JPH03122035A - Patterned laminated glass plate and its manufacturing method - Google Patents

Abstract

PURPOSE:To obtain a laminated glass having pattern rich in steric feeling, having strong adhesive strength between a glass sheet and an intermediate layer and simply producible by bonding the glass sheet to glass sheet or plastic sheet through the intermediate layer obtained by gelling an epoxy group- containing vinyl chloride resin sol into which a material having pattern is dispersed. CONSTITUTION:An epoxy resin group-containing vinylchloride resin sol into which a material having pattern is dispersed is applied to one side or both sides of at least either one plate of glass sheet and glass sheet or transparent plastic sheet (e.g. acrylic resin sheet or polycarbonate resin sheet). Then another sheet is superposed to the applied layer or the above-mentioned sol is packed between the glass sheet and glass sheet or plastic sheet and then the superposed sheets are thermally bonded. As a result, the resultant pattern-containing laminated glass can be used as a building material for furniture, decorative panel or window glass, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a patterned laminated glass plate used for furniture doors and building materials such as decorative panels and window glasses. It relates to a patterned laminated glass sheet having an adhesive interlayer in which a pattern material is distributed between the sheets or plastic sheets.

[Prior Art] Conventionally, a patterned laminated glass plate has been proposed in which a transparent resin layer is provided between glass plates and a pattern is applied to the resin layer.

JP-A No. 63-236735 discloses that an intermediate decorative body in which pattern pieces made of highly reflective metal foil are interspersed on at least one side of a synthetic resin film is sandwiched and bonded between two glass plates. A patterned laminated glass sheet is disclosed. However, this patterned laminated glass plate has the disadvantage that the pattern pieces are scattered only on the surface of the synthetic resin film, so the pattern lacks a three-dimensional effect and the decorative effect is poor. Since the parts that are in contact with the glass plate are not bonded, there is a drawback that the adhesive strength between the glass plate and the synthetic resin film is weak. Furthermore, polyvinyl butyral resin film, which has been shown as the only synthetic resin film, has the disadvantage of low productivity because the bonding process to the glass plate is complicated. In other words, polybutyral resin film requires a lot of time to wash the film to remove the baking soda that is sprinkled on the film surface to prevent self-adhesion, and to condition the humidity after cutting. After being crimped, it requires a complicated process of placing it in an autoclave and heating and crimping it.

There is also a method of cooling the film before storing and transporting it in order to omit washing the film, but this requires a complicated process associated with cooling and handling.

Furthermore, Japanese Patent Application Laid-Open No. 63-147845 discloses a patterned laminated glass plate in which two glass plates are sandwiched and bonded together with an intermediate layer in which a pattern made of natural objects is embedded in a synthetic resin. ing. However, this patterned laminated glass plate is made by temporarily fixing a pattern made of natural shapes in a desired position on the top surface of the glass plate with synthetic resin liquid, then stacking another glass plate through a frame. It has the drawback of low productivity because it must be manufactured through a complicated process of injecting a synthetic resin liquid into the inner space of two sealed glass plates and curing the synthetic resin liquid.

[Problems to be Solved by the Invention] The present invention provides a laminated glass plate with a pattern that has a rich three-dimensional effect, has strong adhesive strength between the glass plate and the interlayer film, and can be easily manufactured, and a method for manufacturing the same. The purpose is to provide.

[Means for Solving the Problems] Under the above circumstances, the inventors of the present invention investigated various patterned laminated glasses, and found that the use of an epoxy group-containing vinyl chloride resin sol as the material for the intermediate layer and the use of epoxy group-containing vinyl chloride resin sol. The inventors have discovered that the above object can be achieved by dispersing a pattern material in a vinyl chloride resin sol, and have completed the present invention. .

That is, the present invention provides a patterned laminated glass plate characterized in that a glass plate and a glass plate or a plastic plate are bonded by an intermediate layer made of a gelled epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed. It is something.

The present invention also provides a method of applying an epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed to one or both sides of at least one of the glass plate and the glass plate or the plastic plate, and then stacking the other plate or combining the glass plate and the plastic plate. The present invention provides a method for producing a patterned laminated glass plate, which comprises dispersing a pattern material between glass plates or plastic plates, filling them with an epoxy group-containing vinyl chloride resin sol, and then heating and bonding them.

The present invention will be explained in detail below.

At least one of the glass plate or plastic plate used in the present invention must be transparent. Examples of transparent plastic plates include acrylic resin, polycarbonate resin, polyethylene terephthalate resin,
polyethylene naphthalate resin, polyacetal resin,
Thermoplastic resins such as polyamide resins, epoxy resins, diallyl phthalate resins, unsaturated polyester resins,
Examples include molded sheets of thermosetting resins such as phenolic resins.

The thickness of the glass plate or plastic plate can be drilled as appropriate depending on the required strength, but it is usually 0.5 mm.
-20 mm is used.

The pattern material to be dispersed in the epoxy group-containing vinyl chloride resin sol needs to be fine in order to be easily dispersed in the sol and to give the pattern a three-dimensional effect. A material with a diameter of approximately 30 mrrr-0.5 mm is used.

The shape of the pattern material is not particularly limited, and various shapes can be applied, such as spheres, hemispheres, spherical bodies, ellipsoids, cones, pyramids, hermaphrodites, etc., cubes, rectangular parallelepipeds, etc.
Examples include prismatic bodies such as oblique prisms, cylindrical bodies such as right cylinders and oblique cylinders, cylindrical bodies such as cylinders and rectangular cylinders, flakes, needle-like bodies, fine particles, and powders.

Among these shapes, when thin flakes are dispersed, their flat surfaces face various directions, so depending on the direction in which you view the laminated glass plate, the points that emit reflected light will change, and the pattern will change. Therefore, it has a great decorative effect and is preferable. The planar shape of this flake body can be various shapes, such as circles, ellipses, semicircles, triangles, squares, polygons such as pentagons and hexagons, rhombuses, trapezoids, stars, scales, strips, etc. can be mentioned. Pattern bodies having these shapes may be used alone or in combination of two or more types. Furthermore, it is preferable that the patterned material be colored because it has a decorative effect.

Specific examples of pattern materials include the following strips and fine grains.

(1) Strips of heat-resistant resin (polyester, etc.) films or sheets whose surfaces are colored by metal vapor deposition (2) Strips of dyed fibers (3) Strips of colored paper (4) Minerals (e.g. mica, etc.) and colored mineral flakes, colored fine particles of calcium carbonate, silicon carbide, etc.; (5) transparent or opaque colored synthetic resin fine particles or strips (e.g. flaky flakes, etc.); (6) reflective The amount of the strip pattern material of metal foil (for example, gold foil, silver foil, etc.) mixed into the epoxy group-containing vinyl chloride resin sol can be adjusted as appropriate, usually in the range of 0.905 to 10% by weight.

The epoxy group-containing vinyl chloride resin used in the present invention includes +) a copolymer of vinyl chloride, a monomer having an epoxy group, and an optional monomer copolymerizable with these; i) A typical example is a vinyl chloride polymer to which an epoxy group is added.

Examples of the monomer having an epoxy group in i) are:
Glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl-p-vinyl benzoate, methylglycidyl itaconate, glycidyl ethyl maleate, glycidyl vinyl sulfonate, glycidyl ( Examples include glycidyl esters of unsaturated acids such as meta)allylsulfonate, epoxide olefins such as butadiene monooxide, vinylcyclohexene monooxide, and 2-methyl-5,6-nipoxyhexene. In addition, examples of monomers having an epoxy group and monomers used as necessary other than vinyl chloride include carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; methyl vinyl ether, inbutyl vinyl ether, and cetyl vinyl ether. vinyl ethers such as; vinylidene such as vinylidene chloride and vinylidene fluoride; diethyl maleate,
Butylbenzyl maleate, di-2-hydroxyethyl maleate, dimethyl itaconate, methyl (meth)acrylate, ethyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. unsaturated carboxylic acid esters; olefins such as ethylene and propylene; unsaturated nitrites such as (meth)acrylonitrile; and aromatic vinyls such as styrene, σ-methylstyrene, and p-methylstyrene. These monomers are appropriately selected according to needs such as adjusting the gelling properties and hardness of the epoxy group-containing vinyl chloride resin.

In order to obtain epoxy group-containing vinyl chloride resin using these raw materials, well-known methods such as suspension polymerization and emulsion polymerization can be adopted, but it is necessary to maintain appropriate fluidity of the epoxy group-containing vinyl chloride resin sol. For this purpose, emulsion polymerization or microsuspension polymerization, which is popular for producing vinyl chloride resin for paste processing, is desirable.

Further, as a method for adding an epoxy group (ii), a method can be used in which vinyl chloride resin is dehydrochlorinated by heat treatment or contact with an alkali compound, and then epoxidized with an organic peracid or the like. In this case as well, the vinyl chloride resin before dehydrochlorination is preferably a vinyl chloride resin for paste processing.

The desired content of epoxy groups in the epoxy group-containing vinyl chloride resin is 0.5% by weight or more. 0.5
If it is less than % by weight, the adhesive strength with glass tends to be insufficient.

The average degree of polymerization of epoxy group-containing vinyl chloride resin is 600~
3,000 is desirable. If it is smaller than 600, the penetration resistance strength of the laminated glass will decrease if the ratio of the epoxy group-containing vinyl chloride resin in the intermediate layer of the present invention is large.

Moreover, if it is larger than 3,000, excessive heat is required to gel the epoxy group-containing vinyl chloride resin sol, which not only reduces productivity but also causes discoloration or a large amount of unstable This results in an increase in manufacturing costs.

As the plasticizer constituting the epoxy group-containing vinyl chloride resin sol of the present invention, those generally referred to as plasticizers for polyvinyl chloride can be widely used.

For example, fatty acid plasticizers include dioctyl adipate, butyl diglycol adipate, dioctyl azelate, dibutyl sebacate, diisodecyl adipate, etc., and phthalate plasticizers include dioctyl phthalate, dibutyl phthalate, diisobutyl 7 Examples of the phosphoric acid plasticizers include tricylenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate,
Examples include trischloroethyl phosphate, trischloroethyl phosphite, and tributyl phosphate. Examples of epoxy derivatives include evoquinated soybean oil and epoxy fatty acid monoesters. Polyester plasticizers can also be used in some cases. The appropriate composition ratio of the plasticizer in the epoxy group-containing vinyl chloride resin sol is 20 to 80 parts by weight based on 100 parts by weight of the epoxy group-containing vinyl chloride resin. If the amount of plasticizer is too large, the strength of the film after heating and gelling will decrease, and if it is too small, it will become hard and the fluidity of the epoxy group-containing vinyl chloride resin sol will not be ensured.

Further, it is desirable that the epoxy group-containing vinyl chloride resin sol of the present invention contains a heat stabilizer and an ultraviolet absorber.

Examples of heat stabilizers include fatty acid alkylated tin compounds such as butyltin laurate, butyltin malate, and octyltin maleate, and alkyltin-containing sulfur compounds such as di-normal octyltin bis(in-octylthioglycolic acid ester) salt. Suitably used. It is also possible to use a metal soap type stabilizer together with these.

Benzotriazole-based UV absorbers are excellent, such as 2(2'-hydroxy-5'methylphenyl)benzotriazole, 2(2'hydroxy-3'-
tertiary-butyl-5'methylphenyl)-5-talolobenzotriazole, 2(2''-hydroxy-3''
, 5″-tert-butylphenyl)-5-chloro-
Penztriazole, 2 (2'-hydroxy-4'-
Octoxyphenyl)benzotriazole and the like are preferably used.

The epoxy group-containing vinyl chloride resin sol may further contain antioxidants, lubricants, fillers, colorants, etc., if necessary. Phenolic antioxidants are excellent as antioxidants, such as 2,6-ditertiary antioxidants.
Butyl-p-cresol, 2.2″-methylenebis(4
-methyl-6-tert-butylphenol), 4.4
'-Butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-
6-ta-L-sary-butylphenol) and the like.

Furthermore, if necessary, resin crosslinking agents, thickeners, diluents, etc. that are compatible with vinyl chloride resins such as vinyl chloride resins for pest processing that do not contain epoxy groups, acrylic resins, and epoxy resins, as well as silane-based and titanate resins, may be added. Coupling agents and the like can be mixed with the epoxy group-containing vinyl chloride resin sol.

The epoxy group-containing vinyl chloride resin sol is prepared by mixing the resin, plasticizer, etc. with the various materials mentioned above, according to a conventional method.
This is done after defoaming. Since the epoxy group-containing vinyl chloride resin sol is in liquid form, dust and foreign matter can be easily removed using a filter, and storage and transportation are handled in closed systems such as tanks and pipelines, so quality control is difficult. Not only is it easy to use, but it is also suitable for automation.

The viscosity of the epoxy group-containing vinyl chloride resin sol adjusted as described above is not particularly limited, but in order to make it easier to disperse the pattern material and to make it easier to degas,
It is preferable to set it within the range of 3,0OOcps to 100.0OOcps.

Mixing and dispersion of the pattern material into the epoxy group-containing vinyl chloride resin sol can be carried out by various known mixing means, but mixing using a vacuum defoaming mixer is preferred in order to prevent air bubbles from being mixed in.

In the patterned laminated glass plate of the present invention, the pattern material is dispersed between the glass plate and the glass plate or the plastic plate;
An intermediate layer made of a gelled epoxy group-containing vinyl chloride resin sol is sandwiched and bonded. The thickness of this intermediate layer can be determined as appropriate depending on the required three-dimensional effect of the pattern, but is usually adjusted to 0.2 mm to 5.0 mm.

The patterned laminated glass plate of the present invention also includes a laminated plate in which a plurality of glass plates or plastic plates are stacked and bonded via an intermediate layer.

Next, the method for manufacturing the patterned laminated glass plate of the present invention will be described in detail.

The epoxy group-containing vinyl chloride resin sol containing the pattern material prepared as described above was applied to the plate coater O-Lukor 5-.
It is applied directly to the surface of a glass plate or plastic plate, which has been cleaned in advance, if desired, using a coating machine such as a screen coater, flow coater, or spray coater. Coating herein is defined as including deep coating in which one or both sides of a glass plate or plastic plate is immersed in plastisol and residual sol is removed.

A glass plate or plastic plate coated with an epoxy group-containing vinyl chloride resin sol is stacked on another glass plate or plastic plate and heated to gel the sol to form an intermediate layer.

In some cases, prior to superposition, the applied sol may be heated, superimposed, and further heated to complete gelation.

Normally, the required temperature in this step is 130°C to 200°C, and the optimum temperature and required time depend on the composition of the epoxy group-containing vinyl chloride resin sol, the degree of polymerization and composition of the epoxy group-containing vinyl chloride resin, and the particle size. The optimal value is determined by

In this step, it is possible to stop gelation at an appropriate stage and leave irregularities on the surface of the gelled layer to facilitate the subsequent degassing and press-bonding steps by selecting the temperature and time. Furthermore, if the glass plate or plastic plate is heated in advance before the previous coating is applied, gelation will begin immediately after coating due to the heat possessed by the glass or plastic, so coating and gelation are performed in the -step. It is also possible.

The glass plates or plastic plates having the gelled epoxy group-containing vinyl chloride resin sol layer are stacked together, degassed if desired, and then heated to form a laminated glass. Conventionally, this step has been called a preliminary crimping step, and conventional crimping devices can generally be used. Typically, there is a rubber bag method in which a laminate is placed in a vacuum bag and heated while being degassed under reduced pressure, and a roll press method in which the laminate is passed through a roll and a heating furnace. For both methods, methods that can be made continuous and automated have been proposed and implemented in the past studies for improvement. The degree of decompression and the linear pressure of the rolls in this process may be the same as those used for pre-press bonding in the production of laminated glass using plasticized polyvinyl butyral films, but the heating temperature and time may be different from the glass plate surface or plastic plate surface. It is necessary to adjust it appropriately depending on the state of the gelled layer formed in the process.

That is, when glass plates or plastic plates having gelled layers that have been sufficiently gelled by sufficient heating in the previous heating gelling step are placed so that the gelled layers face each other,
Heating in this step may be done in a relatively short time. On the other hand, when using a glass plate or plastic plate that does not undergo the first heating process or is stopped at an insufficient stage, it takes a long time to heat (IO minutes to 30 minutes) and the temperature becomes high. (15
0°C to 220°C). If the final gelation of the epoxy group-containing vinyl chloride resin sol is insufficient, the resulting laminated glass plate will have reduced transparency and insufficient adhesive strength and penetration resistance.

In addition, in the manufacturing method of the present invention, a method for providing an intermediate layer between a glass plate and a glass plate or a plastic plate is to use an epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed in a glass plate or a plastic plate as described above. Instead of applying at least one glass plate and at least one
It can also be manufactured by filling the gap between two glass plates or plastic plates with an epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed. As a method for filling the epoxy group-containing vinyl chloride resin sol containing a pattern material, a method known as a conventional casting method can be used. [9 The body filled with Epoquin group-containing vinyl chloride resin is heated. Heating is usually performed at a temperature range of 150°C to 220°C for 10 minutes to 30 minutes.

Through the above steps, a patterned laminated glass plate can be manufactured in which a glass plate and a glass plate or a plastic plate are bonded by an intermediate layer made of a gelled epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed.

[Example] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Comprised of 90% by weight of vinyl chloride and 10% by weight of glycidyl methacrylate, average particle size 1.0 μm1 average degree of polymerization 1.60
0.0 epoxy base, 100 parts by weight of vinyl chloride resin, 60 parts by weight of dioctyl phthalate, 4 parts by weight of dibutyltin polymethylkabutide, 0.3 parts by weight of 2,2'-methylenebis4-methyl-6-tertbutylphenol, and aluminum. Scale-like strips of polyester film colored orange, yellow, and blue (thickness: 0.03
mm, length 0, 5 mm, width 0.5 mm) 0.1 part by weight were mixed and defoamed using a vacuum high-speed defoaming mixer to obtain an epoxy group-containing vinyl chloride resin sol, which was then processed by the doctor blade method. 300mm x 300mm 1 thickness 2.0
After coating the sol on a glass plate of 18 mm, and placing a glass plate of the same size on top of the sol so that no air bubbles remain.
By heating at 0°C for 30 minutes, a patterned laminated glass plate having a 0.38 mm gelled epoxy group-containing vinyl chloride resin layer was obtained.

The obtained laminated glass plate has three colored flake-like colored pattern materials scattered in the intermediate layer, and has a beautiful multicolored spotted pattern. In addition, the adhesive strength of this laminated glass plate is 4 on average.
, 0 kg/cm, and the adhesive strength of a laminated glass plate with an epoxy-containing vinyl chloride resin gel as an intermediate layer containing no pattern material is 4.5 kg/cra,
There wasn't much difference.

[Effects of the Invention] The patterned laminated glass plate according to the structure of the present invention as described above has a pattern material scattered in the intermediate layer, so the pattern has an excellent three-dimensional effect, and in particular, the pattern material is a thin piece. In this case, the planes of the dispersed flakes are oriented in various directions, so depending on the direction from which the laminated glass plate is viewed, the point at which reflected light is emitted changes, the situation of the pattern changes, and the decorative effect is great.

In addition, as the intermediate layer uses a gelatinized epoxy group-containing vinyl chloride resin sol in which the pattern material is dispersed, the pattern material is easily dispersed, the adhesive strength is strong, and the manufacturing process is simple and productivity is high. is excellent.

The patterned laminated glass plate of the present invention can be used for furniture, decorative panels,
It can be used for building materials such as window glass.

Patent Applicant: Nippon Zeon Co., Ltd.

Claims (1)

[Scope of Claims] 1. A patterned laminated glass plate, characterized in that a glass plate and a glass plate or a plastic plate are bonded by an intermediate layer made of a gelled epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed. 2 The pattern material is (1) a strip of heat-resistant resin film or sheet whose surface is colored by metal vapor deposition, (2) a strip of dyed fiber, (3) a strip of colored paper, (4) uncolored or colored. (5) fine particles or strips of transparent or opaque colored synthetic resin; and (6) strips of reflective metal foil. A patterned laminated glass plate according to claim 1. 3 Applying an epoxy group-containing vinyl chloride resin sol in which a pattern material is dispersed to one or both sides of at least one of the glass plate and the glass plate or the plastic plate, overlapping the other plate, and then heating and joining them. A method for producing a distinctive patterned laminated glass plate. 4 The patterning agent is (1) a strip of heat-resistant resin film or sheet whose surface is colored by metal vapor deposition, (2) a strip of dyed fiber, (3) a strip of colored paper, (4) uncolored or colored. (5) fine particles or strips of transparent or opaque colored synthetic resin; and (6) strips of reflective metal foil. The manufacturing method according to claim 3.