WO2011040444A1 - 合わせガラス用中間膜及び合わせガラス - Google Patents
合わせガラス用中間膜及び合わせガラス Download PDFInfo
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- WO2011040444A1 WO2011040444A1 PCT/JP2010/066916 JP2010066916W WO2011040444A1 WO 2011040444 A1 WO2011040444 A1 WO 2011040444A1 JP 2010066916 W JP2010066916 W JP 2010066916W WO 2011040444 A1 WO2011040444 A1 WO 2011040444A1
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- laminated glass
- weight
- interlayer film
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- particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10614—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 comprising particles for purposes other than dyeing
- B32B17/10633—Infrared radiation absorbing or reflecting agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10651—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 comprising colorants, e.g. dyes or pigments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10678—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 comprising UV absorbers or stabilizers, e.g. antioxidants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, 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
- 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.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
Definitions
- the present invention relates to an interlayer film for laminated glass used for laminated glass such as an automobile or a building, and more specifically, an interlayer film for laminated glass capable of enhancing the heat shielding property of laminated glass, and the interlayer film for laminated glass. It is related with the laminated glass using.
- Laminated glass is superior in safety even if it is damaged by an external impact and the amount of glass fragments scattered is small. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc.
- the laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates. High heat-insulating properties are required for laminated glass used in such vehicle and building openings.
- Infrared rays having a wavelength longer than 780 nm longer than visible light have a smaller amount of energy than ultraviolet rays.
- infrared rays have a large thermal effect, and once infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays. Therefore, in order to improve the heat shielding property of the laminated glass, it is necessary to sufficiently block infrared rays.
- heat shielding particles such as tin-doped indium oxide particles (ITO particles) or antimony-doped tin oxide particles (ATO particles) have been used for interlayer films for laminated glass. ing.
- the following Patent Document 1 includes 96.5 to 99.6% by weight of a synthetic resin and 0.2 to 3.0% by weight of an ultraviolet absorber. And an interlayer film for laminated glass containing 0.02 to 0.5% by weight of a yellow dye.
- ITO particles or ATO particles do not absorb near infrared rays sufficiently. Therefore, it is difficult to greatly enhance the heat shielding property of the laminated glass only by adding ITO particles or ATO particles to the intermediate film.
- CARB California Air Resources Board
- the CARB regulates the heat energy that passes through the laminated glass and flows into the automobile, reducing the fuel consumed by the air conditioner and reducing the fuel consumption of the automobile. I was considering improving it. Specifically, the CARB had planned to introduce cool car regulations (Cool Cars Standards).
- Tts Total Solar Transmission
- the Tts is an index of heat ray shielding.
- heat-reflective laminated glass using a metal thin film or heat ray reflective PET generally referred to as a thermal reaction type, reflects not only infrared rays but also communication waves in the communication wavelength region.
- the heat ray reflective laminated glass is used for the windshield, it is necessary to cut out the heat ray reflective portion in order to cope with many sensors.
- the average Tts of the entire windshield using the heat ray reflective laminated glass having a Tts of 50% is about 53%. Therefore, in a type of laminated glass that transmits communication waves and absorbs infrared rays, Tts was expected to be allowed up to 53%.
- the laminated glass is required not only to have a high heat shielding property but also to have a high visible light transmittance (Visible Transmittance).
- the visible light transmittance is desirably 70% or more. That is, it is required to increase the heat shielding property while keeping the visible light transmittance high.
- An object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass having a low Tts and a high visible light transmittance, and a laminated glass using the interlayer film for laminated glass.
- thermoplastic resin a plasticizer, a heat shielding particle, a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound, and a yellow dye
- the content of the heat shielding particles is in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and the total content of the components and the yellow dye is 0.25 parts by weight or less.
- An interlayer film for laminated glass is provided.
- the heat shielding particles are preferably metal oxide particles.
- the content of the component is in the range of 0.001 to 0.04 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the content of the yellow dye is in the range of 0.005 to 0.24 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- thermoplastic resin a plasticizer, a thermal barrier particle, at least one component of a phthalocyanine compound, a naphthalocyanine compound and an anthocyanin compound, and a yellow dye.
- an interlayer film for laminated glass containing the heat shielding particles at a rate of 0.05 to 12 g / m 2 and the components and the yellow dye at a rate of 1.5 g / m 2 or less in total. Is done.
- the heat shielding particles are preferably metal oxide particles.
- the component is contained at a ratio of 0.005 to 0.2 g / m 2 .
- the yellow dye is contained at a ratio of 0.025 to 1.45 g / m 2 .
- the laminated glass according to the present invention comprises first and second laminated glass constituent members and an intermediate film sandwiched between the first and second laminated glass constituent members, and the intermediate film comprises: An interlayer film for laminated glass constituted according to the present invention is included or the interlayer film for laminated glass.
- the interlayer film sandwiched between the first and second laminated glass constituent members is the laminated glass configured according to the present invention.
- the interlayer film for laminated glass according to the present invention contains a thermoplastic resin, a plasticizer, heat shielding particles, at least one component of a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound, and a yellow dye. Since the content of the heat shielding particles relative to the thermoplastic resin or in the interlayer film for laminated glass and the total content of the components and the yellow dye are within the specific range, the Tts is sufficiently low and the visible light A laminated glass having a sufficiently high transmittance can be obtained.
- FIG. 1 is a cross-sectional view schematically showing an example of laminated glass using an interlayer film for laminated glass according to an embodiment of the present invention.
- the interlayer film for laminated glass according to the present invention contains a thermoplastic resin, a plasticizer, heat shielding particles, at least one component of a phthalocyanine compound, a naphthalocyanine compound, and an anthocyanin compound, and a yellow dye.
- a phthalocyanine compound a phthalocyanine compound, a naphthalocyanine compound, and an anthocyanin compound, and a yellow dye.
- component X at least one component of the phthalocyanine compound, naphthalocyanine compound and anthracocyanine compound.
- the content of the heat shielding particles is in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and the component X and the yellow color are added.
- the total content of the dye is 0.25 parts by weight or less.
- the interlayer film for laminated glass according to the present invention contains the heat shielding particles in a ratio of 0.05 to 12 g / m 2 and the total of the component X and the yellow dye is 1.5 g / m 2 or less. It contains in the ratio.
- the main feature of the present invention is that the heat shielding particles, the component X and the yellow dye are used in combination, and the content of the thermoplastic resin or the content ratio in the interlayer film for laminated glass is the above. To meet the relationship. Thus, a laminated glass having a sufficiently low Tts (Total Solar Transmission) and a sufficiently high visible light transmittance (Visible Transmission) can be obtained. That is, by using the interlayer film for laminated glass according to the present invention, the heat shielding property and transparency of the laminated glass can be enhanced.
- the interlayer film for laminated glass for example, the required performance of cool car regulations (Cool Cars Standards) planned to be introduced by the California Air Resources Board (CARB (California Air Resources Board)) is achieved.
- a laminated glass can be obtained.
- the Tts of the laminated glass can be 53% or less.
- the visible light transmittance of the laminated glass can be 70% or more.
- the performance of the Tts and the visible light transmittance is the performance required by the cool car regulation.
- the Tts is measured, for example, by a measurement method defined by cool car regulations that are scheduled to be introduced.
- the visible light transmittance is measured in accordance with, for example, JIS R3211 (1998).
- thermoplastic resin The said thermoplastic resin contained in the intermediate film for laminated glasses which concerns on this invention is not specifically limited.
- a conventionally well-known thermoplastic resin can be used as said thermoplastic resin.
- the said thermoplastic resin only 1 type may be used and 2 or more types may be used together.
- thermoplastic resin examples include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin. Thermoplastic resins other than these may be used.
- the thermoplastic resin is preferably a polyvinyl acetal resin.
- the adhesive force of the interlayer film to the laminated glass constituent member can be further increased.
- the polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde.
- the polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate.
- the degree of saponification of the polyvinyl alcohol is generally in the range of 80 to 99.8 mol%.
- the preferable lower limit of the polymerization degree of the polyvinyl alcohol is 200, the more preferable lower limit is 500, the preferable upper limit is 3,000, and the more preferable upper limit is 2,500.
- the said polymerization degree is too low, there exists a tendency for the penetration resistance of a laminated glass to fall.
- the said polymerization degree is too high, shaping
- the aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde.
- Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde.
- propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, n-butyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, and n-butyraldehyde is more preferable.
- the said aldehyde only 1 type may be used and 2 or more types may be used together.
- the hydroxyl group content (hydroxyl content) of the polyvinyl acetal resin is preferably in the range of 15 to 40 mol%.
- the more preferable lower limit of the hydroxyl group content is 18 mol%, and the more preferable upper limit is 35 mol%. If the hydroxyl group content is too low, the adhesion of the interlayer film may be lowered. On the other hand, if the hydroxyl group content is too high, the flexibility of the intermediate film is lowered, and problems in handling the intermediate film are likely to occur.
- the content of hydroxyl groups in the polyvinyl acetal resin is a value obtained by dividing the amount of ethylene groups to which the hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%). .
- the amount of the ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of polyvinyl alcohol as a raw material is bonded in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. it can.
- the preferable lower limit of the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is 0.1 mol%, the more preferable lower limit is 0.3 mol%, the still more preferable lower limit is 0.5 mol%, and the preferable upper limit is 30 mol%.
- a more preferred upper limit is 25 mol%, a still more preferred upper limit is 20 mol%, and a particularly preferred upper limit is 10 mol%. If the degree of acetylation is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be reduced. If the degree of acetylation is too high, the moisture resistance of the interlayer film may be lowered.
- the degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, It is a value indicating the mole fraction obtained by dividing by the percentage (mol%).
- the amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.
- the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60 mol%, the more preferable lower limit is 63 mol%, the preferable upper limit is 85 mol%, the more preferable upper limit is 75 mol%, and the further preferable upper limit is 70 mol%. If the degree of acetalization is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be low. When the said acetalization degree is too high, reaction time required in order to manufacture polyvinyl acetal resin may become long.
- the degree of acetalization is a value obtained by dividing the amount of ethylene group to which the acetal group is bonded by the total amount of ethylene groups in the main chain, as a percentage (mol%).
- the degree of acetalization was determined by measuring the amount of acetyl groups and the amount of vinyl alcohol (hydroxyl content) by a method based on JIS K6728 “Testing methods for polyvinyl butyral”, and calculating the mole fraction from the obtained measurement results. Then, it can be calculated by subtracting the amount of acetyl groups and the amount of vinyl alcohol from 100 mol%.
- the degree of acetalization (degree of butyralization) and the amount of acetyl group can be calculated from the results measured by a method in accordance with JIS K6728 “Testing methods for polyvinyl butyral”.
- the said plasticizer contained in the intermediate film for laminated glasses which concerns on this invention is not specifically limited.
- a conventionally known plasticizer can be used as the plasticizer.
- the said plasticizer only 1 type may be used and 2 or more types may be used together.
- plasticizer examples include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphate plasticizers such as organic phosphate plasticizers and organic phosphorous acid plasticizers. It is done. Of these, organic ester plasticizers are preferred.
- the plasticizer is preferably a liquid plasticizer.
- the monobasic organic acid ester is not particularly limited.
- examples include esters.
- Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol.
- Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid, and decylic acid.
- the polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms.
- Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.
- the organic ester plasticizer is not particularly limited, and triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n- Octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di -2-Ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol Rudi-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, te
- the organic phosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
- the plasticizer is preferably at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH), and triethylene glycol di-2 More preferred is ethylhexanoate.
- the interlayer film for laminated glass according to the present invention contains at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH) as the plasticizer.
- 3GO triethylene glycol di-2-ethylhexanoate
- 3GH triethylene glycol di-2-ethylbutyrate
- it contains triethylene glycol di-2-ethylhexanoate, and more preferably.
- the content of the plasticizer in the interlayer film for laminated glass according to the present invention is not particularly limited.
- a preferable lower limit of the plasticizer content is 25 parts by weight, a more preferable lower limit is 30 parts by weight, a further preferable lower limit is 35 parts by weight, and a preferable upper limit is 75 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the upper limit is 60 parts by weight, and a more preferable upper limit is 50 parts by weight.
- the interlayer film for laminated glass according to the present invention includes heat shielding particles.
- the heat shielding particles are preferably particles formed of a metal oxide. Only 1 type may be used for a heat-shielding particle and 2 or more types may be used together.
- Infrared rays having a wavelength longer than that of visible light of 780 nm or more have a smaller energy amount than ultraviolet rays.
- infrared rays have a large thermal effect, and once infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays.
- heat shielding particles By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked.
- a heat shielding particle means the particle
- heat shielding particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles).
- Aluminum doped zinc oxide particles (AZO particles), niobium doped titanium oxide particles, sodium doped tungsten oxide particles, cesium doped tungsten oxide particles, thallium doped tungsten oxide particles, rubidium doped tungsten oxide particles, tin doped indium oxide particles (ITO particles)
- Metal oxide particles such as tin-doped zinc oxide particles and silicon-doped zinc oxide particles, and lanthanum hexaboride (LaB 6 ) particles. Heat shielding particles other than these may be used.
- the heat shielding particles are preferably metal oxide particles, more preferably ATO particles, GZO particles, ITO particles, or cesium-doped tungsten oxide particles, and ITO particles. More preferably.
- the lattice constant of the crystal of the ITO particles is in the range of 10.11 to 10.16 in order to sufficiently improve the heat ray shielding property.
- the crystal lattice constant of the ITO particle crystal is included in the range of 10.11 to 10.16%, and the crystal lattice constant of the ITO particle crystal used in Examples described later is also 10.11 to 10. It is included in the range of 16cm.
- the preferred lower limit of the average particle diameter of the heat shielding particles is 10 nm, the more preferred lower limit is 20 nm, the preferred upper limit is 100 nm, the more preferred upper limit is 80 nm, and the still more preferred upper limit. Is 50 nm.
- the average particle diameter satisfies the above preferable lower limit
- the heat ray shielding property can be sufficiently enhanced.
- the transparency of the laminated glass can be increased.
- the above “average particle diameter” indicates the volume average particle diameter.
- the average particle diameter can be measured using a particle size distribution measuring device (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.
- the content of the heat shield particles is preferably in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the interlayer film for laminated glass according to the present invention preferably contains the heat shielding particles at a rate of 0.05 to 12 g / m 2 .
- the content of the heat shield particles is in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin, or the interlayer film for laminated glass contains the heat shield particles. It may be contained at a rate of 0.05 to 12 g / m 2 .
- the Tts can be sufficiently obtained.
- the visible light transmittance can be sufficiently increased.
- the Tts can be 53% or less, and the visible light transmittance can be 70% or more.
- the content of the heat shielding particles is in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and the interlayer film for laminated glass is the heat shielding particles. May be contained at a rate of 0.05 to 12 g / m 2 .
- the haze value of the laminated glass obtained will become high.
- the more preferable lower limit of the content of the heat shielding particles is 0.1 parts by weight, the still more preferable lower limit is 0.14 parts by weight, and the still more preferable lower limit is 0.5 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- An even more preferred lower limit is 0.55 parts by weight, a particularly preferred lower limit is 0.6 parts by weight, a more preferred upper limit is 1.5 parts by weight, a still more preferred upper limit is 1.2 parts by weight, and a still more preferred upper limit is 1 part by weight.
- Parts, even more preferable upper limit is 0.9 parts by weight, and particularly preferable upper limit is 0.8 parts by weight.
- the more preferable lower limit of the content of the heat shielding particles in the interlayer film for laminated glass is 0.5 g / m 2
- the still more preferable lower limit is 0.8 g / m 2
- the still more preferable lower limit is 1.2 g / m 2
- especially preferred lower limit is 2 g / m 2
- more preferable upper limit is 9 g / m 2
- even more preferred upper limit is 8 g / m 2
- An even more preferred upper limit is 5 g / m 2
- a particularly preferred upper limit is 4 g / m 2 .
- the component X is at least one component among phthalocyanine compounds, naphthalocyanine compounds, and anthracocyanine compounds.
- the component X is not particularly limited.
- conventionally known phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds can be used.
- As for the said component X only 1 type may be used and 2 or more types may be used together.
- the combination of the heat shielding particles, the component X and the yellow dye can sufficiently block infrared rays (heat rays).
- Examples of the component X include phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, a derivative of naphthalocyanine, an anthocyanin, and an anthocyanin derivative.
- the phthalocyanine compound and the phthalocyanine derivative preferably each have a phthalocyanine skeleton.
- the naphthalocyanine compound and the naphthalocyanine derivative preferably each have a naphthalocyanine skeleton. It is preferable that each of the anthocyanin compound and the derivative of the anthracyanine has an anthracyanine skeleton.
- the component X is at least one selected from the group consisting of phthalocyanine, phthalocyanine derivatives, naphthalocyanine, and naphthalocyanine derivatives. Preferably, it is at least one of phthalocyanine and phthalocyanine derivatives. Since the said component X can fully improve the heat-shielding property, it is preferable that the said component X contains a metal, and it is more preferable that it contains copper. The component X preferably contains a metal or copper as a central metal. Moreover, since the shielding property of a heat ray can be improved further, the said component X is preferably a naphthalocyanine compound containing a metal, and more preferably a naphthalocyanine compound containing copper.
- the total content of the component X and the yellow dye is preferably 0.25 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.
- the intermediate film for laminated glasses which concerns on this invention contains the said component X and the said yellow dye in the ratio of 1.5 g / m ⁇ 2 > or less in total.
- the total content of the component X and the yellow dye is 0.25 parts by weight or less, or the interlayer film for laminated glass is the component X and What is necessary is just to contain the said yellow dye in the ratio of 1.5 g / m ⁇ 2 > or less in total.
- the total content of the component X and the yellow dye relative to 100 parts by weight of the thermoplastic resin, and the total content of the component X and the yellow dye in the interlayer film for laminated glass are not more than the above values.
- the Tts can be made sufficiently low, and the visible light transmittance can be made sufficiently high.
- the Tts can be 53% or less, and the visible light transmittance can be 70% or more.
- the total content of the component X and the yellow dye is 0.25 parts by weight or less
- the interlayer film for laminated glass is the component X
- the preferable lower limit of the total content of the component X and the yellow dye is 0.005 parts by weight with respect to 100 parts by weight of the thermoplastic resin, more preferably 0.03 parts by weight, and still more preferably 0.04 parts by weight.
- Parts by weight, particularly preferred lower limit is 0.07 parts by weight
- preferred upper limit is 0.24 parts by weight
- more preferred upper limit is 0.2 parts by weight
- still more preferred upper limit is 0.18 parts by weight
- particularly preferred upper limit is 0.00. 15 parts by weight.
- the particularly preferred lower limit is 0.25 g / m 2
- the preferred upper limit is 1.5 g / m 2
- the more preferred upper limit is 1.2 g / m 2
- the still more preferred upper limit is 1 g / m 2
- the particularly preferred upper limit is 0.00. 7 g / m 2 .
- the content of the component X is preferably in the range of 0.001 to 0.04 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the interlayer film for laminated glass according to the present invention preferably contains the component X at a rate of 0.005 to 0.2 g / m 2 .
- the Tts can be further reduced, and the above The visible light transmittance can be further increased.
- the more preferable lower limit of the content of the component X is 0.002 parts by weight, the still more preferable lower limit is 0.005 parts by weight, and the particularly preferable lower limit is 0.01 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- a more preferred upper limit is 0.025 parts by weight, a still more preferred upper limit is 0.022 parts by weight, and a particularly preferred upper limit is 0.02 parts by weight.
- a more preferred lower limit of the content of the component X in the interlayer film for a laminated glass is 0.01 g / m 2, still more preferred lower limit 0.028 g / m 2, especially preferred lower limit is 0.055 g / m 2, more a preferred upper limit is 0.15 g / m 2, still more preferred upper limit 0.13 g / m 2, particularly preferred upper limit is 0.12 g / m 2.
- the Tts can be further reduced.
- the visible light transmittance can be further increased.
- the yellow dye contained in the interlayer film for laminated glass according to the present invention is not particularly limited. Only 1 type of yellow dye may be used and 2 or more types may be used together.
- the yellow dye preferably absorbs transmitted light of 380 to 500 nm, more preferably absorbs transmitted light of 390 to 480 nm, more preferably absorbs transmitted light of 395 to 460 nm. Is more preferable, and it is particularly preferable to effectively absorb transmitted light of 400 to 450 nm.
- the Tts can be further reduced by using a yellow dye.
- the preferable lower limit of the maximum absorption wavelength of the yellow dye is 380 nm, the more preferable lower limit is 390 nm, the still more preferable lower limit is 395 nm, the particularly preferable lower limit is 400 nm, and the preferable upper limit is 500 nm, more preferable.
- the upper limit is 480 nm, the more preferable upper limit is 460 nm, and the particularly preferable upper limit is 450 nm.
- the maximum absorption wavelength of the yellow dye is a solution in which 0.01 part by weight of the yellow dye is dissolved in 100 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) (cell length: 1 mm, It can be measured with a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech) using a quartz cell.
- 3GO triethylene glycol di-2-ethylhexanoate
- the yellow dye examples include anthraquinone dye, quinoline dye, isoquinoline dye, monoazo dye, disazo dye, quinophthalone dye, perylene dye, triphenylmethane dye, and methine dye.
- anthraquinone dyes are preferable from the viewpoint of further improving the heat shielding property of the interlayer film for laminated glass.
- the yellow dye content is preferably in the range of 0.005 to 0.24 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- the interlayer film for laminated glass according to the present invention preferably contains the yellow dye at a rate of 0.025 to 1.45 g / m 2 .
- the Tts can be further reduced, and The visible light transmittance can be further increased.
- the more preferable lower limit of the yellow dye content is 0.01 parts by weight, the still more preferable lower limit is 0.04 parts by weight, and the particularly preferable lower limit is 0.06 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- a more preferred upper limit is 0.2 parts by weight, a still more preferred upper limit is 0.15 parts by weight, and a particularly preferred upper limit is 0.1 parts by weight.
- the Tts can be further reduced.
- the visible light transmittance can be further increased.
- the interlayer film for laminated glass according to the present invention includes an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescent whitening as necessary.
- An additive such as an agent and an infrared absorber may be contained.
- the interlayer film for laminated glass according to the present invention preferably contains an antioxidant.
- the interlayer film for laminated glass according to the present invention preferably contains an ultraviolet absorber.
- FIG. 1 An example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is typically shown with sectional drawing.
- a laminated glass 1 shown in FIG. 1 includes an intermediate film 2 and first and second laminated glass constituting members 3 and 4.
- the intermediate film 2 is used to obtain a laminated glass.
- the interlayer film 2 is an interlayer film for laminated glass.
- the intermediate film 2 is sandwiched between the first and second laminated glass constituting members 3 and 4. Therefore, the laminated glass 1 is constituted by laminating the first laminated glass constituting member 3, the intermediate film 2, and the second laminated glass constituting member 4 in this order.
- the intermediate film 2 contains a thermoplastic resin, a plasticizer, the heat shielding particles 5, the component X, and a yellow dye.
- the intermediate film 2 contains a plurality of heat shielding particles 5.
- the intermediate film 2 may have a multilayer structure of two or more layers.
- the first and second laminated glass constituent members 3 and 4 include glass plates and PET (polyethylene terephthalate) films.
- the laminated glass 1 includes not only laminated glass in which an intermediate film is sandwiched between two glass plates, but also laminated glass in which an intermediate film is sandwiched between a glass plate and a PET film or the like.
- the laminated glass 1 is a laminated body provided with a glass plate, and preferably at least one glass plate is used.
- the glass plate examples include inorganic glass and organic glass.
- the inorganic glass examples include float plate glass, heat ray absorbing plate glass, heat ray reflecting plate glass, polished plate glass, mold plate glass, mesh plate glass, wire plate glass, and green glass.
- a heat ray absorbing plate glass as said inorganic glass, and it is more preferable to use the heat ray absorbing plate glass based on JISR3208.
- the organic glass is a synthetic resin glass substituted for inorganic glass.
- Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates.
- the poly (meth) acrylic resin plate examples include a polymethyl (meth) acrylate plate.
- the thickness of the first and second laminated glass constituting members 3 and 4 is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. Moreover, when the laminated glass structural members 3 and 4 are glass plates, the thickness of the glass plates is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass constituting members 3 and 4 are PET films, the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.
- the manufacturing method of the laminated glass 1 is not particularly limited.
- the intermediate film 2 is sandwiched between the first and second laminated glass constituent members 3 and 4 and passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure.
- the air remaining between the laminated glass constituent members 3 and 4 and the intermediate film 2 is deaerated. Thereafter, it is pre-adhered at about 70 to 110 ° C. to obtain a laminate.
- the laminate is put in an autoclave or pressed and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa.
- the laminated glass 1 can be obtained.
- Laminated glass 1 can be used for automobiles, railway vehicles, aircraft, ships and buildings.
- the laminated glass 1 can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.
- the laminated glass 1 can be used for other purposes. Since the Tts is low and the visible light transmittance is high, the laminated glass 1 is suitably used for an automobile.
- the Tts of the laminated glass 1 is preferably 53% or less, preferably 50% or less, and preferably 40% or less. Furthermore, from the viewpoint of obtaining a laminated glass that is more excellent in transparency, the visible light transmittance of the laminated glass 1 is preferably 70% or more.
- interlayer film for laminated glass in the plane direction of the interlayer film for laminated glass (interlayer film body for laminated glass), all the regions may be the interlayer film for laminated glass according to the present invention, and only some of the regions according to the present invention are laminated.
- An interlayer film for glass may be used.
- an intermediate film obtained by changing a part of the conventional interlayer film for laminated glass to the interlayer film for laminated glass according to the present invention is also included in the present invention.
- the interlayer film for laminated glass according to the present invention may be an interlayer film for laminated glass used in a partial region of the interlayer film for laminated glass (interlayer film body for laminated glass).
- Example 1 (1) Preparation of dispersion 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), 0.28 parts by weight of ITO particles (manufactured by Mitsubishi Materials), naphthalocyanine compound (“FF- IRSORB 203 ”) 0.004 parts by weight and 0.234 parts by weight of a yellow dye (anthraquinone dye, maximum absorption wavelength 450 nm," ORACE Yellow GHS “manufactured by Ciba Japan Co., Ltd.) and phosphorus as a dispersant. After adding the acid ester compound, it was mixed in a horizontal microbead mill to obtain a mixed solution.
- a yellow dye anthraquinone dye, maximum absorption wavelength 450 nm
- ORACE Yellow GHS manufactured by Ciba Japan Co., Ltd.
- FF-IRSORB 203 manufactured by Fuji Film Co., Ltd.
- the obtained interlayer film for laminated glass was sandwiched by transparent glass (length 30 cm ⁇ width 30 cm ⁇ thickness 2.5 mm) from both ends to obtain a laminate.
- This laminated body is put in a rubber bag, deaerated at a vacuum degree of 2.6 kPa for 20 minutes, then transferred to an oven while being deaerated, and further kept at 90 ° C. for 30 minutes and vacuum-pressed to prepare a laminated body. Crimped.
- the laminated body temporarily bonded under pressure at 135 ° C. and a pressure of 1.2 MPa in an autoclave was pressed for 20 minutes to obtain a laminated glass 2.
- Examples 2 to 9 and Comparative Examples 1 to 5 A dispersion, an interlayer film for laminated glass, and laminated glasses 1 and 2 were produced in the same manner as in Example 1 except that the composition of the interlayer film for laminated glass was changed as shown in Table 1 below.
- Tts and Tds Solar Direct Transmission
- the Tts and the Tds of the obtained laminated glass 1 were measured.
- the Tts and the Tds were measured according to JIS R3106 (1998) using a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech).
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Abstract
Description
本発明に係る合わせガラス用中間膜は、熱可塑性樹脂と、可塑剤と、遮熱粒子と、フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも一種の成分と、黄色染料とを含有する。以下、フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも一種の成分を、成分Xと記載することがある。
本発明に係る合わせガラス用中間膜に含まれている上記熱可塑性樹脂は特に限定されない。上記熱可塑性樹脂として、従来公知の熱可塑性樹脂を用いることができる。上記熱可塑性樹脂は1種のみが用いられてもよく、2種以上が併用されてもよい。
本発明に係る合わせガラス用中間膜に含まれている上記可塑剤は特に限定されない。上記可塑剤として、従来公知の可塑剤を用いることができる。上記可塑剤は、1種のみが用いられてもよく、2種以上が併用されてもよい。
本発明に係る合わせガラス用中間膜は遮熱粒子を含む。該遮熱粒子は、金属の酸化物により形成された粒子であることが好ましい。遮熱粒子は1種のみが用いられてもよく、2種以上が併用されてもよい。
上記成分Xは、フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも一種の成分である。
本発明に係る合わせガラス用中間膜に含まれている黄色染料は、特に限定されない。黄色染料は1種のみが用いられてもよく、2種以上が併用されてもよい。黄色染料は、380~500nmの透過光を効果的に吸収することが好ましく、390~480nmの透過光を効果的に吸収することがより好ましく、395~460nmの透過光を効果的に吸収することが更に好ましく、400~450nmの透過光を効果的に吸収することが特に好ましい。この結果、上記遮熱粒子及び上記成分Xに加えて、黄色染料を用いることにより、上記Ttsをより一層低くすることができる。熱線の遮蔽性を充分に高めることができることから、黄色染料の極大吸収波長の好ましい下限は380nm、より好ましい下限は390nm、更に好ましい下限は395nm、特に好ましい下限は400nm、好ましい上限は500nm、より好ましい上限は480nm、更に好ましい上限は460nm、特に好ましい上限は450nmである。例えば、上記黄色染料の極大吸収波長は、トリエチレングリコールジ-2-エチルヘキサノエート(3GO)100重量部に対して、上記黄色染料0.01重量部を溶解させた溶液(セル長1mm、石英セル)を用いて、分光光度計(日立ハイテク社製「U-4100」)にて測定することができる。
本発明に係る合わせガラス用中間膜は、必要に応じて、紫外線吸収剤、酸化防止剤、光安定剤、難燃剤、帯電防止剤、顔料、染料、接着力調整剤、耐湿剤、蛍光増白剤及び赤外線吸収剤等の添加剤を含有していてもよい。本発明に係る合わせガラス用中間膜は、酸化防止剤を含有することが好ましい。本発明に係る合わせガラス用中間膜は、紫外線吸収剤を含有することが好ましい。
図1に、本発明の一実施形態に係る合わせガラス用中間膜を用いた合わせガラスの一例を模式的に断面図で示す。
(1)分散液の作製
トリエチレングリコールジ-2-エチルヘキサノエート(3GO)40重量部、ITO粒子(三菱マテリアル社製)0.28重量部、ナフタロシアニン化合物(富士フィルム社製「FF-IRSORB 203」)0.004重量部、及び、黄色染料(アンスラキノン染料、極大吸収波長450nm、チバ・ジャパン社製「ORACET Yellow GHS」)0.234重量部を混合し、さらに、分散剤としてリン酸エステル化合物を添加した後、水平型のマイクロビーズミルにて混合し、混合液を得た。その後、混合液にアセチルアセトン0.1重量部を撹拌下で添加し、分散液を作製した。分散液中のITO粒子の体積平均粒径は35nmであった。なお、ナフタロシアニン化合物(富士フィルム社製「FF-IRSORB 203」)は銅を含有している。
ポリビニルブチラール樹脂(ブチラール化度68.5モル%、水酸基の含有率30.5モル%)100重量部に対し、得られた分散液全量を添加し、ミキシングロールで充分に溶融混練した後、押出機を用いて押出して、厚み0.76mmの中間膜を得た。
得られた合わせガラス用中間膜を、その両端からJIS R3208に準拠した2枚の熱線吸収板ガラス(縦30cm×横30cm×厚さ2.0mm)で挟み込み、積層体を得た。この積層体をゴムバック内に入れ、2.6kPaの真空度で20分間脱気した後、脱気したままオーブン内に移し、更に90℃で30分間保持して真空プレスし、積層体を予備圧着した。オートクレーブ中で135℃及び圧力1.2MPaの条件で、仮圧着された積層体を20分間圧着し、合わせガラス1を得た。
合わせガラス用中間膜の組成を下記の表1に示すように変更したこと以外は、実施例1と同様にして、分散液、合わせガラス用中間膜、及び、合わせガラス1,2を作製した。
(1)Tts、及び、Tds(Solar Direct Transmittance)の測定
上記クールカー規制により定められた測定方法に従って、得られた合わせガラス1の上記Tts及び上記Tdsを測定した。具体的には、分光光度計(日立ハイテク社製「U-4100」)を用いて、JIS R3106(1998)に準拠して、上記Tts及び上記Tdsを測定した。
分光光度計(日立ハイテク社製「U-4100」)を用いて、JIS R3211(1998)に準拠して、得られた合わせガラス1の波長380~780nmにおける上記可視光線透過率を測定した。
ヘーズメーター(東京電色社製「TC-HIIIDPK」)を用いて、JIS K6714に準拠して、得られた合わせガラス1のヘーズ値を測定した。
結果を下記の表1に示す。
なお、表1には合わせガラス1の測定結果を示しているが、合わせガラス2に関しても同様に、Ttsが低く、かつ可視光線透過率が高い合わせガラスを得ることができた。
2…合わせガラス用中間膜
3…第1の合わせガラス構成部材
4…第2の合わせガラス構成部材
5…遮熱粒子
Claims (10)
- 熱可塑性樹脂と、
可塑剤と、
遮熱粒子と、
フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも一種の成分と、
黄色染料とを含有し、
前記熱可塑性樹脂100重量部に対して、前記遮熱粒子の含有量が0.01~2重量部の範囲内であり、かつ前記成分及び前記黄色染料の合計の含有量が0.25重量部以下である、合わせガラス用中間膜。 - 前記遮熱粒子は金属酸化物粒子である、請求項1に記載の合わせガラス用中間膜。
- 前記熱可塑性樹脂100重量部に対して、前記成分の含有量が0.001~0.04重量部の範囲内である、請求項1又は2に記載の合わせガラス用中間膜。
- 前記熱可塑性樹脂100重量部に対して、前記黄色染料の含有量が0.005~0.24重量部の範囲内である、請求項1又は2に記載の合わせガラス用中間膜。
- 熱可塑性樹脂と、
可塑剤と、
遮熱粒子と、
フタロシアニン化合物、ナフタロシアニン化合物及びアントラシアニン化合物の内の少なくとも一種の成分と、
黄色染料とを含有し、
前記遮熱粒子を0.05~12g/m2の割合で含有し、かつ前記成分及び前記黄色染料を合計で1.5g/m2以下の割合で含有する、合わせガラス用中間膜。 - 前記遮熱粒子は金属酸化物粒子である、請求項5に記載の合わせガラス用中間膜。
- 前記成分を0.005~0.2g/m2の割合で含有する、請求項5又は6に記載の合わせガラス用中間膜。
- 前記黄色染料を0.025~1.45g/m2の割合で含有する、請求項5又は6に記載の合わせガラス用中間膜。
- 第1,第2の合わせガラス構成部材と、
前記第1,第2の合わせガラス構成部材の間に挟み込まれた中間膜とを備え、
前記中間膜が、請求項1~8のいずれか1項に記載の合わせガラス用中間膜を含むか、該合わせガラス用中間膜である、合わせガラス。 - 前記第1,第2の合わせガラス構成部材の間に挟み込まれた前記中間膜が、前記合わせガラス用中間膜である、請求項9に記載の合わせガラス。
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EP20100820559 EP2484649B1 (en) | 2009-09-29 | 2010-09-29 | Intermediate film for laminated glass, and laminated glass |
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WO2013118890A1 (ja) * | 2012-02-10 | 2013-08-15 | 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 |
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JP2014088494A (ja) * | 2012-10-30 | 2014-05-15 | Sumitomo Metal Mining Co Ltd | 熱線遮蔽樹脂シート材および自動車 |
JP2014104643A (ja) * | 2012-11-27 | 2014-06-09 | Toray Ind Inc | 積層フィルムならびに遮熱部材 |
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Also Published As
Publication number | Publication date |
---|---|
EP2484649A1 (en) | 2012-08-08 |
EP2484649B1 (en) | 2013-12-18 |
JPWO2011040444A1 (ja) | 2013-02-28 |
US20120171479A1 (en) | 2012-07-05 |
JP5685084B2 (ja) | 2015-03-18 |
CN102574740A (zh) | 2012-07-11 |
EP2484649A4 (en) | 2013-02-27 |
CN103922614A (zh) | 2014-07-16 |
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