JP2001192245A - Method for manufacturing laminated glass - Google Patents
Method for manufacturing laminated glassInfo
- Publication number
- JP2001192245A JP2001192245A JP2000380254A JP2000380254A JP2001192245A JP 2001192245 A JP2001192245 A JP 2001192245A JP 2000380254 A JP2000380254 A JP 2000380254A JP 2000380254 A JP2000380254 A JP 2000380254A JP 2001192245 A JP2001192245 A JP 2001192245A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- laminated glass
- film
- intermediate film
- laminated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10614—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
- B32B17/10633—Infrared radiation absorbing or reflecting agents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/476—Tin oxide or doped tin oxide
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、着色、熱線や紫外線遮
断膜、電波透過等各種の機能性超微粒子を適宜有する樹
脂中間膜層を用いて合せ処理することでなる合せガラス
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminated glass by performing a laminating process using a resin intermediate film layer appropriately having various functional ultrafine particles such as a colored film, a heat ray or ultraviolet ray shielding film, and a radio wave transmission. .
【０００２】[0002]
【従来技術】近年、建築用ガラスにおけるクリアや着
色、断熱や紫外線遮断および電波透過等の機能付与はも
ちろん、車輌用ガラスにおいても車内に通入する太陽輻
射エネルギーを遮蔽し、車内の温度上昇、冷房負荷を低
減させる目的から熱線遮蔽ガラス、さらに人的物的両面
や環境に優しくするため紫外線遮蔽を付加したものが車
輌用に採用されている。また最近は特に該車輌用ガラス
において、グリーン色調で充分な可視光透過率を有しな
がら高熱線紫外線遮蔽性能を持ちかつ各種電波の高透過
性能が要求されるようになってきており、なかでも微粒
子あるいは超微粒子を合せガラスの中間層に分散したよ
うなものとしては次のようなものが知られている。2. Description of the Related Art In recent years, in addition to providing functions such as clearing and coloring, heat insulation, blocking of ultraviolet rays, and transmission of radio waves in architectural glass, the shielding of solar radiant energy passing into the vehicle also increases the temperature in the vehicle. For the purpose of reducing the cooling load, a heat ray shielding glass, and a glass to which an ultraviolet ray shielding is added in order to make it both human and physical and environmentally friendly, are used for vehicles. In recent years, in particular, the glass for vehicles has been required to have a high heat ray ultraviolet ray shielding performance and a high transmission performance of various radio waves while having a sufficient visible light transmittance in a green color tone. The following are known as fine particles or ultrafine particles dispersed in an interlayer of laminated glass.
【０００３】例えば特開平2-22152 号公報には、短波長
光線遮断性合せガラス用中間膜が記載されており、特定
された一般式で表されるベンゾトリアゾール誘導体から
なる群より運ばれる少なくとも１種の光吸収剤と、少な
くとも90重量％が 250〜400nmの粒径範囲にある粒径分
布の微粒子状無機物質とを含有する可塑化ポリビニルブ
チラール樹脂よりなり、400nm 以下の波長の光を実質的
に遮断し、かつ450nm以上の波長の光を実質的に透過さ
せるものが開示され、光吸収剤の含有量が0.4〜6 重量
％であり、微粒子状無機物質の含有量が 2〜17重量％で
あることが開示されている。[0003] For example, Japanese Patent Application Laid-Open No. 222152/1990 describes an interlayer film for a laminated glass having a short-wavelength light-blocking property, and at least one of the benzotriazole derivatives represented by a specified general formula is carried. A plasticized polyvinyl butyral resin containing at least 90% by weight of a light-absorbing agent and at least 90% by weight of a particulate inorganic material having a particle size distribution in a particle size range of 250 to 400 nm. A light-absorbing agent having a content of 0.4 to 6% by weight and a particulate inorganic substance having a content of 2 to 17% by weight. Is disclosed.
【０００４】また例えば、特開平4-160041号公報には、
自動車用窓ガラスが記載されており、透明板状部材間に
平均粒径0.1 μm 以下の超微粒子とガラス成分との混合
層を形成してなるものが記載され、透明板状部材間に２
超微粒子とガラス成分とを挟み、ガラス成分によって透
明板状部材同士を接着すること、あるいは透明板状部材
間にプラスチツクの中間層（PVB)を設け、この中間層と
各板状部材との間に夫々粒径0.1 μm 以下の超微粒子と
ガラス成分との混合層を形成してなること、あるいは平
均粒径0.3 〜0.5 μm のスペーサ用微粒子を混合層中に
混在させること等が開示されている。For example, Japanese Patent Laid-Open No. 4-160041 discloses that
It describes an automotive window glass, in which a mixed layer of ultrafine particles having an average particle diameter of 0.1 μm or less and a glass component is formed between transparent plate members.
By sandwiching the ultrafine particles and the glass component and bonding the transparent plate members to each other with the glass component, or by providing a plastic intermediate layer (PVB) between the transparent plate members, and between the intermediate layer and each plate member. Discloses that a mixed layer of ultrafine particles having a particle size of 0.1 μm or less and a glass component is formed, or that fine particles for a spacer having an average particle size of 0.3 to 0.5 μm are mixed in the mixed layer. .
【０００５】また例えば、特開平4-261842号公報には、
合わせガラスが記載されており、有機ガラスと、透明体
と、有機ガラス及び透明体間に配設された中間膜と、を
有する合わせガラスであって、中間膜が、ビニルシラン
をグラフト変性したエチレン・エチルアクリレート共重
合樹脂を含有する樹脂組成物にて形成されているものが
開示され、樹脂組成物が、ビニルシランをグラフト変性
したエチレン・エチルアクリレート共重合樹脂100 重量
部と二酸化ケイ素微粒子3 〜30重量部とを含有すること
が開示されている。[0005] For example, Japanese Patent Application Laid-Open No. 4-218642 discloses that
Laminated glass is described, and is a laminated glass having an organic glass, a transparent body, and an intermediate film disposed between the organic glass and the transparent body, wherein the intermediate film is ethylene-ethylene graft-modified with vinylsilane. Disclosed is a resin composition containing an ethyl acrylate copolymer resin, wherein the resin composition is a vinylsilane graft-modified ethylene / ethyl acrylate copolymer resin (100 parts by weight) and silicon dioxide fine particles (3 to 30 parts by weight) Parts are disclosed.
【０００６】[0006]
【発明が解決しようとする問題点】前述したような、例
えば特開平2-22152 号公報等に記載された短波長光線遮
断性合せガラス用中間膜は、ポリビニルブチラール樹脂
に添加される少なくとも90重量％が250 〜400nm の粒径
範囲にある粒径分布の微粒子状無機物質が光散乱剤とし
て400nm 以下の紫外線部分を散乱させるようにして光吸
収剤の選択的吸収を促進し400nm 以下の波長の光を実質
的に遮断するとともに、例えば450 〜700nmの波長範囲
で光線透過率が70％以上等、450nm 以上の波長の光を実
質的に透過させ透明性を保持し、しかも100Wの白色電球
像の縁における観察で濁りが無く、黄色味を示す波長42
0nm における光線透過率も50％以上であって、良好な接
着性を示すというものであるが、断熱性微粒子状無機物
質の粒径が比較的大きいことはもちろんその添加量も例
えば2 〜17重量％と多くすることが必要である。As described above, for example, the interlayer film for a short-wavelength light-shielding laminated glass described in Japanese Patent Application Laid-Open No. 222152/1990 is at least 90% by weight added to a polyvinyl butyral resin. % Is in the particle size range of 250 to 400 nm, so that the fine particle-like inorganic substance having a particle size distribution scatters the ultraviolet part of 400 nm or less as a light scattering agent, and promotes the selective absorption of the light absorbing agent, and has a wavelength of 400 nm or less. While substantially blocking light, it substantially transmits light having a wavelength of 450 nm or more, such as a light transmittance of 70% or more in a wavelength range of 450 to 700 nm, and maintains transparency, and furthermore, a 100 W white light bulb image. Wavelength 42 showing no yellowish color with no turbidity observed at the edge of
Although the light transmittance at 0 nm is 50% or more and shows good adhesiveness, the particle size of the heat-insulating particulate inorganic material is relatively large, and the amount of addition is, for example, 2 to 17% by weight. It is necessary to increase as much as%.
【０００７】また、例えば特開平4-160041号公報に記載
された自動車用窓ガラスは、透明板状部材間に平均粒径
0.1 μm 以下の超微粒子と有機ケイ素あるいは有機ケイ
素化合物のガラス成分との混合層を形成するようにし、
合わせガラスのガラス同士あるいはプラスチツクの中間
層であるポリビニルブチラール（PVB)とガラスを接合し
たというものであって、ヒータ用としてのデイフロスタ
機能、冷暖房効率アップ用としての赤外線反射機能及び
／またはシート抵抗が約500 Ω／口である電磁シールド
機能を有することとなるというものであり、PVB やエチ
レン−酢酸ビニル共重合体系樹脂膜(EVA) 等の中間膜の
みで２枚のガラスを接合した通常の合せガラスの構成の
中で断熱機能、紫外線遮断機能、電波透過機能あるいは
無色乃至着色を同時に発現し得るようなものではない
し、また通常の合せガラスと同等の接着力を得ることが
できるか危惧されるところであり、コスト的にもアップ
する要因があるものである。Further, for example, a window glass for an automobile described in Japanese Patent Application Laid-Open No. 4-160041 has an average particle size between transparent plate members.
To form a mixed layer of ultrafine particles of 0.1 μm or less and a glass component of organosilicon or organosilicon compound,
It is made by bonding the glass of laminated glass or polyvinyl butyral (PVB), which is an intermediate layer of plastic, to the glass. It has a defroster function for heaters, an infrared reflection function for improving cooling and heating efficiency, and / or a sheet resistance. It has an electromagnetic shielding function of about 500 Ω / port. It is a standard laminated film that combines two glasses with only an intermediate film such as PVB or ethylene-vinyl acetate copolymer resin film (EVA). It is not possible to simultaneously exhibit the heat insulating function, the ultraviolet blocking function, the radio wave transmitting function or the colorless or colored function in the structure of the glass, and it is feared that the adhesive strength equivalent to that of ordinary laminated glass can be obtained. There are factors that increase the cost.
【０００８】また、例えば特開平4-261842号公報に記載
された合わせガラスは、有機ガラスを使用するためのも
のであって、ビニルシランをグラフト変性したエチレン
・エチルアクリレート共重合樹脂100 重量部に対し、粒
径が0.1 〜400mμのコロイダルシリカや超微粒子シリカ
等の二酸化ケイ素微粒子3 〜30重量部とを含有するよう
にし、粒径を400mμ以下とすることで可視光線の波長(4
00〜780nm)より短いため、中間膜を通過する光の散乱を
防ぎ、その中間膜のくもり改善を効果的にしようとする
ものであるものの、そのくもり度（ヘイズ）はJIS K671
4 に基づく測定で４％以下程度であり、必ずしも充分な
自動車用窓ガラス、特にフロントガラスとは言い難いも
のである。Further, for example, the laminated glass described in Japanese Patent Application Laid-Open No. 4-218842 is for using organic glass, and is based on 100 parts by weight of an ethylene / ethyl acrylate copolymer resin obtained by graft-modifying vinylsilane. And 3 to 30 parts by weight of fine particles of silicon dioxide such as colloidal silica or ultrafine silica having a particle diameter of 0.1 to 400 μm.
Since the wavelength is shorter than (00 to 780 nm), scattering of light passing through the intermediate film is prevented, and the haze of the intermediate film is effectively improved. However, the haze is JIS K671.
It is about 4% or less in the measurement based on 4 and is not necessarily a sufficient automotive window glass, especially a windshield.
【０００９】[0009]
【問題点を解決するための手段】本発明は、従来のこの
ような点に鑑みてなしたものであり、従来から使用され
ている合せガラス用中間膜層に影響を与えることなく、
中間膜層に機能性超微粒子を適宜分散し含有せしめるこ
とで、断熱性能や紫外線遮断性能や電波透過性能等の機
能特性を付与し、しかもクリア乃至着色の色調の制御お
よび透視性の確保や反射性とぎらつき感の防止等をバラ
ンスよくもたらしめ、従来の合せガラスと変わらない品
質を得るようにでき、特殊成分組成ガラスや特殊表面加
工ガラスを必要とせず、かつ現在使用中の合せガラス製
造ラインをそのままで合せガラス化処理作業で行うこと
ができ、例えばガラスとガラス、ガラスとプラスチッ
ク、バイレイヤガラス等を安価にかつ容易にしかもガラ
スの大きさや形態に自由自在に対応し得て製造でき、建
築用窓材はもちろん自動車用窓材、飛行機用窓材、こと
に風防用ガラスにも充分適用でき、最近のニーズに最適
なものとなる有用な機能的な合せガラスの製造方法を提
供するものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of such conventional points, and has no influence on a conventionally used interlayer film for laminated glass.
By appropriately dispersing and including the functional ultrafine particles in the intermediate film layer, functional properties such as heat insulation performance, ultraviolet shielding performance, radio wave transmission performance, etc. are imparted, and furthermore, control of clear to colored color tones, and securing of transparency and reflection. Laminated glass that can be used in a well-balanced manner to achieve the same quality as conventional laminated glass, without the need for special component glass or special surface-treated glass, and that is currently in use The line can be used as it is in the laminated vitrification process. For example, glass and glass, glass and plastic, bilayer glass, etc. can be manufactured inexpensively and easily, and can be freely adapted to the size and form of glass. It can be applied not only to window materials for construction, but also to window materials for automobiles, window materials for airplanes, and especially for windshields. There is provided a method of manufacturing ability specific laminated glass.
【００１０】すなわち、本発明の合せガラスの製造方法
は、少なくとも２枚の透明ガラス板状体の間に中間膜層
を有する合せガラスの製造方法において、可塑剤を用い
て成形してなるポリビニルブチラール系樹脂膜の中に粒
径が 0.2μｍ以下の機能性超微粒子を分散せしめてなる
中間膜を用いて、オートクレーブ法により、減圧下で常
温から120 ℃まで昇温する中で80〜120 ℃の温度範囲で
20〜30分間の加熱により合せガラス化処理することを特
徴とする。That is, a method for producing a laminated glass according to the present invention is a method for producing a laminated glass having an intermediate film layer between at least two transparent glass plates, which is obtained by molding using a plasticizer. Using an intermediate film in which functional ultrafine particles having a particle size of 0.2 μm or less are dispersed in a resin film, the temperature is raised from room temperature to 120 ° C. under reduced pressure by an autoclave method. In the temperature range
It is characterized in that the glass is laminated by heating for 20 to 30 minutes.
【００１１】また、本発明の合せガラスの製造方法は、
前記機能性超微粒子の混合割合が、10.0wt％以下である
ことを特徴とする。Further, the method for producing a laminated glass of the present invention comprises:
The mixing ratio of the functional ultrafine particles is 10.0 wt% or less.
【００１２】さらに、本発明の合せガラスの製造方法
は、中間膜にフッ素樹脂、シリコーンレジン、またはシ
リコーンゴムからなる有機樹脂の微粒子の各単独もしく
はこれらを組み合わせて含有させて中間膜とガラスとの
接着強度を低下させることを特徴とする。Further, the method for producing a laminated glass according to the present invention is characterized in that the intermediate film contains fine particles of an organic resin comprising a fluororesin, a silicone resin, or a silicone rubber, alone or in combination thereof, so that the intermediate film and the glass The adhesive strength is reduced.
【００１３】またさらに、本発明の合せガラスの製造方
法は、ガラス表面へプライマー塗布、フッ素樹脂、シリ
コーンレジン、またはシリコーンゴムからなる有機樹脂
を被覆して中間膜とガラスとの接着強度を低下させるこ
とを特徴とする。Still further, in the method for producing a laminated glass according to the present invention, the surface of the glass is coated with a primer, and an organic resin comprising a fluororesin, a silicone resin or a silicone rubber is coated to reduce the adhesive strength between the interlayer and the glass. It is characterized by the following.
【００１４】さらに、本発明の合せガラスの製造方法
は、中間膜用樹脂膜表面に均一な凹凸のしぼを設けたこ
とを特徴とする。Further, the method for producing a laminated glass according to the present invention is characterized in that the resin film for the intermediate film is provided with a grain having uniform irregularities.
【００１５】ここで、前記したように、中間膜層の中に
粒径が0.2 μm 以下の機能性超微粒子を分散せしめてな
るものとしたのは、可視光域の散乱反射を抑制しなが
ら、例えば日射透過率が65％以下等熱線遮蔽性能等超微
粒子の機能特性を充分発揮しつつ、超低ヘーズ値、電波
透過性能、透明性を確保するためと、超微粒子を含有せ
しめても従来の合せガラス用中間膜として例えば接着
性、透明性、耐久性等の物性を維持し、通常の合せガラ
ス製造ラインで通常作業で合せガラス化処理ができるよ
うにするためである。好ましくは粒径が0.15μm 以下程
度であり、より好ましくは約0.10〜0.001 μm 程度であ
る。なお粒径分布の範囲については、例えば約0.03〜0.
01μm 程度と均一化されていることがよい。Here, as described above, the functional ultrafine particles having a particle size of 0.2 μm or less are dispersed in the intermediate film layer, while the scattering and reflection in the visible light region are suppressed. For example, while maintaining the ultra-low haze value, radio wave transmission performance, and transparency while fully exhibiting the functional characteristics of ultrafine particles such as isothermal ray shielding performance with solar transmittance of 65% or less, even if ultrafine particles are contained, This is because, for example, physical properties such as adhesiveness, transparency, and durability are maintained as an interlayer film for a laminated glass, and a laminated glass production line can be subjected to a laminated glass forming process in a normal operation. Preferably, the particle size is about 0.15 μm or less, and more preferably, about 0.10 to 0.001 μm. The range of the particle size distribution is, for example, about 0.03 to 0.
It is preferable that the thickness be as uniform as about 01 μm.
【００１６】また、中間膜層への機能性超微粒子の混合
割合が10.0wt％以下であるとしたのは、可視光域の散乱
反射を抑制しながら、例えば日射透過率が65％以下等熱
線遮蔽性能等超微粒子の機能特性を充分発揮する量を確
保し、さらに超低ヘーズ値、電波透過性能、透明性であ
るようにし、しかも超微粒子を含有せしめても従来の合
せガラス用中間膜として例えば接着性、透明性、耐久性
等の物性を維持し、通常の合せガラス製造ラインによる
通常作業で合せガラス化処理ができるようにするため
で、前記粒径とも深い関係にあり、10.0wt％を超えるよ
うになると次第に上記要件を特に自動車用窓材はもちろ
ん建築用窓材としても実現し難くなるためである。こと
に例えば建築用合せガラス向けとして可視光透過率Tvが
35％以上の場合は無機顔料系超微粒子の混合割合が約10
〜0.1 wt％程度必要であり、建築用としては約９〜0.01
wt％程度、より好ましくは８〜0.05wt％程度であり、自
動車用としては好ましい混合割合としては約2.0 〜0.01
wt％程度、より好ましくは1.5 〜0.05wt％程度、さらに
好ましくは1.0 〜0.1wt ％程度である。いずれにしても
合せガラスとしての性能保持とめざす機能性能との兼ね
合いでその混合割合（含有量）は決定されるものであ
る。The reason why the mixing ratio of the functional ultrafine particles to the intermediate film layer is 10.0 wt% or less is that, for example, an isothermic ray having a solar transmittance of 65% or less while suppressing scattering and reflection in the visible light region. Securing enough amount to exhibit the functional properties of ultrafine particles such as shielding performance, and ensuring ultra-low haze value, radio wave transmission performance, and transparency, and even including ultrafine particles as a conventional interlayer for laminated glass For example, in order to maintain physical properties such as adhesiveness, transparency, and durability, and to perform a laminated vitrification process by a normal operation using a normal laminated glass manufacturing line, the particle size is deeply related to the above particle size, and 10.0 wt%. This is because it becomes increasingly difficult to realize the above requirements not only as window materials for automobiles but also as window materials for construction. In particular, for example, visible light transmittance Tv for laminated glass for construction
In the case of 35% or more, the mixing ratio of inorganic pigment type ultrafine particles is about 10
About 0.1 wt%, about 9-0.01%
wt%, more preferably about 8 to 0.05 wt%, and a preferable mixing ratio for automobiles is about 2.0 to 0.01 wt%.
wt%, more preferably about 1.5 to 0.05 wt%, even more preferably about 1.0 to 0.1 wt%. In any case, the mixing ratio (content) is determined depending on the balance between the performance retention as a laminated glass and the desired functional performance.
【００１７】さらに、中間膜が、ポリビニルブチラール
系樹脂膜(PVB系) 、あるいはエチレン−酢酸ビニル共重
合体系樹脂膜(EVA系) であるとしたのは、これらが合せ
ガラス用中間膜として汎用性のものであるから好まし
く、合せガラスとしての品質をニーズに整合し得るよう
な中間膜層となるものであれば特に限定するものではな
い。具体的には可塑性PVB 〔積水化学工業社製、三菱モ
ンサント社製等〕、EVA〔デュポン社製、武田薬品工業
社製、デュラミン〕、変性EVA 〔東ソー社製、メルセン
Ｇ〕等である。なお、紫外線吸収剤、抗酸化剤、帯電防
止剤、熱安定剤、滑剤、充填剤、着色、接着調整剤等を
適宜添加配合する。Further, the reason why the intermediate film is a polyvinyl butyral resin film (PVB type) or an ethylene-vinyl acetate copolymer type resin film (EVA type) is that these are versatile as interlayer films for laminated glass. It is not particularly limited as long as it becomes an intermediate film layer that can match the quality as a laminated glass to needs. Specific examples include plastic PVB (manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.), EVA (manufactured by DuPont, Takeda Pharmaceutical Co., Ltd., duramine), and modified EVA (manufactured by Tosoh Corporation, Mersen G). In addition, an ultraviolet absorber, an antioxidant, an antistatic agent, a heat stabilizer, a lubricant, a filler, a coloring agent, an adhesion regulator and the like are appropriately added and blended.
【００１８】なお、中間膜として、本超微粒子入り中間
膜と従来の中間膜とを、例えば両者を重ね合わせるある
いは本超微粒子入り中間膜を従来の中間膜でサンドイッ
チする等の構成とするものとしてもよい。As the intermediate film, the intermediate film containing the present ultrafine particles and the conventional intermediate film may be formed by, for example, superposing the two or sandwiching the intermediate film containing the present ultrafine particles with the conventional intermediate film. Is also good.
【００１９】またさらに、機能性超微粒子が、Sn、Ti、
Si、Zn、Zr、Fe、Al、Cr、Co、Ce、In、Ni、Ag、Cu、P
t、Mn、Ta、W 、V 、Moの金属、酸化物、窒化物、硫化
物あるいはSbやF のドープ物の各単独物、もしくはこれ
らの中から少なくとも２種以上を選択してなる複合物、
またはさらに当該単独物もしくは複合物に有機樹脂を含
む混合物または有機樹脂物を被覆した被膜物であるもの
としたのは、各単独もしくは複合物、混合物、被膜物と
して断熱性能、紫外線遮蔽性能、着色性能、遮光性等を
適宜発現し、建築用や自動車用に求められる種々の機能
性および性能を合せガラスとして発現せしめるためであ
る。Further, the functional ultrafine particles may be composed of Sn, Ti,
Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, P
t, Mn, Ta, W, V, Mo metals, oxides, nitrides, sulfides, Sb or F doped materials, or composites of at least two selected from these ,
Alternatively, the single substance or the composite is a mixture containing an organic resin or a coated substance coated with an organic resin substance. This is because the performance, light-shielding properties, and the like are appropriately expressed, and various functions and performances required for architectural and automotive use are expressed as a laminated glass.
【００２０】また機能性超微粒子としては、例えばSn、
Ti、Si、Zn、Zr、Fe、Al、Cr、Co、Ce、In、Ni、Ag、C
u、Pt、Mn、Ta、W 、V 等のほかMoなどの各種金属。例
えばSnO2、TiO2、SiO2、ZrO2、ZnO 、Fe2O3 、Al2O3 、
FeO 、Cr2O3 、Co2O3 、CeO2、In2O3 、NiO 、MnO 、Cu
O 等の各種酸化物。例えばTiN 、AlN 等の窒化物、ある
いは窒素酸化物。例えばZnS 等の硫化物。例えば9wt%Sb
2O3-SnO2(ATO) 〔住友大阪セメント社製〕、F-SnO2等の
ドープ物。さらに例えばSnO2-10wt%Sb2O3 、In2O3-5wt%
SnO2(ITO) 〔三菱マテリアル社製〕等の複合物である。
フッ素樹脂、PTFE、ルブロン〔ダイキン工業（株）〕、
セフラルル−ブ〔セントラル硝子（株）〕、低分子量TF
E などが挙げられ、またATO やITO は自動車用としてそ
の要件を備え特に好ましいものである。The functional ultrafine particles include, for example, Sn,
Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, C
Various metals such as Mo in addition to u, Pt, Mn, Ta, W, V, etc. For example, SnO 2 , TiO 2 , SiO 2 , ZrO 2 , ZnO, Fe 2 O 3 , Al 2 O 3 ,
FeO, Cr 2 O 3, Co 2 O 3, CeO 2, In 2 O 3, NiO, MnO, Cu
Various oxides such as O. For example, nitrides such as TiN and AlN, or nitrogen oxides. For example, sulfides such as ZnS. For example, 9wt% Sb
Doped substances such as 2 O 3 -SnO 2 (ATO) [manufactured by Sumitomo Osaka Cement Co., Ltd.] and F-SnO 2 . Further, for example, SnO 2 -10wt% Sb 2 O 3 , In 2 O 3 -5wt%
Compounds such as SnO 2 (ITO) [manufactured by Mitsubishi Materials Corporation].
Fluororesin, PTFE, Lubron (Daikin Industries, Ltd.),
Cefralrub [Central Glass Co., Ltd.], low molecular weight TF
E, etc., and ATO and ITO are particularly preferable because of their requirements for automobiles.
【００２１】さらに例えばCo2O3-Al2O3(TM3410、0.01〜
0.02μm)、TiO2-NiO-Co2O3-ZnO(TM3320 、0.01〜0.02μ
m)、Fe2O3-ZnO-Cr2O3(TM3210、0.01〜0.02μm)〔それぞ
れ大日精化工業社製〕等の無機顔料超微粒子が挙げら
れ、また例えば具体的にはTiO2超微粒子としては IT-S-
UD〔0.02μm 、出光石油化学社製〕、UF01〔0.018 μ
m、タイオキサイド・ケミカルズ社製〕等、Fe2O3 超微
粒子としてはナノタイト〔超微粒子球形ヘマタイト、0.
06μm 、昭和電工社製〕等が挙げられ、具体的に挙げて
いない超微粒子でも適宜必要に応じて求められる機能特
性を合せガラスの品質を維持しつつ発揮することができ
るものであれば特に限定することなく使用できることは
言うまでもない。Further, for example, Co 2 O 3 -Al 2 O 3 (TM3410, 0.01 to
0.02 μm), TiO 2 -NiO-Co 2 O 3 -ZnO (TM3320, 0.01-0.02 μm
m), Fe 2 O 3 -ZnO-Cr 2 O 3 (TM3210, 0.01 to 0.02 μm) inorganic pigment ultrafine particles such as (each manufactured by Dainichi Seika Kogyo Co., Ltd.), and for example, specifically, TiO 2 IT-S-
UD (0.02 μm, Idemitsu Petrochemical Co., Ltd.), UF01 (0.018 μm
m, manufactured by Taioxide Chemicals Co., Ltd.), as Fe 2 O 3 ultrafine particles, nanotites (ultrafine spherical hematite, 0.
06 μm, manufactured by Showa Denko KK), etc., and are not particularly limited as long as the ultrafine particles not specifically mentioned can exert the required functional properties as needed while maintaining the quality of the laminated glass. Needless to say, it can be used without doing so.
【００２２】またさらに、有機系紫外線吸収剤あるいは
有機系熱線吸収剤については、有機系紫外線吸収剤とし
ては例えば2-(2'-ヒドロキシ-5'-メチルフェニル) ベン
ゾトリアゾール、2-(2'-ヒドロキシ-3',5'- ジ・tert-
ブチルフェニル) ベンゾトリアゾール、2-(2'-ヒドロキ
シ-3'-tert- ブチル-5'-メチルフェニル) -5- クロロベ
ンゾトリアゾール、2-(2'-ヒドロキシ-3',5'- ジ・tert
- ブチルフェニル)-5-クロロベンゾトリアゾール、2-
(2'-ヒドロキシ-3',5'- ジ・tert- アミルフェニル) ベ
ンゾトリアゾール等のベンゾトリアゾール系誘導体、ま
た例えば2,4-ジヒドロキシベンゾフェノン、2-ヒドロキ
シ-4- メトキシベンゾフェノン、2-ヒドロキシ-4- オク
トキシベンゾフェノン、2-ヒドロキシ-4- ドデシルオキ
シベンゾフェノン、2,2'- ジヒドロキシ-4- メトキシベ
ンゾフェノン、2,2'- ジヒドロキシ-4,4'-ジメトキシベ
ンゾフェノン、2-ヒドロキシ-4- メトキシ-5- スルホベ
ンゾフェノン等のベンゾフェノン系誘導体、また2-エチ
ルヘキシル-2- シアノ-3,3'-ジフェニルアクリレート、
エチル-2- シアノ-3,3'-ジフェニルアクリレート等のシ
アノアクリレート系誘導体などが挙げられる。具体的に
は例えばTINUVIN327〔チバガイギー社製〕等である。Further, as for the organic ultraviolet absorber or the organic heat ray absorber, examples of the organic ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2 ' -Hydroxy-3 ', 5'-di-tert-
Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- tert
-Butylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole derivatives such as benzotriazole, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy Benzophenone derivatives such as -5-sulfobenzophenone, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate,
And cyanoacrylate derivatives such as ethyl-2-cyano-3,3'-diphenylacrylate. Specifically, it is, for example, TINUVIN327 (manufactured by Ciba Geigy).
【００２３】さらに有機系熱線吸収剤としては例えばNI
R-AM1 〔帝国化学産業社製〕、ことに近赤外線吸収剤と
してはSIR-114 、SIR-128 、SIR-130 、SIR-132 、SIR-
169、SIR-103 、PA-1001 、PA-1005 〔三井東圧化学社
製〕等が挙げられる。特に建築用や自動車用に求められ
る合せガラスの品質を維持しつつ発揮するものであれ
ば、限定することなく使用できることは言うまでもな
い。Further, as an organic heat ray absorbent, for example, NI
R-AM1 (manufactured by Teikoku Chemical Industry Co., Ltd.), especially as near-infrared absorbing agents SIR-114, SIR-128, SIR-130, SIR-132, SIR-
169, SIR-103, PA-1001, and PA-1005 (manufactured by Mitsui Toatsu Chemicals, Inc.). Needless to say, any material can be used without limitation, as long as it exhibits the quality of laminated glass required for construction and automobile use.
【００２４】さらに、PTFEなどのフッ素樹脂、シリコ−
ンレジン、シリコ−ンゴムなどの有機樹脂の微粒子が挙
げられ、これらはPVB 膜とガラスなどの透明板との接着
強度を低減するために用いられる。すなわちATO 、ITO
などの金属酸化物は規格以上の接着強度を付与するよう
なことが起こりうるために、パンメル値を適宜下げて調
整し規格値内に下げるために、例えば前記ガラス表面へ
のプライマ−塗布、前記フッ素樹脂、シリコ−ンレジ
ン、シリコ─ンゴム等の有機樹脂を被覆した被膜物など
と同様の目的で用いる。Furthermore, fluororesins such as PTFE, silicone
Fine particles of organic resins such as resin and silicone rubber are used, and these are used to reduce the adhesive strength between the PVB film and a transparent plate such as glass. ATO, ITO
Since metal oxides such as may give an adhesive strength higher than the standard, it is possible to adjust the Pummel value appropriately and lower it to the standard value, for example, primer coating on the glass surface, It is used for the same purpose as a film coated with an organic resin such as a fluororesin, a silicone resin, and a silicone rubber.
【００２５】また、一般にガラスアンテナ付きガラスの
シート抵抗値としては、例えば20KΩ／口以上の抵抗値
であって、特にアンテナと接触する際には、10M Ω／口
以上の高抵抗値であることが好ましく、10M Ω／口未満
のシート抵抗値では、積層体にする以前のガラス板の電
波透過性に比し充分安定確実に１dB（絶対値として）以
内の変動差内に収めることができないものであり、より
充分安定確実に１dB以内の変動差内、例えば0.8 dB以内
の変動差内とするためには15M Ω／口以上、さらに電波
透過性能および光学特性ならびに物理的化学的特性を充
分満足する好ましい積層体のシート抵抗値としては20M
Ω／口以上10G Ω／口以下程度の範囲であり、より好ま
しいシート抵抗値としては22M Ω／口以上10G Ω／口以
下程度の範囲である。In general, the sheet resistance of glass with a glass antenna is, for example, a resistance value of 20 KΩ / port or more, and especially a high resistance value of 10 MΩ / port when contacting with an antenna. It is preferable that the sheet resistance value of less than 10 MΩ / port cannot be sufficiently stable and surely within 1 dB (as an absolute value) within the fluctuation difference, compared with the radio wave transmission of the glass sheet before forming the laminate. It is more than 15MΩ / per mouth to ensure stable stability within the fluctuation difference of 1dB or less, for example, within 0.8dB, and fully satisfies radio wave transmission performance, optical characteristics, and physical and chemical characteristics. The preferred sheet resistance of the laminate is 20M
The range is from about Ω / port to about 10 GΩ / port, and the more preferable sheet resistance is from about 22 MΩ / port to about 10 GΩ / port.
【００２６】該ガラス板状体とほぼ同等の電波透過性能
を有する前記積層体と特に光学特性上で巧みに相互に絡
ませ相乗効果をもたらしめるようにすることで、電波透
過性能および熱線遮蔽性能を高めたことはもちろん、格
段に優れた光学的機能を備える卓越した特に自動車用窓
ガラスとして最適なものとしたものである。The above-mentioned laminate having almost the same radio wave transmission performance as the glass plate-like body is entangled with each other particularly on the optical characteristics to bring about a synergistic effect, so that the radio wave transmission performance and the heat ray shielding performance can be obtained. It is, of course, the most suitable as a window glass for automobiles, which has outstanding optical functions.
【００２７】すなわち、自動車用窓ガラスとして、電波
透過性能を前記ガラス板状体に限り無く近づけほぼ同等
としかつ熱線遮蔽性能を日射透過率が65％以下と格段に
高め居住性をさらに向上したなかで、運転者や搭乗者等
が安全上等で必要である可視光透過率を65％以上とした
透視性、例えば可視光透過率が70％以上等を確保し法規
上もクリアできるようにでき、しかも運転者や搭乗者等
における透視性低下、誤認あるいは目の疲労等の防止に
必要である可視光反射率を従来の値よりさらに低減せし
めることができ、最適な電波透過型熱線紫外線遮蔽合せ
ガラスとなる。自動車用として好ましくは可視光透過率
が68〜70％以上、可視光反射率が14％以下、しかも日射
透過率が60％以下、刺激純度が15〜10％以下であり、建
築用として好ましくは可視光透過率が30％以上、可視光
反射率が20％以下、しかも日射透過率が65％以下、刺激
純度が20％以下である。That is, as a window glass for an automobile, the radio wave transmission performance is made almost as close as possible to the above-mentioned glass plate, and the heat ray shielding performance is remarkably reduced to a solar radiation transmittance of 65% or less, thereby further improving the comfort. This allows drivers and passengers to secure visible light transmittance of 65% or more, which is necessary for safety, etc., for example, to ensure visible light transmittance of 70% or more, etc. In addition, it is possible to further reduce the visible light reflectance necessary for preventing the visibility of the driver, passengers, etc. from lowering the visibility, erroneous recognition, eye fatigue, etc. It becomes glass. Preferably, the visible light transmittance is 68 to 70% or more, the visible light reflectance is 14% or less, the solar radiation transmittance is 60% or less, and the stimulus purity is 15 to 10% or less for automobiles. Visible light transmittance is 30% or more, visible light reflectance is 20% or less, solar radiation transmittance is 65% or less, and stimulus purity is 20% or less.
【００２８】さらにまた、前記電波透過型熱線紫外線遮
蔽の合せガラスは、例えばガラス板状体の周辺部の黒枠
内で周縁端からある幅で全周部分または給電点部よりや
や大きめの部分を除いて、あるいは該給電点部と同様に
ししかもモール（枠体）を一体成型または後付けする部
分を除き、さらには該アンテナ導体部分の全部または一
部を除いて超微粒子を含む機能性中間膜を採用する等、
その構成は適宜自在になし得ることは言うまでもない。Furthermore, the laminated glass of the radio wave transmitting type heat ray ultraviolet ray shielding is, for example, in a black frame around a glass plate-like body, except for a portion having a certain width from a peripheral edge and a portion slightly larger than a power feeding point portion. Or a functional intermediate film containing ultrafine particles except for a part where a molding (frame body) is integrally molded or attached, and all or a part of the antenna conductor part is removed. Etc.
Needless to say, the configuration can be made freely.
【００２９】さらにまた、中間膜が熱線遮蔽性能を有し
てかつシート抵抗値を半導体膜乃至絶縁膜と高い値であ
ることにより、AM電波、FM電波等の放送における受信障
害あるいはTV映像でのゴ−スト現象等の電波障害などを
より確実に発現しないようにすることができ、充分な電
波透過性能を有するガラスを得て、環境に優しいものと
することができるものである。また例えば、ガラスアン
テナ素子に前記高抵抗の熱線遮蔽性能を有する膜を直接
積層した場合においても、電波受信性能の低下には影響
を及ぼすことがないようにしたと言えるものとなるもの
である。Furthermore, since the intermediate film has a heat ray shielding performance and the sheet resistance is higher than that of the semiconductor film or the insulating film, it is difficult to receive AM radio waves, FM radio waves, or the like, or to interfere with TV images. It is possible to more reliably prevent the occurrence of radio interference such as a ghost phenomenon, to obtain glass having sufficient radio wave transmission performance, and to make the glass environmentally friendly. Further, for example, even when the film having the high-resistance heat ray shielding performance is directly laminated on the glass antenna element, it can be said that it does not affect the deterioration of the radio wave reception performance.
【００３０】また、前記したようにガラス板状体として
は無機質ガラス、有機ガラスあるいはこれらの複合ガラ
ス、特に所謂フロート法で製造された無機質で透明なク
リア乃至着色ガラス、強化ガラスやそれに類するガラ
ス、プライマ−や各種機能性膜等被覆膜付きガラスであ
って、好ましくは例えばグリーン系ガラスやブロンズ系
ガラスであり、さらに例えばグレー系ガラスやブルー系
ガラス等にも採用可能である。また合せガラスのほか複
層ガラス、バイレヤ−ガラス等、さらに平板あるいは曲
げ板等各種板ガラス製品として使用できることは言うま
でもない。また板厚としては例えば約1.0mm 程度以上約
12mm程度以下であり、建築用としては約2.0mm 程度以上
約10mm程度以下が好ましく、自動車用としては約1.5mm
程度以上約3.0mm 程度以下が好ましく、より好ましくは
約2.0mm 程度以上約2.5mm 程度以下のガラスである。As described above, the glass plate may be made of an inorganic glass, an organic glass or a composite glass thereof, in particular, an inorganic transparent clear or colored glass produced by a so-called float method, a tempered glass or a glass similar thereto. It is a glass with a coating film such as a primer or various functional films, preferably, for example, a green glass or a bronze glass, and further, for example, a gray glass or a blue glass. Needless to say, it can be used as a laminated glass, a double-layer glass, a bilayer glass, etc., as well as various flat glass products such as a flat plate or a bent plate. Also, for example, the thickness is about 1.0 mm or more.
About 12 mm or less, about 2.0 mm or more and about 10 mm or less is preferable for architectural use, and about 1.5 mm for automobile use.
The glass is preferably from about 3.0 mm to about 3.0 mm, more preferably from about 2.0 mm to about 2.5 mm.
【００３１】さらに、PVB 系またはEVA 系樹脂膜が、粒
径が0.2 μm 以下の機能性超微粒子を可塑剤中に80.0wt
％以下分散せしめて機能性超微粒子分散可塑剤とし、次
いで該機能性超微粒子分散可塑剤をPVB 系またはEVA 系
樹脂溶液中に、PVB 系またはEVA 系樹脂に対し機能性超
微粒子分散可塑剤を50wt％以下少なくとも分散添加し、
適宜その他の添加剤を加え、混合混練して膜用原料樹脂
から得たこととしたのは、可塑剤溶液中に前記機能性超
微粒子を分散せしめる方が分散し易く、粒径が0.2 μm
以下の機能性超微粒子の分散を充分均一化することがで
き、透明性が得られるためであり、その混合量が80.0wt
％を超えると次第に分散が難しくなって均一化が確実で
なくなり易くなるためであり、好ましくは20.0wt％程度
以下、より好ましくは10.0wt％程度以下、さらに好まし
くは5.0wt ％以下0.5wt ％以上程度であって、少なすぎ
ても前記効果がなくなる。Further, a PVB-based or EVA-based resin film is coated with functional ultrafine particles having a particle size of 0.2 μm or less in a plasticizer by 80.0 wt.
% Or less to obtain a functionalized ultrafine particle-dispersed plasticizer, and then add the functionalized ultrafine particle-dispersed plasticizer to a PVB-based or EVA-based resin solution in a PVB-based or EVA-based resin solution. 50wt% or less dispersed addition,
Other additives were added as appropriate, and the mixture was kneaded and obtained from the raw material resin for the film.The reason for dispersing the functional ultrafine particles in a plasticizer solution was to disperse the particles more easily, and the particle size was 0.2 μm.
The dispersion of the following functional ultrafine particles can be sufficiently uniform, and transparency is obtained.
%, It becomes difficult to disperse gradually and uniformity tends to be unreliable, so that it is preferably about 20.0% by weight or less, more preferably about 10.0% by weight or less, further preferably 5.0% by weight or less and 0.5% by weight or more. The above effect is lost even if the amount is too small.
【００３２】またPVB 系またはEVA 系樹脂に対し機能性
超微粒子分散可塑剤の分散添加が50wt％を超えると、PV
B 系またはEVA 系樹脂中での分散のみでなく、合せガラ
スの中間膜としての性能に支障をきたすようになり易い
からであり、好ましくは45wt％程度以下、より好ましく
は40wt％程度以下10wt％程度以上である。また、混合混
練には通常のミキサー、バンバリーミキサーやブラベン
ダーミキサー、ニーダー等を用いる。When the amount of the functionalized ultrafine particle dispersing plasticizer added to the PVB-based or EVA-based resin exceeds 50% by weight, PV
This is because not only the dispersion in the B-based or EVA-based resin, but also the performance of the laminated glass as an interlayer tends to be impaired, preferably about 45 wt% or less, more preferably about 40 wt% or less 10 wt%. More than a degree. For mixing and kneading, an ordinary mixer, Banbury mixer, Brabender mixer, kneader or the like is used.
【００３３】さらにまた、可塑剤としては、例えばジオ
クチルフタレート(DOP) 、ジイソデシルフタレート(DID
P)、ジトリデシルフタレート(DTDP)、ブチルベンジルフ
タレート(BBP) などのフタル酸エステル、またトリクレ
シルホスフェート(TCP) 、トリオクチルホスフェート(T
OP) などのリン酸エステル、またトリブチルシトレー
ト、メチルアセチルリシノレート(MAR) などの脂肪酸エ
ステル、またトリエチレングリコール・ジ-2- エチルブ
チレート(3GH) 、テトラエチレングリコール・ジヘキサ
ノールなどのポリエーテルエステルなど、またさらにこ
れらの混合物が挙げられる。Further, as the plasticizer, for example, dioctyl phthalate (DOP), diisodecyl phthalate (DID)
P), phthalic acid esters such as ditridecyl phthalate (DTDP) and butylbenzyl phthalate (BBP), and tricresyl phosphate (TCP) and trioctyl phosphate (T
OP) and other fatty acid esters such as tributyl citrate and methyl acetyl ricinolate (MAR), and polyesters such as triethylene glycol di-2-ethyl butyrate (3GH) and tetraethylene glycol dihexanol. Examples thereof include ether esters and the like, and further, mixtures thereof.
【００３４】さらに、前記PVB 系樹脂を溶解する溶剤と
しては、例えばエチルアルコ−ル、n-プロピルアルコ−
ル、イソプロピルアルコ−ル、n-ブチルアルコ−ル、メ
チレンクロライド等が挙げられる。さらにまた、前記EV
A 系樹脂を溶解する溶剤としては、例えばトルエン、キ
シレン、メチレンクロライド等が挙げられる。Further, as the solvent for dissolving the PVB resin, for example, ethyl alcohol, n-propyl alcohol
Isopropyl alcohol, n-butyl alcohol, methylene chloride and the like. Furthermore, the EV
Examples of the solvent that dissolves the A-based resin include toluene, xylene, and methylene chloride.
【００３５】さらに、前記膜用原料樹脂の膜化として
は、常法の型押出し法またはカレンダーロール法等であ
る。中間膜の膜厚としては約0.2 〜1.2mm 程度、好まし
くは約0.3 〜0.9mm 程度である。Further, the film forming of the raw material resin for the film may be carried out by a conventional mold extrusion method or a calender roll method. The thickness of the intermediate film is about 0.2 to 1.2 mm, preferably about 0.3 to 0.9 mm.
【００３６】さらに、前記合せガラス化処理としては、
オートクレーブ法、減圧下で常温から120 ℃まで昇温す
る中で80〜120 ℃の温度範囲で20〜30分間の加熱等であ
り、膜表面に均一な凹凸のしぼを設ける。なお、場合に
よって種々の簡易な合せガラス化処理を適宜適用できる
ことは言うまでもない。Further, as the above-mentioned laminated vitrification treatment,
In the autoclave method, heating is performed at a temperature range of 80 to 120 ° C. for 20 to 30 minutes while the temperature is raised from room temperature to 120 ° C. under reduced pressure, and a uniform uneven grain is provided on the film surface. It is needless to say that various simple laminated vitrification treatments can be appropriately applied in some cases.
【００３７】[0037]
【作用】前述したとおり、本発明の合せガラスは、着
色、熱線や紫外線遮断膜、電波透過等各種の機能性能を
有する粒径が0.2 μm 以下である超微粒子を適宜分散含
有せしめた樹脂中間膜層でもって合せ処理することでな
る合せガラスとその製造方法としたことにより、従来か
ら使用されている合せガラス用中間膜層に影響を与える
ことなく、断熱性能や紫外線遮断性能や電波透過性能等
の機能特性を付与し、しかもクリア乃至着色の色調の制
御およびヘーズ値が極めて低く優れた透視性の確保なら
びに反射性とぎらつき感の防止等をバランスよくもたら
しめ、例えば自動車用安全ガラスに係わるJIS R 3212の
各試験等をクリアする等、従来の合せガラスと変わらな
い品質を得ることができ、特殊成分組成ガラスや特殊表
面加工ガラスを必要とせず、かつ現在使用中の合せガラ
ス製造ラインをそのままで合せガラス化処理と作業で行
うことができ、安価にかつ容易にしかもガラスの大きさ
や形態に自由自在に対応し得て合せガラスを得ることが
できるものである。As described above, the laminated glass of the present invention is a resin interlayer in which ultrafine particles having a particle size of 0.2 μm or less having various functional properties such as coloring, heat ray and ultraviolet ray shielding, and radio wave transmission are appropriately dispersed and contained. The laminated glass and the method of manufacturing the laminated glass can be laminated and processed without affecting the conventionally used interlayer film for laminated glass. Control properties of clear or colored, haze value is extremely low, excellent transparency is ensured, and reflection and glare are prevented in a well-balanced manner. It can achieve the same quality as conventional laminated glass, such as clearing each test of JIS R 3212, etc., and does not require special component composition glass or special surface processed glass In addition, the laminated glass production line currently in use can be used as it is in the laminated glass forming process and work, and the laminated glass can be obtained inexpensively and easily, and can be freely adapted to the size and form of the glass. Things.
【００３８】ひいては、冷暖房効果を高め居住性を向上
せしめるような優れた日射透過率、環境や人に優しくな
る紫外線遮断等を有するとともに、比較的高いものから
低いものまで幅広い可視光線透過率を有するものとする
ことができ、AM電波、FM電波TV電波帯等の放送における
受信障害などの低減をすることができ、通常のフロ−ト
ガラス並の電波透過性能であることから、車輌用のテレ
ビ、ラジオ、携帯電話等のためのガラスアンテナの受信
性能を低下させることなく、あるいはゴ−スト現象等の
電波障害を低減することができ、本来のガラスアンテナ
性能を発揮させ、車輌内外での快適な環境を確保するこ
とができることとなり、電波透過性能を必要とする無色
から有色と各種色調、はたまたガラスとガラス、ガラス
と合成樹脂板、バイレヤ−等の合せガラスとして使用可
能な電波透過型熱線紫外線遮蔽ガラス等となり、建築用
窓材としてはもちろん、特に自動車用窓材、例えばフロ
ントウインドー、リヤウインドーあるいはサイドウイン
ドーまたはサンルーフ、シェードバンド等に、ことに風
防用ガラスにも充分適用でき、また飛行機用窓材等幅広
く適用でき、最近のニーズに最適なものとなる有用な機
能性を有する合せガラスの製造方法を提供するものであ
る。In addition, it has an excellent solar radiation transmittance to enhance the air-conditioning effect and enhance the comfort of living, and has an ultraviolet shielding property that is friendly to the environment and people, and has a wide range of visible light transmittance from relatively high to low. It can reduce the reception interference in broadcasting such as AM radio wave, FM radio wave TV radio band, etc., and because it has the same radio transmission performance as ordinary float glass, it can be used for vehicle TV, It can reduce the radio interference such as ghost phenomenon without deteriorating the reception performance of the glass antenna for radio, mobile phone, etc. The environment can be secured, and from colorless to colored and various colors that require radio wave transmission performance, glass to glass, glass to synthetic resin plate, It becomes a radio wave transmitting type heat ray ultraviolet ray shielding glass which can be used as a laminated glass for yarns, etc., and is used not only as a window material for construction, but also especially for a window material for automobiles, for example, a front window, a rear window or a side window or a sunroof, a shade band, etc. In particular, the present invention provides a method for producing a laminated glass having useful functionality, which can be applied to windshield glass, and can be widely applied to window materials for airplanes and the like, and is most suitable for recent needs.
【００３９】[0039]
【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明は係る実施例に限定されるものではな
い。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.
【００４０】実施例１ 20wt％ATO(導電性アンチモン含有錫酸化物) 超微粒子
（粒径0.02μm 以下）分散含有DOP(ジオクチルフタレー
ト) 10ｇと通常の DOP 130ｇをPVB(ポリビニルブチラー
ル) 樹脂 485ｇに添加し、他の紫外線吸収剤等とともに
３本ロールのミキサーにより約70℃で約15分間程度練り
込み混合した。得られた製膜用原料樹脂を型押出機にて
190 ℃前後で厚み約0.8mm 程度にフイルム化しロールに
巻き取った。なお、フイルム表面には均一な凹凸のしぼ
を設けた。 Example 1 10 g of 20 wt% ATO (conductive tin oxide-containing tin oxide) ultrafine particles (particle size: 0.02 μm or less) dispersed DOP (dioctyl phthalate) and 130 g of ordinary DOP were added to 485 g of PVB (polyvinyl butyral) resin. Then, the mixture was kneaded with a three-roll mixer at about 70 ° C. for about 15 minutes together with other ultraviolet absorbers and mixed. The obtained film-forming raw material resin is extruded using a mold extruder.
The film was formed into a film with a thickness of about 0.8 mm at around 190 ° C and wound on a roll. The film surface was provided with a uniform uneven grain.
【００４１】次に大きさ約300mmx300mm 、厚さ約2.3mm
のクリアガラス基板(FL2.3) を２枚用意し、該基板と同
じ大きさに前記フイルムを裁断し、調製した中間膜を該
２枚のクリアガラス基板の間に挟み積層体とした。Next, the size is about 300 mm x 300 mm and the thickness is about 2.3 mm
Were prepared, and the above-mentioned film was cut into the same size as the substrate, and the prepared intermediate film was sandwiched between the two clear glass substrates to form a laminate.
【００４２】次いで該積層体をゴム製の真空袋に入れ、
袋内を脱気減圧し、約80〜110 ℃程度で約20〜30分程度
保持した後一旦常温までにし、袋から取り出した積層体
をオートクレーブ装置に入れ、圧力約10〜14kg／cm2 、
温度約110 〜140 ℃程度で約20〜40分間程度の加圧加熱
して合せガラス化処理をした。Next, the laminate was placed in a rubber vacuum bag,
The inside of the bag was degassed and decompressed, and kept at about 80 to 110 ° C. for about 20 to 30 minutes, then brought to room temperature once, and the laminate taken out of the bag was put into an autoclave, and the pressure was about 10 to 14 kg / cm 2 ,
The laminated glass was formed by heating under pressure at a temperature of about 110 to 140 ° C. for about 20 to 40 minutes.
【００４３】得られた合せガラスについて下記の測定お
よび評価を行った。 〔光学特性〕：分光光度計（340 型自記、日立製作所
製）で波長340 〜1800nmの間の透過率を測定し、JIS Z
8722及びJIS R 3106又はJIS Z 8701によって可視光透過
率Tv(380〜780nm)、日射透過率Ts(340〜1800nm) 、刺激
純度（％）、色調等を求めた。 〔くもり度〕：ヘーズ値H をJIS K6714 に準拠して行い
求めた。建築用としては３％以下、自動車用としては１
％以下を合格とした。 〔電波透過性〕：KEC 法測定（電界シールド効果測定
器）によって、電波10〜1000MHzの範囲の反射損失値（d
B）を通常の板厚3mm のクリアガラス(FL3t)単板品と対
比。その差の絶対値（△dB）が２dB以内を合格とした。 〔接着性〕： −18±0.6 ℃の温度で16±4 時間放置し
調整後、ハンマー打でのガラスの剥離での中間膜露出程
度。少ないものを合格とした。 〔耐熱性〕： 100 ℃の煮沸水中にて2 時間程度煮沸し
た後、周辺10mmを除き、残りの部分での泡の発生、くも
り、ガラスのひび割れ等の異常がないものを合格とし
た。 〔耐湿性〕： 50±2 ℃、相対湿度95±4 ％の調整内に
２週間静置した後、泡の発生、くもり、ガラスのひび割
れ等の異常がないものを合格とした。 〔電気的特性〕：三菱油化製表面高抵抗計（HIRESTA HT
-210）によって測定。 （シート抵抗値）（M Ω／口）。10M Ω／口以上合格。 〔なお、基本的にはJIS R 3212等安全ガラス、特に合せ
ガラスの項に準拠。〕 その結果、可視光透過率Tvが約76.8％程度、日射透過率
Tsが約58.6％程度、刺激純度Peが0.7 ％程度で淡いグレ
ー系のニュートラル色調、反射によるギラツキもなく、
ヘーズ値Ｈが約0.3 ％程度となり、充分優れた熱線遮蔽
性等の光学特性、格段に高い表面抵抗率で通常単板ガラ
ス並み、例えば80MHz(FMラジオ波帯) 、約520 〜1630KH
z(AMラジオ波帯) 等特に通常単板ガラスと同等の電波透
過性を示し、かつ充分安定な優れた接着性と耐熱性なら
びに耐湿性を示しいずれも合格であり、通常の合せガラ
スと変わらない合せガラスを得ることができ、優れた居
住性をもちかつ運転者や搭乗者あるいは環境に優しく安
全性が高くしかもAM帯をはじめ各種電波を快適に受信が
でき、建築用窓ガラスはもちろん自動車用窓ガラス、こ
とにアンテナ導体と同時に備える自動車用窓ガラスに対
しても充分採用でき、期待に充分答えることができるも
のであった。The following measurement and evaluation were performed on the obtained laminated glass. [Optical characteristics]: Measure the transmittance between 340 and 1800 nm using a spectrophotometer (Model 340, manufactured by Hitachi, Ltd.)
Visible light transmittance Tv (380 to 780 nm), solar transmittance Ts (340 to 1800 nm), stimulus purity (%), color tone, etc. were determined according to 8722 and JIS R 3106 or JIS Z 8701. [Degree of haze]: Haze value H was determined according to JIS K6714. 3% or less for architectural use, 1% for automotive use
% Or less was accepted. [Electromagnetic wave transmission]: Reflection loss value (d
B) is compared with a normal 3mm clear glass (FL3t) single plate product. An absolute value (△ dB) of the difference was considered to be within 2 dB. [Adhesiveness]: Leaving at -18 ± 0.6 ° C for 16 ± 4 hours, adjusting and then exposing the intermediate film by peeling off the glass by hammering. A small number was accepted. [Heat resistance]: After boiling in boiling water at 100 ° C for about 2 hours, except for 10 mm around, there was no abnormality such as generation of bubbles, cloudiness, cracks in the glass, etc., and passed. [Moisture resistance]: After standing for 2 weeks in an adjustment at 50 ± 2 ° C. and a relative humidity of 95 ± 4%, those having no abnormality such as generation of bubbles, fogging and cracks in the glass were judged as acceptable. [Electrical characteristics]: Mitsubishi Yuka surface high resistance meter (HIRESTA HT
-210). (Sheet resistance) (MΩ / port). Passed 10MΩ / mouth or more. [Basically, it complies with safety glass, especially JIS R 3212, especially laminated glass. As a result, the visible light transmittance Tv is about 76.8%, the solar transmittance
Ts is about 58.6%, stimulus purity Pe is about 0.7%, light gray neutral color tone, no glare due to reflection,
The haze value H is about 0.3%, and the optical properties such as the heat ray shielding property are excellent enough, the surface resistivity is remarkably high, and it is on par with a single sheet glass. For example, 80 MHz (FM radio wave band), about 520 to 1630 KH
z (AM radio wave band) etc.Especially show the same radio wave transmission as normal single-pane glass, and show sufficiently stable and excellent adhesiveness, heat resistance and moisture resistance, all passed and no difference from ordinary laminated glass Laminated glass can be obtained, has excellent livability, is safe for drivers and passengers or the environment, is safe, and can receive various radio waves including the AM band comfortably. It could be used sufficiently for window glass, especially for automobile window glass provided with an antenna conductor, and could sufficiently meet expectations.
【００４４】なお、他に耐候性（例、サンシヤインウエ
ザーメーターで約1000時間：可視光透過率がほぼ変化が
ないこと）等の種々の特性をも評価したところ、いずれ
も合格するものであった。In addition, when various properties such as weather resistance (eg, about 1000 hours with a sunshine weather meter: almost no change in visible light transmittance) were evaluated, all of them passed. there were.
【００４５】実施例２ 20wt％ATO(導電性アンチモン含有錫酸化物) 超微粒子
（粒径0.02μm 以下）分散含有3GH(トリエチレングリコ
−ル -ジ- ２- エチルブチレ−ト) 10ｇと通常の3GH 13
0 ｇをPVB(ポリビニルブチラール) 樹脂 485ｇに添加
し、さらに接着調整剤としてトスパ−ル120(東芝シリコ
−ン) を５ｇ添加し、他の紫外線吸収剤等とともに３本
ロールのミキサーにより約70℃で約15分間程度練り込み
混合した。得られた製膜用原料樹脂を型押出機にて190
℃前後で厚み約0.8mm 程度にフイルム化しロールに巻き
取り、実施例１と同様にして表面には均一な凹凸のしぼ
を設けた厚み約0.8mm 程度の中間膜を得た。次に大きさ
約300mmx300mm 、厚さ約2.0mm のクリアガラス基板(FL
2) を用いて実施例１と同様にして積層体とした。次い
で実施例１と同様にして合せガラス化処理をした。 Example 2 10 g of 20 wt% ATO (conductive antimony-containing tin oxide) ultrafine particles (particle size: 0.02 μm or less) dispersed 3GH (triethylene glycol-di-2-ethylbutyrate) 10 g and ordinary 3GH 13
0 g was added to 485 g of PVB (polyvinyl butyral) resin, and 5 g of Tospar 120 (Toshiba Silicone) was further added as an adhesion regulator. For about 15 minutes. The obtained film-forming raw material resin is 190
The film was formed into a film having a thickness of about 0.8 mm at about ℃ and wound up on a roll to obtain an intermediate film having a thickness of about 0.8 mm provided with uniform unevenness on the surface in the same manner as in Example 1. Next, a clear glass substrate (FL with a size of about 300 mm x 300 mm and a thickness of about 2.0 mm)
Using 2), a laminate was obtained in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００４６】得られた合せガラスは、Tvが76.5％、Tsが
58.5％、Ｈが0.4 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。The obtained laminated glass has a Tv of 76.5% and a Ts of
58.5%, H: 0.4%, etc. As in the case of Example 1, excellent properties such as excellent optical properties and radio wave transmission properties and quality, etc. were exhibited in a well-balanced manner.
【００４７】実施例３ 20wt％ITO(導電性錫含有インジウム酸化物) 超微粒子
（粒径0.1 μm 以下）分散含有BBP(ブチルベンジルフタ
レート) 10ｇと通常の BBP90ｇをPVB 樹脂 323ｇに添加
し、実施例１と同様にして表面には均一な凹凸のしぼを
設けた厚み約0.8mm 程度の中間膜を得た。次に大きさ約
300mmx300mm 、厚さ約2.0mm のクリアガラス基板(FL2)
を用いて実施例１と同様にして積層体とした。次いで実
施例１と同様にして合せガラス化処理をした。 Example 3 20 g of ITO (conductive tin-containing indium oxide) ultrafine particles (particle diameter: 0.1 μm or less) dispersed BBP (butylbenzyl phthalate) 10 g and 90 g of ordinary BBP were added to 323 g of PVB resin. In the same manner as in Example 1, an intermediate film having a thickness of about 0.8 mm having a surface with uniform unevenness was obtained. Then about the size
300mmx300mm, clear glass substrate (FL2) about 2.0mm thick
To obtain a laminate in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００４８】得られた合せガラスは、Tvが76.3％、Tsが
51.5％、Ｈが0.4 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。またパンメル値は７〜８程度で
あり、建築用合せガラスに適するものであった。The resulting laminated glass has a Tv of 76.3% and a Ts of
51.5%, H: 0.4%, etc. As in Example 1, excellent properties such as excellent optical properties and properties such as radio wave transmission and quality were well balanced. In addition, the Pummel value was about 7 to 8, which was suitable for laminated glass for construction.
【００４９】実施例４ 20wt％ITO(導電性錫含有インジウム酸化物) 超微粒子
（粒径0.1 μm 以下）分散含有BBP(ブチルベンジルフタ
レート) 10ｇと通常の BBP90ｇをPVB 樹脂 323ｇに添加
し、さらに接着調整剤としてトスパ−ル120(東芝シリコ
−ン) を５ｇ添加し、実施例１と同様にして表面には均
一な凹凸のしぼを設けた厚み約0.8mm 程度の中間膜を得
た。次に大きさ約300mmx300mm 、厚さ約2.0mm のクリア
ガラス基板(FL2) を用いて実施例１と同様にして積層体
とした。次いで実施例１と同様にして合せガラス化処理
をした。 Example 4 10 g of 20 wt% ITO (conductive tin-containing indium oxide) ultra-fine particles (particle diameter: 0.1 μm or less) dispersed BBP (butyl benzyl phthalate) and 90 g of ordinary BBP were added to 323 g of PVB resin and further bonded. 5 g of Tospar 120 (Toshiba Silicone) was added as an adjusting agent, and an intermediate film having a thickness of about 0.8 mm having a surface with uniform unevenness was obtained in the same manner as in Example 1. Next, using a clear glass substrate (FL2) having a size of about 300 mm × 300 mm and a thickness of about 2.0 mm, a laminate was formed in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００５０】得られた合せガラスは、Tvが76.2％、Tsが
51.6％、Ｈが0.4 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。またパンメル値は３〜４程度で
あり、自動車用合せガラスとして適するものであった。The obtained laminated glass has a Tv of 76.2% and a Ts of
51.6%, H: 0.4%, etc. As in the case of Example 1, excellent properties such as excellent optical properties and radio wave transmission properties, quality, etc. were exhibited in a well-balanced manner. In addition, the Pummel value was about 3 to 4, which was suitable as a laminated glass for automobiles.
【００５１】実施例５ 実施例３の成分と量に対し、さらに有機系熱線吸収剤10
ｇ添加し、実施例１と同様にして表面均一凹凸のしぼを
設けた厚み約0.8mm 程度の中間膜を得た。次に実施例２
と同様のクリアガラス基板(FL2) を用いて実施例１と同
様にして積層体とし、次いで実施例１と同様にして合せ
ガラス化処理をした。 Example 5 An organic heat ray absorbent 10 was added to the components and amounts of Example 3.
g was added to obtain an intermediate film having a thickness of about 0.8 mm provided with a grain having uniform unevenness on the surface in the same manner as in Example 1. Next, Example 2
Using the same clear glass substrate (FL2) as in Example 1, a laminated body was formed in the same manner as in Example 1, and then a laminated glass treatment was performed in the same manner as in Example 1.
【００５２】得られた合せガラスは、Tvが64.3％、Tsが
32.8％、Ｈが0.4 ％等、やや可視光透過率が下がるもの
の実施例１よりことに断熱性能が優れ、他は実施例１と
同様に優れた光学特性ならびに電波透過性、品質等の各
物性をバランスよく示す所期のものであった。The obtained laminated glass has a Tv of 64.3% and a Ts of
32.8%, H is 0.4%, etc. Although the visible light transmittance is slightly lowered, the heat insulation performance is more excellent than that of Example 1, and the other properties are the same as those of Example 1, such as excellent optical properties and radio wave transmission and quality. Was intended to show a good balance.
【００５３】実施例６ 20wt％ITO 超微粒子（粒径0.1 μm 以下）分散含有 DID
P(ジイソデシルフタレート)7ｇと通常のDIDP95ｇをPVB
樹脂 323ｇに添加し、実施例１と同様にして表面均一凹
凸のしぼを設けた厚み約0.8mm 程度の中間膜を得た。次
に同様の大きさと厚みのクリアガラスのうち１枚をグリ
ーンガラス基板(NFL2)に替えて用い、実施例１と同様に
して積層体とした。次いで実施例１と同様にして合せガ
ラス化処理をした。 Example 6 DID containing 20 wt% ITO ultrafine particles (particle size: 0.1 μm or less) dispersed
PVB with 7 g of P (diisodecyl phthalate) and 95 g of ordinary DIDP
It was added to 323 g of the resin to obtain an interlayer having a thickness of about 0.8 mm provided with a grain having a uniform surface unevenness in the same manner as in Example 1. Next, one of the clear glasses having the same size and thickness was used in place of the green glass substrate (NFL2), and a laminate was obtained in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００５４】得られた合せガラスは、Tvが73.3％、Tsが
42.0％、Ｈが0.2 ％等、実施例１より断熱性能にかなり
優れるほか、実施例１と同様に優れた光学特性ならびに
電波透過性、品質等の各物性をバランスよく示す所期の
ものであった。The obtained laminated glass had a Tv of 73.3% and a Ts of
42.0%, H: 0.2%, etc., which are much better than the first embodiment in heat insulation performance, and exhibit the same excellent optical properties as in the first embodiment as well as various physical properties such as radio wave transmission and quality. Was.
【００５５】実施例７ 20wt％ITO 超微粒子（粒径0.1 μm 以下）分散含有 DID
P(ジイソデシルフタレート)7ｇと通常のDIDP95ｇをPVB
樹脂 323ｇに添加し、さらに接着調整剤としてトスパ−
ル120(東芝シリコ−ン) を５ｇ添加し、実施例１と同様
にして表面均一凹凸のしぼを設けた厚み約0.8mm 程度の
中間膜を得た。次に同様の大きさと厚みのクリアガラス
のうち１枚をグリーンガラス基板(NFL2)に替えて用い、
実施例１と同様にして積層体とした。次いで実施例１と
同様にして合せガラス化処理をした。 Example 7 DID containing 20 wt% ITO ultrafine particles (particle size: 0.1 μm or less) dispersed
PVB with 7 g of P (diisodecyl phthalate) and 95 g of ordinary DIDP
Add to 323g of resin
Then, 5 g of a No. 120 (Toshiba Silicone) was added to obtain an intermediate film having a thickness of about 0.8 mm provided with a grain having a uniform uneven surface as in Example 1. Next, one of the clear glass of the same size and thickness was used instead of the green glass substrate (NFL2),
A laminate was obtained in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００５６】得られた合せガラスは、Tvが73.2％、Tsが
42.1％、Ｈが0.2 ％等、実施例１より断熱性能にかなり
優れるほか、実施例１と同様に優れた光学特性ならびに
電波透過性、品質等の各物性をバランスよく示す所期の
ものであった。The obtained laminated glass had a Tv of 73.2% and a Ts of
42.1%, H is 0.2%, etc. The heat insulation performance is considerably better than that of Example 1, and the same optical properties as in Example 1 and the properties such as radio wave transmission and quality are well balanced. Was.
【００５７】実施例８ 実施例６と同様の成分と量で、実施例１と同様にして表
面均一凹凸のしぼを設けた厚み約0.8mm 程度の中間膜を
得た。次に同様の大きさと厚みのクリアガラスのうち１
枚をブルーガラス基板(BFL2)に替えて用い、実施例１と
同様にして積層体とした。次いで実施例１と同様にして
合せガラス化処理をした。 Example 8 Using the same components and amounts as in Example 6, an intermediate film having a thickness of about 0.8 mm was provided in the same manner as in Example 1. Next, one of the clear glasses of similar size and thickness
The laminate was used in the same manner as in Example 1 except that the substrate was replaced with a blue glass substrate (BFL2). Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００５８】得られた合せガラスは、Tvが76.0％、Tsが
49.5％、Ｈが0.2 ％等、実施例１より断熱性能がやや優
れるほか、実施例１と同様に優れた光学特性ならびに電
波透過性、品質等の各物性をバランスよく示す所期のも
のであった。The obtained laminated glass has Tv of 76.0% and Ts of
49.5%, H is 0.2%, etc. The insulation performance is a little better than that of Example 1, and it is the expected one which shows excellent physical properties such as excellent optical properties and radio wave transmission and quality as well as Example 1. Was.
【００５９】実施例９ 実施例８と同様の厚み約0.8mm 程度の中間膜を用い、次
に同様の大きさと厚みのクリアガラスのうち１枚をブロ
ンズガラス基板(MFL2)に替えて用い、実施例１と同様に
して積層体とし、次いで実施例１と同様にして合せガラ
ス化処理をした。 Example 9 An intermediate film having a thickness of about 0.8 mm similar to that of Example 8 was used, and then one of clear glass having the same size and thickness was used instead of a bronze glass substrate (MFL2). A laminate was formed in the same manner as in Example 1, and then subjected to a laminated vitrification treatment in the same manner as in Example 1.
【００６０】得られた合せガラスは、Tvが75.1％、Tsが
52.1％、Ｈが0.2 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。The resulting laminated glass had a Tv of 75.1% and a Ts of
52.1%, H: 0.2%, etc. As in Example 1, excellent optical properties and properties such as radio wave transmission and quality were well balanced.
【００６１】実施例10 実施例８と同様の厚み約0.8mm 程度の中間膜を用い、次
に同様の大きさと厚みのクリアガラスのうち１枚をグレ
ーガラス基板(GFL2)に替えて用い、実施例１と同様にし
て積層体とし、次いで実施例１と同様にして合せガラス
化処理をした。 Example 10 An intermediate film having a thickness of about 0.8 mm similar to that of Example 8 was used, and one of the clear glasses having the same size and thickness was used instead of a gray glass substrate (GFL2). A laminate was formed in the same manner as in Example 1, and then subjected to a laminated vitrification treatment in the same manner as in Example 1.
【００６２】得られた合せガラスは、Tvが76.0％、Tsが
54.5％、Ｈが0.2 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。The obtained laminated glass has a Tv of 76.0% and a Ts of
54.5%, H was 0.2%, etc. As in Example 1, excellent optical properties and properties such as radio wave transmission and quality were well-balanced.
【００６３】実施例11 40wt％無機顔料超微粒子であるTM3410〔Co2O3-Al2O3 、
粒径0.01〜 0.02 μm、大日精化工業社製〕分散含有DOP
20ｇと通常の TCP( トリクレシルホスフェート)120ｇ
をPVB(ポリビニルブチラール) 樹脂 480ｇに添加したも
のを実施例１と同様にして練り込み混合した。これを実
施例１と同様にして厚み約0.8mm 程度の中間膜を得た。
次いで実施例１と同様にして合せガラス化処理をした。 Example 11 TM3410 [Co 2 O 3 -Al 2 O 3 , 40 wt%
Particle size 0.01 to 0.02 μm, manufactured by Dainichi Seika Kogyo Co., Ltd.)
20g and normal TCP (tricresyl phosphate) 120g
Was added to 480 g of PVB (polyvinyl butyral) resin and kneaded and mixed in the same manner as in Example 1. In the same manner as in Example 1, an intermediate film having a thickness of about 0.8 mm was obtained.
Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００６４】得られた合せガラスは、Tvが73.8％、Tsが
50.2％、Peが7.8 ％の鮮やかなブルー系の色調であっ
て、Ｈが0.2 ％等、着色に係わる影響を除けば、ほぼ実
施例１と同様に優れた光学特性ならびに電波透過性、品
質等の各物性をバランスよく示す所期のものであった。The obtained laminated glass had a Tv of 73.8% and a Ts of
A vivid blue color tone of 50.2% and Pe of 7.8%, and excellent optical properties, radio wave transmission and quality similar to those of Example 1 except for the influence of coloring such as H of 0.2%. It was an expected thing which shows each physical property in a good balance.
【００６５】実施例12 30wt％無機顔料超微粒子であるTM3320〔TiO2-NiO-Co2O3
-ZnO、粒径0.01〜0.02μm 、大日精化工業社製〕分散含
有DOP 30ｇと通常の MAR( メチルアセチルリシノレー
ト)100ｇをPVB(ポリビニルブチラール) 樹脂 480ｇに添
加したものを実施例１と同様にして練り込み混合した。
これを実施例１と同様にして厚み約0.8mm程度の中間膜
を得た。次いで実施例１と同様にして合せガラス化処理
をした。 Example 12 TM3320 [TiO 2 -NiO-Co 2 O 3
-ZnO, particle size 0.01 to 0.02 μm, manufactured by Dainichi Seika Kogyo Co., Ltd.) A dispersion obtained by adding 30 g of DOP containing dispersion and 100 g of normal MAR (methyl acetyl ricinoleate) to 480 g of PVB (polyvinyl butyral) resin as in Example 1. And kneaded and mixed.
In the same manner as in Example 1, an intermediate film having a thickness of about 0.8 mm was obtained. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００６６】得られた合せガラスは、Tvが77.8％、Tsが
60.2％、Peが13.8％の鮮やかなグリーン系の色調であっ
て、Ｈが0.2 ％等、着色に係わる影響を除けば、実施例
１と同様に優れた光学特性ならびに電波透過性、品質等
の各物性をバランスよく示す所期のものであった。The obtained laminated glass had a Tv of 77.8% and a Ts of
It is a vivid green color tone with 60.2% and Pe of 13.8%, and has excellent optical characteristics, radio wave transmission, quality and the like as in Example 1 except for the influence of coloring such as H of 0.2%. It was the expected one showing each physical property in a well-balanced manner.
【００６７】実施例13 30wt％無機顔料超微粒子であるTM3210〔Fe2O3-ZnO-Cr2O
3 、粒径0.01〜0.02μm 、大日精化工業社製〕分散含有
DOP 20ｇと通常の 3GH( トリエチレングリコール・ジ-2
- エチルブチレート)150ｇをPVB(ポリビニルブチラー
ル) 樹脂 480ｇに添加したものを実施例１と同様にして
練り込み混合した。これを実施例１と同様にして厚み約
0.8mm 程度の中間膜を得た。次いで実施例１と同様にし
て合せガラス化処理をした。 Example 13 TM3210 [Fe 2 O 3 —ZnO—Cr 2 O, 30 wt% inorganic pigment ultrafine particles
3 , particle size 0.01 to 0.02 μm, manufactured by Dainichi Seika Kogyo Co., Ltd.)
DOP 20g and normal 3GH (triethylene glycol di-2
A mixture of 150 g of ethyl butyrate) and 480 g of PVB (polyvinyl butyral) resin was kneaded and mixed in the same manner as in Example 1. This is performed in the same manner as in Example 1 to obtain a thickness of about
An interlayer of about 0.8 mm was obtained. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００６８】得られた合せガラスは、Tvが67.8％、Tsが
51.8％、Peがやや高めではあるが鮮やかなグリーン系の
色調であって、Ｈが0.2 ％等、可視光透過率がやや低下
するなど着色に係わる影響を受けるものの、実施例１と
同様に優れた光学特性ならびに電波透過性、品質等の各
物性をバランスよく示す所期のものであった。The obtained laminated glass had a Tv of 67.8% and a Ts of
51.8%, Pe is slightly higher, but is a vivid greenish color tone. H is 0.2%, etc., but is affected by coloring such as slightly lowering the visible light transmittance, but is excellent as in Example 1. The optical properties and the properties such as radio wave transmission and quality were well-balanced.
【００６９】実施例14 20wt％ATO 超微粒子分散メチルエチルケトン溶液10ｇと
3GH(トリエチレングリコール・ジ-2- エチルブチレー
ト)150ｇをPVB(ポリビニルブチラール) 樹脂 490ｇに添
加し、接着調整剤、紫外線吸収剤などとともに３本ロ−
ルのミキサ−により約80℃で約20mmHgに減圧しながら約
１時間程度加熱練り込み混合した。これを実施例１と同
様にして厚み約0.8mm 程度の中間膜を得た。次いで実施
例１と同様にして合せガラス化処理をした。 Example 14 10 g of a 20 wt% ATO ultrafine particle dispersed methyl ethyl ketone solution
150 g of 3GH (triethylene glycol / di-2-ethyl butyrate) is added to 490 g of PVB (polyvinyl butyral) resin, and three bottles are added together with an adhesion regulator and an ultraviolet absorber.
The mixture was heated and kneaded for about 1 hour at about 80 ° C. while reducing the pressure to about 20 mmHg with a mixer. In the same manner as in Example 1, an intermediate film having a thickness of about 0.8 mm was obtained. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００７０】得られた合せガラスは、Tvが76.4％、Tsが
51.6％、Ｈが0.4 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。The obtained laminated glass had a Tv of 76.4% and a Ts of
51.6%, H: 0.4%, etc. As in the case of Example 1, excellent properties such as excellent optical properties and radio wave transmission properties, quality, etc. were exhibited in a well-balanced manner.
【００７１】実施例15 約100 ℃程度に加熱して水飴状になったPVB(ポリビニル
ブチラール) 樹脂 490ｇにATO 超微粒子２ｇを添加し、
紫外線吸収剤などとともに３本ロ−ルのミキサ−により
約80℃程度で約１時間程度加熱練り込み混合した。これ
を実施例１と同様にして厚み約0.8mm 程度の中間膜を得
た。次いで実施例１と同様にして合せガラス化処理をし
た。 Example 15 2 g of ATO ultrafine particles were added to 490 g of PVB (polyvinyl butyral) resin which was heated to about 100 ° C. and turned into a syrup.
The mixture was kneaded by heating with a three-roll mixer at about 80 ° C. for about 1 hour together with an ultraviolet absorber and the like. In the same manner as in Example 1, an intermediate film having a thickness of about 0.8 mm was obtained. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.
【００７２】得られた合せガラスは、Tvが77.5％、Tsが
55.7％、Ｈが0.2 ％等実施例１と同様に優れた光学特性
ならびに電波透過性、品質等の各物性をバランスよく示
す所期のものであった。なお、パンメル値については、
実施例１と２ならびに実施例５〜15においても実施例３
と４のようにして適宜建築用あるいは自動車用として調
整して用いることができることは言うまでもない。The resulting laminated glass had a Tv of 77.5% and a Ts of
55.7%, H: 0.2%, etc. As in Example 1, excellent properties such as excellent optical properties and properties such as radio wave transmission and quality were well balanced. For the Pummel value,
Example 3 in Examples 1 and 2 and Examples 5 to 15
Needless to say, it can be appropriately adjusted and used for construction or automobile as shown in (4) and (4).
【００７３】[0073]
【発明の効果】以上前述したように、本発明は粒径0.2
μm 以下の機能性超微粒子を中間膜層に分散含有する合
せガラスの製造方法としたことにより、従来から使用さ
れている合せガラス用中間膜層に大きな影響を与えるこ
となく、断熱性能や紫外線遮断性能や電波透過性能等の
機能特性を付与し、しかもクリア乃至着色の色調の制御
およびヘーズ値が極めて低く優れた透視性の確保ならび
に反射性とぎらつき感の防止等をバランスよくもたらし
め、従来の合せガラスと変わらない品質を得るようにで
き、現在使用中の合せガラス製造ラインをそのままで合
せガラス化処理と作業で行うことができ、安価にかつ容
易にしかもガラスの大きさや形態に自由自在に対応し得
て実施でき、ひいては冷暖房効果を高め居住性を向上せ
しめ、環境や人に優しく、幅広い透視性を得ることがで
き、AM電波、FM電波TV電波帯等を通常のフロ−トガラス
並の電波透過性能として車輌用のテレビ、ラジオ、携帯
電話等のためのガラスアンテナ性能を確保でき、本来の
ガラスアンテナ性能を発揮させ、建屋や車輌内外での快
適な環境を確保することができることとなり、無色から
有色と各種色調の合せガラスとして使用可能な電波透過
型熱線紫外線遮蔽ガラス等となり、各種建築用窓材とし
てはもちろん、特に各種自動車用窓材、ことに風防用ガ
ラス、また飛行機用窓材、その他産業用ガラス等幅広く
適用でき、最近のニーズに最適なものとなる有用な機能
性を有する合せガラスの製造方法を提供することができ
る。As described above, the present invention has a particle size of 0.2.
The production method of laminated glass that contains functional ultra-fine particles of μm or less dispersed in the interlayer film layer has no significant effect on the interlayer film layer for laminated glass that has been conventionally used. In addition to imparting functional properties such as performance and radio wave transmission performance, it provides a well-balanced control of clear to colored color tone, extremely low haze value, excellent transparency and prevention of reflection and glare. The same quality as laminated glass can be obtained, and the laminated glass production line currently in use can be used as it is by laminating and working, and it is inexpensive and easy, and the size and shape of the glass can be freely adjusted. Can be implemented to meet the needs, and by extension, enhance the air-conditioning effect and improve the comfort of living, it is friendly to the environment and people, and can obtain a wide range of transparency, AM radio wave, FM radio wave TV The radio wave band etc. can be secured as a radio wave transmission performance equivalent to that of ordinary float glass, so that the glass antenna performance for TVs, radios, mobile phones, etc. for vehicles can be secured, the original glass antenna performance can be exhibited, and it can be used inside and outside buildings and vehicles. It is possible to secure a comfortable environment, and it will be a radio wave transmission type heat ray ultraviolet shielding glass etc. that can be used as a laminated glass of colorless to colored and various colors, as well as various architectural window materials, especially various automotive window materials, In particular, it is possible to provide a method for producing a laminated glass having useful functionality that can be widely applied to windshield glass, window materials for airplanes, other industrial glass, and the like, and is most suitable for recent needs.
Claims (5)
に中間膜層を有する合せガラスの製造方法において、可
塑剤を用いて成形してなるポリビニルブチラール系樹脂
膜の中に粒径が 0.2μｍ以下の機能性超微粒子を分散せ
しめてなる中間膜を用いて、オートクレーブ法により、
減圧下で常温から120 ℃まで昇温する中で80〜120 ℃の
温度範囲で20〜30分間の加熱により合せガラス化処理す
ることを特徴とする合せガラスの製造方法。In a method for producing a laminated glass having an intermediate film layer between at least two transparent glass plates, a polyvinyl butyral-based resin film formed using a plasticizer has a particle size of 0.2. Using an intermediate film in which functional ultra-fine particles of μm or less are dispersed, by an autoclave method,
A process for producing a laminated glass, comprising laminating by heating at a temperature in the range of 80 to 120 ° C. for 20 to 30 minutes while raising the temperature from normal temperature to 120 ° C. under reduced pressure.
wt％以下であることを特徴とする請求項１記載の合せガ
ラスの製造方法。2. The mixing ratio of the functional ultrafine particles is 10.0
The method for producing a laminated glass according to claim 1, wherein the content is not more than wt%.
ン、またはシリコーンゴムからなる有機樹脂の微粒子の
各単独もしくはこれらを組み合わせて含有させて中間膜
とガラスとの接着強度を低下させることを特徴とする請
求項１または２記載の合わせガラスの製造方法。3. The adhesive strength between the intermediate film and the glass is reduced by incorporating, in the intermediate film, fine particles of an organic resin made of a fluororesin, a silicone resin, or a silicone rubber alone or in combination thereof. A method for producing a laminated glass according to claim 1.
脂、シリコーンレジン、またはシリコーンゴムからなる
有機樹脂を被覆して中間膜とガラスとの接着強度を低下
させることを特徴とする請求項１または２記載の合わせ
ガラスの製造方法。4. The glass surface is coated with a primer, or coated with an organic resin made of fluororesin, silicone resin or silicone rubber to reduce the adhesive strength between the intermediate film and the glass. Production method of laminated glass.
を設けたことを特徴とする請求項１乃至４のいずれかに
記載の合わせガラスの製造方法。5. The method for producing a laminated glass according to claim 1, wherein a grain having uniform unevenness is provided on the surface of the resin film for the intermediate film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000380254A JP3537089B2 (en) | 1995-01-23 | 2000-12-14 | Manufacturing method of laminated glass |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-7944 | 1995-01-23 | ||
| JP794495 | 1995-01-23 | ||
| JP2000380254A JP3537089B2 (en) | 1995-01-23 | 2000-12-14 | Manufacturing method of laminated glass |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16548995A Division JP3154645B2 (en) | 1995-01-23 | 1995-06-30 | Automotive laminated glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001192245A true JP2001192245A (en) | 2001-07-17 |
| JP3537089B2 JP3537089B2 (en) | 2004-06-14 |
Family
ID=26342355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000380254A Expired - Lifetime JP3537089B2 (en) | 1995-01-23 | 2000-12-14 | Manufacturing method of laminated glass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3537089B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199850A (en) * | 2005-01-21 | 2006-08-03 | Sumitomo Metal Mining Co Ltd | Heat ray-shading component-containing master batch, heat ray-shading transparent resin-molded article and heat ray-shading transparent resin laminate |
| JP5503088B1 (en) * | 2013-09-17 | 2014-05-28 | 株式会社クラレ | Sheet containing polyvinyl acetal |
| JP2015059218A (en) * | 2014-03-13 | 2015-03-30 | 株式会社クラレ | Sheet containing polyvinyl acetal |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101497454B1 (en) * | 2013-09-03 | 2015-03-03 | (주)합동하이텍그라스 | Method for Manufacturing Laminated Glass with EVA |
-
2000
- 2000-12-14 JP JP2000380254A patent/JP3537089B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199850A (en) * | 2005-01-21 | 2006-08-03 | Sumitomo Metal Mining Co Ltd | Heat ray-shading component-containing master batch, heat ray-shading transparent resin-molded article and heat ray-shading transparent resin laminate |
| JP5503088B1 (en) * | 2013-09-17 | 2014-05-28 | 株式会社クラレ | Sheet containing polyvinyl acetal |
| WO2015040663A1 (en) * | 2013-09-17 | 2015-03-26 | 株式会社クラレ | Sheet containing polyvinyl acetal |
| JP2015059218A (en) * | 2014-03-13 | 2015-03-30 | 株式会社クラレ | Sheet containing polyvinyl acetal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3537089B2 (en) | 2004-06-14 |
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