JPH0365539A - Production of laminated glass - Google Patents

Abstract

PURPOSE:To obtain a laminated glass ensuring the chips produced in its breakage not to be scattered, by putting a spacer or sealing material on the periphery of a lamination of a plastisol coated between a pair of glass plates. CONSTITUTION:A glass plate 1 is coated with a plastisol 2 comprising (A) 100 pts.wt. of a vinyl chloride resin containing 0.1-20wt.% of epoxy group, (B) 20-80 pts.wt. of a plasticizer (e.g. dioctyl adipate), (C) a thermal stabilizer, (D) a ultraviolet light absorber and (E) an antioxidant, and a spacer or a sealing material 4 is peripherally put, and then a second glass plate is laid thereon so as not to entrain air bubbles.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention has a structure in which two or more glass plates are bonded together through a film obtained from plastisol of vinyl chloride resin. The present invention relates to a method for manufacturing laminated glass that prevents fragments from scattering when the glass is blown, and that can be mass-produced at low cost with a reduced number of steps.

(Prior art) Conventionally, laminated glass has been manufactured using a plastic film called an interlayer film, typically made of plasticized polyvinyl butyral.
It has been manufactured by sandwiching the glass between two or more sheets of glass, deaerating the glass, pressurizing it, and heating it.

However, this conventional manufacturing method requires membrane processing such as cleaning and cutting of the membrane, humidity conditioning of the membrane, and the need to place the membrane in a vacuum bag, perform preliminary pressure bonding, and then place it in an autoclave and pressurize and heat it. There were problems with low performance and high production costs. On the other hand, as membranes other than plasticized polyvinyl butyral, plasticized vinyl chloride resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, etc. have been proposed; Crimp,
Processes similar to those for plasticized polyvinyl butyral, such as main crimping, are required, and low productivity and high production costs have not been improved.

Another method is to inject liquid acrylic resin between glass plates with a certain gap, but since the resin is a liquid, it is necessary to completely hermetically seal the edges of the glass plates in advance. For example, there are methods such as inserting a gasket between the glass plates and fixing the periphery with a clamp, or sealing the periphery of the glass with a sealant or bead in advance, but this sealing is time-consuming and time-consuming when manufacturing laminated glass. Furthermore, since the liquid resin is injected between the narrow glass plates, workability and productivity deteriorate.

(Problems to be Solved by the Invention) The purpose of the present invention is to solve the problem of the low productivity of the conventional method for manufacturing laminated glass using an interlayer film, and as a result, it is possible to solve the problem by using a specific liquid substance. This makes it possible to omit the above-mentioned complicated work associated with the use of membranes, and by omitting the pressure bonding process using an autoclave and simplifying the sealing method around the glass, it is possible to increase the productivity of continuous production online. The inventors have discovered that it is possible to manufacture a laminated glass with high and even low cost, and have developed the present invention based on this knowledge.

(Means for Solving the Problems) Thus, according to the present invention, it is possible to seal the periphery of the laminate by interposing a spacer or a sealing material in the periphery of the laminate where plastisol exists between the glass plates. A method of manufacturing characterized laminated glass is provided.

The polymer for plastisol used in the present invention is preferably one that has adhesive properties to glass and has the property of gelling without melting under appropriate heating conditions; examples include epoxy group-containing vinyl chloride resin. can give.

The epoxy group-containing vinyl chloride resin used in the present invention is: 1) a copolymer of vinyl chloride, a monomer having an epoxy group, and an optional monomer copolymerizable with these; 2) Typical examples include a vinyl chloride copolymer with an epoxy group added thereto, and 3) a vinyl chloride copolymer dispersed with an epoxy group-containing resin that is compatible with the vinyl chloride copolymer. The epoxy group content in the epoxy group-containing resin is 0.1 to 20% by weight, preferably 0.5 to 10% by weight.

In (ii), examples of monomers having epoxy groups include glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether;
glycidyl methacrylate, glycidyl acrylate,
Glycidyl esters of unsaturated acids such as glycidyl-p-vinylbenzoate, methylglycidyl itaconate, glycidyl ethyl maleate, glycidyl vinyl sulfonate, glycidyl (meth)allylsulfonate, butadiene monoxide, vinylcyclohexene monooxide, 2-methyl Examples include epoxide olefins such as -5,6-epoxyhexene. Monomers having an epoxy group and monomers that can be copolymerized with vinyl chloride as necessary include fatty acid vinyls such as vinyl acetate and vinyl propionate, olefins such as ethylene and propylene, vinylidene chloride, Examples include vinylidene halides such as vinylidene fluoride, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether, and cetyl vinyl ether, and allyl compounds such as allyl chloride and methyl allyl ether.

In order to obtain the vinyl chloride copolymer used in the present invention using these monomers, well-known methods for polymerizing vinyl chloride such as suspension polymerization and emulsion polymerization can be employed. . For example, when used as a plastisol,
For the purpose of maintaining appropriate fluidity of plastisol, emulsion polymerization or ξ-chloro suspension polymerization, which is a preferred method for producing vinyl chloride resin for paste processing, is preferred.

In 2), examples of the method for adding an epoxy group include a method in which the 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 3), the epoxy group-containing resin refers to a copolymer of a monomer having an epoxy group and a monomer copolymerizable therewith.

The vinyl chloride resin used in the present invention may be mixed with plasticizers, stabilizers, ultraviolet absorbers, antioxidants, lubricants, fillers, colorants, etc., depending on the purpose. Furthermore, it is also possible to use a resin compatible with vinyl chloride, such as another vinyl chloride resin, acrylic resin, or epoxy resin.

A wide variety of plasticizers that are generally called plasticizers for polyvinyl chloride can be used. For example, aliphatic plasticizers include dioctyl adipate, butyl diglycol adivate, dioctyl azelate, dibutyl sebacate, diisodecyl adipate, etc., and phthalic acid plasticizers include dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, Examples include butylbenzyl phthalate, dilauryl phthalate, and dioctyl phthalate, and examples of phosphoric acid plasticizers include tricylenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate, trischloroethyl phosphate, trischloroethyl phosphite, Examples include tributyl phosphate. Examples of epoxy derivatives include epoxidized soybean oil and epoxy fatty acid monoester. Polyester plasticizers can also be used in some cases.

The appropriate amount of the plasticizer to be blended is 20 to 80 parts by weight per 100 parts by weight of the vinyl chloride resin. If there is too much plasticizer, the film strength will decrease, and if it is too little, it will become hard.

Suitable heat stabilizers include alkylated tin compounds of fatty acids such as butyltin laurate, butyltin maleate, and octyltin maleate, and alkyltin-containing sulfur compounds such as di-n-octyltin bis(isooctylthioglycolic acid ester) salt. used for. 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'
-tert-butyl-5'-methylphenyl)-5-
Chlorobenzotriazole, 2 (2'-hydroxy-
3',5'-tert-butylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-4'-
Octoxyphenyl)benzotriazole and the like are preferably used.

Phenolic antioxidants are excellent as antioxidants, such as 2,6-ditertiary-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol), and 4.4-ditertiary-butyl-p-cresol. Butylidene bis(3-methyl-6-tert-butylphenol)
, 4,4'-thiobis(3-methyl-6-tert-
butylphenol), etc.

Further, if necessary, a crosslinking agent, a thickener, a diluent, a silane type or titanate type coupling agent, etc. are added.

Plastisol is prepared by blending resin, plasticizer, various compounding materials, etc. and defoaming according to a conventional method.

Since plastisol is in liquid form, dust and foreign matter can be removed using filters, etc., and storage and transportation are handled in closed systems such as tanks and pipelines, making quality control easy and suitable for automation. There is.

The plastisol prepared in this way is applied to glass using a coating machine such as a blade coater, roll coater, screen coater, flow coater, or spray coater, and a spacer or sealant is placed around it (Figure 1). . Place a glass plate on top of it, taking care not to introduce any air bubbles.

Examples of spacers used in the present invention include metals such as steel, brass, and aluminum, synthetic resins such as polyvinyl chloride, polypropylene, and polymethyl methacrylate, or rubbers such as neoprene rubber and silicone rubber, and are shaped like pipes, round rods, etc. It is a solid material processed into a rectangular bar shape with precise thickness. Further, the spacer may be coated with a sealant if necessary.

Examples of the sealant used in the present invention include butyl rubber sealant, polyisobutylene sealant, polysulfide sealant, polyurethane sealant, silicone sealant, and the like. This sealing material is applied using, for example, a special applicator, or a string-shaped sealing material (tape) is placed around the glass plate using a jig. The width and height of the sealing material to be used are determined as appropriate depending on the thickness of the plastisol layer and the width of the part to which plastisol is not applied.

Note that if these operations of the present invention are not performed, the glass plate may slide or the plastisol may protrude, resulting in the laminated glass often becoming uneven in thickness or containing air bubbles. These become important defects in terms of the quality of laminated glass.

The laminate thus sealed at the periphery is heated. The plastisol layer is melted and gelled to form a strong elastic membrane.

As a heating method here, heating devices used in normal paste processing, such as hot air circulation heating, (far) infrared heating, dielectric heating, and induction heating, can be used.

Furthermore, since air bubbles are prevented from entering between the glass plates during plastisol filling, a pressurizing and heating device such as an autoclave is not required.

(Effects of the Invention) Thus, according to the present invention, compared to the conventional technology, a series of operations such as cleaning, drying, cutting, and humidity conditioning of the membrane associated with handling the membrane can be omitted, and since it is a liquid substance, it is possible to eliminate the need for a closed system. Since it can be handled easily, there is no need for a large-scale lean room. Furthermore, since the pressure bonding process using an autoclave can be omitted and the glass periphery can be easily sealed in a short time, the series of processes can be carried out in continuous online production, making it possible to manufacture laminated glass with high productivity and at low cost. becomes.

(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

Example 1 Consisting of 92% vinyl chloride, 3% glycidyl methacrylate, and 5% ethylene, average particle size lμ, average degree of polymerization 120
0 parts of epoxy group-containing vinyl chloride resin, 60 parts of dioctyl phthalate, 30 parts of dioctyl adipate,
4 parts of dibutyltin polymercaptide and 0.3 parts of 2.2'-methylenebis4-methyl-6-tert-butylphenol are placed in a vacuum type high speed defoaming mixer, mixed and defoamed.

The above epoxy group-containing vinyl chloride plastisol was applied to a glass plate of 300 wm x 30 QIlII and 3 mm thick using a blade coater to a thickness of 0.8 wa, leaving a 2 u wide margin around the glass plate.

Next, a 2 fl width spacer (Figure 2) was placed on the adhesive margin around the glass plate, and a glass plate (thickness 3 m) was placed on top of it to avoid air bubbles, and the spacer was passed between rubber rollers for preliminary pressure bonding. . Then, this laminate was heated at 180° C. for 30 minutes to obtain a transparent laminated glass.

Example 2 - 60 parts of dioctyl phthalate and 4 parts of dibutyltin polymercaptide to 100 parts of an epoxy group-containing vinyl chloride resin consisting of 95% vinyl chloride and 5% glycidyl methacrylate and having an average particle size of 1 μ and an average degree of polymerization of 1000. and 2.2
0.3 part of '-methylenebis4-methyl-6-tert-butylphenol is placed in a vacuum high speed defoaming mixer, mixed and defoamed.

The above epoxy group-containing vinyl chloride plastisol was applied to a glass plate measuring 300 m x 300 m and 3 fl thick using a roll coater to a thickness of 0.8 fl, leaving a 3 u wide margin around the glass plate.

Next, a sealing material (butyl rubber sealant) was applied to a width of 2 nm and a thickness of 1 m to the periphery of the glass plate, and a glass plate (thickness: 311 mm) was laminated thereon to prevent air bubbles from entering. The sealant protruding from the periphery of the glass plate was scraped off, and the laminate was heated at 180° C. for 30 minutes to obtain a transparent laminated glass.

Comparative Example 1 A commercially available interlayer film for laminated glass (polyvinyl butyral) with a thickness of 30 + wil was adjusted to have a moisture content of 0.5 wt%, and was sandwiched between glass plates of 300 m x 30 ON and 31 m thick, and 70 to 75 m thick. Preliminary pressure bonding was carried out by passing between rubber rollers at 130°C.
- Heat and pressure bonding was carried out for 30 minutes in a pneumatic autoclave to obtain a bubble-free laminated glass.

Comparative Example 2 A laminated glass was obtained in the same manner as in Example 2, except that the sealant was not used in Example 2.

In order to investigate the performance of the laminated glass obtained in Examples 1 and 2 and Comparative Examples 1 and 2, transparency and
The penetration resistance strength and adhesiveness were measured and the results are shown in the table.

1. Transparency (visible light transmittance) from 380nm to 750n using a spectrophotometer (newly manufactured by Hitachi)
The transmittance was measured up to m.

2. Penetration resistance After the laminated glass was left in an atmosphere at 20° C. for 2 hours, a 2.27 kg steel ball was dropped from a height of 4 m into the center of the laminated glass to check for penetration.

3. 227g of adhesive laminated glass after being left in an atmosphere of 23℃ for 2 hours
A steel ball was dropped from a height of 9 m, and the total weight of the smoldered glass was measured from the opposite side of the impact surface.

4. Laminated glass production time An interlayer film or plastisol is sandwiched between glass plates, the laminate is heat-pressed, and the time required to obtain a transparent laminated glass is measured.

From Table 0 showing the evaluation results, the laminated glass according to the present invention can satisfy the performance of laminated glass.

Table Example 1. In both Example 2, laminated glass with thickness accuracy can be produced in a short time, and also has the function of laminated glass. On the other hand, although the laminated glass of Comparative Example 1 has thickness accuracy,
It takes about twice as much time to create laminated glass as in the example. Although Comparative Example 2 can produce laminated glass in a short time, it cannot be used because it lacks thickness accuracy.

[Brief explanation of drawings]

Figures 1 (a), (b) and (C) are spacers, and (0) (b) of the sealing material are as follows. 1 Ni glass plate, 2 Plastisol, 3 Ni glass spacer-14
: Seal material, 5: Wire wire (0.75mmφ), 6:
Sealing material [Butyl rubber sealant (thickness 0.62mm)] (C) Figure 1 Figure 2

Claims (2)

[Claims] (1) A method for manufacturing laminated glass, which comprises sealing the periphery of the laminate by interposing a spacer or a sealing material around the periphery of the laminate where plastisol exists between the glass plates. (2) The method for producing laminated glass according to claim 1, wherein the plastisol is a plastisol containing an epoxy group-containing vinyl chloride resin as an essential component.