WO2012026530A1 - 熱可塑性樹脂発泡体、熱可塑性樹脂発泡体の製造方法および光反射材 - Google Patents
熱可塑性樹脂発泡体、熱可塑性樹脂発泡体の製造方法および光反射材 Download PDFInfo
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- WO2012026530A1 WO2012026530A1 PCT/JP2011/069190 JP2011069190W WO2012026530A1 WO 2012026530 A1 WO2012026530 A1 WO 2012026530A1 JP 2011069190 W JP2011069190 W JP 2011069190W WO 2012026530 A1 WO2012026530 A1 WO 2012026530A1
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- Prior art keywords
- thermoplastic resin
- sheet
- resin foam
- foam
- melt
- Prior art date
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- 239000006260 foam Substances 0.000 title claims abstract description 70
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 47
- 230000008025 crystallization Effects 0.000 claims abstract description 47
- 239000002667 nucleating agent Substances 0.000 claims abstract description 36
- 239000011342 resin composition Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 238000005187 foaming Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- -1 polybutylene terephthalate Polymers 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 description 14
- 239000005020 polyethylene terephthalate Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 11
- 239000001569 carbon dioxide Substances 0.000 description 11
- MBSRTKPGZKQXQR-UHFFFAOYSA-N 2-n,6-n-dicyclohexylnaphthalene-2,6-dicarboxamide Chemical compound C=1C=C2C=C(C(=O)NC3CCCCC3)C=CC2=CC=1C(=O)NC1CCCCC1 MBSRTKPGZKQXQR-UHFFFAOYSA-N 0.000 description 10
- 238000004898 kneading Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KTGYQIVJDQMAAG-UHFFFAOYSA-N 1-n,3-n,5-n-tris(2-methylcyclohexyl)benzene-1,3,5-tricarboxamide Chemical compound CC1CCCCC1NC(=O)C1=CC(C(=O)NC2C(CCCC2)C)=CC(C(=O)NC2C(CCCC2)C)=C1 KTGYQIVJDQMAAG-UHFFFAOYSA-N 0.000 description 1
- FTPQDBUUQXJGNL-UHFFFAOYSA-N 1-n,3-n,5-n-tris(4-methylcyclohexyl)benzene-1,3,5-tricarboxamide Chemical compound C1CC(C)CCC1NC(=O)C1=CC(C(=O)NC2CCC(C)CC2)=CC(C(=O)NC2CCC(C)CC2)=C1 FTPQDBUUQXJGNL-UHFFFAOYSA-N 0.000 description 1
- QCHZUINRDLKKJX-UHFFFAOYSA-N 1-n,3-n,5-n-tritert-butylbenzene-1,3,5-tricarboxamide Chemical compound CC(C)(C)NC(=O)C1=CC(C(=O)NC(C)(C)C)=CC(C(=O)NC(C)(C)C)=C1 QCHZUINRDLKKJX-UHFFFAOYSA-N 0.000 description 1
- RHAQYANXPOZLJB-UHFFFAOYSA-N 1-n,4-n-bis(2-methylcyclohexyl)cyclohexane-1,4-dicarboxamide Chemical compound CC1CCCCC1NC(=O)C1CCC(C(=O)NC2C(CCCC2)C)CC1 RHAQYANXPOZLJB-UHFFFAOYSA-N 0.000 description 1
- WPMXHFCEZBAZLM-UHFFFAOYSA-N 1-n,4-n-diphenylcyclohexane-1,4-dicarboxamide Chemical compound C1CC(C(=O)NC=2C=CC=CC=2)CCC1C(=O)NC1=CC=CC=C1 WPMXHFCEZBAZLM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- DQZIIYZFPVNFFM-UHFFFAOYSA-N 4-(dibenzylcarbamoyl)cyclohexane-1-carboxylic acid Chemical compound C1CC(C(=O)O)CCC1C(=O)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 DQZIIYZFPVNFFM-UHFFFAOYSA-N 0.000 description 1
- LBCFQDVGIJFIRN-UHFFFAOYSA-N 4-(dicyclohexylcarbamoyl)cyclohexane-1-carboxylic acid Chemical compound C1CC(C(=O)O)CCC1C(=O)N(C1CCCCC1)C1CCCCC1 LBCFQDVGIJFIRN-UHFFFAOYSA-N 0.000 description 1
- WKPLFYFTQNLMOZ-UHFFFAOYSA-N 6-(dicyclohexylcarbamoyl)naphthalene-2-carboxylic acid Chemical compound C1=CC2=CC(C(=O)O)=CC=C2C=C1C(=O)N(C1CCCCC1)C1CCCCC1 WKPLFYFTQNLMOZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium erythorbate Chemical compound [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 235000010352 sodium erythorbate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/032—Impregnation of a formed object with a gas
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/113—Fluorescence
Definitions
- the present invention relates to a thermoplastic resin foam having fine bubbles inside, a method for producing a thermoplastic resin foam, and a light reflecting material.
- a synthetic resin film or sheet reflecting light is used for backlights such as electric signboards, lighting fixtures, and displays.
- a light reflecting plate obtained by processing a synthetic resin film or sheet into a three-dimensional shape has been proposed (for example, see Patent Document 1).
- the film or sheet of the thermoplastic resin foam is processed into a three-dimensional shape, it is deformed due to strain during molding or shrinkage after molding. Therefore, means for preventing the deformation of the light reflecting plate by fixing the light reflecting plate subjected to the shape processing and the metal casing has been proposed (see, for example, Patent Document 2).
- thermoplastic resin foam film or sheet having many fine bubbles or pores therein has been proposed (see, for example, Patent Document 3). Since the film or sheet of the thermoplastic resin foam has a fine average cell diameter of about 10 ⁇ m, it has a high reflectance.
- thermoplastic resin foam and light reflecting material which have a high reflectance even if it thins, and this thermoplastic resin foam.
- the present inventors have added a specific melt-type crystallization nucleating agent to a thermoplastic resin, and have high reflectivity even when thinned. It has been found that a resin foam can be produced and the above problems can be solved. The present invention has been made based on this finding.
- thermoplastic comprising a crystalline thermoplastic resin (A) and a resin composition containing a melt-type crystallization nucleating agent (B), and has therein bubbles having an average cell diameter of less than 1 ⁇ m.
- Resin foam ⁇ 2> The thermoplastic resin foam according to ⁇ 1>, wherein the crystalline thermoplastic resin (A) is a crystalline polyester resin, ⁇ 3> The melt-type crystallization nucleating agent (B) is contained in an amount of 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the crystalline thermoplastic resin (A).
- thermoplastic resin foam according to ⁇ 4> The thermoplastic resin foam according to any one of ⁇ 1> to ⁇ 3>, wherein the total reflectance at a light wavelength of 550 nm is 100% or more in terms of aluminum oxide ratio, ⁇ 5>
- the production method according to ⁇ 6> wherein the crystalline thermoplastic resin (A) is a crystalline polyester resin, and ⁇ 8> the melt-type crystallization nucleating agent (B) is crystalline.
- the present invention relates to a thermoplastic resin foam having a high reflectance even when it is thinned, a method for producing a thermoplastic resin foam, and an electric signboard, a lighting apparatus, and a display backlight having excellent light reflectance using the same. Reflective materials such as lighting boxes can be provided.
- thermoplastic resin foam of the present invention is obtained by foaming a crystalline thermoplastic resin (A) and a resin composition containing a melt-type crystallization nucleating agent (B). First, a crystalline thermoplastic resin (A) is demonstrated among the thermoplastic resin foams of this invention.
- Crystalline thermoplastic resin Crystallinity means that the resin molecules form a regular steric configuration structure (crystal structure) in a temperature range of Tg or higher. Such crystallinity is defined based on the amount of crystallization by a differential scanning calorimeter.
- the crystallinity in the present invention means that the amount of heat calculated from the exothermic peak (crystallization peak) is 5.0 J / g when the temperature is measured at 10 ° C./min after heating the thermoplastic resin to the melting temperature or higher. The above is said. More preferably, it is 10.0 J / g or more. Preferably, it is 50 J / g or less.
- thermoplastic resin (A) examples include polyester, polyamide, white-colored linear polyphenylene sulfide, syndiotactic polystyrene, and polyether ketone.
- polyester is particularly preferable.
- the crystalline thermoplastic resins may be used alone or in combination of two or more.
- polyester examples include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polybutylene isoterephthalate, polybutylene isona.
- copolymer polyester such as phthalate.
- polyethylene terephthalate resin is particularly preferable in terms of crystallinity and foamability.
- the thermoplastic resin is preferably non-crosslinked from the viewpoint of recycling.
- the thermoplastic resin in the present invention preferably has a mass fraction (hereinafter also referred to as a degree of crosslinking in the present invention) of less than 10% of the crosslinked part of the thermoplastic resin.
- a crosslinking agent or a crosslinking aid may be added so that the degree of crosslinking of the thermoplastic resin is preferably less than 10%.
- melt-type crystallization nucleating agent is a nucleating agent characterized in that when added to a thermoplastic resin, it melts and disperses in the resin at the time of melt-kneading and agglomerates and solidifies in the cooling and solidification process. It shows that.
- the melt-type crystallization nucleating agent (B) is melt-dispersed in the crystalline thermoplastic resin (A) during molding.
- the melt-type crystallization nucleating agent (B) is precipitated in the crystalline thermoplastic resin (A) at the time of solidification after cooling or gas impregnation after molding.
- the melt-type crystallization nucleating agent (B) is crystallized.
- the precipitated melt-type crystallization nucleating agent (B) serves as a starting point for bubble nucleus formation.
- a reflective material having a high reflectance can be obtained.
- the melt-type crystallization nucleating agent used in the present invention is not particularly limited, but N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide, trimesic acid tris (t-butylamide), trimesic acid tricyclohexylamide, trimesic acid Tri (2-methylcyclohexylamide), trimesic acid tri (4-methylcyclohexylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 1,4-cyclohexanedicarboxylic acid di ( 2-methylcyclohexylamide), 1,4-cyclohexane dicarboxylic acid dibenzylamide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide and 1 2,3,
- the specific gravity of the thermoplastic resin foam is preferably 0.7 or less, more preferably 0.65 or less, and still more preferably 0.5 or less.
- the blending amount of (B) is 0.1 to 2 parts by mass with respect to 100 parts by mass of the crystalline thermoplastic resin (A).
- the amount is preferably 0.25 to 1.5 parts by mass. If the blending amount of the melt-type crystallization nucleating agent is too small, crystal nuclei generated through the crystallization process of the melt-type crystallization nucleating agent by gas impregnation are difficult to be generated, and the bubble size distribution of the foam becomes large. . Also, if the amount of the melt-type crystallization nucleating agent is too large, crystallization proceeds too much, the crystal nuclei become too large and become particulate, and the function as a cell nucleating agent is not sufficient, so a high expansion ratio is obtained. Can't get.
- thermoplastic resin (A) before foaming with respect to the thermoplastic resin (A) before foaming, a crystallization accelerator, a cell nucleating agent, an antioxidant, an antistatic agent, an ultraviolet light inhibitor, a light stabilizer, a fluorescent whitening agent, a pigment, and a dye
- Various additives such as a compatibilizing agent, a lubricant, a reinforcing agent, a flame retardant, a plasticizer, a thickener, and a thickener can be appropriately blended within a range not impairing the object of the present invention.
- the resin containing the said additive may be laminated
- a resin composition is obtained by melt-kneading the crystalline thermoplastic resin (A) and the melt-type crystallization nucleating agent (B) using, for example, a kneader or an extruder.
- the kneading conditions such as the kneading temperature and the kneading time can be appropriately set depending on the melting temperature of the crystalline thermoplastic resin (A) and the melt-type crystallization nucleating agent (B).
- the obtained resin composition is formed into a sheet shape with an extruder or the like to produce a resin sheet, and then the resin sheet and the separator are overlapped and wound to form a roll.
- the resin sheet By holding this roll in a pressurized inert gas atmosphere, the resin sheet is allowed to contain an inert gas. Further, the resin sheet containing the inert gas is heated to a temperature equal to or higher than the softening temperature of the crystalline thermoplastic resin (A) under normal pressure to be foamed. Thus, a thermoplastic resin foam is obtained.
- inert gas examples include helium, nitrogen, carbon dioxide, and argon.
- the inert gas permeation time and the inert gas permeation amount until the resin sheet is saturated vary depending on the type of resin to be foamed, the type of inert gas, the permeation pressure, and the thickness of the sheet.
- carbon dioxide is more preferable from the viewpoint of gas permeability (speed, solubility) into the resin.
- an organic solvent may be included in the resin sheet before the inert gas is contained in the pressurized inert gas atmosphere in the roll composed of the resin sheet and the separator.
- the organic solvent include benzene, toluene, methyl ethyl ketone, ethyl formate, acetone, acetic acid, dioxane, m-cresol, aniline, acrylonitrile, dimethyl phthalate, nitroethane, nitromethane, and benzyl alcohol.
- acetone is more preferable from the viewpoints of handleability and economy.
- the average diameter of the bubbles present in the thermoplastic resin foam of the present invention is less than 1 ⁇ m. Among these, 0.75 ⁇ m or less is preferable, and 0.5 ⁇ m or less is particularly preferable. If the average cell diameter is too large, the desired high reflectance cannot be obtained.
- the total reflectance of light of the thermoplastic resin foam is preferably 98% or more in terms of aluminum oxide ratio at 550 nm. Among these, it is preferable that it is 100% or more, and it is especially preferable that it is 101% or more.
- the total reflectance described here refers to the reflection of an aluminum oxide white plate (210-0740: manufactured by Hitachi High-Tech Fielding) at a wavelength of 550 nm of a spectrophotometer (U-4100: manufactured by Hitachi High-Tech Fielding). The rate is 100% and is expressed as a relative value.
- the average bubble diameter d was determined by substituting it into the following equation.
- d t / (0.616 ⁇ M)
- Specific gravity The specific gravity of the foam sheet was measured by an underwater substitution method.
- Foaming ratio It computed as ratio (rho) s / (rho) f of specific gravity ((rho) f) of the foam sheet measured by the underwater substitution method and specific gravity ((rho) s) of resin before foaming.
- Reflectance The light transmittance of a sample obtained by cutting a 0.8 mm thick sample and a 0.8 mm thick sample into a 0.3 mm thickness was measured.
- Each sample was measured for spectral total reflectance at a light wavelength of 550 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Tech) under the condition of a spectral slit of 4 nm.
- a spectrophotometer U-4100 manufactured by Hitachi High-Tech
- an aluminum oxide white plate 210-0740: manufactured by Hitachi High-Tech Fielding Co., Ltd.
- the measured value was a value relative to the reference.
- DSC60A (trade name) manufactured by Shimadzu Corporation was used as the DSC.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 101%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 101%.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 101%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 101%.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 101%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 101%.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 101%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 101%.
- melt-type crystallization nucleating agent trade name: TF1, manufactured by Nippon Nippon Chemical Co., Ltd.
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 100%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 100%.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 101%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 101%.
- melt-type crystallization nucleating agent trade name: NU-100, Shin Nippon Rika
- the average cell diameter of the obtained sheet was as fine as 0.5 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 100%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 100%.
- Comparative Example 2 A foam was obtained in the same manner as in Example 1 except that 1.0 part by mass of modified SEBS (trade name: Dynalon 8630P, manufactured by JSR) was added to the polyethylene terephthalate of Comparative Example 1. The average cell diameter of the obtained sheet was 1.6 ⁇ m. The thickness of the foam was 0.8 mm. The total reflectance of the foam sheet was 100%. The total reflectance of the sheet cut to a thickness of 0.3 mm was 98%.
- modified SEBS trade name: Dynalon 8630P, manufactured by JSR
- Example 3 A foam was obtained in the same manner as in Example 1 except that 3.0 parts by mass of modified PE (trade name: Bondfast E, manufactured by Toyobo Co., Ltd.) was added to the polyethylene terephthalate of Comparative Example 1.
- the average cell diameter of the obtained sheet was 3.0 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 99%.
- the total reflectance of the sheet cut out to a thickness of 0.3 mm was 97%.
- the average cell diameter of the obtained sheet was as fine as 10 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 96%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 89%.
- the average cell diameter of the obtained sheet was as fine as 20 ⁇ m.
- the thickness of the foam was 0.8 mm.
- the total reflectance of the foam sheet was 94%.
- the total reflectance of the sheet cut to a thickness of 0.3 mm was 89%.
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Abstract
Description
しかしながら、当該熱可塑性樹脂発泡体のフィルムまたはシートを立体的な形状に加工すると、成形時のひずみや成形後の収縮により変形してしまう。そこで、形状加工を施した光反射板と金属製ケーシングとを固定することにより光反射板の変形を防止する手段が提案されている(例えば特許文献2参照)。
本発明は、上記の問題点を解決し、薄肉化しても高い反射率を有する熱可塑性樹脂発泡体および光反射材ならびに該熱可塑性樹脂発泡体の製造方法を提供することを課題とする。
<1>結晶性熱可塑性樹脂(A)に、溶融型結晶化核剤(B)を含む樹脂組成物を用いてなり、内部に平均気泡径1μm未満の気泡を有することを特徴とする熱可塑性樹脂発泡体、
<2>前記結晶性熱可塑性樹脂(A)が結晶性ポリエステル樹脂であることを特徴とする<1>に記載の熱可塑性樹脂発泡体、
<3>前記溶融型結晶化核剤(B)が結晶性熱可塑性樹脂(A)100質量部に対し0.1~2.0質量部含まれることを特徴とする<1>又は<2>に記載の熱可塑性樹脂発泡体、
<4>光波長550nmの全反射率が酸化アルミニウム比で100%以上であることを特徴とする<1>~<3>のいずれか1項に記載の熱可塑性樹脂発泡体、
<5><1>~<4>のいずれか1項に記載の熱可塑性樹脂発泡体を用いて成形されていることを特徴とする光反射材、
<6>結晶性熱可塑性樹脂(A)と溶融型結晶化核剤(B)とを含有する樹脂組成物のシートを加圧不活性ガス雰囲気中に保持して不活性ガスを含有させる工程と、不活性ガスを含有させた該シートを常圧下で加熱発泡させる工程とからなる製造方法、
<7>前記結晶性熱可塑性樹脂(A)が結晶性ポリエステル樹脂であることを特徴とする<6>に記載の製造方法、及び
<8>前記溶融型結晶化核剤(B)が結晶性熱可塑性樹脂(A)100質量部に対し0.1~2.0質量部含まれることを特徴とする<6>または<7>に記載の製造方法。
結晶性とは、Tg以上のある温度領域において、樹脂分子が規則的な立体配置構造(結晶構造)を形成することを意味する。こうした結晶性は示差走査熱量計による結晶化熱量に基づき定義される。本発明における結晶性とは、熱可塑性樹脂を融解温度以上に加熱した後、10℃/minで降温測定をした際に、発熱ピーク(結晶化ピーク)から算出される熱量が5.0J/g以上のものをいう。より好ましくは、10.0J/g以上である。好ましくは、50J/g以下である。
本発明において用いることのできる結晶性熱可塑性樹脂(A)として、例えば、ポリエステル、ポリアミド、白発色のリニア型ポリフェニレンサルファイド、シンジオタクチックポリスチレン、ポリエーテルケトン等が挙げられる。その中でも、特にポリエステルが好ましい。本発明において、結晶性熱可塑性樹脂は一種単独で用いても、二種以上を組み合わせて用いてもよい。
本発明において、リサイクルの観点から熱可塑性樹脂は非架橋であることが好ましい。本発明における熱可塑性樹脂は、熱可塑性樹脂のうち架橋している部分の質量分率(以下、本発明において、架橋度ともいう。)が10%未満であることが好ましい。熱可塑性樹脂の架橋度が好ましくは10%未満になるように架橋剤や架橋助剤を添加してもよい。
溶融型結晶化核剤とは、熱可塑性樹脂に添加すると溶融混練時に樹脂中に溶融分散し、降温凝固過程において凝集固化することを特徴とする造核剤のことを示す。
本発明において、成形時に溶融型結晶化核剤(B)は結晶性熱可塑性樹脂(A)に対して溶融分散する。成形後の降温固化時もしくはガス含浸時において、溶融型結晶化核剤(B)は結晶性熱可塑性樹脂(A)中に析出する。その結果、溶融型結晶化核剤(B)は結晶化する。発泡過程において、析出した溶融型結晶化核剤(B)が気泡核形成の起点となる。その結果、内部に平均気泡径1μm未満の微細な孔を均一に有した発泡体を得ることができる。こうした発泡体は成形されることにより、高い反射率を有する反射材を得ることができる。
本発明において用いられる溶融型結晶化核剤として特に制限はないが、N,N’-ジシクロヘキシル-2,6-ナフタレンジカルボキサミド、トリメシン酸トリス(t-ブチルアミド)、トリメシン酸トリシクロヘキシルアミド、トリメシン酸トリ(2-メチルシクロヘキシルアミド)、トリメシン酸トリ(4-メチルシクロヘキシルアミド)、1,4-シクロヘキサンジカルボン酸ジアニリド、1,4-シクロヘキサン酸ジカルボン酸ジシクロヘキシルアミド、1,4-シクロヘキサン酸ジカルボン酸ジ(2-メチルシクロヘキシルアミド)、1,4-シクロヘキサン酸ジカルボン酸ジベンジルアミド、2,6-ナフタレンジカルボン酸ジシクロヘキシルアミド、1,2,3,4-ブタンテトラカルボン酸テトラシクロヘキシルアミド及び1,2,3,4-ブタンテトラカルボン酸テトラアニリドなどが挙げられる。これらは単独で用いても、二種以上を混合して用いてもよい。これらの中では、特にN,N’-ジシクロヘキシル-2,6-ナフタレンジカルボキサミドが透明性、生成される結晶粒径の点で好適である。
本発明において、熱可塑性樹脂発泡体の比重は0.7以下であることが好ましく、より好ましくは0.65以下、更に好ましくは0.5以下である。本発明において、比重が大きくなる、すなわち発泡倍率が小さくなると、気泡率の低下による反射率の低下、成形性の低下または軽量化効果の減少に繋がる。
本発明において、(B)の配合量は結晶性の熱可塑性樹脂(A)100質量部に対して0.1~2質量部である。好ましくは0.25~1.5質量部である。溶融型結晶化核剤の配合量が少なすぎると、ガス含浸による溶融型結晶化核剤の結晶化工程を経ることで生成される結晶核が生成されにくく、発泡体の気泡径分布が大きくなる。また、溶融型結晶化核剤の配合量が多すぎると、結晶化が進行しすぎてしまい、結晶核が大きくなりすぎて粒子状となり、気泡核剤としての働きが十分でないため高い発泡倍率を得ることができない。
結晶性熱可塑性樹脂(A)と、溶融型結晶化核剤(B)とを例えば混練機や押出機などを用いて溶融混練することにより樹脂組成物が得られる。混練温度や混練時間等の混練条件は、結晶性熱可塑性樹脂(A)および溶融型結晶化核剤(B)の溶融する温度で適宜設定することができる。得られた樹脂組成物を押出機などでシート状に成形し樹脂シートを作製した後、当該樹脂シートとセパレータとを重ねて巻くことによりロール状にする。このロールを加圧不活性ガス雰囲気中に保持することにより当該樹脂シートに不活性ガスを含有させる。さらに、不活性ガスを含有させた当該樹脂シートを常圧下で結晶性熱可塑性樹脂(A)の軟化温度以上に加熱して発泡させる。こうして熱可塑性樹脂発泡体は得られる。
有機溶剤としては、ベンゼン、トルエン、メチルエチルケトン、ギ酸エチル、アセトン、酢酸、ジオキサン、m-クレゾール、アニリン、アクリロニトリル、フタル酸ジメチル、ニトロエタン、ニトロメタン、ベンジルアルコールなどが挙げられる。その中でも、取り扱い性および経済性の観点からアセトンがより好ましい。
以下、本発明を実施例に基づいてさらに詳細に説明するが、本発明はこれらに限定されるものではない。
実施例および比較例について、下記の評価を行った。各試験とその評価は以下の方法で行った。
(1)シート厚
サンプルの4角、4辺及びシートの中心における厚みをマイクロメータにより測定し、合計9点の平均値をシート厚とした。
(2)平均気泡径
ASTMD3576-77に準じて求めた。シートの断面のSEM写真を撮影し、SEM写真上に水平方向と垂直方向に直線を引き、直線が横切る気泡の弦の長さtを平均した。写真の倍率をMとして、下記式に代入して平均気泡径dを求めた。
d=t/(0.616×M)
(3)比重
水中置換法により、発泡体シートの比重を測定した。
(4)発泡倍率
水中置換法により測定された発泡体シートの比重(ρf)と発泡前の樹脂の比重(ρs)との比ρs/ρfとして算出した。
(5)反射率
0.8mm厚のサンプル及び0.8mm厚のサンプルから0.3mm厚に削り出して得られたサンプルの光線透過率を測定した。各サンプルを分光光度計(日立ハイテク社製U-4100)にて分光スリット4nmの条件にて光線波長550nmでの分光全反射率の測定を行った。リファレンスは酸化アルミニウム白色板(210-0740:(株)日立ハイテクフィールディング製)を使用し、測定値はリファレンスに対する相対値とした。
(6)結晶性
各実施例及び比較例に記載の樹脂について、示差走査熱量計(DSC)を用いて、融解温度以上に加熱した後、10℃/minで降温し、その際測定された発熱ピーク(結晶化ピーク)の熱量を測定した。DSCとしては島津製作所製DSC60A(商品名)を用いた。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を0.25質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は101%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を0.5質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は101%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を1.0質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は101%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を1.5質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は101%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:TF1、新日本理化製)を1.0質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は100%であった。厚さ0.3mmに削り出したシートの全反射率は100%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を0.1質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は101%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を2.0質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は0.5μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は100%であった。厚さ0.3mmに削り出したシートの全反射率は100%であった。
以下の比較例において、従来の発泡核剤であるポリエステルエラストマー(比較例1)、変性SEBS(変性スチレン-ブチレン-スチレン共重合体)(比較例2)、変性PE(比較例3)を用いた。これらはいずれも結晶性熱可塑性樹脂(A)を溶融させると同時に溶融するが、樹脂組成物と降温固化時もしくはガス含浸時に結晶化しないものである。
ポリエチレンテレフタレート(商品名:SA1206、ユニチカ製、IV値=1.05、発熱ピークの熱量:35J/g)100質量部に対してポリエステル系エラストマー(商品名:ハイトレル2551、東レ製)を2.0質量部添加した以外は実施例1と同様にして発泡体を得た。得られたシートの平均気泡径は1.0μmを超えていた。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は101%であった。厚さ0.3mmに削り出したシートの全反射率は100%であった。
比較例1のポリエチレンテレフタレートに変性SEBS(商品名:ダイナロン8630P、JSR製)を1.0質量部添加した以外は実施例1と同様にして発泡体を得た。得られたシートの平均気泡径は1.6μmであった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は100%であった。厚さ0.3mmに削り出したシートの全反射率は98%であった。
比較例1のポリエチレンテレフタレートに変性PE(商品名:ボンドファーストE、東洋紡製)を3.0質量部添加した以外は実施例1と同様にして発泡体を得た。得られたシートの平均気泡径は3.0μmであった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は99%であった。厚さ0.3mmに削り出したシートの全反射率は97%であった。
ポリエチレンテレフタレート(商品名:NEH2070、ユニチカ製、IV値=0.85、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を0.05質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は10μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は96%であった。厚さ0.3mmに削り出したシートの全反射率は89%であった。
ポリエチレンテレフタレート(商品名:J125S、三井化学製、IV値=0.77、降温結晶化ピーク=35J/g)100質量部に対して溶融型結晶化核剤(商品名:NU-100、新日本理化製)を3.0質量部配合して、二軸押出機で加熱溶融混練した後、得られた樹脂組成物を0.5mm厚×100mm幅×100mm長にシート成形した。この樹脂シートを圧力容器に入れ、17℃で5.5MPaの条件で72時間、炭酸ガスを浸透させた。その後220℃に設定した熱風循環式発泡炉で1分間の加熱発泡を行った。得られたシートの平均気泡径は20μmと微細であった。発泡体の厚さは0.8mmであった。発泡体シートの全反射率は94%であった。厚さ0.3mmに削り出したシートの全反射率は89%であった。
Claims (8)
- 結晶性熱可塑性樹脂(A)に、溶融型結晶化核剤(B)を含む樹脂組成物を用いてなり、内部に平均気泡径1μm未満の気泡を有することを特徴とする熱可塑性樹脂発泡体。
- 前記結晶性熱可塑性樹脂(A)が結晶性ポリエステル樹脂であることを特徴とする請求項1に記載の熱可塑性樹脂発泡体。
- 前記溶融型結晶化核剤(B)が結晶性熱可塑性樹脂(A)100質量部に対し0.1~2.0質量部含まれることを特徴とする請求項1又は2に記載の熱可塑性樹脂発泡体。
- 光波長550nmの全反射率が酸化アルミニウム比で100%以上であることを特徴とする請求項1~3のいずれか1項に記載の熱可塑性樹脂発泡体。
- 請求項1~4のいずれか1項に記載の熱可塑性樹脂発泡体を用いて成形されていることを特徴とする光反射材。
- 結晶性熱可塑性樹脂(A)と溶融型結晶化核剤(B)とを含有する樹脂組成物のシートを加圧不活性ガス雰囲気中に保持して不活性ガスを含有させる工程と、不活性ガスを含有させた該シートを常圧下で加熱発泡させる工程とからなる熱可塑性樹脂発泡体の製造方法。
- 前記結晶性熱可塑性樹脂(A)が結晶性ポリエステル樹脂であることを特徴とする請求項6に記載の熱可塑性樹脂発泡体の製造方法。
- 前記溶融型結晶化核剤(B)が結晶性熱可塑性樹脂(A)100質量部に対し0.1~2.0質量部含まれることを特徴とする請求項6または7に記載の熱可塑性樹脂発泡体の製造方法。
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CN201180004043.1A CN102575044B (zh) | 2010-08-27 | 2011-08-25 | 热塑性树脂发泡体、热塑性树脂发泡体的制造方法和光反射材 |
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WO2013094461A1 (ja) * | 2011-12-21 | 2013-06-27 | 古河電気工業株式会社 | ポリエステル樹脂発泡体、それを用いた光反射材、およびポリエステル樹脂発泡体の製造方法 |
JP2015197449A (ja) * | 2014-03-31 | 2015-11-09 | 古河電気工業株式会社 | 熱可塑性樹脂多孔質シート、熱可塑性樹脂多孔質シートの製造方法および熱可塑性樹脂多孔質反射シート |
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US10357904B2 (en) | 2015-10-30 | 2019-07-23 | Nike, Inc. | Method of foaming an injection molded precursor |
US10308779B2 (en) | 2015-10-30 | 2019-06-04 | Nike, Inc. | Method of foaming a milled precursor |
JP6740119B2 (ja) * | 2016-12-27 | 2020-08-12 | オムロン株式会社 | 袋状構造体及びその製造方法、カフ、並びに血圧計 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04268345A (ja) * | 1991-02-25 | 1992-09-24 | Furukawa Electric Co Ltd:The | 飽和ポリエステル樹脂発泡体の製造方法 |
WO1997001117A1 (fr) | 1995-06-23 | 1997-01-09 | The Furukawa Electric Co., Ltd. | Plaque reflechissante |
JP2002122863A (ja) | 2000-10-17 | 2002-04-26 | Hitachi Ltd | 液晶表示装置 |
WO2002066233A1 (en) * | 2001-02-21 | 2002-08-29 | New Japan Chemical Co., Ltd. | Successively biaxial-oriented porous polypropylene film and process for production thereof |
JP2004138715A (ja) | 2002-10-16 | 2004-05-13 | Furukawa Electric Co Ltd:The | 光反射板およびその製造方法 |
WO2007142260A1 (ja) * | 2006-06-08 | 2007-12-13 | The Furukawa Electric Co., Ltd. | 熱可塑性樹脂発泡体 |
JP2010191038A (ja) | 2009-02-17 | 2010-09-02 | Seiko Epson Corp | 液晶表示装置の駆動方法、液晶表示装置および電子機器 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6632850B2 (en) * | 2001-04-04 | 2003-10-14 | 3M Innovative Properties Company | Microporous materials and methods of making the same |
DE10233703B4 (de) * | 2002-07-24 | 2008-04-17 | Basf Ag | Verfahren zur Herstellung nanozellularer, partikelförmiger Polymerschäume und deren Verwendung zur Herstellung von Formteilen |
-
2011
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- 2011-08-25 KR KR1020127010114A patent/KR101494503B1/ko active IP Right Grant
- 2011-08-25 EP EP11819993.4A patent/EP2610288A4/en not_active Withdrawn
- 2011-08-25 JP JP2012502789A patent/JP5697055B2/ja active Active
- 2011-08-26 TW TW100130603A patent/TWI453239B/zh active
-
2012
- 2012-12-13 HK HK12112877.9A patent/HK1172047A1/xx unknown
-
2013
- 2013-02-26 US US13/777,050 patent/US8623930B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04268345A (ja) * | 1991-02-25 | 1992-09-24 | Furukawa Electric Co Ltd:The | 飽和ポリエステル樹脂発泡体の製造方法 |
WO1997001117A1 (fr) | 1995-06-23 | 1997-01-09 | The Furukawa Electric Co., Ltd. | Plaque reflechissante |
JP2002122863A (ja) | 2000-10-17 | 2002-04-26 | Hitachi Ltd | 液晶表示装置 |
WO2002066233A1 (en) * | 2001-02-21 | 2002-08-29 | New Japan Chemical Co., Ltd. | Successively biaxial-oriented porous polypropylene film and process for production thereof |
JP2004138715A (ja) | 2002-10-16 | 2004-05-13 | Furukawa Electric Co Ltd:The | 光反射板およびその製造方法 |
WO2007142260A1 (ja) * | 2006-06-08 | 2007-12-13 | The Furukawa Electric Co., Ltd. | 熱可塑性樹脂発泡体 |
JP2010191038A (ja) | 2009-02-17 | 2010-09-02 | Seiko Epson Corp | 液晶表示装置の駆動方法、液晶表示装置および電子機器 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2610288A4 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013094461A1 (ja) * | 2011-12-21 | 2013-06-27 | 古河電気工業株式会社 | ポリエステル樹脂発泡体、それを用いた光反射材、およびポリエステル樹脂発泡体の製造方法 |
JPWO2013094461A1 (ja) * | 2011-12-21 | 2015-04-27 | 古河電気工業株式会社 | ポリエステル樹脂発泡体、それを用いた光反射材、およびポリエステル樹脂発泡体の製造方法 |
JP2015197449A (ja) * | 2014-03-31 | 2015-11-09 | 古河電気工業株式会社 | 熱可塑性樹脂多孔質シート、熱可塑性樹脂多孔質シートの製造方法および熱可塑性樹脂多孔質反射シート |
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CN102575044B (zh) | 2014-03-12 |
KR101494503B1 (ko) | 2015-02-17 |
BR112013004459A2 (pt) | 2016-06-07 |
US8623930B2 (en) | 2014-01-07 |
US20130172438A1 (en) | 2013-07-04 |
TW201213411A (en) | 2012-04-01 |
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