complex

Abstract

Provided is a composite body which comprises a resin foam and a resin member that is different from the resin foam and is reduced in the deterioration in the appearance of the resin member.　A composite body comprising: a resin foam which is formed using a foaming agent comprising 1-chloro-2,3,3,3-tetrafluoropropene; and a resin member which is different from the resin foam and comprises a resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, a poly(phenylene ether) resin, an acrylonitrile-butadiene-styrene resin and a styrene-acrylonitrile copolymer resin.

Description

Technical Field

[0001] The present invention relates to a composite.

Background Art

[0002] Foams are used in various fields as cushioning materials and packaging materials that utilize their cushioning properties. When producing foams, foaming agents are often used. In Patent Document 1, a method of foaming polystyrene, which is a type of thermoplastic resin, using 1-chloro-3,3,3-trifluoropropene is disclosed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Foams are usually often used in combination with other members. Examples of other members include resin members composed of resin. The present inventors combined a foam of a thermoplastic resin obtained using 1-chloro-3,3,3-trifluoropropene described in Patent Document 1 with a resin member containing a predetermined resin and found that when stored for a long period of time, the resin member causes appearance deterioration such as discoloration or deformation.

[0005] An object of the present invention is to provide a composite that includes a resin foam and a resin member different from the resin foam and can suppress appearance deterioration of the resin member.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] (1) A resin foam formed using a foaming agent containing 1-chloro-2,3,3,3-tetrafluoropropene, A composite comprising a resin component different from a resin foam, which contains a resin selected from the group consisting of polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, and styrene-acrylonitrile copolymer resin. (2) 1-chloro-2,3,3,3-tetrafluoropropene is selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1-chloro-2,3,3,3-tetrafluoropropene, The composite according to (1), wherein the content of (Z)-1-chloro-2,3,3,3-tetrafluoropropene relative to the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 30% by mass or more. (3) The composite according to (2), wherein the content of (Z)-1-chloro-2,3,3,3-tetrafluoropropene relative to the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 75% by mass or more. (4) The composite according to any one of (1) to (3), wherein the resin foam comprises a thermosetting resin foam selected from the group consisting of polyurethane foam, polyisocyanurate foam, and phenolic resin foam. (5) A composite according to any one of (1) to (3), wherein the resin foam comprises a thermoplastic resin foam containing at least one selected from the group consisting of polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, polyolefin resin, polyvinyl chloride resin, (meth)acrylic resin, polyester resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyamide resin, polysulfone resin, polyetheretherketone resin, and polyetherketone resin. (6) A composite according to any one of (1) to (5), comprising two types of resin foams. (7) A composite according to any one of (1) to (6), wherein the resin foam contains two or more types of resin. (8) The complex according to any one of (1) to (7), wherein the blowing agent further comprises at least one compound selected from the group consisting of hydrofluoroolefin, hydrochlorofluoroolefin (except 1-chloro-2,3,3,3-tetrafluoropropene), hydrochloroolefin, chlorofluoroolefin, fluoroolefin, chloroolefin, olefin, hydrofluorocarbon, hydrochlorocarbon, hydrochlorofluorocarbon, chlorofluorocarbon, fluorocarbon, chlorocarbon, hydrocarbon, hydrofluoroether, carbon dioxide, organic acid, alcohol, ether, aldehyde, ketone, water, and nitrogen. (9) The complex according to any one of (1) to (8), wherein the blowing agent comprises at least one selected from the group consisting of 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,3-tetrafluoropropene, cyclopentane, n-pentane, isopentane, isobutane, n-butane, trans-1,2-dichloroethylene, carbon dioxide, and nitrogen. [Effects of the Invention]

[0008] According to the present invention, a composite material can be provided that includes a resin foam and a resin component different from the resin foam, and that can suppress deterioration of the appearance of the resin component. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram showing an example of a resin foam and resin component in a composite. [Figure 2] This is a schematic diagram showing another example of resin foam and resin components in a composite. [Modes for carrying out the invention]

[0010] The meanings of the terms used in this invention are as follows: A numerical range represented using "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, for halogenated hydrocarbons, the abbreviation of the compound is indicated in parentheses after the compound name, but in this specification, the abbreviation may be used instead of the compound name as needed. In addition, in some cases, only the numbers and lowercase letters after the hyphen (-) are used as the abbreviation (for example, "1224yd" for "HCFO-1224yd"). Furthermore, in this specification, where a compound name or a compound abbreviation is used without further specification, it refers to at least one selected from the Z-isomer and the E-isomer, more specifically, the Z-isomer or the E-isomer, or a mixture of the Z-isomer and the E-isomer in any proportion. When (E) or (Z) is added after a compound name or compound abbreviation, it refers to the E-isomer or Z-isomer of the respective compound. For example, 1224yd(Z) refers to the Z-isomer, and 1224yd(E) refers to the E-isomer.

[0011] In this specification, hydrofluoroolefin is a compound consisting of a carbon atom, a hydrogen atom, and a fluorine atom, and having a double bond. In this specification, hydrochlorofluoroolefin is a compound consisting of a carbon atom, a hydrogen atom, a fluorine atom, and a chlorine atom, and having a double bond. In this specification, hydrochloroolefin is a compound consisting of a carbon atom, a hydrogen atom, and a chlorine atom, and having a double bond. In this specification, chlorofluoroolefin is a compound consisting of a carbon atom, a fluorine atom, and a chlorine atom, and having a double bond. In this specification, fluoroolefin is a compound consisting of carbon atoms and fluorine atoms and having a double bond. In this specification, chloroolefin is a compound consisting of carbon atoms and chlorine atoms and having a double bond. In this specification, a hydrofluorocarbon is a compound consisting of carbon atoms, hydrogen atoms, and fluorine atoms, and which does not have unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a hydrochlorocarbon is a compound composed of carbon atoms, hydrogen atoms, and chlorine atoms and having no unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a hydrochlorofluorocarbon is a compound composed of carbon atoms, hydrogen atoms, fluorine atoms, and chlorine atoms and having no unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a chlorofluorocarbon is a compound composed of carbon atoms, fluorine atoms, and chlorine atoms and having no unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a fluorocarbon is a compound composed of carbon atoms and fluorine atoms and having no unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a chlorocarbon is a compound composed of carbon atoms and chlorine atoms and having no unsaturated bonds (e.g., double bonds, triple bonds). In this specification, a hydrofluoroether is a compound composed of carbon atoms, hydrogen atoms, fluorine atoms, and an etheric oxygen atom and having no unsaturated bonds (e.g., double bonds, triple bonds).

[0012] A characteristic point of the composite of the present invention is that a resin foam formed using 1-chloro-2,3,3,3-tetrafluoropropene (CF3-CF=CHCl, HCFO-1224yd) as a blowing agent is used. Although the detailed mechanism by which the effects of the present invention are obtained is unclear, it is presumed as follows. First, when a resin foam obtained using 1-chloro-3,3,3-trifluoropropene described in Patent Document [1] is combined with a specific resin member different from the above resin foam and used, it is considered that 1-chloro-3,3,3-trifluoropropene affects the appearance deterioration of the resin member different from the above resin foam. That is to say, in the resin foam obtained using 1-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene remains in pores and the like even after the formation of the resin foam, and the remaining 1-chloro-3,3,3-trifluoropropene affects a specific resin member different from the above resin foam over time, causing appearance deterioration. On the other hand, in the case of a resin foam using 1224yd as a foaming agent used in the present invention, even if 1224yd remains in pores and the like in the resin foam, the solubility of 1224yd itself in the resin member is relatively low, and as a result, it is considered that the appearance deterioration of the resin member different from the resin foam used in combination is suppressed.

[0013] The composite of the present invention includes a resin foam formed using a foaming agent containing 1224yd and a resin member different from the resin foam (hereinafter, also simply referred to as "resin member") containing a specific resin. Hereinafter, first, the members included in the composite will be described in detail.

[0014] <Resin foam> The resin foam is a foam composed of a resin formed using a foaming agent containing 1224yd. The resin foam contains at least one kind of resin. The resin foam may contain one kind of resin or may contain two or more kinds of resins.

[0015] Examples of the resin foam include a thermoplastic resin foam and a thermosetting resin foam. The thermoplastic resin foam is a foam formed using a thermoplastic resin and a foaming agent containing 1224yd. That is, it is a foam containing a thermoplastic resin. Furthermore, the above-mentioned thermosetting resin foam is a foam formed using a thermosetting resin and a foaming agent containing 1224yd.

[0016] (Thermoplastic foam) Specific examples of thermoplastic resins contained in thermoplastic resin foams include polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, polyolefin resin, polyvinyl chloride resin, (meth)acrylic resin, polyester resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyamide resin, polysulfone resin, polyetheretherketone resin, and polyetherketone resin. Specific examples of polyolefin resins include polyethylene resin and polypropylene resin. Furthermore, the polyolefin resin may be amorphous or crystalline. Specific examples of polyester resins include polyethylene terephthalate resin, polybutylene terephthalate resin, fully aromatic polyester resin, and polyarylate resin. Modified polyphenylene ether resins are polymer alloys of polyphenylene ether resin and other thermoplastic resins (e.g., polystyrene resin).

[0017] As thermoplastic resins, low-density polyethylene resin, high-density polyethylene resin, polypropylene resin, flexible polyvinyl chloride resin, rigid polyvinyl chloride resin, polystyrene resin, acrylonitrile-butadiene-styrene resin, and polycarbonate resin are preferred because they offer superior thermal insulation properties in their foamed form. Low-density polyethylene refers to a polyethylene with a density of (g / cm³). 3 ) is polyethylene with a density of 0.910 or more and less than 0.930, and high-density polyethylene is polyethylene with a density (g / cm³). 3 ) is polyethylene with a ratio of 0.942 or higher. Flexible polyvinyl chloride refers to polyvinyl chloride in which the plasticizer (e.g., phthalate ester) content is 10% by mass or more of the total amount, while rigid polyvinyl chloride resin refers to polyvinyl chloride in which the plasticizer (e.g., phthalate ester) content is 1% by mass or less of the total amount.

[0018] Thermoplastic resins may be used individually or in combination of two or more types. For example, when using two or more thermoplastic resins, the two or more thermoplastic resins can be mixed together, and then the resulting mixture can be foamed using a foaming agent.

[0019] (Thermosetting resin foam) Specific examples of thermosetting resin foams include polyurethane foam, polyisocyanurate foam, and phenolic resin foam. The polyurethane foam described above is a resin foam obtained by mixing a polyol having two or more hydroxyl groups and a polyisocyanate having two or more isocyanate groups with a blowing agent containing 1224yd, and simultaneously carrying out a foaming reaction and a resinification reaction. Examples of polyurethane foams include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, and integral skin foam. Flexible polyurethane foam is a type of foam in which the air bubbles within the foam are interconnected. Typically, it has a foaming ratio of approximately 10 to 60 times and an apparent density of 16 to 100 kg / m³. 3 It refers to a relatively lightweight plastic foam that is soft and resilient. Rigid polyurethane foam is a type of foam in which each individual air bubble is independent. Therefore, when a gas that does not conduct heat well is sealed within these bubbles, the rigid polyurethane foam maintains excellent thermal insulation performance over a long period of time. Semi-rigid polyurethane foam is an intermediate material between rigid polyurethane foam and flexible polyurethane foam, and its foam contains a mixture of interconnected and independent air bubbles. Integral skin foam is a foam that comprises a core portion exhibiting relatively low density cushioning properties and a skin portion bonded to the core portion and positioned on the surface of the foam, exhibiting relatively high density and high durability.

[0020] Rigid polyurethane foam is preferred as the polyurethane foam. In the case of rigid polyurethane foam, the average number of hydroxyl groups of the polyol is preferably 2 to 8, and more preferably 2.5 to 7.5. If it is above the lower limit of the above range, the compressive strength of the resulting foam is improved and shrinkage is suppressed, so dimensional stability tends to be good. If it is below the upper limit of the above range, the viscosity of the polyol does not become too high, so fluidity and moldability during foaming and molding tend to be good. The average number of hydroxyl groups of the polyol is the molar average of the number of hydroxyl groups of all polyols contained.

[0021] The weight-average molecular weight (Mw) of the polyol is preferably 100 to 3000, and more preferably 150 to 2000. If Mw is below the upper limit of the above range, shrinkage of the resulting foam is suppressed, and dimensional stability tends to be good. If Mw is above the lower limit of the above range, the resulting foam is less likely to become brittle. The Mw of the polyol is the average value of the Mw of all polyols contained in it.

[0022] The average hydroxyl value of the above polyol is preferably 100 to 800 mg KOH / g, more preferably 200 to 700 mg KOH / g, and even more preferably 300 to 600 mg KOH / g. If the average hydroxyl value is above the lower limit of the above range, shrinkage of the resulting foam is suppressed and dimensional stability is good. If the average hydroxyl value is below the upper limit, the resulting foam is less likely to become brittle. The average hydroxyl value of the above polyol may be calculated by weighting the hydroxyl values ​​of all the polyols contained, or it may be a value measured by mixing all the polyols contained.

[0023] Specific examples of polyols include polyether polyols, polyester polyols, polycarbonate polyols, polymers in which the main chain consists of hydrocarbon polymers and hydroxyl groups are introduced at the terminals, and polyhydric alcohols. Polyester ether polyols or polycarbonate polyols may be used as the polyol. The polyol may be used alone, or a mixture of two or more types may be used.

[0024] Specific examples of polyisocyanates include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; and modified polyisocyanates obtained by modifying these. More specifically, examples include polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (polymeric MDI), xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, or modified versions thereof. Specific examples of the above-mentioned modified compounds include prepolymer-type modified compounds, isocyanurate-type modified compounds, urea-type modified compounds, and carbodiimide-type modified compounds. Of these, polymeric MDI or its modified compounds are preferred in terms of reactivity and the strength of the resulting foam, and polymeric MDI modified compounds are more preferred. Polyisocyanates may be used individually or in mixtures of two or more types.

[0025] From the viewpoint of reactivity, the amount of polyisocyanate used is preferably 50 to 300, which is calculated by multiplying the number of isocyanate groups by 100 to the total number of active hydrogens in polyols and other compounds having active hydrogens.

[0026] The polyisocyanurate foam described above is a polyurethane foam having an isocyanurate ring, formed using a blowing agent containing 1224yd.

[0027] The phenolic resin foam described above is a resin foam obtained by mixing phenol and aldehyde with a foaming agent containing 1224 yd, and simultaneously carrying out foaming and resinification reactions.

[0028] (Foaming agent) The foaming agent contains 1224yd. 1224yd may be (Z)-1-chloro-2,3,3,3-tetrafluoropropene (1224yd(Z)) alone, (E)-1-chloro-2,3,3,3-tetrafluoropropene (1244yd(E)) alone, or a mixture of 1224yd(Z) and 1224yd(E). In the foaming agent, the molar ratio of the content of 1224yd(E) to the content of 1224yd(Z) (moles of 1224yd(E) / molars of 1224yd(Z)) can be 0 / 100 to 100 / 0. In particular, the content of 1224yd(Z) relative to the total mass of 1224yd (the sum of the masses of 1224yd(Z) and 1224yd(E)) is preferably 30% by mass or more, more preferably 75% by mass or more, even more preferably 90% by mass or more, and especially preferably 95% by mass or more. Most preferably 99% by mass or more. The upper limit is preferably 99.9% by mass, and preferably substantially 100% by mass. When the content of 1224yd(Z) is 30% by mass or more (preferably 75% by mass or more), the decomposition and oxidation of 1224yd are further suppressed. Also, when the content of 1224yd(Z) is 30% by mass or more, the deterioration of the appearance of the resin component is further suppressed.

[0029] As a blowing agent, 1224yd may be used alone, or 1224yd may be used in combination with other blowing agents. Other known blowing agents can be used as appropriate. These known blowing agents may be either so-called chemical blowing agents or physical blowing agents.

[0030] Other specific examples of blowing agents include inorganic chemical blowing agents such as sodium bicarbonate and ammonium carbonate, organic chemical blowing agents such as azodicarbonamide, N,N'-dinitrosopentamethylenetetramine, 4,4'-oxybis(benzenesulfonylhydrazide), and azobisisobutyronitrile, and water. Examples of physical blowing agents include hydrofluoroolefins, hydrochlorofluoroolefins (excluding 1-chloro-2,3,3,3-tetrafluoropropene), hydrochloroolefins, olefins, chlorofluoroolefins, fluoroolefins, chloroolefins, hydrofluorocarbons, hydrochlorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, fluorocarbons, chlorocarbons, hydrocarbons, hydrofluoroethers, carbon dioxide, organic acids, alcohols, ethers, aldehydes, ketones, and nitrogen.

[0031] Specific examples of hydrofluoroolefins include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), and 1,1,3,3,3-pentafluoropropene. Lopen (HFO-1225zc), 3,3,3-trifluoropropene (HFO-1243zf), 3,3-difluoropropene (HFO-1252zf), 2-fluoropropene (HFO-1261yf), 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336mcy) f) 1,3,3,4,4,4-Hexafluoro-1-butene (HFO-1336ze), Tetrafluorobutene (HFO-1354), 1,1,1,2,4,4,5,5,5-Nonafluoropentene (HFO-1429myz), 1,1,1,4,4,5,5,5-Octafluoropenta-2-ene (HFO-1438mzz), 1,3,4,4,4-Pentafluoro-3- Examples include difluoromethyl-1-butene (HFO-1438ezy), (C2F5)(CF3)C=CH2, (CF3)2CFCH=CF2, (CF3)2CFCF=CHF, 1,1-difluoroethylene (HFO-1132a), 1,1,2-trifluoroethylene (HFO-1123), and 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye).

[0032] Specific examples of hydrochlorofluoroolefins (excluding 1224yd) include 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), and 2-chloro Examples include -1,1,3,3-tetrafluoropropene (HCFO-1224xc), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2-fluoroethylene (HCFO-1121a), 1,2-dichloro-1-fluoroethylene (HCFO-1121), 1-chloro-1-fluoroethylene (HCFO-1131a), 1-chloro-2-fluoroethylene (HCFO-1131), 1-chloro-2,2-difluoroethylene (HCFO-1122), and 1,1,2-trifluoro-2-chloroethylene (HCFO-1113).

[0033] Specific examples of hydrochloroolefins include chloroethylene and 1,2-dichloroethylene.

[0034] Specific examples of chlorofluoroolefins include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,1,2-trichloro-2-fluoroethylene, and 2-chloro-1,1,3,3,3-pentafluoro-1-propene (CFO-1215xc).

[0035] Specific examples of fluoroolefins include hexafluoropropene (FO-1216) and octafluoro-2-butene (FO-1318my).

[0036] A specific example of a chloroolefin is tetrachloroethylene.

[0037] Specific examples of olefins include ethylene and propylene.

[0038] Specific examples of hydrofluorocarbons include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC-245eb), and 1,1,1,2,3,3,3-heptafluoropropane. Pan (HFC-227ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 2-f Luolopropane (HFC-281ea), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), difluoromethane (HFC-32), 1,1,1,2,2-pentafluoroethane (HFC-125), 1,1,2-triph Examples include ruoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), fluoroethane (HFC-161), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10mee), trifluoromethane (HFC-23), and fluoromethane (HFC-41).

[0039] Specific examples of hydrochlorocarbons include chloroform, 1,1,1,2,3-pentachloropropane (HCC-240dB), and 2-chloropropane.

[0040] Specific examples of hydrochlorofluorocarbons include chlorodifluoromethane (HCFC-22), chlorofluoromethane (HCFC-31), trichlorodifluoroethane (HCFC-122), 1,1,2-trichloro-1,2-difluoroethane (HCFC-122a), 1,1,1-trichloro-2,2-difluoroethane (HCFC-122b), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1,1,1,2-tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 2-chloro-1,1,1-trifluoroethane (HCFC-133a), and 1,1-dichloro-1-fluoroethane. Examples include chloroethane (HCFC-141b), 1,1-difluoro-2-chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a), 1-chloro-1,1-difluoroethane (HCFC-142b), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab), 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db), and 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0041] Specific examples of chlorofluorocarbons include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trichlorotrifluoroethane (CFC-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), chloropentafluoroethane (CFC-115), dichlorohexafluoropropane (CFC-216), 2,2,3,3-tetrachlorohexafluorobutane (CFC-316), and dichlorooctafluorobutane (CFC-318).

[0042] Specific examples of fluorocarbons include 1,1,1,2,2,2-hexafluoroethane (FC-116), octafluoropropane (FC-218), and 1,1,1,2,2,3,3-heptafluoropropane (FC-227ca).

[0043] Specific examples of hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane, and heptane.

[0044] Specific examples of hydrofluoroethers include CHF2-O-CHF2, CHF2-O-CH2F, CH2F-O-CH2F, CH2F-O-CH3, cyclo-CF2-CH2-CF2-O, cyclo-CF2-CF2-CH2-O, CHF2-O-CF2-CHF2, CF3-CF2-O-CH2F, CHF2-O-CHF-CF3, CHF2-O-CF2-CHF2, CH2F-O-CF2-CHF2, CF3-O-CF2-CH3, CHF2-CHF-O-CHF2, CF3-O-CHF-CH2F, CF3-CHF-O-CH2F, C F3-O-CH2-CHF2, CHF2-O-CH2-CF3, CHF2-CF2-O-CH2F, CHF2-O-CF2-CH3, CHF2-CF2-O-CH3, CHF2-CF2-O-CH3, CH2F-O-CHF-CH2F, CHF2-CHF-O-CH2F, CF Examples include 3-O-CHF-CH3, CF3-CHF-O-CH3, CHF2-O-CH2-CHF2, CF3-O-CH2-CH2F, CF3-CH2-O-CH2F, CF2H-CF2-CF2-O-CH3, CF3CF2CF2-O-CH3, and C4H9-O-CH3.

[0045] Specific examples of alcohols include methanol, ethanol, propanol, and isopropanol.

[0046] Specific examples of ethers include dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, dipropyl ether, diisopropyl ether, dimethoxymethane, diethoxyethane, dipropoxymethane, and dibutoxymethane.

[0047] Specific examples of aldehydes include formaldehyde, acetaldehyde, propanal, butanal, and isobutanal.

[0048] Specific examples of ketones include ketones, methyl ethyl ketone, methyl isobutyl ketone, and perfluoroethyl isopropyl ketone.

[0049] Specific examples of organic acids include methyl formate, ethyl formate, and formic acid.

[0050] While the above examples illustrate other foaming agents included in the foaming agent, the other foaming agents are not limited to those listed above, and other foaming agents (for example, 1-chloro-3,3,3-trifluoro-1-propyne (CF3-C≡CCl)) may also be used.

[0051] Preferably, as a blowing agent, the mixture contains, along with 1224yd, at least one compound selected from the group consisting of hydrofluoroolefins, hydrochlorofluoroolefins (excluding 1-chloro-2,3,3,3-tetrafluoropropene), hydrochloroolefins, olefins, chlorofluoroolefins, fluoroolefins, chloroolefins, hydrofluorocarbons, hydrochlorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, fluorocarbons, chlorocarbons, hydrocarbons, hydrofluoroethers, carbon dioxide, organic acids, alcohols, ethers, aldehydes, ketones, water, and nitrogen (hereinafter also referred to as "compound X"). As for compound X, at least one selected from the group consisting of 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,3-tetrafluoropropene, cyclopentane, n-pentane, isopentane, isobutane, n-butane, trans-1,2-dichloroethylene, carbon dioxide, and nitrogen is more preferred in terms of superior thermal insulation of the foam, improved solubility of the blowing agent to adjust the foaming properties, and availability and cost. Compound X may be used alone or in combination of two or more compounds.

[0052] The amount of foaming agent containing 1224yd used can be appropriately set depending on the foaming ratio of the final product, the type of foaming agent, and the resin temperature during molding, and is not particularly limited, but is preferably 0.2 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of resin material (e.g., thermoplastic resin or thermosetting resin). The content of 1224yd in the blowing agent is not particularly limited, but is preferably 1 to 100% by mass, more preferably 20 to 100% by mass, even more preferably 30 to 100% by mass, particularly preferably 50 to 100% by mass, and most preferably 70 to 100% by mass, relative to the total mass of the blowing agent.

[0053] When compound X is used, the amount of compound X used is not particularly limited, but it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total mass of 1224yd and compound X. Furthermore, it is preferably 95% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less. When compound X is used, the amount of 1224yd used is not particularly limited, but it is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more, relative to the total mass of 1224yd and compound X. Furthermore, it is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. In particular, when compound X is 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,3-tetrafluoropropene, cyclopentane, n-pentane, isopentane, isobutane, n-butane, trans-1,2-dichloroethylene, carbon dioxide, and nitrogen, the amount of compound X used relative to the total mass of 1224yd and compound X is preferably 1% by mass or more, more preferably 10% by mass or more. Furthermore, 95% by mass or less is preferred, 90% by mass or less is more preferred, 80% by mass or less is even more preferred, 70% by mass or less is particularly preferred, 40% by mass or less is most preferred, and 30% by mass or less is particularly most preferred.

[0054] (Method for manufacturing resin foam) As a method for producing resin foam, known methods can be used, and typically, a method is used to produce resin foam using a foaming agent containing 1224yd and a resin material (for example, a thermoplastic resin or a thermosetting resin). The following sections will explain the methods for producing thermosetting resin foams and thermoplastic resin foams separately.

[0055] When producing polyurethane foam as a thermosetting resin foam, polyisocyanate and polyol are mixed with a blowing agent containing 1224y, and the polyisocyanate and polyol are reacted to produce foam. The amount of foaming agent used is preferably 10 to 100 parts by mass, more preferably 12 to 60 parts by mass, and even more preferably 15 to 50 parts by mass, per 100 parts by mass of polyol.

[0056] Furthermore, foam stabilizers and catalysts may be used when manufacturing polyurethane foam. Foam stabilizers are used to form good bubbles. Examples of foam stabilizers include silicone-based foam stabilizers and fluorine-containing compound-based foam stabilizers. Commercially available foam stabilizers can be used. The amount of foam stabilizer used can be selected as appropriate, and its content is preferably 0.1 to 10 parts by mass per 100 parts by mass of polyol, as this facilitates the formation of better bubbles.

[0057] A urethane catalyst is used as a catalyst to promote the urethane reaction. As a urethane catalyst, tertiary amines are preferred in terms of reactivity. Specific examples of tertiary amines include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N”,N”-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, and 1,8-diaza Examples include bicyclo[5.4.0]undecene-7-triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, and N-methyl-N-(N,N-dimethylaminoethyl)ethanolamine.

[0058] Furthermore, other ingredients besides those mentioned above may be used as needed. Other known compounding agents can be used as the above-mentioned components. Specific examples of these compounding agents include fillers, antioxidants, flame retardants, plasticizers, colorants, antifungal agents, antifoaming agents, dispersants, and anti-discoloration agents. Specific examples of fillers include calcium carbonate and barium sulfate. Specific examples of antioxidants include antioxidants and UV absorbers. The amount of the other components mentioned above can be appropriately selected depending on the purpose, but 0.1 to 30 parts by mass per 100 parts by mass of polyol is preferred.

[0059] In terms of reactivity, the amount of catalyst used is preferably 0.1 to 100 parts by mass, and more preferably 0.1 to 20 parts by mass, per 100 parts by mass of polyol. By adjusting the amount of catalyst used within the above range, the time from the start of mixing of the foaming components to the start of the reaction (cream time), the time from the start of mixing to the start of resin curing (gel time), or the time from the start of mixing to the completion of foaming and resin curing (tack-free time) can be well adjusted.

[0060] Furthermore, when producing polyisocyanurate foam as a thermosetting resin foam, similar to polyurethane foam, polyisocyanate and polyol are mixed with a blowing agent containing 1224y, and the polyisocyanate and polyol are reacted to produce foam. When producing polyisocyanurate foam, it is preferable to use a trimerization reaction accelerating catalyst that promotes the trimerization reaction of isocyanate groups. As catalysts to promote the trimerization reaction, organic acid metal salts other than tin salts, lead salts, and mercury salts, quaternary ammonium salts, and combinations of the above metal salts and quaternary ammonium salts are preferred in terms of reactivity.

[0061] Excluding tin salts, lead salts, and mercury salts, specific examples of organic acid metal salts include, in terms of reactivity, carboxylate metal salts of potassium acetate, potassium 2-ethylhexanoate, or bismuth 2-ethylhexanoate. Specific examples of quaternary ammonium salts include tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate; and quaternary ammonium compounds obtained by anion exchange reaction of quaternary ammonium carbonates, which are obtained by reacting tertiary amines such as N,N,N',N'-tetramethylethylenediamine with diester carbonates, with 2-ethylhexanoic acid.

[0062] Specific manufacturing methods for thermosetting resin foams include, for example, the injection method, in which raw materials are injected into a mold or other frame and foamed; the continuous board molding method, in which raw materials are supplied between two surface materials and foamed, thereby producing a laminate in which thermosetting resin foam is sandwiched between these surface materials; and the spray method, in which raw materials are applied by spraying. The conditions for the above manufacturing method are appropriately selected depending on the type of thermosetting resin and foaming agent used.

[0063] The method for producing a foam by foaming a thermoplastic resin using a foaming agent containing 1224yd is not limited and includes, for example, the extrusion foaming method, injection foaming method, foam blowing method, bead foaming method, and press foaming method.

[0064] The extrusion foaming method involves melting and mixing thermoplastic resin and foaming agent in an extruder. training This method involves extruding the molten material into the atmosphere through the extrusion port at the tip of the extruder to cause foaming. Injection foaming is a method of manufacturing by introducing thermoplastic resin and a foaming agent into an injection molding machine, injecting the molten material into a mold, and obtaining a foamed material within the mold. The foam blow method is a method of obtaining a foam by sandwiching a parison containing thermoplastic resin and a foaming agent, extruded from an extruder, between molds and blowing air into the inside to form the desired shape. The bead foaming method involves creating thermoplastic resin particles and incorporating a foaming agent into the particles under pressure. Soaking This method involves first causing a mixture to foam by changing the temperature and pressure, then creating foam particles, and finally obtaining the foam through in-mold foam molding. The press foaming method is a method of obtaining a foam by placing a sheet containing thermoplastic resin and a foaming agent into a heated press mold and allowing it to foam.

[0065] 1224yd falls under the category of a so-called physical blowing agent, and the method of mixing it with thermoplastic resin and the timing of its use are similar to those of known physical blowing agents.

[0066] The most suitable manufacturing method is selected depending on the application of the thermoplastic resin. For example, when manufacturing building insulation materials using polystyrene resin as the thermoplastic resin, it is preferable to select the extrusion foaming method and the bead foaming method. When manufacturing automotive interior components using polyolefin resin (particularly polyethylene resin and polypropylene resin) as the thermoplastic resin, it is preferable to select the injection molding method. The conditions for the above manufacturing method are appropriately selected depending on the type of thermoplastic resin and foaming agent used.

[0067] Specific examples of resin foam shapes include sheet-like, plate-like, rod-like, tubular, spherical (bead-like), and combinations thereof. Note that "sheet-like" means a thickness of 1000 μm or less, while "plate-like" means a thickness of more than 1000 μm. The density of the resin foam is selected to be optimal depending on the application, ranging from 0.02 to 0.96 g / cm³. 3 In many cases, this is the case. The above density is a value measured according to JIS K7222. The average bubble diameter of resin foam is selected to be optimal depending on the application, but it is often between 10 and 1200 μm. The average bubble diameter of the resin foam is determined by measuring the diameter of 50 bubbles using an optical microscope (magnification: 50x) and taking the average value. Note that the bubble diameter refers to the diameter of the long axis.

[0068] <Resin components> A resin component is a component made of resin, distinct from the resin foam described above. The resins included in the resin component are polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, or styrene-acrylonitrile copolymer resin (SAN). The polystyrene resin may be high-impact polystyrene (HIPS) or general-purpose polystyrene (GPPS). For resin components containing the above resins, the influence from the resin foam formed using a foaming agent containing 1224yd is reduced compared to when other foaming agents are used, and the desired effect can be obtained. Furthermore, the phrase "different from resin foam" above means that the resin component is not a resin foam formed using a foaming agent containing 1224yd, and the resin component is a component that does not contain 1224yd. The resin component may be a foam or a non-foam material.

[0069] Specific examples of resin component shapes include sheet-like, plate-like, rod-like, tubular, spherical (bead-like), and combinations thereof.

[0070] <complex> The composite of the present invention includes the resin foam and resin member described above. The composite of the present invention may contain only one type of resin foam, or it may contain two or more types of resin foam. Furthermore, the composite of the present invention may contain one type of resin member, or it may contain two or more types of resin members.

[0071] Furthermore, the composite of the present invention may contain multiple resin foams, for example, two resin foams may be arranged in the composite so as to sandwich a resin member. Furthermore, the composite of the present invention may contain multiple resin members; for example, two resin members may be arranged in the composite so as to sandwich a resin foam.

[0072] In the composite of the present invention, the resin foam and the resin member may be arranged adjacent to each other (in direct contact), or they may be arranged with other members (for example, an adhesive layer) described later in between. The resin foam and the resin component may be placed with space between them.

[0073] The composite may include other components besides the resin foam and resin components. For example, the composite may include other organic components, such as other resins, rubber, or elastomers, in addition to the resin contained in the resin component. Other resins included in other organic materials include polyolefin resin, polyvinyl chloride resin, (meth)acrylic resin, polyester resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyamide resin, polysulfone resin, polyetheretherketone resin, polyetherketone resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polytetrafluoroethylene, polyurethane resin, phenolic resin, melamine resin, and urea resin. Specific examples of rubber included in other organic materials include natural rubber, silicone rubber, urethane rubber, butyl rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, nitrile rubber, fluororubber, ethylene propylene diene rubber, hydrogenated nitrile rubber, vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber, tetrafluoroethylene-purple orovinyl ether rubber, and fluorosilicone rubber. Specific examples of elastomers included in other organic materials include olefin-based elastomers, polyvinyl chloride-based elastomers, polystyrene-based elastomers, polyester-based elastomers, and polyamide-based elastomers.

[0074] Other components may include those containing inorganic materials. Specific examples of the inorganic materials mentioned above include metals, carbon materials, and glass.

[0075] As described above, the resin foam and the resin component may be arranged via other components, and in this embodiment, the other component may be a component that functions as a so-called adhesion layer. An adhesion layer is a layer that improves the adhesion between components. Specific examples of an adhesion layer include an adhesive layer and a bonding layer, both of which contain resin.

[0076] The shape of the composite depends on the shape of the resin foam and the resin components, and examples include sheet-like, plate-like, rod-like, tubular, spherical (bead-like), and combinations thereof. Furthermore, the arrangement of the resin foam and resin components within the composite is not restricted, and the optimal arrangement can be selected according to the application. For example, as shown in Figure 1, a laminate (composite) may be formed by stacking a layered resin foam 10 and a layered resin member 12 adjacent to each other. Alternatively, as shown in Figure 2, a laminate (composite) may be formed by sandwiching the layered resin foam 10 between two layered resin members 12. Furthermore, the resin foam may be arranged so as to cover at least a portion (preferably the entire surface) of the surface of a resin member of a predetermined shape (for example, sheet-like, plate-like, spherical, or tubular).

[0077] Various known methods can be applied to produce the composite. For example, a composite material can be fabricated by laminating a resin foam and a resin component, and then, if necessary, heat-pressing them together using a press or other means. Furthermore, for example, when forming a resin foam by the spray method as described above, a composite can be created by spraying the resin foam raw material onto a resin member to form a resin foam that covers at least a portion of the surface of the resin member. Alternatively, a composite can be created in which a resin foam is sandwiched between two resin members by injecting the raw material between two resin members and allowing it to foam.

[0078] Foams can be applied to a variety of uses, such as packaging materials, packing materials, cushioning materials, heat insulation materials, heat retention materials, cold retention materials, sound-absorbing materials, soundproofing materials, vibration damping materials, building materials, cushioning materials, supplies, and containers. More specifically, these include components for ships, vehicles (e.g., vibration damping materials for automobiles, sound absorbing materials for automobiles, interior components for automobiles), building materials (e.g., building insulation materials, building joint materials, flashing materials), civil engineering materials (e.g., building protective materials), electrical equipment materials (e.g., refrigerator materials (panels for refrigerated and frozen vehicles), refrigerated display case materials, air conditioner materials, audio equipment materials), medical materials (e.g., medical supplies materials, nursing care supplies materials, rehabilitation supplies materials), aircraft materials, furniture materials (e.g., bedding materials, chair materials), housing materials, industrial products (e.g., vibration damping pad materials, air seal materials, gasket materials, mask materials, filter materials), packaging materials, agricultural materials, and stationery materials. [Examples]

[0079] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Examples 1-9 and 11-17 are examples, and Examples 10 and 18 are comparative examples.

[0080] <Effect on the appearance of other resins (visual observation evaluation)> Polycarbonate resin sheets (PC sheets), polystyrene resin sheets (PS sheets), polyphenylene ether resin sheets (PPE sheets), and acrylonitrile-butadiene-styrene resin sheets (ABS sheets) were prepared as resin sheets. Test specimens (25 mm × 30 mm × 2 mm) were prepared from each resin sheet for measurement. The test specimens were placed in Pyrex® inner tubes and inserted into a SUS316 pressure vessel with an internal volume of 200 cc (maximum operating temperature 300 °C, maximum operating pressure 20 MPa). After sealing the pressure vessel, the inside of the pressure vessel was evacuated. Next, the composition shown in each example (80 g) was filled into the pressure vessel. The pressure vessel was placed in a constant temperature bath maintained at 50 °C and allowed to stand for 120 hours. After 120 hours, the pressure vessel was removed from the constant temperature bath, the test specimens were removed from the pressure vessel, their appearance was observed, and they were evaluated according to the following criteria.

[0081] A: No change B: Slight discoloration or deformation (including swelling) may be observed, but it does not affect practical use. C: Obvious discoloration or deformation (including swelling) is observed, to the extent that it poses a practical problem.

[0082] <Stability Test> One piece each of iron (SS400, 25mm x 30mm x 3.2mm), copper (25mm x 30mm x 2mm), and aluminum (25mm x 30mm x 2mm) were prepared as metal pieces. The metal pieces were placed together in an internal tube made of Pyrex®. A 200cc pressure-resistant container made of SUS316 (maximum operating temperature 300°C, maximum operating pressure 20MPa) containing the internal tube with the metal pieces was evacuated, and the composition shown in each example (60g) was filled into it. It was placed in a hot air circulating constant temperature bath and left to stand at a constant temperature of 175°C for 14 days. After 14 days, the pressure-resistant container was removed from the constant temperature bath, and the acid content of the composition was analyzed as follows. The pressure vessel was left to stand until it reached room temperature after the above test. Four absorption bottles, each containing 100 ml of pure water, were connected in series with conduits to the pressure vessel. The valve of the pressure vessel was gradually opened to introduce the composition into the water in the absorption bottles, and the acid contained in the composition was extracted. The water from the first and second absorption bottles was combined, one drop of indicator (BTB: bromothymol blue) was added, and the mixture was titrated with a 1 / 100N-NaOH alkaline standard solution. Simultaneously, the water from the third and fourth absorption bottles was combined and titrated in the same manner to create a measurement blank. From these measured values ​​and the measurement blank values, the concentration of acid contained in the composition after the test was determined as the HCl concentration and evaluated according to the following criteria. The results are shown in Table 1. A: Acid content (HCl equivalent) 3 mass ppm or less B: Acid content (HCl equivalent) more than 3 mass ppm and less than 5 mass ppm C: Acid content (HCl equivalent) exceeding 5 mass ppm

[0083] <Examples 1-10> The compositions listed in Table 1 and the resin plates (PC plates, PS plates, PPE plates, ABS plates) listed in Table 1 were prepared, and the above-mentioned <Effect on the appearance of other resins (visual observation evaluation)> and <Stability tests> were performed. The compositions prepared were those containing a blowing agent selected from the group consisting of 1224yd(Z), 1224yd(E), and 1233zd(E), in the compositions shown in Table 1. In Table 1, each component column represents the mass percentage (mass%) of each component relative to the total amount of 1224yd(Z), 1224yd(E), and 1233zd(E).

[0084] [Table 1]

[0085] As shown in the visual observation evaluation results in Table 1 above, it was confirmed that 1224yd has little effect on any of the resins. In particular, a comparison of Examples 1-9 confirmed that when the content of 1224yd(Z) relative to the total amount of 1224yd(Z) and 1224yd(E) is 30% by mass or more, the impact on other resins is minimal. Furthermore, from a comparison of Examples 1 to 9, it was confirmed that when the content of 1224yd(Z) relative to the total amount of 1224yd(Z) and 1224yd(E) is 30% by mass or more (preferably 75% by mass or more), the stability is excellent.

[0086] Furthermore, if cyclopentane, n-pentane, isopentane, isobutane, n-butane, or trans-1,2-dichloroethylene is used instead of 1224yd(E) in Example 1, the same trend as in Example 1 can be obtained.

[0087] <Examples 11-18> The evaluation of the influence on the appearance of the other resins mentioned above will be carried out using the liquefied compositions shown in each example in Table 2. In the table, 1224yd refers to the isomer ratio (mass ratio) of 1224yd(Z) / 1224yd(E) = 99.4 / 0.6. Note that the column for each component in Table 2 represents the mass percentage (mass%) of each component relative to the total amount of 1224yd, cyclopentane, and 1233zd(E).

[0088] [Table 2]

[0089] As shown in Table 2 above, it has been confirmed that 1224yd has little effect on any of the resins. In particular, a comparison of Examples 11-17 confirms that when the content of 1224yd(Z) relative to the total amount of 1224yd(Z) and cyclopentane is 70% by mass or more, the impact on other resins is less.

[0090] Furthermore, if n-pentane, isopentane, isobutane, n-butane, or trans-1,2-dichloroethylene is used instead of cyclopentane in Examples 12-14, similar trends to those in Examples 12-14 can be obtained.

[0091] <Composite Evaluation> Using the method described in Example 1 of Japanese Patent Publication No. 2015-105340 as a reference, resin foams 1 to 10 (polyurethane foams) are obtained by using the compositions described in Examples 1 to 10 as foaming agents. Furthermore, we prepared separate resin boards made of PC, PS, PPE, and ABS. PC boards are laminated so as to sandwich the resin foam 1, thereby obtaining a composite (see Figure 2) in which the PC boards and resin foam 1 are laminated in this order. Alternatively, instead of PC boards, PS boards, ABS boards, or PPE boards are used, and composites are made by sandwiching the resin foam 1 between the respective resin boards. Alternatively, instead of resin foam 1, resin foams 2 to 10 can be used to obtain composites in which resin foams 2 to 10 are sandwiched between resin plates. After leaving these composites at 70°C for three weeks, the appearance of each resin plate was observed, and results similar to those in Table 1 were confirmed. For example, no particular change was observed in the PC plate of the composite formed by laminating resin foam 1 (a resin foam formed using the composition of Example 1 as a foaming agent) with a PC plate, but discoloration was observed in the PC plate of the composite formed by laminating resin foam 10 (a resin foam formed using the composition of Example 10 as a foaming agent) with a PC plate.

[0092] Furthermore, except for using the compositions described in Examples 1 to 10 as foaming agents, integral skin foams 1 to 10 were prepared according to the description in Example 1A of Japanese Patent Publication No. 2018-507956, and the resulting integral skin foams were used in place of resin foams 1 to 10. The composite was then prepared according to the procedure described in <Composite Evaluation> above, and the appearance of each resin plate was observed. Results showing a similar trend to those in Table 1 were confirmed.

[0093] Furthermore, the entire contents of the specifications, claims, drawings, and abstracts of Japanese Patent Application No. 2019-183589, filed on October 4, 2019, and Japanese Patent Application No. 2020-076632, filed on April 23, 2020, are incorporated herein by reference as disclosure of the present invention. [Explanation of Symbols]

[0094] 10 Resin foam 12 Resin components

Claims

1. A resin foam formed using a foaming agent containing 1-chloro-2,3,3,3-tetrafluoropropene, A resin component different from the resin foam, comprising a resin selected from the group consisting of polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, and styrene-acrylonitrile copolymer resin, The resin foam includes a metal member in contact with the resin foam, The 1-chloro-2,3,3,3-tetrafluoropropene is selected from the group consisting of (Z)-1-chloro-2,3,3,3-tetrafluoropropene and (E)-1-chloro-2,3,3,3-tetrafluoropropene, A composite in which the content of (Z)-1-chloro-2,3,3,3-tetrafluoropropene relative to the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 75% by mass or more.

2. The composite according to claim 1, wherein the resin foam comprises a thermosetting resin foam selected from the group consisting of polyurethane foam, polyisocyanurate foam, and phenolic resin foam.

3. The composite according to claim 1, wherein the resin foam comprises a thermoplastic resin foam containing at least one selected from the group consisting of polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, polyolefin resin, polyvinyl chloride resin, (meth)acrylic resin, polyester resin, modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyamide resin, polysulfone resin, polyetheretherketone resin, and polyetherketone resin.

4. A composite according to any one of claims 1 to 3, comprising two types of the aforementioned resin foams.

5. The composite according to any one of claims 1 to 4, wherein the resin foam comprises two or more resins.

6. The complex according to any one of claims 1 to 5, wherein the blowing agent further comprises at least one compound selected from the group consisting of hydrofluoroolefin, hydrochlorofluoroolefin (excluding 1-chloro-2,3,3,3-tetrafluoropropene), hydrochloroolefin, chlorofluoroolefin, fluoroolefin, chloroolefin, olefin, hydrofluorocarbon, hydrochlorocarbon, hydrochlorofluorocarbon, chlorofluorocarbon, fluorocarbon, chlorocarbon, hydrocarbon, hydrofluoroether, carbon dioxide, organic acid, alcohol, ether, aldehyde, ketone, water, and nitrogen.

7. The composite according to any one of claims 1 to 5, wherein the blowing agent further comprises at least one selected from the group consisting of 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluoro-2-butene, 1,3,3,3-tetrafluoropropene, cyclopentane, n-pentane, isopentane, isobutane, n-butane, trans-1,2-dichloroethylene, carbon dioxide, and nitrogen.

8. The composite according to any one of claims 1 to 7, wherein the content of 1-chloro-2,3,3,3-tetrafluoropropene relative to the total mass of the foaming agent is 70 to 100% by mass.

9. The composite according to any one of claims 1 to 8, wherein the content of (Z)-1-chloro-2,3,3,3-tetrafluoropropene relative to the total mass of 1-chloro-2,3,3,3-tetrafluoropropene is 95% by mass or more.

10. The composite according to any one of claims 1 to 9, wherein the resin member different from the resin foam is a non-foamed material.

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