Roofing member

Abstract

A roofing component with good sealing properties is provided for the top layer. A roofing component has: 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 being composed of a foamed polyurethane layer, and the top layer comprising a fluoropolymer.

Description

Technical Field

[0001] This invention relates to roof components. Background Technology

[0002] One method for repairing roofs is to form a resin-containing layer on the roof substrate.

[0003] Patent document 1 discloses a construction structure for forming an insulating foam layer, a reinforced waterproof layer, and a surface layer on specified roofing or other blank materials.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Utility Model Publication No. 3131191 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] The aforementioned roof components preferably exhibit good sealing properties across each layer.

[0009] The inventors studied the construction structure described in Patent Document 1 and found that the surface layer (top layer) was not sufficiently sealed.

[0010] Therefore, the objective of this invention is to provide a roof component with good sealing properties at the top layer.

[0011] Solution for solving the problem

[0012] The inventors conducted in-depth research and found that the problem can be solved by the following configuration.

[0013] [1] A roof component having:

[0014] Substrate,

[0015] The polyurethane layer disposed on the aforementioned substrate, and

[0016] The top layer disposed on the aforementioned polyurethane layer,

[0017] At least a portion of the aforementioned polyurethane layer is composed of a foamed polyurethane layer.

[0018] The aforementioned top layer contains a fluoropolymer.

[0019] [2] The roofing component according to [1], wherein the aforementioned fluoropolymer has units based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters.

[0020] [3] According to the roofing component of [1] or [2], wherein the content of fluorine atoms in the aforementioned fluoropolymer is 1 to 80% by mass.

[0021] [4] The roof component according to any one of [1] to [3], wherein the glass transition temperature of the aforementioned fluoropolymer is below 100°C.

[0022] [5] The roof component according to any one of [1] to [4], wherein the aforementioned fluoropolymer has a cross-linked structure.

[0023] [6] The roof component according to any one of [1] to [5], wherein the aforementioned fluoropolymer is a fluoropolymer having polar crosslinking groups or a crosslinked product of a fluoropolymer having polar crosslinking groups.

[0024] [7] According to the roof component of [6], the aforementioned fluoropolymer with polar crosslinking groups is a fluoropolymer with hydroxyl groups.

[0025] [8] According to the roof component of [7], wherein the hydroxyl value of the aforementioned fluoropolymer with hydroxyl groups is 20 to 100 mg KOH / g.

[0026] [9] The roof component according to any one of [1] to [8], wherein the glass transition temperature of the aforementioned top layer is below 100°C.

[0027]

[10] The roof component according to any one of [1] to [9], wherein the aforementioned top layer further comprises pigment.

[0028]

[11] The roof component according to any one of [1] to

[10] , wherein the elongation of the aforementioned top layer is 1.0% or more.

[0029]

[12] The roof component according to any one of [1] to

[11] , wherein the aforementioned substrate is slate.

[0030]

[13] The roofing member according to any one of [1] to

[12] , wherein the aforementioned polyurethane layer has a foamed polyurethane layer and a non-foamed polyurethane layer sequentially from the aforementioned substrate side.

[0031]

[14] The roof component according to any one of [1] to

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

[0032] The effects of the invention

[0033] According to the present invention, a roof component with good sealing properties can be provided for the top layer. Attached Figure Description

[0034] Figure 1 A simplified side view is provided to illustrate an example of the roof component of the present invention. Detailed Implementation

[0035] The meanings of the terms used in this invention are as follows.

[0036] (Meth)acrylates refer to the collective term for acrylates and methacrylates. Similarly, (meth)acrylic acid refers to the collective term for acrylic acid and methacrylic acid. Furthermore, (meth)acrylic resins refer to resins formed primarily from polymers based on (meth)acrylate units.

[0037] In polymers, a unit refers to a group of atoms directly formed by the polymerization of monomers, based on one molecule of the monomer, and a group of atoms obtained by chemically transforming a portion of the monomeric atoms after polymerization. It should be noted that the content (mol%) of each unit relative to all units contained in the polymer is determined by analyzing the polymer using nuclear magnetic resonance spectroscopy (NMR).

[0038] The hydroxyl value was determined according to the method of JIS K 0070-3 (1992).

[0039] The glass transition temperature (Tg) of the top layer is the temperature at which the maximum tanδ (loss tangent) value is measured using DMA (Dynamic Viscoelasticity Measurement).

[0040] The glass transition temperature (Tg) is the value of the midpoint glass transition temperature determined by differential scanning calorimetry (DSC).

[0041] Number-average molecular weight (Mn) is the value determined by gel permeation chromatography using polystyrene as a standard.

[0042] The thickness of the roof components was measured using an eddy current thickness gauge. For example, the EDY-5000 manufactured by Sankoudenshi Inc. can be used as an eddy current thickness gauge. The thickness of each layer within the roof components was measured by observing the cross-section of the roof components using a scanning electron microscope equipped with an energy-dispersive X-ray analyzer.

[0043] When the composition contains a solvent, the mass of the solid component of the composition refers to the mass of the composition after the solvent has been removed. It should be noted that any component in the composition other than the solvent, even if it is in liquid form, is considered a solid component. It should also be noted that the mass of the solid component of the composition is determined by the mass remaining after heating 1g of the composition at 130°C for 20 minutes.

[0044] The roof component of the present invention (hereinafter also referred to as the roof component) has: a substrate; a polyurethane layer disposed on the substrate; 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 comprises a fluoropolymer.

[0045] The mechanism by which the top layer of a roof component with this configuration achieves good sealing is not necessarily clear, but it is worth considering below.

[0046] That is, the top layer of this roofing component contains a fluoropolymer. It is believed that this top layer has good adhesion to the polyurethane layer, thus improving the adhesion of the top layer.

[0047] First, the composition of this roof component will be explained with reference to the attached drawings.

[0048] Figure 1 This is a simplified side view of the layer structure of a roof member 10 (this roof member) as an embodiment of the present invention. The roof member 10 has: a substrate 12, a foamed polyurethane layer 14, a non-foamed polyurethane layer 16, and a top layer 18, which are arranged sequentially.

[0049] Figure 1 In the process, the foamed polyurethane layer 14 and the non-foamed polyurethane layer 16 are integrally formed to form the polyurethane layer 20.

[0050] Figure 1 The diagram shows that 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 can be omitted. That is, the foamed polyurethane layer 14 can be the polyurethane layer 20 itself.

[0051] The roof component 10 may have other layers as long as it does not violate the spirit of the invention.

[0052] The components that make up this roof structure are described in detail below.

[0053] This roof component has a base material.

[0054] The substrate can be non-metallic materials (slate, tile, concrete, waterproof resin sheet, wood, etc.) or metallic materials.

[0055] From the perspective of the weather resistance of roof components, slate is preferred as the base material.

[0056] The thickness of the substrate is preferably 0.5 to 50 mm, and particularly preferably 1 to 20 mm.

[0057] This roofing component has a polyurethane layer.

[0058] At least a portion of the polyurethane layer is composed of a foamed polyurethane layer. A foamed polyurethane layer refers to a layer containing foamed polyurethane.

[0059] From the perspective of the thermal insulation of the roof components, the thickness of the polyurethane foam layer is preferably 0.5 to 50 mm, and particularly preferably 1 to 20 mm.

[0060] As a type of foamed polyurethane, examples of foamed polyurethane formed by reacting and curing a mixture of foamed polyurethane raw materials comprising a polyol, a polyisocyanate and / or an isocyanate-terminated polyurethane prepolymer having two or more (e.g., two to ten) hydroxyl groups, and a foaming agent.

[0061] Polyether polyols and polyester polyols are preferred as polyols, with polyether polyols being particularly preferred. The hydroxyl value of the polyol is preferably 300–800 mg KOH / g. The number of hydroxyl groups in the polyol is preferably 3–8.

[0062] Examples of polyisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, polyisocyanates described as curing agents contained in the composition (f) described below, polymers of these polyisocyanates, and modified forms. Toluene diisocyanate and diphenylmethane diisocyanate are preferred as polyisocyanates.

[0063] Isocyanate-terminated polyurethane prepolymers refer to prepolymers with isocyanate groups obtained by reacting a polyol with an excess equivalent of polyisocyanate.

[0064] Examples of foaming agents include water, low-boiling-point fluorinated hydrocarbons, and low-boiling-point hydrocarbons, with water alone or in combination with other foaming agents being particularly preferred.

[0065] The above-mentioned polyurethane foam raw material mixture may also contain other components besides those mentioned above. Examples of other components include catalysts, crosslinking agents, chain extenders, flame retardants, fillers, and reinforcing fibers.

[0066] The foamed polyurethane layer is preferably formed as follows: a foamed polyurethane raw material mixture is formed by mixing raw material components just before coating; the foamed polyurethane raw material mixture is coated onto a substrate; and the foamed polyurethane raw material mixture is foamed and cured on the substrate. The foamed polyurethane raw material mixture is preferably formed as follows: a first component containing polyols, foaming agents, etc., and a second component containing polyisocyanates are mixed just before coating.

[0067] Examples of coating methods include those using sprayers, applicators, die coaters, bar coaters, roller coaters, comma coaters, etc., with spraying being preferred. Sprays that mix and blow the first and second components described above are particularly preferred.

[0068] The polyurethane layer preferably also has a non-foamed polyurethane layer. A non-foamed polyurethane layer refers to a layer containing non-foamed polyurethane.

[0069] From the perspective of the waterproofness of the roof components, the thickness of the non-foamed polyurethane layer is preferably 1 to 10,000 μm, and particularly preferably 10 to 1,000 μm.

[0070] The non-foamed polyurethane layer can exist on the substrate side as a reference, or it can exist on the opposite side of the substrate as a reference.

[0071] Preferably, the polyurethane layer has a structure consisting of a foamed polyurethane layer and a non-foamed polyurethane layer sequentially from the substrate side.

[0072] As a non-foaming polyurethane layer, for example, a layer formed by reacting a non-foaming polyurethane raw material mixture can be mentioned. The non-foaming polyurethane raw material mixture contains compounds having two or more (e.g., 2 to 10) hydroxyl groups, as well as polyisocyanates and / or isocyanate-terminated polyurethane prepolymers, and does not contain foaming agents such as water.

[0073] Examples of polyols include polyether polyols, polyester polyols, and hydroxyl-containing vinyl polymers, with polyether polyols being particularly preferred. The hydroxyl value of the polyol is preferably 50–800 mg KOH / g.

[0074] As a polyisocyanate, examples include polyisocyanates listed as raw materials for the aforementioned foamed polyurethane foam, and end-capped polyisocyanates whose isocyanate groups are end-capped by end-capping agents.

[0075] The above-mentioned non-foamed polyurethane raw material mixture may contain other components listed as raw materials for the aforementioned foamed polyurethane foam, and may also contain solvents.

[0076] The non-foamed polyurethane layer is preferably formed as follows: a non-foamed polyurethane raw material mixture is coated on the surface where the non-foamed polyurethane layer is to be formed, and the non-foamed polyurethane raw material mixture is cured on the surface to form the layer. When using a capped polyisocyanate, after the coating film of the non-foamed polyurethane raw material mixture is formed, the coating film is heated and decapped, thereby curing the layer.

[0077] Examples of coating methods include the use of sprayers, applicators, die coaters, bar coaters, roller coaters, comma coaters, roller brushes, brushes, and scrapers.

[0078] This roofing component has a top layer disposed on the aforementioned polyurethane layer.

[0079] From the perspective of the weather resistance of the roof components, the thickness of the top layer is preferably 1 to 1000 μm, and particularly preferably 10 to 100 μm.

[0080] The top layer can be directly laminated on the foamed polyurethane layer or directly laminated on the non-foamed polyurethane layer.

[0081] Furthermore, the thickness ratio of the top layer to the polyurethane foam layer (thickness of the top layer / thickness of the polyurethane foam 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 components will be maintained for a longer period of time.

[0082] The Tg of the top layer is preferably above 0°C, more preferably above 15°C, and particularly preferably above 20°C. The Tg is preferably below 100°C, more preferably below 75°C, further preferably below 55°C, and particularly preferably below 45°C. If the Tg of the top layer is within the above range, the top layer exhibits excellent flexibility, allowing for easy and suitable adjustment of elongation, and excellent adhesion. Furthermore, it exhibits excellent water resistance, maintaining the coating appearance and adhesion even after a water resistance test.

[0083] The top layer preferably has flexibility, and its elongation is preferably 1.0% or more, more preferably 2.0% or more, and particularly preferably 3.0% or more. The elongation is preferably 100.0% or less, more preferably 50.0% or less, and particularly preferably 10.0% or less. If the elongation of the top layer is within the above range, the adhesion to the polyurethane layer is further improved.

[0084] The top layer contains a fluoropolymer.

[0085] The aforementioned fluoropolymers may or may not have a cross-linked structure. From the perspective of weather resistance and water resistance of the top layer, it is preferable that the fluoropolymer forms a cross-linked structure in the top layer.

[0086] Unless otherwise specified, the characteristics (suitable conditions, etc.) of the fluoropolymers detailed below can be satisfied by fluoropolymers with cross-linked structures, or by fluoropolymers without cross-linked structures, or by both.

[0087] The following will discuss fluoropolymers with cross-linked structures, especially those also known as fluoropolymers F. 1 Fluoropolymers that do not have a cross-linked structure, especially those also known as fluoropolymers F 0 .

[0088] Fluoropolymer F 0 The preferred material is a fluoropolymer that has crosslinking groups but no crosslinking structure.

[0089] Fluoropolymer F 1 Preferably, it is a fluoropolymer F containing crosslinking groups. 0 Cross-linked compounds.

[0090] The top layer is preferably made of a fluoropolymer F containing fluoroolefin-based units (hereinafter also referred to as unit A1) and units having crosslinking groups (hereinafter also referred to as unit A2). 0And thus formed. In other words, the top layer preferably uses a fluoropolymer F containing the aforementioned fluoropolymer. 0 It is formed by the composition (hereinafter also referred to as composition (f)).

[0091] Using the above-mentioned fluoropolymer F 0 In certain circumstances, the crosslinking groups of the fluoropolymer F0 can be reacted to form a fluoropolymer F1 with a crosslinked structure. It should be noted that, as described later, a specified curing agent can also be used to react the crosslinking groups.

[0092] Fluoropolymers (F-containing polymers) 0 and / or F 1 It is also preferred that the unit has one or more monomers selected from the group consisting of vinyl ethers and vinyl esters. The above unit may belong to unit A2 as described below, or it may belong to unit A3.

[0093] In addition, fluoropolymer F 0 It may have two or more units A2 or A3, which will be described later, and may have both units A2 and A3.

[0094] Fluoroolefins are olefins in which one or more hydrogen atoms are replaced by fluorine atoms. One or more unsubstituted hydrogen atoms in a fluoroolefin may be replaced by chlorine atoms. The number of carbon atoms in a fluoroolefin is preferably 2 to 8, and particularly preferably 2 to 4.

[0095] Examples of fluoroolefins include CF2=CF2, CF2=CFCl, CF2=CHF, CH2=CF2, CF2=CFCF3, CF2=CHCF3, CF3CH=CHF, and CF3CF=CH2. From a copolymerization perspective, CF2=CF2, CF2=CFCl, CF3CH=CHF, and CF3CF=CH2 are preferred as fluoroolefins, CF2=CF2 and CF2=CFCl are more preferred, and CF2=CFCl is particularly preferred.

[0096] Fluoroolefins can be used in combination with two or more types.

[0097] Regarding the content of unit A1, from the perspective of the weather resistance of this roof component, relative to the fluoropolymer F... 0 The total number of units contained therein is preferably 20-70 mol%, more preferably 40-60 mol%, and particularly preferably 45-55 mol%.

[0098] Unit A2 is preferably a unit based on a monomer having crosslinking groups (hereinafter also referred to as monomer A2). Unit A2 may have two or more crosslinking groups. Monomer A2 is preferably a compound without fluorine atoms.

[0099] Alternatively, unit A2 can also be a unit obtained by converting the crosslinking groups contained in the unit into different crosslinking groups. For example, such unit A2 can be obtained by reacting the hydroxyl groups contained in the unit with polycarboxylic acid, its anhydride, etc., to convert some or all of the hydroxyl groups into carboxyl groups.

[0100] Examples of crosslinking groups include hydroxyl, carboxyl, amino, alkoxysilyl, epoxy, and oxetyl groups. Polar crosslinking groups are preferred. Specific examples of polar crosslinking groups include hydroxyl, carboxyl, and amino groups.

[0101] When the crosslinking group is a polar crosslinking group, that is, when the fluoropolymer is a fluoropolymer with a polar crosslinking group, or a crosslinked product of a fluoropolymer with a polar crosslinking group, the urethane structure of the aforementioned polyurethane is also polar. Therefore, the fluoropolymer (fluoropolymer F...) 0 and / or F 1 The improved affinity between the top layer and the polyurethane layer enhances the adhesion between the top layer and the polyurethane layer, making it the preferred choice.

[0102] Furthermore, as a polar crosslinking group, hydroxyl and carboxyl groups are preferred, with hydroxyl groups being particularly preferred, in order to further improve the impact resistance, flexibility, and chemical resistance of the top layer.

[0103] Examples of monomers A2 with a hydroxyl crosslinking group include allyl alcohols, and vinyl ethers, vinyl esters, allyl ethers, allyl esters, and (meth)acrylates having hydroxyl groups, with allyl alcohols and formula X being preferred. 11 -Z 11 The monomer shown (hereinafter also referred to as monomer A21).

[0104] X 11 The octet is CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO- or CH2=CHCH2O-, preferably CH2=CHO- or CH2=CHCH2O-.

[0105] Z 11 It is a monovalent organic group having 2 to 42 carbon atoms and a hydroxyl group. The organic group can be chain-like or branched. Furthermore, the organic group can be formed by a ring structure or may contain a ring structure.

[0106] The organic groups mentioned above are preferably alkyl groups having 2 to 6 carbon atoms and hydroxyl groups, alkyl groups containing 6 to 8 carbon atoms and hydroxyl groups, and polyoxyalkylene groups having hydroxyl groups.

[0107] As monomer A 21 A specific example could be 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. It should be noted that "-cycloC6H" 10 -” indicates a cyclohexyl group (-cycloC6H) 10 The binding site of -) is usually 1,4-.

[0108] Monomer A 21 Two or more can be used together.

[0109] Monomer A2 with a carboxyl crosslinking group can be exemplified by polymerizable unsaturated carboxylic acids such as (meth)acrylic acid, with preferred formula X. 12 -Z 12 The monomer shown (hereinafter also referred to as monomer A) 22 ).

[0110] X 12 The values ​​are CH2=CH-, CH(CH3)=CH-, or CH2=C(CH3)-, with CH2=CH- or CH2=C(CH3)- being preferred.

[0111] Z 12 It is a carboxyl group or a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, preferably a carboxyl group or a carboxyl alkyl group having 1 to 10 carbon atoms.

[0112] Examples of monomers A22 include CH2=CHCOOH, CH2=C(CH3)COOH, and CH2=CH(CH2). n1 COOH, CH2=C(CH3)(CH2) n1 The compound shown is COOH (where n1 represents an integer from 1 to 10).

[0113] Two or more monomers A22 can be used together.

[0114] As for monomer A2, for example, monomer A21 or monomer A22 can be used, or both monomer A21 and monomer A22 can be used.

[0115] The content of unit A2 relative to fluoropolymer F 0The total number of units contained herein is preferably 0.5 to 40 mol%, more preferably 3 to 35 mol%, and particularly preferably 4 to 15 mol%.

[0116] Fluoropolymer F 0 Preferably, it also 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, and particularly preferably has a unit based on one or more monomers selected from the group consisting of vinyl ethers and vinyl esters.

[0117] Monomer A3 does not have cross-linking groups.

[0118] Monomer A3 is preferably free of fluorine atoms.

[0119] Unit A3 is preferred based on formula X 2 -Y 2 The unit shown is a monomer.

[0120] X 2 The fluoropolymers are CH2=CHC(O)O-, CH2=C(CH3)C(O)O-, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O-. From the perspective of the excellent weather resistance of fluoropolymers, CH2=CHOC(O)-, CH2=CHCH2OC(O)-, CH2=CHO-, or CH2=CHCH2O- are preferred, and CH2=CHO- is particularly preferred.

[0121] Y 2 It is a monovalent hydrocarbon group with 1 to 24 carbon atoms. The monovalent hydrocarbon group can be straight-chain or branched. In addition, the monovalent hydrocarbon group can be formed by a ring structure or contain a ring structure. Furthermore, the monovalent hydrocarbon group can be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.

[0122] As a monovalent hydrocarbon group, alkyl, cycloalkyl, aryl, aralkyl, and cycloalkylalkyl are preferred, with particularly preferred alkyl groups having 2 to 12 carbons, cycloalkyl groups having 6 to 10 carbons, aryl groups having 6 to 10 carbons, aralkyl groups having 7 to 12 carbons, and cycloalkylalkyl groups having 6 to 10 carbons.

[0123] Examples of alkyl groups include methyl, ethyl, tert-butyl, hexyl, octyl (2-ethylhexyl, etc.), nonyl, decyl, and dodecyl.

[0124] Examples of cycloalkyl groups include cyclohexyl.

[0125] Examples of aralkyl groups include benzyl groups.

[0126] Examples of cycloalkyl groups include cyclohexylmethyl. Examples of aryl groups include phenyl and naphthyl.

[0127] It should be noted that the hydrogen atoms of the cycloalkyl or cycloalkylalkyl moiety, and the aryl or aralkyl alkyl moiety, may optionally be replaced by an alkyl group. In this case, the carbon number of the alkyl group as a substituent is not included in the carbon number of the cycloalkyl, cycloalkylalkyl, aryl, and aralkyl groups.

[0128] Two or more monomers A3 can be used together.

[0129] Examples of monomers A3 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl tert-valerate, vinyl neononanoate (HEXION trade name "VeoVa9"), vinyl neodecanoate (HEXION trade name "VeoVa 10"), vinyl tert-carbonate, vinyl benzoate, tert-butyl benzoate, tert-butyl methacrylate, and benzyl methacrylate.

[0130] The content of unit A3 relative to fluoropolymer F 0 The total number of units contained herein is preferably 1 to 60 mol%, more preferably 10 to 55 mol%, and particularly preferably 30 to 50 mol%.

[0131] Fluoropolymers (F-containing polymers) 0 and / or F 1 The fluorine atom content relative to the total mass of the fluoropolymer is preferably 1-80% by mass, more preferably 1-50% by mass, further preferably 10-40% by mass, and particularly preferably 15-35% by mass. If the fluorine atom content is within the above range, the weather resistance and sealing properties of the top layer are superior.

[0132] Fluoropolymer F 0 Compared to fluoropolymer F 0 The unit comprises, preferably, 20-70 mol%, 0.5-40 mol%, 1-60 mol%, more preferably, 40-60 mol%, 3-35 mol%, 10-55 mol%, and particularly preferably, 45-55 mol%, 4-15 mol%, and 30-50 mol%, respectively.

[0133] Fluoropolymer F with hydroxyl groups 0 The hydroxyl value is preferably 1-200 mg KOH / g, more preferably 20-100 mg KOH / g, even more preferably 35-65 mg KOH / g, and particularly preferably 45-65 mg KOH / g.

[0134] In this case, the fluoropolymer F0 Or fluoropolymer F, which is its crosslinker 1 It readily exhibits excellent affinity with polyurethane, and the adhesion between the top layer and the polyurethane layer is easily improved.

[0135] Fluoropolymers (F-containing polymers) 0 and / or F 1 The temperature gradient (Tg) of the roofing component is preferably above 0°C, more preferably above 15°C, further preferably above 20°C, and particularly preferably above 30°C. The Tg is preferably below 100°C, more preferably below 75°C, and particularly preferably below 55°C. By adjusting the Tg to the above range, the top layer exhibits superior flexibility. Furthermore, it is less likely to damage the appearance of the roofing component when absorbing water.

[0136] Fluoropolymer F 0 The Mn content is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, and particularly preferably 15000 or more. The Mn content is preferably 50000 or less, more preferably 25000 or less. By adjusting the Mn content to the above range, the balance between tensile strength and strength of the top layer is better and more excellent.

[0137] Fluoropolymer F 0 The preferred specific solution is as follows.

[0138] • A fluoropolymer 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 units selected from the group consisting of vinyl ethers without crosslinking groups and vinyl esters. 0 .

[0139] • A fluoropolymer 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 without crosslinking groups and vinyl esters, wherein the contents of the above units are 40–60 mol%, 3–35 mol%, and 10–55 mol%, respectively, relative to all units contained in the fluoropolymer. 0 .

[0140] • A fluoropolymer comprising unit A1 based on CF2=CFCl, unit A2 based on a vinyl ether having a hydroxyl group, and unit A3 based on a vinyl ether without a crosslinking group, wherein the contents of the above units are 45-55 mol%, 4-15 mol%, and 30-50 mol%, respectively, relative to all units of the fluoropolymer. 0 .

[0141] If the above scheme is adopted, then the fluoropolymer F 0 Among the included units, the alternating copolymerization rate of unit A1 and other units is prone to increase, resulting in excellent weather resistance of this roof component.

[0142] Fluoropolymer F 0 Two or more types can be used.

[0143] Fluoropolymer F in composition (f) 0 The content of [the substance] is preferably 10-90% by mass, more preferably 30-80% by mass, and particularly preferably 50-70% by mass relative to the total solid content of composition (f).

[0144] Composition (f) may, as needed, contain fluoropolymer F 0 Other components (hereinafter also referred to as additives). Examples of such components include fluoropolymers F... 0 Other than polymers, curing agents, curing catalysts, solvents, fillers (inorganic fillers such as silica, organic fillers such as resin beads), organosilicon compounds, pigments (organic pigments, inorganic pigments, bright pigments using metals or mica, etc.), dyes, ultraviolet 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 low-pollution treatment agents.

[0145] The composition (f) also preferably contains a curing agent.

[0146] The curing agent 1 molecule in this invention has two or more ions that can react with the fluoropolymer F 0 The cross-linking groups it possesses react with. The curing agent reacts with the fluoropolymer F. 0 When the crosslinking groups it possesses react, the fluoropolymer F 0 Crosslinking to form fluoropolymer F 1 Curing agents typically have 2 to 30 groups that can react with crosslinking groups.

[0147] Examples of curing agents include compounds having two or more (e.g., 2 to 30) isocyanate groups or epoxy groups in one molecule.

[0148] Polyisocyanate-based curing agents are preferred as curing agents.

[0149] Polyisocyanate-based curing agents refer to compounds that have two or more isocyanate groups or capped isocyanate groups in one molecule.

[0150] Examples of polyisocyanates include alicyclic polyisocyanates, aliphatic polyisocyanates, and aromatic polyisocyanates. Among aromatic polyisocyanates, those with an isocyanate alkyl group bonded to an aromatic core are preferred. Polyisocyanates can also be polyisocyanate derivatives having an isocyanate group. Examples of polyisocyanate derivatives include polymers and modified forms of polyisocyanates (adducts, urea esters, biuret esters, isocyanurate esters, etc.).

[0151] Examples of aliphatic polyisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanate-hexane, lysine diisocyanate, lysine triisocyanate, 4-isocyanate-methyl-1,8-octamethylene diisocyanate, and 2-isocyanate-glutarate bis(2-isocyanate-ethyl) ester.

[0152] Examples of alicyclic polyisocyanates include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornene diisocyanate, and hydrogenated xylene diisocyanate.

[0153] Examples of aromatic polyisocyanates include xylene diisocyanate and other aromatic diisocyanates.

[0154] The polyisocyanate-based curing agent can be a compound in which two or more isocyanate groups of the aforementioned polyisocyanate are capped by a capping agent. The isocyanate groups capped by the capping agent are removed by heating during the curing of composition (f), becoming isocyanate groups, which then react with the fluoropolymer F. 0 The cross-linking groups, such as hydroxyl groups, react to make the fluoropolymer F... 0 Crosslinking.

[0155] End-capping agents are compounds with active hydrogen, such as alcohols, phenols, active methylene groups, amines, imines, acid amides, lactams, oximes, pyrazoles, imidazoles, imidazolines, pyrimidines, and guanidines.

[0156] Contains end-capped polyisocyanate-based curing agents and fluoropolymers F with crosslinking groups such as hydroxyl groups. 0 The composition (f) has the following characteristics: the two do not react at room temperature, thus having shelf life, meaning that the two do not need to be mixed to form composition (f) before coating.

[0157] The content of the curing agent (e.g., a 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 relative to the total solid content of composition (f).

[0158] The composition (f) also preferably contains a curing catalyst.

[0159] A curing catalyst is a compound that promotes the formation of cross-linked structures using a curing agent, and can be selected from known curing catalysts depending on the type of curing agent.

[0160] Among them, the curing catalyst is preferably a tin catalyst that promotes the isocyanate group reaction (tin octoate, tributyltin laurate, dibutyltin dilaurate, etc.).

[0161] Two or more solidification catalysts can be used together.

[0162] When composition (f) contains a curing catalyst, the content of the curing catalyst relative to the total solid content of composition (f) is preferably 0.00001 to 5% by mass, and particularly preferably 0.0001 to 1% by mass.

[0163] Composition (f) preferably also contains pigments. Since the polyurethane layer in contact with the top layer is prone to discoloration upon light exposure, it is preferable to form a top layer containing pigments to reduce light transmittance and prevent discoloration of the polyurethane layer.

[0164] Examples of pigments mentioned above include inorganic and organic pigments. Pigments can also be glossy pigments that incorporate metals or mica, etc.

[0165] Titanium oxide is an example of an inorganic pigment.

[0166] Two or more pigments can be used together.

[0167] When composition (f) contains pigment, the pigment content relative to the total solid components of composition (f) is preferably 1 to 60% by mass, and particularly preferably 15 to 35% by mass.

[0168] Composition (f) may contain resins other than the fluoropolymers 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.

[0169] When composition (f) contains the above-described resin, the content of the above-described resin is preferably less than 100 parts by weight, more preferably less than 80 parts by weight, and particularly preferably less than 50 parts by weight, relative to 100 parts by weight of the fluoropolymer in composition (f).

[0170] Composition (f) preferably contains fluoropolymer F 0 It is obtained by mixing with at least one of the above-mentioned additives, as needed. In this case, composition (f) may contain a solvent. When composition (f) contains a solvent, the fluoropolymer F... 0 The additives can be dissolved or dispersed in a solvent. The composition (f) can be a solvent-free powder type.

[0171] The solvent used is one that is inactive to the components contained in composition (f) (such as an organic solvent without active hydrogen). For example, if a curing agent containing isocyanate groups is used as the curing agent, a solvent without groups such as hydroxyl groups that can react with isocyanate groups is used. Alternatively, if a capped polyisocyanate-based curing agent is used, coating and drying the composition (f) to remove the solvent, followed by heating, can cure the fluoropolymer F. 0 Cross-linking allows the use of solvents containing active hydrogen such as hydroxyl groups.

[0172] When composition (f) contains a solvent, the solvent is preferably an organic solvent.

[0173] Examples of organic solvents include ketones, esters, and hydrocarbons.

[0174] Two or more organic solvents can be used together.

[0175] Regarding the content of organic solvent in composition (f), from the perspective of storage stability and coating efficiency of composition (f), it is preferably 10 to 90% by mass, and particularly preferably 35 to 60% by mass, relative to the total mass of composition (f).

[0176] As a method for forming the top layer, for example, the following method can be used: applying the composition (f) onto a polyurethane layer to obtain a coating layer, and curing the obtained coating layer to obtain a coating film (top layer).

[0177] Examples of coating methods include those using sprayers, applicators, die coaters, bar coaters, roller coaters, comma coaters, roller brushes, brushes, and scrapers.

[0178] If the composition (f) contains a solvent, after coating the composition (f), it can be heated and dried to remove the solvent from the composition (f).

[0179] When composition (f) contains a curing agent, the curing of the coating layer can be carried out, for example, by heating. The heating temperature is preferably 30–250°C, more preferably 50–150°C.

[0180] The curing of the coating can be carried out, either outdoors or indoors, without heat treatment.

[0181] The top layer may contain a portion of the fluoropolymer F in an uncrosslinked state. 0 And / or a curing agent added as needed.

[0182] There are no restrictions on the manufacturing method of this roofing component. For example, a polyurethane layer can be formed on the substrate, and a top layer can be formed on the formed polyurethane layer. In this case, the polyurethane layer can be formed sequentially from the substrate side, consisting of a foamed polyurethane layer, a non-foamed polyurethane layer, or only a foamed polyurethane layer.

[0183] When implementing the above manufacturing method, the substrate may already be part of the roof. That is, the existing roof can be used as the substrate to implement the above manufacturing method and form this roof component. In this case, the above manufacturing method can be implemented with the substrate as part or all of the roof of the building, assembled into the building without changing its shape.

[0184] Example

[0185] The present invention will now be described in detail with examples. However, the present invention is not limited to these examples. It should be noted that the mixing amounts of each component in Table 1 described below represent mass. In addition, Examples 1 to 3 are exemplary cases, and Example 4 is a comparative example.

[0186] <Abbreviations and details of the ingredients used>

[0187] ·CTFE: Chlorotrifluoroethylene

[0188] EVE: Ethyl vinyl ether

[0189] CHVE: Cyclohexyl vinyl ether

[0190] ·2EHVE: 2-Ethylhexylvinyl ether

[0191] HBVE: 4-Hydroxybutylvinyl ether

[0192] • Composition A1: A composition comprising a fluoropolymer A1 manufactured by the method described below.

[0193] • Composition A2: A composition comprising fluoropolymer A2 manufactured by the method described below.

[0194] • Composition A3: A composition comprising fluoropolymer A3 manufactured by the manufacturing method described below.

[0195] • Composition A4: A composition comprising fluoropolymer A4 manufactured by the manufacturing method described below.

[0196] Composition B1: A composition comprising a hydroxyl-containing acrylate polymer, toluene, and butyl acetate (ACRYDICA-801P, trade name of DIC Corporation. The hydroxyl value of the hydroxyl-containing acrylate polymer is 50 mg KOH / g).

[0197] • Pigment: Ti-Pure R-960 (Titanium oxide pigment, trade name from DuPont)

[0198] • Curing catalyst: 10,000 times diluted xylene solution of dibutyltin dilaurate

[0199] • Polyisocyanate-based curing agent: Isocyanurate-modified hexamethylene diisocyanate (CORONATE HX, trade name from Tosoh Corporation)

[0200] • Foamed polyurethane raw materials: Commercially available foamed polyurethane raw materials formed by combining a second component containing polyurethane prepolymer and polyisocyanate with a first component containing polyol and foaming agent.

[0201] The coating is applied by spraying a mixture of the two components described above, which is then blown into the air. The first and second components are mixed at a mass ratio of 1:1 and then blown into the air to cause the coating to foam and cure, thereby obtaining a foamed polyurethane coating with heat insulation properties.

[0202] • Non-foaming polyurethane raw material: A commercially available non-foaming polyurethane raw material formed by combining a second component containing polyurethane prepolymer and polyisocyanate with a first component containing polyol.

[0203] Using a spray in which the above two components are mixed and blown, the first component and the second component are mixed at a mass ratio of 1:1 and blown during coating to cure the coating film, thereby obtaining a non-foaming polyurethane coating film.

[0204] (Manufacturing of fluoropolymer A1)

[0205] A 50% xylene 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-butyl peroxypentanoate was introduced into an autoclave and heated to 65 °C for 11 hours for polymerization. The autoclave solution was then filtered to obtain a solution containing fluoropolymer A1 (solution A1, fluoropolymer concentration 60% by mass, fluorine atom content of 27% by mass).

[0206] Fluoropolymer A1 is a polymer comprising, in sequence, 50 mol%, 25 mol%, 15 mol%, and 10 mol% of CTFE-based units, EVE-based units, CHVE-based units, and HBVE-based units. Fluoropolymer A1 has a hydroxyl value of 52 mg KOH / g, a Tg of 40℃, and a Mn of 20000.

[0207] (Manufacturing of fluoropolymer A2)

[0208] In the manufacture of fluoropolymer A1, the type and amount of monomer used are changed, but a solution containing fluoropolymer A2 is obtained in the same way (solution A2, fluoropolymer concentration 60% by mass, fluorine atom content of fluoropolymer 29% by mass).

[0209] Fluoropolymer A2 is a polymer comprising, in sequence, 50 mol%, 40 mol%, and 10 mol% of CTFE-based units, EVE-based units, and HBVE-based units. Fluoropolymer A2 has a hydroxyl value of 57 mg KOH / g, a Tg of 25℃, and a Mn of 20000.

[0210] (Manufacturing of fluoropolymer A3)

[0211] In the manufacture of fluoropolymer A1, the type and amount of monomers used are changed, but a solution containing fluoropolymer A3 is obtained in the same way (solution A3, fluoropolymer concentration 60% by mass, fluorine atom content of fluoropolymer 23% by mass).

[0212] Fluoropolymer A3 is a polymer comprising, in sequence, 50 mol%, 26 mol%, 9 mol%, and 15 mol% of CTFE-based units, CHVE-based units, HBVE-based units, and 2EHVE-based units. Fluoropolymer A3 has a hydroxyl value of 40 mg KOH / g, a Tg of 25℃, and a Mn of 10000.

[0213] (Manufacturing of fluoropolymer A4)

[0214] In the manufacture of fluoropolymer A1, the type and amount of monomers used are changed, but a solution containing fluoropolymer A4 is obtained in the same way (solution A4, fluoropolymer concentration 45% by mass, fluorine atom content of fluoropolymer 24% by mass).

[0215] Fluoropolymer A4 is a polymer comprising, in sequence, 50 mol%, 43 mol%, 5 mol%, and 2 mol% of CTFE-based units, CHVE-based units, EVE-based units, and HBVE-based units. Fluoropolymer A4 has a hydroxyl value of 6.5 mg KOH / g, a Tg of 45℃, and a Mn of 32000.

[0216] (Preparation of Composition A1)

[0217] 16.7g of solution A1, 40g of pigment, and 43.3g of xylene were mixed in a gyratory mill to obtain a pigment paste. 37g of the obtained pigment paste, 51g of solution A1, 10g of xylene, and 2g of curing catalyst were then mixed in the gyratory mill. During coating, 6.1g of a polyisocyanate-based curing agent was added to this mixture and mixed to form a composition, which was then sprayed. This sprayed composition is referred to as composition A1.

[0218] (Preparation of compositions A2 to A4)

[0219] In the manufacture of composition A1, solutions A2 to A4 are used instead of solution A1, and otherwise compositions A2 to A4 are obtained in the same manner.

[0220] <Preparation of Test Subjects>

[0221] (Example 1)

[0222] The two components of the polyurethane foam raw material are mixed in a two-liquid mixing blower and blown onto a 0.07m × 0.15m slate substrate (1.0mm thick). After the mixture is applied, it is foamed and cured within 10 to 60 seconds to form a polyurethane foam layer (thickness: approximately 10mm).

[0223] Next, the two components of the non-foamed polyurethane raw material are mixed in a two-liquid mixing blower and blown onto the above-mentioned foamed polyurethane layer. After the mixture is applied, it is cured within 60 seconds to form a non-foamed polyurethane layer (thickness: approximately 10 μm).

[0224] Next, after spraying composition A1 onto the above-mentioned non-foamed polyurethane layer, the mixture was allowed to stand at 23°C for 1 week to crosslink and cure, forming the top layer (thickness: approximately 30 μm).

[0225] Thus, a laminate A1 was obtained having a substrate, a foamed polyurethane layer, a non-foamed polyurethane layer, and a top layer in sequence. The resulting laminate is provided for evaluation as described later.

[0226] (Examples 2~5)

[0227] As shown in Table 1, the composition used to form the top layer is modified, and in addition, laminates 2 to 5 are obtained in the same manner.

[0228] The resulting stacked body will be evaluated later.

[0229] <Evaluation>

[0230] (Seamless fit)

[0231] The determination is made according to the grid method (JIS K5600-5-6). The top layer of the laminate is cut into a checkerboard pattern with 2mm intervals and 50 grids. Adhesive tape is then applied to the grid, and the tape is peeled off. The number of grids that were not peeled off (number of grids not peeled off / 50) is measured.

[0232] It should be noted that in the meshes that have been delaminated, the top layer has delaminated in the form of peeling off from the unfoamed polyurethane layer.

[0233] (Top-level Tg)

[0234] A top layer was fabricated separately on a PTFE resin sheet and then peeled off. The peeled top layer was measured using DMA (Dynamic Viscoelasticity Measurement), and the temperature at which the maximum tanδ value was shown was taken as the Tg (°C) of the top layer.

[0235] It should be noted that the Tg of the top layer is essentially the same as that of the fluoropolymer with cross-linked structure formed in the top layer.

[0236] (elongation)

[0237] A separate top layer was fabricated on a PTFE sheet and then peeled off to obtain a test piece consisting of only the top layer. Tensile testing was performed using a tensile testing machine (ORIEnTEC TENSILON RTC-1310A) until the test piece broke, and the elongation (%) of the top layer was determined. The testing conditions were as follows: according to tensile test JIS K7127, the tensile speed was set to 50 mm / min. It should be noted that the elongation (%) is calculated by defining the length of the test piece before tensile testing as L0 and the length of the test piece at break as L... f The following formula can be used to find it.

[0238] Elongation (%) = (L) f -L0)×100 / L0

[0239] (50℃ water resistance test)

[0240] For the obtained laminate, the immersion water temperature was set to 50°C. In addition, a water resistance test was conducted at 50°C based on the test method JIS K5600-6-2 "Liquid Resistance (Water Immersion Method)". For the laminate after the water resistance test, the appearance change and the tightness were evaluated.

[0241] • Appearance changes

[0242] Based on JIS K5600-8-2, the appearance of the laminate after the test is determined according to the following criteria.

[0243] A: No foaming

[0244] B: Bubbles of size 1-2 or density 1-2 are produced.

[0245] C: Bubbles with a size of 3 or higher or a density of 3 or higher.

[0246] • Fit

[0247] The fit of the top layer in the laminated body after the test was determined using the same method as the fit evaluation described above.

[0248] <Results>

[0249] The table below shows the types of compositions used in each example and the results of the evaluation.

[0250] [Table 1]

[0251]

[0252] It should be noted that 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 as a disclosure of the specification of this invention.

[0253] Explanation of reference numerals in the attached figures

[0254] 10. Roofing components

[0255] 12 Substrate

[0256] 14. Polyurethane foam layer

[0257] 16 Non-foamed polyurethane layers

[0258] 18 Top Floor

[0259] 20 Polyurethane layers

Claims

1. A roof component having: Substrate, A polyurethane layer disposed on the substrate, and The 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 fluoropolymer. The fluoropolymer is a fluoropolymer with polar crosslinking groups, or a crosslinked product of a fluoropolymer with polar crosslinking groups. The fluoropolymer with polar crosslinking groups is a fluoropolymer with hydroxyl groups. The hydroxyl value of the fluoropolymer having hydroxyl groups is 35-65 mg KOH / g.

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

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

4. The roofing component according to claim 1 or 2, wherein, The glass transition temperature of the fluoropolymer is below 100°C.

5. The roofing component according to claim 1 or 2, wherein, The fluoropolymer has a cross-linked structure.

6. The roofing component according to claim 1 or 2, wherein, The glass transition temperature of the top layer is below 100°C.

7. The roofing component according to claim 1 or 2, wherein, The top layer also contains pigments.

8. The roofing component according to claim 1 or 2, wherein, The elongation of the top layer is 1.0% or more.

9. The roofing component according to claim 1 or 2, wherein, The substrate is slate.

10. The roofing component according to claim 1 or 2, wherein, The polyurethane layer comprises, from the substrate side, a foamed polyurethane layer and a non-foamed polyurethane layer in sequence.

11. The roofing component according to claim 1 or 2, wherein, The thickness ratio of the top layer to the foamed polyurethane layer is 0.00001 to 1.0.

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