JP2015164892A - Intermediate film for laminated glass, laminated glass, and method for fitting laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass which has high thermochromic properties and high visible light transmittance.SOLUTION: The intermediate film for laminated glass according to the present invention includes a thermochromic layer, a first resin layer containing a thermoplastic resin, and a second resin layer containing a thermoplastic resin. The first resin layer is disposed on the side of a first surface of the thermochromic layer, and the second resin layer is disposed on the side of a second surface opposite to the first surface of the thermochromic layer. The infrared transmittance at a wavelength of 780-2,100 nm of the first resin layer is higher than the infrared transmittance at a wavelength of 780-2,100 nm of the second resin layer.

Description

  The present invention relates to an interlayer film for laminated glass used for laminated glass for automobiles and buildings. The present invention also relates to a laminated glass using the interlayer film for laminated glass and a method for attaching the laminated glass.

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. 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.

  In recent years, the performance required for laminated glass has also diversified, and a film having thermochromic properties that transmits infrared rays at a temperature lower than a certain temperature and exhibits heat shielding properties by blocking infrared rays at a temperature above a certain temperature is used. There is a need for interlayer films for laminated glass. As films having such thermochromic properties, Patent Documents 1 and 2 disclose thermochromic films containing vanadium dioxide or substituted vanadium dioxide in which some of the vanadium atoms of vanadium dioxide are substituted with other atoms. Yes. When the vanadium dioxide or the substituted vanadium dioxide is less than the phase transition temperature, both visible light and infrared light are transmitted. Above the phase transition temperature, only visible light is transmitted, and the thermochromic property is expressed by blocking the infrared light. ing.

JP 2000-233929 A JP 2004-346260 A

  A laminated glass using an intermediate film having thermochromic properties is required to achieve both high thermochromic properties and high visible light transmittance (Visible Transmittance). That is, in the laminated glass, it is necessary to increase the visible light transmittance while maintaining high thermochromic properties.

  However, when an interlayer film for laminated glass and a laminated glass are produced using a conventional film having thermochromic properties as described in Patent Documents 1 and 2, it is not possible to achieve both high thermochromic properties and high visible light transmittance. Sometimes.

  An object of the present invention is to provide an interlayer film for laminated glass having high thermochromic properties and high visible light transmittance, and a laminated glass using the interlayer film for laminated glass and a method for attaching the laminated glass. That is.

  According to a wide aspect of the present invention, a thermochromic layer, a first resin layer containing a thermoplastic resin, and a second resin layer containing a thermoplastic resin, the first resin layer being the thermostat. The first resin layer is disposed on the first surface side of the chromic layer, and the second resin layer is disposed on the second surface side opposite to the first surface of the thermochromic layer; An interlayer film for laminated glass is provided in which the infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the thermochromic layer includes a thermoplastic resin and vanadium dioxide particles or a part of vanadium atoms of vanadium dioxide, the group consisting of tungsten, molybdenum, niobium, and tantalum. Substituted vanadium dioxide particles substituted with at least one atom selected from.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the second resin layer includes metal oxide particles.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the metal oxide particles are tin-doped indium oxide particles or tungsten oxide particles.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin in the first resin layer is a polyvinyl acetal resin, and the thermoplastic resin in the second resin layer is polyvinyl. Acetal resin.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the first resin layer includes a plasticizer, and the second resin layer includes a plasticizer.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the first resin layer contains an ultraviolet shielding agent.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the second resin layer contains an ultraviolet shielding agent.

  According to a wide aspect of the present invention, the first laminated glass member, the second laminated glass member, and the interlayer film for laminated glass described above are provided, and the first laminated glass member and the second laminated glass are provided. The interlayer film for laminated glass is disposed between the members, the first laminated glass member is disposed outside the first resin layer in the interlayer film for laminated glass, and the There is provided a laminated glass in which the second laminated glass member is disposed outside the second resin layer in the interlayer film for laminated glass.

  In a specific aspect of the laminated glass according to the present invention, the infrared transmittance at a wavelength of 780 to 2100 nm of the first laminated glass member is higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second laminated glass member. .

  According to a wide aspect of the present invention, there is provided a method for attaching the laminated glass described above to an opening between an external space and an internal space into which heat rays are incident from the external space in a building or a vehicle. Attaching the laminated glass to the opening so that one laminated glass member is located on the outer space side and the second laminated glass member is located on the inner space side A method is provided.

  In the interlayer film for laminated glass according to the present invention, the first resin layer, the thermochromic layer, and the second resin layer are arranged in this order, and the wavelength of the first resin layer is 780. Since the infrared transmittance at ˜2100 nm is higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer, both the thermochromic property and the visible light transmittance of the laminated glass using the interlayer film for laminated glass are high. can do.

FIG. 1 is a partially cutaway sectional view showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a partially cutaway cross-sectional view showing a laminated glass using an interlayer film for laminated glass according to an embodiment of the present invention.

  Hereinafter, the present invention will be clarified by describing specific embodiments and examples of the present invention with reference to the drawings.

  In FIG. 1, the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is typically shown with a partially notched cross-sectional view.

  The intermediate film 1 shown in FIG. 1 is a multilayer intermediate film. The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass. The intermediate film 1 includes a thermochromic layer 2, a first resin layer 3 disposed on the first surface 2 a side of the thermochromic layer 2, and a second opposite to the first surface 2 a of the thermochromic layer 2. And a second resin layer 4 disposed on the surface 2b side. The first resin layer 3 is laminated on the first surface 2 a of the thermochromic layer 2. The second resin layer 4 is laminated on the second surface 2 b of the thermochromic layer 2. The thermochromic layer 2 is an intermediate layer and has thermochromic properties. The first and second resin layers 3 and 4 are surface layers in this embodiment. The thermochromic layer 2 is disposed between the first and second resin layers 3 and 4. The thermochromic layer 2 is sandwiched between the first and second resin layers 3 and 4. Therefore, the intermediate film 1 has a multilayer structure in which the first resin layer 3, the thermochromic layer 2, and the second resin layer 4 are laminated in this order.

  Other layers may be disposed between the thermochromic layer 2 and the first resin layer 3 and between the thermochromic layer 2 and the second resin layer 4, respectively. It is preferable that the thermochromic layer 2 and the first resin layer 3 and the thermochromic layer 2 and the second resin layer 4 are directly laminated, respectively. Examples of the other layer include a layer containing a thermoplastic resin such as polyvinyl acetal resin, a layer containing polyethylene terephthalate, polyethylene naphthalate, and the like, and a layer formed of an inorganic compound such as a metal foil. When these other layers are included, only one type of layer may be included, or two or more different layers may be included.

  The thermochromic layer has thermochromic properties. The thermochromic layer is not particularly limited as long as it has thermochromic properties.

  The infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer. From another viewpoint, the infrared absorption rate of the first resin layer is lower than the infrared absorption rate of the second resin layer.

  Conventionally, a laminated glass using an interlayer film has a problem that it is difficult to achieve both high thermochromic properties and high visible light transmittance (Visible Transmittance).

  On the other hand, in the interlayer film for laminated glass according to the present invention, the thermochromic layer is provided, and the first and second resin layers are further disposed on both sides of the thermochromic layer. Since the infrared transmittance of the resin layer 1 is higher than the infrared transmittance of the second resin layer, the thermochromic property and the visible light transmittance of the laminated glass using the interlayer film for laminated glass according to the present invention Both can be high.

  In order to develop a good thermochromic property, the thermochromic layer is composed of at least one atom selected from the group consisting of tungsten, molybdenum, niobium, and tantalum in which vanadium dioxide particles or vanadium atoms of vanadium dioxide are partly included. It is preferred to include substituted substituted vanadium dioxide particles. In order to develop good thermochromic properties, the thermochromic layer preferably contains a thermoplastic resin and vanadium dioxide particles or the substituted vanadium dioxide particles.

  In the intermediate film including the thermochromic layer as described above, the heat shielding property can be improved. A laminated glass having low Tds (direct solar energy transmitted through a glazing), which is an index of thermal insulation, can be obtained.

  Below the phase transition temperature of vanadium dioxide or substituted vanadium dioxide, the visible light transmittance and infrared transmittance of the thermochromic layer are high. Above the phase transition temperature of vanadium dioxide or substituted vanadium dioxide, it is considered that the infrared transmittance of the thermochromic layer is lowered while the visible light transmittance of the thermochromic layer is high.

  The first resin layer transmits a relatively large amount of infrared light. For this reason, many infrared rays which permeate | transmitted the said 1st resin layer reach the said thermochromic layer. Above the phase transition temperature such as vanadium dioxide or substituted vanadium dioxide, the infrared rays reaching the thermochromic layer are inhibited from being transmitted by the thermochromic layer and partially reflected. Moreover, since the infrared transmittance of the first resin layer is high, most of the infrared light reflected by the thermochromic layer is transmitted through the first resin layer. As a result, at a temperature higher than the phase transition temperature of vanadium dioxide or substituted vanadium dioxide, an increase in the temperature of the intermediate film when infrared rays are incident on the intermediate film can be suppressed. For this reason, the heat shielding property above the phase transition temperature of the vanadium dioxide or substituted vanadium dioxide of the interlayer film for laminated glass according to the present invention is increased, and further, the light resistance is excellent, so a high visible light transmittance is maintained for a long time. it can. Moreover, the temperature rise of the internal space of a building or a vehicle can be effectively suppressed by attaching the laminated glass using the intermediate film for laminated glasses which concerns on this invention to the opening part of a building or a vehicle.

  On the other hand, if a part of infrared rays passes through the first resin layer and the thermochromic layer, the transmitted infrared rays reach the second resin layer. Since the infrared transmittance of the second resin layer is relatively low, the second resin layer effectively blocks infrared transmission. For this reason, the amount of heat rays passing through the entire intermediate film can be reduced. Also by this, the heat-shielding property of the interlayer film for laminated glass according to the present invention is increased, and the laminated glass using the interlayer film for laminated glass according to the present invention is attached to an opening of a building or a vehicle. Or the temperature rise of the interior space of a vehicle can be suppressed effectively.

  In addition, as a result of reducing the amount of infrared rays reaching the second resin layer, the deterioration of the second resin layer can be suppressed, and the light resistance of the entire intermediate film is increased. For this reason, high visible light transmittance can be maintained over a long period of time. Furthermore, when the second resin layer contains a heat shielding compound such as a heat shielding particle, the deterioration of the heat shielding compound can be suppressed, and high heat shielding properties can be maintained for a long period of time.

  Since the infrared transmittance of the first resin layer at a wavelength of 780 to 2100 nm is higher than the infrared transmittance of the second resin layer at a wavelength of 780 to 2100 nm, the first resin layer and the second resin layer And the composition is preferably different. In addition, even if the composition of the first resin layer and the second resin layer is the same, by making the thickness of the first resin layer thinner than the thickness of the second resin layer, The infrared transmittance of the first resin layer at a wavelength of 780 to 2100 nm can be made higher than the infrared transmittance of the second resin layer at a wavelength of 780 to 2100 nm.

  When the infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is Tx1, and the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer is Tx2, Tx1 is higher than Tx2. Tx1 is preferably 10% or more higher than Tx2, more preferably 20% or more, more preferably 25% or more, further preferably 30% or more, because the heat shielding property of the laminated glass is further enhanced. Particularly preferred. The upper limit of the value of (Tx1-Tx2) is not particularly limited, but (Tx1-Tx2) is preferably 70% or less, and preferably 60% or less because the transparency of the laminated glass is further increased. More preferably, it is more preferably 50% or less, and particularly preferably 40% or less. In order to further improve the heat shielding and transparency of the laminated glass, the preferable lower limit of Tx1 is 60%, the preferable upper limit is 90%, the more preferable lower limit is 65%, the more preferable upper limit is 85%, and the more preferable lower limit is 70%. A more preferred upper limit is 80%. In order to further improve the heat shielding and transparency of the laminated glass, the preferable lower limit of Tx2 is 20%, the preferable upper limit is 75%, the more preferable lower limit is 25%, the more preferable upper limit is 65%, and the more preferable lower limit is 30. %, A more preferred upper limit is 55%, a particularly preferred lower limit is 35%, and a particularly preferred upper limit is 50%.

  The infrared transmittances Tx1 and Tx2 at wavelengths of 780 to 2100 nm of the first resin layer or the second resin layer are measured as follows.

  A 1st resin layer or a 2nd resin layer is laminated | stacked between two sheets of clear glass (thickness 2.5mm), and a laminated glass is produced. The weight coefficient of 780 to 2100 nm shown in Appendix Table 2 of JIS R3106 (1998) is used and normalized as a new weight coefficient of infrared transmittance. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). The obtained spectral transmittance is obtained by multiplying the newly normalized weight coefficient, and the infrared transmittance at a wavelength of 780 to 2100 nm is calculated. That is, among the weight coefficients of 300 to 2100 nm shown in Appendix 2 of JIS R3106 (1998), the weight coefficient of 780 to 2100 nm is used, and each weight coefficient of 780 to 2100 nm is set to 780 to 2100 nm. By dividing by the total value of the weight coefficients, the newly normalized weight coefficient of infrared transmittance at 780 to 2100 nm is obtained. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). By multiplying the obtained spectral transmittance by the newly normalized weight coefficient, the infrared transmittance at a wavelength of 780 to 2100 nm is calculated.

  The thermochromic layer preferably contains a thermoplastic resin. The thermoplastic resin in the thermochromic layer is preferably a polyvinyl acetal resin. The thermochromic layer preferably contains a plasticizer, and more preferably contains a polyvinyl acetal resin and a plasticizer. The thermochromic layer preferably contains an ultraviolet shielding agent, and preferably contains an antioxidant.

  The first resin layer includes a thermoplastic resin. The thermoplastic resin in the first resin layer is preferably a polyvinyl acetal resin. The first resin layer preferably includes a plasticizer, and more preferably includes a polyvinyl acetal resin and a plasticizer. The first resin layer preferably contains an ultraviolet shielding agent, and preferably contains an antioxidant.

  The second resin layer includes a thermoplastic resin. The thermoplastic resin in the second resin layer is preferably a polyvinyl acetal resin. The second resin layer preferably contains a plasticizer, and more preferably contains a polyvinyl acetal resin and a plasticizer. The second resin layer preferably contains an ultraviolet shielding agent, and preferably contains an antioxidant.

  The second resin layer preferably contains a heat shielding compound. When the second resin layer contains a heat-shielding compound, the infrared transmittance of the first resin layer is higher than the infrared transmittance of the second resin layer. The first resin layer may contain a heat shielding compound. Further, when the content (% by weight) of the heat shielding compound in the first resin layer is less than the content (% by weight) of the heat shielding compound in the second resin layer, the first It is easy to make the infrared transmittance of the resin layer higher than the infrared transmittance of the second resin layer. Examples of the heat-shielding compound include heat-shielding particles such as metal oxide particles, and at least one component among the phthalocyanine compounds, naphthalocyanine compounds, and anthracocyanine compounds (hereinafter sometimes referred to as component X). Can be mentioned. In addition, a heat-shielding compound means the compound which can absorb infrared rays. When the first resin layer or the second resin layer contains a plurality of heat shielding compounds, the total content (% by weight) of the heat shielding compounds in the first resin layer is the second resin layer. It is preferably less than the total content (% by weight) of the above heat-shielding compounds in the resin layer, more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, 2% by weight or less is particularly preferable, and 0.4% by weight or more is most preferable. Furthermore, since the heat shielding property is further increased, the total content (% by weight) of the heat shielding compound in the second resin layer and the total content of the heat shielding compound in the first resin layer. The difference from the amount (% by weight) is preferably 2% by weight or less.

  Hereinafter, the details of the material constituting the first and second resin layers will be described.

(Thermoplastic resin)
The first and second resin layers include a thermoplastic resin. The thermochromic layer preferably contains a thermoplastic resin. The thermoplastic resin is not particularly limited. A conventionally well-known thermoplastic resin can be used as a thermoplastic resin. As for a thermoplastic resin, only 1 type may be used and 2 or more types may be used together. The thermoplastic resin in the first resin layer, the thermoplastic resin in the second resin layer, and the thermoplastic resin in the thermochromic layer may be the same or different.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl alcohol resin, and polyester resin. Thermoplastic resins other than these may be used.

  Since the versatility is high, the thermoplastic resin is preferably a polyvinyl acetal resin or a polyester resin. By the combined use of the polyvinyl acetal resin and the plasticizer, the adhesion of the first and second resin layers to other layers such as the laminated glass member, the resin layer, and the thermochromic layer is further increased.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl alcohol can be produced, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol is generally in the range of 70 to 99.8 mol%.

  The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, preferably 5000 or less, more preferably 4000 or less, still more preferably 3500 or less, particularly preferably 3000 or less, and most preferably 2500 or less. . When the average degree of polymerization is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the average degree of polymerization is not more than the above upper limit, the intermediate film can be easily molded. The average degree of polymerization of the polyvinyl alcohol is determined by a method based on JIS K6726 “Testing method for polyvinyl alcohol”.

  The number of carbon atoms of the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used when manufacturing the said polyvinyl acetal resin is not specifically limited. The carbon number of the acetal group in the polyvinyl acetal resin is preferably 3 or 4. When the carbon number of the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the intermediate film is sufficiently low.

  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. , N-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Among these, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, propionaldehyde, n-butyraldehyde or isobutyraldehyde is more preferable, and n-butyraldehyde is still more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

  The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, still more preferably 20 mol% or more, particularly preferably 28 mol% or more, preferably 40 mol. % Or less, more preferably 35 mol% or less, still more preferably 32 mol% or less. When the hydroxyl group content is at least the above lower limit, the adhesive strength of the interlayer film is further increased. Further, when the hydroxyl group content is not more than the above upper limit, the flexibility of the interlayer film is increased, and the handling of the interlayer film is facilitated.

  The hydroxyl group content of the polyvinyl acetal resin is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which the hydroxyl group is bonded by the total amount of ethylene groups in the main chain, as a percentage. The amount of the ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring according to JIS K6726 “Testing method for polyvinyl alcohol”.

  The degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.5 mol% or more, preferably 30 mol% or less. More preferably, it is 25 mol% or less, more preferably 20 mol% or less, particularly preferably 15 mol% or less, and most preferably 3 mol% or less. When the acetylation degree is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer is increased. When the acetylation degree is not more than the above upper limit, the moisture resistance of the interlayer film and the laminated glass is increased.

  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. 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 degree of acetalization of the polyvinyl acetal resin (in the case of polyvinyl butyral resin, the degree of butyralization) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol%. Hereinafter, it is 70 mol% or less more preferably. When the degree of acetalization is not less than the above lower limit, the compatibility between the polyvinyl acetal resin and the plasticizer increases. When the degree of acetalization is less than or equal to the above upper limit, the reaction time required for producing a polyvinyl acetal resin is shortened.

  The degree of acetalization is a value indicating the mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain, as a percentage.

  The degree of acetalization can be calculated by a method based on JIS K6728 “Testing method for polyvinyl butyral”.

  The hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from results measured by a method based on JIS K6728 “Testing methods for polyvinyl butyral”. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl content), the acetalization degree (butyralization degree), and the acetylation degree are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral”. It is preferable to calculate from the results measured by.

  Examples of the polyester resin include polyalkylene terephthalate resin and polyalkylene naphthalate resin. Examples of the polyalkylene terephthalate resin include polyethylene terephthalate, polybutylene terephthalate, and poly-1,4-cyclohexanedimethylene terephthalate. Among them, the polyalkylene terephthalate resin is preferably a polyethylene terephthalate resin because it is chemically stable and the long-term stability of the vanadium dioxide particles when vanadium dioxide particles are dispersed is further enhanced. Examples of the polyalkylene naphthalate resin include polyethylene naphthalate and polybutylene naphthalate.

(Plasticizer)
From the viewpoint of further enhancing the adhesive strength of the interlayer film, the first resin layer preferably contains a plasticizer, the second resin layer preferably contains a plasticizer, and the thermochromic layer is a plasticizer. It is preferable to contain. When the thermoplastic resin in the first resin layer, the second resin layer, and the thermochromic layer is a polyvinyl acetal resin, respectively, the first resin layer, the second resin layer, and the thermo resin It is particularly preferred that each chromic layer contains a plasticizer.

  The plasticizer is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the plasticizer 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. For example, a glycol ester obtained by reaction of glycol with a monobasic organic acid, and triethylene glycol or tripropylene glycol with a monobasic organic acid. 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-ethyl butyrate, 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 Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, adipine Examples include a mixture of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified sebacic acid alkyd, and a mixture of phosphate ester and adipic acid ester. Organic ester plasticizers other than these may be used.

  The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  The plasticizer is preferably a diester plasticizer represented by the following formula (1).

  In the above formula (1), R1 and R2 each represent an organic group having 2 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. . R1 and R2 in the formula (1) are each preferably an organic group having 5 to 10 carbon atoms, and more preferably an organic group having 6 to 10 carbon atoms.

  The plasticizer preferably contains at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH). More preferably, it contains 2-ethylhexanoate.

  The content of the plasticizer is not particularly limited. In the first resin layer, the second resin layer, and the thermochromic layer, the content of the plasticizer is preferably 25 parts by weight or more, more preferably, 100 parts by weight of the thermoplastic resin. It is 30 parts by weight or more, more preferably 35 parts by weight or more, preferably 75 parts by weight or less, more preferably 60 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 40 parts by weight or less. When the content of the plasticizer is not less than the above lower limit, the penetration resistance of the laminated glass is further enhanced. When the content of the plasticizer is not more than the above upper limit, the transparency of the interlayer film is further enhanced.

(Thermal barrier compound)
Component X:
The second resin layer preferably contains a heat shielding compound. The second resin layer preferably includes at least one component X among a phthalocyanine compound, a naphthalocyanine compound, and an anthracocyanine compound. The second resin layer preferably contains at least one component X of phthalocyanine compounds, naphthalocyanine compounds and anthracocyanine compounds, or contains heat shielding particles described later. The first resin layer may contain the component X. The thermochromic layer may contain the component X. The component X is a heat shielding compound. By using the component X in at least one layer of the entire intermediate film, infrared rays (heat rays) can be effectively blocked. When the second resin layer contains the component X, infrared rays can be blocked more effectively.

  The component X is not particularly limited. As component X, 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.

  Examples of the component X include phthalocyanine, a derivative of phthalocyanine, naphthalocyanine, a derivative of naphthalocyanine, anthracyanine, an anthracocyanine derivative, and the like. 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.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X is preferably at least one selected from the group consisting of phthalocyanine, phthalocyanine derivatives, naphthalocyanine, and naphthalocyanine derivatives. More preferably, it is at least one of phthalocyanine and phthalocyanine derivatives.

  From the viewpoint of effectively increasing the heat shielding property and maintaining the visible light transmittance at a higher level over a long period of time, the component X preferably contains a vanadium atom or a copper atom. The component X preferably contains a vanadium atom, and preferably contains a copper atom. The component X is more preferably at least one of a phthalocyanine containing a vanadium atom or a copper atom and a phthalocyanine derivative containing a vanadium atom or a copper atom. From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the component X preferably has a structural unit in which an oxygen atom is bonded to a vanadium atom.

  When the first resin layer, the second resin layer or the thermochromic layer contains the component X, in the first resin layer, the second resin layer, and the thermochromic layer 100% by weight, Each content of the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight or more, further preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more, preferably It is 0.2% by weight or less, more preferably 0.1% by weight or less, further preferably 0.05% by weight or less, particularly preferably 0.04% by weight or less, and most preferably 0.02% by weight or less. When the content of the component X is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high. For example, the visible light transmittance can be 70% or more.

Thermal barrier particles:
The second resin layer preferably includes heat shielding particles. The first resin layer may contain heat shielding particles. The thermochromic layer preferably contains heat shielding particles. The heat shielding particles are a heat shielding compound. Infrared rays (heat rays) can be effectively blocked by using a heat-shielding compound in at least one layer of the entire intermediate film. When the second resin layer contains heat shielding particles, infrared rays can be blocked more effectively.

  From the viewpoint of further improving the heat shielding property of the laminated glass, the heat shielding particles are more preferably metal oxide particles. The heat shielding particles are preferably particles (metal oxide 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 780 nm longer than visible light have a smaller amount of energy than ultraviolet rays. However, 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. By using the heat shielding particles, infrared rays (heat rays) can be effectively blocked. The heat shielding particles mean particles that can absorb infrared rays.

Specific examples of the 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) And 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. Among these, metal oxide particles are preferable because of their high heat ray shielding function, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferable, and ITO particles or tungsten oxide particles are particularly preferable. In particular, tin-doped indium oxide particles (ITO particles) are preferable, and tungsten oxide particles are also preferable because they have a high heat ray shielding function and are easily available.

  The tungsten oxide particles are generally represented by the following formula (X1) or the following formula (X2). In the interlayer film for laminated glass according to the present invention, tungsten oxide particles represented by the following formula (X1) or the following formula (X2) are preferably used.

W _y O _z Formula (X1)

  In the above formula (X1), W represents tungsten, O represents oxygen, and y and z satisfy 2.0 <z / y <3.0.

M _x W _y O _z Formula (X2)

  In the above formula (X2), M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu , Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta And at least one element selected from the group consisting of Re, W represents tungsten, O represents oxygen, and x, y, and z represent 0.001 ≦ x / y ≦ 1, and 2.0 <z / y ≦ 3.0 is satisfied.

  From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. The tungsten oxide particles include metal-doped tungsten oxide particles. Specific examples of the metal-doped tungsten oxide particles include sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, and rubidium-doped tungsten oxide particles.

From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, cesium-doped tungsten oxide particles are particularly preferable. From the viewpoint of further increasing the heat shielding properties of the interlayer film and the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the formula: Cs _0.33 WO ₃ .

  The average particle diameter of the heat shielding particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, more preferably 0.05 μm or less. When the average particle size is not less than the above lower limit, the heat ray shielding property is sufficiently increased. When the average particle size is not more than the above upper limit, the dispersibility of the heat shielding particles is increased.

  The “average particle diameter” indicates a volume average particle diameter. The average particle diameter can be measured using a particle size distribution measuring apparatus (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.

  In the case where the first resin layer, the second resin layer, or the thermochromic layer contains the heat shielding particles, the first resin layer, the second resin layer, and the thermochromic layer in 100% by weight The content of each of the heat shielding particles is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, still more preferably 1% by weight or more, particularly preferably 1.5% by weight or more, preferably 6%. It is not more than wt%, more preferably not more than 5.5 wt%, still more preferably not more than 4 wt%, particularly preferably not more than 3.5 wt%, and most preferably not more than 3.0 wt%. When the content of the heat shielding particles is not less than the above lower limit and not more than the above upper limit, the heat shielding property is sufficiently high and the visible light transmittance is sufficiently high.

When the first resin layer, the second resin layer, or the thermochromic layer contains the heat shielding particles, the first resin layer, the second resin layer, and the thermochromic layer are Each layer preferably contains hot particles at a rate of 0.1 g / m ² or more and 12 g / m ² or less. When the ratio of the heat shielding particles is within the above range, the heat shielding property is sufficiently high, and the visible light transmittance is sufficiently high. The proportion of the heat shielding particles is preferably 0.5 g / m ² or more, more preferably 0.8 g / m ² or more, still more preferably 1.5 g / m ² or more, particularly preferably 3 g / m ² or more, preferably Is 11 g / m ² or less, more preferably 10 g / m ² or less, still more preferably 9 g / m ² or less, and particularly preferably 7 g / m ² or less. When the ratio is equal to or higher than the lower limit, the heat shielding property is further enhanced. The said visible light transmittance becomes it still higher that the said ratio is below the said upper limit.

(UV shielding agent)
The first resin layer preferably contains an ultraviolet shielding agent. The second resin layer preferably contains an ultraviolet shielding agent. The thermochromic layer preferably contains an ultraviolet shielding agent. More preferably, both the first resin layer and the second resin layer contain an ultraviolet shielding agent. It is more preferable that all of the first resin layer, the second resin layer, and the thermochromic layer contain an ultraviolet shielding agent. By using the ultraviolet shielding agent, even if the interlayer film and the laminated glass are used for a long period of time, the visible light transmittance is more unlikely to decrease. As for this ultraviolet shielding agent, only 1 type may be used and 2 or more types may be used together.

  The ultraviolet shielding agent includes an ultraviolet absorber. The ultraviolet shielding agent is preferably an ultraviolet absorber.

  Conventionally known general UV screening agents are, for example, metal UV screening agents, metal oxide UV screening agents, benzotriazole UV screening agents (benzotriazole compounds), and benzophenone UV screening agents (benzophenone). Compound), triazine-based UV screening agent (triazine compound), malonic acid ester-based UV screening agent (malonic acid ester compound), oxalic acid anilide-based UV screening agent (oxalic acid anilide compound) and benzoate-based UV screening agent (benzoate compound) Etc.

  Examples of the metallic ultraviolet shielding agent include platinum particles, particles in which the surface of the platinum particles is coated with silica, palladium particles, particles in which the surface of the palladium particles is coated with silica, and the like. The ultraviolet shielding agent is preferably not a heat shielding particle.

  Examples of the metal oxide ultraviolet shielding agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface may be coat | covered as said metal oxide type ultraviolet-ray shielding agent. Examples of the coating material on the surface of the metal oxide ultraviolet shielding agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.

  Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a band gap energy of 5.0 eV or more, for example.

  Examples of the benzotriazole-based ultraviolet shielding agent include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (“TinvinP” manufactured by BASF), 2- (2′-hydroxy-3 ′, 5 ′). -Di-t-butylphenyl) benzotriazole ("Tinvin 320" manufactured by BASF), 2- (2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole (manufactured by BASF " Tinuvin 326 ") and 2- (2'-hydroxy-3 ', 5'-di-amylphenyl) benzotriazole (" Tinvin 328 "manufactured by BASF) and the like. The benzotriazole-based ultraviolet shielding agent is preferably a benzotriazole-based ultraviolet shielding agent containing a halogen atom, and more preferably a benzotriazole-based ultraviolet shielding agent containing a chlorine atom, because of its excellent ability to absorb ultraviolet rays. .

  Examples of the benzophenone-based ultraviolet shielding agent include octabenzone (“Chimasorb 81” manufactured by BASF).

  Examples of the triazine-based ultraviolet shielding agent include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (“Tinuvin 1577FF” manufactured by BASF Corporation). ) And the like.

  Examples of the malonic ester-based ultraviolet screening agent include 2- (p-methoxybenzylidene) malonic acid dimethyl, tetraethyl-2,2- (1,4-phenylenedimethylidene) bismalonate, and 2- (p-methoxybenzylidene) -bis. (1,2,2,6,6-pentamethyl-4-piperidinyl) malonate and the like.

  As a commercial item of the said malonic acid ester type | system | group ultraviolet shielding agent, Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all are the Clariant company make) are mentioned.

  Examples of the oxalic acid anilide-based ultraviolet shielding agent include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2-ethylphenyl) -N ′. Oxalic acid diamides having an aryl group substituted on a nitrogen atom, such as-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxyanilide ("Sanduvor VSU" manufactured by Clariant) Can be mentioned.

  Examples of the benzoate-based ultraviolet shielding agent include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (“Tinvin 120” manufactured by BASF).

  In order to suppress a decrease in visible light transmittance of the interlayer film and the laminated glass after aging, the ultraviolet shielding agent is 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5- It is preferably chlorobenzotriazole (“Tinvin 326” manufactured by BASF) or 2- (2′-hydroxy-3 ′, 5′-di-amylphenyl) benzotriazole (“Tinvin 328” manufactured by BASF). It may be (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole.

  In the case where the first resin layer, the second resin layer, or the thermochromic layer contains the ultraviolet shielding agent, 100% by weight of the first resin layer, the second resin layer, and the thermochromic layer. Each content of the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, still more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, preferably Is 2.5% by weight or less, more preferably 2% by weight or less, still more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is not less than the above lower limit and not more than the above upper limit, a decrease in visible light transmittance after time is further suppressed. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the first resin layer, the second resin layer, and the thermochromic layer, the time course of the interlayer film and the laminated glass is increased. The subsequent decrease in visible light transmittance can be remarkably suppressed. Further, if the content of the ultraviolet shielding agent in 100% by weight of the second resin layer is larger than the content of the ultraviolet shielding agent in 100% by weight of the first resin layer, the aging of the interlayer film and the laminated glass will occur. The subsequent decrease in visible light transmittance can be further significantly suppressed.

(Antioxidant)
The first resin layer preferably contains an antioxidant. The second resin layer preferably contains an antioxidant. The thermochromic layer preferably contains an antioxidant. It is preferable that both the first resin layer and the second resin layer contain an antioxidant. More preferably, all of the first resin layer, the second resin layer, and the thermochromic layer contain an antioxidant. As for this antioxidant, only 1 type may be used and 2 or more types may be used together.

  Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. The phenolic antioxidant is an antioxidant having a phenol skeleton. The sulfur-based antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.

  The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, and stearyl. -Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-butylphenol), 2,2'-methylenebis- (4-ethyl- 6-t-butylphenol), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-hydroxy-5-tert-butylphenyl) Butane, tetrakis [methylene-3- (3 ′, 5′-butyl-4-hydroxyphenyl) propionate] methane, 1,3,3-tris- (2-methyl-4-hydro) Loxy-5-t-butylphenol) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,3′- and t-butylphenol) butyric acid glycol ester and bis (3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid) ethylene bis (oxyethylene). One or more of these antioxidants are preferably used.

  Examples of the phosphorus antioxidant include tridecyl phosphite, tris (tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (decyl) pentaerythritol diphos. Phyto, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl ester phosphorous acid, tris (2,4-di-t -Butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, and the like. One or more of these antioxidants are preferably used.

  Examples of commercially available antioxidants include “IRGANOX 245” manufactured by BASF, “IRGAFOS 168” manufactured by BASF, “IRGAFOS 38” manufactured by BASF, “Smilizer BHT” manufactured by Sumitomo Chemical, and “ Irganox 1010 "and the like.

  In the case where the first resin layer, the second resin layer, or the thermochromic layer contains the antioxidant, the first resin layer, the second resin layer, and the thermochromic layer in 100% by weight Each content of the antioxidant is preferably 0.1% by weight or more, preferably 2% by weight or less, more preferably 1.8% by weight or less. When the content of the antioxidant is not less than the above lower limit, the high visible light transmittance of the interlayer film and the laminated glass is maintained for a longer period of time. When the content of the antioxidant is not more than the above upper limit, an excessive antioxidant is hardly generated to obtain the addition effect.

(Adhesive strength modifier)
It is preferable that at least one of the first resin layer and the second resin layer includes an adhesive force adjusting agent. It is preferable that the first resin layer contains an adhesive strength adjusting agent. The second resin layer preferably contains an adhesive strength adjusting agent. It is more preferable that both the first resin layer and the second resin layer contain an adhesive force adjusting agent. By using the adhesive strength modifier, the adhesion between the interlayer film and the glass is controlled, and a laminated glass having excellent penetration resistance can be obtained. Furthermore, when a ball drop test is performed as a penetration resistance test, the first resin layer and the second resin layer contain an adhesion adjusting agent, thereby reducing the glass fragments of the laminated glass. The effect of being able to be obtained. In particular, when the adhesive strength adjusting agent is a metal salt, the glass fragments of the laminated glass are further reduced. As for the said adhesive force regulator, only 1 type may be used and 2 or more types may be used together.

  The adhesive strength adjusting agent is not particularly limited, and is preferably a metal salt, and is preferably at least one metal salt selected from the group consisting of alkali metal salts, alkaline earth metal salts, and Mg salts. The metal salt preferably contains at least one metal selected from K and Mg. The metal salt is more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, and a magnesium carboxylate having 2 to 16 carbon atoms or More preferably, it is a carboxylic acid potassium salt having 2 to 16 carbon atoms. Although it does not specifically limit as said C2-C16 carboxylic acid magnesium salt and said C2-C16 carboxylic acid potassium salt, For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, 2-ethylbutanoic acid Examples include magnesium, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.

  Content of the said adhesive force regulator is not specifically limited. In the first resin layer and the second resin layer, with respect to 100 parts by weight of the thermoplastic resin, each content of the adhesive strength modifier is preferably 0.0005 parts by weight, and preferably 0 upper limit. 0.05 parts by weight. The penetration resistance of laminated glass becomes high as content of the said adhesive force regulator is 0.0005 weight part or more. When the content of the adhesion adjusting agent is 0.05 parts by weight or less, the transparency of the interlayer film for laminated glass is further enhanced. The minimum with more preferable content of the said adhesive force regulator is 0.002 weight part, and a more preferable upper limit is 0.02 weight part. In addition, when the first and second resin layers have a laminated structure of two or more layers, in the surface layer in contact with the laminated glass member, and when the first and second resin layers have a single layer structure, In the first and second resin layers, with respect to 100 parts by weight of the thermoplastic resin, a preferable lower limit is 0.0005 parts by weight and a preferable upper limit is 0.05 parts by weight.

  Since the moisture resistance of the first resin layer is increased, the total content of alkali metal, alkaline earth metal and Mg in the first and second resin layers is preferably 300 ppm or less. For example, the alkali metal, alkaline earth metal, and Mg may be included as a metal derived from the adhesive strength modifier, or may be included as a metal derived from a neutralizing agent used when a polyvinyl acetal resin is synthesized. The total content of alkali metal, alkaline earth metal and Mg in the first and second resin layers is more preferably 200 ppm or less, further preferably 150 ppm or less, and particularly preferably 100 ppm or less. . In addition, when the first and second resin layers have a laminated structure of two or more layers, in the surface layer in contact with the laminated glass member, and when the first and second resin layers have a single layer structure, In the first and second resin layers, the total content of alkali metal, alkaline earth metal and Mg is preferably 300 ppm or less, more preferably 200 ppm or less, and even more preferably 150 ppm or less. 100 ppm or less is particularly preferable. In addition, when the first and second resin layers have a laminated structure of two or more layers, in the surface layer in contact with the laminated glass member, and when the first and second resin layers have a single layer structure, In the first and second resin layers, the total Mg content is preferably 300 ppm or less, more preferably 200 ppm or less, further preferably 150 ppm or less, and particularly preferably 100 ppm or less. preferable.

(Thermochromic ingredient)
From the viewpoint of further improving the thermochromic property, the thermochromic layer is composed of at least one atom selected from the group consisting of tungsten, molybdenum, niobium, and tantalum in which vanadium dioxide particles or vanadium atoms of vanadium dioxide are partly included. It is preferred to include substituted substituted vanadium dioxide particles. From the viewpoint of further improving the thermochromic property, the thermochromic layer more preferably contains the substituted vanadium dioxide particles. At least one atom selected from the group consisting of tungsten, molybdenum, niobium and tantalum is a dopant atom. The phase transition temperature can be changed by substituting some of the vanadium atoms in vanadium dioxide with atoms such as tungsten, molybdenum, niobium, and tantalum.

  By including the vanadium dioxide particles or the substituted vanadium oxide particles, the transmittance of the infrared region in the temperature range below the transition temperature of the interlayer film for laminated glass obtained is high, and the red in the temperature range above the transition temperature. The transmittance of the outer region is low, and the optical characteristic change is large between the temperature range below the transition temperature and the temperature range above the transition temperature.

  From the viewpoint of further increasing the thermochromic property, in the substituted vanadium dioxide atom, the content of the dopant atom is preferably 0.2% by weight or more, more preferably in a total of 100% by weight of the vanadium dioxide atom and the dopant atom. Is 0.5% by weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more, preferably 10% by weight or less, more preferably 8% by weight or less, still more preferably 6% by weight or less, Preferably it is 5 weight% or less. When the content of the dopant atom is not less than the above lower limit, the transition temperature of the substituted vanadium dioxide atom is effectively lowered. When the content of the dopant atom is not more than the above upper limit, the crystallinity of vanadium dioxide is effectively maintained.

  The content of the dopant atom can be measured by fluorescent X-ray analysis using an energy dispersive X-ray fluorescence apparatus (“EDX-800HS” manufactured by Shimadzu Corporation).

  In the disubstituted vanadium oxide particles, the substitution rate of the dopant atoms (hereinafter sometimes abbreviated as substitution rate) is preferably 0.2 atomic% or more, more preferably 0.5 atomic% or more, preferably 3 atoms. % Or less. The phase transition temperature of the said substituted vanadium dioxide particle can be easily adjusted as the said substitution rate is more than the said minimum. When the substitution rate is less than or equal to the upper limit, thermochromic properties are further improved.

  The said substitution rate is the value which showed the ratio of the number of dopant atoms which substituted the vanadium atom to the sum total of the number of vanadium atoms and the number of dopant atoms which substituted the vanadium atom in percentage. The number of vanadium atoms and the number of dopant atoms substituting vanadium atoms are measured by X-ray fluorescence analysis using, for example, an energy dispersive X-ray fluorescence apparatus (“EDX-800HS” manufactured by Shimadzu Corporation). be able to.

  From the viewpoint of further improving thermochromic properties, the vanadium dioxide atom preferably has a rutile structure, and the substituted vanadium dioxide atom preferably contains a vanadium dioxide atom having a rutile structure.

  The average particle diameter of the vanadium dioxide particles and the substituted vanadium dioxide particles is preferably 200 nm or less, more preferably 150 nm or less. When the average particle size is not more than the upper limit, thermochromic properties are further enhanced. The lower limit of the average particle diameter is not particularly limited, but it is considered that the limit is substantially about 20 nm.

  The method for measuring the average particle size is not particularly limited, and for example, it can be measured by particle size distribution measurement by a dynamic light scattering method using a particle size distribution meter. The average particle diameter is preferably a dispersion diameter (D50) obtained by particle size distribution measurement by the dynamic light scattering method. The dispersion diameter (D50) is a short diameter of 50 or more of the substituted vanadium dioxide particles measured by a dynamic light scattering method after the substituted vanadium dioxide particles according to the present invention are dispersed in a dispersion medium. Mean value.

  Examples of the measurement method of the average particle diameter other than the particle size distribution measurement by the dynamic light scattering method include observation of the shape of the vanadium dioxide particles and the substituted vanadium dioxide particles by a scanning electron microscope (SEM).

  The average crystallite size of the vanadium dioxide particles and the substituted vanadium dioxide particles is preferably 40 nm or more, more preferably 60 nm or more, preferably 200 nm or less, more preferably 150 nm or less. When the average crystallite diameter is not less than the above lower limit, the grain boundary portion in the particle is reduced, the proportion of vanadium dioxide that can exist as a single crystal is increased, and the thermochromic property is further enhanced. When the average crystallite diameter is not more than the above upper limit, the phase transition occurs uniformly, and the thermochromic property is further enhanced.

The crystallite diameter means the crystallite size determined from the half width of the diffraction peak in the X-ray diffraction method. For example, the crystallite size can be calculated by calculating the half width from diffraction data obtained using an X-ray diffractometer (“RINT1000” manufactured by Rigaku Corporation) and applying Scherrer's equation. Specifically, it can be measured by adopting the crystallite size calculated from the half-value width when VO _{2 has} the strongest peak 2θ = 27.86 °. In this series of analyses, for example, the half width and crystallite size can be calculated using analysis software (“PDXL” manufactured by Rigaku Corporation).

  The method for producing the substituted vanadium dioxide particles is not particularly limited, and examples thereof include a thermal decomposition method, a solid phase method, and a hydrothermal method.

  The total content of the vanadium dioxide and the substituted vanadium dioxide particles in 100% by weight of the thermochromic layer is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, preferably 3% by weight or less. More preferably, it is 2% by weight or less. When the total content of the vanadium dioxide and the substituted vanadium dioxide particles is not less than the above lower limit and not more than the above upper limit, the thermochromic property is further improved.

  When the thermochromic layer contains a thermoplastic resin, the total content of the vanadium dioxide and the substituted vanadium dioxide particles with respect to 100 parts by weight of the thermoplastic resin is preferably 0.01 parts by weight or more. Preferably it is 0.1 parts by weight or more, preferably 3 parts by weight or less, more preferably 2 parts by weight or less. When the total content of the vanadium dioxide and the substituted vanadium dioxide particles is not less than the above lower limit and not more than the above upper limit, the thermochromic property is further improved.

(Other ingredients)
The interlayer film for laminated glass according to the present invention contains additives such as a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesion modifier, a moisture-resistant agent, and a fluorescent brightening agent as necessary. May be. As for these additives, only 1 type may be used and 2 or more types may be used together.

(Other details of interlayer film for laminated glass)
The interlayer film for laminated glass according to the present invention is preferably used by being disposed between the first laminated glass member and the second laminated glass member.

  The interlayer film for laminated glass according to the present invention is formed in an opening between an external space (first space) and an internal space (second space) into which heat rays are incident from the external space in a building or a vehicle. It is preferably used to obtain a laminated glass to be attached. In this case, it is preferable that the first resin layer of the first and second resin layers is disposed on the external space side.

  The thickness of the interlayer film for laminated glass according to the present invention is not particularly limited. From the viewpoint of practical use and from the viewpoint of sufficiently increasing the heat shielding property, the thickness of the intermediate film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less. is there. When the thickness of the intermediate film is not less than the above lower limit, the penetration resistance of the laminated glass is increased.

  The thickness of the thermochromic layer is preferably 0.01 mm or more, more preferably 0.04 mm or more, further preferably 0.07 mm or more, preferably 0.3 mm or less, more preferably 0.2 mm or less, still more preferably 0. .18 mm or less, particularly preferably 0.16 mm or less. When the thickness of the thermochromic layer is not less than the above lower limit, the heat shielding property of the laminated glass is further enhanced. When the thickness of the thermochromic layer is not more than the above upper limit, the transparency of the laminated glass is further increased.

  The thicknesses of the first and second resin layers are preferably 0.1 mm or more, more preferably 0.2 mm or more, still more preferably 0.25 mm or more, particularly preferably 0.3 mm or more, preferably 1.0 mm. Hereinafter, it is more preferably 0.6 mm or less, still more preferably 0.5 mm or less, still more preferably 0.45 mm or less, and particularly preferably 0.4 mm or less. When the thickness of the first and second resin layers is equal to or greater than the lower limit, the penetration resistance of the laminated glass is further enhanced. When the thickness of the first and second resin layers is not more than the above upper limit, the transparency of the laminated glass is further increased. The thickness of the first resin layer is preferably 0.05 mm or more and more preferably 0.10 mm or more than the thickness of the second resin layer. By making the thickness of the first resin layer thinner than the thickness of the second resin layer within the preferable range, the infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is set to be the second resin. The infrared transmittance at a wavelength of 780 to 2100 nm of the layer can be effectively increased.

  The manufacturing method of the interlayer film for laminated glass according to the present invention is not particularly limited. A conventionally known method can be used as a method for producing the intermediate film. For example, the manufacturing method etc. which knead | mix each component mentioned above and shape | mold an intermediate film are mentioned. Since it is suitable for continuous production, an extrusion method is preferred. In particular, the first and second resin layers are preferably formed by extrusion.

  The kneading method is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, or the like. Especially, since it is suitable for continuous production, a method using an extruder is preferable, and a method using a twin screw extruder is more preferable.

  In addition, when obtaining the intermediate film for laminated glasses which concerns on this invention, after producing the 1st resin layer, the thermochromic layer, and the 2nd resin layer separately, the 1st resin layer, the thermochromic layer, and the 1st The intermediate layer may be obtained by laminating two resin layers, and the laminating method is not particularly limited. For example, a heat laminating method etc. are mentioned as a lamination method.

  Alternatively, the first resin layer, the thermochromic layer, and the second resin layer may be laminated by coextrusion to obtain an intermediate film. Alternatively, an intermediate film may be obtained by laminating a second resin layer on the thermochromic layer side of a coextruded product prepared by coextrusion of the first resin layer and the thermochromic layer. An intermediate film may be obtained by laminating the first resin layer on the thermochromic layer side of the coextruded product prepared by coextrusion of the second resin layer and the thermochromic layer.

  In addition, an intermediate film may be obtained by applying a composition for forming the first and second resin layers on the surface of the thermochromic layer to form the first and second resin layers. .

  Since the production efficiency of the intermediate film is excellent, the first resin layer and the second resin layer preferably contain the same polyvinyl acetal resin, and more preferably contain the same polyvinyl acetal resin and the same plasticizer. preferable.

(Laminated glass)
The laminated glass according to the present invention includes a first laminated glass member, a second laminated glass member, and an intermediate film disposed between the first and second laminated glass members. This intermediate film is the above-mentioned intermediate film for laminated glass. The first laminated glass member is disposed outside the first resin layer in the interlayer film for laminated glass. The second laminated glass member is disposed outside the second resin layer in the interlayer film for laminated glass.

  The laminated glass according to the present invention is preferably a laminated glass attached to an opening between an external space and an internal space into which heat rays are incident from the external space in a building or a vehicle. In this case, it is preferable that the first laminated glass member of the first and second laminated glass members is disposed so as to be located on the external space side.

  In FIG. 2, an example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is shown with sectional drawing.

  A laminated glass 11 shown in FIG. 2 includes an intermediate film 1 and first and second laminated glass members 21 and 22. The intermediate film 1 is sandwiched between the first and second laminated glass members 21 and 22. A first laminated glass member 21 is laminated on the first surface 1 a of the intermediate film 1. A second laminated glass member 22 is laminated on a second surface 1 b opposite to the first surface 1 a of the intermediate film 1. A first laminated glass member 21 is laminated on the outer surface 3 a of the first resin layer 3 in the intermediate film 1. A second laminated glass member 22 is laminated on the outer surface 4 a of the second resin layer 4 in the intermediate film 1.

  The infrared transmittance at a wavelength of 780 to 2100 nm of the first laminated glass member is preferably higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second laminated glass member. In this case, the first laminated glass member transmits a relatively large amount of infrared rays. Furthermore, most of the infrared rays transmitted through the first laminated glass member also pass through the first resin layer. For this reason, many infrared rays which permeate | transmitted the said 1st laminated glass member and the said 1st resin layer reach the said thermochromic layer. The infrared rays that reach the thermochromic layer are blocked from being transmitted by the thermochromic layer and partially reflected. Moreover, since the infrared transmittance of the first laminated glass member and the first resin layer is high, most of the infrared rays reflected by the thermochromic layer are the first resin layer and the first resin layer. It penetrates the laminated glass member. As a result, the temperature rise of the laminated glass when infrared rays are incident on the laminated glass can be suppressed. For this reason, since the heat shielding property of the laminated glass is high and the light resistance is excellent, a high visible light transmittance can be maintained for a long period of time. Moreover, the temperature rise of the internal space of a building or a vehicle can be effectively suppressed by attaching the said laminated glass to the opening part of a building or a vehicle.

  On the other hand, if a part of infrared rays passes through the first laminated glass member, the first resin layer, and the thermochromic layer, the transmitted infrared rays reach the second resin layer. Since the infrared transmittance of the second resin layer is relatively low, the second resin layer effectively blocks infrared transmission. Furthermore, since the infrared transmittance of the second laminated glass member is also relatively low, the second laminated glass member effectively blocks infrared transmission. For this reason, the quantity of the heat ray which passes the whole laminated glass can be reduced. Also by this, the heat-shielding property of a laminated glass becomes high, and the temperature rise of the interior space of a building or a vehicle can be effectively suppressed by attaching this laminated glass to the opening part of a building or a vehicle.

  When the infrared transmittance at a wavelength of 780 to 2100 nm of the first laminated glass member is Ty1, and the infrared transmittance at a wavelength of 780 to 2100 nm of the second laminated glass member is Ty2, Ty1 is higher than Ty2 as described above. It is preferable. Ty1 is preferably 10% or more higher than Ty2, more preferably 15% or more, and even more preferably 20% or more because the heat shielding property of the laminated glass is further enhanced. The upper limit of the value of (Ty1-Ty2) is not particularly limited, but (Ty1-Ty2) is preferably 50% or less and 40% or less because the transparency of the laminated glass is further increased. More preferably, it is more preferably 30% or less, and particularly preferably 25% or less. In order to further improve the heat shielding and transparency of the laminated glass, the preferred lower limit of Ty1 is 50%, the preferred upper limit is 90%, the more preferred lower limit is 55%, the more preferred upper limit is 88%, and the more preferred lower limit is 60%, A more preferred upper limit is 86%. In order to further improve the heat shielding and transparency of the laminated glass, the preferred lower limit of Ty2 is 40%, the preferred upper limit is 88%, the more preferred lower limit is 45%, the more preferred upper limit is 86%, and the more preferred lower limit is 55. %, A more preferred upper limit is 70%, a particularly preferred lower limit is 60%, and a particularly preferred upper limit is 65%.

  The infrared transmittance at the wavelength of 780 to 2100 nm of the entire two layers of the first laminated glass member and the first resin layer is T1, the wavelength of the entire two layers of the second laminated glass member and the second resin layer When the infrared transmittance at 780 to 2100 nm is T2, T1 is preferably higher than T2. In this case, the heat shielding property of the laminated glass is increased. T1 is preferably 10% or more higher than T2, more preferably 15% or more, more preferably 20% or more, and more preferably 30% or more because the heat shielding property of the laminated glass is further increased. More preferably, it is more preferably 40% or more, still more preferably 50% or more, and particularly preferably 60% or more. The upper limit of the value of (T1-T2) is not particularly limited, but (T1-T2) is preferably 90% or less and more preferably 85% or less because the transparency of the laminated glass is further increased. More preferably, it is 80% or less.

  In addition, infrared transmittance T1 in the wavelength of 780-2100 nm of the whole two layers, the 1st laminated glass member and the 1st resin layer, is measured as follows.

  A laminated glass in which a first laminated glass member, a first resin layer, and a clear glass (thickness 2.5 mm) are laminated in this order is produced. The weight coefficient of 780 to 2100 nm shown in Appendix Table 2 of JIS R3106 (1998) is used and normalized as a new weight coefficient of infrared transmittance. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). The obtained spectral transmittance is obtained by multiplying the newly normalized weight coefficient, and the infrared transmittance T1 having a wavelength of 780 to 2100 nm is calculated. That is, among the weight coefficients of 300 to 2100 nm shown in Appendix 2 of JIS R3106 (1998), the weight coefficient of 780 to 2100 nm is used, and each weight coefficient of 780 to 2100 nm is set to 780 to 2100 nm. By dividing by the total value of the weight coefficients, the newly normalized weight coefficient of infrared transmittance at 780 to 2100 nm is obtained. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). By multiplying the obtained spectral transmittance by a newly normalized weight coefficient, an infrared transmittance T1 having a wavelength of 780 to 2100 nm is calculated.

  Further, the infrared transmittance T2 at a wavelength of 780 to 2100 nm of the entire two layers of the second laminated glass member and the second resin layer is measured as follows.

  A laminated glass in which the second laminated glass member, the second resin layer, and the clear glass (thickness 2.5 mm) are laminated in this order is produced. The weight coefficient of 780 to 2100 nm shown in Appendix Table 2 of JIS R3106 (1998) is used and normalized as a new weight coefficient of infrared transmittance. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). The obtained spectral transmittance is obtained by multiplying the newly normalized weight coefficient, and the infrared transmittance T2 having a wavelength of 780 to 2100 nm is calculated. That is, among the weight coefficients of 300 to 2100 nm shown in Appendix 2 of JIS R3106 (1998), the weight coefficient of 780 to 2100 nm is used, and each weight coefficient of 780 to 2100 nm is set to 780 to 2100 nm. By dividing by the total value of the weight coefficients, the newly normalized weight coefficient of infrared transmittance at 780 to 2100 nm is obtained. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), the spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass is obtained according to JIS R3106 (1998). By multiplying the obtained spectral transmittance by a newly normalized weight coefficient, an infrared transmittance T2 having a wavelength of 780 to 2100 nm is calculated.

  Examples of the first and second laminated glass members include glass plates and PET (polyethylene terephthalate) films. The laminated glass 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. Laminated glass is a laminated body provided with a glass plate, and preferably at least one glass plate is used. The first and second laminated glass members are each a glass plate or a PET (polyethylene terephthalate) film, and the intermediate film includes at least one glass plate as the first and second laminated glass members. It is preferable. It is particularly preferable that both the first and second laminated glass members are glass plates.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass 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. 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. Examples of the poly (meth) acrylic resin plate include a polymethyl (meth) acrylate plate.

  The first laminated glass member and the second laminated glass member are each preferably clear glass or heat ray absorbing plate glass. Since the infrared transmittance is high and the heat shielding property of the laminated glass is further enhanced, the first laminated glass member is preferably clear glass. Since the infrared transmittance is low and the heat shielding property of the laminated glass is further enhanced, the second laminated glass member is preferably a heat ray absorbing plate glass. The heat ray absorbing plate glass is preferably green glass. It is preferable that the first laminated glass member is clear glass and the second laminated glass member is a heat ray absorbing plate glass. The heat ray absorbing plate glass is a heat ray absorbing plate glass based on JIS R3208.

  Although the thickness of the said 1st, 2nd laminated glass member is not specifically limited, Preferably it is 1 mm or more, Preferably it is 5 mm or less. When the laminated glass member is a glass plate, the thickness of the glass plate is preferably 1 mm or more, and preferably 5 mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more, and preferably 0.5 mm or less.

  The manufacturing method of the said laminated glass is not specifically limited. For example, the intermediate film is sandwiched between the first and second laminated glass members, passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, thereby the first and second laminated glasses. The air remaining between the member and the intermediate film is deaerated. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, a laminated glass can be obtained.

  The laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass is preferably laminated glass for buildings or vehicles, and more preferably laminated glass for vehicles. The said intermediate film and the said laminated glass can be used besides these uses. The intermediate film and the laminated glass can be used for an automobile windshield, side glass, rear glass, roof glass, or the like. Since the heat shielding property is high and the visible light transmittance is high, the interlayer film and the laminated glass are suitably used for automobiles.

(How to attach the laminated glass)
The attachment method of the laminated glass which concerns on this invention is a method of attaching the laminated glass mentioned above to the opening part between external space and internal space into which a heat ray injects from this external space in a building or a vehicle.

  Specifically, the laminated glass is attached to the opening so that the first laminated glass member is located on the outer space side and the second laminated glass member is located on the inner space side. That is, external space / first laminated glass member / (other layer /) first resin layer / (other layer /) thermochromic layer / (other layer /) second resin layer / (other layer) /) A laminated glass is attached so that it may be arrange | positioned in order of a 2nd laminated glass member / internal space. Preferably, external space / first laminated glass member / first resin layer / (other layer /) thermochromic layer / (other layer /) second resin layer / second laminated glass member / internal space The outer space / first laminated glass member / (other layer /) first resin layer / thermochromic layer / second resin layer / (other layer /) second It is preferable to arrange in order of laminated glass member / internal space, and external space / first laminated glass member / first resin layer / thermochromic layer / second resin layer / second laminated glass member / internal space. It is preferable to arrange in this order. The arrangement form includes a case where another member is disposed between the outer space and the first laminated glass member, and the other member is disposed between the inner space and the second laminated glass member. The case where it is arranged is included.

  In the laminated structure, the other layer and the other member may or may not exist. Sunlight including heat rays enters the laminated glass from the external space, and the sunlight including heat rays passing through the laminated glass is guided to the internal space. When the laminated glass is attached to the opening as described above, the outer surface of the first laminated glass member serves as a heat ray incident surface. Further, the heat rays enter the first resin layer earlier than the second resin layer.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited only to the following examples.

  In order to form the first and second resin layers, the following materials were used.

Thermoplastic resin:
PVB1 (polyvinyl butyral resin acetalized with n-butyraldehyde, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, butyralization degree 68.5 mol%)

  In addition, the hydroxyl group content, acetylation degree, and butyralization degree (acetalization degree) of the polyvinyl butyral were measured by a method based on ASTM D1396-92. In addition, also when measured by JIS K6728 “Testing method for polyvinyl butyral”, the same numerical values as the method based on ASTM D1396-92 were shown.

Plasticizer:
3GO (triethylene glycol di-2-ethylhexanoate)

Other ingredients:
T-326 (UV shielding agent, 2- (2′-hydroxy-3′-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, “Tinuvin 326” manufactured by BASF)
BHT (Antioxidant, 2,6-di-t-butyl-p-cresol)
ITO (ITO particles, tin-doped indium oxide particles)

  In addition, the following thermochromic layers were prepared.

TC1 (thermochromic layer): produced by the following procedure:
Vanadium oxide (V) V ₂ O ₅ and vanadium oxide (III) V ₂ O ₃ are blended so as to have a molar ratio of 1: 1, and the tungsten oxide (VI) WO ₃ powder has a molar ratio of vanadium to tungsten. The mixture was added in a molar ratio of 99.0: 1 and mixed to obtain a mixture. The obtained mixture was heated from room temperature to 1000 ° C. in a nitrogen stream at a heating rate of 10 ° C./min, and held for 5 hours after reaching 1000 ° C. to obtain vanadium oxide particles.

  The obtained vanadium oxide particles were pulverized over 1 hour using a Dynomill RESERCH LAB type (manufactured by Shinmaru Enterprises Co., Ltd.) to obtain substituted vanadium oxide particles doped with tungsten. Thereafter, 3000 parts by weight of polyethylene terephthalate resin, 1.3 parts by weight of substituted vanadium oxide particles, 1.3 parts by weight of condensed ricinoleic acid polyglycerin ester (SY glycerase CR-ED, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) as a dispersant, The composition was sufficiently kneaded with a mixing roll to obtain a composition. The obtained composition was extruded with an extruder to obtain a single-layer thermochromic layer TC1 having a thickness of 100 μm.

  Moreover, the following laminated glass members (glass) were prepared.

Clear glass (length 30cm x width 30cm x thickness 2.5mm)
Green glass (heat-absorbing plate glass in accordance with JIS R3208, length 30 cm x width 30 cm x thickness 2.5 mm)
Light green glass (heat-absorbing plate glass according to JIS R3208, length 30 cm x width 30 cm x thickness 2.5 mm)
Dark green glass (heat-absorbing plate glass according to JIS R3208, length 30 cm x width 30 cm x thickness 2.5 mm)
UV green glass (heat ray absorbing plate glass according to JIS R3208, length 30 cm x width 30 cm x thickness 2.5 mm)

(Preparation of resin layer A1)
For 100 parts by weight of polyvinyl butyral resin (PVB1), 40 parts by weight of plasticizer (3GO), 0.8 part by weight of ultraviolet shielding agent (T-326), and 0.2 part by weight of antioxidant (BHT) The mixture was added and sufficiently kneaded with a mixing roll to obtain a composition.

  The obtained composition was extruded using an extruder to obtain a single resin layer A1 having a thickness of 380 μm and 430 μm.

(Preparation of resin layer B1)
An amount of 0.4% by weight in the resin layer B1 from which the heat shielding particles (ITO) can be obtained was added to and mixed with 40 parts by weight of the plasticizer (3GO) to obtain a plasticizer dispersion.

  To 100 parts by weight of the polyvinyl butyral resin (PVB1), the total amount of the plasticizer dispersion, 0.8 part by weight of the ultraviolet shielding agent (T-326), and 0.2 part by weight of the antioxidant (BHT) are added, The composition was sufficiently kneaded with a mixing roll to obtain a composition.

  The obtained composition was extruded by an extruder to obtain a single resin layer B1 having a thickness of 380 μm.

  In addition, in the said Table 2 and following Table 3, the compounding quantity of 3GO, T-326, and BHT shows the compounding quantity (weight part) with respect to 100 weight part of polyvinyl butyral resin (PVB). The blending amount of ITO indicates the blending amount (% by weight) in 100% by weight of the resin layer.

Example 1
(1) Production of interlayer film for laminated glass The obtained thermochromic layer TC1 was sandwiched between the obtained resin layer A1 having a thickness of 380 μm and the obtained resin layer B1 having a thickness of 380 μm to obtain an interlayer film.

(2) Production of laminated glass The obtained intermediate film was cut into a size of 30 cm in length and 30 cm in width. Also, two clear glasses (length 30 cm × width 30 cm × thickness 2.5 mm) were prepared. The obtained intermediate film was sandwiched between the two clear glasses, held at 90 ° C. for 30 minutes with a vacuum laminator, and vacuum pressed to obtain a laminate. In the laminated body, the intermediate film portion protruding from the glass plate was cut off to obtain a laminated glass.

(Examples 2 to 5)
The type of the first resin layer, the type of the second resin layer, the type of the thermochromic layer, and the types of the first and second laminated glass members are set in the same manner as in Example 1 as shown in Table 4 below. And the intermediate film and the laminated glass were produced like Example 1 except having changed the kind of laminated glass member as shown in following Table 4.

(Example 6)
In the same manner as in Example 1, except that the thickness of the resin layer A1 used for the first resin layer was changed to 330 μm and the resin layer A1 having a thickness of 430 μm was used as the second resin layer, Laminated glass was produced.

(Comparative Example 1)
The same thermochromic layer as in Example 1 was sandwiched between the obtained resin layer A1 and the obtained resin layer A1 to obtain an intermediate film. A laminated glass was obtained in the same manner as in Example 1 except that the obtained interlayer film was used.

(Comparative Example 2)
The same thermochromic layer as in Example 1 was sandwiched between the obtained resin layer A1 and the obtained resin layer A1 to obtain an intermediate film. A laminated glass was obtained in the same manner as in Example 1 except that the obtained interlayer film was used and that the first and second laminated glass members were changed to green glass.

(Evaluation)
(1) Measurement of visible light transmittance (A light Y value, A-Y (380 to 780 nm)) Using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), in accordance with JIS R3211 (1988). The visible light transmittance at a wavelength of 380 to 780 nm of the obtained laminated glass was measured.

(2) Measurement of Tts (Total solar energy transmitted through a glazing) Based on ISO 13837, a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech) was used, and the obtained laminated glass at 23 ° C and 100 ° C. Tts was calculated by measuring the transmittance / reflectance at a wavelength of 300 to 2500 nm at ° C. From the obtained measurement value, ΔTts ((Tts at 23 ° C.) − (Tts at 100 ° C.)) was obtained. It shows that it is excellent in thermochromic property, so that the value of (DELTA) Tts is large.

  The laminated structure and evaluation results of the laminated glass are shown in Table 4 below. Further, in the column of “resin layer” of the infrared transmittance in Table 4 below, the infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is Tx1, and the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer is shown. When the rate was Tx2, the relationship between Tx1 and Tx2 was described. In the column of “Laminated glass member” of the infrared transmittance in Table 4 below, the infrared transmittance at a wavelength of 780 to 2100 nm of the first laminated glass member is Ty1, and the infrared transmittance at a wavelength of 780 to 2100 nm of the second laminated glass member. The relationship between Ty1 and Ty2 is described when the transmittance is Ty2.

  The infrared transmittances Tx1 and Tx2 at wavelengths of 780 to 2100 nm of the first resin layer or the second resin layer were measured as follows. The first resin layer or the second resin layer was laminated between two sheets of clear glass (thickness 2.5 mm) to produce a laminated glass. The weight coefficient of 780 to 2100 nm shown in Appendix Table 2 of JIS R3106 (1998) was used and normalized as a new weight coefficient of infrared transmittance. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass was obtained in accordance with JIS R3106 (1998). The obtained spectral transmittance was calculated by multiplying a newly normalized weight coefficient, and the infrared transmittance at a wavelength of 780 to 2100 nm was calculated. That is, among the weight coefficients of 300 to 2100 nm shown in Appendix 2 of JIS R3106 (1998), the weight coefficient of 780 to 2100 nm is used, and each weight coefficient of 780 to 2100 nm is set to 780 to 2100 nm. By dividing by the total value of the weight coefficients, the newly normalized weight coefficient of infrared transmittance at 780 to 2100 nm was obtained. Subsequently, using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), spectral transmittance at a wavelength of 780 to 2100 nm of the laminated glass was obtained in accordance with JIS R3106 (1998). The infrared transmittance at a wavelength of 780 to 2100 nm was calculated by multiplying the obtained spectral transmittance by a newly normalized weight coefficient.

DESCRIPTION OF SYMBOLS 1 ... Intermediate film 1a ... 1st surface 1b ... 2nd surface 2 ... Thermochromic layer 2a ... 1st surface 2b ... 2nd surface 3 ... 1st resin layer 3a ... Outer surface 4 ... 2nd Resin layer 4a ... Outer surface 11 ... Laminated glass 21 ... First laminated glass member 22 ... Second laminated glass member

Claims (11)

A thermochromic layer, a first resin layer containing a thermoplastic resin, and a second resin layer containing a thermoplastic resin,
The first resin layer is disposed on the first surface side of the thermochromic layer, and the second resin layer is a second surface opposite to the first surface of the thermochromic layer. It is arranged on the surface side,
The interlayer film for laminated glass, wherein the infrared transmittance at a wavelength of 780 to 2100 nm of the first resin layer is higher than the infrared transmittance at a wavelength of 780 to 2100 nm of the second resin layer.   Substituted vanadium dioxide particles in which the thermochromic layer is substituted with a thermoplastic resin and at least one atom selected from the group consisting of tungsten, molybdenum, niobium and tantalum, vanadium dioxide particles or vanadium atoms of vanadium dioxide. The interlayer film for laminated glass according to claim 1, comprising:   The interlayer film for laminated glass according to claim 1 or 2, wherein the second resin layer contains metal oxide particles.   The interlayer film for laminated glass according to claim 3, wherein the metal oxide particles are tin-doped indium oxide particles or tungsten oxide particles.   The thermoplastic resin in the first resin layer is a polyvinyl acetal resin, and the thermoplastic resin in the second resin layer is a polyvinyl acetal resin. Interlayer film for laminated glass.   The interlayer film for laminated glass according to any one of claims 1 to 5, wherein the first resin layer contains a plasticizer and the second resin layer contains a plasticizer.   The interlayer film for laminated glass according to any one of claims 1 to 6, wherein the first resin layer contains an ultraviolet shielding agent.   The interlayer film for laminated glass according to any one of claims 1 to 7, wherein the second resin layer contains an ultraviolet shielding agent. A first laminated glass member;
A second laminated glass member;
The interlayer film for laminated glass according to any one of claims 1 to 8,
The interlayer film for laminated glass is disposed between the first laminated glass member and the second laminated glass member,
The first laminated glass member is arranged outside the first resin layer in the interlayer film for laminated glass, and the first resin layer is arranged outside the second resin layer in the interlayer film for laminated glass. Laminated glass in which two laminated glass members are arranged.   The laminated glass according to claim 9, wherein the infrared transmittance of the first laminated glass member at a wavelength of 780 to 2100 nm is higher than the infrared transmittance of the second laminated glass member at a wavelength of 780 to 2100 nm. A method for attaching the laminated glass according to claim 9 or 10 to an opening between an external space and an internal space into which heat rays are incident from the external space in a building or a vehicle,
Laminated glass that attaches the laminated glass to the opening so that the first laminated glass member is located on the external space side and the second laminated glass member is located on the internal space side How to install.

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