JP3301591B2 - Interlayer for laminated glass and laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is combined in a glass
It relates to interlayer and laminated glass .

[0002]

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 radiation energy passing into the vehicle glass 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 for both human and physical aspects and environmental friendliness are used for vehicles. In recent years, in particular, the glass for vehicles has been required to have a green color tone, a sufficient visible light transmittance, a high heat ray ultraviolet ray shielding performance, and a high transmission performance of various radio waves. Among them, the following application is known as one in which fine particles or ultrafine particles are dispersed in an intermediate layer of laminated glass.

For example, Japanese Patent Application Laid-Open No. 222152/1990 describes an intermediate film for a short-wavelength light-shielding laminated glass in which a light absorbing agent and a particulate infinite substance are contained in a plasticized polyvinyl butyral resin. Japanese Patent Application Laid-Open No. 4-160041 discloses an automotive laminated glass in which a mixed layer of ultrafine particles and a glass component is formed between transparent plate-shaped members. A laminated glass having an interlayer containing fine particles of silicon dioxide in an ethyl acrylate copolymer resin is disclosed. Furthermore, two laminated glass applications (Japanese Patent Application No. 07-007944, 07
No. 165489) discloses a laminated glass in which functional fine particles are dispersed in a laminated interlayer film.

However, the above laminated glass is obtained by mixing functional ultrafine particles into a laminated intermediate film, and directly bonding and laminating the glass and the intermediate film. The particle size and the like affected the adhesive strength between the glass and the interlayer and was not preferable. For example, when the fine particles are of an oxide type, the adhesive strength to glass is increased, and when the fine particles are for an automobile, the shock absorbing power at the time of breakage of the laminated glass is reduced, and there is a problem in safety.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in consideration of the above-mentioned problems, without affecting the conventionally used interlayer film for laminated glass. Functional particles such as heat insulation performance, ultraviolet shielding performance, radio wave transmission performance, etc. are imparted by appropriately dispersing and containing functional ultra-fine particles, and furthermore, control of clear to colored color tones, transparency, and reflection and glare are provided. It provides a well-balanced prevention of sticking, etc. and can obtain the same quality as conventional laminated glass, does not require special component composition glass or special surface processed glass, and keeps the currently used laminated glass production line as it is Can be performed in a laminated vitrification process, for example, glass-to-glass, glass-to-plastic, bilayer glass, etc., at low cost and easily, and in the size and form of glass. Freely it can be manufactured obtained in response,
The present invention can be applied not only to window materials for construction but also to window materials for automobiles, window materials for airplanes, and especially windshields, and to provide useful functional laminated glass which is optimal for recent needs.

[0006]

DISCLOSURE OF THE INVENTION For laminated glass of the present invention
The intermediate film is formed between at least two transparent glass plates.
In an interlayer film for laminated glass provided with a laminated interlayer film,
Interlayer film a laminated intermediate layer of a three-layer, Ri particle size in the middle layer of the second layer of the three layers in the name are dispersed the following functional ultrafine particles 0.2 [mu] m, the mixing ratio of the functional ultrafine particles Is 10.0 ~
0.01 wt%, and the functional ultrafine particles are oxide-based.
The first and third interlayer films are made of polyvinyl butyral.
The second interlayer film is a vinyl chloride resin.
There is a feature.

[0007] The interlayer film for laminated glass of the present invention comprises:
The functional ultrafine particles may be conductive antimony-containing tin oxide or
Is a conductive tin-containing indium oxide.
You.

Further, the laminated glass of the present invention is characterized in that
1. The penetration resistance and prevention characterized by using the intermediate film according to 1.
Available as front windshield glass with excellent sound properties
Automotive window glass.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, the reason why the functional ultrafine particles having a particle size of 0.2 μm or less are dispersed in the intermediate film of the second layer is as follows. In order to ensure ultra-low haze value, radio wave transmission performance and transparency while suppressing the scattering reflection in the visible light region, while fully exhibiting the functional characteristics of fine particles such as solar radiation transmittance of 65% or less, such as isothermal ray shielding performance. Even if it contains ultrafine particles, it can maintain the physical properties such as adhesiveness, transparency, and durability as a conventional interlayer film for laminated glass, so that the laminated glass can be processed by ordinary work in a normal laminated glass production line. To do that. Preferably the particle size is 0.15μ
m or less, more preferably about 0.10 to 0.001 μm
It is about. The range of the particle size distribution is, for example, about
It is preferable that the uniformity is about 0.03 to 0.01 μm.

The reason why the mixing ratio of the functional ultrafine particles to the intermediate film of the second layer is not more than 10.0% by weight is that the diffuse reflection in the visible light region is suppressed and the solar transmittance is, for example, 65%. Ensure that the amount of ultra-fine particles, such as the following, is sufficient to exhibit the functional properties of ultra-fine particles, such as the following, so that they have low haze value, radio wave transmission performance, and transparency. As an intermediate film, for example, to maintain physical properties such as adhesiveness, transparency, and durability, and to enable a laminated glass processing in a normal operation by a normal laminated glass production line, there is a deep relationship with the particle size, When the content exceeds 10.0 wt%, it becomes difficult to realize the above requirements not only as window materials for automobiles but also as window materials for construction. In particular, for example, when the visible light transmittance Tv is 35% or more for laminated glass for architectural purposes, the mixing ratio of the inorganic pigment-based ultrafine particles needs to be about 10 to 0.1 wt%, and about 9 to 0.01 wt% for architectural laminated glass. %, More preferably about 8 to 0.05% by weight, and a preferable mixing ratio for automobiles is about 2.
It is about 0 to 0.01% by weight, more preferably about 1.5 to 0.05% by weight, and further preferably about 1.0 to 0.1% by weight. 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.

Furthermore, the first and third layers intermediate film was a polyvinyl butyral resin film (PVB system)
These are preferred because they are versatile as interlayer films for laminated glass. Specifically, plastic PVB (manufactured by Sekisui Chemical Co., Ltd., Mitsubishi Monsanto Co., Ltd.), UV absorber, antioxidant, antistatic agent, heat stabilizer, lubricant, filler, coloring, adhesion modifier, etc. are appropriately added. Can be blended. In the case of using a vinyl chloride resin as the second intermediate film, Ru can be improved soundproofing performance.

Furthermore, the laminated glass having the above-mentioned structure can be used as various window materials for construction, etc., and, of course, especially as window materials for automobiles, for example, front glass, rear glass, rear glass with shade band, side glass or sunroof glass, or the like. It can be used for various other glasses and the like.

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 manufactured 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 flat or bent plates. In addition, the plate thickness is, for example,
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.

Further, the film forming of the raw material resin for the intermediate film may be carried out by a conventional mold extrusion method or 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.

[0015] Further, as the 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.

[0016]

As described above, the interlayer film for laminated glass of the present invention can be used without affecting the interlayer film for laminated glass conventionally used, for example, JIS R 3212 relating to safety glass for automobiles. etc. to clear each test or the like, it is possible to obtain a quality unchanged the conventional laminated glass. A laminated glass using a composite film obtained by bonding and laminating a vinyl chloride resin film also has excellent penetration resistance and soundproofing properties in addition to the above-mentioned characteristics, and is useful as a window glass for automobiles, which is useful as a front windshield glass. Another object of the present invention is to provide a window glass for an automobile which has excellent transparency, weather resistance, impact resistance and the like, and can contribute to the safety and comfort of passengers in the vehicle.

[0017]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

EXAMPLE 1 10 g of 20 wt% ATO (conductive antimony-containing tin oxide) ultrafine particles (particle size: 0.02 μm or less) dispersed DOP (dioctyl phthalate) and 100 g of ordinary DOP were mixed with 450 g of PVC (polyvinyl chloride) resin. The mixture was added and 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 heated to 190 ° C. with a mold extruder.
The film was formed into a film having a thickness of about 0.8 mm before and after and wound around a roll. This is designated as film (A).

Next, the two films (B) and (A) obtained from the polyvinyl butyral resin are laminated with a polyvinyl butyral resin layer (B) / polyvinyl chloride resin layer (A) / polyvinyl butyral resin. The layers were superposed to form a layer (B) to obtain a three-layer laminated interlayer film. This intermediate film is
Sandwich from both sides with two float glass of 2.3mm thickness, 30cm square, put the unpressed sandwich body in a rubber bag, deaerate at 20torr vacuum for 20 minutes, then 90 ℃ in deaerated state And transfer the temperature to
Hold for 30 minutes. The sandwich thus temporarily pressed by the vacuum press is then pressured to 12 kg in an autoclave.
Thermocompression bonding was performed at 135 ° C./cm 2 at a temperature of 135 ° C. to produce a transparent laminated glass.

Next, the laminate is placed in a rubber vacuum bag,
The inside of the bag is degassed and decompressed, and is maintained at about 80 to 110 ° C. for about 20 to 30 minutes. After that, the temperature is once brought to room temperature, and the laminate taken out of the bag is placed in an autoclave, and the pressure is about 10 to 14 kg / cm 2
At a temperature of about 110 to 140 ° C. for about 20 to 40 minutes under pressure and heat, a laminated vitrification treatment was performed.

The following measurements and evaluations 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 construction, 1 for automobile
% 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 within 2 dB as a pass. [Adhesion]: 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 few were accepted. [Heat resistance]: After boiling for about 2 hours in boiling water at 100 ° C, except for the surrounding area of 10mm, those with no abnormalities such as occurrence of blockage, clouding, and cracks in the glass were accepted. [Moisture resistance]: After being allowed to stand for 2 weeks within the adjustment of 50 ± 2 ° C. and 95 ± 4% of relative humidity, those having no abnormality such as occurrence of shielding, fogging, cracking of glass, etc. were judged as acceptable. [Electrical characteristics]: Mitsubishi Yuka surface high resistance meter (HIRESTA HT
-210).

Passed 10 MΩ / port (sheet resistance value) or more.

As a result, the visible light transmittance Tv is about 77.7%, the solar transmittance Ts is about 55.0%, the stimulus purity Pe is about 0.7%, the pale gray neutral color tone, there is no glare due to reflection, and the haze value H It is about 0.3%, and it has optical characteristics such as excellent heat shielding properties, extremely high surface resistivity and is comparable to that of single-pane glass, for example, 80 MHz (FM radio wave band), about 520
161630KHz (AM radio wave band) etc.Especially shows the same radio wave transmission as normal single-pane glass, and shows sufficiently stable and excellent adhesiveness, heat resistance and moisture resistance, all passed and it is different from ordinary laminated glass Can not get laminated glass
Was .

In addition, when various properties such as weather resistance (eg, about 1000 hours with a sunshine weather meter: visible light transmittance hardly changes) were also evaluated, all of them passed. there were.

Further, in the automotive window glass having the same configuration, when the intermediate film was controlled to be maintained at a temperature in the range of 10 ° C. to 50 ° C., the same result as described above was obtained, and the quietness in the vehicle interior was improved. It was a significant contribution.

The obtained sample was measured for its acoustic radiation power by an acoustic radiation power measuring system, its acoustic transmission loss was measured by a reverberation chamber method, and was further subjected to JIS 3211 and JI.
When evaluated according to the rules of S3212 and JIS R3205, etc., it was found to be sufficiently provided with the expected performance as an automotive window glass and excellent.

EXAMPLE 2 10 g of 20 wt% ITO (conductive indium oxide containing indium oxide) ultrafine particles (particle diameter: 0.1 μm or less) dispersed BBP (butylbenzyl phthalate) and 70 g of ordinary BBP were added to 300 g of a PVC resin. A laminated vitrification treatment was performed in the same manner as in Example 1.

Next, a size of about 300 mm x 300 mm and a thickness of about 2.0 mm
Using the clear glass substrate (FL2) described above, a laminate was produced in the same manner as in Example 1. Next, a laminated vitrification treatment was performed in the same manner as in Example 1.

The resulting laminated glass has a Tv of 71.3% and a Ts of
46.1%, H: 0.4%, etc. As in 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 7 to 8, which was suitable for laminated glass for construction.

It is needless to say that the Pummel value can be appropriately adjusted and used for construction or automobiles as in Embodiment 2 in Embodiment 1.

[0031]

As described above, according to the present invention, the interlayer film for laminated glass in which the functional ultrafine particles are dispersed and contained in the interlayer film layer has a great effect on the conventionally used interlayer film for laminated glass. It can be applied to a wide variety of window materials for construction, of course, especially for window materials for automobiles, especially for windshields, window materials for airplanes, other industrial glass, etc. A laminated glass having useful functionality can be provided. Further, as described above, according to the automotive window glass of the present invention, the loss coefficient can be secured near the maximum value, and the whole glass can have high damping performance. Higher safety and higher occupancy, such as excellent characteristics, low noise inside the vehicle, including muffled noise, and quietness, and excellent transparency, weather resistance, impact resistance, and penetration resistance. An object of the present invention is to provide an automotive window glass having a property.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 27/12

Claims (3)

(57) [Claims] An interlayer film for laminated glass having a laminated interlayer film provided between at least two transparent glass plates , wherein the interlayer film is composed of three laminated interlayer films. particle size in the middle layer of the second layer of the three layers in the dispersed following functional ultrafine particles 0.2μm in Ri Na, the mixing ratio of the functional ultrafine particles
10.0 to 0.01 wt%, and the functional ultrafine particles are oxide-based
Wherein the first and third interlayer films are polyvinyl butyral.
A second layer intermediate film made of vinyl chloride resin.
The interlayer film for a laminated glass, wherein Aburadea Rukoto. 2. The method according to claim 1, wherein the functional ultrafine particles are conductive antimony.
The intermediate for laminated glass according to claim 1 , which is a tin-containing tin oxide or a conductive tin-containing indium oxide.
Membrane . 3. An intermediate film according to claim 1 is used.
Front windsea with excellent penetration resistance and soundproofing
Automotive window glass useful as glass.