JP2009298661A - Method for producing plastic film-inserted laminated glass and plastic film-inserted laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing plastic film-inserted laminated glass, in which a plastic film is not wrinkled when the plastic film is interposed between resin intermediate films and the plastic film-interposed films are interposed between two glass sheets, each of which is curved to have a curved surface, to produce the laminated glass. <P>SOLUTION: The method for producing plastic film-inserted laminated glass comprises the steps of: inserting the plastic film between the resin intermediate films and superposing them on one another to obtain a laminate; and inserting the laminated film between two curved glass sheets to produce the laminated glass, otherwise, comprises the steps of: layering the resin intermediate film, the plastic film, the resin intermediate film and the curved glass sheet in this order on one curved glass sheet to obtain a laminate; and deaerating the space between the curved glass sheets of the laminate. At these steps, the environmental temperature during the working time and the temperatures of the resin intermediate film and the plastic film are controlled within 10-25&deg;C. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a laminated glass produced by laminating a glass plate, a resin intermediate film, a transparent plastic film, a resin intermediate film, and a glass plate in this order, and particularly relates to a laminated glass used for an automobile window.

  A laminate of two glass plates using two resin interlayers sandwiching a plastic film, particularly a polyethylene terephthalate film, is known as a laminated glass having a heat ray reflecting function.

  Usually, a laminated glass is subjected to a high-temperature and high-pressure treatment using an autoclave, and a glass plate and a polyester film are heat-sealed by a resin intermediate film.

  For example, in Patent Document 1, a flexible laminated body in which a heat ray reflective plastic film having a thin film formed on a polyester film is sandwiched between two resin intermediate films is sandwiched and laminated between two glass plates. Laminated glass is disclosed.

  Patent Document 2 discloses that when a PET film or PEN film on which an infrared reflecting film is formed is heated at 199 to 204 ° C. or 227 to 243 ° C. and the PET film or PEN film is used on a curved surface, It is disclosed that wrinkles are not caused by shrinkage.

    Furthermore, in Patent Document 3, a plastic film-inserted laminated glass using a biaxially stretched thermoplastic support film having a thickness of 30 to 70 μm and a thermal shrinkage of 0.3 to 0.6% in the stretching direction A manufacturing method is disclosed.

  Patent Document 4 discloses that when a polyvinyl acetal resin and a polyester film are laminated, an amino-based silane coupling agent is applied to the polyester film to improve the mechanical strength of the interface.

Patent Document 5 discloses that an amino-based silane coupling agent is applied to a polyester film to form a hard coat layer.
JP-A-56-32352 JP-T-2004-503402 Japanese Patent No. 3669709 JP 2001-106556 A JP 2004-195741 A

  When making a laminated glass with a plastic film sandwiched between resin interlayers and sandwiching it between two glass plates, in the case of a glass plate bent into a curved shape, wrinkles occur in the plastic film and appearance defects A problem arises.

  This invention makes it a subject to provide the manufacturing method of a plastic film insertion laminated glass which does not produce a wrinkle in a plastic film, when using the glass plate bent by the curved surface shape.

  The method for producing a plastic film-inserted laminated glass of the present invention is a method for producing a plastic film-inserted laminated glass produced using a laminated film in which a plastic film is sandwiched between two resin interlayers. The manufacturing method includes at least the following three steps (step 1, step 2, step 3), and the steps 1 and 2 are divided into the environmental temperature at the time of operation, the resin interlayer and the plastic. It is a manufacturing method of the plastic film insertion laminated glass characterized by being performed in the temperature range whose film temperature is 10-25 degreeC.

  Step 1: Inserting a plastic film between resin intermediate films to form a laminated film, and inserting the laminated film between two curved glass plates to form a laminated body, or one curved glass A step of sequentially laminating a resin intermediate film, a plastic film, a resin intermediate film, and a curved glass plate on a plate in this order.

  Process 2: The process of deaeration between the curved glass of the laminated body obtained at the process 1.

  Process 3: The process of pressurizing and heating the laminated body after deaeration.

  In the plastic film-inserted laminated glass of the present invention, a curved glass plate is used as the glass plate, and the radius of curvature of the curved glass plate is in the range of 0.9 m to 3 m. It is a plastic film insertion laminated glass produced by a method for producing an insertion laminated glass.

  The plastic film-inserted laminated glass of the present invention is a plastic film-inserted laminated glass characterized in that an infrared reflecting film is formed on one side of the plastic film.

  The plastic film-inserted laminated glass of the present invention is the plastic film-inserted laminated glass, wherein the infrared reflective film has four or more dielectric films so as to satisfy the following conditions (1) and (2): A plastic film-inserted laminated glass having a maximum value of reflection exceeding 50% in a wavelength region of 900 to 1400 nm.

(1) a dielectric film counted in order from the polymer resin sheet surface, the maximum value of the refractive index of the even-numbered layer n _emax, the minimum value and n _emin, the maximum value of the refractive index of the odd-numbered layer n _omax, minimum when the value was _n omin, n _emax <n omin or n _omax <n _emin.

(2) When the refractive index of the i-th layer is n _i and the thickness is d _i , 225 nm ≦ n _i · d _i ≦ 350 nm for infrared rays having a wavelength λ of 900 to 1400 nm.

Further, the plastic film-inserted laminated glass of the present invention is the plastic film-inserted laminated glass, wherein TiO _2, Nb ₂ O ₅ or Ta ₂ O ₅ is used as the high refractive index dielectric film, and the low refractive index dielectric film is used. It is a plastic film-inserted laminated glass characterized in that an infrared reflecting film is formed using SiO ₂ .

  Moreover, the plastic film-inserted laminated glass of the present invention is characterized in that in the plastic film-inserted laminated glass, the resin intermediate film is an infrared absorbing film containing conductive oxide particles as an infrared absorbing material. Plastic film-inserted laminated glass.

  Moreover, the plastic film insertion laminated glass of the present invention is the plastic film insertion laminated glass, wherein the thickness of the resin intermediate film is in the range of 0.3 to 1.2 mm.

  The plastic film-inserted laminated glass of the present invention is an infrared-reflecting laminated glass characterized in that the curved plate glass is an infrared-absorbing glass in the plastic-film-inserted laminated glass.

  The plastic film-inserted laminated glass of the present invention is the plastic film-inserted laminated glass, wherein the plastic film with an infrared reflecting film formed by laminating a dielectric film has the following (A), (B), (C): It is a near-infrared reflective laminated glass characterized by satisfying any of the conditions.

  (A) The thermal shrinkage of the plastic film with an infrared reflecting film is in the range of 0.5 to 4% in the temperature range of 90 to 150 ° C.

  (B) The elastic modulus of the plastic film is in the temperature range of 90 to 150 ° C. and in the range of 30 to 2000 MPa.

  (C) When a tensile force of 10 N is applied per 1 m width of the plastic film in the temperature range of 90 to 150 ° C., the elongation percentage of the plastic film is 0.3% or less.

  The plastic film-inserted laminated glass of the present invention is characterized in that in the plastic film-inserted laminated glass, a film of a silane coupling agent is formed on the surface of the plastic film on which the infrared reflective film is not formed. It is a plastic film insertion laminated glass.

  Moreover, the plastic film insertion laminated glass of the present invention is the plastic film insertion laminated glass, wherein a hard coat film is formed between the plastic film and the infrared reflective film. is there.

  Furthermore, the plastic film-inserted laminated glass of the present invention is the above-mentioned plastic film-inserted laminated glass, wherein the visible light transmittance defined in JIS R3211-1998 is 70% or more. Or, at least one glass plate is a heat-absorbing glass, and is a plastic film-inserted laminated glass.

  A plastic insertion laminated glass produced by using two glass plates curved in the same shape by a laminated film in which a plastic film is sandwiched between two resin intermediate films, with no appearance of wrinkles in the plastic film and good appearance A method for producing a plastic film-inserted laminated glass is provided.

  Especially when making laminated glass using curved glass with different radii of curvature, depending on the location and the direction of the same location, such as the glass used in automobile and vehicle windows, A plastic film-inserted laminated glass that does not cause wrinkles in the plastic film can be produced.

  The plastic film insertion laminated glass 1 as shown in FIG. 1 is produced by the method for producing a plastic film insertion laminated glass of the present invention.

  The plastic film insertion laminated glass 1 is a laminated glass produced using a laminated film 15 in which both sides of a plastic film 12 are sandwiched between resin intermediate films 11 and 13.

  A hot melt type adhesive such as polyvinyl butyral (PVB) or ethylene vinyl acetate (EVA) is suitably used for the resin intermediate film.

  The plastic film is preferably prepared by a stretching method. Among plastic films made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, polyether sulfone, nylon, polyarylate, cycloolefin polymer, and the like. You can choose from to use.

  In particular, the crystalline polyethylene terephthalate film (PET film) formed by the biaxial stretching method has excellent heat resistance and can be used in a wide range of temperature environments, and is highly transparent and produced in large quantities. Therefore, the quality is stable and suitable.

  In the method for producing a plastic film-inserted laminated glass of the present invention, the production method includes at least the following three steps (step 1, step 2 and step 3).

  Step 1: Inserting a plastic film between resin intermediate films to form a laminated film, and inserting the laminated film between two curved glass plates to form a laminated body, or one curved glass A step of sequentially laminating a resin intermediate film, a plastic film, a resin intermediate film, and a curved glass plate on a plate in this order.

  Process 2: The process of deaeration between the curved glass of the laminated body obtained at the process 1.

  Process 3: The process of pressurizing and heating the laminated body after deaeration.

  It is preferable to perform the process 1 and the process 2 in the temperature range of 10-25 degreeC, more preferably the temperature range of 15-25 degreeC of the environmental temperature at the time of work, and the temperature of a plastic film and a resin intermediate film.

  When the plastic film or the resin intermediate film is at a temperature higher than 25 ° C., the plastic film is wrinkled when the plastic film and the resin intermediate film are overlapped, and the generated wrinkle does not disappear in the degassing of the process 2 The wrinkles remain after the step of applying pressure and heating in step 3 to cause poor appearance.

  Also, if it is performed at a temperature lower than 10 ° C, the glass is significantly dewed when taken out to the room temperature / humidity process, and there is a concern about the deterioration of the resin intermediate film. This may cause trouble with the dropping device. In addition, when a person performs lamination work, workability is poor due to cold.

  If the thickness of the plastic film is less than 30 μm, the film is likely to be deformed and wrinkles are likely to occur. In addition, it is difficult to handle the film, and when an infrared reflective film is formed, the film tends to curl due to the stress of the infrared reflective film. On the other hand, if the thickness of the film is greater than 200 μm, an appearance defect due to poor deaeration occurs at the time of bonding, so the thickness is desirably 30 μm to 200 μm.

  The curved glass plate is obtained by bending soda-lime glass heated to a temperature equal to or higher than the softening point by a float method, and the use of a three-dimensional curved glass plate is simple.

  The three-dimensionally curved glass plate is a glass plate having a different radius of curvature depending on the location, such as a spherical surface, an elliptical spherical surface, or a front glass of an automobile.

  The curvature radius of the curved glass plate is desirably 0.9 m to 3 m.

  If the curvature radius is smaller than 0.9 m, the plastic film is likely to be wrinkled in the laminating process. Therefore, the curvature radius is preferably 0.9 m or more.

  In addition, when the radius of curvature is increased, the shape is close to a flat surface, and there is almost no effect of the present invention that the wrinkles of the plastic film do not occur, and the effect of the present invention appears when the radius of curvature of the curved glass is 3 m or less. .

  In step 1, a laminate 2 is produced by stacking a plastic film, a resin intermediate film, and a curved glass plate.

  The degassing in the step 2 is not particularly limited, but a method of degassing by pressing from both sides of the laminate 2 with a pressing roll 20 as shown in FIG. 2, as shown in FIGS. A method of attaching a tube 30 made of a rubber-based resin around the laminate 2 and exhausting air from the nozzle 31 to deaerate the laminate in a vacuum bag 40 as shown in FIGS. This can be done by putting the body 2 and exhausting air from the nozzle 41. A vacuum pump can be preferably used for exhausting air.

  Step 3 is the same as the method for producing a laminated glass using one resin interlayer, and the pressure and heat treatment by the autoclave is performed at a temperature of 90 to 150 ° C. and at a pressure of 1 MPa or less for about 30 minutes. It is preferable.

  The plastic film is preferably cut into a shape smaller than the curved glass plate used for the window.

  By making the shape smaller than the glass plate, wrinkles that occur near the sides of the glass plate can be avoided.

  In the method for producing the laminated plastic film-inserted glass of the present invention, a plastic film with an infrared reflective film having an infrared reflective film formed on one side can be suitably used.

Examples of the infrared reflection film include a metal film such as Au, Ag, Cu, and Al, and a dielectric film such as TiO ₂ , Nb ₂ O ₅ , Ta ₂ O ₅ , SiO ₂ , Al ₂ O ₃ , ZrO ₂ , and MgF _2. The multilayer film can be suitably used.

    In particular, an infrared reflection film formed by laminating a dielectric film transmits electromagnetic waves used for communication, and thus can be used in vehicles such as automobiles without impairing the functions of indoor communication devices. It is a reflective film.

  The infrared reflective film can be formed on a plastic film by sputtering. As a film formation method other than sputtering, a metal film may be formed by vapor deposition or ion plating, and a dielectric film is formed by CVD, vapor deposition, ion plating, or the like. May be.

  As shown in FIG. 7, the infrared reflective film formed by laminating the dielectric films is composed of 4 or more and 11 or less dielectric films so as to satisfy the following conditions (1) and (2). Therefore, it is desirable to have a maximum value of reflection exceeding 50% in the wavelength region from 900 nm to 1400 nm.

(1) The dielectric films are counted in order from the polymer resin sheet surface, the maximum value of the refractive index of the even-numbered layer 52 is n _emax , the minimum value is n _emin, and the maximum value of the refractive index of the odd-numbered layer 53 is no _max when the minimum value was _n omin, n _emax <n omin or n _omax <n _emin.

(2) When the refractive index of the i-th layer is n _i and the thickness is d _i , 225 nm ≦ n _i · d _i ≦ 350 nm for infrared rays having a wavelength λ of 900 to 1400 nm.

  When the number of laminated dielectric films constituting the infrared reflecting film 51 is 3 or less, reflection in the near infrared region is insufficient, and it is desirable that the number is 4 or more.

  In addition, as the number of layers increases, the maximum value of reflection in the near infrared region increases and the color in the visible light region becomes nearly colorless, so that a better infrared reflection film is obtained, but if the number of layers exceeds 12, it is manufactured. Since the cost increases and a problem arises in durability due to an increase in film stress due to an increase in the number of films, it is preferable to have 11 layers or less.

  Furthermore, the infrared reflective film 51 formed by laminating dielectric films has a wavelength of 900 nm to 1400 nm in order to exhibit effective heat insulation against sunlight thermal radiation while maintaining the transmittance in the visible light range. It is important that the reflectivity of the region has a maximum value exceeding 50%. This is shown in JIS R3106-1998 in consideration of the energy distribution of the wavelength of sunlight and the wavelength that becomes heat due to absorption, while minimizing the absorption and reflection in the visible light region that cause a decrease in the visible light transmittance. In order to effectively reduce the solar radiation transmittance, it is necessary to reflect light in the wavelength region from 900 nm to 1400 nm having a relatively large weight coefficient for calculating the solar radiation transmittance described in JIS R3106-1998. Therefore, it is effective to have a maximum of reflection in the wavelength region from 900 nm to 1400 nm. Furthermore, in order to exhibit effective heat insulation performance, it is important that the maximum value of reflection is 50% or more.

The dielectric film laminated film 51 may be formed using TiO _2, Nb ₂ O _5, or Ta ₂ O ₅ as a high refractive index dielectric film and SiO ₂ as a low refractive index dielectric film. This is desirable because a maximum value of reflection of 50% can be obtained.

  When manufacturing a plastic film-inserted laminated glass using the plastic film 60 with an infrared reflective film on which the infrared reflective film 51 is formed, the following (A), (B), ( It is preferable to have the characteristics as shown in C) because a plastic film-inserted laminated glass without wrinkles can be obtained in the plastic film 60 with an infrared reflecting film.

  (A) The thermal shrinkage of the plastic film with an infrared reflecting film is in the range of 0.5 to 4% in the temperature range of 90 to 150 ° C.

  (B) The elastic modulus of the plastic film is in the temperature range of 90 to 150 ° C. and in the range of 30 to 2000 MPa.

  (C) When a tensile force of 10 N is applied per 1 m width of the plastic film in the temperature range of 90 to 150 ° C., the elongation percentage of the plastic film is 0.3% or less.

  About the plastic film 60 with an infrared reflective film after forming the infrared reflective film 51 on the plastic film 50, (A) the thermal shrinkage rate is in the range of 0.5 to 4% in the temperature range of 90 to 150 ° C. It is desirable to select and use one.

  When the thermal shrinkage rate of the plastic film 60 with an infrared reflecting film at 90 to 150 ° C. is smaller than 0.5%, the film with the infrared reflecting film is bumped around the curved glass and the appearance defects that become wrinkles are found. appear.

  On the other hand, if the thermal shrinkage rate is greater than 4%, the infrared reflective film cannot withstand the shrinkage of the film, and an appearance defect that cracks into cracks occurs.

  Therefore, in order to prevent the wrinkles of the heat ray reflective film-coated plastic film 60 and the cracks of the infrared reflective film 51 from occurring in the alignment process, the thermal shrinkage rate of the plastic film 60 with the infrared reflective film is 90 to 150 ° C. In the temperature range, it is preferably in the range of 0.5 to 3%, more preferably, the thermal shrinkage rate of the plastic film 60 with an infrared reflecting film at 90 to 150 ° C. is in the range of 0.5 to 2%. is there.

  In a transparent plastic film, a plastic film produced by a stretching method such as a sequential biaxial stretching method is preferably used because stress during film formation remains in the film and the stress is relaxed and easily contracted by heat treatment. be able to.

  In order to prevent the plastic film 50 from being wrinkled even in a high temperature state of 90 to 150 ° C. in the high temperature and high pressure treatment by the autoclave, (B) the elastic modulus of the plastic film 50 is 90 to 150. It is desirable that it is 30MPa-2000MPa in the temperature range of ° C, More preferably, it is 30MPa-500MPa.

  The elastic modulus of the plastic film 50 can be obtained from a stress-strain curve in a temperature range of 90 to 150 ° C. using a viscoelasticity measuring device. When the elastic modulus of the plastic film 50 is less than 30 MPa, the plastic film 50 is easily deformed by a slight external force, and a wrinkled appearance defect is likely to occur on the entire surface of the laminated glass. In addition, when the elastic modulus of the plastic film 50 is greater than 2000 MPa, when applied to three-dimensionally curved glass, the air between the resin intermediate film and the plastic film is not completely removed in the high-temperature and high-pressure treatment by the autoclave. Prone to deaeration.

  Alternatively, in order to prevent the plastic film from wrinkling even in a high temperature state of 90 to 150 ° C. in the high temperature and high pressure treatment by the autoclave, (C) the elongation rate of the plastic film 50 is 90 to 150 ° C. In the high temperature range, when a tensile force of 10 N is applied per 1 m width to the plastic film 50, the elongation is preferably 0.3% or less.

  The tensile force of 10 N applied per 1 m width of the plastic film 50 is when the plastic film sandwiched between the resin interlayers is heated to high temperature and high pressure by an autoclave, and the plastic film and the glass plate are thermally fused by the resin interlayer. This corresponds to the tensile force generated in the plastic film to stretch the plastic film.

  The elongation percentage of the plastic film is measured by the following procedures 1 to 5.

  Procedure 1 A plastic film is cut into a length of 15 mm and a width of 5 mm to obtain a measurement sample. Fixing jigs are attached to both ends of the measurement sample, and the length of exposure of the measurement sample between the fixing jigs at both ends is set to 10 mm.

  Procedure 2 A tensile force of 10 N is applied to the measurement sample per 1 m width of the plastic film. In the case of the measurement sample shown in Procedure 1, a load of 0.05 N is applied.

Procedure 3 Measure the length L ₀ of the measurement sample between the fixing jigs.

  Procedure 4 Heat to a predetermined measurement temperature between 90 and 150 ° C. at 5 ° C./min, and measure the length L between the fixing jigs of the measurement sample at the measurement temperature.

Procedure 5 Elongation rate (%) is calculated by (L ₀ -L) / L × 100.

    Furthermore, as shown in FIG. A silane coupling agent film 55 is preferably formed on the surface of the plastic film 50 where the infrared reflective film 51 is not formed.

  The silane coupling agent improves the adhesion between the plastic film and the resin intermediate film, and a silane coupling agent having an amino group, an isocyanate group, an epoxy group, or the like can be used.

  A hard coat film 54 is preferably formed between the plastic film 50 and the infrared reflective film 51.

  Depending on the plastic film inserted between the resin intermediate films, adhesion to the resin intermediate film may be poor, or when an infrared reflective film is formed, white turbidity may occur, and the hard coat film 54 is formed at the interface. This can solve these problems.

  The hard coat film and the silane coupling agent film can be formed by spraying, spin coating, roll coating, dipping, or the like with chemicals for forming the respective films.

  Furthermore, the visible light transmittance specified in JIS R3106-1998 of the plastic film-inserted laminated glass is 70% or more so that the visible light of sunlight is taken into the room to create a comfortable bright indoor space. Is desirable.

  Moreover, when using the plastic insertion laminated glass of this invention for the front glass of a motor vehicle, it is important that the visible light transmittance prescribed | regulated by JISR3211 is 70%.

  Moreover, the heat-shielding property of this invention can be improved by using heat ray absorption glass for a glass plate, and it is preferable.

  Hereinafter, with reference to the drawings, the present invention will be described in detail by way of examples and comparative examples. In addition, this invention is not limited to the Example shown below.

Example 1
A plastic film-inserted laminated glass 3 shown in FIG. 9 was produced using a plastic film 61 with an infrared reflecting film obtained by laminating the dielectric film shown in FIG. 8 on the plastic film 12 shown in FIG.

  As the plastic film 50, a PET film having a thickness of 100 μm is used, and a hard coat film 54 is applied to one side of the plastic film 50, and an infrared reflecting film 51 is formed thereon, thereby forming a plastic film 61 with a heat ray reflecting film. It was.

  As the hard coat film 54, an acrylic hard coat film having a thickness of 5 μm was roll-coated.

Infrared reflection film 51, using a TiO ₂ film on the dielectric film 53, using the SiO ₂ film on the dielectric film 52, and alternately laminating a dielectric film 53 and the dielectric film 52. The thickness of the TiO ₂ film was 105 nm, and the thickness of the SiO ₂ film was 175 nm. The dielectric film 53 has five layers and the dielectric film 52 has four layers, and the infrared reflection film 51 has nine layers in which TiO ₂ films (thickness 105 nm) and SiO ₂ films (thickness 175 nm) are alternately laminated. It is a multilayer film.

  The dielectric film was sequentially formed on the hard coat film 54 by sputtering.

  On the surface of the plastic film 50 opposite to the surface on which the hard coat film 54 was formed, a film 55 of a silane coupling agent was formed by a roll coating method.

  The thermal contraction rate was measured as follows according to JIS C 2318.

  As shown in FIG. 10, a strip-shaped film 200 having a length of 150 mm and a width of 40 mm was cut out, and a marked line was marked with a diamond pen at a distance of about 100 mm in the vicinity of the center in each width direction. After marking the marked line, the strip-shaped film 200 was divided into two equal parts of 150 mm × 20 mm.

  One of the test pieces 202 divided into two equal parts was suspended vertically in a hot-air circulating thermostat, heated to a measurement temperature of 130 ° C. at a temperature increase rate of about 5 ° C./min, and held at the measurement temperature for about 30 minutes.

  Thereafter, the hot air circulating thermostat was opened to the atmosphere, naturally cooled at about 20 ° C./min, and further maintained at room temperature for 30 minutes.

  A thermocouple thermometer was used to measure the temperature, and the temperature distribution in the hot air circulating thermostat was set within ± 1 ° C.

  The distance L1 and L2 between the marked lines were used for the test piece 201 that had been kept at room temperature and the test piece 202 that had been heated to the measurement temperature, using a scanning laser microscope 1LM21D manufactured by Lasertec. Measured.

  The thermal contraction rate (%) was calculated by (L1-L2) / L1 × 100.

  In addition, three strip-shaped films 200 were cut out for each of the MD direction and the TD direction of the PET film, and the average value of the thermal contraction rate measured for the three sheets was used.

  As the resin intermediate films 11 and 13, PVB films having a thickness of 0.38 mm were used.

  A curved glass plate having a size of 250 mm × 350 mm and a thickness of 2 mm was used.

  The curvature radius of the curved glass plate was between 0.9 m and 1 m, the peripheral portion was 0.9 m, and the central portion was 1 m.

  The plastic film with a heat ray reflective film, the resin intermediate film, and the curved glass were laminated in the following steps 1 to 3 to produce a plastic film-inserted laminated glass 1.

  Step 1: The curved glass plates 10 and 14, the resin intermediate films 11 and 13, and the plastic film 61 with a heat ray reflective film are placed in a room where the room temperature is 18 ° C. and left for 1 hour, and the temperature of each member is 18 ° C. Confirmed to be. Thereafter, on the curved glass plate 14, the resin intermediate film 13, the plastic film 61 with a heat ray reflective film, the resin intermediate film 11, and the curved glass plate 10 were sequentially stacked to obtain a laminate 2.

  Step 2: The laminated body 2 obtained in Step 1 is placed in the rubber vacuum bag 40 shown in FIGS. 5 and 6 in the same room where the room temperature is 18 ° C. where the Step 1 is performed. It was. Air was sucked from the exhaust nozzle 31 using an exhaust pump (not shown), and the inside of the vacuum bag was depressurized with a low pressure.

  Step 3: In a state where the laminate 2 in Step 2 was put in the vacuum bag 40 and deaerated, the vacuum bag 40 containing the laminate 2 was put in an autoclave and heated under pressure for 15 minutes. The pressurization was 0.2 MPa, and the heating was performed at 95 ° C.

  Next, the laminate 2 was taken out from the autoclave and taken out from the vacuum bag 40. At this stage, the laminate had already been fused by the resin interlayer.

  Again, the laminated body 2 in the fused state was placed in an autoclave and heated under pressure for 30 minutes. Pressurization heating was performed at a pressure of 1 MPa and a heating temperature of 140 ° C.

  The produced plastic film-inserted laminated glass 3 was free from wrinkles of the plastic film with a heat ray reflective film and cracks of the infrared reflective film, and a plastic film-inserted laminated glass having a good appearance was obtained.

  In addition, a laminated glass that has a maximum value of reflection at a wavelength of 900 nm to 1200 nm and has a maximum reflectance of 60% or more and reflects infrared rays satisfactorily is obtained, and a plastic film with an infrared reflection film before the lamination process has The infrared reflection characteristics were almost unchanged.

Example 2
As the plastic film with a heat ray reflective film, the plastic film 62 with an infrared reflective film formed by laminating a metal film 83 on one surface of the plastic film 50 shown in FIG. 11 was used.

  Silver was used for the metal film 83, and a zinc oxide film 82 was formed between the metal film 83 and the plastic film 50 and on the metal film 83.

  Both the metal film and the zinc oxide film were formed by sputtering.

  As the plastic film 50, a PET film having a thickness of 50 μm was used.

  Other than that, the plastic film-inserted laminated glass 4 shown in FIG.

  Similarly to Example 1, the plastic film-inserted laminated glass of this example also had a good appearance with no wrinkles observed on the plastic film.

Example 3
In step 2, without using the vacuum bag used in Example 1, as shown in FIGS. 3 and 4, a rubber-based resin tube 30 was attached to the periphery of the laminate 2 and deaerated. All in the same manner as in Example 1, a plastic film-inserted laminated glass 3 shown in FIG. 9 was produced.

  The plastic film-inserted laminated glass of this example also had a good appearance in which no wrinkles were observed on the plastic film.

Example 4
A plastic film 60 with a heat ray reflective film shown in FIG. 7 was produced by using a PET film having a thickness of 50 μm as the plastic film 50 and forming the heat ray reflective film 51 similar to that of Example 1 on one surface of the plastic film 50.

  When the heat shrinkage rate of this plastic film 60 with a heat ray reflective film was measured in the same manner as in Example 1, it was 1.5% in the MD direction and 1% in the TD direction. Further, using this plastic film 60 with a heat ray reflective film, a plastic-inserted laminated glass 5 shown in FIG. 13 was produced in the same manner as in Example 1.

  For the glass plates 10 and 14, bent float glass having the same size and thickness as in Example 1 and having a radius of curvature of 2.8 to 3 m was used.

Similarly to Example 1, the plastic-inserted laminated glass 2 of this example was free from wrinkles of the plastic film with a heat ray reflective film and cracks of the infrared reflective film, and a plastic-inserted laminated glass having a good appearance was obtained.
Example 5
A plastic film 63 with an infrared reflecting film shown in FIG. 14 was produced. For the plastic film 50, the PET film used in Example 4 was used. On both sides of the plastic film 50, an acrylic hard coat layer 54 was laminated with a thickness of 2 μm. Further, the plastic film 50 was implemented on one side of the plastic film 50. A heat ray reflective film 51 was formed in the same manner as in Example 1.

  The thermal contraction rate of the plastic film 63 with an infrared reflecting film was measured in the same manner as in Example 1, and was 1% in the MD direction and 0.6% in the TD direction.

  Further, using this plastic film 63 with an infrared reflecting film, a plastic insertion laminated glass 6 shown in FIG.

  The plastic-inserted laminated glass 6 of this example was also free from the wrinkles of the infrared-reflective film-attached plastic film 63 and the infrared-reflective film 51, and a plastic-inserted laminated glass having a good appearance was obtained.

Example 6
As the plastic film 50, a PET film having a thickness of 100 μm and a thermal shrinkage rate at 150 ° C. of 4% in the MD direction and 3.5% in the TD direction was used. In the same manner as in Example 5, an acrylic hard coat layer 54 having a thickness of 2 μm was formed on this PET film and simultaneously heat treated at 50 ° C. to obtain a plastic film 63. An infrared reflective film similar to that in Example 5 was formed on the plastic film 202, thereby producing a plastic film 63 with an infrared reflective film.

  The thermal contraction rate of the plastic film 63 with the infrared reflecting film was measured in the same manner as in Example 1. As a result, it was 2.0% in the MD direction and 1.6% in the TD direction.

  Further, using this plastic film 63 with an infrared reflecting film, a plastic-inserted laminated glass 6 shown in FIG.

  The plastic-inserted laminated glass 6 produced in this example was free from wrinkles of the plastic film with a heat ray reflective film and cracks of the infrared reflective film, and a plastic-inserted laminated glass having a good appearance was obtained.

Example 7
A plastic film-inserted laminated glass 7 shown in FIG. 16 was produced in the same manner as in Example 1. Two flat glass plates 104 and 144 having a thickness of 300 mm × 300 mm and a thickness of 2 mm and two PVB films 114 and 134 having a thickness of 0.38 mm were used, and the plastic film 203 was sandwiched between the PVB films 114 and 134. . As the plastic film 203, a polyethylene terephthalate film (PET film) (thickness 50 μm) having an elastic modulus at 130 ° C. of 40 MPa was used.

  The produced plastic film laminated glass 7 was a plastic film-inserted laminated glass having no appearance on the plastic film 203 and having a good appearance.

Example 8
A plastic film insertion laminated glass 8 using a curved glass plate as shown in FIG. 17 was produced in the same manner as in Example 7 except that a curved glass was used. As the curved glass plates 10 and 14, two glass plates having a radius of curvature of 1200 mm, a size of 250 mm × 350 mm, and a thickness of 2 mm were used.

  The plastic film-inserted laminated glass 8 produced in this example was also a plastic film-inserted laminated glass with no appearance of wrinkles and good appearance.

Example 9
A PET film having a thickness of 100 μm is used as the plastic film 50, and an infrared reflection film 51 is formed on one surface of the plastic film 50 by alternately laminating hard coat films 54 and dielectric films 52 and 53, as shown in FIG. A plastic film 64 with an infrared reflective film was produced.

  An acrylic hard coat film was used as the hard coat film 54 and laminated on one side of the plastic film 50 with a thickness of 5 μm.

The infrared reflecting film 51 uses a TiO ₂ film (thickness of 105 nm) as the dielectric film 53 and a SiO ₂ film (thickness of 175 nm) as the dielectric film 52, and has a film configuration similar to that of the first embodiment. The film was formed.

  The elastic modulus at 130 ° C. of the plastic film 64 with an infrared reflecting film was 1000 MPa.

  Using this plastic film 64 with an infrared reflecting film, a plastic film-inserted laminated glass 9 having the configuration shown in FIG. 19 was produced in the same manner as in Example 1.

  The plastic film-inserted laminated glass 9 of this example also had a good appearance with no wrinkles observed.

Example 10
A plastic insertion laminated glass 7 shown in FIG. 16 was produced. As the glass plates 104 and 144, flat glass plates made of soda lime glass by a float method having a thickness of 300 mm × 300 mm and a thickness of 2 mm were used.

  As the plastic film 203, a PET film (thickness: 100 μm) was used. The elongation of the PET film measured at a temperature of 150 ° C. and a tensile force of 10 N per 1 m of the width of the film was 0.02% in the MD direction and 0.13% in the TD direction. .

  The elongation percentage was measured according to Procedure 1 to Procedure 5 using a Rigaku thermomechanical analyzer (PTC10A).

  Further, a PVB film having a thickness of 0.38 mm was used for the resin intermediate films 114 and 134.

  The glass plate 144, the resin intermediate film 134, the plastic film 203, the resin intermediate film 114, and the glass plate 104 are sequentially stacked, and the excess portions of the resin intermediate film 114, the plastic film 203, and the resin intermediate film 134 that protrude from the edge of the glass plate are removed. After cutting and removing, a plastic-inserted laminated glass 7 was produced in the same manner as in Example 1.

  The produced plastic-inserted laminated glass 7 was a plastic-inserted laminated glass having a good appearance with no wrinkle-like appearance defects in the plastic film 203 with an infrared reflecting film.

Example 11
The glass plates 10 and 14 are all the same as in Example 8 except that a glass plate made of soda lime glass by a float method with a thickness of 2 mm and a radius of curvature of 1200 mm is used. A plastic insertion laminated glass 8 shown in FIG.

  In the produced plastic-inserted laminated glass 4, as in Example 8, a plastic-inserted laminated glass having no appearance of wrinkle-like appearance on the plastic film 203 and having a good appearance was obtained.

Example 12
A plastic insertion laminated glass 6 shown in FIG. 15 was produced in the same manner as in Example 8 except that the plastic film 63 with an infrared reflecting film shown in FIG. 14 was used instead of the plastic film 203.

  The plastic film 63 with an infrared reflecting film was produced as follows.

An acrylic hard coat film 54 is laminated on both sides of the PET film 50 to a thickness of 5 μm. Further, the infrared reflecting film 51 includes an Nb ₂ O ₅ film as a dielectric film 52 and an SiO ₂ film as a dielectric film 53. Nb ₂ O ₅ film (thickness 115 nm), SiO ₂ film (thickness 175 nm), Nb ₂ O ₅ film (thickness 115 nm), SiO _{2 on} one side of the PET film 20 having a hard coat layer formed thereon. A film (thickness 175 nm), an Nb ₂ O ₅ film (thickness 115 nm), an SiO ₂ film (thickness 175 nm), and an Nb ₂ O ₅ film (thickness 115 nm) were sequentially formed by sputtering.

  The elongation rate at 150 ° C. of the plastic film 63 with an infrared reflecting film in which the hard coat film 54 and the infrared reflecting film 51 are formed (state in which a tensile force of 10 N is applied per 1 m of the film width) is MD direction. It was 0.01% or less and 0.19% in the TD direction.

  A plastic insertion laminated glass 6 shown in FIG. 15 was produced in the same manner as in Example 1 by using a plastic film 63 with an infrared reflecting film.

  The produced plastic-inserted laminated glass 6 was a plastic-inserted laminated glass having a good appearance with no wrinkle-like appearance defect in the plastic film 64 with an infrared reflecting film.

Comparative Example 1
A plastic film-inserted laminated glass was produced in the same manner as in Example 1 except that Steps 1 and 2 described in Example 1 were performed at a room temperature of 28 ° C.

  In the produced plastic film-inserted laminated glass, wrinkles were observed in the plastic film at the periphery thereof, and the appearance was poor, which was not suitable for practical use.

Comparative Example 2
The plastic film 60 with an infrared reflective film of FIG. 7 was produced. Using the PET film used in Example 1 as the plastic film 50, a heat ray reflective film 51 formed by alternately forming 20 layers of the same dielectric films 52 and 53 as in Example 1 is formed.
When the thermal shrinkage rate at 150 ° C. of this plastic film 60 with an infrared reflecting film was measured in the same manner as in Example 1, it was 0.4% in the MD direction and 0.2% in the TD direction.

  Furthermore, the plastic insertion laminated glass 5 shown in FIG. 13 was produced in the same manner as in Example 1 by using the plastic film 60 with the infrared ray reflective film with the heat ray reflective film.

  Wrinkles of the plastic film 60 with a heat ray reflective film were observed in the peripheral part of the produced plastic-inserted laminated glass 5, and it was not suitable for practical use due to poor appearance.

Comparative Example 3
A plastic film 63 with an infrared reflecting film shown in FIG. 14 was produced. As the plastic film 50, a PET film having a thickness of 100 μm having a thermal shrinkage rate at 150 ° C. of 1.0% in the MD direction and 0.5% in the TD direction was used. As in Example 3, an acrylic hard coat layer 54 having a thickness of 2 μm was formed on this PET film, and an infrared reflective film 51 similar to that in Example 1 was formed on one side of the hard coat layer.

  When the thermal shrinkage rate of this plastic film 61 with an infrared reflecting film was measured in the same manner as in Example 1, it was 0.3% in the MD direction and 0.2% in the TD direction.

  Further, using this plastic film 63 with an infrared reflecting film, a plastic-inserted laminated glass 6 having the configuration shown in FIG. 15 was produced in the same manner as in Example 1.

  Wrinkles of the plastic film 63 with a heat ray reflective film were observed in the periphery of the produced plastic-inserted laminated glass 6, and practical use was difficult due to poor appearance. Further, cracks were also observed in the infrared reflective film 51 in the wrinkled portion.

Comparative Example 4
For the plastic film 50, a PET film having a thickness of 100 μm with a thermal shrinkage rate at 150 ° C. of 8% in the MD direction and 7% in the TD direction is formed, and an acrylic hard coat layer 24 is formed on the PET film with a thickness of 2 μm. Furthermore, the infrared reflective film 51 similar to Example 1 was formed, and the plastic film 63 with an infrared reflective film shown in FIG. 14 was produced.

  When the heat shrinkage rate of the plastic film 63 with the infrared reflecting film was measured in the same manner as in Example 1, it was 7% in the MD direction and 6% in the TD direction.

  Further, using this plastic film 63 with an infrared reflecting film, a plastic-inserted laminated glass 6 having the configuration shown in FIG. 15 was produced in the same manner as in Example 1.

  In the produced plastic-inserted laminated glass 6, there was no wrinkle-like defect in the plastic film 63 with a heat ray reflective film, but cracks were generated on the entire surface of the infrared reflective film 51, making practical use difficult.

Comparative Example 5
The glass plates 10 and 14 have a size of 250 mm × 350 mm, a thickness of 2 mm, a radius of curvature near the periphery is a minimum value of 0.7 m, and a radius of curvature at the center is 0.8 m. A plastic insertion laminated glass 3 shown in FIG. 9 was produced in the same manner as in Example 1 except that two glass plates having the same shape were used.

  Wrinkles of the plastic film 61 with a heat ray reflective film were observed in the peripheral part of the produced plastic-inserted laminated glass 3, and it was not suitable for practical use due to poor appearance.

Comparative Example 6
A plastic film-inserted laminated glass 8 was produced in the same manner as in Example 8 except that a PET film having an elastic modulus of 20 MPa at 130 ° C. was used as the plastic film 203. Wrinkled appearance defects occurred on the entire surface of the plastic film-inserted laminated glass 3 produced in this comparative example.

Comparative Example 7
A plastic film-inserted laminated glass 9 with an infrared reflecting film was produced in the same manner as in Example 9 except that a PET film having an elastic modulus of 3000 MPa at 130 ° C. was used for the plastic film 20 of FIG.

  In the plastic film-inserted laminated glass 9 produced in this comparative example, the air remained between the PVB and the plastic film in the center of the glass, which was in a poorly deaerated state, and was not practical.

Comparative Example 8
A plastic insertion laminated glass 7 shown in FIG. 16 is produced in the same manner as in Example 8 except that a PET film (thickness: 100 μm) having an elongation rate of 0.3% at 150 ° C. is used as the plastic film 203. did.

  Wrinkled appearance defects occurred on the entire surface of the produced plastic-inserted laminated glass 7.

Comparative Example 9
A plastic insertion laminated glass 8 shown in FIG. 17 was produced in the same manner as in Example 9 except that a PET film (thickness: 100 μm) with an elongation rate of 0.3% at 150 ° C. was used as the plastic film 203. did.

  Similar to Comparative Example 7, wrinkled appearance defects occurred on the entire surface of the produced plastic-inserted laminated glass 8.

It is a schematic sectional drawing of plastic insertion glass. It is a schematic sectional drawing which shows the deaeration method using a roll. It is a schematic plan view which shows the deaeration method using a tube. It is a schematic sectional drawing which shows the deaeration method using a tube. It is a schematic plan view which shows the deaeration method using a vacuum bag. It is a schematic plan view which shows the deaeration method using a vacuum bag. It is a schematic sectional drawing which shows the structure of the infrared reflective film laminated | stacked on the plastic film. It is a schematic sectional drawing which shows the structure of the infrared rays reflecting film laminated | stacked on the plastic film, the film | membrane of a silane coupling agent, and a hard-coat film | membrane. It is a schematic sectional drawing of plastic insertion glass. It is a figure for demonstrating the measurement of a heat contraction rate. It is a schematic sectional drawing of the plastic film with a heat ray reflective film by a metal film. It is a schematic sectional drawing of the plastic insertion glass formed using the plastic film with a heat ray reflective film by a metal film. It is a schematic sectional drawing of plastic insertion glass. It is a schematic sectional drawing which shows the structure of the hard-coat film | membrane laminated | stacked on both surfaces of the plastic film, and the infrared reflective film laminated | stacked on one side. It is a schematic sectional drawing of the plastic insertion glass which consists of this invention. It is a schematic sectional drawing of the plastic insertion glass which uses a flat glass plate. It is a schematic sectional drawing of plastic insertion glass. It is a schematic sectional drawing which shows the structure of the plastic film with a heat ray reflective film. It is a schematic sectional drawing of plastic insertion glass.

Explanation of symbols

1, 3, 4, 5, 6, 7, 8, 9 Plastic insertion laminated glass 2 Laminated body 10, 14 Curved glass plate
11, 13 Resin intermediate film 12 Plastic film 15 Laminated film 20 Pressing roll 30 Tube 31 Exhaust nozzle 40 Vacuum bag 41 Exhaust nozzle 50 Plastic film 51 Infrared reflective film 52 Even-numbered dielectric film 53 Odd-numbered dielectric film 54 Hard Coat film 55 Silane coupling agent film 60, 61, 62, 63, 64 Plastic film 82 formed with infrared reflecting film Zinc oxide film 83 Metal film 104, 144 Flat glass plate 114, 134 PVB film 200 Strip-shaped film ( Thermal shrinkage measurement sample)
201 Test piece (non-heated piece)
202 Test piece (heated piece)
203 Plastic film

Claims (12)

In a method for producing a plastic film-inserted laminated glass produced using a laminated film in which a plastic film is sandwiched between two resin interlayers, the thickness of the plastic film is in the range of 30 to 200 μm, and the production method Includes at least the following three steps (step 1, step 2, step 3), and includes step 1 and step 2 in a temperature range in which the ambient temperature during operation, the temperature of the resin intermediate film and the plastic film are 10 to 25 ° C. A method for producing a laminated plastic film-inserted glass, which is performed.
Step 1: Inserting a plastic film between resin interlayers to form a laminated film, and inserting the laminated film between two glass plates to form a laminated body, or on one glass plate , A step of sequentially laminating a resin intermediate film, a plastic film, a resin intermediate film, and a glass plate in this order.
Process 2: The process of deaerating between the glass of the laminated body obtained at the process 1.
Process 3: The process of pressurizing and heating the laminated body after deaeration.   A curved glass plate is used as the glass plate, and the radius of curvature of the curved glass plate is in a range of 0.9 m to 3 m. Plastic film inserted laminated glass.   The plastic film-inserted laminated glass according to claim 2, wherein an infrared reflecting film is formed on one side of the plastic film. The infrared reflective film is formed by laminating 4 or more and 11 or less dielectric films so as to satisfy the following conditions (1) and (2), and exceeds 50% in the wavelength region from 900 nm to 1400 nm. 4. The plastic film-inserted laminated glass according to claim 2, having a maximum value of reflection.
(1) Count the dielectric films in order from the plastic film side, the maximum value of the refractive index of the even-numbered layer is n _emax , the minimum value is n _emin , the maximum value of the refractive index of the odd-numbered layer is no _max , and the minimum value is when the _n omin, n _emax <n omin or n _omax <n _emin.
(2) When the refractive index of the i-th layer is n _i and the thickness is d _i , 225 nm ≦ n _i · d _i ≦ 350 nm for infrared rays having a wavelength λ of 900 to 1400 nm. An infrared reflecting film is formed by using TiO _2, Nb ₂ O ₅ or Ta ₂ O ₅ for a high refractive index dielectric film and SiO ₂ for a low refractive index dielectric film. Item 5. A plastic film-inserted laminated glass according to Item 4.   The plastic film-inserted laminated glass according to any one of claims 2 to 5, wherein the resin intermediate film is an infrared absorbing film containing conductive oxide particles as an infrared absorbing material.   The plastic film-inserted laminated glass according to any one of claims 2 to 6, wherein the thickness of the resin intermediate film is in the range of 0.3 to 1.2 mm. 8. The plastic film with an infrared reflecting film formed by laminating a dielectric film satisfies any one of the following conditions (A), (B), and (C): The near-infrared reflective laminated glass of crab.
(A) The thermal shrinkage of the plastic film with an infrared reflecting film is in the range of 0.5 to 4% in the temperature range of 90 to 150 ° C.
(B) The elastic modulus of the plastic film is in the temperature range of 90 to 150 ° C. and in the range of 30 to 2000 MPa.
(C) When a tensile force of 10 N is applied per 1 m width of the plastic film in the temperature range of 90 to 150 ° C., the elongation percentage of the plastic film is 0.3% or less.   9. The plastic film-inserted laminated glass according to claim 2, wherein a film of a silane coupling agent is formed on the surface of the plastic film on which the infrared reflecting film is not formed. .   The plastic film-inserted laminated glass according to any one of claims 2 to 9, wherein a hard coat film is formed between the plastic film and the infrared reflective film.   The plastic film-inserted laminated glass according to any one of claims 2 to 10, wherein the visible light transmittance defined in JIS R3211-1998 is 70% or more.   The plastic film-inserted laminated glass according to any one of claims 2 to 11, wherein at least one glass plate is heat ray absorbing glass.

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