KR0180477B1 - Rough-sufaced polyvinyl butyral sheet and method of forming same - Google Patents
Rough-sufaced polyvinyl butyral sheet and method of forming same Download PDFInfo
- Publication number
- KR0180477B1 KR0180477B1 KR1019960701369A KR19960701369A KR0180477B1 KR 0180477 B1 KR0180477 B1 KR 0180477B1 KR 1019960701369 A KR1019960701369 A KR 1019960701369A KR 19960701369 A KR19960701369 A KR 19960701369A KR 0180477 B1 KR0180477 B1 KR 0180477B1
- Authority
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- South Korea
- Prior art keywords
- particles
- sheet
- pvb
- polyvinyl butyral
- matrix
- Prior art date
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000009472 formulation Methods 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims description 30
- 239000004971 Cross linker Substances 0.000 claims description 20
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 10
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 9
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000007788 roughening Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- 241000352262 Potato virus B Species 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- -1 aliphatic aldehydes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000008241 heterogeneous mixture Substances 0.000 description 3
- OJXOOFXUHZAXLO-UHFFFAOYSA-M magnesium;1-bromo-3-methanidylbenzene;bromide Chemical compound [Mg+2].[Br-].[CH2-]C1=CC=CC(Br)=C1 OJXOOFXUHZAXLO-UHFFFAOYSA-M 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000005336 safety glass Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WWMIMRADNBGDHP-UHFFFAOYSA-N 2-hydroxyhexanedial Chemical compound O=CC(O)CCCC=O WWMIMRADNBGDHP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- OWMNWOXJAXJCJI-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1OC1COCC1CO1 OWMNWOXJAXJCJI-UHFFFAOYSA-N 0.000 description 1
- YXPZEGOFLHNCCI-UHFFFAOYSA-N 2-[2-(2-formylphenoxy)ethoxy]benzaldehyde Chemical compound O=CC1=CC=CC=C1OCCOC1=CC=CC=C1C=O YXPZEGOFLHNCCI-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- UOPOVDXLQHCGPJ-UHFFFAOYSA-N 2-[4-(2-oxoethyl)phenyl]acetaldehyde Chemical compound O=CCC1=CC=C(CC=O)C=C1 UOPOVDXLQHCGPJ-UHFFFAOYSA-N 0.000 description 1
- YKCSYIYQRSVLAK-UHFFFAOYSA-N 3,5-dimethyl-2-phenylmorpholine Chemical compound CC1NC(C)COC1C1=CC=CC=C1 YKCSYIYQRSVLAK-UHFFFAOYSA-N 0.000 description 1
- NZXKMTOTHHFKJB-UHFFFAOYSA-N 4-[2-(4-formylphenoxy)ethoxy]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1OCCOC1=CC=C(C=O)C=C1 NZXKMTOTHHFKJB-UHFFFAOYSA-N 0.000 description 1
- BJIUNQZHYLBUNL-UHFFFAOYSA-N 6-heptoxy-6-oxohexanoic acid Chemical compound CCCCCCCOC(=O)CCCCC(O)=O BJIUNQZHYLBUNL-UHFFFAOYSA-N 0.000 description 1
- OIUGWVWLEGLAGH-UHFFFAOYSA-N 6-nonoxy-6-oxohexanoic acid Chemical compound CCCCCCCCCOC(=O)CCCCC(O)=O OIUGWVWLEGLAGH-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical group N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IQDQMRZGMILNMQ-UHFFFAOYSA-N naphthalene-2,6-dicarbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(C=O)=CC=C21 IQDQMRZGMILNMQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005406 washing Methods 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
- C08L29/00—Compositions 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F116/00—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F116/02—Homopolymers 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F116/04—Acyclic compounds
- C08F116/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
-
- 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
- C08J2329/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- C08J2429/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
거친표면을 가진 폴리비닐부티랄(PVB)시이트를 제조함에 있어서, 교차결합된 PVB의 단단한 탄성입자들이 제제내에 존재하며, 상기 입자들은 제제가 압출다이개구부를 통하여 방출될 때 기계적으로 방해하여 성형되는 시이트의 표면을 거칠게 만든다.In preparing a polyvinyl butyral (PVB) sheet having a rough surface, rigid elastic particles of cross-linked PVB are present in the formulation, which are formed by mechanical interference when the formulation is released through the extrusion die opening. Roughen the surface of the sheet.
Description
[발명의 명칭][Name of invention]
거친 표면을 갖는 폴리비닐 부티랄 시이트 및 그의 제조방법Polyvinyl butyral sheet having a rough surface and manufacturing method thereof
[발명의 상세한 설명]Detailed description of the invention
[발명의 배경][Background of invention]
본 발명은 폴리비닐부티랄(PVB)을 함유하는 시이트, 보다 상세하게는 이러한 시이트의 거친 표면, 및 그 제조방법에 관한 것이다.The present invention relates to a sheet containing polyvinyl butyral (PVB), more particularly to the rough surface of such a sheet, and to a process for producing the sheet.
PVB를 함유하는 가소화된 시이트는 적층안전유리에 있어서 유리 또는 단단한 플라스틱 패널(이하, 적층패널)과 함께 사용되는 충격흡수층으로 알려져 있다.Plasticized sheets containing PVB are known as impact absorbing layers for use with glass or rigid plastic panels (hereinafter referred to as laminated panels) in laminated safety glass.
또한, 상기한 바와 같은 적층유리의 제조시에 탈기를 용이하게 하기 위하여 시이트의 주(major) 평면을 거칠게 하는 것도 알려져 있다.It is also known to rough the major plane of the sheet in order to facilitate degassing during the production of the laminated glass as described above.
더욱 상세하게는, 적층패널의 평탄한 표면과 이 면에 접촉하는 PVB 시이트의 거친 표면상에 존재하는 미세한 밸리(valley)들의 선단사이에 형성된 미세한 채널(channel)들을 통하여, 상기 두 표면사이의 경계면에 압력 또는 진공이 적용될 경우, 상기 두 멤버사이의 공기가 빠져나가게 된다.More specifically, at the interface between the two surfaces, through fine channels formed between the flat surface of the laminated panel and the tip of the fine valleys present on the rough surface of the PVB sheet in contact with the surface. When pressure or vacuum is applied, the air between the two members will escape.
U.S. 4,654,179호에 압출시에 표면거칠기(surface roughness)를 형성하기 위해 교차결합된 PVB의 사용이 개시되어 있다. 상기 특허에서는 단일 PVB상(phase)이 사용되며 거칠기는 PVB 분자량분포의 함수로서 설명되는데, 교차결합수준이 증가함에 의해 얻어지는 분자량분포가 넓을수록 표면거칠기의 정도가 낮아진다. 상기 U.S. 4,654,179호 특허에서, 교차결합된 PVB와 교차결합되지 않은 PVB는 화학적으로, 분자적으로 균질한 한 덩어리로 전체를 이룬다. 상기 특허에 따르면, 거칠기는 PVB의 합성동안에 사용된 교차결합제의 농도를 변화시킴으로써 조절되며, 교차결합제의 농도가 높을수록 시이트 거칠기는 낮아진다.U.S. 4,654,179 discloses the use of crosslinked PVBs to form surface roughness during extrusion. In this patent a single PVB phase is used and the roughness is explained as a function of the PVB molecular weight distribution, the wider the molecular weight distribution obtained by increasing the level of crosslinking, the lower the degree of surface roughness. U.S. In the 4,654,179 patent, cross-linked PVBs and non-cross-linked PVBs are entirely made up of one chemically and molecularly homogeneous mass. According to this patent, the roughness is controlled by varying the concentration of the crosslinker used during the synthesis of PVB, and the higher the crosslinker concentration, the lower the sheet roughness.
상기 특허의 기술은 성공적이지만, 교차결합된 PVB를 이용하여 PVB 사이트의 거칠기를 조절하기 위해 PVB 합성동안에 수지의 화학적 성질을 변화시키는 것에만 의존하지 않는, 보다 응용이 자유로운 방법을 제공하는 것이 바람직하다.While the technique of this patent is successful, it is desirable to provide a more application free method that does not rely solely on changing the chemical properties of the resin during PVB synthesis to control the roughness of PVB sites using crosslinked PVBs. .
[발명의 요약][Summary of invention]
본 발명에서는 선행기술의 단점을 해소할 수 있는, PVB 시이트의 일면 또는 양면을 거칠게 만드는 향상된 기술이 제공된다.The present invention provides an improved technique for roughening one or both sides of a PVB sheet, which can address the disadvantages of the prior art.
따라서, 본 발명의 주요목적은 교차결합된 PVB에 의해 거칠기가 형성되는 거친 표면을 갖는 PVB 시이트를 제공하는 것이다.It is therefore a primary object of the present invention to provide a PVB sheet having a rough surface on which roughness is formed by crosslinked PVB.
본 발명의 다른 목적은 거칠기의 질을 나타내는 파라미터들(폭(amplitude)과 피치(pitch)를 포함)을 용이하게 변경시킬 수 있는, 상기 PVB 시이트의 쉬운 제조방법을 제공하는 것이다.It is another object of the present invention to provide an easy method for manufacturing the PVB sheet, which can easily change parameters (including amplitude and pitch) indicating the quality of roughness.
본 발명의 다른 목적들은 이하의 상세한 설명 및 청구범위들로부터 부분적으로 자명해지고 명백해 질 것이다.Other objects of the invention will be in part apparent and apparent from the following detailed description and claims.
상기 목적들과 다른 목적들은 매트릭스내에 전체적으로 불규칙하게 분산되어 있으며 시이트 표면상에 거칠기를 형성하기 위해 시이트의 표면으로부터 미시적(microscopically)으로 돌출되어 있는 교차결합된 PVB의 분리된 입자들을 함유하는 가소화된 폴리비닐 부티랄 매트릭스를 포함하는 시이트에 의해 달성된다.These and other objects are plasticized containing discrete particles of cross-linked PVB which are distributed throughout the matrix irregularly and protrude microscopically from the surface of the sheet to form roughness on the sheet surface. Achieved by a sheet comprising a polyvinyl butyral matrix.
입자들의 양은 바람직하게는 매트릭스와 입자들의 전체량의 1 내지 40중량%이고; 입자들의 크기는 1 내지 100미크론이며, 입자들의 합성시에 존재하는 교차결합제의 농도에 의해 측정되는 강도(stiffness)는 폴리비닐 알콜 100부당 교차결합제 약 0.6 내지 0.30부의 농도로부터 얻어지는 강도이다.The amount of particles is preferably 1 to 40% by weight of the total amount of the matrix and the particles; The size of the particles is from 1 to 100 microns and the stiffness measured by the concentration of the crosslinker present in the synthesis of the particles is the strength obtained from the concentration of about 0.6 to 0.30 parts of the crosslinker per 100 parts of polyvinyl alcohol.
본 발명에서는 PVB가 함유된 가소화된 제제(formulation)를 다이개구부를 통하여 압출함으로써 PVB 시이트를 제조하는 방법에 있어서, 압출하기 전에 교차결합된 PVB의 단단하고 탄성있는 입자들을 상기 제제에 첨가하는 단계가 조합된 방법이 제공되는 데, 상기 입자들은 압출동안에 제제중의 PVB와는 다른 상(phase)을 형성하며, 제제가 다이개구부를 통과하는 것을 방해함으로써 성형되는 시이트의 표면을 거칠게 만든다.In the present invention, a method for producing a PVB sheet by extruding a plasticized formulation containing PVB through the die opening, the step of adding the hard and elastic particles of cross-linked PVB to the formulation before extrusion A combined method is provided, wherein the particles form a different phase from the PVB in the formulation during extrusion and roughen the surface of the sheet being formed by preventing the formulation from passing through the die opening.
[도면의 간단한 설명][Brief Description of Drawings]
본 발명을 설명함에 있어서 참고가 될 첨부도면은 본 발명에 따른 시이트의 표면의 100배 확대된 광현미경사진이다.The accompanying drawings, which are referred to in the description of the present invention, are optical micrographs magnified 100 times of the surface of the sheet according to the present invention.
[발명의 상세한 설명]Detailed description of the invention
본 발명에 따른 시이트제제는 가소제와 혼합된 제1 PVB 성분과 제2 PVB 성분을 포함하는 불균질성(heterogeneous) 폴리머 혼합물로서, 상기 제1 PVB 성분은 (제1성분과 제2성분의 전체량에 대해) 소량의 제2 PVB 성분 입자들이 분산되어 있는 매트릭스상을 형성하며, 제2 PVB 성분은 교차결합된 폴리비닐 부티랄을 함유한다. 매트릭스상은 교차결합되지 않은 PVB이거나, 또는 분산상에 비하여 약간 교차결합된 PVB이거나, 또는 교차결합되지 않은 PVB와 약간 교차결합된 PVB의 혼합물이다.The sheet preparation according to the present invention is a heterogeneous polymer mixture comprising a first PVB component and a second PVB component mixed with a plasticizer, wherein the first PVB component is based on the total amount of the first component and the second component. ) A small amount of the second PVB component particles form a matrix phase, the second PVB component containing cross-linked polyvinyl butyral. The matrix phase is either uncrosslinked PVB, or slightly crosslinked PVB relative to the disperse phase, or a mixture of uncrosslinked PVB and slightly crosslinked PVB.
분산된 PVB상은 매트릭스보다 더 교차결합되어 있어서 유동학적으로 매트릭스와는 다르며, 입자(particulate)형태로서, 시이트로 용융성형되는 동안 매트릭스와는 달리 단단하며 탄성적이다. 이는 제1도에 도시되어 있는데, 제1도에서 입자들(10)은 시이트의 표면에 돌출되어 존재하며, 부호 12는 매트릭스이다. 교차결합된 정도가 클수록, 분산된 입자상은 압출중의 불균질한 두가지 상의 혼합물내에서, 그리고 그후 형성된 시이트내에서 입자들의 원래형태를 보존하기에 적합한 용융전단점도(melt shear viscosity)를 갖는다. 그러한 용융전단점도(20sec.-1)는 매트릭스상보다 3배(가장 바람직하게는 적어도 5배) 큰 것이 바람직하다. 이러한 점도차이는 용융공정동안 단단하며 탄성적인 입자들이 매트릭스와 균질화되는 것을 방지한다. 즉, 더 교차결합된 상이 압출동안에 용융상태임에도 불구하고 원래의 전체형태를 유지하게 된다.The dispersed PVB phase is more crosslinked than the matrix so that it is rheologically different from the matrix and in the form of particles, which are hard and elastic unlike the matrix during melt molding as a sheet. This is shown in FIG. 1, in which the particles 10 are protruding on the surface of the sheet and 12 is a matrix. The greater the degree of crosslinking, the more dispersed the dispersed phase has a melt shear viscosity suitable for preserving the original shape of the particles in the mixture of the two heterogeneous phases during extrusion and in the sheet formed thereafter. Such melt shear viscosity (20 sec.- 1 ) is preferably three times greater (most preferably at least five times) than the matrix phase. This difference in viscosity prevents the hard and elastic particles from homogenizing with the matrix during the melting process. That is, the more crosslinked phase retains its original overall form despite being molten during extrusion.
불균질성 혼합물의 퍼포먼스(performance)는 연속상 또는 분산상이 단속으로 사용되어 분산입자들이 존재하지 않는 경우와는 다르기 때문에, 성형된 시이트(제1도)내의 분산상의 입자형태를 보존함에 있어서 그 퍼포먼스는 예측하기 어렵다.Since the performance of a heterogeneous mixture is different from the case where a continuous phase or a dispersed phase is used for intermittent use and no dispersed particles are present, the performance is predicted in preserving the particle shape of the dispersed phase in the molded sheet (FIG. 1). Difficult to do
이는 U.S. 4,654,179호의 PVB 제제의 변형으로서, 상기 특허에서의 제1도의 매트릭스만으로 된 시이트와 제1도의 분산상만으로 된 시이트는 균질성이다. 즉 분산된 입자가 존재하지 않는다. 본 발명에서는 압출제제(extruding formulation)가 다이개구부로 방출됨에 따라 불균질성 혼합물의 단단한 분산상으로 인해 표면을 거칠게 하는 파쇄부위(fracture sites)가 형성된다. 더욱 구체적으로는, 압출제제가 다이개구부를 통하여 주위대기로 방출되면서 압출제제의 압력이 해제됨에 따라 분산상의 입자들은 낮은 점도의 매트릭스로부터 이탈되어 성형되어지는 시이트의 표면을 기계적으로 방해하여 거칠게 만든다.This is U.S. As a variation of the PVB formulation of 4,654,179, the sheet consisting only of the matrix of FIG. 1 in the patent and the sheet consisting only of the dispersed phase of FIG. 1 are homogeneous. That is, there are no dispersed particles. In the present invention, as the extruding formulation is released into the die opening, fracture sites are formed that roughen the surface due to the hard dispersed phase of the heterogeneous mixture. More specifically, as the extruded agent is released to the ambient atmosphere through the die opening, the pressure of the extruded agent is released, so that the dispersed phase particles are separated from the low viscosity matrix and mechanically disturb the surface of the sheet to be formed.
이는 제1도에 도시되어 있는데, 제1도에서 시이트의 플라스틱은 고정되어 있고 교차 결합된 PVB의 불규칙하게 분산된 입자들(10)은 매트릭스와 합체되어 매트릭스내에 묻혀 있으며, 시이트의 주요면에 분리될 수 없게 미시적으로 돌출되어서(즉, 어떠한 표면혼란(surface disturbance)도 존재하지 않는다), 그 면상에 거친 표면을 형성한다.This is shown in FIG. 1, in which the plastic of the sheet is fixed and irregularly dispersed particles 10 of the cross-linked PVB are incorporated into the matrix and buried in the matrix and separated on the main face of the sheet. It protrudes microscopically (ie, no surface disturbance exists), forming a rough surface on that surface.
표면거칠기는 다수의 미시적인 피크와 밸리에 의해 형성되며, 피크 빈도수(peak frequency)(주어진 방향과 거리에서의 피크수)와 피크높이(또는 넓이)로 규정된다. 본 발명에서의 표면거칠기는 크기, 강도 및 분산상의 입자수의 함수이다.Surface roughness is formed by a number of microscopic peaks and valleys, defined by peak frequency (number of peaks in a given direction and distance) and peak height (or width). Surface roughness in the present invention is a function of the size, strength and number of particles in the dispersed phase.
이러한 파라미터들(parameters)은 피크빈도수와 피크높이에 다소의 영향을 미친다.These parameters have some effect on peak frequency and peak height.
피크빈도수는 파쇄부위의 수와 상관관계가 있으며, 분산상의 입자양 또는 입자수에 의해 큰 영향을 받으며, 분산상의 농도가 증가할수록 빈도수가 증가한다. 따라서, 압출제제내의 분산상의 농도가 증가함에 따라 일정거리상(주어진 크기분포 및 입자들의 강도에 따라)에 더 많은 피크가 형성된다.The peak frequency is correlated with the number of fracture sites and is greatly influenced by the amount of particles in the dispersion phase or the number of particles, and the frequency increases as the concentration of the dispersion phase increases. Thus, as the concentration of the dispersed phase in the extrudate formulation increases, more peaks are formed over a distance (depending on the given size distribution and the strength of the particles).
미세입자의 양은 제제내의 전체 PVB 중량의 50중량%까지 될 수 있지만, 바람직한 농도는 1 내지 40중량%, 가장 바람직하게는 3 내지 20중량%이다. 이러한 범위내에서, 바람직한 높은 빈도수가 얻어지며, 빈도수가 높으면 적층과정동안의 탈기가 양호하게 이루어진다.The amount of microparticles can be up to 50% by weight of the total PVB in the formulation, but the preferred concentration is 1 to 40% by weight, most preferably 3 to 20% by weight. Within this range, a desirable high frequency is obtained, and a high frequency results in good degassing during the lamination process.
분산상의 농도가 (매트릭스와 분산상의 합계중량에 기초하여) 1중량% 미만일 경우에는, 빈도수에 영향을 미치지 않는 것으로 예측되며; 분산상의 농도가 40 내지 50중량% 이상으로 증가하면 그에 따른 별다른 효과가 없어서 비경제적이다.If the concentration of the dispersed phase is less than 1% by weight (based on the total weight of the matrix and the dispersed phase), it is predicted to have no influence on the frequency; Increasing the concentration of the dispersed phase to more than 40 to 50% by weight is uneconomical because there is little effect.
표면거칠기의 피크높이는 주로 분산상 입자의 크기와 강도에 대한 함수로서, 입자의 크기가 크고 단단할수록 피크높이는 높아진다. (합성동안의 교차결합제의 농도에 의해 조절된) 교차결합의 정도가 증가할수록, 각각의 교차결합된 입자의 크기가 증가하는 것으로 여겨진다.The peak height of the surface roughness is primarily a function of the size and strength of the dispersed phase particles. The larger and harder the particles, the higher the peak height. As the degree of crosslinking (adjusted by the concentration of the crosslinking agent during synthesis) increases, it is believed that the size of each crosslinked particle increases.
통상(압출전의) 수지는 각각의 입자들의 응집체의 형태로 존재하기 때문에, 응집되지 않은 입자들의 크기는 편리하게 측정되지 못한다. 그러나, 그러한 응집체들은 시이트 성형시의 용융공정동안에 분쇄된다. 응집되지 않은 입자들에 대해서, 입자크기는 혼합되지 않은 분산상을 스크리닝하여 미리 정해진 크기 이상의 크기를 갖는 입자들을 제거함으로써 고정될 수 있다. 그러나, 그러한 스크리닝은 교차결합된 분산상 물질을 형성하는 합성반응동안에 바람직한 크기 분포가 얻어지는 경우에는 불필요할 수도 있다. 입자강도(particle stiffness)는 분산상 입자들의 교차결합수준에 대한 함수이며, 입자들을 형성하는 폴리비닐알콜(PVOH)과 부티르알데히드와의 합성반응동안에 존재하는 교차결합제의 농도에 의해 측정된다.Since conventional (pre-extrusion) resins exist in the form of aggregates of individual particles, the size of the non-aggregated particles is not conveniently measured. However, such aggregates are pulverized during the melting process in sheet forming. For unaggregated particles, the particle size can be fixed by screening the unmixed dispersed phase to remove particles having a size above a predetermined size. However, such screening may be unnecessary if the desired size distribution is obtained during the synthesis reaction to form the crosslinked dispersed phase material. Particle stiffness is a function of the level of crosslinking of dispersed phase particles and is measured by the concentration of crosslinker present during the synthesis of polyvinyl alcohol (PVOH) and butyraldehyde forming the particles.
일반적으로, 미성숙(premature)피크의 붕괴없이 우수한 탈기를 얻기 위한 거칠기 피크높이는 분산상 입자의 크기분포가 1 내지 100미크론, 바람직하게는 1 내지 50미크론 사이일 때 얻어진다. 100미크론 이상의 입자들은 광학적 결합들, 즉 완성된 적층안전유리에서 시각적으로 분명히 드러나는 거친 반점들(hard spots)(불투명한 불연속부위)을 초래한다.In general, the roughness peak height for obtaining good degassing without collapse of the premature peak is obtained when the size distribution of the dispersed phase particles is between 1 and 100 microns, preferably between 1 and 50 microns. Particles over 100 microns result in optical bonds, ie hard spots (opaque discontinuities) that are clearly visible in the finished laminated safety glass.
서브미크론 입자들은 바람직한 정도의 탈기성능을 나타내는 적절한 거칠기를 제공하지 못한다.Submicron particles do not provide adequate roughness that exhibits the desired degree of degassing performance.
허용할만한 입자강도는 매트릭스상 형성시에(만약 사용되었다면) 사용된 교차결합제보다 적어도 3배에 달하는 농도의 교차결합제를 합성시에 사용함으로써 얻어진다. 그러한 농도는 바람직하게는 PVOH 100부당 교차결합제 0.06 내지 0.30부, 가장 바람직하게는 0.08 내지 0.20부이다.Acceptable particle strength is obtained by the use of a crosslinker in synthesis at least three times the concentration of the crosslinker used in the matrix formation (if used). Such concentration is preferably 0.06 to 0.30 parts, most preferably 0.08 to 0.20 parts of the crosslinker per 100 parts of PVOH.
본 발명의 시이트는 (시이트를 형성하는 플라스틱이 냉각되어 굳어진 후에) 유백색을 나타내며, 거친 표면을 형성하는 피크로부터의 광산란으로 인해 시각적으로 불투명하며, 거친표면은 만져서 느껴질 수 있다. 이러한 거칠기 및 불투명성은 일시적이며, 프리라미네이트(prelaminate) 제조동안의 상승된 온도에서, 그리고 그후에 유리와 같은 하나 이상의 적층부재와 함께 최종 적층제(laminate)를 형성할 때의 고온과 고압에서 시이트의 PVB가 용융될 때 상기의 거칠기 및 불투명성은 없어진다. 최종 적층공정후에, 광학적으로 매우 투명한 실질적으로 헤이즈가 없는 (haze-free) 구조물이 얻어지며, 이 구조물에서 교차결합된 입자들은 입자들의 굴절률이 매트릭스의 굴절률에 매우 근접하기 때문에, 전형적으로는 단지 ±0.0003(또는 그 이하)의 굴절률 유니트정도로만 다르기 때문에 매트릭스 PVB로부터 시각적으로 구별할 수 없으며 광학적으로는 동일하다. 상기한 적층공정은 당분야에서는 통상적인 것이며, 본 발명의 특징이 아니다.The sheet of the present invention has a milky white color (after the plastic forming the sheet has cooled and hardened), and is visually opaque due to light scattering from the peaks forming the rough surface, and the rough surface can be felt by touching. This roughness and opacity is temporary, the PVB of the sheet at elevated temperatures during prelaminate manufacturing and then at high temperatures and pressures when forming the final laminate with one or more laminates, such as glass. The roughness and opacity are lost when is melted. After the final lamination process, a substantially haze-free structure is obtained which is optically very transparent, in which crosslinked particles typically have only ± because the refractive index of the particles is very close to the refractive index of the matrix. Because they differ only by a refractive index unit of 0.0003 (or less), they are not visually distinguishable from the matrix PVB and are optically identical. The lamination process described above is conventional in the art and is not a feature of the present invention.
본 발명의 시이트를 성형하기 위한 불균질성 PVB 혼합물은, 두가지 상(phases)을 혼합물의 용융없이 기계적으로 건조혼합한 후 용융성형하거나 또는 약간의 용융이 발생하도록 강력 혼합기에서 혼합한 후 용융압출함으로써 제조된다.Heterogeneous PVB mixtures for forming the sheet of the present invention are prepared by mechanically dry mixing the two phases without melting the mixture followed by melt molding or by melt extrusion after mixing in a strong mixer such that some melting occurs. .
본 발명의 거친 표면을 가진 시이트는 약 5 내지 60밀(0.13 내지 1.52㎜)의 비임계적인(non-critical) 두께를 갖는다.The rough surfaced sheet of the present invention has a non-critical thickness of about 5 to 60 mils (0.13 to 1.52 mm).
본 발명에 사용될 수 있는 교차결합된 PVB에 대하여, 분자간 교차결합을 형성하기 위한 교차결합제와 PVOH와의 화학반응은 U.S. 4,654,179호의 칼럼 2, 20∼48행에 기재되어 있으며, 그 내용은 본 명세서에 참고문헌으로 언급된다. 안정된 분자간 가교를 형성하기 위해 두 개의 인접한 PVOH 분자체인의 각각에 존재하는 한쌍의 히드록실기와 반응할 수 있는 활성기(active groups)를 갖는 어떠한 교차결합제도(교차결합제의 혼합물을 포함하여) 사용될 수 있다.For crosslinked PVBs that can be used in the present invention, the chemical reaction of PVOH with crosslinkers to form intermolecular crosslinks is described in U.S. Pat. 4,654,179, column 2, lines 20 to 48, the contents of which are incorporated herein by reference. Any crosslinking agent (including mixtures of crosslinking agents) with active groups capable of reacting with a pair of hydroxyl groups present in each of two adjacent PVOH molecular chains to form a stable intermolecular crosslink can be used. have.
사용가능한 교차결합제로는 디글리시딜 에테르비스페놀 A; 디알데히드와 트리알데히드와 같은 적어도 두 개의 CHO기를 포함하는 알데히드류 등이 포함된다. 1993년 2월 2일자로 공개된 일본공개 5-25213호에 기재된 바와 같이 모노부티랄 결합에 의해 교차결합된 PVB가 사용될 수 있다. 바람직한 교차결합제는 디알데히드, 예로서 옥살알데히드와 더 복잡한 디알데히드, 및 CHO기의 카보닐 결합사이에 지방족기(불포화된 것이거나 또는 불포화되지 않은 것), 방향족기 또는 혼합된 지방족/방향족기를 포함하는 트리알데히드이다. 특히 기능적인 디알데히드류에는 프로판디알, 숙신알데히드, 아디프알데히드, 2-히드록시헥산디알등과 같은 지방족 알데히드; 프탈알데히드, 1,4-벤젠디아세트알데히드, 4,4-(에틸렌디옥시)디벤즈알데히드, 2,6-나프탈렌 디카르브알데히드등과 같은 방향족 디알데히드가 포함된다. 사용가능한 트리알데히드류에는 N,N',N-(3,3',3-트리스포밀에틸)이소시아누레이트등이 포함된다. 상기한 교차결합제들의 혼합물 및 다른 교차결합제들도 적합하다.Crosslinkers that can be used include diglycidyl ether bisphenol A; Aldehydes including at least two CHO groups such as dialdehyde and trialdehyde, and the like. PVBs crosslinked by monobutyral bonds can be used as described in Japanese Patent Application Laid-Open No. 5-25213, published February 2, 1993. Preferred crosslinkers include aliphatic groups (unsaturated or unsaturated), aromatic groups or mixed aliphatic / aromatic groups between dialdehydes such as oxalaldehyde and more complex dialdehydes, and carbonyl bonds of CHO groups. It is trialdehyde. Particularly functional dialdehydes include aliphatic aldehydes such as propanedial, succinaldehyde, adialdehyde, 2-hydroxyhexanedial and the like; Aromatic dialdehydes such as phthalaldehyde, 1,4-benzenediacetaldehyde, 4,4- (ethylenedioxy) dibenzaldehyde, 2,6-naphthalene dicarbaldehyde and the like. Trialdehydes that can be used include N, N ', N- (3,3', 3-trisforylethyl) isocyanurate and the like. Mixtures of the aforementioned crosslinkers and other crosslinkers are also suitable.
바람직한 디알데히드는 글루타르알데히드, 4,4'-(에틸렌디옥시)디벤즈알데히드 및 2-히드록시헥산디알로 구성된 군으로부터 선택된다.Preferred dialdehydes are selected from the group consisting of glutaraldehyde, 4,4 '-(ethylenedioxy) dibenzaldehyde and 2-hydroxyhexanedial.
교차결합은 실질적으로 PVOH와 부티르알데히드와의 축합에 의한 PVB의 생성과 함께 일어난다. 교차결합된 PVB를 제공하기 위한 교차결합제의 농도는 교차결합제의 분자량에 따라 달라지는데, 분자량이 클수록 요구되는 사용량이 많아진다. 바람직한 디알데히드와 트리알데히드에 대하여, 사용되는 농도는 PVOH 100부당 약 0.06 내지 약 0.30부, 가장 바람직하게는 0.08 내지 0.20부이다. 교차결합된 PVB 수지는 공지의 수성 아세틸화(aqueous acetalization) 또는 용매성 아세틸화(solvent acetalization)에 의해 제조되며, 이 방법에 있어서 PVOH를 산촉매의 존재하에 부티르알데히드와 반응시켜 PVB를 생성시키고, 촉매를 중화한 다음 PVB 수지를 분리, 안정화 및 건조한다. 반응속도에 따라서, 교차결합제는 부티르알데히드의 첨가전에 또는 부티르알데히드와 동시에 촉매화된 축합반응 혼합물에 첨가된다.Crosslinking occurs substantially with the production of PVB by condensation of PVOH with butyraldehyde. The concentration of the crosslinker to provide crosslinked PVB depends on the molecular weight of the crosslinker, the higher the molecular weight the higher the required amount of use. For preferred dialdehydes and trialdehydes, the concentration used is from about 0.06 to about 0.30 parts, most preferably 0.08 to 0.20 parts per 100 parts of PVOH. Crosslinked PVB resins are prepared by known aqueous acetylation or solvent acetalization, in which PVOH is reacted with butyraldehyde in the presence of an acid catalyst to produce PVB, The catalyst is neutralized and then the PVB resin is separated, stabilized and dried. Depending on the reaction rate, the crosslinking agent is added to the catalyzed condensation mixture prior to the addition of butyraldehyde or concurrently with butyraldehyde.
용매시스템에 있어서, 첨가순서는 다소 다를 수 있다; 예를 들면 PVB가 용액내에 존재하게 된 후에 교차결합제를 첨가하는 것이 필요할 수 있다.For solvent systems, the order of addition may vary somewhat; For example, it may be necessary to add a crosslinker after PVB has been present in solution.
또한 원래 교차결합되지 않은 PVB의 인 시튜(in situ) 교차결합도 본 발명의 범위에 속한다. 예를 들면, 용매공정(solvent process)에 의하여 교차결합되지 않은 PVB를 제조한 후, 합성반응용기내의 용액중의 교차결합되지 않은 PVB에 산촉매와 교차결합제(예로서, 테트라에틸 오르소 실란)를 적절한 농도로 첨가하여 PVB 수지성분을 교차결합시킨다. 제1도의 시이트의 제제중의 교차결합된 PVB 상은 이러한 방법으로 만들어진다.In situ crosslinking of PVB that was not originally crosslinked is also within the scope of the present invention. For example, after preparing uncrosslinked PVB by a solvent process, an acid catalyst and a crosslinking agent (e.g., tetraethyl ortho silane) are added to the uncrosslinked PVB in a solution in a synthesis vessel. The PVB resin component is crosslinked by adding in an appropriate concentration. The crosslinked PVB phase in the formulation of the sheet of FIG. 1 is made in this way.
용매공정에 있어서, 아세틸화는 PVB를 용해하고 아세틸화의 종료시에 균질한 용액을 생성하기에 충분한 용매의 존재하에 수행된다. 물로써 고체입자들을 침전시킴으로써 용액으로부터 PVB를 분리한 후 세척, 건조한다. 사용되는 용매는 에탄올과 같은 저급지방족 알콜류이다.In the solvent process, acetylation is carried out in the presence of sufficient solvent to dissolve PVB and produce a homogeneous solution at the end of acetylation. The PVB is separated from the solution by precipitating solid particles with water, followed by washing and drying. Solvents used are lower aliphatic alcohols such as ethanol.
수성공정(aqueous process)에 있어서, 아세틸화는 약 20℃의 온도에서 산촉매의 존재하에 PVOH의 수용액에 부티르알데히드를 첨가한 후, 미세하게 분할된 형태로 중간체 PVB를 침전시키기 위해 혼합물을 교반하고, 반응혼합물이 바람직한 종료점까지 진행될 때까지 가열하면서 교반을 계속함으로써 수행된다.In the aqueous process, acetylation is carried out by adding butyraldehyde to an aqueous solution of PVOH in the presence of an acid catalyst at a temperature of about 20 ° C., followed by stirring the mixture to precipitate the intermediate PVB in finely divided form. And stirring is continued while heating until the reaction mixture proceeds to the desired end point.
시이트의 성형에 있어서, PVB 혼합물은 PVB 100부당 약 20∼80부, 전형적으로는 통상의 적층안전유리 용도로서 25∼45부의 가소제로써 가소화된다. 후자의 농도는 일반적으로 중량으로 17∼25%의 비닐알콜을 함유하는 폴리비닐 부티랄에 대해 사용된다. 대개는, 통상적으로 적용되는 PVB 가소제는 다염기산 또는 다가알콜의 에스테르이다. 특히 적합한 가소제는 트리에틸렌 글리콜 디-(2-에틸부티레이트), 디헥실아디페이트, 디옥틸아디페이트, 헵틸아디페이트 및 노닐아디페이트의 혼합물, 디부틸세바세이트, 오일-변형된 세바시드알키드와 같은 폴리머가소제 및 U.S. 3,841,890호에 개시된 것과 같은 포스페이트와 아디페이트의 혼합물과 U.S. 4,144,217호에 개시된 것과 같은 아디페이트와 알킬벤질프탈레이트의 혼합물 등이다. 또한, U.S. 5,013,780호에 개시된 혼합물도 사용가능하다. 다른 적당한 가소제들은 공지되어 있으며, 이들은 당 분야의 기술자들에게는 자명할 것이다. 분산상에 의하여 흡수된 가소제 양은 교차결합수준 및 시간, 혼합의 강도 및 온도에 따라 달라질 수 있다.In forming the sheets, the PVB mixture is plasticized with about 20 to 80 parts per 100 parts of PVB, typically 25 to 45 parts plasticizer for typical laminated safety glass applications. The latter concentration is generally used for polyvinyl butyral containing 17-25% vinyl alcohol by weight. Usually, PVB plasticizers commonly applied are esters of polybasic acids or polyalcohols. Particularly suitable plasticizers are triethylene glycol di- (2-ethylbutyrate), dihexyl adipate, dioctyl adipate, a mixture of heptyl adipate and nonyl adipate, dibutyl sebacate, oil-modified sebaside alkyds Polymer Plasticizers and US Mixtures of phosphates and adipates, such as those disclosed in U.S. Pat. Mixtures of adipates and alkylbenzylphthalates as disclosed in US Pat. No. 4,144,217 and the like. In addition, U.S. Mixtures disclosed in 5,013,780 may also be used. Other suitable plasticizers are known and will be apparent to those skilled in the art. The amount of plasticizer absorbed by the dispersed phase can vary depending on the level and time of crosslinking, the strength and temperature of the mixing.
시이트는 당 분야의 기술자들에게 공지된 시스템에 의해서 제조되는데, 예를 들면 통상의 시이팅 다이, 바람직하게는 본 발명에 의하여 제공되는 거칠기를 정교하게 조절하기 위한 표면-냉각된 다이 립(surface-cooled die lip)을 갖는 시이팅 다이를 통한 압출에 의해 제조된다.The sheet is produced by a system known to those skilled in the art, for example a conventional seating die, preferably a surface-cooled die lip for finely controlling the roughness provided by the present invention. by extrusion through a seating die with a cooled die lip).
이와 관련하여, 거칠기에 영향을 주는 상술한 수지 파라미터들이 일단 최적화되면 상기한 립 냉각(lip cooling)은 필요하지 않을 수 있다. 더욱 상세하게는(약 175∼215℃의 온도에서) 용융된 폴리머액과 같은 프리믹스된 불균질성 혼합물은 성형되는 시이트의 길이와 폭에 실질적으로 일치되는, 수평으로는 길고 수직으로는 좁은 다이개구부를 통하여 압출된다. 또는, 두가지 PVB 성분의 배치(batch) 프리믹싱대신에 매트릭스상과 분산상은 각각 별도로 혼합압출기에 투입되어 상술한 바대로 시이트로 가공될 수도 있다. 또한 시이트를 성형하기 위해 다이롤을 적용하는 압출시스템도 사용가능한 데, 예를 들면 U.S. 4,112,166호의 제5도와 제6도에 도시되고 명세서에 설명된 바와 같은 다이의 출구에 거의 근접하게 위차한, 또는 그러한 다이의 표면을 형성하는 다이롤의 특별히 제조된 표면상으로 폴리머가 캐스팅된다.In this regard, the lip cooling described above may not be necessary once the above-described resin parameters affecting roughness are optimized. More specifically (at a temperature of about 175-215 ° C.), premixed heterogeneous mixtures, such as molten polymer liquids, are formed through horizontally long and vertically narrow die openings that substantially match the length and width of the sheet being formed. Extruded. Alternatively, instead of batch premixing of the two PVB components, the matrix phase and the dispersed phase may be separately introduced into a mixed extruder and processed into sheets as described above. Extrusion systems are also available which apply die rolls to form the sheet, for example U.S. Pat. The polymer is cast onto a specially prepared surface of the die roll, which is located in close proximity to the outlet of the die as shown in FIGS. 5 and 6 of 4,112,166, or as described in the specification, or which forms the surface of such a die.
본 발명에 따른 시이트는 가소제 이외에 염료, 자외선 안정화제, 점착조절용 염, 항산화제와 같은 다른 첨가제를 포함할 수 있으며, 필요한 경우에는 적층효율을 향상시키기 위하여 첨가제로 처리될 수 있다. 본 발명의 시이트는, 선택적으로, U.S. 4,316,868호에 개시된 시스템을 이용하여 시이트내에 도입될 수 있는 눈부심방지(anti-glare)용 PVB 경사밴드(gradient band)를 시이트의 가장자리에 인접한 한쪽 사이드를 따라 포함할 수 있다.The sheet according to the present invention may include other additives such as dyes, UV stabilizers, adhesion control salts, and antioxidants in addition to the plasticizer, and may be treated with additives to improve the lamination efficiency if necessary. The sheet of the present invention is optionally, U.S. Anti-glare PVB gradient bands may be included along one side adjacent the edge of the sheet, which may be introduced into the sheet using the system disclosed in 4,316,868.
하기의 실시예들에서의 거칠기 특성은 실제 거칠기를 측정하기 위해 추적바늘(tracing stylus)을 이용하는, 오하이오주 신시내티시 소재의 마아르사(Mahr Corporation)제 모델 S8P 퍼토미터(Perthometer)를 이용하여 측정하였다.Roughness characteristics in the following examples were measured using a Model S8P Perthometer from Mahr Corporation, Cincinnati, Ohio, using a tracing stylus to measure actual roughness. It was.
여기서, DIN 4768(1990년 5월)에 따라 규정된 RZ(미크론 단위, μ)는 밸리에서 피크까지의 평균높이를 의미하며, 이는 함께 정렬된 5개의 각각의 측정길이 1e중의 각각의 밸리에서 피크까지의 높이는 평균치이다. 1e는 요구치로 고정될 수 있으며, 여기서는 2.5㎜이다. 빈도수는 DIN 4762에 따른 이 시스템에서 참고길이 1m의 범위내에서의 프로파일 요철들(profile irregularities)(Sm)(μ)사이의 평균거리로 특징지워지는 데, 상기 1m은 요구치로 고정될 수 있으며, 여기서는 12.5㎜이다. Sm을 측정함에 있어서, Ra로 지칭되는 파라미터가 사용되는데, 이는 평가길이 1m내에서의 평균라인(line)으로 부터의 거칠기 프로파일의 모든 이탈의 평균치이다.Where R Z (micron units, μ), defined according to DIN 4768 (May 1990), means the average height from valley to peak, in each valley of five respective measuring lengths 1e aligned together The height to the peak is average. 1e can be fixed to the required value, here 2.5 mm. The frequency is characterized by the average distance between profile irregularities (Sm) (μ) in the range of 1m of reference length in this system according to DIN 4762, which 1m can be fixed as required Here it is 12.5 mm. In measuring Sm, a parameter called R a is used, which is the average of all deviations of the roughness profile from the average line within 1 m of the evaluation length.
용융전단 점도(ment shear viscosity)(20sec-1에서)는 모세관 압출 레오미터인 인스트론 모텔 #4208(모세관 길이 = 1.246인치(3.16㎝), 직경 = 0.025인치(0.064㎝), 입구각 = 90℃)을 이용하여 측정하였다.The ment shear viscosity (at 20 sec −1 ) is the Instron Motel # 4208 (capillary length = 1.246 inches (3.16 cm), diameter = 0.025 inches (0.064 cm), inlet angle = 90 ° C., a capillary extrusion rheometer. ) Was measured.
본 발명은 하기 실시예에서 더 상세하게 설명되나, 하기 실시예는 단지 예시적인 것이며, 본 발명을 한정하거나 제한하고자 하는 것은 아니다. 특별히 지적하지 않는 한 모든 양은 중량으로 표시된다.The invention is described in more detail in the following examples, which are illustrative only and not intended to limit or limit the invention. Unless otherwise noted, all amounts are in weight.
[실시예 1∼4]EXAMPLES 1-4
[교차결합된 PVB 수지의 제조][Preparation of Crosslinked PVB Resin]
잔류 폴리비닐 아세테이트 함량이 2% 이하인 폴리비닐 알콜(PVOH) 수지를 90∼95℃의 물중에 교반하여 용해시켜 8% 용액으로 만든다. 이 PVOH 용액 5524㎏을 교반반응기에 투입하고, 그 온도를 18℃로 조정한다.A polyvinyl alcohol (PVOH) resin having a residual polyvinyl acetate content of 2% or less is dissolved in water at 90-95 ° C. to make an 8% solution. 5524 kg of this PVOH solution is put into a stirring reactor, and the temperature is adjusted to 18 degreeC.
이 용액에 267㎏의 부티르알데히드와 다양한 양(표 1 참조)의 50% 글루타르알데히드 수용액을 첨가하여 온도를 약 12℃로 낮춘다.To this solution is added 267 kg of butyraldehyde and various amounts of 50% glutaraldehyde aqueous solution (see Table 1) to lower the temperature to about 12 ° C.
그런 다음 16㎏의 35% 질산수용액을 투입하고, 혼합물을 12℃∼16℃의 온도에서 30분간 방치한다. 첫번째 질산투입후 1시간 경과후에 46.5㎏의 질산을 다시 투입한다. 30분후에 혼합물을 87℃로 45분동안 가열한 후, 이 온도에서 3시간 동안 유지한다. 반응기의 내용물을 pH 4.0의 75℃ 물로 세척한다.Then, 16 kg of 35% nitric acid solution was added thereto, and the mixture was left at a temperature of 12 ° C. to 16 ° C. for 30 minutes. One hour after the first nitric acid injection, 46.5 kg of nitric acid is added again. After 30 minutes the mixture is heated to 87 ° C. for 45 minutes and then held at this temperature for 3 hours. The contents of the reactor are washed with 75 ° C. water at pH 4.0.
그런 다음 수산화칼륨 수용액을 첨가하여 pH 9.5∼10.5로 만들고, 이 pH에서 내용물을 75℃로 2시간 동안 유지한다. 75℃의 물을 추가로 첨가하여 pH 7.5로 낮춘다. PVB 슬러리를 원심분리하여 수분함량 2% 이하가 되도록 건조한다. 수지 100부당 32부의 디핵실아디페이트로 가소화된 PVB수지의 용융전단점도를 204℃에서 측정하고, 그 결과를 표 1에 나타내었다.An aqueous potassium hydroxide solution is then added to bring the pH to 9.5-10.5, and the contents are held at 75 ° C. for 2 hours. Additional water at 75 ° C. is added to lower the pH to 7.5. The PVB slurry is centrifuged and dried to a moisture content of 2% or less. The melt shear viscosity of the PVB resin plasticized with 32 parts of dinuclear siladiate per 100 parts of resin was measured at 204 ° C., and the results are shown in Table 1.
용융전단 점도의 증가는 글루타르알데히드를 이용한 교차결합에 의해 수지의 강도가 증가했다는 것을 보여준다.The increase in melt shear viscosity shows that the strength of the resin was increased by crosslinking with glutaraldehyde.
실시예 2,3 및 4의 수지는 하기 실시예들에서 분산상으로 사용된다.The resins of Examples 2, 3 and 4 are used as the dispersed phase in the following examples.
[실시예 5]Example 5
[거친 표면을 갖는 PVB 시이트의 제조][Production of PVB Sheet with Rough Surface]
강력 혼합기를 이용하여, 32부의 디헥실 아디페이트를 실시예 1의 PVB 수지 90부(글루타르알데히드 0.01pph)와 실시예 4의 PVB 수지 10부(글루타르알데히드 0.135pph)와 함께 혼합한다. 그런 다음 가소화된 불균질성 PVB 혼합물은 압출기내에서 용융되고, 용융물의 상태로, 한싸의 마주보는 다이립에 의하여 경계지워진 선단부에 장방형의 다이개구부를 가지며 표면의 온도가(온도조절액의 내부순환에 의해) 163℃로 유지되는 시이팅다이를 통해 압출된다. 용융물의 온도는 약 194℃이며, 다이개구부에서의 압력은 967psi(6667KPa)이다. 압출된 시이트의 두께는 약 0.76㎜이고, 다이로부터 약 10.5fpm(32mpm)으로 방출된다. 압출된 시이트의 각각의 면에는 거친 표면이 형성되어 있다. 측정결과, R는 63.3미크론이었다.Using a strong mixer, 32 parts of dihexyl adipate is mixed with 90 parts of PVB resin of Example 1 (0.01 pph glutaraldehyde) and 10 parts of PVB resin of Example 4 (glutaraldehyde 0.135 pph). The plasticized heterogeneous PVB mixture is then melted in the extruder, in the form of a melt, with a rectangular die opening at the tip bordered by a single opposite die lip, with a temperature of the surface (internal circulation of the thermostat). Extruded through a seating die maintained at 163 ° C.). The temperature of the melt is about 194 ° C. and the pressure at the die opening is 967 psi (6667 KPa). The extruded sheet is about 0.76 mm thick and is ejected from the die at about 10.5 fpm (32 mpm). On each side of the extruded sheet a rough surface is formed. As a result, R was 63.3 microns.
이는 실시예 1의 수지(U.S. 4,654,179호에 개시된, 분산상이 없는 수지)만을 이용하여 상술한 시이트 성형공정에 따라 성형한 시이트의 R가 20.1미크론인 것과 대비된다.This is in contrast to the R of 20.1 micron sheet formed according to the sheet forming process described above using only the resin of Example 1 (the resin having no dispersed phase disclosed in U.S. 4,654,179).
[실시예 6]Example 6
분산상의 농도는 일정하게(10%)하고, 분산상의 교차결합수준을 다양하게 변경하여, 실시예 5의 공정을 반복한다.The concentration of the dispersed phase is kept constant (10%), the crosslinking level of the dispersed phase is varied in various ways, and the process of Example 5 is repeated.
교차결합정도는 교차결합된 분산성을 합성하는데 사용된 글루타르알데히드의 농도에 대한 함수로서 측정된다. 결과는 다음과 같다.The degree of crosslinking is measured as a function of the concentration of glutaraldehyde used to synthesize the crosslinked dispersibility. The result is as follows.
상기의 결과는 (교차결합의 정도 또는 분산상의 용융전단점도로서 정의되는) 입자강도가 증가할수록 R도 증가한다는 것을 보여준다.The results show that R increases with increasing particle strength (defined as the degree of crosslinking or melt shear viscosity of the dispersed phase).
[실시예 7]Example 7
본 실시예는 빈도수(frequency)에 대한 분산성의 농도의 효과를 보여준다.This example shows the effect of concentration of dispersibility on frequency.
강력혼합기를 사용하여, 32부의 디헥실아디페이트와 PVB 수지(교차결합체가 함유되지 않음) 및 다양한 비율의 실시예 2의 수지(0.100pph 글루타르알데히드)를 혼합한다. 그런다음 가소화된 불균질성 PVB 혼합물을 압출기내에서 용융시켜 용융물의 상태로 다이개구부를 통하여 63℃로 유지되는 인접한 회전다이롤의 표면상으로 압출한다. 다이롤의 반대면에서 용융폴리머와 접촉된 다이블레이드의 온도는 약 149℃이다. 용융물 온도는 약 198℃이고, 다이의 압력은 약 380psi(2620KPa)이다. 약 0.8㎜ 두께의 시이트가 약 4.5mpm으로 다이롤로부터 방출된다. 압출된 시이트의 각각의 면에는 거친 표면이 형성되어 있다.Using a strong mixer, 32 parts of dihexyl adipate and PVB resin (with no crosslinker) and various proportions of Example 2 resin (0.100 pph glutaraldehyde) are mixed. The plasticized heterogeneous PVB mixture is then melted in an extruder and extruded onto the surface of adjacent rotating die rolls maintained at 63 ° C. through the die opening in the form of a melt. The temperature of the diblade in contact with the molten polymer on the opposite side of the die roll is about 149 ° C. The melt temperature is about 198 ° C. and the die pressure is about 380 psi (2620 KPa). A sheet about 0.8 mm thick is ejected from the die roll at about 4.5 mpm. On each side of the extruded sheet a rough surface is formed.
다이롤과 접촉된 시이트면의 반대면의 R와 Sm을 측정하였고, 그 결과는 다음과 같다.R and Sm on the opposite side of the sheet surface in contact with the die roll were measured, and the results are as follows.
상기 결과는 분산상이 증가함에 따라 Sm(피크사이의 거리)이 감소(따라서, 피크빈도수는 증가)하므로, 피크빈도수는 분산상의 농도에 대한 함수임을 보여준다.The results show that as the dispersed phase increases, the Sm (distance between the peaks) decreases (and therefore the peak frequency increases), so that the peak frequency is a function of the concentration of the dispersed phase.
비교적 일정한 Ra에서, Sm은 분산상 함량이 증가함에 따라 감소할 것이다. 그러나 Ra 값이 크게 증가할 경우에는, Ra와 Sm 사이의 관계 때문에 Sm은 원하는 정도로 감소되지는 않을 것이다.At a relatively constant Ra, Sm will decrease as the dispersed phase content increases. However, if the Ra value increases significantly, Sm will not decrease to the desired degree because of the relationship between Ra and Sm.
[실시예 8]Example 8
본 실시예는 R에 대한 분산상의 입자크기의 효과를 보여준다.This example shows the effect of the particle size of the dispersed phase on R.
교차결합된 분산상의 퍼포먼스를 시뮬레이트 하기 위하여, 교차결합된 PVB 입자 대신에 알려진 입자크기를 갖는 유리구슬들(또는 연마된 유리분말)을 유리/매트릭스 비율을 5/95로 하여 실시예 1의 PVB(매트릭스)와 함께 사용한 것을 제외하고는 실시예 5의 공정을 반복한다. 결과는 다음과 같다.In order to simulate the performance of the crosslinked dispersed phase, the glass beads (or polished glass powder) having a known particle size instead of the crosslinked PVB particles were prepared using the PVB of Example 1 with a glass / matrix ratio of 5/95. The process of Example 5 is repeated except for use with the matrix). The result is as follows.
상기 결과는 입자크기가 증가함에 따라 Rz도 증가함을 보여준다. 본 실시예에서는 유리구슬들이 사용되었지만, 거칠기형성 메카니즘은 교차결합된 PVB 분산상을 사용한 경우에도 동일할 것이다.The results show that Rz also increases with increasing particle size. Although glass beads were used in this example, the roughening mechanism would be the same even when using a crosslinked PVB dispersed phase.
유리 대신에 다양한 입자크기(이러한 크기는 교차결합정도에 따라 직접 비례적으로 달라지는 것으로 여겨진다)의 교차결합된 PVB를 대체한 경우에도 동일한 효과가 나타날 것으로 가정된다.The same effect is assumed to be substituted for the crosslinked PVBs of various particle sizes (which are considered to be directly proportional to the extent of crosslinking) instead of glass.
매트릭스와 분산상의 굴절율이 본질적으로 거의 동일한 경우에는 시이트내의 입자의 크기를 측정하는 것이 어렵기 때문에 교차결합된 PVB를 사용하지 않았다.If the indices of refraction of the matrix and the dispersed phase are essentially the same, cross-linked PVB was not used because it is difficult to measure the size of the particles in the sheet.
상술한 실시예들은 시이트제제를 구성하는 불균질성의 PVB 혼합물중의 두성분, 즉 각각 별도로 제조된 유동학적으로 서로 다른 분산상과 매트릭스상의 비율을 변경시킴으로써 수지합성후의 시이트 거칠기 파라미터들을 조정하기 위한 변형가능한 기술로서 본 발명의 주요한 예를 예시한 것이다.The above-described embodiments are deformable techniques for adjusting sheet roughness parameters after resin synthesis by changing the ratios of two components in the heterogeneous PVB mixture constituting the sheet formulation, ie, rheologically different dispersed and matrix phases, each prepared separately. The main examples of the present invention are illustrated as follows.
상술한 내용들은 단지 예시를 위한 것이지, 본 발명을 제한하는 의미는 아니다. 당 분야의 기술자라면 여러 가지 변형과 변경을 용이하게 생각해낼 수 있을 것이다. 그러므로, 상술한 내용들은 단지 예시적인 것이며, 본 발명의 범위는 후술하는 특허청구의 범위에 의하여 확실해진다.The above description is for illustrative purposes only and is not meant to limit the invention. Those skilled in the art will be able to easily conceive of various variations and modifications. Therefore, the foregoing descriptions are merely illustrative, and the scope of the present invention is ascertained by the claims that follow.
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/US1993/008859 WO1995007940A1 (en) | 1993-09-17 | 1993-09-17 | Rough-surfaced polyvinyl butyral sheet and method of forming same |
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| KR0180477B1 true KR0180477B1 (en) | 1999-05-15 |
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