or may not have a crosslinked structure. In particular, from the viewpoint of weather resistance and water resistance of the top layer, it is preferable that the fluorine-containing polymer forms a crosslinked structure in the top layer. The characteristics of fluorine-containing polymers (preferred conditions, etc.) detailed below may be satisfied by fluorine-containing polymers having a crosslinked structure, by fluorine-containing polymers not having a crosslinked structure, or by both, unless otherwise specified. The following describes fluorine-containing polymers having a crosslinked structure, particularly fluorine-containing polymer F 1 In other words, fluorine-containing polymers that do not have a crosslinking structure are particularly referred to as fluorine-containing polymers F 0 It is also said that. Fluoropolymer F 0 Preferably, it is a fluorine-containing polymer that has crosslinkable groups but does not have a crosslinked structure. Fluoropolymer F 1 This is a fluorine-containing polymer F having a crosslinkable group. 0 It is preferable that it be a crosslinked product.

[0022] The top layer is preferably formed using a fluoropolymer F containing a unit based on a fluoroolefin (hereinafter also referred to as unit A1) and a unit having a crosslinkable group (hereinafter also referred to as unit A2). In other words, the top layer is preferably formed using a composition (hereinafter also referred to as composition (f)) containing the above fluoropolymer F. 0 When using the above fluoropolymer F, it is possible to react the crosslinkable group possessed by the fluoropolymer F to form a fluoropolymer F having a crosslinked structure. When reacting the crosslinkable group, a predetermined curing agent may be used as described later. 0 It is preferable that the fluoropolymer (fluoropolymer F and / or F) has a unit based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters. The above unit may correspond to unit A2 or unit A3 described later. The fluoropolymer F may also have two or more of unit A2 or unit A3 described later, and further may have both unit A2 and unit A3. 0 A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. The fluoroolefin may have one or more hydrogen atoms not substituted with fluorine atoms substituted with chlorine atoms. The number of carbon atoms of the fluoroolefin is preferably 2 to 8, particularly preferably 2 to 4. 0 Examples of fluoroolefins include CF2 = CF2, CF2 = CFCl, CF2 = CHF, CH2 = CF2, CF2 = CFCF3, CF2 = CHCF3, CF3CH = CHF, CF3CF = CH2. From the viewpoint of copolymerizability, CF2 = CF2, CF2 = CFCl, CF3CH = CHF, and CF3CF = CH2 are preferable, CF2 = CF2 and CF2 = CFCl are more preferable, and CF2 = CFCl is particularly preferable. 1 Fluoroolefins may be used in combination of two or more. The top layer is preferably formed using a fluoropolymer F containing a unit based on a fluoroolefin (hereinafter also referred to as unit A1) and a unit having a crosslinkable group (hereinafter also referred to as unit A2). In other words, the top layer is preferably formed using a composition (hereinafter also referred to as composition (f)) containing the above fluoropolymer F. 0 When using the above fluoropolymer F, it is possible to react the crosslinkable group possessed by the fluoropolymer F to form a fluoropolymer F having a crosslinked structure. When reacting the crosslinkable group, a predetermined curing agent may be used as described later. 1 It is preferable that the fluoropolymer (fluoropolymer F and / or F) has a unit based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters. The above unit may correspond to unit A2 or unit A3 described later. The fluoropolymer F may also have two or more of unit A2 or unit A3 described later, and further may have both unit A2 and unit A3. 0 A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. The fluoroolefin may have one or more hydrogen atoms not substituted with fluorine atoms substituted with chlorine atoms. The number of carbon atoms of the fluoroolefin is preferably 2 to 8, particularly preferably 2 to 4.

[0023] Examples of fluoroolefins include CF2 = CF2, CF2 = CFCl, CF2 = CHF, CH2 = CF2, CF2 = CFCF3, CF2 = CHCF3, CF3CH = CHF, CF3CF = CH2. From the viewpoint of copolymerizability, CF2 = CF2, CF2 = CFCl, CF3CH = CHF, and CF3CF = CH2 are preferable, CF2 = CF2 and CF2 = CFCl are more preferable, and CF2 = CFCl is particularly preferable. Fluoroolefins may be used in combination of two or more. A fluoroolefin is an olefin in which one or more hydrogen atoms are substituted with fluorine atoms. The fluoroolefin may have one or more hydrogen atoms not substituted with fluorine atoms substituted with chlorine atoms. The number of carbon atoms of the fluoroolefin is preferably 2 to 8, particularly preferably 2 to 4. The content of unit A1 is determined from the standpoint of the weather resistance of this roofing material, using fluorine-containing polymer F. 0 The amount is preferably 20 to 70 mol%, more preferably 40 to 60 mol%, and particularly preferably 45 to 55 mol% relative to the total units contained.

[0024] Unit A2 is preferably a unit based on a monomer having a crosslinking group (hereinafter also referred to as monomer A2). Unit A2 may have two or more crosslinking groups. Monomer A2 is preferably a compound that does not contain a fluorine atom. Furthermore, unit A2 may be a unit obtained by converting the crosslinking group contained in the unit to a different crosslinking group. Examples of such unit A2 include unit A2 obtained by reacting the hydroxyl group contained in the unit with a polycarboxylic acid or its acid anhydride, thereby converting some or all of the hydroxyl group to a carboxyl group. Examples of crosslinkable groups include hydroxyl groups, carboxyl groups, amino groups, alkoxysilyl groups, epoxy groups, and oxetanyl groups. Polar crosslinkable groups are preferred. Specific examples of polar crosslinkable groups include hydroxyl groups, carboxyl groups, and amino groups. When the crosslinkable group is a polar crosslinkable group, that is, when the fluorine-containing polymer is a fluorine-containing polymer having a polar crosslinkable group, or when it is a crosslinked product of a fluorine-containing polymer having a polar crosslinkable group, the urethane structure of the polyurethane is also polar, and therefore the fluorine-containing polymer (fluorine-containing polymer F 0 and / or F 1 This is preferable because it increases the affinity between the material and polyurethane, and improves the adhesion between the top layer and the polyurethane layer. Furthermore, as polar crosslinking groups, hydroxyl groups and carboxyl groups are preferred, with hydroxyl groups being particularly preferred, from the viewpoint of further improving the impact resistance, flexibility, and chemical resistance of the top layer.

[0025] Monomer A2, whose crosslinkable group is a hydroxyl group, includes allyl alcohol, and vinyl ethers, vinyl esters, allyl ethers, allyl esters, and (meth)acrylates having a hydroxyl group, and formula X 11-Z 11 A monomer represented by (hereinafter also referred to as monomer A21) is preferred. X 11 The compound is CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, with CH2=CHO- or CH2=CHCH2O- being preferred. Z 11 This is a monovalent organic group having 2 to 42 carbon atoms and containing a hydroxyl group. The above organic group may be linear or branched. Furthermore, the above organic group may consist of a ring structure or contain a ring structure. The above organic groups are preferably C2-C6 alkyl groups having a hydroxyl group, C6-C8 alkyl groups including a cycloalkylene group having a hydroxyl group, and polyoxyalkylene groups having a hydroxyl group.

[0026] A specific example of monomer A21 is CH2=CHO-CH2-cycloC6H 10 -CH2OH, CH2=CHCH2O-CH2-cycloC6H 10 -CH2OH, CH2=CHOCH2CH2OH, CH2=CHCH2OCH2CH2OH, CH2=CHOCH2CH2CH2CH2OH, CH2=CHCH2OCH2CH2CH2CH2OH, CH2=CHOCH2-cycloC6H 10 -CH2O(CH2CH2O) 15 H is one example. 10 - represents a cyclohexylene group, (-cycloC6H 10 The binding site for -) is usually 1,4-. Monomer A21 may be used in combination of two or more types.

[0027] Monomer A2, whose crosslinking group is a carboxyl group, is a polymerizable unsaturated carboxylic acid such as (meth)acrylic acid, and formula X 12 -Z 12 A monomer represented by (hereinafter also referred to as monomer A22) is preferred. X 12CH2=CH-, CH(CH3)=CH-, or CH2=C(CH3)-, and it is preferable that CH2=CH- or CH2=C(CH3)-. Z 12 This is a carboxyl group or a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms and a carboxyl group, and is preferably a carboxyl group or a carboxyalkyl group having 1 to 10 carbon atoms.

[0028] Examples of monomer A22 include CH2=CHCOOH, CH2=C(CH3)COOH, and CH2=CH(CH2). n1 COOH, CH2=C(CH3)(CH2) n1 Examples include compounds represented by COOH (where n1 is an integer between 1 and 10). Monomer A22 may be used in combination of two or more types.

[0029] For example, monomer A2 may be monomer A21, monomer A22, or both monomer A21 and monomer A22. The content of unit A2 is fluorine-containing polymer F 0 The amount is preferably 0.5 to 40 mol%, more preferably 3 to 35 mol%, and particularly preferably 4 to 15 mol% relative to the total units contained.

[0030] Fluoropolymer F 0 It is preferable that it further includes a unit (hereinafter also referred to as unit A3) based on one or more monomers selected from the group consisting of vinyl ethers, vinyl esters, allyl ethers, allyl esters, and (meth)acrylates (hereinafter also referred to as monomer A3), and it is particularly preferable that it has a unit based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters. Monomer A3 does not have a crosslinking group. It is preferable that monomer A3 does not contain fluorine atoms.

[0031] Unit A3 is given by equation X 2 -Y 2 A monomer-based unit represented by this unit is preferred. X2 The compound is CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, and from the viewpoint of excellent weather resistance of the fluorine-containing polymer, it is preferably CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-, and CH2=CHO- is particularly preferred.

[0032] Y 2 This is a monovalent hydrocarbon group having 1 to 24 carbon atoms. The monovalent hydrocarbon group may be linear or branched. Furthermore, the monovalent hydrocarbon group may consist of a ring structure or contain a ring structure. Furthermore, the monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. Preferred monovalent hydrocarbon groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and cycloalkylalkyl groups, with C2-C12 alkyl groups, C6-C10 cycloalkyl groups, C6-C10 aryl groups, C7-C12 aralkyl groups, and C6-C10 cycloalkylalkyl groups being particularly preferred. Examples of alkyl groups include methyl, ethyl, tert-butyl, hexyl, octyl (such as 2-ethylhexyl), nonyl, decyl, and dodecyl groups. Examples of cycloalkyl groups include the cyclohexyl group. An example of an aralkyl group is the benzyl group. Examples of cycloalkylalkyl groups include the cyclohexylmethyl group. Examples of aryl groups include the phenyl group and the naphthyl group. Furthermore, the hydrogen atoms of a cycloalkyl group or the cycloalkyl portion of a cycloalkylalkyl group, or the aryl portion of an aryl group or aralkyl group, may be substituted with alkyl groups. In this case, the number of carbon atoms of the alkyl group as a substituent is not included in the number of carbon atoms of the cycloalkyl group, cycloalkylalkyl group, aryl group, and aralkyl group.

[0033] Monomer A3 may be used in combination of two or more types. Examples of monomer A3 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl neononanoate (HEXION product name "Beova 9"), vinyl neodecanoate (HEXION product name "Beova 10"), vinyl versatate, vinyl benzoate, tert-butyl vinyl benzoate, tert-butyl (meth)acrylate, and benzyl (meth)acrylate. The content of unit A3 is fluorine-containing polymer F 0 The amount is preferably 1 to 60 mol%, more preferably 10 to 55 mol%, and particularly preferably 30 to 50 mol% relative to the total units contained.

[0034] Fluorine-containing polymer (Fluorine-containing polymer F 0 and / or F 1 The fluorine atom content of the polymer is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass, relative to the total mass of the fluorine-containing polymer. When the fluorine atom content is within the above range, the weather resistance and adhesion of the top layer are superior.

[0035] Fluoropolymer F 0 is a fluorine-containing polymer F 0 It is preferable that, relative to all units contained, units A1, A2, and A3 are included in the following order: 20-70 mol%, 0.5-40 mol%, and 1-60 mol%, more preferably 40-60 mol%, 3-35 mol%, and 10-55 mol%, and particularly preferably 45-55 mol%, 4-15 mol%, and 30-50 mol%.

[0036] Fluorine-containing polymer F having hydroxyl groups 0 The hydroxyl value is preferably 1 to 200 mg KOH / g, more preferably 20 to 100 mg KOH / g, even more preferably 35 to 65 mg KOH / g, and particularly preferably 45 to 65 mg KOH / g. In this case, fluorine-containing polymer F0 or a fluorine-containing polymer F which is a crosslinked product thereof. 1 However, it has excellent affinity with polyurethane, and the adhesion between the top layer and the polyurethane layer is easily improved.

[0037] Fluorine-containing polymer (Fluorine-containing polymer F 0 and / or F 1 The Tg of the ) is preferably 0°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, and particularly preferably 30°C or higher. The above Tg is preferably 100°C or lower, more preferably 75°C or lower, and particularly preferably 55°C or lower. By adjusting the above Tg to the above range, the flexibility of the top layer is further improved. In addition, the appearance of the roof member is less likely to be damaged when water is absorbed.

[0038] Fluoropolymer F 0 The manganese (Mn) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, and particularly preferably 15,000 or more. The above Mn is preferably 50,000 or less, and more preferably 25,000 or less. By adjusting the above Mn to the above range, the stretchability and strength of the top layer are better balanced.

[0039] Fluoropolymer F 0 The preferred specific embodiments are as follows: Fluorine-containing polymer F comprising: Unit A1 based on CF2=CFCl; Unit A2 based on one or more monomers selected from the group consisting of vinyl ethers having hydroxyl groups and allyl ethers having hydroxyl groups; and Unit A3 based on one or more elements selected from the group consisting of vinyl ethers and vinyl esters that do not have crosslinking groups. 0 . A fluorine-containing polymer F comprising unit A1 based on CF2=CFCl, unit A2 based on one or more monomers selected from the group consisting of vinyl ethers having hydroxyl groups and allyl ethers having hydroxyl groups, and unit A3 based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters that do not have crosslinking groups, wherein the content of the above units relative to the total units of the fluorine-containing polymer is 40-60 mol%, 3-35 mol%, and 10-55 mol%, respectively. 0 . A fluorine-containing polymer F comprising unit A1 based on CF2=CFCl, unit A2 based on vinyl ether having a hydroxyl group, and unit A3 based on vinyl ether without a crosslinking group, wherein the content of the above units relative to the total units of the fluorine-containing polymer is 45-55 mol%, 4-15 mol%, and 30-50 mol%, respectively. 0 . In the above embodiment, the fluorine-containing polymer F 0 In the units included, the alternating copolymerization rate between unit A1 and units other than unit A1 tends to be high, resulting in excellent weather resistance of this roofing material.

[0040] Fluoropolymer F 0 You may use two or more types. Fluorine-containing polymer F in composition (f) 0 The content of is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and particularly preferably 50 to 70% by mass, based on the total solid content of composition (f).

[0041] Composition (f) may optionally contain a fluorine-containing polymer F 0 Other components (hereinafter also referred to as additives) may be included. Examples of such components include fluorine-containing polymer F 0Other polymers, curing agents, curing catalysts, solvents, fillers (inorganic fillers such as silica, organic fillers such as resin beads, etc.), silicone compounds, pigments (organic pigments, inorganic pigments, metallic or mica-based pigments, etc.), dyes, UV absorbers, light stabilizers, matting agents, degassing agents, heat stabilizers, thickeners, dispersants, surfactants (fluorinated surfactants, etc.), antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, and decontamination agents are also mentioned.

[0042] Composition (f) may also preferably contain a curing agent. The curing agent in the present invention is a fluorine-containing polymer F 0 It has two or more groups in one molecule that can react with the crosslinking group of the curing agent and the fluorine-containing polymer F. 0 When it reacts with the crosslinkable group it possesses, a fluorine-containing polymer F is formed. 0 The cross-linked fluorine-containing polymer F 1 A crosslinking group is formed. The curing agent typically has 2 to 30 groups that can react with the crosslinking group.

[0043] Examples of curing agents include compounds having two or more (e.g., 2 to 30) isocyanate groups or epoxy groups in one molecule.

[0044] Polyisocyanate-based curing agents are preferred as curing agents. Polyisocyanate-based curing agents are compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule. Examples of polyisocyanates include alicyclic polyisocyanates, aliphatic polyisocyanates, and aromatic polyisocyanates. As aromatic polyisocyanates, those in which an isocyanate alkyl group is bonded to an aromatic nucleus are preferred. Polyisocyanates may also be polyisocyanate derivatives having an isocyanate group. Examples of polyisocyanate derivatives include polymers and modified forms of polyisocyanates (adducts, allophanates, biuretes, isocyanurates, etc.).

[0045] Examples of aliphatic polyisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, lysine triisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and bis(2-isocyanatoethyl)2-isocyanatoglutarate. Examples of alicyclic polyisocyanates include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylylene diisocyanate. Examples of aromatic polyisocyanates include aromatic diisocyanates such as xylylene diisocyanate.

[0046] The polyisocyanate-based curing agent may be a compound in which two or more isocyanate groups of the polyisocyanate described above are blocked by a blocking agent. The isocyanate groups blocked by the blocking agent become isocyanate groups when the blocking agent is removed by heating during the curing of composition (f), and the fluorine-containing polymer F 0 It reacts with crosslinking groups such as hydroxyl groups to form a fluorine-containing polymer F 0 To bridge the gap. Blocking agents are compounds containing active hydrogen, such as alcohols, phenols, active methylene compounds, amines, imines, acid amides, lactams, oximes, pyrazoles, imidazoles, imidazolines, pyrimidines, and guanidines. A block-type polyisocyanate curing agent and a fluorine-containing polymer F having crosslinkable groups such as hydroxyl groups. 0 Composition (f) containing these two substances has the advantage of being storable because the two substances do not react at room temperature, and it is not necessary to mix them immediately before painting to form composition (f).

[0047] The content of the curing agent (e.g., polyisocyanate-based curing agent) in composition (f) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 20% by mass, based on the total solid content of composition (f).

[0048] Composition (f) may also preferably contain a curing catalyst. A curing catalyst is a compound that promotes the formation of crosslinked structures using a curing agent, and can be selected from known curing catalysts depending on the type of curing agent. Among these, tin catalysts that promote the reaction of isocyanate groups (such as tin octoate, tributyltin laurate, and dibutyltin dilaurate) are preferred as curing catalysts. Two or more curing catalysts may be used in combination. If composition (f) contains a curing catalyst, the content of the curing catalyst is preferably 0.00001 to 5% by mass, and particularly preferably 0.0001 to 1% by mass, relative to the total solid content of composition (f).

[0049] Composition (f) may also preferably contain a pigment. Since the polyurethane layer in contact with the top layer is often prone to discoloration due to light irradiation, it is preferable to use a top layer containing a pigment to reduce light transmittance and prevent discoloration of the polyurethane layer. Examples of the above-mentioned pigments include inorganic pigments and organic pigments. The pigment may also be a luminous pigment using metal or mica. Examples of inorganic pigments include titanium dioxide. Two or more pigments may be used in combination. If composition (f) contains a pigment, the pigment content is preferably 1 to 60% by mass, and particularly preferably 15 to 35% by mass, relative to the total solids content of composition (f).

[0050] Composition (f) may contain resins other than the fluorine-containing polymers of the present invention. Examples of such resins include alkyd resins, polyester resins, epoxy resins, vinyl acetate resins, (meth)acrylic resins, vinyl chloride resins, phenolic resins, modified polyester resins, acrylic silicone resins, and silicone resins. If composition (f) contains the above-mentioned resin, the amount of the above-mentioned resin is preferably less than 100 parts by mass, more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass or less, per 100 parts by mass of the fluorine-containing polymer in composition (f).

[0051] Composition (f) is a fluorine-containing polymer F 0 Preferably, it is obtained by mixing it with at least one of the above-mentioned additives, which may be added as needed. In this case, composition (f) may contain a solvent. If composition (f) contains a solvent, the fluorine-containing polymer F 0 The additives may be dissolved or dispersed in the solvent. Composition (f) may also be a solvent-free powder type. The solvent used is one that is inert to the components contained in composition (f) (such as an organic solvent that does not contain active hydrogen). For example, if the curing agent contains an isocyanate group, a solvent that does not have groups that can react with the isocyanate group, such as a hydroxyl group, is used. Also, if a blocked polyisocyanate curing agent is used, the solvent is removed by coating and drying composition (f), and then heating to form a fluorine-containing polymer F. 0 Since crosslinking is possible, solvents containing active hydrogen such as hydroxyl groups can also be used.

[0052] If composition (f) contains a solvent, an organic solvent is preferred. Examples of organic solvents include ketones, esters, and hydrocarbons. Two or more organic solvents may be used in combination. The content of the organic solvent in composition (f) is preferably 10 to 90% by mass, and particularly preferably 35 to 60% by mass, based on the total mass of composition (f), from the viewpoint of storage stability and coating efficiency of composition (f).

[0053] One method for forming the top layer is to apply composition (f) onto a polyurethane layer to obtain a coating layer, and then cure the obtained coating layer to obtain a coating film (top layer). Painting methods include, for example, sprays, applicators, die coaters, bar coaters, roll coaters, comma coaters, roller brushes, brushes, and spatulas. If composition (f) contains a solvent, after coating with composition (f), it may be heated and dried to remove the solvent from composition (f). If composition (f) contains a curing agent, the coating layer can be cured, for example, by heating. The heating temperature is preferably 30 to 250°C, and more preferably 50 to 150°C. The curing of the paint layer may be carried out by leaving it outdoors or indoors without any special heating treatment.

[0054] The top layer is a fluorine-containing polymer F 0 And / or may contain, in an uncrosslinked form, a curing agent added as needed.

[0055] There are no limitations on the manufacturing method of this roofing component. For example, a polyurethane layer may be formed on a base material, and a top layer may be formed on the formed polyurethane layer. In this case, the polyurethane layers may be formed in the order of a foamed polyurethane layer and a non-foamed polyurethane layer from the base material side, or only a foamed polyurethane layer may be formed. At the time the above manufacturing method is carried out, the base material may already be part of the roof. That is, the above manufacturing method may be carried out using an existing roof as the base material to create the roof component. In this case, the above manufacturing method may be carried out while the base material remains assembled to the building as part or all of the building's roof. [Examples]

[0056] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these examples. The amounts of each component in Table 1, described later, are based on mass. Examples 1 to 3 are examples, and Example 4 is a comparative example.

[0057] <Abbreviations and details of ingredients used> • CTFE: Chlorotrifluoroethylene • EVE: Ethyl vinyl ether CHVE: Cyclohexyl vinyl ether • 2EHVE: 2-ethylhexyl vinyl ether • HBVE: 4-hydroxybutyl vinyl ether

[0058] • Composition A1: A composition containing fluorine-containing polymer A1, manufactured by the manufacturing method described below. • Composition A2: A composition containing fluorine-containing polymer A2, manufactured by the manufacturing method described below. • Composition A3: A composition containing fluorine-containing polymer A3, manufactured by the manufacturing method described below. • Composition A4: A composition containing fluorine-containing polymer A4, manufactured by the manufacturing method described below. • Composition B1: A composition containing a hydroxyl group-containing acrylate polymer, toluene, and butyl acetate (Acrydic A-801P, DIC Corporation trade name. The hydroxyl value of the hydroxyl group-containing acrylate polymer is 50 mg KOH / g). • Pigment: Ti-Pure R-960 (Titanium dioxide pigment, DuPont brand name) • Curing catalyst: 10,000-fold diluted xylene solution of dibutyltin dilaurate • Polyisocyanate-based curing agent: Isocyanurate-modified hexamethylene diisocyanate (Coronate HX, Tosoh Corporation product name)

[0059] • Foamed polyurethane raw material: A commercially available foamed polyurethane raw material consisting of a combination of a second component containing a polyurethane prepolymer and polyisocyanate, and a first component containing a polyol and a blowing agent. By using a sprayer that mixes the two components mentioned above, and applying the mixture by mixing the first and second components in a mass ratio of 1:1 during application, and then foaming and hardening the coating film, a foamed polyurethane coating film with heat-insulating properties can be obtained. • Non-foaming polyurethane raw material: A commercially available non-foaming polyurethane raw material consisting of a combination of a second component containing a polyurethane prepolymer and polyisocyanate, and a first component containing a polyol. By using a sprayer that mixes the two components mentioned above and spraying them, a non-foaming polyurethane coating can be obtained by mixing the first and second components in a mass ratio of 1:1 during application and then curing the coating film.

[0060] (Production of fluorine-containing polymer A1) A 50% by mass solution (20 mL) of xylene (645 g), CTFE (437 g), EVE (72 g), CHVE (142 g), HBVE (87 g), potassium carbonate (12.3 g), and tert-butylperoxypivalate in xylene was introduced into an autoclave and heated, and polymerization was carried out at 65°C for 11 hours. Subsequently, the autoclave solution was filtered to obtain a solution containing fluorine-containing polymer A1 (Solution A1, fluorine-containing polymer concentration 60% by mass, fluorine atom content of fluorine-containing polymer 27% by mass). Fluorine-containing polymer A1 was a polymer containing units based on CTFE, EVE, CHVE, and HBVE in the following order: 50 mol%, 25 mol%, 15 mol%, and 10 mol%, respectively. The hydroxyl value of fluorine-containing polymer A1 was 52 mgKOH / g, the Tg was 40°C, and the Mn was 20,000.

[0061] (Production of fluorine-containing polymer A2) In the production of fluorine-containing polymer A1, a solution containing fluorine-containing polymer A2 (solution A2, fluorine-containing polymer concentration 60% by mass, fluorine atom content of fluorine-containing polymer 29% by mass) was obtained in the same manner as in the production of fluorine-containing polymer A1, except that the type and amount of monomer used were changed. Fluorine-containing polymer A2 was a polymer containing 50 mol%, 40 mol%, and 10 mol% of units based on CTFE, EVE, and HBVE, respectively. The hydroxyl value of fluorine-containing polymer A2 was 57 mgKOH / g, the Tg was 25°C, and the Mn was 20,000.

[0062] (Production of fluorine-containing polymer A3) In the production of fluorine-containing polymer A1, a solution containing fluorine-containing polymer A3 (solution A3, fluorine-containing polymer concentration 60% by mass, fluorine atom content of fluorine-containing polymer 23% by mass) was obtained in the same manner as in the production of fluorine-containing polymer A1, except that the type and amount of monomer used were changed. Fluorine-containing polymer A3 was a polymer containing units based on CTFE, CHVE, HBVE, and 2EHVE in the following proportions: 50 mol%, 26 mol%, 9 mol%, and 15 mol%, respectively. The hydroxyl value of fluorine-containing polymer A3 was 40 mgKOH / g, its Tg was 25°C, and its Mn was 10,000.

[0063] (Manufacturing of fluorine-containing polymer A4) In the production of fluorine-containing polymer A1, a solution containing fluorine-containing polymer A4 (solution A4, fluorine-containing polymer concentration 45% by mass, fluorine atom content of fluorine-containing polymer 24% by mass) was obtained in the same manner as in the production of fluorine-containing polymer A1, except that the type and amount of monomer used were changed. Fluorine-containing polymer A4 was a polymer containing units based on CTFE, CHVE, EVE, and HBVE in the following proportions: 50 mol%, 43 mol%, 5 mol%, and 2 mol%, respectively. The hydroxyl value of fluorine-containing polymer A4 was 6.5 mgKOH / g, the Tg was 45°C, and the Mn was 32,000.

[0064] (Manufacturing of Composition A1) 16.7 g of solution A1, 40 g of pigment, and 43.3 g of xylene were mixed in a rocking mill to obtain a pigment paste. 37 g of the obtained pigment paste, 51 g of solution A1, 10 g of xylene, and 2 g of curing catalyst were mixed in a rocking mill. For painting, 6.1 g of polyisocyanate-based curing agent was added to this mixture and mixed to form a composition, which was then sprayed. This sprayed composition is called composition A1.

[0065] (Manufacturing of compositions A2 to A4) Compositions A2 to A4 were obtained in the same manner as in the preparation of composition A1, except that solutions A2 to A4 were used instead of solution A1.

[0066] <Preparation of test specimens> (Example 1) A 0.07m x 0.15m slate substrate (1.0mm thick) was coated with a two-component sprayer containing two components of foamed polyurethane raw materials. The mixture was then sprayed onto the substrate and allowed to foam and harden for 10 to 60 seconds to form a foamed polyurethane layer (approximately 10mm thick). Next, the two components of the non-foaming polyurethane raw material were mixed on the foamed polyurethane layer using a two-component spraying machine and sprayed onto the surface. The mixture was then cured for 60 seconds to form a non-foaming polyurethane layer (thickness: approximately 10 μm). Next, composition A1 was spray-painted onto the non-foaming polyurethane layer and then left to crosslink and harden at 23°C for one week to form a top layer (thickness: approximately 30 μm). In this way, a laminate A1 was obtained having a base material, a foamed polyurethane layer, a non-foamed polyurethane layer, and a top layer in this order. The obtained laminate was subjected to the evaluation described later.

[0067] (Examples 2-5) Laminates 2 to 5 were obtained in the same manner, except that the composition used to form the top layer was changed as shown in Table 1. The resulting laminate was subjected to the evaluation described later.

[0068] <Rating> (Adhesion) The determination was made using the cross-cut method (JIS K 5600-5-6). The top layer of the laminate was cut into a grid of 50 squares at 2 mm intervals, adhesive tape was applied to it, and then the adhesive tape was peeled off. The number of squares that were not peeled off by the adhesive tape (number of squares that were not peeled off / 50) was measured. In all cases where delamination occurred, the top layer separated from the non-foamed polyurethane layer.

[0069] (Top layer Tg) A top layer was fabricated separately on a PTFE resin sheet and peeled off. The peeled top layer was then measured using DMA (dynamic viscoelasticity measurement), and the temperature at which the maximum tanδ value was observed was defined as the top layer's Tg (°C). Furthermore, the Tg of the top layer described above substantially coincides with the Tg of the fluorine-containing polymer having a cross-linked structure formed in the top layer.

[0070] (Growth rate) A top layer was fabricated separately on a PTFE plate and peeled off to obtain a test specimen consisting of a single top layer. The specimen was pulled using a tensile testing machine (ORIEnTEC TENSILON RTC-1310A) until fracture, and the elongation (%) of the top layer was determined. The measurement conditions conformed to tensile testing JIS K7127, with a tensile speed of 50 mm / min. The elongation (%) was calculated by dividing the length of the specimen before pulling by L0 and the length of the specimen at fracture by L. f It can be calculated using the following formula. Growth rate (%) = (L f -L0) × 100 / L0

[0071] (50°C water resistance test) The obtained laminates were subjected to a 50°C water resistance test based on the test method JIS K5600-6-2 "Liquid Resistance (Water Immersion Method)," except that the immersion water temperature was set to 50°C. After the water resistance test, the appearance change and adhesion of the laminates were evaluated. • Changes in appearance The appearance of the laminate after testing was evaluated according to the following criteria based on JIS K5600-8-2. A: No blister packing B: Blisters of size 1-2 or with a density of 1-2 C: Contains blister packs with a size of 3 or larger or a generation density of 3 or higher. • Adhesion The adhesion of the top layer in the laminate after testing was determined using the same method as the adhesion evaluation described above.

[0072] <Result> The table below shows the types of compositions used in each example and the results of their evaluation.

[0073] [Table 1]

[0074] Furthermore, the entire contents of the specification, claims, abstract, and drawings of Japanese Patent Application No. 2021-046253, filed on March 19, 2021, are incorporated herein by reference as disclosure of the specification of the present invention. [Explanation of symbols]

[0075] 10 Roofing components 12 Base material 14. Foamed polyurethane layer 16 Non-foaming polyurethane layer 18 Top Tier 20 Polyurethane layer

Claims

1. Substrate and A polyurethane layer disposed on the aforementioned substrate, A roof member having a top layer disposed on the polyurethane layer, At least a portion of the polyurethane layer is composed of a foamed polyurethane layer, The top layer contains a fluorine-containing polymer, The fluorine-containing polymer is either a fluorine-containing polymer having hydroxyl groups, or a crosslinked product of a fluorine-containing polymer having hydroxyl groups. A roofing component comprising a fluorine-containing polymer having hydroxyl groups, wherein the hydroxyl value is 35 to 65 mg KOH / g.

2. The roof member according to claim 1, wherein the fluorine-containing polymer has units based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters.

3. The roofing member according to claim 1 or 2, wherein the fluorine atom content in the fluorine-containing polymer is 1 to 80% by mass.

4. The roof member according to any one of claims 1 to 3, wherein the glass transition temperature of the fluorine-containing polymer is 100°C or less.

5. The roof member according to any one of claims 1 to 4, wherein the fluorine-containing polymer has a crosslinked structure.

6. The roof member according to any one of claims 1 to 5, wherein the glass transition temperature of the top layer is 100°C or less.

7. The roof member according to any one of claims 1 to 6, wherein the top layer further comprises a pigment.

8. The roof member according to any one of claims 1 to 7, wherein the elongation rate of the top layer is 1.0% or more.

9. The roofing member according to any one of claims 1 to 8, wherein the base material is slate.

10. The roof member according to any one of claims 1 to 9, wherein the polyurethane layer comprises, from the base material side, a foamed polyurethane layer and a non-foamed polyurethane layer in that order.

11. The roof member according to claims 1 to 10, wherein the ratio of the thickness of the top layer to the foamed polyurethane layer is 0.00001 to 1.0.

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