WO2012133668A1 - ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 - Google Patents
ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 Download PDFInfo
- Publication number
- WO2012133668A1 WO2012133668A1 PCT/JP2012/058406 JP2012058406W WO2012133668A1 WO 2012133668 A1 WO2012133668 A1 WO 2012133668A1 JP 2012058406 W JP2012058406 W JP 2012058406W WO 2012133668 A1 WO2012133668 A1 WO 2012133668A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- polyvinyl acetal
- acetal resin
- shrinkage rate
- heat shrinkage
- Prior art date
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 114
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 90
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title abstract description 4
- 239000005340 laminated glass Substances 0.000 claims abstract description 39
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 107
- 239000011354 acetal resin Substances 0.000 claims description 88
- -1 organic acid salt Chemical class 0.000 claims description 38
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- 239000000155 melt Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XUHUMYVYHLHMCD-UHFFFAOYSA-N tris(2-cyclohexylphenyl) phosphite Chemical compound C1CCCCC1C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C1CCCCC1)OC1=CC=CC=C1C1CCCCC1 XUHUMYVYHLHMCD-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
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- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
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- 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
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- 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
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
-
- 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
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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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
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
- Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
Definitions
- the present invention relates to a polyvinyl acetal-based resin film that shrinks within an appropriate range during heat lamination, a method for producing the same, a multilayer structure using the film in at least one layer, a solar cell encapsulant using the film, and
- the present invention relates to a solar cell module, an interlayer film for laminated glass using the film, and laminated glass.
- laminated glass for automobiles and windshields for automobiles are provided with a film such as polyvinyl acetal resin between two inorganic glass or organic glass, and heated and pressed to laminate the glass.
- a film such as polyvinyl acetal resin between two inorganic glass or organic glass, and heated and pressed to laminate the glass.
- a multilayer structure having a function of preventing glass fragments from scattering or preventing a person or an object from penetrating the glass and jumping outside is used.
- a solar cell (crystalline silicon, thin film silicon, metal compound thin film, organic thin film, and transparent or opaque electrode layer) is disposed between two glass or weather-resistant plastic films, It has been widely practiced that after a film such as a polyvinyl acetal resin is disposed between the cell and the glass on both sides, the film is melted and flowed by heating and pressure-bonding the whole to fill the gap. However, when manufacturing such a multilayer structure, bubbles may occur at the end of the polyvinyl acetal resin layer, or unfilled portions of the polyvinyl acetal resin may occur in the structure, resulting in a defective product. there were.
- Patent Documents 1 to 3 As a filler, embossing is provided on the surface to facilitate degassing, and the creep property is optimized to facilitate degassing. A method has been proposed.
- Patent Document 4 proposes a method in which the shape of the end portion of the glass is defined and easily degassed, and an unfilled portion is not generated.
- Patent Documents 5 to 7 describe thermal shrinkage rates of sheets and films containing polyvinyl acetal resin.
- Patent Document 5 uses an interlayer film for laminated glass in which the difference in shrinkage rate in each part is within ⁇ 1% as an attempt to impart degassing performance during lamination and impact resistance of laminated glass. It is described that the shrinkage rate when the intermediate film is heated at 54 ° C. for 10 minutes is about 2%.
- Patent Document 6 describes using a polyvinyl acetal resin film shape exhibiting a positive shrinkage change rate as an attempt to obtain a specific film that is particularly useful as an intermediate layer for laminated glass in a curved windshield. It is described that the shrinkage rate when the film is heated at 71 ° C.
- Patent Document 7 describes using an embossed sheet on which an emboss having a specific shape is formed as an attempt to reduce thickness variation and thermal shrinkage due to sheet distortion. It is described that the shrinkage rate when heated for 10 minutes is about 2.5%.
- Japanese Patent Laid-Open No. 9-40444 Japanese Patent Laid-Open No. 2001-19499 Japanese Unexamined Patent Publication No. 2000-178044 JP 2008-156135
- Patent Documents 1 to 3 have the effect of removing the remaining air, there are not enough countermeasures against warping of the glass end face, generation of bubbles due to deformation, or generation of unfilled portions. It was not possible to prevent or suppress the trouble caused by.
- Patent Document 4 there is a problem that the glass is limited.
- Patent Documents 5 to 7 bubbles generated by evaporation of water present in the intermediate film cannot be sufficiently suppressed under high temperature conditions (about 150 ° C.) such as laminating with glass. There was a problem.
- FIG. 1A is a cross-sectional view of an end portion of a multilayer body before lamination of heat strengthened glass.
- FIG. 1B is a cross-sectional view of the end of the multilayer body when a defect occurs after lamination of the heat-strengthened glass.
- the distance between the heat-strengthened glass 1 and the glass 2 is the end from the center of the glass as shown in FIG. May be wider.
- the polyvinyl acetal resin film 3 having a relatively uniform thickness in this state, the polyvinyl acetal resin film 3 is formed at the end where the distance between the heat strengthened glass 1 and the glass 2 is wide.
- the unfilled portion of the polyvinyl acetal resin that is, a gap such as a bubble 5 (vacuum independent gap), or a tunnel from the end toward the center as shown in FIG.
- a phenomenon that a large space (tunnel-like defect 4) occurs is observed.
- This unfilled part is not only a problem in appearance, but moisture that enters from the outside during use may accumulate in this unfilled part and cause delamination and whitening, which is a problem as a multilayer structure. there were.
- FIG. 2A is a cross-sectional view of the vacuum laminating apparatus immediately before pressing during vacuum laminating
- FIG. 2B is an enlarged cross-sectional view of the end surface portion of the multilayer structure during pressing
- c) is an enlarged cross-sectional view of the end surface portion of the multilayer structure when the pressure is released after vacuum lamination. As shown in FIG.
- FIG. 3A is a view showing a state in which two laminated bodies are placed in the vacuum laminator or vacuum bag system, and the state is viewed from the upper surface with the upper lid removed.
- 3B is a diagram illustrating a state in which four stacked bodies are set and viewed from the upper surface with the upper lid removed.
- two to four stacked bodies 6 are often set at a time on the vacuum laminator table 10 or in the vacuum bag.
- the glass existing on the side closest to the outer periphery of the device or the bag (referred to as a defect frequent appearance part 11) tends to be pressed in a state where it is pressed from the other part and the glass end is bent (FIG. 3 (a) and (B)), defects are likely to occur in the defect frequent appearance part 11.
- an object of the present invention is a polyvinyl acetal-based resin film used as a layer of a multilayer structure such as a laminated glass for construction, an automobile windshield, or a solar cell module, and a polyvinyl acetal at an end portion in the multilayer structure It is to provide a film capable of preventing bubbles from being formed in the layer and generating an unfilled portion of the polyvinyl acetal layer, a production method thereof, and a multilayer structure obtained by using the film.
- the inventors have studied these measures, and as a result, by heat laminating using a film in which the thermal shrinkage rate of at least one direction of the film, in particular, one side is controlled within a specific range, As a result of finding that generation
- the present invention relates to a film having a thickness distribution in the width direction of 10% or less and a volatile content of 1.0% by mass or less.
- the heat shrinkage rate MD1 is the value with the larger heat shrinkage rate in the flow direction parallel to the film and perpendicular to the width direction, and the other value is the heat shrinkage rate MD2.
- heat shrinkage MD3 heat shrinkage MD1, heat shrinkage MD2 and heat shrinkage MD3
- the heat shrinkage rate in the width direction parallel to the film and perpendicular to the flow direction is determined.
- both the thermal contraction rate TD1 and the thermal contraction rate TD2 are 0% or less, and the absolute values of the respective thermal contraction rates in the width direction are the same in the flow direction of the same part. It is preferable that it is below the absolute value of thermal contraction rate.
- the film of the present invention is preferably used for thermal lamination. Moreover, it is preferable that the film of this invention has an embossing or a continuous recessed part with an elevation difference of 20 micrometers or more on the surface.
- the film of the present invention preferably contains 1 to 1000 ppm of an organic acid salt of a metal having a valence of 2 or more in terms of metal atoms with respect to the polyvinyl acetal resin in terms of achieving a more stable heat shrinkage rate. More preferably, it is 10 ppm or more.
- the temperature of the polyvinyl acetal resin when extruding from the die is 150 to 250 ° C., and the roll closest to the die lip and the die lip
- the present invention relates to a method for producing a polyvinyl acetal-based resin film in which the distance from the contact point of the film is 5 to 15 cm and the film forming speed is 0.4 to 20 m / min.
- the present invention also relates to a multilayer structure obtained by layering the polyvinyl acetal resin film and glass or a durable film.
- the polyvinyl acetal resin film is preferably on at least one surface.
- the present invention relates to a solar cell module using the polyvinyl acetal resin film as a sealing material or a laminated glass using an intermediate film.
- the present invention by using a polyvinyl acetal resin film that shrinks within an appropriate range at the time of heat lamination, bubbles are bitten into the polyvinyl acetal resin at the end of the multilayer structure, or the polyvinyl acetal resin Generation
- production of an unfilled part can be prevented and multilayer structures, such as a laminated glass for construction with excellent external appearance and durability, an automobile windshield, and a solar cell module, can be obtained.
- FIG. 1 is an example of a cross-sectional view of a vacuum laminating apparatus and a multilayer structure according to an embodiment of the present invention. It is an example of the top view at the time of setting the multilayer structure concerning embodiment of this invention to a vacuum laminator. It is an example of the top view of the polyvinyl acetal type-resin film for the heat contraction rate measurement of the film concerning embodiment of this invention.
- the present invention relates to a film having a thickness distribution in the width direction of 10% or less and a volatile content of 1.0% by mass or less.
- the heat shrinkage rate MD1 is the value with the larger heat shrinkage rate in the flow direction parallel to the film and perpendicular to the width direction, and the other value is the heat shrinkage rate MD2.
- heat shrinkage MD3 heat shrinkage MD1, heat shrinkage MD2 and heat shrinkage MD3
- heat shrinkage MD3 is a polyvinyl acetal resin film of 3 to 20%.
- the polyvinyl acetal resin used in the polyvinyl acetal resin film of the present invention is obtained by acetalizing a polyvinyl alcohol resin with an aldehyde, and is produced by, for example, a method described later. However, it is not limited to the method.
- the polyvinyl alcohol resin used as the raw material for the polyvinyl acetal resin can be obtained, for example, by polymerizing a vinyl ester monomer and saponifying the obtained polymer.
- a method for polymerizing the vinyl ester monomer a conventionally known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied.
- the polymerization initiator an azo initiator, a peroxide initiator, a redox initiator, or the like is appropriately selected depending on the polymerization method.
- saponification reaction a known alcoholysis or hydrolysis using a known alkali catalyst or acid catalyst can be applied.
- the degree of saponification of the polyvinyl alcohol resin used in the present invention is not particularly limited, but is preferably 95 mol% or more, more preferably 98% or more, and particularly 99% or more is a carboxylic acid generated by decomposition. It is preferable for reducing the amount.
- vinyl ester monomers examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, and palmitic acid.
- vinyl, vinyl stearate, vinyl oleate, vinyl benzoate and the like can be mentioned, with vinyl acetate being particularly preferred.
- the vinyl ester monomer when polymerized, it can be copolymerized with other monomers within a range not impairing the gist of the present invention.
- other monomers include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene, acrylic acid or salts thereof, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-acrylate.
- Acrylic esters such as propyl, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methacrylic acid and its salts, methyl methacrylate, Methacrylic acid such as ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Acid ester Acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and its salt,
- the vinyl ester monomer When the vinyl ester monomer is polymerized, it may be carried out in the presence of a thiol compound such as thiol acetic acid or mercaptopropionic acid, or other chain transfer agent.
- a thiol compound such as thiol acetic acid or mercaptopropionic acid, or other chain transfer agent.
- a polyvinyl alcohol-type resin is previously used at high temperature, for example, 90, before reaction. It is preferable to dissolve sufficiently at a temperature of at least ° C.
- the concentration of the aqueous solution is preferably 5 to 40% by mass, more preferably 5 to 20% by mass, and particularly preferably 8 to 15% by mass. If the concentration is too low, productivity is poor, and if the concentration is too high, stirring during the reaction becomes difficult, and gelation due to intermolecular hydrogen bonding of the polyvinyl alcohol resin occurs, resulting in uneven reaction.
- a polyvinyl acetal resin can be obtained by adding an aldehyde to such a polyvinyl alcohol resin aqueous solution and reacting it under acidic conditions.
- aldehydes for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, hexylaldehyde, benzaldehyde and the like are used.
- an aldehyde compound having 1 to 12 carbon atoms more preferred is a saturated alkyl aldehyde compound having 1 to 6 carbon atoms, and particularly preferred is a saturated alkyl aldehyde compound having 1 to 4 carbon atoms.
- butyraldehyde is a solar cell. It is preferable from the viewpoint of the mechanical properties of the film when it is used for applications of laminated glass. Moreover, aldehydes may use a single thing and may use 2 or more types together. Furthermore, a small amount of polyfunctional aldehydes or aldehydes having other functional groups may be used in a range of 20% by mass or less of the total aldehydes.
- the catalyst for reacting the aldehydes with the polyvinyl alcohol resin aqueous solution is not particularly limited, and any of organic acids and inorganic acids can be used.
- organic acids and inorganic acids can be used.
- inorganic acids are preferable, and hydrochloric acid, sulfuric acid, and nitric acid are particularly preferable because a sufficient reaction rate can be obtained and washing after the reaction is easy.
- the concentration of the acid used in the reaction depends on the type of acid used, but in the case of hydrochloric acid, sulfuric acid and nitric acid, it is preferably 0.01 to 5 mol / l, more preferably 0.1 to 2 mol / l. If the acid concentration is too low, the reaction rate is slow, and it takes time to obtain the desired degree of acetalization and the desired physical properties of the polyvinyl acetal resin. When the concentration of the acid is too high, it is difficult to control the reaction, and an aldehyde trimer is easily generated.
- a known method may be mentioned.
- the method of adding an acid catalyst after adding to the above is mentioned.
- the method of adding the aldehyde or acid catalyst to be added in a lump or sequentially, or divided addition, and the method of adding a mixed solution of an aqueous solution of polyvinyl alcohol and an aldehyde or an acid catalyst to an acid catalyst or a solution containing an aldehyde are also included.
- the reaction temperature is not particularly limited and is preferably 0 to 80 ° C. However, in order to obtain the film of the present invention, a porous polyvinyl acetal resin that is easily washed after the reaction is preferably used. It is preferable to carry out the reaction at a relatively low temperature of 0 to 40 ° C., preferably 5 to 20 ° C. until the acetal particles are precipitated. Thereafter, in order to drive the reaction, it is preferable to increase the reaction temperature. For example, it is preferable to carry out the reaction at 50 to 80 ° C., particularly 65 to 75 ° C. from the viewpoint of productivity.
- the particles of the polyvinyl acetal resin obtained by these reactions are preferably porous in order to efficiently remove remaining acids and aldehydes.
- it is necessary to adjust the viscosity of the reaction solution, the stirring speed, the shape of the stirring blade, the shape of the reaction vessel, the reaction temperature, the reaction speed, the method of adding the catalyst and aldehydes. is there.
- the reaction temperature is too high, the polyvinyl acetal-based resin is fused and hardly becomes porous.
- the alkali titer value is preferably adjusted to be a positive value.
- the alkali titer is a value (mL) defined by the amount of 0.01 mol / l hydrochloric acid required for alkali titration of 100 g of polyvinyl acetal meter resin.
- the polyvinyl acetal resin obtained by the reaction is neutralized with an alkali compound, but in order to obtain the film of the present invention, aldehydes remaining in the resin are removed as much as possible before the alkali neutralization.
- a method of driving the reaction under conditions where the reaction rate of the aldehyde is high, a method of sufficiently washing with water or a water / alcohol mixed solvent, a method of chemically treating the aldehyde, and the like are useful.
- the alkali compound used for alkali neutralization include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as ammonia, triethylamine, and pyridine.
- the alkali titer value of the polyvinyl acetal resin after alkali washing is preferably 0.1 to 30, and more preferably 1 to 20. If the alkali titer value is too low, the hydrolysis resistance is lowered. Conversely, if the alkali titer value is too high, coloring tends to occur during film production.
- the average degree of polymerization of the polyvinyl acetal resin used in the present invention is preferably 800 to 4000, and more preferably 1000 to 3000.
- the polyvinyl acetal resin preferably has an average degree of acetalization (vinyl acetal unit content) measured in accordance with JIS K6728: 1977 of 50 to 90 mol%, preferably 55 to 88 mol%. More preferred is 60 to 85 mol%.
- the polyvinyl acetal resin used in the present invention preferably has a vinyl alcohol unit amount of 10 to 50 mol%, more preferably 12 to 45 mol%, more preferably 15 to 40, as measured in accordance with JIS K6728: 1977. More preferred is mol%. If the vinyl alcohol unit amount is more than 50 mol%, the hygroscopicity becomes high, which may cause metal corrosion due to absorbed water, deterioration of insulation, and peeling of the polyvinyl acetal resin film from the base material. is there. On the other hand, when the vinyl alcohol unit amount is less than 10 mol%, there is a possibility that problems such as a decrease in mechanical strength and poor adhesion to a substrate may occur during hot pressing.
- the polyvinyl acetal resin used in the present invention preferably has a vinyl ester unit amount measured based on JIS K6728: 1977 of 4 mol% or less, more preferably 2 mol% or less, and more preferably 1 mol% or less. Further preferred. If the vinyl acetate unit amount exceeds 4 mol%, acetic acid, which is a corrosive substance, may be generated due to decomposition by heat and hydrolysis by moisture. Moreover, there is a possibility that the polyvinyl acetal resin is likely to be colored due to the production of olefin by the elimination of acetic acid.
- the values of the above-mentioned degree of acetalization, vinyl alcohol unit content and vinyl ester unit content are the values for the total amount of acetalization degree (vinyl acetal unit content), vinyl alcohol unit content and vinyl ester unit content. is there.
- the amount of chloride ion, sulfate ion, and nitrate ion derived from the acetalization catalyst contained in the polyvinyl acetal resin used in the present invention is preferably 100 ppm or less, more preferably 50 ppm or less, More preferably, it is 20 ppm or less. Since these strong acid ions cause corrosion of metal components used in solar cell modules and the like, it is preferable that they be less.
- the polyvinyl acetal resin used in the present invention preferably contains a divalent or higher metal organic acid salt in order to stabilize the heat shrinkage rate.
- the divalent or higher metal include alkaline earth metals such as calcium or magnesium, copper, zinc, aluminum, titanium, zirconium, vanadium or chromium, and organic acids include formic acid, acetic acid, citric acid, oxalic acid or Examples thereof include sulfonic acid.
- magnesium acetate is particularly preferable in that the effect of stabilizing the heat shrinkage rate is high.
- the content is not particularly limited as long as the desired physical properties can be expressed and the other physical properties are not adversely affected, but the metal atom mass concentration with respect to the polyvinyl acetal resin is preferably 1 to 1000 ppm, and more preferably 3 to 800 ppm is preferred. If the mass concentration of the metal atom is less than 1 ppm, it tends not to be sufficient to stabilize the thermal shrinkage, and if it exceeds 1000 ppm, other physical properties may be adversely affected.
- the polyvinyl acetal resin used for the film of the present invention includes a plasticizer, an antioxidant, an ultraviolet absorber, an adhesion modifier, an antiblocking agent, and a pigment as long as the resulting film does not impair the effects of the present invention. Additives such as dyes and functional inorganic compounds are added as necessary.
- the plasticizer used in the film of the present invention is not particularly limited.
- di- (2-butoxyethyl) -adipate (DBEA), di- (2-butoxyethyl) -sebacate (DBES) Di- (2-butoxyethyl) -azeleic acid ester, di- (2-butoxyethyl) -glutaric acid ester, di- (2-butoxyethoxyethyl) -adipic acid ester (DBEEA), di- (2-butoxy) Ethoxyethyl) -sebacic acid ester (DBEES), di- (2-butoxyethoxyethyl) -azeleic acid ester, di- (2-butoxyethoxyethyl) -glutaric acid ester, di- (2-hexoxyethyl) -adipic acid ester Di- (2-hexoxyethyl) -sebacic acid ester, di- (2-hexoxye
- a plasticizer in which the sum of the carbon number and oxygen number constituting the plasticizer molecule is 28 or more is preferable.
- the addition amount is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the polyvinyl acetal resin. Two or more plasticizers may be used in combination.
- the polyvinyl acetal film of the present invention may contain an antioxidant.
- the antioxidant to be used include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants. Agents are particularly preferred.
- phenolic antioxidants examples include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl Acrylate compounds such as -6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, 2,6-di-t-butyl-4-methylphenol, 2,6 -Di-t-butyl-4-ethylphenol, octadecyl-3- (3,5-) di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6- t-butylphenol), 4,4′-butylidene-bis (4-methyl-6-t-butylphenol), 4,4′-butylidene-bis (6-t-butyl-m-cresol), 4,4 -Thiobis (3-methyl-6-t-butyl
- phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2-t-butyl).
- sulfur-based antioxidants examples include dilauryl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, lauryl stearyl 3,3′-thiodipropionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thiopropionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane.
- antioxidants can be used alone or in combination of two or more.
- the blending amount of the antioxidant is in the range of 0.001 to 5 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polyvinyl acetal resin.
- UV inhibitors used include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ 'dimethylbenzyl) phenyl] -2H-benzo Triazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- Benzotriazole ultraviolet absorbers such as (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2,2,6,6-tetramethyl -4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) se
- adhesion control agent for example, those described in International Publication No. 03/033583 can be used, and the addition of alkali metal salts and / or alkaline earth metal salts of organic acids is preferably used.
- potassium acetate and / or magnesium acetate are preferred.
- the addition amount is preferably from 1 to 1000 ppm, more preferably from 3 to 800 ppm, still more preferably from 5 to 500 ppm, based on the mass of the metal atom, relative to the polyvinyl acetal resin.
- the optimum addition amount of the adhesion modifier varies depending on the additive used, and also depends on the location where the resulting module and laminated glass are used, but the adhesion of the resulting film to the glass is determined by the Pummel test (Pummel test). test: described in WO 03/033583 A1, etc.)
- Pummel test Pummel test
- test described in WO 03/033583 A1, etc.
- it is preferably adjusted to 3 to 10, particularly 3 to 6 when high penetration resistance is required, and 7 when high glass scattering prevention is required. It is preferable to adjust to ⁇ 10.
- high glass scattering prevention property is required, it is also a useful method not to add an adhesion modifier.
- the adhesiveness adjusting agent may be the same as or similar to the shrinkage rate stabilizer such as a divalent or higher metal organic acid salt for stabilizing the heat shrinkage rate described above.
- the total amount of the same kind of metals is preferably within the above range.
- Examples of the functional inorganic compound used include a light reflecting material, a light absorbing material, a thermal conductivity improving material, an electrical property improving material, a gas barrier property improving material, and a mechanical property improving material.
- a composition containing a polyvinyl acetal resin appropriately added and kneaded with these additives is formed into a film and used for thermal lamination.
- a film is produced.
- the resin temperature at the time of extrusion is preferably 150 to 250 ° C, more preferably 180 to 230 ° C. If the resin temperature becomes too high, the polyvinyl acetal resin is decomposed and the content of volatile substances is increased. On the other hand, if the temperature is too low, the content of volatile substances increases. In order to efficiently remove the volatile substance, it is preferable to remove the volatile substance from the vent port of the extruder by reducing the pressure.
- the volatile content in the polyvinyl acetal resin film of the present invention is 1.0% by mass or less, preferably 0.8% by mass or less, and more preferably 0.6% by mass or less. . If it exceeds 1.0% by mass, foaming occurs due to heating of the laminate, and the thermal shrinkage rate becomes larger than the desired physical property value, so that the glass or the solar battery cell tends to be displaced.
- the polyvinyl acetal-based film of the present invention is preferably wound immediately after extrusion, after cooling only the surface with a coolant having a specific temperature.
- the temperature is preferably 10 to 40 ° C, more preferably 20 to 30 ° C. If the temperature is too low, the thermal shrinkage rate becomes too low. Conversely, if the temperature is too high, the thermal shrinkage rate becomes too low.
- the position average thickness 5% inside from both ends of the entire film width before trim cut is preferably within ⁇ 10% of the average film thickness, and more preferably within ⁇ 5%.
- the end of the film is stretched more than the central part in the film width direction by shearing at the exit of the die, neck-in immediately after discharge, and stretching after discharge (stretching in the melted state immediately after discharge and in the state after solidification). adjust.
- the end portion of the film is thick, and on the contrary, a non-uniform gap is formed, and it cannot be used.
- the film of the present specification is also useful in that it can be reduced to within 10%, or even within 10%.
- the temperature of the polyvinyl acetal resin when extruding from a die is set to 150 to 250 ° C.
- the distance between the die lip and the contact point of the film in the roll closest to the die lip (first roll) is 5 to 15 cm
- the film forming speed is 0.4 to 20 m / min.
- the distance between the die lip and the contact point of the film is preferably 6 to 10 cm
- the film forming speed is preferably 0.4 to 10 m / min.
- the method of achieving the film physical properties required in the present invention is to sandwich the end portion between clips and forcibly stretch, thicken the end portion, and further pass the end portion between the rolling rolls.
- a method of stretching greatly can also be used.
- the average thickness was measured by continuously cutting the film into a square of 3 cm ⁇ 3 cm (accuracy: 0.5 mm or less) in the width direction (continuously cut from one end, and the opposite end had a half length. In the case, it is cut out together with the previous part and measured, and is proportionally converted to an area of 3 cm ⁇ 3 cm), and the mass of each cut out test piece is measured to a unit of 0.01 g. The same measurement was performed at three positions by changing the position in the length direction (MD), and the average value (0.01 g unit) of the obtained mass (the weight of the test piece having the same position in the width direction) was measured in the width direction. The “position average thickness” at the position of.
- the film is cut out in the same width direction at the start of cutting so that the positions in the width direction of the test pieces are aligned.
- the arithmetic average of all the “position average thickness” measured three times is referred to as “film average thickness”, (“position average thickness” ⁇ “film average thickness”) / “film average thickness”.
- the absolute value of “sa” ⁇ 100 is the thickness distribution (%) at each position in the width direction.
- the thickness distribution at all positions in the width direction is preferably within 10%, and more preferably within 5%. By setting the thickness distribution within this range, generation of unfilled portions of the polyvinyl acetal resin can be suppressed.
- the thermal shrinkage rate of the film is measured by the following method. That is, the film is cut out at a length of 10 cm over the entire width, and the humidity is adjusted for 2 days at 20 ° C. and 30% RH by a method that does not suppress the dimensional change of the film (such as placing on a net shelf as it is). Thereafter, as shown in FIG. 4, from both ends of the moisture-conditioned product film 12 in the width direction, the position of 5% of the entire width of the product film 12 is the center of each of the sample A13 and the sample B14. A sample is cut out in a square sheet shape parallel to the width direction, and the heat shrinkage rate of the cut out portion is measured.
- the larger value is the heat shrinkage rate MD1
- the smaller value is the heat shrinkage rate MD2.
- the sample is cut into a square sheet parallel to the flow direction and the width direction so that the center position of the full width of the product film 12 is the center of the sample C15, and the thermal contraction rate of the cut portion is measured.
- the measured thermal contraction rate in the flow direction of sample C15 is defined as thermal contraction rate MD3.
- the samples A13 to C15 are cut out so that the position of 5% of the full width from the both ends of the film or the center position of the full width and the center line that bisects the sample overlap.
- Samples A13 to C15 have a square shape of 5 cm in the width direction and 5 cm in the length direction. Without fixing, the sample is placed horizontally on a Teflon (registered trademark) sheet placed in a hot air dryer at 150 ° C. and held for 30 minutes. At this time, the thermal shrinkage rate is obtained for each of MD and TD by measuring the length in the flow direction or the width direction before and after the heat treatment in units of 0.1 cm, and using the following formulas (III) and (IV). The same measurement is measured three times at each position, and the average value is defined as the heat shrinkage rate at that position.
- Teflon registered trademark
- the heat shrinkage rate in the flow direction of sample A13 is the heat shrinkage rate MD1
- the heat shrinkage rate in the flow direction of sample B14 is the heat shrinkage rate MD2
- the heat shrinkage rate in the width direction of sample A13 is TD1.
- the thermal contraction rate in the width direction of sample B14 is defined as TD2. That is, the thermal shrinkage rate MD1 and the thermal shrinkage rate TD1 represent the thermal shrinkage rate in the flow direction and the width direction of the same sample, and the thermal shrinkage rate MD2 and the thermal shrinkage rate TD2 also represent the heat in the flow direction and the width direction of the same sample. It represents the shrinkage rate.
- the thermal contraction rate in the flow direction of the sample C15 is defined as MD3, and the thermal contraction rate in the width direction is defined as TD3.
- MD3 thermal contraction rate in the flow direction of the sample C15
- TD3 thermal contraction rate in the width direction
- the heat shrinkage of the film is performed by laminating a polyvinyl acetal resin layer between two sheets of glass when laminating in the process as described above.
- the gap may be non-uniform or non-uniform during the process, and the volume of the polyvinyl acetal resin may be insufficient with respect to the space between the glasses, resulting in an unfilled portion of the polyvinyl acetal resin. It is an object of the present invention to attempt to remedy this problem by the resin content filled by thermal shrinkage.
- the thermal shrinkage rate is in the range of 3 to 20%, preferably 3.5 to 18%, preferably 4 to 15% for all of the thermal shrinkage rate MD1, the thermal shrinkage rate MD2, and the thermal shrinkage rate MD3. Is more preferable.
- the heat shrinkage rate in the flow direction is less than 3%, the amount of filling between the glass of the polyvinyl acetal resin is insufficient, so it is insufficient to prevent the occurrence of unfilled parts, and when it exceeds 20%
- the shrinkage of the film is too great, and the two glasses are displaced or the solar cells disposed inside are displaced.
- the heat shrinkage rate in the flow direction is in the range of 3 to 20%, but the heat shrinkage rate in the width direction (TD direction) is also 0. % Or less (that is, expansion), and the absolute value of the thermal contraction rate in the TD direction is preferably equal to or less than the thermal contraction rate in the MD direction of the same sample.
- the thermal contraction rate in the TD direction is more preferably -10.0 to 0.1%, and the absolute value thereof is equal to or less than the thermal contraction rate in the MD direction of the same sample.
- one of the samples A13 and B14 has a large thermal shrinkage.
- the thermal shrinkage ratio between the sample A15 and the sample B14 of the sample A13 and the sample B14 and the sample C15 is in a specific range. Among these, the case where the following conditions are satisfied is particularly preferable.
- the ratio of heat shrinkage ratio MD1 / heat shrinkage ratio MD2 is more preferably 2.0 or more.
- the upper limit of the ratio of the heat shrinkage ratio MD1 / the heat shrinkage ratio MD2 is not particularly limited, but is preferably 4.0 or less and preferably 3.0 or less from the viewpoint of handling in manufacturing. Is more preferable and 2.5 or less is particularly preferable.
- the ratio of heat shrinkage ratio MD2 / heat shrinkage ratio MD3 is more preferably 0.8 or more, and more preferably 1.2 or less.
- the melt index in the present specification is an average value of values (g / 10 minutes) obtained by measuring a film sufficiently finely cut five times at a barrel set temperature of 150 ° C. and a load of 2.16 kg according to JIS K7210. It is.
- the melt index of the film of the present invention is preferably in the range of 0.05 to 5 g / 10 minutes, more preferably 0.08 to 3 g / 10 minutes. If the melt index is less than 0.05 g / 10 min, the resin does not flow well during lamination, and the resin does not flow in the gaps. When the melt index exceeds 5 g / 10 minutes, the resin flows due to the pressure at the time of lamination, and the number of cases where defects occur.
- the thickness of the film made of the polyvinyl acetal resin used in the solar cell module of the present invention is not particularly limited, but is preferably 0.38 mm to 2.28 mm. If it is thinner than 0.38 mm, the space around the solar cells and functional units cannot be sufficiently filled. If it is thicker than 2.28 mm, the cost of the film itself is high and the cycle time of the laminating process is also long. This is not preferable.
- the thickness of the film made of polyvinyl acetal resin used for laminated glass for construction and safety glass for automobiles is not particularly limited, but is preferably 0.30 mm to 2.28 mm. If it is thinner than 0.30 mm, it cannot satisfy the penetration resistance performance of laminated glass for construction and safety glass for automobiles. If it is thicker than 2.28 mm, the glass shifts when the polyvinyl acetal resin softens at high temperatures. Is not preferable.
- the width of the film of the present invention is not particularly limited, but is preferably from 300 mm to 3300 mm, and has a width in the range of 0 to +10 mm (and the length after cutting) from the size of the laminate to prevent defects and film loss. It is preferable from the viewpoint of reduction. If the width is too narrow than the size of the laminated body, the chipped portion of the end face becomes large or it is necessary to use a plurality of sheets, which is not convenient. In addition, inorganic glass generally has a maximum width of 3200 mm, and a 3300 mm film is unnecessary, and is inconvenient in handling.
- winding method and the like there is no particular limitation on the winding method and the like, and it is exemplified that it is wound around a plastic core or metal core having an arbitrary diameter or wall thickness, or is cut into a use size and stacked in a bag. In any case, it is possible to eliminate the necessity of drying again at the time of use by making the packaging moisture-proof in order to prevent moisture absorption to the film. Moreover, you may insert films, such as polyethylene, between films in order to prevent blocking between films.
- Storage and transportation are not particularly limited as long as the object of the present invention is not impaired, but is preferably 20 ° C. or less, preferably 5 ° C. or less from the viewpoint of stabilization of heat shrinkage, moisture resistance, and anti-blocking properties. More preferably.
- the film of the present invention preferably has an embossment having a height difference of 20 ⁇ m or more or a continuous concave portion on the surface of the film in order to improve the deaeration property in the laminating process. That is, the difference in thickness between the thickest part and the thinnest part of the film is preferably 20 ⁇ m or more, and more preferably 40 to 150 ⁇ m.
- a conventionally known method can be used as a conventionally known method can be used. Examples thereof include a method for providing a melt fracture structure by adjusting the extrusion conditions, a method for imparting an embossed structure to the extruded film, and the like.
- the shape and depth of the emboss are not particularly limited as long as the object of the present invention is not impaired, but examples include a shape in which pyramidal protrusions with a base of 1 mm and a height of 0.1 mm are arranged without gaps.
- the embossing usage is not particularly limited, but it is passed between a metal roll and an embossed die roll on a heated surface while paying attention to temperature and press pressure so that the heat shrinkage rate is within the range.
- the embossing method can be exemplified.
- the polyvinyl acetal resin film of the present invention may be multilayered as long as the physical properties and purpose are not impaired.
- the multilayer film is composed of two types of polyvinyl acetal resin compositions, two layers (A / B type), two types, three layers (A / B / A type), one type of polyvinyl acetal resin composition, and another type. 2 layers (A / B type) made of resin composition, 2 types, 3 layers (A / B / A type) or combinations of various resin compositions (A / B / C / A, A / B /) C / B / A, etc.), and those obtained by adding a functional material to any one of these layers can also be used.
- the film of the present invention is preferably on at least one surface. Furthermore, in addition to the configuration in which these multilayers are similarly arranged in the entire width direction (entire surface), a thin colored layer (A / B (colored) / A) is provided only at the end portion to form a laminated glass. It is possible to devise such as providing a thin colored part to reduce the direct incidence of sunlight from the upper part to provide an antiglare effect.
- the solar cell module of the present invention can take a known structure as the structure of the solar cell module, except that the film of the present invention is used for all or part of the filler.
- the type of solar battery cell used in the present invention is not particularly limited, and examples include a crystal cell and a thin film cell, and examples of the crystal cell include single crystal silicon and polycrystalline silicon.
- examples of the thin film type cell include a thin film silicon type such as amorphous silicon and a laminate of the same and a polycrystalline thin film, a compound semiconductor type using CIS, CIGS, CdTe, GaAs, and the like, and an organic solar cell type.
- the film of the present invention is inserted and laminated between a transparent substrate such as glass and the crystal cell and / or between the crystal cell and the back glass or back sheet.
- the solar cell module of the present invention can be obtained.
- the film of this invention is inserted between the surface transparent substrate with which the photovoltaic cell was mounted
- the film of the present invention is inserted between a surface transparent substrate and a substrate on which solar cells are mounted.
- the film of the present invention can also be used as an adhesive layer for laminating with a transparent substrate, a back sheet, other reinforcing substrates and the like for these laminates.
- the backsheet used in the solar cell module of the present invention is not particularly limited, but preferably used is one having excellent weather resistance and low moisture permeability, a polyester film, a fluorine resin film, and a laminate thereof, In addition, those in which an inorganic compound is laminated can be used.
- the back sheet is hard and difficult to deform, the problem of the end portion is the same as that of glass, but a flexible sheet is relatively difficult to occur.
- the present invention is effective because the gap between the back sheet and the glass may vary due to the warp of the glass due to heat, the pressure change in the laminating process described above, and the like even in a flexible case.
- the peel strength in a 180 ° C. peel test is preferably 5 N / cm or more, more preferably 7 N / cm or more, and more preferably 10 N / cm. More preferably, it is not less than cm.
- the laminated glass of the present invention is obtained by placing the resin of the present invention or inserting a film between two or more glasses and laminating them. Moreover, what equipped the functional unit in the position which contacts the polyvinyl acetal type-resin film of this invention inside this laminated glass is especially useful.
- the glass used in the present invention is not particularly limited, but float glass, tempered glass, meshed glass, bent glass, template glass, organic glass, and the like can be used.
- a weather-resistant plastic film can be used.
- the thickness of the glass is not particularly limited, but is preferably 1 to 10 mm, and more preferably 2 to 6 mm.
- the laminated glass for construction, the automobile safety glass and the solar cell module of the present invention are produced by a known method, and the film of the present invention is used as a filler.
- heat-strengthened glass is wavy due to its manufacturing process, and when the two glasses are combined, the gap between the ends may be wider than the center.
- the polyvinyl acetal-based resin is difficult to flow in and tends to be unfilled. In the unfilled portion, bubbles (independent of vacuum) and tunnel-like defects are likely to occur.
- polyvinyl acetal resin is filled by shrinkage in the portion that becomes the defect, and the defect can be prevented. The range of the heat shrinkage rate will be described later.
- the laminated glass for construction, the safety glass for automobiles and the solar cell module of the present invention include known frames and sealing agents, junction boxes, mounting jigs and mounts, antireflection films, various facilities using solar heat, rain gutters It can be combined with a structure or the like.
- the laminated method for obtaining the laminated glass for construction, the safety glass for automobiles and the solar cell module of the present invention can be a known method, for example, a method using a vacuum laminator device, a method using a vacuum bag, Examples include a method using a vacuum ring and a method using a nip roll.
- a method of adding to the autoclave process after provisional pressure bonding can be additionally performed.
- a vacuum laminator device for example, a known device used for manufacturing a solar cell is used, and lamination is performed at a temperature of 100 to 200 ° C., particularly 130 to 160 ° C. under a reduced pressure of 1 to 30000 Pa.
- a method using a vacuum bag or a vacuum ring is described, for example, in EP12356683B1, for example, laminated at 130-145 ° C. under a pressure of about 20000 Pa.
- the laminator or bag When laminating with a vacuum laminator or vacuum bag, from the viewpoint of efficiency, the laminator or bag often contains 2 to 4 laminates at a time. In this case, the outermost periphery of the device or bag The glass near the side tends to be pressed from the other part and the glass end is bent (see FIGS. 3A and 3B). Since the end strongly pressed in this way returns to its original shape due to stress when the pressure is released, a situation occurs where the end opens, and at this time, the polyvinyl acetal-based fat layer in the middle is insufficient in volume, In some cases, bubbles (vacuum independent space) and tunnel-like defect portions continuous from the end portion may occur. However, by using the film of the present invention, polyvinyl acetal is filled by shrinkage in the portions that become bubbles or defects, and the defects can be prevented. The range of the heat shrinkage rate will be described later.
- a nip roll for example, there is a method in which after the first temporary pressure bonding is performed at a temperature equal to or lower than the flow start temperature of the polyvinyl acetal resin, the pressure bonding is further performed under conditions close to the flow start temperature. Specifically, for example, there is a method of heating to 30 to 70 ° C. with an infrared heater or the like, then degassing with a roll, further heating to 50 to 120 ° C., and then press-bonding with a roll to bond or temporarily bond.
- the autoclave process that is additionally performed after the temporary pressure bonding is performed for about 2 hours at a temperature of 130 to 145 ° C. under a pressure of about 1 to 1.5 MPa, depending on the thickness and configuration of the solar cell module and the laminated glass. Is done.
- the laminated glass for buildings and the safety glass for automobiles of the present invention are used as members for windows, windshields, walls, roofs, solariums, soundproof walls, show windows, balconies, handrail walls, or partition glass members for meeting rooms, etc. It can also be used as a home appliance.
- % and part mean “% by mass” and “part by mass”, respectively, unless otherwise specified.
- the volatile content was determined by the formula (V) by heating 100 g of resin or film at 140 ° C. for 30 minutes. Three 5 cm square films were cut out at the position where the thermal shrinkage was measured, and the volatile content of each film was measured. The average value thereof was defined as the volatile content (%) of the film.
- the content of vinyl acetate units, the content of vinyl alcohol units, and the average degree of acetalization in polyvinyl butyral (hereinafter sometimes abbreviated as “PVB”) resin were measured based on the provisions of JIS K6728: 1977, respectively.
- Example 1 Polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) (PVA-1: polymerization degree 1700, saponification degree 99 mol%) 7.5% aqueous solution 1700 kg was added to a 2 m 3 reactor equipped with a stirrer. Then, 74.6 kg of butyraldehyde and 0.13 kg of 2,6-di-t-butyl-4-methylphenol were charged, and the whole was cooled to 14 ° C. To this, 160.1 L of hydrochloric acid having a concentration of 20% by mass was added, and butyralization of PVA was started. Ten minutes after the addition of hydrochloric acid was completed, the temperature was raised to 65 ° C. over 90 minutes, and the reaction was further performed for 120 minutes.
- PVA Polyvinyl alcohol
- PVB resin (PVB-1).
- the obtained PVB resin was 0.9 mol% vinyl acetate units and 28.5 mol% vinyl alcohol units. Moreover, the average acetalization degree of PVB resin was 70.6 mol%.
- a coat hanger die having a 40 mm diameter full flight single screw extruder and a 60 cm wide flexible lip was used to form a film with a lip opening of 0.8 mm at the center and 0.4 mm at the end.
- the lip opening was adjusted within a range of ⁇ 20% by measuring the film thickness before winding.
- the distance of the film contact point between the die lip and the first roll was 7 cm, and the film forming speed was 0.5 m / min.
- a film having a width of 112 cm before trim cut, a thickness of 4 cm from the end of 765 ⁇ m and a thickness of 770 ⁇ m on the opposite side and a thickness of 760 ⁇ 30 ⁇ m in the middle is obtained, and the trim cut at a portion of 5 cm from the end
- the paper was wound up (BF-1).
- This roll is again slitted with a single-blade leather at the center, the film is divided into two parts on the left and right sides to make a width of 51 cm, and then wound on the roll with another winding shaft, two PVB rolls (BF -2: left facing the winding direction, 3: facing right). Of these, BF-2 was used, and the following measurements and evaluations were performed.
- the maximum value of the thickness distribution of the BF-2 film was 5%, and the volatile content was 0.4% by mass.
- the thermal shrinkage rate is as follows: thermal shrinkage rate MD1 is 11.5%, thermal shrinkage rate TD1 is -3.1% (expansion), thermal shrinkage rate MD2 is 5.4%, thermal shrinkage rate TD2 is -0.3%, The heat shrinkage ratio MD3 was 6.8%, and the heat shrinkage ratio TD3 was -0.9%.
- the melt index was measured at 150 ° C. and 2.16 kg using a sample obtained by cutting this film with a scissors to 5 mm square or less, it was 0.23 g / 10 min.
- the thickness distribution was measured by the measurement method described in paragraph 0057 of this specification, and the heat shrinkage rate was measured by the measurement method described in paragraph 0058 of this specification. The same measurement was performed in the following examples and comparative examples.
- a laminated glass was produced using a vacuum muraminator manufactured at a hot plate temperature of 145 ° C., a vacuum of 10 ⁇ 1 Pa, and a lamination time of 30 minutes.
- the laminated glass there were only two bubbles of 0.5 mm or less at the edge portion, and there was no PVB defect portion, and a product having a good appearance was obtained.
- Example 2 A film sample having a width of 51 cm and a length of 51 cm centered on the central portion of BF-1 of Example 1 (BF-4).
- the thickness distribution, volatile content, and heat shrinkage rate of this film were measured in the same manner as in Example 1.
- the maximum value of the thickness distribution is 3%
- the volatile content is 0.4% by mass
- the thermal shrinkage rate is 6.4% for the thermal shrinkage rate MD1, -0.9% for the thermal shrinkage rate TD1, and MD2 for the thermal shrinkage rate.
- the thermal shrinkage rate TD2 was -1.0%
- the thermal shrinkage rate MD3 was 7.6%
- the thermal shrinkage rate TD3 was -0.3%.
- the melt index was measured at 150 ° C.
- Example 2 A laminated glass was produced in the same manner as in Example 1 except that this film was used. Although five bubbles of 0.5 mm or less were observed at the edge portion, there was no PVB defect.
- Example 3 The BF-2 of Example 1 was unwound again, passed through a metal roll (diameter 40 cm) with a surface temperature of 120 ° C., and then a hard rubber roll was placed on the opposite side of the metal emboss roll (diameter 40 cm) with a surface temperature of 120 ° C. Then, the gap between both rolls was adjusted to 0.7 mm, and the film roll was passed at a speed of 1 m / min to obtain a film roll having an embossed surface in which a square pyramid having a low side of 1 mm and a height of 100 ⁇ m was continuous on the film surface. The width of the film after embossing was 51.3 cm.
- the maximum thickness distribution of this film is 3%, the volatile content is 0.3% by mass, and the heat shrinkage is 10.2% for the heat shrinkage MD1, -2.0% for the heat shrinkage TD1, and the heat shrinkage.
- the rate MD2 was 4.8%, the heat shrinkage rate TD2 was -0.4%, the heat shrinkage rate MD3 was 5.2%, and the heat shrinkage rate TD3 was -0.9%.
- the melt index was measured at 150 ° C. and 2.16 kg using a sample obtained by cutting this film with a scissors to 5 mm square or less, it was 0.23 g / 10 min.
- This film was cut into a length of 51 cm to obtain a sample film having a width of 51.3 cm ⁇ a length of 51 cm, and the center of the heat-tempered glass used in Example 1 and the center of the film were aligned and overlapped. In the same manner, a laminated glass was obtained. There were no bubbles in the laminated glass, and no PVB deficient part was seen.
- Example 4 A pellet was obtained in the same manner as in Example 1 except that magnesium acetate was added at 100 ppm by mass based on PVB resin during pelletization, and a film having a film width of 112 cm was obtained in the same manner (BF) -5) Further, in the same manner as in Example 1, the paper was wound up on two rolls 51 cm wide by a slitter to obtain BF-6 (left to the right) and BF-7 (right to the right).
- the maximum thickness distribution of BF-6 is 6%, the volatile content is 0.4% by mass, the heat shrinkage rate is 13.8% for heat shrinkage MD1, -4.1% for heat shrinkage TD1,
- the shrinkage MD2 was 6.7%, the heat shrinkage TD2 was ⁇ 0.4%, the heat shrinkage MD3 was 7.6%, and the heat shrinkage TD3 was ⁇ 1.1%.
- the melt index was measured at 150 ° C. and 2.16 kg using a sample obtained by cutting this film with a scissors to 5 mm square or less, it was 0.10 g / 10 min. Thereafter, a laminated glass was produced in the same manner as in Example 1. The laminated glass had good appearance with no bubbles or PVB defects.
- Example 1 (Comparative Example 1) In Example 1, the discharge rate was adjusted so that the film forming speed was 0.3 m / min, the contact distance of the die lip and the film to the first roll was 3 cm, and the following was formed in the same manner, and before the trim cut A film having a width of 87 cm was obtained. Both sides were trimmed by 18 cm to obtain a film roll having a width of 51 cm (BF-8).
- the maximum thickness distribution of BF-8 is 4%, the volatile content is 0.5% by mass, the heat shrinkage rate is 2.1% for heat shrinkage MD1, -0.1% for heat shrinkage TD1, The shrinkage MD2 was 1.8%, the heat shrinkage TD2 was 0.0%, the heat shrinkage MD3 was 1.3%, and the heat shrinkage TD3 was -0.1%.
- melt index was measured at 150 ° C. and 2.16 kg using a sample obtained by cutting the film into 5 mm square or less with a scissors, it was 0.24 g / 10 min. Thereafter, a laminated glass was produced in the same manner as in Example 1. In the laminated glass, many bubbles were observed in the edge portion, and many PVB defect portions extending in a tunnel shape from the edge portion toward the inside were observed in a portion where there were originally voids between the glasses.
- Example 2 In Example 1, a 51 cm ⁇ 51 cm film was cut from BF-2 and held at 10 ° C. and 70% RH for 3 days. There was no dimensional change of the film. The maximum thickness distribution of the obtained film was 5%, the volatile content was 1.4% by mass, and the heat shrinkage after conditioning was 26.2% for heat shrinkage MD1 and -5 for heat shrinkage TD1. 0.9%, heat shrinkage ratio MD2 was 8.6%, heat shrinkage ratio TD2 was -0.5%, heat shrinkage ratio MD3 was 10.1%, and heat shrinkage ratio TD3-1.4%. Further, when the melt index was measured at 150 ° C.
- Example 2 Using this, a laminated glass was produced in the same manner as in Example 1. A large number of bubbles were observed at the center, and a large number of bubbles at the edge portion and a PVB defect portion on the tunnel from the edge toward the inside were observed over the entire circumference.
- Example 3 In Example 1, at the time of film formation, the discharge amount was adjusted to about 3 times so that the film formation speed was 2 m / min, and the contact distance of the die lip and the film to the first roll was 20 cm. (BF-9) was obtained. Thereafter, two rolls having a width of 51 cm were obtained in the same manner as in Example 1, and the same evaluation as in Example 1 was performed using the left (BF-10) facing the winding direction.
- the maximum value of the thickness distribution of this film is 6%, the volatile content is 0.4% by mass, and the thermal shrinkage is 25.1% for the thermal shrinkage MD1, -5.8% for the thermal shrinkage TD1, and the thermal shrinkage.
- the rate MD2 was 7.9%, the thermal shrinkage rate TD2 was ⁇ 4.3%, the thermal shrinkage rate MD3 was 5.3%, and the thermal shrinkage rate TD3 was ⁇ 2.1%. Furthermore, when the melt index was measured at 150 ° C. and 2.16 kg using a sample obtained by cutting the film with a scissors to 5 mm square or less, it was 0.22 g / 10 min. Thereafter, a laminated glass was produced in the same manner as in Example 1. In the laminated glass, many bubbles were observed in the edge portion, and many PVB defect portions extending in a tunnel shape from the edge portion toward the inside were observed in a portion where there were originally voids between the glasses.
- Table 1 shows the physical properties of the polyvinyl acetal resin films of Examples 1 to 4 and Comparative Examples 1 to 3 obtained as described above.
- the present invention prevents the occurrence of unfilled portions in the polyvinyl acetal resin layer at the end of the multilayer structure by using a film that shrinks within an appropriate range during heating lamination, and has a good appearance and durability. It is useful to provide a multilayer structure excellent in.
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Abstract
Description
攪拌機を取り付けた2m3反応器に、ポリビニルアルコール(以下、「PVA」と略記載することがある。)(PVA-1:重合度1700、ケン化度99モル%)7.5%の水溶液1700kgと、ブチルアルデヒド74.6kg、2,6-ジ-t-ブチル-4-メチルフェノール0.13kgを仕込み、全体を14℃に冷却した。これに、濃度20質量%の塩酸160.1Lを添加して、PVAのブチラール化を開始した。塩酸の添加が終了してから10分後より、90分かけて65℃まで昇温し、更に120分反応を行った。その後、室温まで冷却して析出した樹脂をろ過し、樹脂に対して10倍量(質量比)のイオン交換水で10回洗浄した。その後、0.3質量%水酸化ナトリウム水溶液を用いて充分に中和を行った。さらに、樹脂に対して10倍量(質量比)のイオン交換水で10回洗浄し、脱水したのち、乾燥させ、PVB樹脂(PVB-1)を得た。得られたPVB樹脂は、酢酸ビニル単位0.9モル%、ビニルアルコール単位28.5モル%であった。また、PVB樹脂の平均アセタール化度は70.6モル%であった。
実施例1のBF-1の中央部を中心にして幅51cm、長さ51cmのフィルムサンプルを得た(BF-4)。このフィルムの厚さ分布、揮発分、熱収縮率を実施例1と同様に測定した。厚さ分布の最大値は3%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が6.4%、熱収縮率TD1が-0.9%、熱収縮率MD2が5.0%、熱収縮率TD2が-1.0%、熱収縮率MD3が7.6%、熱収縮率TD3が-0.3%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.24g/10分であった。このフィルムを用いた以外は、実施例1と同様に配し、合わせガラスを作製した。0.5mm以下の気泡がエッジ部に5箇所見られたが、PVBの欠損部分は無かった。
実施例1のBF-2を再度巻き出し、表面温度120℃の金属ロール(直径40cm)を通過させ、続いて表面温度120℃の金属製エンボスロール(直径40cm)と反対側に硬質ゴムロールを配し両ロールの間隙を0.7mmに調整した間を1m/分の速度で通過させ、フィルム表面に低辺1mm、高さ100μmの四角錘が連続するエンボス表面を持つフィルムロールを得た。エンボス後のフィルムの幅は51.3cmであった。このフィルムの厚さ分布の最大値は3%、揮発分は0.3質量%、熱収縮率は、熱収縮率MD1が10.2%、熱収縮率TD1が-2.0%、熱収縮率MD2が4.8%、熱収縮率TD2が-0.4%、熱収縮率MD3が5.2%、熱収縮率TD3が-0.9%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.23g/10分であった。このフィルムを長さ方向で51cmに切り出し、幅51.3cm×長さ51cmのサンプルフィルムとし、実施例1で使用した熱強化ガラスの中心と、フィルムの中心を合わせて重ね合わせ、以下実施例1と同様にして合わせガラスを得た。合わせガラスには気泡はなく、PVB欠損部分も見られなかった。
ペレット化の際に酢酸マグネシウムをPVB樹脂に対して質量基準で100ppm添加すること以外は実施例1と同様にしてペレットを得て、同様にして製膜しフィルム幅112cmのフィルムを得て(BF-5)、さらに実施例1と同様にスリッターにて51cm幅の2本のロール上に巻き取り、BF-6(正対して左)、BF-7(正対して右)とした。BF-6の厚さ分布の最大値は6%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が13.8%、熱収縮率TD1が-4.1%、熱収縮率MD2が6.7%、熱収縮率TD2が-0.4%、熱収縮率MD3が7.6%、熱収縮率TD3が-1.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.10g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスには気泡、PVB欠損部分は見られず外観良好であった。
実施例1において、製膜速度を0.3m/分になるよう吐出量を調整し、ダイリップとフィルムの第一ロールへの接触距離が3cmとして、以下は同様に製膜し、トリムカット前の幅87cmのフィルムを得た。両側をそれぞれ18cmトリムカットし、幅51cmのフィルムロールを得た(BF-8)。BF-8の厚さ分布の最大値は4%、揮発分は0.5質量%、熱収縮率は、熱収縮率MD1が2.1%、熱収縮率TD1が-0.1%、熱収縮率MD2が1.8%、熱収縮率TD2が0.0%、熱収縮率MD3が1.3%、熱収縮率TD3が-0.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.24g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスにはエッジ部分に気泡が多数見られ、エッジ部から内側に向かってトンネル状に延びたPVB欠損部分が、元々ガラス間に空隙があった部分に多数見られた。
実施例1においてBF-2から51cm×51cmのフィルムを切り出し、10℃、70%RHで3日間保持した。フィルムの寸法変化は見られなかった。得られたフィルムの厚さ分布の最大値は5%、揮発分は1.4質量%、調湿後の熱収縮率は、熱収縮率MD1が26.2%、熱収縮率TD1が-5.9%、熱収縮率MD2が8.6%、熱収縮率TD2が-0.5%、熱収縮率MD3が10.1%、熱収縮率TD3-1.4%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、発泡し正確な測定は不能であった。これを用い、実施例1と同様に合わせガラスを作製した。中央部に多数の気泡が見られ、かつエッジ部分に多数の気泡とエッジから内部に向かってトンネル上のPVB欠損部分がほぼ全周に渡って観察された。
実施例1において製膜時に、同じ厚さで、製膜速度を2m/分となるよう吐出量を約3倍に調整して、ダイリップとフィルムの第一ロールへの接触距離を20cmとして、フィルムを得た(BF-9)。以下実施例1と同様にして、幅51cmのロールを2本得て、巻き取り方向に正対して左(BF-10)を用い、以下実施例1と同様な評価を行った。このフィルムの厚さ分布の最大値は6%、揮発分は0.4質量%、熱収縮率は、熱収縮率MD1が25.1%、熱収縮率TD1が-5.8%、熱収縮率MD2が7.9%、熱収縮率TD2が-4.3%、熱収縮率MD3が5.3%、熱収縮率TD3が-2.1%であった。さらにこのフィルムを鋏で5mm角以下に切断したものをサンプルとして150℃、2.16kgでメルトインデックスを測定したところ、0.22g/10分であった。以下、実施例1と同様にして合わせガラスを作製した。合わせガラスにはエッジ部分に気泡が多数見られ、エッジ部から内側に向かってトンネル状に延びたPVB欠損部分が、元々ガラス間に空隙があった部分に多数見られた。
上述のようにして得られた実施例1~4および比較例1~3のポリビニルアセタール系樹脂フィルムの物性を表1に示す。
2 ガラス
3 ポリビニルアセタール系樹脂フィルム
4 トンネル状欠点
5 気泡
6 被積層体
7 押さえ用膜
8 大気圧
9 真空空間
10 真空ラミネーターのテーブル(または真空バッグ)
11 欠点頻出部
12 製品フィルム
13 サンプルA
14 サンプルB
15 サンプルC
Claims (13)
- 幅方向の厚さ分布が10%以下、揮発分が1.0質量%以下のフィルムであって、
幅方向の両端からフィルム全幅の5%内側部分について、それぞれ150℃で30分加熱した際に、フィルムに平行かつ幅方向に垂直である流れ方向の熱収縮率が大きい方の値を熱収縮率MD1、もう一方の値を熱収縮率MD2とし、
フィルムの幅方向の中央部分を150℃で30分加熱した際のフィルムに平行かつ幅方向に垂直である流れ方向の熱収縮率を熱収縮率MD3とした場合に、
熱収縮率MD1、熱収縮率MD2および熱収縮率MD3のいずれも3~20%であるポリビニルアセタール系樹脂フィルム。 - 幅方向の両端から全幅の5%内側部分について、それぞれ150℃で30分加熱した際に、フィルムに平行かつ流れ方向に垂直である幅方向の熱収縮率を熱収縮率TD1および熱収縮率TD2とした場合に、熱収縮率TD1および熱収縮率TD2のいずれもが0%以下であって、
それぞれの幅方向の熱収縮率の絶対値が、同じ部分の流れ方向の熱収縮率の絶対値以下である請求項1に記載のポリビニルアセタール系樹脂フィルム。 - 熱ラミネート用である請求項1~3のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- フィルムの表面に高低差20μm以上のエンボスまたは連続した凹部を持つ、請求項1~4のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- さらに、2価以上の金属の有機酸塩をポリビニルアセタール系樹脂に対して、金属原子換算で1~1000ppm含む請求項1~5のいずれか1項に記載のポリビニルアセタール系樹脂フィルム。
- 請求項1~6に記載のフィルムを押出機を用いて製膜するにあたり、ダイから押出す際のポリビニルアセタール系樹脂の温度が150~250℃であり、ダイリップとダイリップから最も近いロールにおけるフィルムの接触地点との距離が5~15cmであり、製膜速度が0.4~20m/分である、ポリビニルアセタール系樹脂フィルムの製造方法。
- 請求項1~6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを有する多層構造体。
- 上記ポリビニルアセタール系樹脂フィルムが少なくとも一方の表面にある、請求項8に記載の多層構造体。
- 請求項1~6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを用いた太陽電池用封止材。
- 請求項10に記載の太陽電池用封止材を用いた太陽電池モジュール。
- 請求項1~6のいずれか1項に記載のポリビニルアセタール系樹脂フィルムを用いた合わせガラス用中間膜。
- 請求項12に記載の合わせガラス用中間膜を用いた合わせガラス。
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KR1020137028646A KR101375204B1 (ko) | 2011-03-29 | 2012-03-29 | 폴리비닐아세탈계 수지 필름 및 그것을 이용한 다층 구조체 |
CN201280015902.1A CN103476841B (zh) | 2011-03-29 | 2012-03-29 | 聚乙烯醇缩醛系树脂薄膜及使用了其的多层结构体 |
JP2012538127A JP5155497B2 (ja) | 2011-03-29 | 2012-03-29 | ポリビニルアセタール系樹脂フィルムおよびそれを用いた多層構造体 |
RU2013147980/05A RU2013147980A (ru) | 2011-03-29 | 2012-03-29 | Пленка поливинилацетальной смолы и изделия с многослойной структурой, использующие пленку |
US14/008,745 US9431560B2 (en) | 2011-03-29 | 2012-03-29 | Polyvinyl acetal resin film and multilayer structure articles using the same |
EP12763997.9A EP2692781A4 (en) | 2011-03-29 | 2012-03-29 | POLY (VINYLACETAL) RESIN FILM AND MULTILAYER STRUCTURE THEREOF |
BR112013024559A BR112013024559A2 (pt) | 2011-03-29 | 2012-03-29 | película de resina de acetato de polivinil, método para produzir a película e artigo de estrutura de camadas múltiplas |
MX2013011187A MX2013011187A (es) | 2011-03-29 | 2012-03-29 | Pelicula de resina de polivinil acetal y articulos con estructura en multicapas que usan la misma. |
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JP2014108517A (ja) * | 2012-11-30 | 2014-06-12 | C I Kasei Co Ltd | 太陽電池用封止シートの製造方法 |
CN105073386A (zh) * | 2013-03-28 | 2015-11-18 | 富士胶片株式会社 | 聚酯膜及其制造方法 |
WO2016125897A1 (ja) * | 2015-02-05 | 2016-08-11 | 積水化学工業株式会社 | 合わせガラス用中間膜及び合わせガラス |
JP2016175835A (ja) * | 2012-06-08 | 2016-10-06 | コーニング インコーポレイテッド | 薄ガラス積層板を積層するための方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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MX2016012621A (es) * | 2014-03-31 | 2017-01-09 | Sekisui Chemical Co Ltd | Pelicula intermedia para vidrio laminado, metodo para fabricar pelicula intermedia para vidrio laminado, y vidrio laminado. |
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WO2018236783A2 (en) * | 2017-06-20 | 2018-12-27 | 3M Innovative Properties Company | ADHESIVE COMPOSITIONS COMPRISING POLY (VINYL ACETAL) RESIN AND ARTICLES CONTAINING THE SAME |
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CN115991919A (zh) * | 2021-10-18 | 2023-04-21 | 长春石油化学股份有限公司 | 聚合物膜及其应用 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4851964A (ja) | 1971-10-27 | 1973-07-21 | ||
JPS6021834A (ja) | 1983-07-12 | 1985-02-04 | Mitsubishi Monsanto Chem Co | 合せガラス用切裁中間膜 |
JPS63195551U (ja) * | 1987-06-04 | 1988-12-15 | ||
JPH06210729A (ja) | 1993-01-19 | 1994-08-02 | Sekisui Chem Co Ltd | 熱可塑性樹脂エンボスシートの製造方法 |
JPH0940444A (ja) | 1994-11-07 | 1997-02-10 | Sekisui Chem Co Ltd | 合わせガラス用中間膜および合わせガラス |
JP2000178044A (ja) | 1998-10-09 | 2000-06-27 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2001019499A (ja) | 1999-07-01 | 2001-01-23 | Sekisui Chem Co Ltd | 合わせガラス用中間膜 |
WO2003033583A1 (de) | 2001-10-11 | 2003-04-24 | Ht Troplast Ag | Pvb-folie für verbundsicherheitsglas und verbundsicherheitsglas |
EP1235683B1 (de) | 1999-10-25 | 2003-08-20 | Ht Troplast Ag | Verfahren und folie zur herstellung von verbundsicherheitsscheiben |
JP2008156135A (ja) | 2006-12-21 | 2008-07-10 | Nippon Sheet Glass Co Ltd | 合わせガラスの製造方法 |
JP2010215493A (ja) * | 2009-02-18 | 2010-09-30 | Mitsubishi Plastics Inc | 合わせガラス用ポリエステルフィルム |
JP2010265161A (ja) * | 2009-04-16 | 2010-11-25 | Central Glass Co Ltd | プラスチックフィルム挿入合わせガラスの製造方法及びプラスチックフィルム挿入合わせガラス |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4851964U (ja) | 1971-10-22 | 1973-07-06 | ||
JPS61135740A (ja) | 1984-12-07 | 1986-06-23 | 帝人株式会社 | 安全ガラス |
US4575540A (en) * | 1984-12-21 | 1986-03-11 | Monsanto Company | Polyvinyl butyral sheet roughness control |
JPH0684943B2 (ja) | 1987-02-10 | 1994-10-26 | 日本鋼管株式会社 | 氷蓄熱槽内の結氷率の測定方法 |
JP3115191B2 (ja) | 1994-08-15 | 2000-12-04 | 明治乳業株式会社 | 冷凍ピッツァの製造方法 |
JPH09314645A (ja) | 1996-05-28 | 1997-12-09 | Sekisui Chem Co Ltd | 可塑剤を含む熱可塑性樹脂シートの製造方法 |
US6383647B1 (en) | 1998-09-30 | 2002-05-07 | Sekisui Chemical Co., Ltd. | Intermediate film for laminated glass and laminated glass |
US7642307B2 (en) * | 2002-03-12 | 2010-01-05 | E.I. Du Pont De Nemours And Company | Low-color stiff PVB laminates |
US20060263608A1 (en) * | 2002-08-14 | 2006-11-23 | Choi Chul W | Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same |
JP3970915B2 (ja) * | 2005-09-29 | 2007-09-05 | 日東電工株式会社 | 光学機能フィルムの製造方法 |
US7625627B2 (en) * | 2005-12-30 | 2009-12-01 | E.I. Du Pont De Nemours And Company | Decorative polyvinyl butyral solar control laminates |
US20080286542A1 (en) * | 2007-05-17 | 2008-11-20 | Richard Allen Hayes | Decorative safety glass |
JP4478990B2 (ja) * | 2007-09-21 | 2010-06-09 | ヤマトミシン製造株式会社 | ミシンの送油ポンプ装置 |
DE102007000816A1 (de) * | 2007-10-05 | 2009-04-09 | Kuraray Europe Gmbh | Photovoltaikmodule mit weichmacherhaltigen Folien auf Basis von Polyvinylacetal mit hohem spezifischen Widerstand |
DE102007055733A1 (de) | 2007-12-07 | 2009-06-10 | Kuraray Europe Gmbh | Photovoltaikmodule mit reflektierenden Klebefolien |
EP2234807B1 (en) * | 2007-12-18 | 2011-06-15 | Kuraray Co., Ltd. | Interlayer film for laminated glass, method for manufacturing the same, and laminated glass containing the same |
JPWO2010005030A1 (ja) * | 2008-07-11 | 2012-01-05 | 三菱樹脂株式会社 | 太陽電池用バックシート |
EP2153989B1 (de) * | 2008-08-01 | 2021-09-29 | Kuraray Europe GmbH | Mehrschichtfolien aus weichmacherhaltigem Polyvinylacetal mit schalldämpfenden Eigenschaften |
-
2012
- 2012-03-29 RU RU2013147980/05A patent/RU2013147980A/ru not_active Application Discontinuation
- 2012-03-29 JP JP2012538127A patent/JP5155497B2/ja not_active Expired - Fee Related
- 2012-03-29 US US14/008,745 patent/US9431560B2/en not_active Expired - Fee Related
- 2012-03-29 MX MX2013011187A patent/MX2013011187A/es active IP Right Grant
- 2012-03-29 EP EP12763997.9A patent/EP2692781A4/en not_active Withdrawn
- 2012-03-29 BR BR112013024559A patent/BR112013024559A2/pt not_active IP Right Cessation
- 2012-03-29 CN CN201510146229.0A patent/CN104816522B/zh not_active Expired - Fee Related
- 2012-03-29 WO PCT/JP2012/058406 patent/WO2012133668A1/ja active Application Filing
- 2012-03-29 KR KR1020137028646A patent/KR101375204B1/ko active IP Right Grant
- 2012-03-29 CN CN201280015902.1A patent/CN103476841B/zh not_active Expired - Fee Related
- 2012-12-06 JP JP2012267633A patent/JP5301724B2/ja not_active Expired - Fee Related
-
2013
- 2013-09-27 MX MX2015009768A patent/MX336684B/es unknown
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4851964A (ja) | 1971-10-27 | 1973-07-21 | ||
JPS6021834A (ja) | 1983-07-12 | 1985-02-04 | Mitsubishi Monsanto Chem Co | 合せガラス用切裁中間膜 |
JPS63195551U (ja) * | 1987-06-04 | 1988-12-15 | ||
JPH06210729A (ja) | 1993-01-19 | 1994-08-02 | Sekisui Chem Co Ltd | 熱可塑性樹脂エンボスシートの製造方法 |
JPH0940444A (ja) | 1994-11-07 | 1997-02-10 | Sekisui Chem Co Ltd | 合わせガラス用中間膜および合わせガラス |
JP2000178044A (ja) | 1998-10-09 | 2000-06-27 | Sekisui Chem Co Ltd | 合わせガラス用中間膜及び合わせガラス |
JP2001019499A (ja) | 1999-07-01 | 2001-01-23 | Sekisui Chem Co Ltd | 合わせガラス用中間膜 |
EP1235683B1 (de) | 1999-10-25 | 2003-08-20 | Ht Troplast Ag | Verfahren und folie zur herstellung von verbundsicherheitsscheiben |
WO2003033583A1 (de) | 2001-10-11 | 2003-04-24 | Ht Troplast Ag | Pvb-folie für verbundsicherheitsglas und verbundsicherheitsglas |
JP2008156135A (ja) | 2006-12-21 | 2008-07-10 | Nippon Sheet Glass Co Ltd | 合わせガラスの製造方法 |
JP2010215493A (ja) * | 2009-02-18 | 2010-09-30 | Mitsubishi Plastics Inc | 合わせガラス用ポリエステルフィルム |
JP2010265161A (ja) * | 2009-04-16 | 2010-11-25 | Central Glass Co Ltd | プラスチックフィルム挿入合わせガラスの製造方法及びプラスチックフィルム挿入合わせガラス |
Non-Patent Citations (1)
Title |
---|
See also references of EP2692781A1 |
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Also Published As
Publication number | Publication date |
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KR20130130870A (ko) | 2013-12-02 |
JP5301724B2 (ja) | 2013-09-25 |
MX2013011187A (es) | 2013-12-16 |
MX336684B (es) | 2016-01-27 |
JP5155497B2 (ja) | 2013-03-06 |
RU2013147980A (ru) | 2015-05-10 |
US20140020759A1 (en) | 2014-01-23 |
EP2692781A1 (en) | 2014-02-05 |
CN103476841A (zh) | 2013-12-25 |
CN104816522B (zh) | 2017-09-15 |
EP2692781A4 (en) | 2014-09-03 |
CN103476841B (zh) | 2015-04-29 |
JP2013091793A (ja) | 2013-05-16 |
US9431560B2 (en) | 2016-08-30 |
JPWO2012133668A1 (ja) | 2014-07-28 |
BR112013024559A2 (pt) | 2016-12-20 |
KR101375204B1 (ko) | 2014-03-17 |
CN104816522A (zh) | 2015-08-05 |
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