JPH02302345A - Production of laminated glass - Google Patents

Abstract

PURPOSE:To accomplish the on-line continuous production of laminated glass by putting a vinyl chloride resin film, through a plastisol layer containing, as the essential component, an epoxy group-contg.. vinyl chloride resin between glass plates followed by hot contact bonding. CONSTITUTION:One surface of a glass plate is coated with a film-forming plastional containing an epoxy group-contg. vinyl chloride resin as the essential component followed by laminating a film containing a vinyl chloride resin as the essential component thereon so as not to contain bubbles and then applying the above plastisol thereon. Finally, a second glass plate is laminated so as not to contain bubbles. The resultant laminate is bound by a thermal contact at ca.180 deg.C for ca.10min, thus obtaining the objective bubble-free laminated glass in high productivity.

Description

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

(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 it between two or more pieces of glass, deaerating it, pressurizing it, and heating it.

However, this conventional manufacturing method requires cleaning and cutting the membrane, processing the membrane such as humidity control, placing it in a vacuum bag, etc., pre-pressing it, and then putting it in an autoclave and pressurizing and heating it, which reduces productivity. There was a problem that the production cost was high. 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; Preliminary 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.

(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. It was discovered that by doing so, it was possible to omit the crimping process using a J autoclave, and it was possible to manufacture laminated glass with high productivity and low cost through online continuous production.Based on this knowledge, the present invention was completed. I ended up letting it happen.

(Means for Solving the Problems) Thus, according to the present invention, (1) a film-forming plastisol layer containing an epoxy group-containing vinyl chloride resin as an essential component is interposed between two or more glass plates; A method for manufacturing a laminated glass (first invention) characterized by heat-pressing a laminate formed by sandwiching films as components, and (2) each surface of two or more glass plates other than the outermost two surfaces A laminated glass characterized in that the laminated glass is coated with a film containing an epoxy group-containing vinyl chloride resin as an essential component, and a laminate obtained by sandwiching the film containing a vinyl chloride resin as an essential component between the coated glass plates is bonded under heat. Manufacturing method (second invention)
is provided.

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) chlorinated Typical examples include a vinyl 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.

In 1), examples of monomers having an epoxy group 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. In addition, 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 propionic vinyl acetate, 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 epoxy group-containing vinyl chloride resin 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. 1 For example, when used as plastisol, in order to maintain appropriate fluidity of plastisol,
Emulsion polymerization or micro-suspension polymerization is preferred as a method for producing vinyl chloride resin for paste processing.

In 2), examples of the method for adding epoxy groups include a method in which a vinyl chloride copolymer 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 content of epoxy groups in these epoxy group-containing vinyl chloride resins is 0.5 to 10% by weight, preferably 1.
It is required that it be 0 to 5.0% by weight.

If the amount is less than 0.5% by weight, the adhesive strength to the glass will be insufficient, and if the amount exceeds 10% by weight, the penetration resistance will be poor as a safety glass.

On the other hand, the vinyl chloride resin used in the present invention is
It is a vinyl chloride homopolymer or a copolymer of vinyl chloride and a monomer copolymerizable with it. As examples of monomers copolymerizable with vinyl chloride, all of the monomers exemplified as monomers used as necessary in the production of epoxy group-containing vinyl chloride resins can be used. As a polymerization method for vinyl chloride resin, well-known methods such as suspension polymerization, emulsion polymerization, and solution polymerization can be used, and the polymerization method may be determined depending on the purpose of use.

The degree of polymerization of the epoxy group-containing vinyl chloride resin and the vinyl chloride resin is preferably 600 to 3,000. When it is smaller than 600, the penetration strength of the laminated glass decreases, and when it is larger than 3000, excessive heat is required to form a resin film, resulting in increased manufacturing costs.

The epoxy group-containing vinyl chloride resin and vinyl chloride resin used in the present invention may contain plasticizers, stabilizers,
Ultraviolet absorbers, antioxidants, lubricants, fillers, colorants, etc. are mixed. 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 referred to as plasticizers for vinyl chloride resins can be used. For example, aliphatic plasticizers include dioctyl adipate, butyl diglycol adipate, dioctyl azelate, dibutyl sebacate, diisodecyl adipate, etc., and phthalate plasticizers include dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, butyl Examples include benzyl phthalate, dilauryl phthalate, dioctyl phthalate, etc. Phosphoric acid plasticizers include tricylenyl phosphate, tricresyl phosphate, talesyl diphenyl phosphate, trischloroethyl phosphate, trischloroethyl phosphite, tributyl phosphate, etc. can be given. Examples of epoxy derivatives include epoxidized soybean oil and epoxy fatty acid monoester.

Polyester plasticizers can also be used in some cases. The blending amount of the plasticizer is 20 to 100 parts by weight of the epoxy group-containing vinyl chloride resin or vinyl chloride resin of the present invention.
80 parts by weight is suitable. 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-normal 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'-terjarifthylphenyl)-5-chloro-benzotriazole, 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' -Butylidenebis(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 according to the conventional method, in addition to resin and plasticizer, if necessary, heat stabilizer, ultraviolet absorber, antioxidant,
This is done by mixing lubricants, fillers, colorants, etc. and defoaming. 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.

Methods for producing the film containing vinyl chloride resin as an essential component used in the present invention include a method in which vinyl chloride resin, etc. is dispersed in a plasticizer, etc., and cast as plastisol or organosol on release paper; Conventional film-forming processing methods for vinyl chloride resin can be applied, such as mixing with a plasticizer or the like and forming a film by extrusion, calendering, or other methods.

In the first invention, plastisol is directly applied to a glass plate or a film containing vinyl chloride resin as an essential component using a coating machine such as a blade coater, roll coater, screen coater, flow coater, or spray coater. Coating herein is defined as including dip coating. To prevent air bubbles from entering, the coated materials are laminated in a structure with plastisol between the glass plate and the membrane, such as glass plate, plastisol, membrane, plastisol, and glass plate. Alternatively, a method in which plastisol is injected between the glass plate and the membrane, a method in which plastisol is placed between the glass plate and the membrane, and pressure bonded, etc. can be used. The glass plate laminated with the membrane via plastisol is then heated, and the plastisol layer gels, forming a strong elastic membrane. As the 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.

In the second invention, the method for coating a glass plate with a film made of epoxy group-containing vinyl chloride resin includes dissolving compounding agents such as epoxy group-containing vinyl chloride resin and various plasticizers and stabilizers in an organic solvent. Plastisol obtained by applying the solution on a glass plate or dipping it and drying it, or by adding various compounding agents such as plasticizers and stabilizers to epoxy group-containing vinyl chloride resin manufactured for plastisol. Examples include a method of coating or dipping a glass plate and heating it.

A film containing a vinyl chloride resin as an essential component is laminated onto the glass plate coated with the epoxy group-containing vinyl chloride resin obtained in this manner via the coated surface.

At this time, the surface of the coating film or the film containing vinyl chloride resin as an essential component may be embossed to facilitate degassing.

After the laminated glass plates are degassed as desired, they are heated to form laminated glass. Conventionally, this process was called a pre-pressing process, and conventional equipment can generally be used.Typically, the rubber bag method involves placing the laminate in a vacuum bag and heating it while degassing under reduced pressure. There is also a roll press method in which the material is passed through a roll and a heating furnace (the collar roller method). The degree of vacuum and roll pressure in this process can be the same as the pre-pressing conditions used in conventional laminated glass production using plasticized polyvinyl butyral films, but the temperature and time need to be adjusted appropriately depending on the film composition and embossed state. There is.

(Effects of the Invention) Thus, according to the present invention, compared to conventional techniques, it is possible to use vinyl chloride resin, which is a general-purpose resin, and the crimping process using an autoclave can be omitted, making continuous production possible. It is possible to obtain inexpensive laminated glass.

(Example) Example 1 15 parts of dioctyl phthalate, 45 parts of dioctyl adipate, and dibutyl were added to 100 parts of an epoxy group-containing vinyl chloride resin consisting of 90% vinyl chloride and 10% glycidyl methacrylate, with an average particle size of 1 μm and an average degree of polymerization of 800. 4 parts of tin polymercaptide, 0.3 parts of 2.2'-methylenebis-4-methyl-6-tert-butylphenol, etc. were placed in a vacuum type high-speed defoaming mixer, and mixed and defoamed.

Next, to 100 parts of a vinyl chloride-ethylene copolymer having an average degree of polymerization of 1200 and consisting of 95% vinyl chloride and 5% ethylene, 10 parts of dioctyl phthalate, 30 parts of dioctyl adipate, 4 parts of dibutyltin polymercaptide, 2. 2
0.3 parts of '-methylenebis4-methyl-6-tert-butylphenol, etc. were mixed well, transferred to two rolls heated to 150°C, and kneaded for 10 minutes to give a thickness of 0.6
A transparent and flexible membrane of 1.0 mm was obtained.

First, plastisol containing epoxy group-containing vinyl chloride as an essential component was coated on one side of a 300 x 300!011 glass plate with a thickness of 3 mm using a blade coater to a thickness of 100 μm, and then vinyl chloride-ethylene copolymer was applied on top of the plastisol to a thickness of 100 μ. A film containing as an essential component is glued together without any air bubbles, and the above plastisol is applied on top of it to a thickness of 100 μm using a blade coater.Finally, a glass plate is glued together without air bubbles. A laminate was obtained. Next, add this to 1
It was heated at 80°C for 10 minutes to obtain a transparent laminated glass without bubbles.

Example 2 Instead of the epoxy group-containing vinyl chloride resin used in Example 1, 80% vinyl chloride, allyl glycidyl ether 3
%, glycidyl methacrylate 5%, vinylidene chloride 1
A laminated glass was obtained in the same manner as in Example 1 except that a vinyl chloride resin consisting of 2% polyvinyl chloride having an average particle diameter of 1.2 μm and an average degree of polymerization of 1600 was used.

Example 3 Plastisol containing epoxy group-containing vinyl chloride resin as an essential component prepared in Example 1 was coated with a blade coater for 2
Apply it to a thickness of 100μ on a glass plate and hold it at 200°.
Immediately after heating at C for 5 minutes and gelling, embossing was applied using an embossing roller.

With the embossed gel layer facing each other, the membrane made in Example 1 containing vinyl chloride-ethylene copolymer as an essential component (the surface was embossed in advance) was sandwiched, and a rubber bag was placed. The mixture was placed in a vacuum chamber and heated at 130'C for 30 minutes to obtain a bubble-free transparent laminated glass.

Comparative Example 1 A commercially available interlayer film for laminated glass (polyvinyl butyral) with a thickness of 30 m1!2 was adjusted to have a moisture content of 0.5 wt%, and sandwiched between two glass plates of 300 mm x 300 mm and 3 mm thick, Pass through rubber rollers at 70-75°C,
Preliminary crimping was performed. After that, 130°C113~15k
The laminated glass without air bubbles was obtained by heating and pressing for 30 minutes in a g/d pneumatic autoclave.

Comparative Example 2 Plastisol containing the epoxy group-containing vinyl chloride resin prepared in Example 1 as an essential component was coated on release paper with a blade coater to a thickness of 0.6 -, and heated at 200°C for 5 minutes. A transparent film was obtained.

A laminated glass was obtained in the same manner as in Example 3, except that this membrane was used instead of the membrane made of vinyl chloride-ethylene copolymer.

In order to investigate the performance of the laminated glass obtained in Examples 1 to 3 and Comparative Examples 1 to 2, transparency, penetration strength, Adhesion was measured and the results are shown in the table.

1. Transparency (visible light transmittance) from 380nm to 75On using a spectrophotometer (Hitachi made)
The transmittance up to the tip was measured.

After leaving the laminated glass 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 second laminated glass to check for penetration.

3. After leaving the adhesive laminated glass in an atmosphere of 23°C for 2 hours,
A 7 g 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. Do not measure if the im sphere penetrates.

The evaluation results are shown in the table. From the table, the laminated glass according to the present invention can satisfy the performance of laminated glass.

Claims (2)

[Claims] (1) Heat-press bonding a laminate consisting of a film containing vinyl chloride resin as an essential component sandwiched between two or more glass plates via a film-forming plastisol layer containing epoxy group-containing vinyl chloride resin as an essential component. A method for manufacturing laminated glass characterized by: (2) Each surface of two or more glass plates other than the outermost surface is coated with a film containing an epoxy group-containing vinyl chloride resin as an essential component, and the film containing a vinyl chloride resin as an essential component is sandwiched between the coated glass plates. 1. A method for producing laminated glass, which comprises heat-pressing a laminate made of