JPH0433937A - Film inhibiting scattering of glass - Google Patents

Abstract

PURPOSE:To obtain the subject film having excellent resistance to scratch without reducing transparency even in using for a long period of time comprising a poly(ethylene terephthalate)-based film having a crosslinked polyurethane-based coating layer on one surface. CONSTITUTION:The aimed film is composed of a poly(ethylene terephthalate)- based film having a crosslinked polyurethane-based coating layer (preferably coating film of crosslinked polyurethane-based resin having self-curing property) on one surface. The surface of the film not having said coating layer is laminated with a glass surface through a small thickness of adhesion-tacking layer to obtain a scattering-inhibiting glass.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a glass shatterproof film and a shatterproof glass.

[Prior Art] A glass shatter prevention film made of poly(ethylene terephthalate) film is known, and is applied to window glass to exhibit the ability to prevent fragments from scattering when the glass is broken.

However, it has the disadvantage that it is easily scratched when cleaning the indoor film surface or when it comes into contact with people or objects, and the transparency is quickly reduced by fine scratches. In order to solve this problem, a glass shatter prevention film made of a poly(ethylene terephthalate) film with a silicone-based, polyfunctional acrylic-based, etc. hard coat applied to the interior surface has been proposed. The hard coat layer peels off after about one year of use, the scratch resistance due to the hard coat is insufficient, and the film has the same disadvantages as the above-mentioned film in that its transparency is significantly reduced.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve the scratch resistance of a poly(ethylene terephthalate) film for glass shatter prevention, and to provide a shatter prevention film that does not lose its transparency even after many years of use. The purpose is to provide new information.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems.
The present invention provides a glass shatterproof film made of a (ethylene terephthalate) film and a shatterproof glass in which the same is attached to glass.

The poly(ethylene terephthalate) film used in the present invention has a thickness of 20 μm to 1000 μm, and is usually produced by extrusion molding followed by stretching.

The poly(ethylene terephthalate) film may be colorless and transparent, or may be colored depending on the intended use and design.
It may also be patterned, or it may be made of aluminum.

It may be coated with metals such as gold, silver, copper, platinum, zinc, tin, iron, stainless steel, nickel, titanium, chromium, indium, etc. or their alloys by vapor deposition, or it may be laminated with another film. good. Also,
Corona treatment or brimer treatment on the surface to be coated with polyurethane or adhesive.

Sandblasting or the like may also be applied.

The cross-linked polyurethane coating used in the present invention contains polyol and polyisocyanate as essential components, and optionally contains chain extenders, curing catalysts, weather resistance improvers, leveling agents, adhesion imparting agents, 9 coloring agents, etc. It is applied onto a poly(ethylene terephthalate) film by reactive casting, flow coating, gravure coating, roll coating, spray coating, etc. and then cured.

Polyol components used in the present invention include polyether bonools such as poly(oxyethylene) polyol, poly(oxypropylene) polyol, and poly(oxytetramethylene) polyol, dehydrated condensates of polybasic acids and polyhydric alcohols, Poly(ε-caprolactone) polyol, poly(alkylene carbonate) polyol, poly(
Polyester polyols such as β-methyl-δ-valerolactone) polyol are mainly used, but in some cases, paraffinic polyols such as hydroxyl-terminated polybutadiene and hydroxyl-terminated polyisoprene, and hydroxyl-terminated dimethylsiloxane are used. Silicone polyols and acrylic polyols can also be used. The number of hydroxyl groups per molecule is preferably 2 or more and 5 or less. If it is smaller than 2,
Toughness and hardenability decrease, and when it is greater than 5, flexibility is insufficient. Further, the molecular weight is preferably 400 or more and 4000 or less. If it is smaller than 400, flexibility is insufficient;
If it is larger than 0, toughness and hardenability will be insufficient. However, these are not uniquely defined; for example, 4000
Even if the molecular weight is larger and the number of hydroxyl groups per molecule is greater than 5, there are few that have good performance (and I think that it should be defined based on the physical properties of the cured product. Preferably, polyols with a molecular weight of less than 1,000 and polyols with a molecular weight of less than 1,000 The above polyols are used in combination, and diols and trifunctional or higher functional polyols are used in combination.

As the polyisocyanate used in the present invention, so-called non-yellowing polyisocyanates can be used from the viewpoint of weather resistance, such as hexamethylene diisocyanate, octamethylene diisocyanate, dodecamethylene diisocyanate, and 2,2,4-trimethyl. xamethylene diisocyanate, 3,3°-diisocyanate probyl ether, 1,4-diisocyanatecyclohexane 3-incyanatomethyl-3,5,5-toC-trimethylcyclohexyl isocyanate, 3-cyclobencune diisocyanate, 4, 4°-Methylenebis(cyclohexyl isocyanate) 2-incyanatoethyl-2,6-
Aliphatic and alicyclic polyisocyanates such as diisocyanatohexanoate and 1,8-diisocyanato-4-incyanatomethyloctane, and those containing an aromatic ring such as xylylene diisocyanate and tetramethylxylylene diisocyanate can also be used. Prepolymer modified products, urea modified products, nurate modified products, biuret modified products, etc. of these non-yellowing incyanates can also be used.

Furthermore, examples of chain extenders used in the present invention include ethylene glycol and propylene glycol.

In addition to alkylene glycols such as 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimetatool, and 1,4-cyclohexanediol, poly(oxyethylene) glycol, Molecular weight of polyether glycol such as poly(oxypropylene) glycol 60-40
Less than 0, trimethylolpropane, glycerin,
Alkyne triols such as trimethylolethane, pentaerythritol, sucrose, etc. having a functional group number of more than 3, and alkylene oxide adducts of these with a molecular weight of less than 400 can be used.

The above polyol and polyisocyanate are essential ingredients,
A cross-linked polyurethane coating consisting of additives such as chain extenders, curing catalysts, weatherability modifiers, leveling agents, adhesion agents, and colorants as required is applied in liquid form onto poly(ethylene terephthalate) films. It is preferable to cure the coating and then harden it. Methods for this include reactive casting, flow coating, gravure coating, roll coating, and spray coating, but these methods do not require solvents, can be applied to a wide range of film thicknesses, and have excellent optical quality. Good reactive casting is the most reasonable and preferred. This involves casting a raw material mixture of a cross-linked urethane coating agent onto a poly(ethylene terephthalate) film and curing it, and from the viewpoint of productivity, it is preferable to use a continuous casting method. For example, a poly(ethylene terephthalate) film is fed out from a roll under tension in two axes and run at a predetermined speed while keeping it horizontal, and two or more liquids are continuously mixed while continuously discharging a fixed amount of raw materials. The raw material liquid mixture is uniformly cast onto the film through a nozzle, die, etc. to form a liquid film, which is then heated and cured in an in-line oven to integrate the cross-linked urethane coating/poly(ethylene terephthalate) film. , which is wound at the end.

The thickness of the cross-linked urethane coating layer is preferably 50 μm or more and 300 μm or less. If it is less than 50 μm, the self-healing property will be insufficient and the manufacturing yield will decrease, and if it is thicker than 300 μm, the product cost will increase. invite

When attaching a film consisting of this crosslinked urethane coating layer/poly(ethylene terephthalate) film to glass, there are several attachment means depending on the purpose. To apply the film on-site after installing the glass,
It is possible to apply a liquid adhesive or adhesive onto the glass or film and adhere it, or to apply adhesive or pressure-sensitive adhesive to the film surface in advance and attach it on-site using a water bonding method. However, the latter is preferable in terms of simplicity. As adhesives and adhesives, re-wetting adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, etc. can be used, and if necessary, a protective film for peeling may be provided on the surface coated with the adhesive or adhesive. good. In addition, to manufacture products in which a film made of cross-linked urethane-based N/poly (ethylene terephthalate) film is attached to glass in advance, in addition to the same method as above, the glass and film can be bonded with a liquid adhesive.

A method of continuous lamination using a nip roll, etc. using an adhesive, film or adhesive sheet or film applied in advance to the glass surface, or introducing it into an autoclave etc. after laminating in the same form as above. , can be pasted by heat and pressure.

In addition to the above-mentioned adhesives and pressure-sensitive adhesives, UV-curable adhesives and pressure-sensitive adhesive liquids include polyvinyl butyral-based thermal adhesive resins, ethylene-vinyl acetate copolymer-based thermal adhesive resins, polyurethane resin-based thermal adhesive resins, etc. can. Of course, a cross-linked urethane coating may be applied after the poly(ethylene terephthalate) film is attached to the glass.

[Example 1 1 Feng 1 To form a polyurethane layer on the surface, each raw material was stirred and mixed uniformly at 30°C in the following weight ratio, and the time from mixing to discharge was 8 seconds, and a film was formed from a T-die nozzle. I spat it out. [Nurate modified product of hexamethylene diisocyanate: 0.42. Hexamethylene diisocyanate 20.09. Polycaprolactone triol (molecular weight 300): 0.22. Polycaprolactone triol (molecular weight 800): 0.22. Polycaprolactone diol (molecular weight 3000): 1].

This mixture was cast onto a 188μ thick running polyester film spread evenly to give a thickness of 100 μm.
Apply to μ.

After coating, the polyurethane layer is heated at 140° C. for 100 minutes to react and cure, and then wound up.

Next, in order to laminate this [polyester film/polyurethane film] onto glass, after pouring the raw material solution of the ultraviolet curing adhesive onto a 6 mm thick glass sheet, the polyester side of the film was placed on the glass side. After applying pressure with a roll, the reaction of the adhesive is completed using a high-pressure mercury lamp. When this sample was subjected to the shot bag test specified in JISR 3205, an excellent drop height of 150 cm, which is a measure of penetration resistance, was obtained.

Claims (1)

[Claims] 1. A glass shatter prevention film made of a poly(ethylene terephthalate) film having a crosslinked polyurethane coating layer on one side. 2. The film according to claim 1, wherein the crosslinked polyurethane coating layer is a coating film of a crosslinked polyurethane resin having self-healing properties. 3. A shatterproof glass obtained by laminating the surface of the poly(ethylene terephthalate) film without the crosslinked polyurethane coating layer of the glass scattering film according to claim 1 on a glass surface via an adhesive-adhesive layer.