JPS5946903B2 - Manufacturing method of patterned laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing patterned laminated glass.

BACKGROUND ART Laminated glass, which is a type of safety glass made by laminating sheet glass with a synthetic resin interlayer, is widely used today for automobiles, aircraft, and architecture. However, in such laminated glass, a pattern is formed on the surface of the interlayer film by direct printing or the like, and then plate glasses are laminated with the interlayer film, or the interlayer film is laminated on both sides of paper, cloth, etc. on which a pattern has been formed in advance, Furthermore, a method of manufacturing a patterned laminated glass by laminating a glass plate to the interlayer film is known, and a polyvinyl butyral film is often used as the interlayer film.

However, since the surface of polyvinyl butyral film has extremely strong adhesiveness at room temperature, it is extremely difficult to directly form a pattern on the surface of the film by printing, etc. When laminating a polyvinyl butyral film on both sides of a material and then laminating a glass plate on the polyvinyl butyral film, the lamination work is difficult, and on the other hand, fine irregularities are added to the film surface to reduce its stickiness. Conventional methods using polyvinyl butyral films have various drawbacks, such as the tendency for uneven printing due to ink to occur if the film is allowed to grow.

As a result of intensive research in order to eliminate the drawbacks of the conventional method as described above, the present inventors have developed an interlayer film obtained by adding a plasticizer to a certain type of resin composition containing vinyl chloride resin, which is a general-purpose resin. He completed the present invention by discovering that there is no tackiness at room temperature. A vinyl chloride thermoplastic resin obtained by copolymerizing with at least one monomer containing glycidyl methacrylate, and containing 1 to 10% by weight of glycidyl methacrylate, as well as ethylene hydrocarbon, vinyl fatty acid, acrylic. The content of at least one monomer selected from acid esters and vinyl ethers is 1
A plasticizer is added to a thermoplastic resin containing 0% by weight or less to form an interlayer film, then an arbitrary pattern is formed on one or both sides of the interlayer film using ink, and then a glass plate is attached to the interlayer film. The present invention relates to a method for manufacturing patterned laminated glass characterized by laminating layers of glass.

The present invention will be explained below with reference to the drawings.

First, in the present invention, as shown in Figure 1, vinyl chloride, glycidyl methacrylate, and at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers are copolymerized. An interlayer film 1 is formed by adding a plasticizer to a vinyl chloride thermoplastic resin (hereinafter referred to as a vinyl chloride thermoplastic resin copolymer, etc.), and then an ordinary ink is applied to one or both sides of the interlayer film 1. For example, using gravure printing method,
Normal printing methods such as screen printing method and transfer printing method,
A monochromatic or multicolored arbitrary pattern 2 is formed by a conventional coating or dipping method, a conventional drawing method using a pen, brush, or the like. The content of glycidyl methacrylate in the vinyl chloride thermoplastic resin copolymer used in the present invention is 1 weight? ~10 weight? be made into

If a copolymer containing 1% by weight or less of the monomer is used as a raw material, the adhesion between the resulting interlayer film and the glass plate will be insufficient, which is not preferable. Furthermore, when using 10% by weight or more of copolymer 9 as a raw material, when the resulting interlayer film is bonded to a glass plate, undesirable coloring occurs due to decreased thermal stability. Further, the content of a monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers is 10% by weight or less. 10% by weight
When using the above copolymers, the yield during polymerization decreases, and the thermal stability when bonding the obtained interlayer film to a glass plate is insufficient, resulting in undesirable coloration.

Furthermore, the ethylene hydrocarbons in the vinyl chloride thermoplastic resin copolymer used in the present invention include ethylene, propylene, isoptylene, and the like.

Examples of vinyl fatty acids include vinyl acetate, vinyl caproate, vinyl pelargonate, vinyl laurate, vinyl myristate, vinyl palmitate, and the like. Examples of acrylic esters include methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and 2-ethyl acrylate.
Includes hydroxyethyl, etc. Vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, cetyl vinyl ether, and the like. To obtain a vinyl chloride thermoplastic resin copolymer by copolymerizing these raw materials,
Polymerization methods such as suspension polymerization, floatation polymerization, and solution polymerization are employed, but suspension polymerization is preferred from the viewpoint of thermal stability and economical efficiency.

The vinyl chloride thermoplastic resin copolymer thus obtained is mixed with various plasticizers and formed into a film by known processing methods, such as calender roll method, extrusion sheet casting method, inflation method, etc. 〇Plasticizer As such, those commonly referred to as plasticizers for polyvinyl chloride can be widely used. For example, esters of phthalic acid, adipic acid, and sebacic acid, epoxy derivatives, and polyester derivatives can be widely used.Specifically, phthalic acid esters include dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, and adipic acid esters. Examples include di-2-ethylhexyl adipate and diisodecyl adipate, and examples of epoxy derivatives include epoxidized soybean oil and epoxy fatty acid monoester. Is the amount of plasticizer in the interlayer film composition 10-50% by weight? It is preferable that When forming a film of a vinyl chloride thermoplastic resin copolymer, in addition to the plasticizers mentioned above, appropriate amounts of stabilizers, lubricants, ultraviolet absorbers, and antioxidants may be mixed depending on the purpose. Depending on the situation, a coloring agent may be mixed as long as it does not interfere with the pattern format described later. In order to facilitate air degassing, fine irregularities are formed using an embossing roll or the like, and a depth of about 20 μm is sufficient.

The ink used to form the arbitrary pattern 2 on one or both sides of the interlayer film 1 is preferably one whose main component is a resin that has excellent compatibility and adhesion to the interlayer film. For example, it is preferable to use an ink containing the vinyl chloride thermoplastic resin copolymer as the main component of the vehicle, and for printing ink, dyes and pigments are mixed in a solvent containing the vinyl chloride thermoplastic resin copolymer. Dispersed and sufficiently kneaded using a ball mill or the like is preferably used.

In addition to the vinyl chloride thermoplastic resin copolymer, the ink may also contain plasticizers, antioxidants, heat stabilizers,
Additives such as light stabilizers may be included, and in particular, when a silane coupling agent is included, the adhesion between the pattern-forming surface and the glass plate is significantly improved. Next, in the present invention, as shown in FIG. 2, after forming an arbitrary pattern 2 as described above, glass plates 3 and 3' are stacked on both sides of the interlayer film 1 and subjected to heating and pressure treatment. By heat-sealing the glass plates 3, 3' and the intermediate film 1, the patterned laminated glass according to the present invention can be manufactured.

At this time, the heating temperature is 80 to 20°C.
At 0'C, a temperature of 100 to 180C is usually suitable, and a particularly high pressure is not required, and the pressure is only necessary for adhesion between the interlayer film and the glass plate, and for removing air bubbles at the interface and within the interlayer film. , 5 to 15 kg/~ is suitable. For hot press bonding, conventional bonding devices used for polyvinyl butyral films, such as a hot press molding machine, a press roll with a heating furnace, and a hydraulic or pneumatic autoclave, can be used.
Since the method for manufacturing patterned laminated glass of the present invention is configured as described above, compared to the method of manufacturing patterned laminated glass using a conventional polyvinyl butyral film, the interlayer film according to the present invention is Since it is non-adhesive at room temperature, the workability in the manufacturing process can be significantly improved, and patterned laminated glass can be manufactured extremely simply and easily.

Furthermore, with the method of the present invention, it is possible to manufacture a wide range of laminated glass with any type of pattern, from extremely clear patterned laminated glass to so-called 6-shaded patterned laminated glass, and the surface unevenness is much different from that of conventional glass. Since it is possible to use an interlayer film that is smaller than the product, it is possible to manufacture laminated glass with a pattern formed with less uneven printing.

Examples of the method of the present invention are shown below.

Does “part” or “%” mean parts by weight or weight, respectively? represents. The adhesion between the interlayer film and the glass plate was measured as follows.

Colored glass at a temperature of -180°±0.6°C16
The glass was left to stand for ±4 hours for adjustment, and after the glass was peeled off by hitting it with a hammer, the degree of exposure of the film was determined using a pre-graded limit sample, and the results were expressed as pummel values according to Table 1.

Based on Table 1, the adhesive properties of the laminated glasses obtained in Examples 1 to 3 and Comparative Examples are shown in Table 2. Example 1 Vinyl chloride 93%, ethylene 5%, glycidyl methacrylate 2
% vinyl chloride-ethylene-glycidyl methacrylate copolymer and dioctyl phthalate (D
OP) 40 parts, tin-based antioxidant 3 parts, ultraviolet absorber 0
．． 3 parts were added and mixed well, and the mixture was formed into a film using an extruder to obtain an intermediate film having a thickness of 0.70.

A pattern is formed on one side of this interlayer film using an ink having the composition shown below using a gravure printing machine, and the interlayer film with the pattern formed thereon is sandwiched between two glass plates and heated and pressed using a conventional method. A patterned laminated glass was produced by laminating the glass with an interlayer film. There was no uneven printing in the pattern. Ink Composition The composition of the copolymer used was the same as that of the thermoplastic copolymer used for the interlayer film.

Example 2 A patterned laminated glass was manufactured under the same conditions as in Example 1 except that the ink composition was different.

There was no uneven printing. Ink Composition Example 3 A patterned laminated glass was manufactured under the same conditions as in Example 1 except that the ink composition was different.

There was no uneven printing. ink composition

[Brief explanation of drawings]

FIGS. 1 and 2 are cross-sectional views showing the configuration during each manufacturing process in the method for manufacturing patterned laminated glass according to the present invention. 1...Intermediate film, 2...Arbitrary pattern, 3
, 34...Glass plate.

Claims (1)

[Scope of Claims] 1. A vinyl chloride thermoplastic resin obtained by copolymerizing vinyl chloride, glycidyl methacrylate, and at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers. and the content of glycidyl methacrylate is 1 to 10% by weight.
, and a thermoplastic resin containing 10% by weight or less of at least one monomer selected from ethylene hydrocarbons, vinyl fatty acids, acrylic esters, and vinyl ethers, and forming an intermediate film by adding a plasticizer to the thermoplastic resin, A method for producing a patterned laminated glass, which comprises forming an arbitrary pattern on one or both sides of the interlayer film using ink, and then laminating a glass plate on the interlayer film. 2. The manufacturing method according to item 1, wherein the monomer is ethylene. 3. The manufacturing method according to item 1 or 2, wherein the main component of the ink vehicle is the thermoplastic resin.