CN102089254B - 夹层玻璃用中间膜 - Google Patents
夹层玻璃用中间膜 Download PDFInfo
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- CN102089254B CN102089254B CN200980126824.0A CN200980126824A CN102089254B CN 102089254 B CN102089254 B CN 102089254B CN 200980126824 A CN200980126824 A CN 200980126824A CN 102089254 B CN102089254 B CN 102089254B
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- 239000005340 laminated glass Substances 0.000 title claims abstract description 165
- 239000004014 plasticizer Substances 0.000 claims abstract description 65
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011354 acetal resin Substances 0.000 claims abstract description 33
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 32
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 239000011521 glass Substances 0.000 claims description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 238000000465 moulding Methods 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 37
- 238000000034 method Methods 0.000 description 19
- 230000007423 decrease Effects 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
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- 230000002745 absorbent Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
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- -1 vinyl acetal resin Chemical compound 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- 230000035939 shock Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- GIMOTOMCGGRGBI-UHFFFAOYSA-M C(CCC)(=O)[O-].C(C)[Mg+] Chemical compound C(CCC)(=O)[O-].C(C)[Mg+] GIMOTOMCGGRGBI-UHFFFAOYSA-M 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
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- 239000004611 light stabiliser Substances 0.000 description 1
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
Classifications
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
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- 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
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- 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
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- 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
- B32B17/10688—Adjustment of the adherence to the glass layers
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- 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
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- 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
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- 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
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- C08K5/0016—Plasticisers
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- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
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- 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
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明的目的在于提供耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。本发明的夹层玻璃用中间膜含有聚乙烯醇缩醛树脂和增塑剂,所述增塑剂以下述通式(1)表示,式(1)中,R1表示苯基,R2表示碳数2~4的亚烷基,n表示4~6。
Description
技术领域
本发明涉及耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。
背景技术
夹层玻璃由于即使受到外部冲击而破损,其玻璃碎片也很少飞散,因而是安全的。因此,夹层玻璃作为汽车、火车等车辆、飞机、建筑物等的窗玻璃等而广泛使用。例如,作为夹层玻璃,可举出使含有聚乙烯醇缩丁醛树脂和增塑剂的夹层玻璃用中间膜介于一对玻璃之间,使其一体化而成的夹层玻璃。
近年来,需要能够有效地遮蔽发动机的驱动音、风摩擦音等的夹层玻璃。作为隔音性优良的夹层玻璃,例如,在专利文献1中公开了,使用了层叠有2层以上经塑化的聚乙烯醇缩醛树脂膜的夹层玻璃用中间膜的夹层玻璃。
作为制造隔音性优良的夹层玻璃用中间膜的方法,可以考虑例如,使用羟基量少的聚乙烯醇缩丁醛树脂的方法、增加相对于聚乙烯醇缩丁醛树脂的增塑剂的含量的方法、使用分子量低的增塑剂的方法等。
然而,若应用使用羟基量少的聚乙烯醇缩丁醛树脂的方法,则存在夹层玻璃的耐湿性下降的问题。另外,由于含有羟基量少的聚乙烯醇缩丁醛树脂的夹层玻璃用中间膜不能得到充分的强度,因此还存在夹层玻璃的耐贯通性会下降的问题。
另外,若应用增加相对于聚乙烯醇缩丁醛树脂的增塑剂的含量的方法、使用分子量低的增塑剂的方法,则由于增塑剂在中间膜的表面渗出,而存在难以控制夹层玻璃用中间膜和玻璃的粘接力的问题。另外,若增塑剂的含量增加,则存在夹层玻璃的耐贯通性大幅下降的问题。
【专利文献】
【专利文献1】日本特开平3-124440号公报
发明内容
本发明的目的在于,提供耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。
本发明提供一种夹层玻璃用中间膜,其特征在于,含有聚乙烯醇缩醛树脂和增塑剂,所述增塑剂以下述通式(1)表示,
式(1)中,R1表示苯基,R2表示碳原子数2~4的亚烷基,n表示4~6。
以下对本发明进行详述。
本发明的夹层玻璃用中间膜含有聚乙烯醇缩醛树脂。
上述聚乙烯醇缩醛树脂的羟基的含有率没有特别限制,优选下限为18摩尔%,优选上限为38摩尔%。若上述羟基的含有率小于18摩尔%,则有时夹层玻璃用中间膜的耐湿性会下降。另外,若上述羟基的含有率小于18摩尔%,则有时夹层玻璃的耐贯通性会下降。若上述羟基的含有率大于38摩尔%,则夹层玻璃用中间膜会变得过硬,因此有时夹层玻璃的隔音性会下降。
上述羟基含有率的更优选的下限为20摩尔%,更优选的上限为36摩尔%。
此外,聚乙烯醇缩醛树脂的羟基的含有率是将羟基所键合的亚乙基量除以主链的总亚乙基量而求得的摩尔分率。羟基所键合的亚乙基量例如可以使用JIS K 6726的“聚乙烯醇试验方法”对成为原料的聚乙烯醇的羟基所键合的亚乙基量进行测定从而求得。
上述聚乙烯醇缩醛树脂的缩醛化度没有特别限制,但是优选下限为0.1摩尔%,优选上限为15摩尔%。上述聚乙烯醇缩醛树脂的缩醛化度小于0.1摩尔%时,有时增塑剂会在中间膜的表面渗出。上述聚乙烯醇缩醛树脂的缩醛化度大于15摩尔%时,有时夹层玻璃用中间膜的耐湿性会下降。上述聚乙烯醇缩醛树脂的缩醛化度的更优选的下限为0.3摩尔%,更优选的上限为14摩尔%。
此外,所谓缩醛化度(日文:アセチル化度),是指从主链的总亚乙基量减去缩醛基所键合的亚乙基量和羟基所键合的亚乙基量而求得的值,除以主链的总亚乙基量而求得的摩尔分率。
上述聚乙烯醇缩醛树脂没有特别限制,为了使其对玻璃的粘接力优异,优选聚乙烯醇缩丁醛树脂。
上述聚乙烯醇缩丁醛树脂的缩丁醛化度没有特别限制,但优选下限为63摩尔%,优选上限为73摩尔%。上述聚乙烯醇缩丁醛树脂的缩丁醛化度小于63摩尔%时,有时增塑剂在中间膜的表面渗出。上述聚乙烯醇缩丁醛树脂的缩丁醛化度大于73摩尔%时,则有时夹层玻璃的耐贯通性会下降。上述聚乙烯醇缩丁醛树脂的缩丁醛化度的更优选下限为65摩尔%,更优选上限为69摩尔%。
此外,所谓缩丁醛化度,是指缩丁醛基所结合的亚乙基量除以主链的总亚乙基量而求得的摩尔分率。缩丁醛基所结合的亚乙基量例如可以使用JIS K 6728的“聚乙烯醇缩丁醛试验方法”来测定。
上述聚乙烯醇缩丁醛树脂通常可以通过将聚乙烯醇缩丁醛化来制造。
上述聚乙烯醇通常可以通过将聚乙酸乙烯酯皂化来制造。
上述聚乙烯醇的聚合度没有特别限制,但优选下限为1000,优选上限为4000。上述聚乙烯醇的聚合度小于1000时,有时夹层玻璃的耐贯通性会下降。若上述聚乙烯醇的聚合度大于4000,则得到的聚乙烯醇缩醛树脂的刚性会变得过大,因此有时夹层玻璃用中间膜的成形会变得困难。上述聚乙烯醇的聚合度的更优选的下限为1300,更优选的上限为3700。
本发明的夹层玻璃用中间膜含有下述通式(1)所表示的增塑剂。下述通式(1)所表示的增塑剂具有羟基,因此即使含量少也可以得到隔音性优良的夹层玻璃用中间膜。可以认为,其理由是因为聚乙烯醇缩醛树脂的分子内氢键、聚乙烯醇缩醛树脂的分子间氢键较弱。
式(1)中,R1表示苯基,R2表示碳原子数2~4的亚烷基,n表示4~6。
上述通式(1)中的R1为苯基。上述通式(1)所表示的增塑剂具有苯基,且n为4~6,由此可以得到耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。
上述通式(1)中的n为4~6。上述n小于4时,夹层玻璃用中间膜的耐贯通性会下降。上述n超过6时,夹层玻璃用中间膜的耐湿性会下降,或者隔音性会下降。
此外,上述通式(1)中的n表示(OR2)基的平均加成摩尔数。平均加成摩尔数n的值可以利用气相色谱分析,算出与各种加成摩尔数对应的峰面积的比,由此来决定。
对于上述通式(1)所表示的增塑剂而言,只要(OR2)基的平均加成摩尔数为4~6即可,也可以包含加成摩尔数小于4的增塑剂、加成摩尔数大于6的增塑剂。
上述通式(1)中的R2为碳原子数2~4的亚烷基。亚烷基的碳原子数为5以上时,有时不能得到高隔音性。上述亚烷基优选为碳原子数2或3的亚烷基,更优选为碳原子数2的亚烷基。
就本发明的夹层玻璃用中间膜中的上述通式(1)所表示的增塑剂的含量而言,相对于聚乙烯醇缩醛树脂100重量份优选下限为15重量份,优选上限为75重量份。但是,若配合上述通式(1)所表示的增塑剂,则夹层玻璃用中间膜的玻璃化转变温度会降低,因此有时得到的夹层玻璃的耐贯通性会下降。所以,为了兼顾优良的隔音性和耐贯通性,考虑到与聚乙烯醇缩醛树脂的组合,优选将上述通式(1)所表示的增塑剂的配合量调整至适当的范围。
例如,上述聚乙烯醇缩醛树脂是羟基的含有率为23~38摩尔%的聚乙烯醇缩丁醛树脂A的情况下,上述通式(1)所表示的增塑剂的含量相对于聚乙烯醇缩丁醛树脂100重量份,优选下限为33重量份,优选上限为75重量份。上述增塑剂的含量小于33重量份时,有时夹层玻璃用中间膜的隔音性会下降。上述增塑剂的含量超过75重量份时,有时不能使夹层玻璃的耐贯通性充分。上述增塑剂的含量的优选的下限为38重量份,优选的上限为71重量份,更优选的下限为45重量份,更优选的上限为70重量份。
上述聚乙烯醇缩丁醛树脂A的羟基的含有率的优选的下限为28摩尔%,优选的上限为37摩尔%,更优选的下限为30摩尔%,更优选的上限为36摩尔%。
此外,上述聚乙烯醇缩丁醛树脂A优选为通过使平均聚合度为1300~4000的聚乙烯醇缩丁醛化而得的聚乙烯醇缩丁醛树脂。
例如,上述聚乙烯醇缩醛树脂是羟基的含有率的下限为18摩尔%、且上限小于23摩尔%的聚乙烯醇缩丁醛树脂B的情况下,或者上述聚乙烯醇缩醛树脂是平均聚合度的下限为1000、且上限小于1300、羟基的含有率为23~35摩尔%的树脂的情况下,上述通式(1)所表示的增塑剂的含量相对于聚乙烯醇缩醛树脂100重量份,优选下限为15重量份,优选上限为50重量份。上述增塑剂的含量小于15重量份时,有时夹层玻璃用中间膜的隔音性会下降。上述增塑剂的含量大于50重量份时,有时会使夹层玻璃的耐贯通性不充分。上述增塑剂的含量的优选的下限为25重量份,优选的上限为42重量份,更优选的下限为28重量份,更优选的上限为40重量份。
上述聚乙烯醇缩丁醛树脂B的羟基的含有率的优选下限为19摩尔%,优选的上限为22.5摩尔%,更优选的下限为20摩尔%,更优选的上限为22摩尔%。
此外,上述聚乙烯醇缩丁醛树脂B优选为通过使平均聚合度为1000~4000的聚乙烯醇缩丁醛化而得到的聚乙烯醇缩丁醛树脂。
本发明的夹层玻璃用中间膜中,只要在不损害本发明的课题的解决的范围内,也可以含有上述通式(1)所表示的增塑剂以外的其他增塑剂。
上述其他增塑剂没有特别的限制,例如,可举出三乙二醇二-2-乙基己酸酯,四乙二醇二-2-乙基己酸酯等二酯化合物。
对于以往的夹层玻璃用中间膜而言,为了降低夹层玻璃用中间膜与玻璃的粘接力而含有碱金属盐、碱土金属盐等金属盐。夹层玻璃用中间膜中不含金属盐时,夹层玻璃用中间膜和玻璃的粘接力变得过强,有时会使夹层玻璃的耐贯通性不充分。但是,本发明的夹层玻璃用中间膜即使不含上述金属盐,也可以得到具有优良的耐贯通性的夹层玻璃。
此外,本发明的夹层玻璃用中间膜也可以含有上述金属盐,例如,可以含有2-乙基丁酸镁、乙酸镁等。上述金属盐的含量没有特别限制,但是相对于上述聚乙烯醇缩醛树脂100重量份,优选的上限为0.1重量份。
本发明的夹层玻璃用中间膜可以含有紫外线吸收剂、抗氧化剂、光稳定剂、防静电剂、颜料、染料、红外线吸收剂等添加剂。
本发明的夹层玻璃用中间膜的厚度没有特别限制,但优选的下限为0.3mm,优选的上限为1.5mm。本发明的夹层玻璃用中间膜的厚度小于0.3mm时,有时夹层玻璃用中间膜的耐贯通性会下降。本发明的夹层玻璃用中间膜的厚度大于1.5mm时,有时会超出适于夹层玻璃的厚度。本发明的夹层玻璃用中间膜的厚度的更优选的下限为0.7mm,更优选的上限为1.35mm。
对本发明的夹层玻璃用中间膜的含水率而言,优选的下限为0.4重量%,优选的上限为2.5重量%。含水率小于0.4重量%时,保存夹层玻璃用中间膜时的吸水速度过大,有时难以控制玻璃与夹层玻璃用中间膜之间的粘接力。另外,含水率小于0.4重量%时,有时得到的夹层玻璃的隔音性会下降。含水率超过2.5重量%时,当将夹层玻璃保持在50℃以上的温度时,有时在夹层玻璃用中间膜的内部或在夹层玻璃用中间膜与玻璃的界面中会产生气泡。含水率的更优选的下限为0.5重量%,更优选的上限为2.45重量%,进一步优选的下限为0.6重量%,进一步优选的上限为2.0重量%。
需要说明的是,本说明书中关于含水率,可以利用下述的方法来测定。
从夹层玻璃用中间膜中提取约10g的试验片。在内部有硅胶的带盖的干燥器内,将所得的试验片静置,将干燥器的盖密封好。然后,将该干燥器在调整至23℃的恒温室中静置。通过该方法,对夹层玻璃用中间膜进行干燥处理。直到夹层玻璃用中间膜的重量不发生变化为止持续进行干燥处理,然后,测定夹层玻璃用中间膜的重量。接着,利用下述式确定夹层玻璃用中间膜的含水率。
夹层玻璃用中间膜的含水率(重量%)={(干燥处理前的中间膜的重量-干燥处理后的中间膜的重量)×100}/(干燥处理前的中间膜的重量)
本发明的夹层玻璃用中间膜的含水率可以通过将所得的夹层玻璃用中间膜在一定的温度、一定的湿度条件下静置一定时间来调整。例如,可以通过在23℃、相对湿度25%的恒温恒湿的条件下,静置数小时~数日来调整含水率。通过对上述温度或上述湿度进行适宜设定,可以调整夹层玻璃用中间膜的含水率。
本发明的夹层玻璃用中间膜可以是单层的夹层玻璃用中间膜,也可以是包含2层以上的树脂膜层叠的多层结构的夹层玻璃用中间膜。本发明的夹层玻璃用中间膜为多层结构时,只要至少一层满足本发明的要件即可。
本发明的夹层玻璃用中间膜是多层结构时,可以将上述含有通式(1)所表示的增塑剂的树脂膜层叠。例如,可举出依次层叠有最外层、中间层、最外层的3层结构的夹层玻璃用中间膜。这样的多层结构的夹层玻璃用中间膜不但耐贯通性、耐湿性和隔音性优良,而且操作性也优良。
对于上述最外层而言,相对于上述聚乙烯醇缩醛树脂100重量份,优选含有上述通式(1)所表示的增塑剂30~50重量份。
上述最外层中所使用的聚乙烯醇缩醛树脂可举出例如通过将平均聚合度为1300~4000的聚乙烯醇缩丁醛化而得到的、羟基的含有率为23~38摩尔%的聚乙烯醇缩丁醛树脂。
上述中间层中,相对于上述聚乙烯醇缩醛树脂100重量份,优选含有上述通式(1)所表示的增塑剂45~80重量份。
作为上述中间层中所使用的聚乙烯醇缩醛树脂,可举出,例如通过将平均聚合度为1000~4000的聚乙烯醇缩丁醛化而得到的、羟基的含有率为20~38摩尔%的聚乙烯醇缩丁醛树脂,或者通过将平均聚合度为1000~1300的聚乙烯醇缩丁醛化而得到的、羟基的含有率为23~35摩尔%的聚乙烯醇缩丁醛树脂等。
对于上述3层结构的夹层玻璃用中间膜,优选上述中间层的上述通式(1)所表示的增塑剂的含量比上述最外层的上述通式(1)所表示的增塑剂的含量更多。
制造本发明的夹层玻璃用中间膜的方法没有特别的限制,例如可举出将增塑剂、任意成分的添加剂和聚乙烯醇缩醛树脂混炼后,成形夹层玻璃用中间膜的方法等。上述混炼的方法没有特别的限制,可举出例如使用挤出机、塑性变形记录仪(Plastograph)、捏合机、班伯里混炼机、砑光辊等的方法等。
使用本发明的夹层玻璃用中间膜可以制造夹层玻璃。
上述夹层玻璃中所使用的玻璃板没有特别的限制,可举出通常使用的透明板玻璃。上述透明板玻璃没有特别的限制,例如可举出浮板玻璃、磨光玻璃、型板玻璃、夹丝网玻璃、夹线板玻璃、着色板玻璃、吸热玻璃、热反射玻璃、绿玻璃等无机玻璃。另外,也可以使用聚碳酸酯、聚丙烯酸酯等有机塑料板。
上述玻璃板也可以使用2种以上的玻璃板。例如,可举出在无机玻璃和有机塑料板之间夹持有本发明的夹层玻璃用中间膜的夹层玻璃等。
上述夹层玻璃的制造方法没有特别的限制,可以使用以往公知的制造方法。
上述夹层玻璃作为汽车用玻璃使用时,可以作为前窗玻璃、侧玻璃,后窗玻璃、车顶玻璃使用。
根据本发明,可以提供耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。
具体实施方式
以下举出实施例进一步详细说明本发明实施方式,但是本发明并不仅限于这些实施例。
(实施例1)
(1)夹层玻璃用中间膜的制作
作为增塑剂,在80℃下、将上述通式(1)中的R1为苯基、R2为亚乙基、平均加成摩尔数n为4的增塑剂45重量份与作为抗氧化剂的2,6-二-叔丁基-p-甲酚(BHT)0.2重量份、紫外线吸收剂(汽巴精化公司制“TINUVIN 326”)0.2重量份的混合物搅拌30分钟,制得增塑剂溶液。
接着,将聚乙烯醇缩丁醛树脂(平均聚合度1700,缩丁醛化度68.5摩尔%,缩醛化度0.9摩尔%,羟基含有率30.6摩尔%)100重量份和上述增塑剂溶液45.4重量份充分地混合,使用挤出机以膜厚达到1.25mm的方式进行挤出成形制作夹层玻璃用中间膜。
将所得的夹层玻璃用中间膜在23℃、相对湿度25%的恒温恒湿的条件下静置。
(2)夹层玻璃的制作
利用2片透明的浮法玻璃(长30cm×宽30cm×厚度2.3mm)夹持所得的夹层玻璃用中间膜,制成层叠体。使用230℃的加热辊使所得的层叠体预压接。使用高压反应釜将预压接了的夹层玻璃在135℃、压力1.2MPa的条件下进行20分钟压接,制作夹层玻璃。
(实施例2~48)
将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表1所示的数值,将含水率按照表1所示进行调整,除此以外,与实施例1同样地试验,制作夹层玻璃用中间膜以及夹层玻璃。
(实施例49)
将增塑剂的含量变更为表1所示的数值,将含水率按照表1所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜以及夹层玻璃。
(实施例50)
作为聚乙烯醇缩丁醛树脂,使用平均聚合度1700、缩丁醛化度63摩尔%、缩醛化度1摩尔%、羟基含有率36摩尔%的聚乙烯醇缩丁醛树脂,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表1所示的数值,将含水率按照表1所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(实施例51~77)
作为聚乙烯醇缩丁醛树脂,使用平均聚合度2450、缩丁醛化度66.5摩尔%、缩醛化度13.4摩尔%、羟基含有率20.1摩尔%的聚乙烯醇缩丁醛树脂,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表2所示的数值,将含水率按照表2所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例1~14)
将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表3所示的数值,将含水率按照表3所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例15~26)
将上述通式(1)中的R1变更为苄基,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表3所示的数值,将含水率按照表3所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例27~38)
将上述通式(1)中的R1变更为正己基,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表4所示的数值,将含水率按照表4所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例39~46)
将上述通式(1)中的R1变更为甲基,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表4所示的数值,将含水率按照表4所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例47~52)
上述通式(1)中的R1变更为正丁基,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表4所示的数值,将含水率按照表4所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
(比较例53~62)
将上述通式(1)中的R1变更为2-乙基己基,将上述通式(1)中的平均加成摩尔数n的值和增塑剂的含量变更为表4所示的数值,将含水率按照表4所示进行调整,除此以外,与实施例1同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
<评价>
对于实施例1~77和比较例1~62中得到的夹层玻璃用中间膜和夹层玻璃进行以下的评价。将结果示于表1~4。
(1)夹层玻璃用中间膜的含水率
从夹层玻璃用中间膜中提取约10g的试验片。在内部有硅胶的带盖的干燥器内,将所得的试验片静置,将干燥器的盖密封好。然后,将该干燥器在调整至23℃的恒温室中静置。通过该方法,对夹层玻璃用中间膜进行干燥处理。直到夹层玻璃用中间膜的重量不发生变化为止持续进行干燥处理,然后,测定夹层玻璃用中间膜的重量。接着,利用下述式确定夹层玻璃用中间膜的含水率。
夹层玻璃用中间膜的含水率(重量%)={(干燥处理前的中间膜的重量-干燥处理后的中间膜的重量)×100}/(干燥处理前的中间膜的重量)
(2)夹层玻璃的隔音性评价
将所得的夹层玻璃切割为长4cm×宽4cm的尺寸,制作隔音性评价用夹层玻璃。使用阻尼试验用的振动发生机(振研公司制“加振机G21-005D”)使隔音性评价用夹层玻璃振动。利用机械阻抗放大器(Rion公司制“XG-81”)对隔音性评价用夹层玻璃的振动特性进行放大,利用FFT谱分析仪(横河Hewlett Packard公司制“FFT analyzer HP3582A”)对振动谱进行解析,算出损失系数。
由所得的损失系数与玻璃的共振频率之比,制造显示25℃下的音频率(Hz)与音响透射损失(dB)之间关系的图,求得音频率1000~4000Hz的范围中的最小的音响透射损失(TL值)。
(3)夹层玻璃的耐贯通性评价
将所得的夹层玻璃(长300mm×宽300mm)调整至其表面温度为23℃。接着,依照JISR 3212,对于夹层玻璃,使质量2260g、直径82mm的刚性球从4m的高度朝着夹层玻璃的中心部分落下。对6片的夹层玻璃进行同样的评价,对于所有6片夹层玻璃,都将刚性球撞击后5秒以内,刚性球未贯通的情况设定为合格。刚性球撞击后5秒以内刚性球未贯通的夹层玻璃为3片以下的情况设定为不合格。刚性球撞击后5秒以内刚性球未贯通的夹层玻璃为4片的情况下,重新对6片的夹层玻璃进行再次的耐贯通性评价。在刚性球撞击后5秒以内,刚性球未贯通的夹层玻璃为5片的情况下,重新对1片夹层玻璃进行追加试验,将在刚性球撞击后5秒以内,刚性球未贯通的情况设为合格。利用同样的方法,对于6片的夹层玻璃,,使质量2260g、直径82mm的刚性球从5m的高度朝着夹层玻璃的中心部分落下,进行耐贯通性评价。
(4)夹层玻璃的耐湿性评价
按照JIS R 3212,将所得的夹层玻璃在50℃、相对湿度95%的恒温恒湿槽中保管2周。测定保管后的夹层玻璃的周边部的白化距离。将从白化最严重的周边部开始的白化距离为5mm以下的夹层玻璃设为○,将白化距离大于5mm且为10mm以下的夹层玻璃设为△,将白化距离大于10mm的夹层玻璃设为×。
【表1】
【表2】
【表3】
【表4】
(实施例78)
(1)树脂组合物A的制作
在作为增塑剂的上述通式(1)中的R1为苯基、R2为亚乙基、平均加成摩尔数n为4的增塑剂44重量份中,添加作为抗氧化剂的2,6-二-叔丁基-p-甲酚0.2重量份和具有苯并三唑结构的紫外线吸收剂(汽巴精化公司制“TINUVIN 326”)0.2重量份,使用搅拌机在80℃进行30分钟搅拌,得到增塑剂溶液。
将所得的增塑剂溶液与聚乙烯醇缩丁醛树脂(PVB:平均聚合度1700、缩丁醛化度68.5mol%、羟基量30.6mol%,乙酰基量0.9mol%)100重量份充分地混合,制作树脂组合物A。
(2)树脂组合物B的制作
在作为增塑剂的上述通式(1)中的R1为苯基,R2为亚乙基、平均加成摩尔数n为4的增塑剂75重量份中,添加作为抗氧化剂的2,6-二-叔丁基-p-甲酚0.2重量份和具有苯并三唑结构的紫外线吸收剂(汽巴精化公司制「TINUVIN 326」)0.2重量份,使用搅拌机在80℃进行30分钟搅拌,得到增塑剂溶液。
将所得的增塑剂溶液与聚乙烯醇缩丁醛树脂(PVB:平均聚合度1700、缩丁醛化度68.5mol%、羟基量30.6mol%、乙酰基量0.9mol%)100重量份充分地混合,制作树脂组合物B。
(3)夹层玻璃用中间膜的制作
将上述树脂组合物A和上述树脂组合物B共挤出,制造具有依次层叠有树脂层A(厚度150μm)、树脂层B(厚度950μm)、树脂层A(厚度150μm)的3层结构的夹层玻璃用中间膜。
(4)夹层玻璃的制作
利用2片透明的浮法玻璃(长30cm×宽30cm×厚度2.3mm)夹持所得的夹层玻璃用中间膜而制成层叠体。将所得的层叠体使用230℃的加热辊进行预压接。使用高压反应釜在135℃、压力1.2MPa的条件下对预压接的夹层玻璃进行20分钟压接,制作夹层玻璃。
(实施例79、80)
将上述通式(1)中的平均加成摩尔数n的值变更为表5所示的数值,除此以外,与实施例76同样地实施,制作夹层玻璃用中间膜和夹层玻璃。
<评价>
对于实施例78~80中得到的夹层玻璃用中间膜和夹层玻璃与实施例1同样地进行评价。结果示于表5。
【表5】
产业上的利用可能性
根据本发明,可以提供一种耐贯通性、耐湿性和隔音性优良的夹层玻璃用中间膜。
Claims (9)
1.一种夹层玻璃用中间膜,其特征在于,
所述夹层玻璃用中间膜含有聚乙烯醇缩醛树脂和增塑剂,所述增塑剂由下述通式(1)表示,
式(1)中,R1表示苯基,R2表示碳数2~4的亚烷基,n表示4~6,
相对于聚乙烯醇缩醛树脂100重量份,由通式(1)表示的增塑剂的含量为15~75重量份,
所述夹层玻璃用中间膜的含水率为2.5重量%以下。
2.根据权利要求1所述的夹层玻璃用中间膜,其特征在于,
聚乙烯醇缩醛树脂的羟基的含有率为18~38摩尔%。
3.根据权利要求2所述的夹层玻璃用中间膜,其特征在于,
聚乙烯醇缩醛树脂的缩醛化度为0.1~15摩尔%。
4.根据权利要求1所述的夹层玻璃用中间膜,其特征在于,
含水率为0.4重量%以上。
5.根据权利要求1所述的夹层玻璃用中间膜,其特征在于,
相对于聚乙烯醇缩醛树脂100重量份,金属盐的含量为0.1重量份以下。
6.根据权利要求1所述的夹层玻璃用中间膜,其特征在于,包含2层以上的树脂膜层叠而成的多层结构。
7.根据权利要求6所述的夹层玻璃用中间膜,其特征在于,由依次层叠有最外层、中间层、最外层的3层结构构成,所述最外层相对于聚乙烯醇缩醛树脂100重量份,含有通式(1)所表示的增塑剂30~50重量份,并且所述中间层相对于聚乙烯醇缩醛树脂100重量份,含有上述通式(1)所表示的增塑剂45~80重量份。
8.根据权利要求7所述的夹层玻璃用中间膜,其特征在于,中间层的通式(1)所表示的增塑剂的含量比最外层的通式(1)所表示的增塑剂的含量多。
9.一种夹层玻璃,其特征在于,2枚玻璃之间夹持有权利要求1所述的夹层玻璃用中间膜。
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CN102089254A (zh) | 2011-06-08 |
JP4686636B2 (ja) | 2011-05-25 |
US20110151269A1 (en) | 2011-06-23 |
EP2301900A4 (en) | 2012-08-22 |
EP2301900A1 (en) | 2011-03-30 |
WO2010008053A1 (ja) | 2010-01-21 |
EP2301900B1 (en) | 2013-08-21 |
JPWO2010008053A1 (ja) | 2012-01-05 |
US8304082B2 (en) | 2012-11-06 |
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