JP2010180068A - Method for manufacturing interlayer for laminated glass for vehicle, interlayer for laminated glass for vehicle and laminated glass for vehicle - Google Patents

Abstract

An object of the present invention is to form, in a colored portion of an interlayer film for laminated glass for vehicles having a colored portion for forming a shade band, an area having almost no color without causing distortion, regardless of its shape. It is an object of the present invention to provide a method for producing the intermediate film that can be produced.
SOLUTION: A first region, a second region provided on an upper side portion and having a visible light transmittance lower than that of the first region by coloring, and at least visible light transmission provided in the second region. A method for manufacturing an intermediate film for laminated glass having a third region whose rate is higher than that of the second region, wherein the upper side portion is colored so that at least the visible light transmittance is lower than that of the first region A step of preparing a material, and a step of irradiating a site to be the third region in the intermediate film material with a high energy ray or performing a chemical treatment, thereby at least making the visible light transmittance higher than that of the second region; , Including.
[Selection] Figure 1

Description

  The present invention relates to a method for producing an interlayer film used for vehicle laminated glass, an interlayer film for vehicle laminated glass obtained by the method, and a vehicle laminated glass using the interlayer film.

  A laminated shade region (shade band) colored green or blue for the purpose of antiglare and heat insulation may be formed on vehicle laminated glass (automobile windshield, etc.). In many cases, the shade band is generally formed by coloring an intermediate film that joins a glass plate of laminated glass into a strip shape. Here, the windshield has a legal region (sometimes referred to as a “field of view” in this specification) where the visible light transmittance should be a predetermined value or more (for example, 70% or more). For this reason, the shade band of the windshield is arranged outside the visual field region, usually at the top.

  In recent years, the use of IT in automobiles has progressed, and in many cases, sensors, a CCD (Charge Coupled Device), a CMOS (Complement Metal Oxide Semiconductor) camera, and the like are installed on the upper inside of a windshield.

  However, as described above, a shade band may be formed in this region. When light is received through a shade band that greatly reduces the light transmittance from the visible region to the infrared region, the sensitivity of the light receiving device decreases. For this reason, conventionally, there are cases where it is difficult to achieve compatibility between the light receiving device and the shade band, such as changing the mounting position of the light receiving device.

  In order to solve these problems, various techniques have been studied so far. For example, a technique for printing a non-colored pattern on a light receiving device installation part by printing a shade band on a glass plate or an intermediate film, or replacing the intermediate film in the shade band part with an uncolored intermediate film as shown in FIG. Techniques (see Patent Document 1 and the like) are disclosed.

However, in the technique of printing the shade band on the intermediate film, there is a possibility that the ink is transferred to the manufacturing facility in the processes after the printing process. Furthermore, the surface of the interlayer film is embossed to prevent blocking phenomenon and improve deaeration during pre-compression, but depending on the size and shape of the embossing, the appearance may be impaired by printing. There is a possibility.
Further, in the technique of replacing the intermediate film in the shade band portion with the non-colored intermediate film, distortion occurs at the joint between the colored intermediate film and the non-colored intermediate film. In particular, the tendency is remarkable in the case of a multilayer intermediate film. Further, in the case of a wedge-shaped intermediate film, it is necessary to replace a non-colored intermediate film having the same wedge angle in a hollow portion, which is very difficult.
Therefore, it has been desired to develop a method for overcoming the drawbacks of the printing technology and forming a non-colored region without causing distortion in the shade band portion of the interlayer film.

International Publication No. 2003/059837 Pamphlet

  The present invention provides an intermediate film which can form a region with little coloration in a colored portion of an intermediate film for vehicle laminated glass having a shade band, regardless of its shape, and without causing distortion. Manufacturing method, seamless intermediate film causing distortion at the boundary between the colored region and the non-colored region in the shade band, and a vehicle having no distortion near the boundary between the colored region and the non-colored region in the shade band It is an object to provide a laminated glass.

In one aspect of the method for producing an interlayer film for laminated glass of the present invention, the first region and the upper side portion are provided adjacent to the first region, and at least the visible light transmittance is lower than the first region by coloring. An intermediate for vehicle laminated glass having a strip-shaped second region and a third region having at least a visible light transmittance higher than that of the second region provided in a predetermined portion in the second region A method for manufacturing a membrane, comprising:
An intermediate film material is prepared in which the portions corresponding to the second region and the third region in the intermediate film are colored so that at least the visible light transmittance is a predetermined value lower than that of the first region in the intermediate film. Process,
A step of irradiating a site to be the third region of the second region of the intermediate film material with a high energy ray or performing chemical treatment so that at least the visible light transmittance is higher than that of the second region. When,
(Hereinafter referred to as “manufacturing method according to the first aspect”).

Another aspect of the method for manufacturing the interlayer film for laminated glass according to the present invention includes a first region, and an upper side portion provided adjacent to the first region and colored so that at least visible light transmittance is higher than that of the first region. Vehicle-laminated glass having a belt-like second region having a reduced height and a third region having at least a visible light transmittance higher than that of the second region provided at a predetermined portion in the second region An intermediate film manufacturing method for
A photosensitive colorant that forms a colored region having at least a visible light transmittance lower than that of the first region by irradiation with a predetermined high energy ray at a portion corresponding to at least the second region of the intermediate film. A step of preparing an intermediate film material to be contained;
Irradiating a portion corresponding to the second region with a predetermined high energy ray to develop the photosensitive color former; and
(Hereinafter referred to as “manufacturing method according to the second aspect”).

  In addition, the present invention provides an interlayer film for vehicle laminated glass obtained by the manufacturing method according to the first aspect or the second aspect.

  The present invention also provides a vehicle laminated glass having a structure in which at least two glass plates are bonded to each other through an interlayer film for vehicle laminated glass obtained by the manufacturing method according to the first aspect or the second aspect. To do.

  According to the manufacturing method of the present invention, it is possible to form an almost uncolored region in the colored portion of the intermediate film for laminated glass having a shade band, regardless of its shape, and without causing distortion. It is. In addition, the interlayer film for laminated glass of the present invention has no seam at the boundary between the colored region of the shade band and the non-colored region, so that no distortion occurs when the laminated glass is used. Furthermore, the vehicle laminated glass of the present invention is excellent in quality because there is no distortion near the boundary between the shade band colored region and the non-colored region.

It is a figure which shows one Embodiment of the vehicle laminated glass intermediate film of this invention. It is a figure which shows another one Embodiment of the vehicle laminated glass intermediate film of this invention. It is a figure which shows typically the method of providing the colorless part for sensor attachment in the shade band area | region of the conventional intermediate film.

The intermediate film for laminated glass for vehicles targeted by the production method of the present invention is provided at the upper side and adjacent to the first region on the upper side and has at least a visible light transmittance lower than that of the first region due to coloring. The vehicle laminated glass intermediate film includes the second region and a third region having at least a visible light transmittance higher than that of the second region, which is provided at a predetermined portion in the second region. .
In the present specification, “upper side” and “lower side” mean the sides that become the upper side and the lower side when the laminated glass is attached to the vehicle, respectively, and the side sides mean the other two sides. Further, “upper side” means a region near the upper side of the laminated glass, and “lower side” means a region near the lower side of the laminated glass.
First, the 1st aspect of the manufacturing method of the intermediate film for vehicle laminated glasses of this invention for manufacturing the said intermediate film for vehicle laminated glass is demonstrated.

  According to a first aspect of the present invention, at least the visible light transmittance of the portions corresponding to the second region and the third region in the intermediate film is lower than the first region in the intermediate film due to coloring. A sheet-like intermediate film material (hereinafter, also referred to as “interlayer film material having a colored region”) prepared, and a third region of the second region in the intermediate film material A method for producing an interlayer film for a laminated glass of a vehicle, comprising: irradiating a site with a high energy ray or applying a chemical treatment to at least make the visible light transmittance higher than that of the second region. It is.

(1-1) Step of preparing an intermediate film material having a colored region The intermediate film material having a colored region is formed by converting a thermoplastic resin composition, which is a raw material of an intermediate film for vehicle laminated glass, into a sheet shape by a conventionally known method. When the film is formed, a band-like region containing a colorant (a portion corresponding to the second region and the third region in the intermediate film. Hereinafter, also referred to as “band-like colored region”) is included in the upper side. It is produced by forming. In addition, when the thermoplastic resin composition is formed into a film, a portion that does not contain a colorant, that is, a portion excluding the band-like colored region of the intermediate film material is a portion corresponding to the first region.

The degree of coloring of the belt-like colored region may be uniform or gradation may be applied. In the latter case, it is preferable that the transmittance is adjusted so that the transmittance gradually increases from the upper side to the lower side of the intermediate film in terms of imparting antiglare property and heat shield property without impeding the driver's view. Further, the boundary between the band-like colored region and the first region having a high visible light transmittance may be blurred unclearly. The size of the belt-like colored region is preferably 50% or less in terms of the area ratio with respect to the entire intermediate film material. Regarding the visible light transmittance of the intermediate film material having the colored region, in the first region where visibility is required in the laminated vehicle glass as the visible light transmittance of the laminated glass when the laminated glass is produced using the interlayer film material. Is preferably 70% or more, and is preferably less than 40% in a strip-shaped colored region where antiglare and heat shielding properties are required.
Note that the visible light transmittance used in this specification refers to the visible light transmittance obtained in accordance with JIS R3106 unless otherwise specified.

  As the thermoplastic resin used in the present invention, a composition having this as a main component is formed into a sheet shape, and when used for a laminated glass of a vehicle, sufficient visibility is ensured, preferably a laminated glass. As long as the visible light transmittance is 70% or more, there is no particular limitation. For example, plasticized polyvinyl acetal resin, plasticized polyvinyl chloride resin, saturated polyester resin, plasticized saturated polyester resin, polyurethane resin, plasticized polyurethane resin, ethylene-vinyl acetate copolymer resin, ethylene- Examples thereof include thermoplastic resins conventionally used for intermediate films such as ethyl acrylate copolymer resins. In particular, it is possible to obtain an intermediate film with excellent balance of performance such as excellent transparency, weather resistance, strength, adhesive strength, penetration resistance, impact energy absorption, moisture resistance, heat insulation and sound insulation. A polyvinyl acetal resin is preferably used. These thermoplastic resins may be used alone or in combination of two or more. “Plasticization” in the plasticized polyvinyl acetal resin means that it is plasticized by adding a plasticizer. The same applies to other plasticized resins.

  The polyvinyl acetal resin is not particularly limited, but a polyvinyl formal resin obtained by reacting polyvinyl alcohol (hereinafter sometimes referred to as “PVA” if necessary) and formaldehyde, reacting PVA with acetaldehyde. Narrowly-obtained polyvinyl acetal resin, polyvinyl butyral resin obtained by reacting PVA and n-butyraldehyde (hereinafter sometimes referred to as “PVB” if necessary), and the like. PVB is suitable because it can provide an excellent intermediate film with a balance of various properties such as excellent transparency, weather resistance, strength, adhesion, penetration resistance, impact energy absorption, moisture resistance, heat insulation and sound insulation. Used. These polyvinyl acetal resins may be used alone or in combination of two or more.

  The PVA used for the synthesis of the polyvinyl acetal resin is not particularly limited, but preferably has an average degree of polymerization of 200 to 5000, more preferably 500 to 3000. The polyvinyl acetal resin is not particularly limited, but preferably has a degree of acetalization of 40 to 85 mol%, more preferably 50 to 75 mol%. The polyvinyl acetal resin preferably has a residual acetyl group content of 30 mol% or less, more preferably 0.5 to 24 mol%.

  The plasticizer used for plasticizing the thermoplastic resin, preferably a polyvinyl acetal resin, is not particularly limited. For example, a monobasic organic acid ester type, a polybasic organic acid ester type And organic acid ester plasticizers, and phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid.

  The amount of plasticizer added to the thermoplastic resin, preferably polyvinyl acetal resin, varies depending on the average degree of polymerization of the thermoplastic resin, the average degree of polymerization of the polyvinyl acetal resin, the degree of acetalization, the amount of residual acetyl groups, etc. Although not limited, it is preferable that it is 10-80 weight part of plasticizers with respect to 100 weight part of thermoplastic resins, preferably polyvinyl acetal resin. If the amount of the plasticizer added relative to 100 parts by weight of the thermoplastic resin, preferably polyvinyl acetal resin is less than 10 parts by weight, plasticization of the thermoplastic resin, preferably polyvinyl acetal resin becomes insufficient, and molding ( Film formation) may be difficult, and conversely, if the amount of the plasticizer added to 100 parts by weight of the thermoplastic resin, preferably polyvinyl acetal resin exceeds 80 parts by weight, the strength of the resulting intermediate film is insufficient. May be.

  The thermoplastic resin composition used for preparing the interlayer film material in the present invention contains the above thermoplastic resin, preferably a plasticized polyvinyl acetal resin as a main component, but has various purposes within a range not impairing the effects of the present invention. Depending on, for example, adhesion modifier, coupling agent, surfactant, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, infrared absorber, fluorescent agent, dehydrating agent, antifoaming agent, charging One kind or two or more kinds of various additives such as an inhibitor and a flame retardant may be contained.

  For example, for the purpose of providing the intermediate film material with an infrared shielding function, infrared shielding fine particles (hereinafter simply referred to as fine particles) can be dispersed and blended in the intermediate film material as an infrared absorber. The average particle size of the fine particles to be dispersed and blended is preferably 0.2 μm or less, and the material of the fine particles is Re, Hf, Nb, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, Metals such as In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, and Mo, oxides, nitrides, sulfides, silicon compounds of the metals, or inorganic fine particles obtained by doping them with Sb or F Can be used. Furthermore, organic infrared absorbers such as phthalocyanine can also be used, and these fine particles can be used alone or as a composite. Specifically, tin oxide (ATO) fine particles doped with antimony and indium oxide (ITO) fine particles doped with tin are preferable.

  In the present invention, the colorant used for forming the colored region of the intermediate film material (the portion corresponding to the second region and the third region in the intermediate film) can be used for plastics, At least the visible light transmittance of the second region is lower than that of the first region, preferably less than 40% as the visible light transmittance when the vehicle laminated glass is used. There is no particular limitation as long as at least the visible light transmittance of the irradiated or processed portion, that is, the third region is higher than that of the second region. Examples thereof include organic pigments and organic dyes such as azo, phthalocyanine, quinacridone, perylene, perinone, dioxazine, anthraquinone, isoindolino, and coumarin. These colorants may be used alone or in combination of two or more.

  In addition, the amount of these colorants to be added to the thermoplastic resin composition depends on the type and composition of the thermoplastic resin used and the type of colorant, but is usually used when forming a colored region in the interlayer film. Can be used without particular limitation. The blending amount of the colorant is preferably an amount that forms a colored region such that at least the visible light transmittance is less than 40% when laminated glass is used.

  Although the thickness of the intermediate film material obtained in the present invention is not particularly limited, it is preferably 0.3 to 1.6 mm as in the case of a normal intermediate film. If the thickness of the interlayer film material is less than 0.3 mm, the strength of the interlayer film material itself may be insufficient. Conversely, if the thickness of the interlayer film material exceeds 1.6 mm, the laminated glass described later A phenomenon in which a glass plate is displaced in a main bonding (final pressure bonding) process by an autoclave at the time of production, that is, a so-called plate displacement phenomenon may occur.

  The method for forming (film forming) the intermediate film material having the colored region is not particularly limited. For example, a non-colored heat comprising a thermoplastic resin, preferably a plasticized polyvinyl acetal resin and an optional component. Each of a thermoplastic resin composition and a thermoplastic resin, preferably a colored thermoplastic resin composition obtained by adding a colorant and an optional component to a plasticized polyvinyl acetal resin, is prepared in advance, and the uncolored thermoplastic resin composition and the above-mentioned The colored thermoplastic resin composition is merged in, for example, a sheet forming die, and molded into a sheet shape while joining both resin compositions so that a colored band having a predetermined shape is formed along the upper side (film formation). By doing so, a desired intermediate film material can be obtained.

In addition, a colored region can be formed by providing a cut portion in advance in the center portion of a sheet formed of a non-colored thermoplastic resin composition and coextruding a thermoplastic resin colored with a pigment or dye. . Furthermore, an intermediate film having a colored region is prepared by preparing a colored thermoplastic resin composition and an uncolored thermoplastic resin composition formed into a sheet shape having a predetermined size and shape, and bonding them in the plane direction. A material can also be formed.
The colored region is appropriately designed in shape, size, color tone, color gradient, etc. according to the required performance such as anti-glare property and heat-shielding property, and is colored by a known technique according to a predetermined design. An intermediate film material having a region can be formed.

The intermediate film material having a colored region used in the present invention is not limited to a single layer structure. For example, when it is desired to obtain an intermediate film having a multilayer structure such as an intermediate film in which resin films having different properties (different loss tangents) are laminated for the purpose of improving the sound insulation performance disclosed in Japanese Patent Application Laid-Open No. 2000-272936 For this, an interlayer film material having a multilayer structure may be used.
Furthermore, an intermediate film having a colored region and having a wedge-shaped cross-sectional shape in the vertical direction is prepared for a head-up display (HUD) as disclosed in Japanese Patent Application Laid-Open No. 2007-223883. If desired, an intermediate film material corresponding to this shape may be used. In this case, the entire cross-sectional shape from the upper side to the lower side of the intermediate film material may be a desired wedge-shaped cross section corresponding to the shape of the finally obtained intermediate film. For example, the thickness of the intermediate film material may monotonously decrease from the upper side to the lower side. Moreover, as long as the thickness of an upper side is larger than the thickness of a lower side, you may have a part with uniform thickness partially.

  The method for producing an interlayer film for laminated glass of the present invention is particularly useful in the case of such an interlayer film having a multilayer structure or an interlayer film having a wedge-shaped cross-sectional shape. In the technique of replacing the intermediate film of the shade band portion with the non-colored intermediate film as in the conventional technique described above, distortion occurs at the joint between the colored intermediate film and the non-colored intermediate film. However, this tendency is remarkable in the case of a multilayer interlayer film. In addition, in the case of an intermediate film having a wedge-shaped cross section, it is necessary to replace the non-colored intermediate film having the same wedge angle in the hollowed-out portion, but it is difficult to replace the wedge angle properly. The distortion of the joint is particularly noticeable. When it is difficult to apply a technique for replacing an uncolored intermediate film such as an interlayer film having a multilayer structure or a wedge-shaped intermediate film, the method for manufacturing an interlayer film for vehicle laminated glass according to the present invention Is particularly useful.

(1-2) Step of forming the third region in the intermediate film material obtained in (1-1) This step is performed on the intermediate film material having the colored region obtained in (1-1) above. By irradiating the site to be the third region of the second region with high energy rays or performing chemical treatment, at least the visible light transmittance of the site is made higher than that of the second region, and the third region This is a step of forming a region.

  Specific examples of the high energy ray include ultraviolet rays, laser light, X-rays, and gamma rays. Specific examples of the chemical treatment include contact with an acid, an acid generator, an oxidizing agent, or a reducing agent. In the production method of the present invention, such irradiation with high energy rays and chemical treatment may be performed alone, or may be performed in combination as necessary.

  Further, when at least the visible light transmittance of the portion to be the third region is made higher than that of the second region by using high energy ray irradiation, at least two glass plates are interposed through the intermediate film material. It is also possible to carry out from the outside of the combined structure after forming a structure obtained by bonding them together (hereinafter referred to as “combined structure”). That is, it is also possible to irradiate the intermediate film material with high energy rays through a glass plate.

  When the third region is made of laminated glass, an image sensor such as a CCD camera or a CMOS camera, an ETC (Electronic Toll Collection System) RF module, or the like is formed in a portion corresponding to the third region of the intermediate film. This is a region provided to allow installation of known sensors such as a radio wave receiving / transmitting antenna, a laser sensor, an infrared sensor, a magnetic sensor, a radar, a sound wave sensor such as a radar, and an optical sensor.

Therefore, the position, shape, size, etc. of the third region are appropriately designed according to the type of sensor used so that the sensors, etc., function sufficiently. is there. In order for the sensors to function sufficiently, it is preferable that the transmittance of light having a wavelength of 850 to 950 nm when the laminated glass of the third region is used is 20% or more.
Further, the visible light transmittance in the third region is higher than the visible light transmittance in the second region. The image sensor such as a CCD camera or a CMOS camera, the radio wave transmission / reception antenna such as an RF module for ETC, a laser, etc. Although it is not particularly limited as long as proper operation of known sensors such as a sensor, an infrared sensor, a magnetic sensor, a sound wave sensor such as a radar, and an optical sensor is ensured, it is usually 40% or more when a laminated glass is used. Is preferable, and 50% or more is particularly preferable.

  Further, in order to ensure visibility when the third region is a laminated glass for a vehicle, the distortion of the portion corresponding to the third region of the intermediate film is transparent according to JIS-R3212 (1998). The strain test value is preferably 2 to 6 minutes.

  Hereinafter, the irradiation with high energy rays and the chemical treatment performed in order to form the third region will be described.

<High-energy radiation>
As a specific method for performing irradiation of high energy rays such as ultraviolet rays, laser light, X-rays, and gamma rays on a predetermined portion to be the third region of the second region set as described above, A method of masking the intermediate film material and irradiating it with high energy rays can be mentioned. As a masking method, (1) a method in which a metal mask provided with an opening having a position, shape, and size corresponding to a third region is placed between an intermediate film material and a high energy ray irradiation source; 2) A method for applying a masking tape to a region other than the predetermined region to be the third region, and the like. Moreover, it can implement similarly when implementing irradiation of a high energy ray with respect to a laminated structure.

  One embodiment of the laminated glass interlayer film of the present invention thus obtained is shown in FIG. 1, and another embodiment is shown in FIG. A vehicle laminated glass interlayer 10 shown in FIG. 1 is a vehicle laminated glass interlayer in which a third region 3 formed in the second region 2 is isolated from the first region 1. Further, the vehicle laminated glass intermediate film 10 shown in FIG. 2 has a vehicle laminated glass intermediate film in which the third region 3 formed in the second region 2 is formed continuously with the first region 1. It is. In the vehicle laminated glass interlayer film of the present invention, the third region formed in the second region (colored region) may be isolated from the first region, and the first region is continuously formed. It may be configured to be adjacent to the region. Hereinafter, even if the processing methods are different, it is possible to adopt both configurations in the same manner.

<Chemical treatment>
As a specific method of performing chemical treatment such as contact with an acid, an acid generator, an oxidizing agent, or a reducing agent on a predetermined portion to be the third region in the second region set as described above The method includes applying or spraying an aqueous solution of these drugs or a solution of an appropriate organic solvent such as alcohol. Moreover, when these chemical | medical agents are gaseous, the method of exposing the predetermined site | part which should become a 3rd area | region with these chemical | medical agents is mentioned. When performing these chemical treatments, it is not essential to perform masking. However, when it is desired to clarify the boundary line between the second region and the third region, a portion other than the predetermined portion to be the third region is used. It is preferable to mask the area. As a masking method, the same method as in the case of irradiation with the high energy beam can be employed.

  Examples of the acid include hydrochloric acid and sulfuric acid. Examples of the acid generator include photoacid generators used in the field of chemically amplified resists. Examples of the oxidizing agent include ozone, hydrogen peroxide, hypochlorous acid, sodium hypochlorite, and potassium hypochlorite. Examples of the reducing agent include hydrogen peroxide and oxalic acid. These acids, acid generators, oxidizing agents, or reducing agents are appropriately selected according to the type of colorant used for the production of the intermediate film material.

  In the production method according to the first aspect of the present invention, it is preferable to perform chemical treatment using a coumarin-based dye as a colorant and an acid generator. Specifically, it is preferable to prepare an intermediate film material having a band-shaped colored region using a coumarin-based dye, and apply an acid generator to a predetermined portion to be the third region of the band-shaped colored region.

  As described above, in the manufacturing method according to the first aspect of the present invention, high energy rays are irradiated to a predetermined portion to be the third region in the second region set as described above, Alternatively, by performing a chemical treatment, a third region having at least a visible light transmittance higher than that of the second region is formed in the second region. This is because the colorant contained in the second region is formed. It is considered that the structure is due to chemical change by irradiation with high energy rays or chemical treatment.

Here, the visible light transmittance of the third region is higher than the visible light transmittance of the second region, and an image sensor such as a CCD camera or a CMOS camera, a radio wave transmission / reception antenna such as an RF module for ETC, a laser, etc. Although it is not particularly limited as long as proper operation of known sensors such as a sensor, an infrared sensor, a magnetic sensor, a sound wave sensor such as a radar, and an optical sensor is ensured, it is usually 40% or more when a laminated glass is used. Is preferable, and 50% or more is particularly preferable.
Further, the visible light transmittance of the third region and the visible light transmittance of the first region are not necessarily equal. Depending on the degree of chemical change in the structure of the colorant, the visible light transmittance of the third region may be smaller than the visible light transmittance of the first region.

  There are various cases regarding the magnitude relationship between the infrared transmittances of the first region, the second region, and the third region. For example, when an organic colorant having absorption in the infrared region is used as the colorant, and the chemical structure of these organic colorants is changed by irradiation with high energy rays or chemical treatment, the third region The infrared transmittance of the second region is larger than the infrared transmittance of the second region, and is equal to or smaller than the infrared transmittance of the first region. In addition, when an intermediate film material in which an organic infrared absorber is dispersed and blended as an infrared absorber over the entire intermediate film material is used, irradiation with a high energy beam or chemical treatment can be performed, so that the third region The infrared transmittance may be larger than the infrared transmittance of the first region and the second region.

  However, in any case, in order to operate the sensors appropriately, when a laminated glass is used, the transmittance of light having a wavelength of 850 to 950 nm in a portion corresponding to the third region is 20% or more. Is preferable, and 40% or more is particularly preferable.

  Next, a second aspect of the method for producing an interlayer film for laminated glass of a vehicle according to the present invention for producing an interlayer film for laminated glass of a vehicle having the third region from the first region will be described.

  According to a second aspect of the present invention, at least a portion of the intermediate film corresponding to the second region is colored with a predetermined value having at least a visible light transmittance lower than that of the first region by irradiation with a predetermined high energy ray. A step of preparing an intermediate film material containing a photosensitive color former that forms a region, a step of irradiating a predetermined high energy ray to a site corresponding to the second region, and coloring the photosensitive colorant, A method for producing an interlayer film for laminated glass of a vehicle.

(2-1) Step of preparing an intermediate film material having a region containing a photosensitive color former An intermediate film having a region containing the photosensitive color developer at a site corresponding to at least the second region in the intermediate film As for the method for producing the material, the intermediate film material containing the photosensitive color former at the portions corresponding to the second region and the third region in the intermediate film has the colored region of (1-1) above. In the production of the interlayer film material, it can be produced in exactly the same manner except that the colorant is replaced with a photosensitive color former.

In addition, if necessary, it is possible to contain the photosensitive color former in the entire intermediate film material, and in this case, a portion corresponding to the second region in a predetermined high energy ray irradiation step to be performed next. Only need to be irradiated. An intermediate film material may be prepared using a composition in which a photosensitive color former is further added to the thermoplastic resin composition.
Further, if necessary, the photosensitive colorant is added to the intermediate film material only in the part corresponding to the second region so that the portion corresponding to the third region in the intermediate film does not contain the photosensitive colorant. It is also possible to contain. In this case, as described in (1-2), the intermediate film material can be formed by a method such as co-extrusion or bonding in the surface direction. In this case, high energy ray irradiation can be performed on the entire intermediate film material.
However, in this step in the second aspect of the present invention, from the viewpoints of economy and workability, an intermediate film material containing a photosensitive color former in the portions corresponding to the second region and the third region of the intermediate film Is preferably prepared.

In the present invention, the photosensitive colorant used for forming the second region of the intermediate film, that is, the region colored by irradiation with a predetermined high energy ray, can be used for plastics, The at least visible light transmittance after irradiation of the predetermined high energy ray in the second region is lower than the first region, preferably less than 40% as the visible light transmittance when the vehicle laminated glass is used, In addition, it is particularly limited if it has light irreversible properties after being irradiated with high energy rays, or has irreversible properties in a temperature environment (usually −20 to 80 ° C.) in which the vehicle is used. It is not a thing.
For example, a composition containing a photo-oxidant and a leuco dye that develops color by photo-oxidation reaction that develops color by ultraviolet irradiation (see JP-A No. 10-181219) and the like can be mentioned.

  Examples of leuco dyes include leuco crystal violet and leucomalachite green. Examples of the photo-oxidant that causes the leuco dye to develop color by ultraviolet rays include benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; 2,4-dimethylthioxanthone, 2- Examples include thioxanthone compounds such as isopropylthioxanthone; 2,2′-bis (-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2-biimidazole and the like.

  Further, the blending amount of these photosensitive color formers in the thermoplastic resin composition depends on the type and composition of the thermoplastic resin used and the type of the photosensitive color former, but the above-described amount of the above-mentioned by irradiation with a predetermined high energy ray. Any blending amount capable of forming a colored region having such visible light transmittance characteristics can be used without particular limitation.

(2-2) High energy ray irradiation step In this step, the intermediate film material having the photosensitive colorant-containing region obtained in (2-1) above is exposed to a portion corresponding to the second region. Irradiation with high energy rays that develop color from the color former. In the case where the intermediate film material prepared in (2-1) is an intermediate film material containing a photosensitive color former in portions corresponding to the second area and the third area in the intermediate film, the third area Only a portion to be masked is irradiated with a predetermined high energy ray. Further, when the intermediate film material is an intermediate film material containing a photosensitive color former, masking is applied to portions corresponding to the first region and the third region, and a predetermined high energy ray is irradiated. . Further, when the intermediate film material contains the photosensitive color former only in the portion corresponding to the second region in the intermediate film, the predetermined high energy beam is irradiated without performing masking.

  Here, irradiation with a predetermined high energy ray to a portion corresponding to the second region containing the photosensitive color former is performed by adhering at least two glass plates to each other through the intermediate film material. After that, it is also possible to carry out from the outside of the combined structure. In other words, by irradiating a portion corresponding to the second region of the intermediate film material with a high energy ray through the glass plate, it is possible to cause the photosensitive colorant at the portion corresponding to the second region to develop color. is there.

  In addition, the method of irradiating the high energy beam from the outside of the laminated structure is particularly an intermediate film material containing a photosensitive colorant only in a portion corresponding to the second region of the intermediate film. Useful when the glass plate used to make the laminated structure does not need to have the property of blocking predetermined high energy rays. On the other hand, when an intermediate film material containing a photosensitive colorant is used in a part other than the part corresponding to the second region, the part other than the part corresponding to the second region by the high energy ray irradiated from the outside In some cases, the glass plate to be used needs to have a property of blocking high energy rays. In such a case, a method of irradiating predetermined high energy rays from the outside of the laminated structure Is not suitable. That is, at which stage of the production of the interlayer film for laminated glass or the laminated glass in the present invention, the high-energy radiation is appropriately selected according to the design of the interlayer film for laminated glass or the laminated glass to be produced. Is.

In the second aspect of the present invention, the portion to be the third region has the same properties as described for the third region in (1-2) above. Therefore, the masking of the portion to be the third region may be performed in a form that matches the position, shape, size, etc. of the third region that is appropriately designed in the same manner as described above. The masking method can be the same as the method described in (1-2) above. Moreover, it can implement similarly when implementing irradiation of a high energy ray with respect to a laminated structure.
The same applies to the transmittance and strain of light in a specific wavelength region when the laminated glass of the third region is used, and this has a region containing the photosensitive color former of (2-1). Adjustment is performed through the step of producing the intermediate film material and the main exposure step.

  In the second energy region, the second region is provided adjacent to the first region on the upper side of the intermediate film and has a visible light transmittance lower than that of the first region by coloring. And at least a third region having a visible light transmittance higher than that of the second region, which is provided in the predetermined region. The vehicle laminated glass intermediate film of the present invention thus obtained is also in the second region (colored region) in the same manner as the vehicle laminated glass intermediate film produced by the method of the first aspect of the present invention. The third region to be formed may be isolated from the first region, or may be configured to be continuously adjacent to the first region.

In the intermediate film obtained by the manufacturing method according to the second aspect, the visible light transmittance of the third region is the same as that of the intermediate film obtained by the manufacturing method according to the first aspect. As long as it is higher than the rate and the proper operation of the sensors is guaranteed, it is not particularly limited. Further, the visible light transmittance of the third region and the visible light transmittance of the first region are not necessarily equal. The visible light transmittance of the third region is usually preferably 40% or more, particularly preferably 50% or more, as the visible light transmittance when a laminated glass is used.
In addition, the magnitude relationship between the infrared transmittances of the first region, the second region, and the third region is not particularly limited. However, in any case, in order to appropriately operate the sensors, a laminated glass is used. In this case, the transmittance of light having a wavelength of 850 to 950 nm in the portion corresponding to the third region is preferably 20% or more, and particularly preferably 40% or more.

  The interlayer film for laminated glass manufactured by the method of the first aspect of the present invention and the interlayer film for laminated glass of vehicle manufactured by the method of the second aspect are colored portions (second ) And the non-colored portion formed in the shade band (third region) has no physical seam, and therefore no distortion occurs when the vehicle laminated glass is used. This is an interlayer film for vehicle laminated glass.

  The present invention provides a vehicle laminated glass manufactured using the vehicle laminated glass interlayer film obtained above. The vehicle laminated glass will be described below.

  The laminated vehicle glass of the present invention has a structure in which at least two glass plates are bonded to each other through the interlayer film for laminated vehicle glass produced by the method of the first aspect or the second aspect of the present invention. Vehicle laminated glass having

  The vehicle laminated glass of the present invention is applied to vehicles such as automobiles, railways and ships, and is particularly preferably applied to automobiles. The visible light transmittance of the laminated glass of the present invention is preferably 70% or more because visibility is required in the portion corresponding to the first region of the intermediate film, and corresponds to the second region. The portion is preferably less than 40% because antiglare and heat shielding properties are required. Moreover, it corresponds to the third region of the interlayer film of the vehicle laminated glass of the present invention from the viewpoint of creating an environment in which these various sensors generally installed and used on the windshield of an automobile are sufficiently functioning. The visible light transmittance of the portion is preferably 40% or more, and particularly preferably 50% or more. From the same viewpoint, the transmittance of light having a wavelength of 850 to 950 nm in the portion corresponding to the third region of the interlayer film of the laminated glass of the present invention is preferably 20% or more, and 40% or more. It is particularly preferred.

  Further, in the laminated glass of the present invention, in order to ensure visibility, the distortion of the portion corresponding to the third region of the interlayer film is 2 to 6 in terms of the perspective strain test value according to JIS-R3212 (1998). Minutes are preferred.

  The characteristics of the portion corresponding to the first region, the second region, and the third region of the interlayer film are the performance of both the interlayer film by the manufacturing method of the present invention and the glass plate used for the vehicle laminated glass, In the present invention, the intermediate film is premised on the combination with the glass plate and the method for producing laminated glass, which are generally used within the scope of known techniques. Is manufacturing. Accordingly, the glass plate and laminated glass manufacturing method described below are usually used except for some of them.

  The glass plate used for the vehicle laminated glass of the present invention includes not only a normal inorganic transparent glass plate but also an organic transparent glass plate such as a polycarbonate plate or a polymethyl methacrylate plate.

  The glass plate may be any glass plate that can be used for vehicles, and is not particularly limited. For example, float plate glass, polished plate glass, flat plate glass, curved plate glass, and parallel plate glass. , Template glass, wire mesh type plate glass, various inorganic glass plates such as glass plates colored within a range not impairing the effects of the present invention, organic glass plates, and the like, and one or more of these are preferably used. It is done. Moreover, although the thickness of the said glass plate should just be selected suitably, it is about 1.8-2.5 mm normally. Furthermore, the glass plate may be provided with a coating that imparts a water repellent function, a hydrophilic function, an antifogging function, and the like.

  Further, in the laminated glass using the interlayer film according to the manufacturing method of the second aspect of the present invention, when the photosensitive color former is a photosensitive color former that develops color by irradiation with ultraviolet rays, the glass plate is shielded from ultraviolet rays. Glass is preferred.

  The method for producing the laminated vehicle glass of the present invention is not special, and the production method similar to that for ordinary laminated glass may be used. That is, for example, the interlayer film of the present invention is sandwiched between two transparent glass plates, this laminated glass structure is placed in a vacuum bag such as a rubber bag, this vacuum bag is connected to an exhaust system, and a vacuum is formed. Pre-adhesion (pre-pressure bonding) was performed at a temperature of about 70 to 110 ° C. while suctioning (degassing) under reduced pressure so that the pressure in the bag was about −65 to −100 kPa (absolute pressure of about 36 to 1 kPa). Then, this pre-bonded laminated glass structure is put in an autoclave, and is heated and pressed under conditions of a temperature of about 120 to 150 ° C. and a pressure of about 0.98 to 1.47 MPa to perform main bonding (main pressing). Thereby, a desired vehicle laminated glass can be obtained.

  The present invention can be used in the field of vehicle laminated glass in which various sensors are mounted on a part of a shade band.

  DESCRIPTION OF SYMBOLS 1 ... 1st area | region, 2 ... 2nd area | region, 3 ... 3rd area | region, 10 ... Vehicle laminated glass intermediate film, 1 '... Intermediate film, 2' ... Shade band, 3 '... Cutting intermediate film

Claims (15)

A first region, a band-shaped second region provided adjacent to the first region on the upper side and having a visible light transmittance at least lower than that of the first region by coloring; and within the second region A method for producing an interlayer film for laminated glass of a vehicle having at least a third region having a visible light transmittance higher than that of the second region provided in a predetermined region,
An intermediate film material is prepared in which the portions corresponding to the second region and the third region in the intermediate film are colored so that at least the visible light transmittance is a predetermined value lower than that of the first region in the intermediate film. Process,
A step of irradiating a site to be the third region of the second region of the intermediate film material with a high energy ray or performing chemical treatment so that at least the visible light transmittance is higher than that of the second region. When,
The manufacturing method of the intermediate film for vehicle laminated glass characterized by the above-mentioned.   The method for producing an interlayer film for laminated glass according to claim 1, wherein the high energy ray is at least one selected from ultraviolet rays, laser light, X-rays and gamma rays.   The method for producing an interlayer film for laminated glass according to claim 1, wherein the chemical treatment is at least one selected from contact with an acid, an acid generator, an oxidizing agent, or a reducing agent.   After adhering at least two glass plates to each other via the intermediate film material to form a combined body, the step of making at least the visible light transmittance of the portion to be the third region higher than the second region, The method for producing an interlayer film for laminated glass according to claim 1, wherein high energy rays are irradiated from the outside of the laminated structure. A first region, a band-shaped second region provided adjacent to the first region on the upper side and having a visible light transmittance at least lower than that of the first region by coloring; and within the second region A method for producing an interlayer film for laminated glass of a vehicle having at least a third region having a visible light transmittance higher than that of the second region provided in a predetermined region,
A photosensitive colorant that forms a colored region having at least a visible light transmittance lower than that of the first region by irradiation with a predetermined high energy ray at a portion corresponding to at least the second region of the intermediate film. A step of preparing an intermediate film material to be contained;
Irradiating a portion corresponding to the second region with a predetermined high energy ray to develop the photosensitive color former; and
The manufacturing method of the intermediate film for vehicle laminated glass characterized by the above-mentioned.   After adhering at least two glass plates to each other through the intermediate film material to form a combined structure, a predetermined high energy ray is irradiated from the outside of the combined structure to a portion corresponding to the second region. The method for producing an interlayer film for laminated glass according to claim 5, wherein a step of coloring the photosensitive color former is performed.   An interlayer film for laminated glass for vehicles obtained by the method according to claim 1.   The interlayer film for laminated glass according to claim 7, wherein a cross-sectional shape in the vertical direction of the interlayer film for laminated glass is a wedge shape in which the thickness on the upper side is larger than the thickness on the lower side.   The interlayer film for laminated glass according to claim 7 or 8, wherein the interlayer film for laminated glass has a multilayer structure.   A vehicle laminated glass having a structure in which at least two glass plates are bonded to each other through an intermediate film obtained by the method according to any one of claims 1 to 6.   A vehicle laminated glass having a structure in which at least two glass plates are bonded to each other through the interlayer film for vehicle laminated glass according to claim 8 or 9.   The vehicle laminated glass according to claim 10 or 11, wherein the glass plate is a glass plate having a shielding property against the predetermined high energy ray, and the intermediate film is an intermediate film obtained by the method according to claim 5.   The vehicle laminated glass according to any one of claims 10 to 12, wherein a visible light transmittance of a portion corresponding to the third region of the interlayer film in the laminated glass is 40% or more.   The vehicle laminated glass according to any one of claims 10 to 13, wherein a portion of the laminated glass corresponding to the third region of the intermediate film has a light transmittance of 20% or more at a wavelength of 850 to 950 nm.   The distortion of a portion corresponding to the third region of the interlayer film in the laminated glass is 2 to 6 minutes as a perspective strain test value according to JIS-R3212 (1998). Vehicle laminated glass as described.

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