JPS5970558A - Laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate, and more specifically to a laminate comprising a functional film and a polyvinyl butyral sheet, which is suitable for use in highly safe laminated windows. It is related to.

Transparent openings where safety is required, such as automobiles,
Laminated glass windows are used in parts of trains, airplanes, etc., and buildings.

The basic composition of a laminated glass window is a transparent plate such as a glass plate sandwiching a thermoplastic resin, such as the widely used polyvinyl butyral sheet, but the laminated glass window V
: It is also known that a film may be interposed for the purpose of imparting functionality. For example, there are methods to use a film with excellent mechanical strength to increase safety, methods to use a transparent film with a conductive film to prevent condensation, or methods that allow visible light to pass through but do not allow near-infrared light to pass through. A method has been proposed in which a film with a selective light transmittance function that is difficult to pass through is interposed.

In addition, as a typical example, instead of placing a functional film between the thermoplastic resin layers, the functional film is attached to one side of a transparent glass plate using an IH contact with adhesive J#, and the functional film is A method of providing a thermoplastic resin layer on other surfaces has also been proposed.

However, when manufacturing laminated glass with a film in between, the film and thermoplastic resin layer are laminated in advance. I'm doing it.

However, in conventional laminates, there is generally a difference in curvature (σ) due to the hygroscopicity and thermal elasticity of the thermoplastic resin layer, or when the laminate is bent during storage or handling as described above. Therefore, peeling may occur between the functional film and the thermoplastic resin layer, and care must be taken in storage and handling methods. In particular, when polyvinyl butyral sheets are used as thermoplastic resins to create functional films and laminates, delicate storage and handling methods are required. This is because the polyvinyl butyral sheet used for laminated glass windows has a low heat softening temperature and expands and contracts depending on the ambient temperature. I do things. Therefore, if you store a laminate of a functional film and a polyvinyl butyral sheet, a peeling phenomenon will occur at the interface between the film and the sheet, and when laminated glass is manufactured using the laminate, peeling will occur. It takes a lot of effort to reattach the parts, and there is a phenomenon of partial peeling between the film and the polyvinyl butyral sheet, which is difficult to remove. In addition, when functional films and polyvinyl butyral sheets are laminated industrially and stored, they may be formed into rolls.Depending on the temperature and humidity of the atmosphere, the shape may be distorted.

In order to overcome such drawbacks, the present inventors investigated and found that in a laminate made of a functional film and a polyvinyl butyral sheet, and a laminate made of a polyvinyl butyral sheet, a functional film, and a polyvinyl butyral sheet, The adhesive force between the functional film and the polyvinyl butyral sheet exceeds a certain value, and by smoothing the surface shape of the polyvinyl butyral sheet surface that comes into contact with the functional film, it can be stored without losing its shape even in the p-outer shape. We have discovered a laminate that can be made.

That is, the present invention provides a laminate made of a polyvinyl butyral sheet functional film, and a laminate made of a polyvinyl butyral sheet, a functional film, and a polyvinyl butyral sheet, in which the surface of the polyvinyl butyral sheet in contact with the functional film has a smooth surface. The present invention relates to a laminate characterized in that the adhesive force at the interface thereof is 100 f/cm or more.

The laminate of the present invention has functionality that can be used as a laminated glass window, has good storage stability, and does not exhibit optical unevenness even when the laminated glass window is produced.

The feature of the present invention is that the polyvinyl butyral surface in contact with the functional film has a uniform and smooth surface, and the adhesive force at the interface is 100 f/cm or more. Adhesive layer applied on both sides
There is a VC. A laminate produced by the method of the present invention, namely a polyvinyl butyral sheet, a laminate array K in which a functional film is laminated, a polyvinyl butyral sheet, a functional film,
A laminate in which polyvinyl butyral sheets are laminated can prevent peeling at the interface between the polyvinyl butyral sheet and the functional film that occurs during storage or handling. Also, the adhesive layer is a laminated glass window! When /C is applied, when the laminated glass window breaks, it can also prevent the loss of visibility caused by < 1 lj IX at the interface. Furthermore, the laminated glass window using the laminate is optically completely free of irregularities.

Each component will be explained in detail below. sa.

As the polyvinyl butyral sheet in the present invention, in principle, any polyvinyl butyral mixed with a thermoplastically processed plasticizer, heat stabilizer, ultraviolet absorber, colorant, etc. is suitable. Polyvinyl butyral, which must be thermoplastically formed, usually contains a large amount of plasticizer. The polyvinyl butyral sheet used for laminated glass usually contains 10 to 60 wt. As the plasticizer, dioctyl phthalate, diethylene glycol, triethylene glycol, etc. can be used.

The sheet thickness is between 0 and 1.5 degrees, preferably 0.
30-0.80m is desirable. The smoothness of the surface in contact with the functional film is within 5μ, preferably within 2μ. The degree of smoothness is determined by a surface profile measuring device described below. This surface smoothness plays an important role not only in improving the shelf life of a laminated glass window laminate, which is the object of the present invention, but also in producing a laminated glass window free from irregularities σ).

In other words, because the functional film or polyvinyl butyral sheet is completely in contact with the entire surface, the smoothness at the interface is not impaired even during the bonding process by heat and pressure, resulting in a homogeneous bond with no unevenness. It can be a glass window.

Even if a polyvinyl butyral sheet with large irregularities is used and any adhesive layer is provided on the surface of the functional film, a laminate with a long shelf life cannot be obtained.

The function of polyvinyl butyral sheet is that the surface that comes into contact with Zetfilm is in contact with glass or rigid plastic deck, and when they are combined, they are completely bonded. , generally 3() to 10
0μσ) There are embossed irregularities. The present invention extends to the internal shape.

Machine-resistant film is plastic film KPah.
This shows the functionality of 4.
The material is a transparent plastic film.

A film or sheet of a polymeric resin such as Kf': l〆r is used. For example, polyethylene terephthalate 1 note, polyethylene 2.6 naphthalate,
Polyesters (i
Polyolefin resins such as polyester resin, polycarbonate resin, polyethylene, polypropylene resin,
Polyvinyl chloride, polysulfone, polyphenylene oxide, polymethacrylic acid ester, polyacrylic beak ester, Boris Elen, etc., polyamide 41'l effect,
Examples include cellulose resins such as polyimide Yujilit, cellophane, and cellulose triacetate.

Among these, biaxially stretched polyethylene terephthalate film is the most suitable film due to its excellent dimensional stability, transparency, smoothness, and mechanical properties.

Examples of the functionality include transparent conductivity and selective light transmittance.

Examples of transparent conductive functionality include a thin film made of indium oxide and tin oxide, and a thin film of tin oxide.

4′ of gold, silver, @, aluminum, etc.? The thin film of the genus etc. should be exposed. Also, among solar energy σ), examples of selectively transmitting properties that pass through invisible infrared rays include gold, scissors, copper, aluminum, nickel, palladium, tin, and the like. Examples include a thin film of a metal alloy or a mixture, a thin film of these metals (σ), a thin film of metal laminated with five attractants on the surface or both sides, and a structure in which these structures are repeatedly laminated. Examples of dielectric materials include titanium oxide and bismuth oxide.

Examples include lead sulfide, tungsten oxide, indium oxide, zirconium oxide, and silicon oxide.

% between functional film and polyvinyl buoy tool sheet
In order to apply a pressure of 10 o y/cm or more to n's force, (an adhesive layer is provided on the geometric film, the following adhesive layer can be mentioned).

Acrylic resin, acrylic ester #1lIl￥,
.

In addition to the organic adhesive layer of epoxy resin, urethane resin, cyanoacrylate resin, vinyl acetate resin, silicone resin, 4% silicone resin, 1% synthetic rubber resin, and 1% synthetic rubber resin, The dielectric materials mentioned above can be used when permeability is determined.

The adhesive layer has transparency, durability (heat, light, water, etc.),
Processability.

In addition to the properties of polyvinylzotyral sheets and σ), excellent adhesive strength is required, and from the viewpoint of those properties, acrylic resins and urethane resins.

Polyester-based resins and the aforementioned dielectrics are preferably used, and more preferably they form dielectrics that can be used when imparting a light selective transmittance function.4 These are applied to both sides of the functional film. Even on the surface, it has no tackiness and has high transparency, which is very good.

There are various methods for applying these metal flucorates, such as alkyl titanates, alkyl zirconates, alkyl silicates, etc. Compounds thereof include, for example, alkyl titanates such as tetra-1-propoxy titanium, Tetra-n-gutoxytitanium, tetrakis(2-ethylhexyloxy)titanium, di-1-poxy-bis(acetynodoacetonato)titanium, dihydroxy-bis(lactato)titanium, and the like. Furkyl zirconate and alkyl silicate are also compounds similar to 7-ruky 71z titanate,
In addition to the above-mentioned alkyl silicates, it is also preferable to use polygonal silicates such as bicylindrical and tetrametallic silicates. Among these f), NL-mer and di-M-mer of tetra-n-butoxytitanium and tetra-n-butoxyzirconate.

A film of titanium oxide or zirconate oxide obtained by a method of hydrolyzing tetramer etc. preferably has a high adhesive strength with a polyvinyl butyral sheet.

The products made by each of the above-mentioned components; those with an adhesive force of 100 f/on or more are again divided into 1!
111: I'm in trouble, so I'm saving it.

When manufacturing laminated glass for handling or use as a laminated glass window, it is possible to obtain a very good glass without peeling when broken. Further, the laminate of the present invention is used for laminated glass windows.

That is, a polyvinyl butyral sheet is placed between two transparent plates,
The laminate of the present invention consisting of a functional film, a polyvinyl butyral sheet is placed, the whole is placed in a vacuum bag, and heat and pressure are applied to form a laminated window, which is used as a safety glass window for automobiles, buildings, etc. . Also, an example of use as a windshield window of an automobile is the present invention' which is made of a transparent plate such as glass, a polyvinyl butyral sheet, and a functional film! *I■
By putting the bodies together in a vacuum bag and applying heat and pressure.

In this case, with a polyvinyl butyral sheet interposed,
It is sandwiched between a glass-like transparent plate and a functional film.

In addition, the surface of the polyvinyl butyral sheet that is not in contact with the functional film of this laminate generally has an uneven shape of 30 to 100 μm, but this surface is coated with a release film.
Preventing the adhesion of polyvinyl butyral sheets l... and preventing the adhesion of dust, etc. are also included in this product.

The measurement of adhesive strength is performed by the following method. 20
The PR layer of the functional film and polyvinyl butyral sheet that has been placed in an atmosphere of ℃ and zo%RH for more than two days is
The adhesion breaking force between the functional film and the polyvinyl butyral sheet is measured at a tensile speed of 26 n/- in the short iK cut of Jt o strip and the ten-fold test (Instron) ν)k. . The degree of smoothness and unevenness of the surface of the polyvinyl butyral sheet were determined using a universal surface profile measuring device Surfcom 30B (manufactured by Tokyo Seimitsu ■).

In addition, the roughness (m) per 200 pm length (smoothness 1)
was used. Surface roughness is generally determined by the slope and straightness of the surface.
, waviness, so-called roughness per minute length, etc., but the smoothness and the amount of unevenness of the embossed shape in the present invention are
It is defined in terms of dust per minute length (20,011 m).

The present invention will be explained in more detail below with reference to Examples.

Example 1 A polyvinyl butyral sheet (Tsukumizu Kagaku Kogyo Koshi 6T type hereinafter abbreviated as PvB) with a thickness of 0.38 U was prepared, and one surface of the pvn, that is, the surface in contact with the functional film, was smoothed. . The smoothing method is a release film coated with silicone resin (base material is polyethylene terephthalate film, thickness 38μ) * P, V B n
On the other hand, molding is performed at 120° C. with a pressure of 50 P/cn for 30 minutes on the tn surface y.

At that time, the unevenness of the smooth surface is J, within 5μ, and the other surface 11'
It was 50 pages and had an embossed shape.

In addition, as a functional film, a biaxially oriented polyethylene terephthalate film (thickness 100 μm) with a usable light transmittance of 88% is used.
) A thin film of silver is deposited by sputtering so that the thickness is 10×K, and titanium oxide is further applied to the thin film of silver.
Film thickness of 50 mm due to reactivity/jittering of titanium metal
I set it up so that it looks like X.

The obtained film had a visible light transmittance of 77% and a solar energy transmittance of 60. A 3% solution of tetrazutidylconate (solvent adhesive globin) as an adhesive layer on both sides of the film that has its selective transmittance.
was coated with a No. 3 σ bar coater and dried at 100° C. for 3 minutes.

The thickness of the adhesive layer after drying was a thin film of 150X.

The smooth surfaces of PVBI71 were placed on both sides of the obtained film and laminated with a roller at room temperature under a pressure of IKy/α to form an f# layer. The adhesion force between the film and PVN of the obtained laminate was measured and found to be 300 f/cm. After storing the FI1-layer body for 2 weeks at 2-5°C under RH 110%, it was left under 25°C RI (K 5 hours) for 80 hours and then flexed and a peel test was performed, but no peeling occurred.
Even if I tried to remove it by hand, I couldn't easily peel it off.

Also, in order to make laminated glass, the thickness of the laminate is 3IIJ.
σ) After sandwiching between glass plates and laminating with p-lar, put it in a vacuum bag, reduce the pressure with a vacuum pump so that atmospheric pressure is applied to the laminated glass, and heat it at 90℃ for 40 minutes, then autoclave. 7゛ person ft below 120℃, 13% /
Apply crA pressure and treat for 40 minutes ■1! Shita.

The obtained laminated glass was coated with a clear material that had no irregularities or unevenness in appearance.

Comparative Example 1 In the example, an embossed Bolivi-Luptillard sheet with an uneven surface of 50 μm on both sides was used.

When the adhesive force was 12 f/cm and the film was wound around a paper tube with an outer diameter of 3 inches, some delamination occurred between the film and the polyvinyl butyral. Also, when a laminated window was made by placing the nuclear sheet between two triple-glazed glass plates, a window with large irregularities was created.

Comparative Example 2 In Example IK, the processed side of the photoselective film was not coated with tetrabutyl zircone-1.

Comparative Example 3 In Example 1, tetrabutyl zirconate was applied to the processed side 2 of the photo-selective Filno®, and the non-IJI+ processed side was not coated.

Example 1 and Comparative Examples 1 to 3 are shown in Table 1.

Examples In Example 1, lanthanum adhesive Takelac A-310 (manufactured by Takeda Pharmaceutical Company Ltd.) and curing agent Takene) were used as adhesive layers.
It was used in combination with A-3 (Yoi Yakuhin Kogyo ■11). The above A-310 and A-3 were mixed at a mixing ratio of 1271 (jury eel ratio), and both sides of the functional film had a thickness after drying. lpi
I applied it as desired.

Thereafter, the product 1@body was obtained in the same manner as in Example 1. Adhesion strength is 1
It was 03 Ri/Go. Paper I with an outer diameter of 3 inches? Although the film was rolled up in ¥3,000 and stored, no peeling phenomenon occurred between the polyvinyl butyral and the functional film. *A laminated glass was produced in the same manner as in Example 1, but it had a clear appearance with no irregularities at all.

Claims (1)

[Claims] In the laminate consisting of a polyvinyl butyral sheet and a functional film, and the laminate consisting of a polyvinyl butyral sheet, a functional film, and a polyvinyl butyral sheet, the 1 side of the polyvinyl butyral sheet in contact with the functional film has a smooth 12 surface. 1. A laminate having an adhesive force at an interface of I OOf / ryn or more.