JP6528686B2 - Heat storage sheet, heat storage laminate, and method of manufacturing heat storage sheet - Google Patents
Heat storage sheet, heat storage laminate, and method of manufacturing heat storage sheet Download PDFInfo
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- JP6528686B2 JP6528686B2 JP2015554831A JP2015554831A JP6528686B2 JP 6528686 B2 JP6528686 B2 JP 6528686B2 JP 2015554831 A JP2015554831 A JP 2015554831A JP 2015554831 A JP2015554831 A JP 2015554831A JP 6528686 B2 JP6528686 B2 JP 6528686B2
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- Prior art keywords
- heat storage
- sheet
- mass
- storage sheet
- heat
- Prior art date
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- 238000005338 heat storage Methods 0.000 title claims description 138
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000011248 coating agent Substances 0.000 claims description 60
- 238000000576 coating method Methods 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 54
- 239000011232 storage material Substances 0.000 claims description 54
- 239000004014 plasticizer Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 40
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 30
- 229920002554 vinyl polymer Polymers 0.000 claims description 30
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 238000001879 gelation Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 9
- 238000009792 diffusion process Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
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- 230000001747 exhibiting effect Effects 0.000 claims description 2
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- 239000007790 solid phase Substances 0.000 claims description 2
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- -1 aliphatic diester Chemical class 0.000 description 13
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000011810 insulating material Substances 0.000 description 10
- 229920002799 BoPET Polymers 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000012188 paraffin wax Substances 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 229920001944 Plastisol Polymers 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 239000004999 plastisol Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- 229910000831 Steel Inorganic materials 0.000 description 5
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
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- 238000010030 laminating Methods 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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- 229920001971 elastomer Polymers 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 206010037660 Pyrexia Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FTSXVYQZLNPTCM-UHFFFAOYSA-N (3-benzoyloxy-2,2,4-trimethylpentyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C)(C)C(C(C)C)OC(=O)C1=CC=CC=C1 FTSXVYQZLNPTCM-UHFFFAOYSA-N 0.000 description 1
- OMVSWZDEEGIJJI-UHFFFAOYSA-N 2,2,4-Trimethyl-1,3-pentadienol diisobutyrate Chemical compound CC(C)C(=O)OC(C(C)C)C(C)(C)COC(=O)C(C)C OMVSWZDEEGIJJI-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- RNVXSRJRDVLSAG-UHFFFAOYSA-N 2-[2-(2-benzoyloxypropoxy)propoxy]propyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)COC(C)COC(C)COC(=O)C1=CC=CC=C1 RNVXSRJRDVLSAG-UHFFFAOYSA-N 0.000 description 1
- CGJPNFOSJVSHDC-UHFFFAOYSA-N 2-benzoyloxybutyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)COC(=O)C1=CC=CC=C1 CGJPNFOSJVSHDC-UHFFFAOYSA-N 0.000 description 1
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 1
- HVWZDMVPWXVEBP-UHFFFAOYSA-N 3-benzoyloxybutyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CCOC(=O)C1=CC=CC=C1 HVWZDMVPWXVEBP-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UMVMVEZHMZTUHD-UHFFFAOYSA-N DL-Propylene glycol dibenzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)COC(=O)C1=CC=CC=C1 UMVMVEZHMZTUHD-UHFFFAOYSA-N 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011101 paper laminate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、各種使用態様に応じた適温保持、省エネルギー化が可能な蓄熱シートに関する。特に、住宅等の居住空間や自動車等の室内の適温保持に有用な蓄熱シートに関する。 The present invention relates to a heat storage sheet capable of maintaining appropriate temperature and saving energy according to various usage modes. In particular, the present invention relates to a heat storage sheet useful for maintaining an appropriate temperature of a living space such as a house or a room such as a car.
近年、住宅やオフィス等の居住空間において省エネルギー化の要請が高まっており、住宅等に使用される建築材料にも省エネルギー化に貢献する材料が求められている。一般的には、床、天井、壁面等に断熱材を用いて冷暖房の効率化が図られているが、さらなる省エネルギー化のために各種材料の検討がなされている。また、自動車や航空機等の閉空間や、冷蔵車等の冷蔵庫内においても同様に省エネルギー化の要請が高い。 In recent years, the demand for energy saving is increasing in living spaces such as houses and offices, and materials that contribute to energy saving are also required for building materials used in houses and the like. In general, thermal insulation materials are used on floors, ceilings, wall surfaces, and the like to improve the efficiency of air conditioning and heating, but various materials are being studied for further energy saving. Similarly, the demand for energy saving is high also in closed spaces such as cars and aircrafts and in refrigerators such as refrigerated cars.
このような材料としては、例えば、石膏ボードに潜熱蓄熱材をカプセル化したものを混ぜ合わせた材料が開示されている（特許文献１参照）。当該材料は壁面等に使用することで、壁面等の熱容量を増加させて省エネルギー化を図るものである。しかし、当該材料は石膏ボード中に蓄熱材が含有されており、柔軟性や取扱い性に乏しく、使用態様に制限があるものであった。 As such a material, for example, a material in which a latent heat storage material encapsulated in gypsum board is mixed is disclosed (see Patent Document 1). By using the said material for a wall surface etc., the heat capacity of a wall surface etc. is made to increase and energy saving is achieved. However, the said material contained the thermal storage material in the gypsum board, it was lacking in the softness | flexibility and the handleability, and there was a restriction | limiting in a usage aspect.
柔軟性のある材料を使用した蓄熱シートとしては、例えば、エラストマまたはゴムからなるシート状の基材に蓄熱材が充填された蓄熱シートが開示されている（特許文献２参照）。しかし、当該蓄熱シートの成形は、液状化したゴム等へ蓄熱材を混合し、ミキサー等による混練や押出成形等を経るため、蓄熱材が破壊され、得られた蓄熱材の染み出しが生じる場合があった。 As a heat storage sheet using a flexible material, for example, a heat storage sheet in which a heat storage material is filled in a sheet-like substrate made of an elastomer or a rubber is disclosed (see Patent Document 2). However, when the heat storage sheet is formed by mixing the heat storage material with liquefied rubber and subjecting the heat storage material to destruction because the heat storage material is subjected to kneading, extrusion molding, etc. using a mixer, etc. was there.
本発明が解決しようとする課題は、蓄熱材の染み出しが生じにくい樹脂系の蓄熱シートを提供することにある。 The problem to be solved by the present invention is to provide a resin-based heat storage sheet in which the heat storage material hardly bleeds out.
より好適には、使用態様に応じた適温保持に貢献できる蓄熱性を有し、良好な柔軟性を有し、かつ蓄熱材の染み出しが生じにくい蓄熱シートを提供することにある。 More preferably, the present invention is to provide a heat storage sheet which has a heat storage property that can contribute to keeping an appropriate temperature according to a usage mode, has a good flexibility, and hardly causes a heat storage material to exude.
本発明においては、塩化ビニル樹脂粒子及び蓄熱材を含有するビニルゾル塗工液のゾルキャスト膜からなる蓄熱シートにより、上記課題を解決した。 In this invention, the said subject was solved by the thermal storage sheet which consists of a sol cast film of the vinyl sol coating liquid containing a vinyl chloride resin particle and a thermal storage material.
本発明の蓄熱シートは、塩化ビニル樹脂をマトリクス材とすることから、石膏ボード等の剛直な材料に比して柔軟性や取扱い性に優れる。また、蓄熱材の染み出しが生じにくいことから、染み出しを抑制するための保護層等が不要となり、当該蓄熱シート単体での流通や使用も可能である。さらに、ロール状とすることもできるため、化粧層や、熱伝導層等の他の機能層との積層加工も容易であり、切断性や加工性も良好であることから各種態様での使用が可能である。 Since the heat storage sheet of the present invention uses a vinyl chloride resin as a matrix material, it is excellent in flexibility and handleability as compared with rigid materials such as gypsum board. In addition, since it is difficult for the heat storage material to exude, a protective layer or the like for suppressing the exfoliation becomes unnecessary, and the heat storage sheet can be circulated or used alone. Furthermore, since it can be in the form of a roll, lamination processing with other functional layers such as a decorative layer and a heat conductive layer is also easy, and its cuttability and processability are also good, so its use in various forms It is possible.
このような本発明の蓄熱シートは、各種用途に使用でき、住宅等の居住空間の壁材や壁紙、自動車、電車、航空機、農業ハウス等の室内、さらには、冷蔵車や冷蔵設備の冷蔵庫内、航空機の庫内等の閉空間、パソコンのＣＰＵや蓄電池などの熱を発生する電気部品に適用する材料等、各種用途において好適に省エネルギー化に貢献できる。 Such a heat storage sheet of the present invention can be used for various applications, such as wall materials and wallpaper of living space such as houses, indoors such as cars, trains, aircrafts, agricultural houses, etc., and also inside refrigerators of refrigerated cars and refrigerators. It can contribute to energy saving suitably in various applications, such as materials applied to closed spaces such as the interior of aircraft storage, electric components such as CPUs and storage batteries of personal computers, etc.
本発明の蓄熱シートは、塩化ビニル樹脂粒子及び蓄熱材を含有するビニルゾル塗工液のゾルキャスト膜からなる蓄熱シートである。 The heat storage sheet of the present invention is a heat storage sheet comprising a sol cast film of a vinyl sol coating liquid containing vinyl chloride resin particles and a heat storage material.
本発明に使用するビニルゾル塗工液は、塩化ビニル樹脂粒子及び蓄熱材が、可塑剤中や、可塑剤と溶剤中に分散、懸濁されたペースト状の塗工液である。 The vinyl sol coating solution used in the present invention is a paste-like coating solution in which vinyl chloride resin particles and a heat storage material are dispersed and suspended in a plasticizer or in a plasticizer and a solvent.
塩化ビニル樹脂粒子の平均粒子径は、０.０１〜１０μｍであることが好ましく、０．１〜５μｍであることが好ましい。塗工液中では、当該粒子が直接分散した状態でも、当該粒子を一次粒子として、球状の二次粒子に凝集した状態で分散した状態であってもよい。また、粒子径の異なる粒子が混合されて、粒度分布のピークが二以上あるものであってもよい。粒子径はレーザー法等により測定できる。 The average particle size of the vinyl chloride resin particles is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. In the coating liquid, even when the particles are directly dispersed, the particles may be dispersed as primary particles in a state of being aggregated into spherical secondary particles. In addition, particles having different particle sizes may be mixed to have two or more peaks of the particle size distribution. The particle size can be measured by a laser method or the like.
ビニルゾル塗工液に使用する塩化ビニル樹脂粒子の形状は、好適な流動性を得やすく、熟成粘度変化が小さいことから、略球形形状であることが好ましい。塩化ビニル樹脂粒子は、乳化重合、懸濁重合により製造されたものが、球形形状を得やすく、また、粒度分布を制御しやすいため好ましい。 The shape of the vinyl chloride resin particles used in the vinyl sol coating solution is preferably substantially spherical because it is easy to obtain suitable fluidity and small in change in aging viscosity. The vinyl chloride resin particles are preferably produced by emulsion polymerization or suspension polymerization, because spherical particles can be easily obtained and the particle size distribution can be easily controlled.
使用する塩化ビニル樹脂の重合度としては、５００〜４０００であることが好ましく、６００〜２０００であることがより好ましい。 The polymerization degree of the vinyl chloride resin to be used is preferably 500 to 4000, and more preferably 600 to 2000.
本発明に使用する塩化ビニル樹脂粒子は、市販されている塩化ビニル樹脂粒子を適宜使用でき、例えば、新第一塩ビ株式会社製ＺＥＳＴ ＰＱ８３，ＰＷＬＴ，ＰＱ９２，Ｐ２４Ｚ等や、株式会社カネカ製ＰＳＬ−６７５，６８５等が挙げられる。 As vinyl chloride resin particles used in the present invention, commercially available vinyl chloride resin particles can be appropriately used. For example, ZEST PQ 83, PWLT, PQ 92, P24 Z, etc. manufactured by Shin-ichi Shiori PVC Co., Ltd., PSL-manufactured by Kaneka Corporation 675, 685 and the like.
ビニルゾル塗工液中の塩化ビニル樹脂の含有量は、塗工液に含まれる固形分（溶媒以外の成分）中の１０〜８０質量％であることが好ましく、２０〜７０質量％であることがより好ましく、３０〜６０質量％であることがさらに好ましい。 It is preferable that it is 10-80 mass% in solid content (components other than a solvent) contained in a coating liquid, and, as for content of vinyl chloride resin in a vinyl sol coating liquid, it is 20-70 mass%. More preferably, it is 30 to 60% by mass.
本発明に使用する蓄熱材は、蓄熱性を有する材料であれば特に限定されないが、固体−液体の相変化による潜熱蓄熱材を使用する事が好ましい。 The heat storage material used in the present invention is not particularly limited as long as it has a heat storage property, but it is preferable to use a latent heat storage material due to a solid-liquid phase change.
潜熱蓄熱材は、相変化による溶融時の染み出し等の問題や、混入時の分散性を考慮して、有機マイクロカプセル中にパラフィンなどの潜熱蓄熱材料を含有した、マイクロカプセル化された蓄熱粒子が好ましい。この蓄熱粒子は、公知のものを用いればよい。蓄熱粒子の粒径は、限定される事はないが、１０〜１０００μｍ程度であることが好ましく、５０〜５００μｍであることがより好ましい。蓄熱粒子の粒子径は、その一次粒子の粒子径が上記範囲であることも好ましいが、一次粒子径が１〜５０μｍ、好ましくは２〜１０μｍの粒子が凝集して二次粒子を形成し、当該二次粒子の粒径が上記範囲となった蓄熱粒子であることも好ましい。このような蓄熱粒子は、圧力やシェアにより破損しやすいが、本発明の構成によれば、当該蓄熱粒子の破損を好適に抑制でき、蓄熱材料の染み出しや漏れが生じにくくなる。特に、外殻が有機材料から形成される場合には温度による破損のおそれも生じるが、本発明の蓄熱シートは、このような潜熱蓄熱材を使用した場合にも蓄熱材料の染み出しや漏れを好適に抑制できる。なお、蓄熱シート中に使用する全蓄熱粒子の粒子径が上記範囲でなくともよく、蓄熱シート中の蓄熱粒子の８０質量％以上が上記範囲の蓄熱粒子であることが好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることが特に好ましい。 The latent heat storage material is a microencapsulated heat storage particle containing a latent heat storage material such as paraffin in an organic microcapsule, taking into consideration problems such as exudation at the time of melting due to phase change, and dispersibility at the time of mixing. Is preferred. The heat storage particles may be known ones. The particle diameter of the heat storage particles is not limited, but is preferably about 10 to 1000 μm, and more preferably 50 to 500 μm. The particle diameter of the heat storage particles is preferably such that the particle diameter of the primary particles is in the above range, but particles having a primary particle diameter of 1 to 50 μm, preferably 2 to 10 μm aggregate to form secondary particles. It is also preferable that they are heat storage particles in which the particle diameter of the secondary particles is in the above range. Such heat storage particles are easily damaged by pressure and shear, but according to the configuration of the present invention, the damage of the heat storage particles can be suitably suppressed, and the heat storage material is less likely to ooze out or leak. In particular, when the outer shell is formed of an organic material, there is a risk of breakage due to temperature, but the heat storage sheet of the present invention exudes or leaks the heat storage material even when such a latent heat storage material is used. It can be suitably suppressed. In addition, the particle diameter of all the heat storage particles used in the heat storage sheet may not be in the above range, and it is preferable that 80% by mass or more of the heat storage particles in the heat storage sheet is the heat storage particles in the above range, 90% by mass or more The content is more preferably 95% by mass or more.
潜熱蓄熱材は、特定の温度の融点において相変化する。すなわち、室温が融点を超えた場合は、固体から液体へ相変化し、室温が融点より下がった場合は、液体から固体へ相変化する。潜熱蓄熱材の融点は、その使用態様に応じて調整すればよく、−２０℃〜１２０℃程度の温度範囲にて固／液相転移を示すものを適宜使用できる。例えば、住宅等の居住空間や、自動車、電車、航空機、農業ハウス等の室内等の適温維持し、省エネルギー化を図る場合には、この融点を日常生活に適した温度、具体的には１０〜３５℃、好ましくは１５〜３０℃に設計した潜熱蓄熱材を混入する事により、適温維持性能を発揮する事ができる。より詳細に冬季又は夏季の適温維持性能を調整する場合には、冬場の暖房効果を持続させる事を目的とすれば２５〜２８℃程度を融点とした潜熱蓄熱材を混入する。もしくは、夏場の冷房効率を持続させる事を目的とすれば２０〜２３℃程度を融点とした潜熱蓄熱材を混入する事ができる。両方の効果を発現するには融点設計の異なる２種類以上の潜熱蓄熱材を混入すればよい。また、冷蔵設備等の庫内の省エネルギー化を図る場合には、−１０℃〜５℃程度の融点の潜熱蓄熱材を使用すればよい。 The latent heat storage material undergoes a phase change at the melting point of a specific temperature. That is, when the room temperature exceeds the melting point, the phase changes from solid to liquid, and when the room temperature falls below the melting point, the phase changes from liquid to solid. The melting point of the latent heat storage material may be adjusted according to the mode of use, and a material exhibiting a solid / liquid phase transition in a temperature range of about -20 ° C to 120 ° C can be suitably used. For example, when energy saving is desired by maintaining the appropriate temperature of a living space such as a house, or a room such as a car, a train, an aircraft, or an agricultural house, the melting point is a temperature suitable for daily life, specifically 10 to By mixing a latent heat storage material designed at 35 ° C., preferably 15 to 30 ° C., appropriate temperature maintenance performance can be exhibited. When adjusting the appropriate temperature maintenance performance in winter or summer in more detail, for the purpose of maintaining the heating effect in winter, a latent heat storage material having a melting point of about 25 to 28 ° C. is mixed. Alternatively, in order to maintain the cooling efficiency in summer, a latent heat storage material having a melting point of about 20 to 23 ° C. can be mixed. In order to exhibit both effects, two or more kinds of latent heat storage materials having different melting point designs may be mixed. Moreover, in order to save energy in a refrigerator such as a refrigerator, a latent heat storage material having a melting point of about -10 ° C to 5 ° C may be used.
ビニルゾル塗工液中の蓄熱材の含有量は、塗工液に含まれる固形分中の１５〜６０質量％であることが好ましく、２０〜６０質量％であることがより好ましい。 It is preferable that it is 15-60 mass% in solid content contained in a coating liquid, and, as for content of the thermal storage material in a vinyl sol coating liquid, it is more preferable that it is 20-60 mass%.
本発明に使用するビニルゾル塗工液は可塑剤を含有することが好ましく、当該可塑剤としては、フタル酸系可塑剤、安息香酸系可塑剤、トリメリット酸系可塑剤、アジピン酸系可塑剤、エポキシ系可塑剤、メタクリレート系可塑剤、ポリエステル系可塑剤、ポリエーテルエステル系可塑剤、脂肪族ジエステル系可塑剤等、汎用の可塑剤を適宜使用できる。また、２種類以上の可塑剤を適宜混合して使用しても良い。 The vinyl sol coating liquid used in the present invention preferably contains a plasticizer, and as the plasticizer, phthalic acid based plasticizer, benzoic acid based plasticizer, trimellitic acid based plasticizer, adipic acid based plasticizer, General-purpose plasticizers such as epoxy plasticizers, methacrylate plasticizers, polyester plasticizers, polyether ester plasticizers, aliphatic diester plasticizers, and the like can be suitably used. In addition, two or more types of plasticizers may be appropriately mixed and used.
なかでも、低温でゲル化できる可塑剤を好ましく使用でき、ゲル化終了温度が１５０℃以下であることが好ましく、１４０℃以下であることがより好ましく、１３０℃以下であることがさらに好ましく、１２０℃以下であることがさらに好ましく、１１０℃以下であることが特に好ましい。上記例示した可塑剤のうち、安息香酸系可塑剤は、ゲル化終了温度を低く設定しやすいことから好ましく使用でき、特に安息香酸エステル系可塑剤を好ましく使用できる。安息香酸エステル系可塑剤としては、１，２−プロピレングリコールジベンゾエート、１，２−ブチレングリコールジベンゾエート、１，３−ブチレングリコールジベンゾエート、ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリプロピレングリコールジベンゾエート、２，２，４−トリメチル−１，３−ペンタンジオールイソブチレートベンゾエート、２，２，４−トリメチル−１，３−ペンタンジオールジベンゾエート等が挙げられる。ゲル化終了温度は、ゲル化膜の光透過性が一定となる温度をゲル化終了温度とできる。 Among them, plasticizers that can gel at low temperatures can be preferably used, and the gelation completion temperature is preferably 150 ° C. or less, more preferably 140 ° C. or less, and still more preferably 130 ° C. or less. C. or less is more preferable, and 110.degree. C. or less is particularly preferable. Among the plasticizers exemplified above, benzoic acid-based plasticizers can be preferably used because the gelation completion temperature can be easily set low, and in particular, benzoate-based plasticizers can be preferably used. Benzoic acid ester plasticizers include 1,2-propylene glycol dibenzoate, 1,2-butylene glycol dibenzoate, 1,3-butylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate Examples include benzoate, 2,2,4-trimethyl-1,3-pentanediol isobutyrate, and 2,2,4-trimethyl-1,3-pentanediol dibenzoate. The end temperature of gelation can be a temperature at which the light transmittance of the gelled film becomes constant as the end temperature of gelation.
本発明に使用する可塑剤は、２５℃における粘度が１５００ｍＰａ・ｓ以下であることが好ましく、１０００ｍＰａ・ｓ以下であることがより好ましく、８００ｍＰａ・ｓ以下であることがさらに好ましく、５００ｍＰａ・ｓ以下であることが特に好ましい。当該範囲とすることで、ビニルゾル塗工液の粘度を低く抑えることができるため、蓄熱材の充填率が高めることができる。なお、可塑剤粘度測定の条件は後述実施例における条件にて測定できる。 The viscosity at 25 ° C. of the plasticizer used in the present invention is preferably 1500 mPa · s or less, more preferably 1000 mPa · s or less, still more preferably 800 mPa · s or less, and 500 mPa · s or less Is particularly preferred. By setting it as the said range, since the viscosity of a vinyl sol coating liquid can be restrained low, the filling rate of a thermal storage material can be raised. In addition, the conditions of plasticizer viscosity measurement can be measured on the conditions in a below-mentioned Example.
本発明に使用する可塑剤は、その重量平均分子量が２００〜３０００であることが好ましく、３００〜１０００であることがより好ましい。当該範囲とすることで、可塑剤自身が染み出しにくく、且つビニルゾル塗工液の粘度を低く抑えることができるため、蓄熱材の充填率が高めることができる。なお、重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィー（以下、「ＧＰＣ」と略記する。）測定に基づきポリスチレン換算した値である。なお、ＧＰＣ測定は以下の条件にて測定できる。 The weight average molecular weight of the plasticizer used in the present invention is preferably 200 to 3,000, and more preferably 300 to 1,000. By setting it as the said range, since the plasticizer itself does not ooze out easily, and the viscosity of a vinyl sol coating liquid can be restrained low, the filling rate of a thermal storage material can be raised. The weight average molecular weight (Mw) is a value converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as "GPC") measurement. GPC measurement can be performed under the following conditions.
［重量平均分子量の測定条件］
測定装置：東ソー株式会社製ガードカラム「ＨＬＣ−８３３０」
カラム：東ソー株式会社製「ＴＳＫ ＳｕｐｅｒＨ−Ｈ」
＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ−Ｍ」
＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺＭ−Ｍ」
＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺ−２０００」
＋東ソー株式会社製「ＴＳＫ ｇｅｌ ＳｕｐｅｒＨＺ−２０００」
検出器：ＲＩ（示差屈折計）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルＩＩバージョン４．１０」
カラム温度：４０℃
展開溶媒：テトラヒドロフラン（ＴＨＦ）
流速：０．３５ｍＬ／分
試料：樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）
標準試料：前記「ＧＰＣ−８０２０モデルＩＩバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。[Measurement conditions of weight average molecular weight]
Measuring device: Guard column "HLC-8330" manufactured by Tosoh Corporation
Column: "TSK SuperH-H" manufactured by Tosoh Corporation
+ "TSK gel Super HZM-M" manufactured by Tosoh Corporation
+ "TSK gel Super HZM-M" manufactured by Tosoh Corporation
+ "TSK gel Super HZ-2000" manufactured by Tosoh Corporation
+ "TSK gel Super HZ-2000" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.35 mL / min Sample: What was a 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)
Standard sample: According to the measurement manual of the above-mentioned "GPC-8020 model II version 4.10", the following monodispersed polystyrene whose molecular weight is known was used.
（標準試料：単分散ポリスチレン）
東ソー株式会社製「Ａ−３００」
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
東ソー株式会社製「Ｆ−２８８」(Standard sample: monodispersed polystyrene)
Tosoh Corporation "A-300"
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation "F-80"
Tosoh Corporation "F-128"
Tosoh Corporation "F-288"
ビニルゾル塗工液中の可塑剤の含有量は、塗工液に含まれる塩化ビニル樹脂１００質量部に対して、３０〜１５０質量部であることが好ましく、３０〜１２０質量部であることがより好ましく、４０〜１００質量部であることがさらに好ましい。 The content of the plasticizer in the vinyl sol coating liquid is preferably 30 to 150 parts by mass, more preferably 30 to 120 parts by mass with respect to 100 parts by mass of the vinyl chloride resin contained in the coating liquid. Preferably, it is further preferably 40 to 100 parts by mass.
本発明に使用するビニルゾル塗工液中には、適宜溶媒を使用することもできる。当該溶媒としては、塩化ビニル樹脂のゾルキャスト法にて使用される溶媒を適宜使用でき、なかでも、ジイソブチルケトン、メチルイソブチルケトンなどのケトン類、酢酸ブチルなどのエステル類、グリコールエーテル類等を好ましく例示できる。これら溶媒は、常温で樹脂をわずかに膨潤して分散を助長しやすく、また、加熱工程で溶融ゲル化を促進しやすいため好ましい。これらの溶媒は単独で用いてもよく、２種以上を混合して用いてもよい。 A solvent can also be suitably used in the vinyl sol coating liquid used for this invention. As the solvent, solvents used in the sol cast method of vinyl chloride resin can be appropriately used. Among them, ketones such as diisobutyl ketone, methyl isobutyl ketone, esters such as butyl acetate, glycol ethers and the like are preferable. It can be illustrated. These solvents are preferable because they slightly swell the resin at normal temperature to facilitate dispersion, and also facilitate melt gelation in the heating step. These solvents may be used alone or in combination of two or more.
また、上記溶媒と共に希釈溶媒を使用してもよい。希釈溶媒としては、樹脂を溶解せず、分散溶媒の膨潤性を抑制する溶媒を好ましく使用できる。このような希釈溶媒としては、例えば、パラフィン系炭化水素、ナフテン系炭化水素、芳香族炭化水素、テルペン系炭化水素などを使用できる。 Moreover, you may use a dilution solvent with the said solvent. As the dilution solvent, a solvent which does not dissolve the resin and suppresses the swelling property of the dispersion solvent can be preferably used. As such a dilution solvent, for example, paraffin hydrocarbons, naphthene hydrocarbons, aromatic hydrocarbons, terpene hydrocarbons and the like can be used.
ビニルゾル塗工液には、塩化ビニル樹脂の脱塩化水素反応を主とする分解劣化、着色を抑制するために熱安定剤を使用することも好ましい。熱安定剤としては、例えば、カルシウム／亜鉛系安定剤、オクチル錫系安定剤、バリウム／亜鉛系安定剤等を使用できる。熱安定剤の含有量は、塩化ビニル樹脂１００質量部に対して、０.５〜１０質量部が好ましい。 In the vinyl sol coating solution, it is also preferable to use a thermal stabilizer in order to suppress the degradation and coloration of the vinyl chloride resin mainly due to the dehydrochlorination reaction. As the heat stabilizer, for example, a calcium / zinc stabilizer, an octyl tin stabilizer, a barium / zinc stabilizer and the like can be used. The content of the heat stabilizer is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
ビニルゾル塗工液には、上記以外の成分として、減粘剤、分散剤、消泡剤等の添加剤を、必要に応じて適宜含有してもよい。これら添加剤の含有量は、各々、塩化ビニル樹脂１００質量部に対して、０.５〜１０質量部が好ましい。 The vinyl sol coating liquid may appropriately contain, as components other than the above, additives such as a viscosity reducing agent, a dispersing agent, and an antifoaming agent, as necessary. The content of each of these additives is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
ビニルゾル塗工液の塗工時の粘度は、所望のシートの厚みや、塗工条件等により適宜調整すればよいが、良好な塗工適正を得やすいことから、１０００ｍＰａ・ｓ以上が好ましく、３０００ｍＰａ・ｓ以上がより好ましく、５０００ｍＰａ・ｓ以上がさらに好ましく、７０００ｍＰａ・ｓ以上が特に好ましい。また、当該粘度の上限は４００００ｍＰａ・ｓ以下が好ましく、３００００ｍＰａ・ｓ以下がより好ましく、２７０００ｍＰａ・ｓ以下がさらに好ましく、２５０００ｍＰａ・ｓ以下が特に好ましい。なお、塗工液粘度測定の条件は後述実施例における条件にて測定できる。 The viscosity at the time of coating of the vinyl sol coating liquid may be appropriately adjusted according to the desired sheet thickness, coating conditions, etc., but is preferably 1000 mPa · s or more, because it is easy to obtain good coating suitability. S or more is more preferable, 5000 mPa · s or more is more preferable, and 7000 mPa · s or more is particularly preferable. The upper limit of the viscosity is preferably 40000 mPa · s or less, more preferably 30000 mPa · s or less, still more preferably 27000 mPa · s or less, and particularly preferably 25000 mPa · s or less. In addition, the conditions of a coating liquid viscosity measurement can be measured on the conditions in a below-mentioned Example.
本発明の蓄熱シートは、上記ビニルゾル塗工液のゾルキャスト膜からなる蓄熱シートであり、詳細には、以下の工程を有する製法にて得られるシートである。
（１）支持体上に、塩化ビニル樹脂粒子及び蓄熱材を含有するビニルゾル塗工液を塗布し、ビニルゾル塗工膜を得る工程、
（２）ビニルゾル塗工膜を加熱してゲル化膜からなる蓄熱シートを形成する工程The heat storage sheet of the present invention is a heat storage sheet comprising a sol cast film of the above-mentioned vinyl sol coating liquid, and more specifically, is a sheet obtained by a manufacturing method having the following steps.
(1) applying a vinyl sol coating solution containing vinyl chloride resin particles and a heat storage material on a support to obtain a vinyl sol coating film,
(2) A process of heating a vinyl sol coating film to form a heat storage sheet comprising a gelled film
（１）の工程においては、支持体上に、塩化ビニル樹脂粒子及び蓄熱材を含有するビニルゾル塗工液を塗布し、ビニルゾル塗工膜を得る。ここで使用する支持体は、蓄熱シートを剥離して流通、使用等する場合には、得られる蓄熱シートを剥離可能で、加熱工程の温度での耐熱性を有するものを適宜使用できる。また、蓄熱シートを他の機能層や基材と積層して使用する場合には、当該他の機能層や基材を支持体としてもよい。 In the step (1), a vinyl sol coating solution containing vinyl chloride resin particles and a heat storage material is applied on a support to obtain a vinyl sol coating film. As the support used here, when the heat storage sheet is peeled, circulated, used, etc., the obtained heat storage sheet can be peeled, and one having heat resistance at the temperature of the heating step can be appropriately used. When the heat storage sheet is used by laminating it on another functional layer or base, the other functional layer or base may be used as a support.
蓄熱シートを剥離する場合の支持体としては、例えば、各種の工程フィルムとして使用される樹脂フィルムを好ましく使用できる。当該樹脂フィルムとしては、例えば、ポリエチレンテレフタレート樹脂フィルム、ポリブチレンテレフタレート樹脂フィルム等のポリエステル樹脂フィルムなどが挙げられる。樹脂フィルムの厚みは特に制限されないが、２５〜１００μｍ程度のものが取扱いや入手が容易である。 As a support in the case of peeling a thermal storage sheet, the resin film used as various process films can be used preferably, for example. Examples of the resin film include polyester resin films such as polyethylene terephthalate resin film and polybutylene terephthalate resin film. The thickness of the resin film is not particularly limited, but one having a thickness of about 25 to 100 μm is easy to handle and obtain.
支持体として使用する樹脂フィルムは、表面が剥離処理されているものを好ましく使用できる。剥離処理に用いられる剥離処理剤としては、例えば、アルキッド系樹脂、ウレタン系樹脂、オレフィン系樹脂、シリコーン系樹脂などが挙げられる。 As the resin film used as a support, one having a surface subjected to release treatment can be preferably used. Examples of the release treatment agent used for the release treatment include alkyd resins, urethane resins, olefin resins and silicone resins.
ビニルゾル塗工液を塗布するキャスト成膜の方法としては、ロールナイフコーター、リバースロールコーターなどの塗工機を使用できる。なかでも、支持体上にビニルゾル塗工液を送り出し、ドクターナイフ等により、一定の厚みの塗工膜を形成する方法を好ましく使用できる。 As a method of cast film formation which applies a vinyl sol coating liquid, coating machines, such as a roll knife coater and a reverse roll coater, can be used. Among them, a method of sending a vinyl sol coating solution onto a support and forming a coating film having a predetermined thickness with a doctor knife or the like can be preferably used.
（２）の工程においては、（１）にて得られたビニルゾル塗工膜を加熱してゲル化させ、支持体上に当該ゲル化膜からなる蓄熱シートを形成する。加熱溶融のゲル化温度は、１６０℃以下が好ましく、１５０℃以下がより好ましく、１４０℃以下がさらに好ましく、１３０℃以下がさらに好ましく、１２０℃以下が特に好ましい。加熱時間は、ゲル化速度等に応じて適宜調整すればよいが、１０秒〜１０分程度が通常である。 In the step (2), the vinyl sol coating film obtained in (1) is heated and gelated to form a heat storage sheet comprising the gelated film on a support. 160 ° C. or less is preferable, 150 ° C. or less is more preferable, 140 ° C. or less is more preferable, 130 ° C. or less is more preferable, and 120 ° C. or less is particularly preferable. The heating time may be suitably adjusted according to the gelation rate etc., but it is usually about 10 seconds to 10 minutes.
溶媒を使用する場合には、上記加熱工程においてゲル化と溶媒の除去を同時に行ってもよいが、上記ゲル化の加熱の前に、予備乾燥を行うことも好ましい。 When a solvent is used, gelation and removal of the solvent may be carried out simultaneously in the heating step, but it is also preferable to carry out pre-drying before heating the gelation.
上記にて形成された蓄熱シートは、蓄熱シートを支持体から剥離する工程により、蓄熱シートとして使用できる。当該剥離は、適宜好適な手法で剥離すればよい。また、各種加工や積層を行うにあたり、支持体上に積層した状態が好ましい場合には、支持体上に積層した状態で流通することもできる。 The heat storage sheet formed above can be used as a heat storage sheet by the process of peeling a heat storage sheet from a support body. The peeling may be performed by a suitable method as appropriate. Moreover, when performing the various processes and lamination, when the state laminated | stacked on a support body is preferable, it can also distribute | circulate in the state laminated | stacked on a support body.
蓄熱シート中の塩化ビニル樹脂の含有量は、１０〜８０質量％であることが好ましく、２０〜７０質量％であることがより好ましく、３０〜６０質量％であることがさらに好ましい。当該範囲とすることで、柔軟性を有するシート形成しやすくなる。蓄熱シート中の蓄熱材の含有量は１０〜８０質量％であることが好ましく、２０〜７０質量％であることがより好ましく、３０〜６０質量％であることがさらに好ましい。当該範囲とすることで、良好な蓄熱効果を得やすく、良好なシート形成性が得られやすくなる。また、蓄熱シート中の可塑剤の含有量は、５〜７５質量％であることが好ましく、１０〜７０質量％であることがより好ましく、２０〜６０質量％であることがさらに好ましい。当該範囲とすることで、良好な塗工適性やシート形成性を得やすくなる。 The content of the vinyl chloride resin in the heat storage sheet is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass. By setting it as the said range, it becomes easy to form the sheet | seat which has flexibility. The content of the heat storage material in the heat storage sheet is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 30 to 60% by mass. By setting it as the said range, it is easy to acquire a favorable thermal storage effect, and it becomes easy to acquire favorable sheet formation property. In addition, the content of the plasticizer in the heat storage sheet is preferably 5 to 75% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass. By setting it as the said range, it becomes easy to obtain favorable coating aptitude and sheet formation property.
本発明の蓄熱シートは、上記のとおりの塩化ビニル樹脂粒子及び蓄熱材を含有するビニルゾル塗工液のゾルキャスト膜からなる蓄熱シートである。当該構成の蓄熱シートは、製造時に蓄熱材にシェアや圧力がかからないため蓄熱材の破壊が生じにくいことから、樹脂系の材料を使用しながらも蓄熱材の染み出しが生じにくい。また、当該蓄熱材による蓄熱性を有すると共に、良好な柔軟性を実現できる。さらに、容易に他の層との積層や加工も可能であることから各種用途や態様での使用が可能である。 The heat storage sheet of the present invention is a heat storage sheet composed of a sol cast film of a vinyl sol coating liquid containing vinyl chloride resin particles as described above and a heat storage material. In the heat storage sheet having the configuration, since the heat storage material is not subjected to shear or pressure at the time of manufacture, destruction of the heat storage material is less likely to occur, and therefore bleeding of the heat storage material is less likely to occur while using resin materials. Moreover, while having the thermal storage property by the said thermal storage material, favorable softness | flexibility is realizable. Furthermore, since lamination and processing with other layers are easily possible, it can be used in various applications and modes.
本発明の蓄熱シートの厚みは、使用態様に応じて適宜調整すればよい。例えば、閉空間の壁面等へ適用する場合には、好適な蓄熱効果を得やすいことから５０μｍ以上が好ましく、１００μｍ以上がより好ましく、５００μｍ以上がさらに好ましく、１ｍｍ以上が特に好ましい。また、好適な柔軟性を得やすく、ロール供給がしやすいことから６ｍｍ以下が好ましく、５ｍｍ以下がより好ましく、３ｍｍ以下がさらに好ましく、２ｍｍ以下が特に好ましい。 The thickness of the heat storage sheet of the present invention may be appropriately adjusted according to the use mode. For example, in the case of applying to a wall surface or the like of a closed space, 50 μm or more is preferable, 100 μm or more is more preferable, 500 μm or more is more preferable, and 1 mm or more is particularly preferable. In addition, 6 mm or less is preferable, 5 mm or less is more preferable, 3 mm or less is more preferable, and 2 mm or less is particularly preferable because it is easy to obtain suitable flexibility and to facilitate roll supply.
本発明の蓄熱シートは、蓄熱性をより向上させる為、これを積層して使用することも好ましい。また、各種の機能層と積層することも好ましい。例えば、不燃紙等の不燃層と積層することで、居住空間への適用おいて、難燃性を向上させることができる。また、例えば、熱拡散層や断熱層と積層することで、蓄熱性をより効果的に発現することもできる。また、居住空間の内壁等へ適用するために、化粧層や装飾層を設けることもできる。 The heat storage sheet of the present invention is also preferably used by laminating it in order to further improve the heat storage property. Moreover, it is also preferable to laminate | stack with various functional layers. For example, by laminating with a noncombustible layer such as noncombustible paper, it is possible to improve the flame retardance in the application to the living space. In addition, for example, by laminating with a heat diffusion layer or a heat insulating layer, it is possible to more effectively express the heat storage property. Moreover, in order to apply to the inner wall etc. of a living space, a makeup layer and a decoration layer can also be provided.
不燃層と積層した構成としては、本発明の蓄熱シートの片面又は両面に不燃紙を積層した構成を例示できる。片面に不燃紙を積層した構成としては、本発明の蓄熱シートを不燃紙に貼り合せた構成であってもよいが、不燃紙上に直接本発明の蓄熱シートを形成するビニルゾル塗工液を塗布、ゲル化した構成とすると形成が容易であるため好ましい。また、両面に不燃紙を有する構成としては、本発明の蓄熱シートの両面に不燃紙を貼り合せた構成であってもよいが、不燃紙上にビニルゾル塗工液を塗布、ゲル化した不燃紙積層蓄熱シートの蓄熱シート面同士を貼り合せることで容易に形成できる。 As a structure laminated | stacked with the incombustible layer, the structure which laminated | stacked incombustible paper on the single side | surface or both surfaces of the thermal storage sheet | seat of this invention can be illustrated. Although the non-combustible paper may be laminated on one side, the heat storage sheet of the present invention may be laminated to the non-combustible paper, but the vinyl sol coating liquid for forming the heat storage sheet of the present invention is directly applied onto the non-combustible paper A gelled structure is preferable because it is easy to form. Moreover, as a structure which has incombustible paper on both surfaces, although the structure which stuck incombustible paper on both surfaces of the thermal storage sheet of this invention may be sufficient, the non-combustible paper is apply | coated and gelled non-combustible paper lamination. It can form easily by pasting the heat storage sheet side of a heat storage sheet.
当該不燃紙としては、不燃性を有するものであれば特に限定しないが、例えば、紙に難燃剤を塗布、含浸、内添しているものを使用できる。難燃剤としては、水酸化マグネシウム、水酸化アルミニウム等の金属水酸化物、リン酸塩、ホウ酸塩、ステファミン酸塩等の塩基性化合物、ガラス繊維等が例示できる。 The non-combustible paper is not particularly limited as long as it has non-combustibility, but for example, paper in which a flame retardant is applied, impregnated and internally added can be used. Examples of the flame retardant include metal hydroxides such as magnesium hydroxide and aluminum hydroxide, basic compounds such as phosphates, borates and stefamic acid salts, and glass fibers.
熱拡散層を積層した構成として室内等の閉空間に適用した場合には、熱拡散層で室内の熱を均一化する効果を持たせるとともに、室内（本発明においては、住宅等の居住空間や、自動車、電車、航空機等の室内、さらには、冷蔵車の冷蔵庫内、航空機の庫内等の閉空間を総称して室内と称することがある。）からの熱を分散して熱抵抗が少なく蓄熱層へ伝える事ができる。蓄熱層では蓄熱粒子により室内の熱吸収及び室内への熱放出がなされ、室内の温度環境下を適温に制御できる。 When the heat diffusion layer is applied to a closed space such as a room as a laminated structure, the heat diffusion layer has the effect of making the heat in the room uniform, and the room (in the present invention, The heat resistance is reduced by distributing heat from indoors such as cars, trains and aircrafts, as well as closed spaces such as inside a refrigerator of a refrigerated car and inside the storage of an aircraft. It can be transmitted to the heat storage layer. In the heat storage layer, heat is absorbed by the heat storage particles and released to the room, so that the temperature environment of the room can be controlled to an appropriate temperature.
熱拡散層としては、熱伝導率が５〜４００Ｗ／ｍ・Ｋの高い熱伝導率を有する層を好ましく使用できる。高い熱伝導率により、局所に集中した熱を拡散して蓄熱層へ伝えて熱効率を向上し、かつ室温を均一化できる。 As the thermal diffusion layer, a layer having a high thermal conductivity of 5 to 400 W / m · K can be preferably used. The high thermal conductivity diffuses locally concentrated heat and transfers it to the heat storage layer, thereby improving the thermal efficiency and making the room temperature uniform.
熱拡散層の材料としては、例えば、アルミニウム、銅、鉄、グラファイトなどが挙げられる。本発明では、特にアルミニウムを好適に用いることができる。アルミニウムが好適な理由として、放射熱の反射による断熱効果も発現することが挙げられる。特に、放射熱による暖房器具では、断熱効果により暖房効率を向上する事ができる。放射熱を主とした暖房器具としては、例えば、電気式床暖房、温水式床暖房、赤外線ヒーターなどが挙げられる。また、防災の視点からも難燃性能を向上させる事ができる。 Examples of the material of the heat diffusion layer include aluminum, copper, iron, graphite and the like. In the present invention, particularly, aluminum can be suitably used. The reason why aluminum is preferable is that it also exhibits an insulation effect by reflection of radiant heat. In particular, in the case of a radiant heater, the heating efficiency can be improved by the heat insulation effect. Examples of the heating device mainly for radiant heat include electric floor heating, hot water floor heating, and an infrared heater. In addition, the flame retardant performance can be improved from the viewpoint of disaster prevention.
熱拡散層の形態としては、上記材料のシートからなる層や、上記材料の蒸着層等の適宜な形態を使用できる。材料としてアルミニウムを使用する場合には、たとえば、アルミ箔、アルミ蒸着層などの湾曲性があるものを好ましく使用できる。 As a form of a thermal diffusion layer, appropriate forms, such as a layer which consists of a sheet of the above-mentioned material, a vapor deposition layer of the above-mentioned material, etc., can be used. In the case of using aluminum as a material, for example, a material having curvature such as an aluminum foil or an aluminum deposition layer can be preferably used.
熱拡散層の層厚は、特に限定されないが、３〜５００μｍ程度とすることで、好適な熱拡散性や取扱い性を確保しやすくなるため好ましい。 The layer thickness of the thermal diffusion layer is not particularly limited, but it is preferable to set it to about 3 to 500 μm because it is easy to ensure suitable thermal diffusivity and handleability.
また、蓄熱層に断熱層を積層した構成とした場合には、蓄熱層の熱吸収及び熱放出が室内側と効果的になされ、室内の適温維持効果を特に好適に発揮することができる。また、室内の熱の流出を防ぐ、もしくは、外気からの熱の影響の軽減にも有効である。本発明の蓄熱積層体は、これら複合作用により、室内の温度変化を抑制し、室内を適温に保つ事ができる。また、エアコンや冷蔵設備等の空調機器を使用した場合に、その消費エネルギーを低減することもできる。これにより、好適に室内の省エネルギー化に貢献できる。 Moreover, when it is set as the structure which laminated | stacked the heat insulation layer on the thermal storage layer, the heat absorption and heat discharge of a thermal storage layer are made | formed effectively with the indoor side, and the indoor suitable temperature maintenance effect can be exhibited especially suitably. In addition, it is also effective in preventing heat flow out of the room or reducing the influence of heat from the outside air. The heat storage laminate of the present invention can suppress the temperature change in the room and keep the room at an appropriate temperature by these combined actions. Moreover, when air conditioners, such as an air conditioner and refrigeration equipment, are used, the energy consumption can also be reduced. Thereby, it can contribute to energy saving of a room suitably.
断熱層としては、熱伝導率が０．１Ｗ／ｍ・Ｋ未満の層を好ましく使用できる。当該断熱層は、蓄熱層から外気への熱の流出を防ぎ、かつ、外気の温度影響を低減させる効果を発揮するものである。断熱層は、熱伝導率が０．１Ｗ／ｍ・Ｋ未満の層を形成できるものであれば特に限定されず、例えば、発泡樹脂シート、断熱材料を含有する樹脂シート等の断熱シートや、押出し法ポリスチレン、ビーズ法ポリスチレン、ポリエチレンフォーム、ウレタンフォーム、フェノールフォーム等の断熱ボード等を適宜使用できる。なかでも、断熱シートは施工性を確保しやすいため好ましく、断熱材料を含有した樹脂シートである事が熱伝導率を低減できるためより好ましい。また、発泡シートは入手が容易であり、安価であるため好ましい。 As the heat insulating layer, a layer having a thermal conductivity of less than 0.1 W / m · K can be preferably used. The said heat insulation layer prevents the outflow of the heat | fever from a thermal storage layer to external air, and exhibits the effect of reducing the temperature influence of external air. The heat insulating layer is not particularly limited as long as it can form a layer having a thermal conductivity of less than 0.1 W / m · K. For example, a heat insulating sheet such as a foamed resin sheet or a resin sheet containing a heat insulating material, or extrusion Thermal insulation boards such as formal polystyrene, bead polystyrene, polyethylene foam, urethane foam, phenol foam and the like can be suitably used. Among them, the heat insulating sheet is preferable because it is easy to secure the workability, and a resin sheet containing a heat insulating material is more preferable because the heat conductivity can be reduced. In addition, a foam sheet is preferable because it is easily available and inexpensive.
断熱層はシート状とすることで施工性を確保しやすくなるが、なかでも、円筒形マンドレル屈曲試験機（ＪＩＳ Ｋ ５６００）による測定値が、マンドレル直径で２〜３２ｍｍであることが好ましい。 Although the heat insulation layer is easily formed into a sheet, the workability can be easily secured, and among them, it is preferable that a value measured by a cylindrical mandrel bending tester (JIS K 5600) is a mandrel diameter of 2 to 32 mm.
断熱層に使用する断熱材料は、蓄熱積層体の断熱性を高めるものであり、例えば、多孔質シリカ、多孔質アクリル、中空ガラスビーズ、真空ビーズ、中空ファイバーなどが挙げられる。この断熱材料５は、公知のものを用いればよい。本発明では、特に、多孔質アクリルを好適として用いる事ができる。断熱材料の粒径は、限定される事はないが、１〜３００μｍ程度である事が好ましい。 The heat insulating material used for the heat insulating layer enhances the heat insulating property of the heat storage laminate, and examples thereof include porous silica, porous acrylic, hollow glass beads, vacuum beads, hollow fibers and the like. The heat insulating material 5 may be a known one. In the present invention, in particular, porous acryl can be suitably used. The particle size of the heat insulating material is not limited, but preferably about 1 to 300 μm.
断熱層として断熱材料を含有する樹脂シートを使用する場合には、断熱材料を、ベースとなる樹脂材料に混入してシート成形を行う。樹脂材料としては、前述と同様に、例えば、ポリ塩化ビニル、ポリフェニレンサルファイド、ポリプロピレン、ポリエチレン、ポリエステル、又はアクリロニトリル−ブタジエン−スチレン樹脂などが挙げられる。ポリエステルとしては、Ａ−ＰＥＴ、ＰＥＴ−Ｇ等を使用できる。なかでも、火災時の低燃焼性の面から、自己消化性である塩化ビニル樹脂を好適に用いる事ができる。 In the case of using a resin sheet containing a heat insulating material as the heat insulating layer, the heat insulating material is mixed with the resin material as a base to perform sheet forming. Examples of the resin material include polyvinyl chloride, polyphenylene sulfide, polypropylene, polyethylene, polyester, and acrylonitrile-butadiene-styrene resin, as described above. As polyester, A-PET, PET-G, etc. can be used. Among them, a vinyl chloride resin that is self-digestible can be preferably used from the viewpoint of low flammability at the time of fire.
シートの成形方法としては、例えば、塩化ビニル樹脂と可塑剤と断熱材料を、押出し成形、カレンダー成形などの成形機を用いてシートの成形を行う。 As a method of forming the sheet, for example, the vinyl chloride resin, the plasticizer, and the heat insulating material are formed into a sheet by using a forming machine such as extrusion molding and calendar molding.
断熱層中の断熱材料の含有量は、断熱層中の２０質量％以上であることが好ましく、２０〜８０質量％であることがより好ましく、３０〜８０質量％であることが更に好ましく、４０〜８０質量％であることが特に好ましい。断熱材の含有量を当該範囲とすることで、好適に断熱効果を発揮でき、また、断熱層を形成しやすくなる。 The content of the heat insulating material in the heat insulating layer is preferably 20% by mass or more, more preferably 20 to 80% by mass, and still more preferably 30 to 80% by mass in the heat insulating layer. It is especially preferable that it is 80 mass%. By making content of a heat insulating material into the said range, a heat insulation effect can be exhibited suitably and it becomes easy to form a heat insulation layer.
断熱層中には、必要に応じて、可塑剤、難燃材等の添加剤を配合してもよい。 In the heat insulating layer, additives such as a plasticizer and a flame retardant may be blended, if necessary.
断熱層の層厚は、特に限定されないが、厚みが増す程室内の保温性が上がる。シートとしての湾曲性や施工性を保有する為には、５０〜３０００μｍ程度である事が好ましい。 The layer thickness of the heat insulating layer is not particularly limited, but as the thickness increases, the heat retention in the room increases. In order to maintain the curability and workability as a sheet, it is preferable to be about 50 to 3000 μm.
本発明の蓄熱シートは、主に建築物の内壁、天井、床などにおける内装材用途として好適に用いられるが、窓のサッシ枠の被服材や、車両等の内装材としても適用可能である。また、建築物の壁、床、天井に限らず、自動車、電車、飛行機などの室内に使用する事も可能である。また、冷蔵設備の低温保持材料や、パソコンのＣＰＵや蓄電池など熱を発生する電気部品の低温維持材料としても使用することも可能である。また、面状発熱体等のヒーターを併用して、蓄熱による省エネルギー効果を発現しても良い。 The heat storage sheet of the present invention is suitably used mainly as an interior material application in an inner wall, a ceiling, a floor and the like of a building, but is also applicable as a covering material of a window sash frame or an interior material such as a vehicle. In addition, it can be used not only in the walls, floors, and ceilings of buildings, but also in rooms such as cars, trains, and planes. In addition, it can also be used as a low temperature holding material of a cold storage facility, or as a low temperature holding material of an electric part that generates heat, such as a CPU of a personal computer and a storage battery. In addition, a heater such as a planar heating element may be used in combination to achieve the energy saving effect by the heat storage.
（実施例１）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４０質量部、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−１０）２４．５質量部、熱安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．５質量部、その他添加剤として減粘剤（ＢＹＫ製 減粘剤ＶＩＳＣＯＢＹＫ−４０４１）３質量部及び分散剤（ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）２質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子径１００〜３００μｍ、融点２６℃）２８質量部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は１０５００ｍＰａ・ｓであった。これをＰＥＴフィルム上に１ｍｍアプリケーターにて塗布した後、１００℃３分間加熱しゲル化させ、厚さ０．７ｍｍの蓄熱シートを形成した。Example 1
40 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92), 24.5 parts by mass of a benzoate based plasticizer (a monosizer PB-10 made by DIC), a heat stabilizer (Nippon Trading Co., Ltd. Glek ML-610A) 1.5 parts by mass, other additives 3 parts by mass of a viscosity reducing agent (manufactured by BYK, viscosity reducing agent VISCOBYK-4041), and a dispersing agent (DISPERPLAST-1142, defoamer BYK-3155) 2 parts by mass Then, 28 parts by mass of a latent heat storage material (Micronar 5001X made by BASF: particle diameter 100 to 300 μm, melting point 26 ° C.) obtained by microencapsulating paraffin was blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 10500 mPa · s. This was applied onto a PET film with a 1 mm applicator, and then heated at 100 ° C. for 3 minutes to cause gelation, thereby forming a heat storage sheet having a thickness of 0.7 mm.
（実施例２）
加熱温度を１７０℃にしたこと以外は実施例１と同様にして蓄熱シートを形成した。(Example 2)
A heat storage sheet was formed in the same manner as in Example 1 except that the heating temperature was 170 ° C.
（比較例１）
ポリエステル系可塑剤５５ｐｈｒ内添の塩ビ樹脂コンパウンド（リケンテクノス製 Ｒ−２８５７ １０−００７７）７０質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（粒子径１００〜３００μｍ、融点２６℃）３０質量部を１６０℃プラストミルにて混合し、Ｔダイ押出成形にて厚さ０．７ｍｍの蓄熱シートを形成した。(Comparative example 1)
70 parts by mass of a vinyl chloride resin compound (R-2857 10-0077, manufactured by Riken Technos Co., Ltd.) containing 55 phr of a polyester plasticizer and 30 parts by mass of a latent heat storage material (particle diameter 100-300 μm, melting point 26 ° C.) microencapsulated with paraffin It mixed in a 160 degreeC plasto mill, and formed the thermal storage sheet | seat of thickness 0.7 mm by T-die extrusion molding.
（参考例１）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）６０質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−１０）３８質量部と、熱安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．５質量部と、脱泡剤（ＢＹＫ製 ＢＹＫ−３１５５）０．５質量部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は３００ｍＰａ・ｓであった。これを実施例１と同様に成形し、厚さ０．７ｍｍのシートを参考例１とした。(Reference Example 1)
60 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92), 38 parts by mass of a benzoate plasticizer (monosizer PB-10 made by DIC), and a heat stabilizer (Nippon Trading Co., Ltd.) Glek ML-610A) 1.5 parts by mass and defoaming agent (BYK made BYK-3155) 0.5 parts by mass were blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 300 mPa · s. This was molded in the same manner as in Example 1, and a sheet of 0.7 mm in thickness was used as Reference Example 1.
上記実施例１〜２、比較例１及び参考例１にて形成したシートにつき、以下の評価を行った。得られた結果を下表に示した。 The following evaluation was performed on the sheets formed in Examples 1 and 2 and Comparative Examples 1 and 1 described above. The obtained results are shown in the following table.
＜可塑剤粘度の測定条件＞
測定装置：Ｂ型粘度計（東京計器株式会社製「ＤＶＭ−Ｂ型」）
測定条件：温度２５℃、Ｎｏ．２ロータ、３０ｒｐｍ<Measurement conditions of plasticizer viscosity>
Measuring device: B-type viscometer ("DVM-B" manufactured by Tokyo Keiki Co., Ltd.)
Measurement conditions: temperature 25 ° C., no. 2 rotors, 30 rpm
＜塗工液粘度の測定条件＞
測定装置：Ｂ型粘度計（トキメック株式会社製「ＢＭ型」）
測定条件：温度２５℃、Ｎｏ．４ロータ、６ｒｐｍ（参考例のみ３０ｒｐｍ）<Measurement conditions of viscosity of coating liquid>
Measuring device: B-type viscometer ("BM type" manufactured by Tokimec Inc.)
Measurement conditions: temperature 25 ° C., no. 4 rotors, 6 rpm (30 rpm for reference only)
＜適温維持性評価試験＞
実施例、比較例及び参考例にて作成したシートを幅５０ｍｍ×長さ５０ｍｍのサイズにした試験体を２枚重ねに積層し、熱伝対をシート中央に挟んで設置した。環境試験機内で外気温を３５℃で２時間保持した後、２０分間で５℃まで下降させ、さらに１時間５℃を保持した。この際、シート内の温度が２８℃〜２０℃の温度を保持した時間を測定し、適温維持性を評価した。評価基準は以下の通りである。
◎：保持時間が５００秒以上
○：保持時間が３００秒以上５００秒未満
×：保持時間が３００秒未満<Appropriate temperature maintenance evaluation test>
The test body which made the sheet | seat created by the Example, the comparative example, and the reference example the size of width 50 mm x length 50 mm was laminated | stacked on 2 sheets, and the thermocouple was pinched | interposed in the sheet center. After keeping the outside temperature at 35 ° C. for 2 hours in the environmental tester, the temperature was lowered to 5 ° C. in 20 minutes and kept at 5 ° C. for an additional hour. Under the present circumstances, the time in which the temperature in a sheet | seat hold | maintained the temperature of 28 degreeC-20 degreeC was measured, and appropriate temperature maintenance was evaluated. Evaluation criteria are as follows.
:: Hold time of 500 seconds or more ○: Hold time of 300 seconds or more and less than 500 seconds ×: Hold time of less than 300 seconds
＜浸み出し評価試験１＞
実施例、比較例及び参考例にて作成したシートを３５℃で２時間保持した後、指触にて蓄熱材成分の浸み出しを評価した。評価基準は以下の通りである。
○：ぬめり感なし
×：ぬめり感あり<Emerging evaluation test 1>
The sheets prepared in Examples, Comparative Examples and Reference Examples were maintained at 35 ° C. for 2 hours, and then the penetration of the heat storage material component was evaluated by finger touch. Evaluation criteria are as follows.
○: No feeling of sliming ×: There is a feeling of sliming
＜浸み出し評価試験２＞
実施例、比較例及び参考例にて作成したシートを幅４０ｍｍ×長さ４０ｍｍのサイズにし、同サイズのろ紙を挟んで積層した試験体を、荷重３４０ｇ／ｃｍ２、４０℃５０％ＲＨ環境下で１５時間圧着し、シートから浸み出した蓄熱材成分をろ紙に移行させた。その後、ろ紙を取り出して細かく裁断し、ＴＨＦに含浸させ１０時間静置して溶出させ、ＧＣ測定を行い、Ｃ１８アルカン量をヘキサン換算値で定量した。<Spillover evaluation test 2>
A sheet prepared in Examples, Comparative Examples and Reference Examples is 40 mm in width × 40 mm in length, and a test body laminated by sandwiching filter paper of the same size under a load of 340 g / cm 2 at 40 ° C. and 50% RH. The components of the heat storage material leaked from the sheet were transferred to filter paper. Thereafter, the filter paper was taken out, cut into small pieces, impregnated with THF, allowed to stand for 10 hours and eluted, GC measurement was performed, and the amount of C18 alkane was quantified by a hexane conversion value.
（実施例３）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４２．２質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−１０：粘度８０ｍＰａ・ｓ）２５．６質量部と、安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．３質量部と、その他添加剤（ＢＹＫ製 減粘剤ＢＹＫＶＩＳＣＯＢＹＫ−４０４１、分散剤ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）あわせて５．６質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子径１００〜３００μｍ、融点２６℃）２５．３部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は７０００ｍＰａ・ｓであった。これをＰＥＴフィルム上に３ｍｍアプリケーターにて塗布した後、１００℃５分間加熱しゲル化させた。その後、ＰＥＴフィルムを剥がし厚さ２ｍｍの蓄熱シートを形成した。(Example 3)
42.2 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92) and 25.6 parts by mass of a benzoate based plasticizer (a monosizer PB-10 made by DIC: viscosity 80 mPa · s) Together with 1.3 parts by weight of a stabilizer (Grek ML-610A, manufactured by Nippon Steel Trading Co., Ltd.), and other additives (BYK, viscosity reducer BYKVISCOBYK-4041, dispersant DISPERPLAST-1142, defoamer BYK-3155) .6 parts by mass and 25.3 parts of a latent heat storage material (Micron 5001X made by BASF: particle diameter 100 to 300 μm, melting point 26 ° C) obtained by microencapsulating paraffin were blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 7000 mPa · s. This was applied on a PET film with a 3 mm applicator, and then heated at 100 ° C. for 5 minutes to cause gelation. Thereafter, the PET film was peeled off to form a heat storage sheet having a thickness of 2 mm.
（実施例４）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４５．０質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−１０：粘度８０ｍＰａ・ｓ）２０．６質量部と、安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．４質量部と、その他添加剤（ＢＹＫ製 減粘剤ＢＹＫＶＩＳＣＯＢＹＫ−４０４１、分散剤ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）あわせて６質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子径１００〜３００μｍ、融点２６℃）２７．０部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は２１５００ｍＰａ・ｓであった。これをＰＥＴフィルム上に３ｍｍアプリケーターにて塗布した後、１００℃５分間加熱しゲル化させた。その後、ＰＥＴフィルムを剥がし厚さ２ｍｍの蓄熱シートを形成した。(Example 4)
45.0 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92) and 20.6 parts by mass of a benzoate based plasticizer (a monosizer PB-10 made by DIC: viscosity 80 mPa · s) Together with 1.4 parts by weight of a stabilizer (Grek ML-610A, manufactured by Nippon Steel Trading Co., Ltd.), and other additives (BYK, viscosity reducer BYKVISCOBYK-4041, dispersant DISPERPLAST-1142, defoamer BYK-3155) A mass part and 27.0 parts of a latent heat storage material (Micronar 5001X made by BASF: particle diameter 100-300 μm, melting point 26 ° C.) obtained by microencapsulating paraffin were blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 21500 mPa · s. This was applied on a PET film with a 3 mm applicator, and then heated at 100 ° C. for 5 minutes to cause gelation. Thereafter, the PET film was peeled off to form a heat storage sheet having a thickness of 2 mm.
（実施例５）
可塑剤を、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−３Ａ：粘度９５ｍＰａ・ｓ））にしたこと以外は実施例３と同様にして蓄熱シートを形成した。なお、塗工液の粘度は１７５００ｍＰａ・ｓであった。(Example 5)
A heat storage sheet was formed in the same manner as in Example 3, except that the plasticizer was changed to a benzoate plasticizer (Monocizer PB-3A manufactured by DIC: viscosity 95 mPa · s). In addition, the viscosity of the coating liquid was 17500 mPa * s.
（実施例６）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４５．０質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 ポリサイザーＷ−８３：粘度６４１ｍＰａ・ｓ）２７．３質量部と、安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．４質量部と、その他添加剤（ＢＹＫ製 減粘剤ＢＹＫＶＩＳＣＯＢＹＫ−４０４１、分散剤ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）あわせて６質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子径１００〜３００μｍ、融点２６℃）２０．３部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は２７０００ｍＰａ・ｓであった。これをＰＥＴフィルム上に３ｍｍアプリケーターにて塗布した後、１００℃５分間加熱しゲル化させた。その後、ＰＥＴフィルムを剥がし、厚さ２ｍｍの蓄熱シートを形成した。(Example 6)
45.0 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92) and 27.3 parts by mass of a benzoate plasticizer (Polysizer W-83 made by DIC: viscosity 641 mPa · s) Stabilizer (Greck ML-610A, manufactured by Nippon Steel Trading Co., Ltd.), and 6 parts in total of 1.4 parts by mass and other additives (BYK viscosity reducer BYKVISCOBYK-4041, dispersant DISPERPLAST-1142, defoamer BYK-3155) Parts and 20.3 parts of a latent heat storage material (Micronar 5001X made by BASF: particle diameter 100-300 μm, melting point 26 ° C.) obtained by microencapsulating paraffin were blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 27000 mPa · s. This was applied on a PET film with a 3 mm applicator, and then heated at 100 ° C. for 5 minutes to cause gelation. Thereafter, the PET film was peeled off to form a heat storage sheet having a thickness of 2 mm.
（実施例７）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４５．０質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 ポリサイザーＷ−８３：粘度６４１ｍＰａ・ｓ１５．５質量部と、トリメチルペンタニルジイソブチレート（イーストマンケミカル製 ＴＸＩＢ：粘度１０ｍＰａ・ｓ）５．１質量部と、安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．４質量部と、その他添加剤（ＢＹＫ製 減粘剤ＢＹＫＶＩＳＣＯＢＹＫ−４０４１、分散剤ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）あわせて６質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子系１００〜３００μｍ、融点２６℃）２７．０質量部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は２４５００ｍＰａ・ｓであった。これをＰＥＴフィルム上に３ｍｍアプリケーターにて塗布した後、１２０℃５分間加熱しゲル化させた。その後、ＰＥＴフィルムを剥がし厚さ２ｍｍの蓄熱シートを形成した。(Example 7)
45.0 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (Zest PQ 92, manufactured by New First Chloride Compound), a benzoate plasticizer (Polysizer W-83, manufactured by DIC: 15.5 parts by mass of viscosity 641 mPa · s, trimethyl) 5.1 parts by mass of pentanyl diisobutyrate (Eastman Chemical TXIB: viscosity 10 mPa · s), 1.4 parts by mass of a stabilizer (Grek ML-610A manufactured by Nippon Steel Trading Co., Ltd.), and other additives (BYK reduction) Latent agent BYKVISCOBYK-4041, dispersant DISPERPLAST-1142, defoamer BYK-3155) 6 parts by mass, a latent heat storage material (Micron 5001X made of BASF: particle system 100-300 μm, melting point 26) obtained by microencapsulating paraffin C) 27.0 parts by mass were blended to prepare a plastisol coating solution. The viscosity of the processing solution was 24500 mPa · s, which was coated on a PET film with a 3 mm applicator, heated at 120 ° C. for 5 minutes for gelation, peeled off the PET film, and stored a 2 mm thick heat storage sheet. It formed.
（実施例８）
不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した積層体であること以外は実施例３と同様にして、厚さ２ｍｍの不燃紙との積層蓄熱シートを形成した。(Example 8)
A laminated heat storage sheet with non-combustible paper having a thickness of 2 mm was formed in the same manner as in Example 3 except that it was a laminate applied to non-combustible paper (Celafoam W150 manufactured by Lintec Corporation).
（実施例９）
不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した積層体であること以外は実施例４と同様にして、厚さ２ｍｍの不燃紙との積層蓄熱シートを形成した。(Example 9)
A laminated heat storage sheet with incombustible paper having a thickness of 2 mm was formed in the same manner as in Example 4 except that the laminate was a laminate applied to incombustible paper (Celafoam W150 manufactured by Lintec Corporation).
（実施例１０）
不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した積層体であること以外は実施例５と同様にして、厚さ２ｍｍの不燃紙との積層蓄熱シートを形成した。(Example 10)
A laminated heat storage sheet with incombustible paper with a thickness of 2 mm was formed in the same manner as in Example 5 except that the laminate was a laminate applied to incombustible paper (Celafoam W150 manufactured by Lintec Corporation).
（実施例１１）
不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した積層体であること以外は実施例６と同様にして、厚さ２ｍｍの不燃紙との積層蓄熱シートを形成した。(Example 11)
A laminated heat storage sheet with non-combustible paper with a thickness of 2 mm was formed in the same manner as in Example 6 except that it was a laminate coated with non-combustible paper (Celafoam W150 manufactured by Lintec Corporation).
（実施例１２）
不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した積層体であること以外は実施例７と同様にして、厚さ２ｍｍの不燃紙との積層蓄熱シートを形成した。(Example 12)
A laminated heat storage sheet with non-combustible paper with a thickness of 2 mm was formed in the same manner as in Example 7 except that the laminate was a laminate applied to non-combustible paper (Celafoam W150 manufactured by Lintec Corporation).
（実施例１３）
重合度９００のポリ塩化ビニル樹脂粒子（新第一塩ビ製 ＺＥＳＴ ＰＱ９２）４２．０質量部と、安息香酸エステル系可塑剤（ＤＩＣ製 モノサイザーＰＢ−１０：粘度８０ｍＰａ・ｓ）２５．２質量部と、安定剤（日辰貿易製 グレックＭＬ−６１０Ａ）１．３質量部と、その他添加剤（ＢＹＫ製 減粘剤ＢＹＫＶＩＳＣＯＢＹＫ−４０４１、分散剤ＤＩＳＰＥＲＰＬＡＳＴ−１１４２、脱泡剤ＢＹＫ−３１５５）あわせて５．４質量部と、パラフィンをマイクロカプセル化した潜熱蓄熱材（ＢＡＳＦ製 ミクロナール５００１Ｘ：粒子径１００〜３００μｍ、融点２６℃）２６．１部を配合し、プラスチゾル塗工液を作成した。塗工液の粘度は８０００ｍＰａ・ｓであった。これを不燃紙（リンテック社製 セラフォームＷ１５０）に塗布した後、１３５℃８分間加熱しゲル化させ、厚さ２ｍｍの蓄熱シートを形成した。このシートの引張最大荷重は１６１．５Ｎ、シート伸び率は２８１％であった。(Example 13)
42.0 parts by mass of polyvinyl chloride resin particles having a degree of polymerization of 900 (made by New First Chloride ZEST PQ 92) and 25.2 parts by mass of a benzoate based plasticizer (a monosizer PB-10 made by DIC: viscosity 80 mPa · s) Together with 1.3 parts by weight of a stabilizer (Grek ML-610A, manufactured by Nippon Steel Trading Co., Ltd.), and other additives (BYK, viscosity reducer BYKVISCOBYK-4041, dispersant DISPERPLAST-1142, defoamer BYK-3155) .4 parts by mass and 26.1 parts of a latent heat storage material (Micron 5001X made by BASF: particle diameter 100 to 300 μm, melting point 26 ° C) obtained by microencapsulating paraffin were blended to prepare a plastisol coating liquid. The viscosity of the coating liquid was 8000 mPa · s. After this was applied to incombustible paper (Celafoam W150, manufactured by Lintec Corporation), it was heated at 135 ° C. for 8 minutes to be gelled to form a heat storage sheet having a thickness of 2 mm. The maximum tensile load of this sheet was 161.5 N, and the sheet elongation was 281%.
（実施例１４）
塗布後の加熱温度を１６０℃８分間にしたこと以外は実施例１３と同様にして蓄熱シートを形成した。このシートの引張最大荷重は１７３．０Ｎ、シート伸び率は３２０％であった。(Example 14)
A heat storage sheet was formed in the same manner as in Example 13 except that the heating temperature after application was 160 ° C. for 8 minutes. The maximum tensile load of this sheet was 173.0 N, and the sheet elongation was 320%.
（実施例１５）
可塑剤を、フタル酸系可塑剤（新日本理化製 サンソサイザーＤＩＮＰ：粘度６５ｍＰａ・ｓ）にしたこと以外は実施例１４と同様にして蓄熱シートを形成した。なお、塗工液の粘度は５５００ｍＰａ・ｓであった。このシートの引張最大荷重は９１．５Ｎ、シート伸び率は１３４％であった。(Example 15)
A heat storage sheet was formed in the same manner as in Example 14 except that the plasticizer was changed to a phthalic acid plasticizer (Sansonizer DINP: viscosity 65 mPa · s, manufactured by Shin Nippon Rika Co., Ltd.). The viscosity of the coating solution was 5500 mPa · s. The maximum tensile load of this sheet was 91.5 N, and the sheet elongation was 134%.
上記実施例３〜１５にて形成したシートにつき、以下の評価を行った。得られた結果を下表に示した。 The following evaluation was performed about the sheet | seat formed in the said Examples 3-15. The obtained results are shown in the following table.
＜可塑剤粘度の測定条件＞
測定装置：Ｂ型粘度計（東京計器株式会社製「ＤＶＭ−Ｂ型」）
測定条件：温度２５℃、Ｎｏ．２ロータ、３０ｒｐｍ<Measurement conditions of plasticizer viscosity>
Measuring device: B-type viscometer ("DVM-B" manufactured by Tokyo Keiki Co., Ltd.)
Measurement conditions: temperature 25 ° C., no. 2 rotors, 30 rpm
＜塗工液粘度の測定条件＞
測定装置：Ｂ型粘度計（トキメック株式会社製「ＢＭ型」）
測定条件：温度２５℃、Ｎｏ．４ロータ、６ｒｐｍ<Measurement conditions of viscosity of coating liquid>
Measuring device: B-type viscometer ("BM type" manufactured by Tokimec Inc.)
Measurement conditions: temperature 25 ° C., no. 4 rotors, 6 rpm
＜引張最大荷重及びシート伸び率の測定条件＞
上記実施例１３〜１５で形成したシートの引張最大荷重及びシート伸び率の測定条件は下記のとおりである。
測定装置：株式会社エーアンドエー「テンシロン万能試験機ＲＴＣ−１２５０Ａ」
測定方法：幅２５ｍｍ長さ７０ｍｍの試験片を引張試験機にて引っ張り、最大荷重及び試験片が切断したときの伸びを測定した。
引張条件：つかみ間隔３０ｍｍ、引張速度２００±２０ｍｍ／分<Measurement conditions of maximum tensile load and sheet elongation>
The measurement conditions of the maximum tensile load and the sheet elongation of the sheet formed in the above Examples 13 to 15 are as follows.
Measuring device: A & A Co., Ltd. "Tensiron universal testing machine RTC-1250A"
Measurement method: A test piece having a width of 25 mm and a length of 70 mm was pulled by a tensile tester, and the maximum load and the elongation when the test piece was cut were measured.
Tension conditions: Gripping distance 30 mm, Tension speed 200 ± 20 mm / min
＜適温維持性評価試験＞
実施例３〜１５にて作成したシートを幅５０ｍｍ×長さ５０ｍｍのサイズにした試験体を２枚重ねに積層し、熱伝対をシート中央に挟んで設置した。環境試験機内で外気温を３５℃で２時間保持した後、５０分間で５℃まで下降させ、さらに１時間５℃を保持した。この際、シート内の温度が２８℃〜２０℃の温度を保持した時間を測定し、外気温の２８℃〜２０℃保持時間（８００秒）からどのくらい適温維持時間が延びたかを計算して、適温維持性を評価した。評価基準は以下のとおりである。
◎：保持時間が＋２００秒以上
○：保持時間が＋５０秒以上２００秒未満
×：保持時間が＋５０秒未満<Appropriate temperature maintenance evaluation test>
The test body which made the sheet | seat created in Examples 3-15 the size of width 50 mm x length 50 mm was laminated | stacked on 2 sheets, and the thermocouple was installed on both sides of the sheet center. After keeping the outside temperature at 35 ° C. for 2 hours in the environmental tester, the temperature was lowered to 5 ° C. in 50 minutes, and kept at 5 ° C. for one hour. At this time, the time during which the temperature in the sheet was kept at 28 ° C to 20 ° C was measured, and how much the appropriate temperature keeping time was extended from the 28 ° C to 20 ° C holding time (800 seconds) of the outside temperature was calculated. The appropriate temperature maintenance was evaluated. Evaluation criteria are as follows.
:: Holding time + 200 seconds or more ○: Holding time + 50 seconds or more and less than 200 seconds ×: Holding time + 50 seconds or less
＜浸み出し評価試験＞
実施例３〜７にて作成したシートを幅４０ｍｍ×長さ４０ｍｍのサイズにし、同サイズのろ紙を挟んで積層した試験体を、荷重３４０ｇ／ｃｍ２、４０℃５０％ＲＨ環境下で１５時間圧着し、シートから浸み出した蓄熱材成分をろ紙に移行させた。その後、ろ紙を取り出して細かく裁断し、ＴＨＦに含浸させ１０時間静置して溶出させ、ＧＣ測定を行い、Ｃ１８アルカン量をヘキサン換算値で定量した。
◎：不検出または０．０５ｍｇ未満
○：０．０５ｍｇ以上０．２ｍｇ未満
×：０．２ｍｇ以上<Spillover evaluation test>
A sheet prepared in Examples 3 to 7 has a size of width 40 mm × length 40 mm, and a test body in which filter sheets of the same size are laminated and stacked is used under a load of 340 g / cm 2 under an environment of 40 ° C. and 50% RH for 15 hours. The pressure was applied, and the heat storage material component that leaked from the sheet was transferred to the filter paper. Thereafter, the filter paper was taken out, cut into small pieces, impregnated with THF, allowed to stand for 10 hours and eluted, GC measurement was performed, and the amount of C18 alkane was quantified by a hexane conversion value.
◎: Not detected or less than 0.05 mg ○: 0.05 mg or more and less than 0.2 mg ×: 0.2 mg or more
＜紙積層時の可塑剤浸透＞
実施例８〜１５にて作成した不燃紙積層シートの不燃紙側について、目視及び指触にて可塑剤の浸み出しを評価した。評価基準は以下の通りである。
○：裏面まで到達する可塑剤の浸透なし
×：裏面まで到達する可塑剤の浸透あり<Plasticizer penetration at the time of paper lamination>
For the non-combustible paper side of the non-combustible paper laminate sheet prepared in Examples 8 to 15, the penetration of the plasticizer was evaluated visually and with a finger. Evaluation criteria are as follows.
○: no penetration of plasticizer reaching back side ×: penetration of plasticizer reaching back side
＜難燃性評価試験＞
実施例８〜１５にて作成したシートを幅５０ｍｍ×横２００ｍｍのサイズにした試験体に、試験体の端から１９ｍｍ（Ａ）、３８ｍｍ（Ｂ）、１３８ｍｍ（Ｃ）の位置に標線を表示した。試験体を水平に設置し、炎の高さを３８ｍｍに調整したガスバーナーの出炎管の中心が標線Ａの中心となるように設置して１５秒間炎にさらして着火させた。燃焼が標線Ｂに到達した時間から標線Ｃに到達した時間（分）、または燃焼の進行が停止した時間と距離を測定した。以上より、標線Ｂから標線Ｃ間の燃焼速度（ｍｍ／分）を計算し、難燃性を評価した。評価の基準は以下の通りである。
◎：燃焼速度５０ｍｍ／分以下または、標線Ｃまで燃焼せずに自己消火
○：燃焼速度５０ｍｍ／分から１００ｍｍ／分
△：燃焼速度１００ｍｍ／分から５００ｍｍ／分
×：燃焼速度５００ｍｍ／分以上<Flame retardancy evaluation test>
On the test body in which the sheet prepared in Examples 8 to 15 has a size of width 50 mm × width 200 mm, mark lines are displayed at positions of 19 mm (A), 38 mm (B) and 138 mm (C) from the end of the test body did. The test body was placed horizontally, and the flame burner was adjusted so that the flame height was adjusted to 38 mm. The center of the flame tube of the gas burner was placed at the center of the marked line A and exposed to flame for 15 seconds to be ignited. The time (minute) when the mark line C was reached from the time when the mark line B was reached, or the time and distance when the progress of the combustion was stopped were measured. From the above, the burning rate (mm / min) between the marking line B and the marking line C was calculated to evaluate the flame retardancy. The criteria for evaluation are as follows.
:: Burning speed 50 mm / min or less or self-extinguishing without burning to the marked line C ○: Burning speed 50 mm / min to 100 mm / min Δ: Burning speed 100 mm / min to 500 mm / min ×: Burning speed 500 mm / min or more
上記表から明らかなとおり、本発明の蓄熱シートは、柔軟な樹脂系のシートでありながら、蓄熱材の染み出しが生じにくいものであった。また、低温でも好適に成形が可能であり、得られた蓄熱シートは良好な蓄熱性を有し、適温保持に優れるものであった。さらに、不燃紙を積層した実施例８〜１５の蓄熱シートは、好適な難燃性を有するものであった。一方、比較例１の樹脂シートは、指触により確認できるほどの顕著な蓄熱材の染み出しが生じるものであった。 As is clear from the above-mentioned table, the heat storage sheet of the present invention was a flexible resin-based sheet, but it was difficult for the heat storage material to bleed out. Moreover, it was able to be suitably molded even at a low temperature, and the obtained heat storage sheet had a good heat storage property and was excellent in maintaining an appropriate temperature. Furthermore, the thermal storage sheet of Examples 8-15 which laminated | stacked incombustible paper had a suitable flame retardance. On the other hand, in the resin sheet of Comparative Example 1, the heat storage material remarkably leaked out so that it could be confirmed by finger touch.
Claims (9)
（２）ビニルゾル塗工膜を加熱してゲル化膜からなる蓄熱シートを形成する工程、を有することを特徴とする蓄熱シートの製造方法。 (1) applying a vinyl sol coating solution containing vinyl chloride resin particles and a heat storage material on a support to obtain a vinyl sol coating film,
(2) A process for producing a heat storage sheet, comprising the steps of: heating a vinyl sol coating film to form a heat storage sheet composed of a gelled film.
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| WO2017170156A1 (en) * | 2016-03-30 | 2017-10-05 | 日本ゼオン株式会社 | Spray coating sol, vinyl chloride resin molded body with spray coating layer, manufacturing method for said molded body, and laminate |
| JP6274373B1 (en) * | 2016-06-22 | 2018-02-07 | Dic株式会社 | Thermal storage composition |
| CN109071848B (en) | 2016-06-22 | 2022-02-15 | Dic株式会社 | Heat accumulation piece |
| JP6460435B2 (en) * | 2016-06-22 | 2019-01-30 | Dic株式会社 | Thermal storage laminate |
| JP6517909B1 (en) * | 2017-11-16 | 2019-05-22 | 株式会社パワーバンクシステム | Cold storage / heat storage sheet and cold storage / heat storage sheet generation method |
| KR102550885B1 (en) * | 2018-11-26 | 2023-07-03 | 후지필름 가부시키가이샤 | Heat storage sheet, heat storage member, electronic device, and manufacturing method of heat storage sheet |
| JP2021127787A (en) * | 2020-02-12 | 2021-09-02 | ナカオ金属工業株式会社 | Heat storage and heat insulating structure |
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| JP2004323778A (en) * | 2003-04-28 | 2004-11-18 | Dainippon Ink & Chem Inc | Halogen-containing resin composition |
| JP5048926B2 (en) * | 2004-02-04 | 2012-10-17 | エスケー化研株式会社 | Thermal insulation |
| JP4637719B2 (en) * | 2004-11-02 | 2011-02-23 | エスケー化研株式会社 | Thermal storage laminate |
| JP2007196465A (en) * | 2006-01-25 | 2007-08-09 | Asahi Kasei Construction Materials Co Ltd | Non-flammable heat storage panel |
| JP5192199B2 (en) * | 2007-08-23 | 2013-05-08 | アキレス株式会社 | Thermal storage thermoplastic resin sheet molding |
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