JPH03197337A - Production of laminated glass - Google Patents

Abstract

PURPOSE:To produce a laminated glass having good productivity, high transparency and large penetration resistance and impact resistance by using a plastic sol containing epoxy-containing vinyl chloride based-resin, liquid epoxy resin, etc., having a specific adhesive strength for a glass sheet. CONSTITUTION:A plastic sol (having 0.1-5wt.% epoxy group content and >=2kg/cm adhesive strength to a glass face) consisting essentially of (A) 100 pts.wt. epoxy group-containing vinyl chloride-based resin (having 600-3000 polymerization degree and 0.005-5wt.% epoxy group content), (B) 1-20 pts.wt. liquid epoxy resin (having <=100000cPs/25 deg.C, preferably <=20000cPs/25 deg.C viscosity), (C) 20-80 pts.wt. curing agent (e.g. 2,4,6-tris(dimethylaminomethyl)phenol) and plasticizer (e.g. dioctyl phthalate) is packed into two sheets of glass and then thermally cured to provide the objective laminated glass.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention has a structure in which two or more glass plates are bonded via 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 broken, reduces the number of steps, and enables mass production at low cost.

[Conventional technology] Conventionally, laminated glass uses a plastic film or a plastic film as an interlayer film.
For example, it has been manufactured by sandwiching plasticized polyvinyl butyral between two or more sheets of glass, degassing, pressurizing, and heating the glass.

However, this conventional manufacturing method requires cleaning, cutting, and
The disadvantages were that productivity was low and production costs were high because it required membrane processing such as humidity conditioning, 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. .

On the other hand, as membranes other than plasticized polyvinyl butyral, Machida vinyl chloride resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, etc. have been proposed; It requires the same processes as plasticized polyvinyl butyral, such as crimping and final crimping, and has not yet been able to address the low productivity and high production costs.

There is also a method of injecting liquid acrylic resin between two glass plates with a predetermined gap between them, 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. However, it had the disadvantage of poor workability and productivity.

Further, the penetration resistance and impact resistance of conventional laminated glass were not fully satisfactory.

C. Problems to be Solved by the Invention] An object of the present invention is to provide a method for manufacturing a laminated glass with good productivity, high transparency, high penetration strength, and high impact resistance.

[Means to solve the problem]

The present inventors conducted studies to solve the low productivity of the conventional method for manufacturing laminated glass using an interlayer film, and found that
By using a specific liquid substance, the above-mentioned complicated operations associated with the use of conventional membranes can be omitted, and by omitting the crushing process using an autoclave, a system with high productivity that can be continuously produced using a computer can be created. We discovered that it is possible to manufacture laminated glass with high penetration resistance and impact resistance, which are important for laminated glass.
Based on this knowledge, we have completed the present invention.

That is, the present invention provides a plastisol containing an epoxy group-containing vinyl chloride resin, an epoxy resin, a curing agent, and a plasticizer as essential components, wherein the platisol film has an adhesive strength of 2 ky/cra or more to a glass surface. have 2
The present invention provides a method for manufacturing laminated glass, which is characterized in that the laminated glass is filled between sheets of glass and then heated.

The epoxy group-containing vinyl chloride resin used in the present invention includes 1) a copolymer mainly consisting of a vinyl chloride unit, a monomer unit having an epoxy group, and an optional monomer unit copolymerizable with these; and 2) a polymer consisting mainly of vinyl chloride units to which an epoxy group is added can be used.

As these epoxy group-containing vinyl chloride resins, resins consisting of vinyl chloride units alone or copolymers whose main constituent units are vinyl chloride units and monomers copolymerizable with vinyl chloride are used. be able to.

In the epoxy group-containing vinyl chloride resin used in the present invention, as copolymerized structural units used as desired, fatty acid vinyls such as vinyl acetate and vinyl propionate, ethylene and propylene such as ethylene, propylene, vinylidene chloride, vinylidene heptadide, etc. Monomer units such as vinylidene halides, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether, and ethyl vinyl ether, and allyl compounds such as allyl chloride and methyl allyl ether can be used.

The monomer units of these desired components can be added to the reaction system in an amount of 10% by weight or less in the epoxy-containing vinyl chloride resin.

1) of the epoxy group-containing vinyl chloride resin used in the present invention
Monomers having epoxy groups used in the vinyl chloride resin include glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methallyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, glycidyl-p-vinyl benzoate,
Glycidyl esters of unsaturated acids such as methyl glycidyl itaconate, glycidyl ethyl maleate, glycidyl vinyl sulfonate, glycidyl (meth)allylsulfonate, sitadiene monooxide, vinylcyclohexene monooxide, 2-methyl-5,6-epoxyhexene Epoxide olefins such as, etc. can be used.

Next, 2) of the epoxy group-containing vinyl chloride resin of the present invention
Examples of the method for adding an epoxy group include a method 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.

It is desirable that the epoxy group-containing vinyl chloride resin used in the present invention be produced by emulsion polymerization or microsuspension polymerization, which is suitable for producing vinyl chloride resins for paste processing, since this increases the fluidity of plastisol.

The degree of polymerization of the epoxy group-containing vinyl chloride resin used in the present invention is preferably 600 to 3,000.

If the degree of polymerization is less than 600, the penetration resistance of the laminated glass will decrease. Moreover, if it is larger than 3000, there is a drawback that a large amount of heat is required in the film forming process.

Further, the epoxy group content of the epoxy group-containing vinyl chloride resin used in the present invention can be from 0.05 to 5% by weight.

On the other hand, the liquid epoxy resin used in the present invention has a phase change of 100.000 at 25°C in terms of miscibility with plastisol.
A liquid epoxy resin with a temperature of less than cps is preferable, and a temperature of 25°C
More preferably, it is 20,000 cps or less.

Highly viscous epoxy resins, with a viscosity of more than 100,000 cps at 25° C., are difficult to mix uniformly into plastisol, resulting in weak adhesion of the laminated glass interlayer to the glass.

- For boat fishing, bisphenol A type liquid epoxy resin, novolac type liquid epoxy resin, polyglycol type liquid epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin,
A tetrafunctional epoxy resin having a tertiary amino nitrogen atom can be suitably used. Plasticizers such as epoxidized soybean oil can also be used.

The epoxy resin used in the present invention can be used in an amount of 1 to 20 parts by weight per 100 parts by weight of the epoxy group-containing vinyl chloride resin.

If the amount of epoxy resin used is less than 1 part by weight, the adhesive strength will be reduced, and if it exceeds 20 parts by weight, the transparency will be reduced.

Further, the epoxy group content in the plastisol at this time is preferably about 0.1 to 5% by weight.

The curing agent used in the present invention can be used without particular limitation as long as it reacts with epoxy groups to form a crosslinked bond. For example, those commonly used as curing agents for epoxy resins can be suitably used. Furthermore, amine-based heat stabilizers, antioxidants, ultraviolet absorbers, and the like that promote reactions between epoxy groups and between epoxy groups and hydroxyl groups can be used.

Examples of the curing agent used in the production method of the present invention include aliphatic diamines such as ethylenediamine and hexamethylene diamine, aliphatic polyamines such as diethylenetriamine and dimethylaminopropylamine, aromatic amines such as 4,4'-diaminodiphenylmethane, and piperidine. , secondary amines such as pyrrolidine, triethyl amine, pyridine, triethanolamine, tertiary amines such as 2,4.6-tris(dimethylaminomethyl)phenol, phthalic anhydride, methyltetrahydrophthalic anhydride, dodecenyl succinic anhydride. Acid anhydrides such as acids, polyaminoamide curing agents having multiple active amino groups and one or more amide groups in the molecule, dicyandiamide which is a latent curing agent, and imidazoles typified by 2-ethyl-4-methylimidazole. UV curing agents such as UV curing agents, polymercaptan curing agents, polyisocyanates, triphenylsulfonium salt catalysts, and the like can be used.

The epoxy group-containing vinyl chloride resin used in the present invention may contain plasticizers, stabilizers, ultraviolet absorbers, antioxidants, etc. depending on the required properties of the laminated glass and the formulation of plastisol.
Lubricants, fillers, colorants, etc. can be mixed.

Furthermore, resins that are compatible with vinyl chloride, such as vinyl chloride-based T# resins and acrylic resins, can be blended.

As the plasticizer to be added to the plastisol used in the present invention, those generally referred to as plasticizers for polyvinyl chloride can be widely used. For example, fatty acid ester plasticizers such as dioctyl adipate, butyl diglycol adipate, dioctyl azelate, dibutyl sebacate, and diisodecyl adipate; heptatal acid plasticizers such as dioctyl phthalate, dibutyl phthalate, diisobutyl heptathalate, and butylbenzyl heptalate; phosphoric acid plasticizers such as tricylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trischloroethyl phosphate, tributyl phosphate, trischloroethyl phosphite, epoxidized soybean oil, epoxy fatty acid monoesters, etc. Derivatives as well as polyester plasticizers can be used.

The blending amount of plasticizer is 1:1 for epoxy group-containing vinyl chloride resin
00 parts by weight, 20 to 80 parts by weight is appropriate. Too much plasticizer will reduce the adhesive strength of the film to the glass surface, while too little will make it too hard, reducing the toughness of the laminated glass and reducing its ability to prevent fragments from scattering.

Thermal stabilizers optionally used in the present invention include alkylated tin compounds of fatty acids such as butyltin laurate, butyltin maleate, octyltin maleate, and di-normal octyltin bis(isooctylthioglycolic acid ester).
Alkyltin-containing sulfur compounds such as salts can be suitably used.

A metal soap stabilizer can also be used together with these.

Also, nitrilotripropionic acid tributylamide, 2
．． Non-metallic stabilizers such as 3-dichloroaniline and epoxy stabilizers can also be used in combination.

Benzotriazole-based UV absorbers are excellent as ultraviolet absorbers that can be used as desired in the present invention, such as 2(2'-hydroxy-52-methylphenylzotriazole, 2(2'
-Hydroxy-3″-tert-butyl-5″-methylphenyl)-5-chlorobenzotriazole, 2
(2'-Hydroxy-3',5'-tert-butylphenyl)-5-talolobenzotriazole, 2(2
″-hydroxy-4°-octoxyphenyl)benzotriazole, hindered amine light stabilizers, and the like can be suitably used.

As the antioxidant optionally used in the present invention, phenolic antioxidants are excellent, such as 2,6-ditertiary-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol) )
, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-
Methyl-6-ternary-butylphenol) and the like can be used.

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

The plastisol used in the present invention can be prepared by mixing and defoaming resins, plasticizers, various compounded materials, etc. in accordance with conventional methods.

In this preparation, since plastisol is in liquid form, dust and foreign matter can be removed using filters, and storage and transportation can be handled in closed systems such as tanks and pipelines, making quality control easy and automated. Also suitable for

In the manufacturing method of the present invention, a laminated glass is manufactured by filling the space between at least two glass plates with the plastisol prepared as described above.

The filling method of the manufacturing method of the present invention is to apply the coating directly to the glass surface using a coating machine such as a blade coater, roll coater, screen coater 70-coater, or spray coater, and then place a glass plate on top of the coater to prevent air bubbles from entering. The following methods are used: bonding, injecting plastisol into the gap between the glass plates, placing plastisol between the glass plates and pressing the glass plates together until the desired thickness is achieved, and a method known as the conventional casting method. can.

The thus stacked laminate is heated, and the plastisol layer is melted and gelled to form a strong elastic film. The heating method here is hot air circulation heating, (far)
Heating devices used in normal paste processing, such as infrared heating, dielectric heating, and induction heating, can be used.

Also, when filling plastisol, air may be removed. Since bubbles are prevented from entering between the glass plates, a pressure heating device such as an autoclave is not required.

In the manufacturing method of the present invention, the adhesion strength of the platisol film formed on the glass surface after mixing within the above range and heat treatment is 2&9/cm or more, preferably 2.5 J! 9/C1
1 or more, preferably 3 kg/cm or more.

If this adhesive strength is low, the penetration resistance and impact resistance will decrease.

The adhesive strength in the present invention was determined by the following method.

That is, the plastisol to be tested was coated on a glass sheet with a thickness of 150 parts m x 50 m rxs and a film thickness of 0.8 m + s.
A test sample was prepared by applying the film to a thickness of 1; then gelling it by heating at 180°C for 10 minutes, leaving it in an atmosphere of 23°C for 2 hours, and making cuts with a razor at 1OIllI1 intervals parallel to the long side of the film. A total of 5 strips of membrane with 4 stripes are prepared on a glass plate.

Approximately 5 ml of each of these inner three strip-shaped membranes was peeled off from one end, held in a chuck, and peeled off perpendicularly to the glass surface at a speed of 300 am/min. The average T-peel adhesive strength was measured. It is expressed in numbers.

The high adhesive strength of the film used in the production method of the present invention is obtained by the plastisol formulation specified in the present invention, but this formulation also varies depending on the types of hardener and plasticizer, as well as other additives. The adhesion strength of the deposited film to the glass surface may become low.

In the production method of the present invention, a Pustisol having the above-mentioned composition is used, which has an adhesive strength of 2 ky/cya or more in a previously conducted adhesive strength test on a glass surface.

[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.

Example 1 Consisting of 92% vinyl chloride, 3% glycidyl methacrylate, and 5% ethylene, average particle size 1. um.

100 parts of epoxy group-containing vinyl chloride resin with an average degree of polymerization of 1400, bisphenol A liquid epoxy resin (Adeka Resin EP-4100 manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent 180 to 200.13000 cps at 25°C) 1
0 parts, 2.4.6-tris(dimethylaminomethyl)phenol 2 parts, dioctyl phthalate 15 parts, dioctyl adipate 20 parts, dibutyltin polymercaptide 4
1 part and 0.3 part of 2,2'-methylenebis-4-methyl-6-tert-butylphenol were placed in a vacuum high-speed defoaming mixer, mixed and defoamed to obtain Pustisol.

This plastisol is 150×50mm, thickness 3+*
The sample was applied to a glass plate of 3.0 mm to a film thickness of 0.8 mm, heated to gel at 180°C for 10 minutes, and an adhesive strength measurement sample was prepared, and an adhesive strength of 3.7 kg/cya was obtained. Ta.

Plastisol prepared with the same formulation was mixed with 300 mrsX
The above plastisol was coated on a glass plate of 300 mm and 3 mm thick using a roll coater to a thickness of 0.8 mm and 1 mm thick. On top of that, glass plates of the same size were bonded together without leaving any air bubbles, and heated to gel at 180°C for 10 minutes to create two transparent laminated glass samples. An impact test was conducted and the results shown were obtained.

The time taken to make the laminated glass was 13 minutes.

Example 2 In Example 1, instead of using bisphenol 8 and 10 parts of liquid epoxy resin, a side chain type flexible liquid epoxy resin (Adeka Resin EP-4000 manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent: 310 to 340.25°) was used. 5000cps in C) to 10
The procedure was the same as in Example 1 except that the adhesive strength was 3,
A plastisol film with an adhesive strength of 8 kg/ctx was obtained, and using this, two transparent laminated glass samples (■) were prepared, and the physical property test values shown were obtained.

The laminated glass preparation time was 15 minutes.

Example 3 In place of 2 parts of 2.4.6-tris(dimethylaminomethyl)phenol in Example 1, methyltetrahydro7
Example 1 except that 10 parts of talic anhydride and 0.2 parts of 2,4.6-)lis(dimethylaminomethyl)phenol were used.
Follow the same procedure as in step 3 using the adhesive strength measurement sample.
The adhesive strength of 5J19/C Maro was obtained, and the indicated physical property test values were obtained for 102 pieces of laminated glass using this.

The laminated glass production time was 12 minutes.

Example 4 100 parts of an epoxy group-containing vinyl chloride resin with an average particle size of 1 μm and an average degree of polymerization of 900, consisting of 97% vinyl chloride and 3% glycidyl methacrylate, and a bisphenol A liquid epoxy resin (epoxy equivalent: 176 to 185.25°C)
(7000 cps), 10 parts of methyltetrahydroheptalic anhydride, 0.1 part of 2,4.6-tris(dimethylaminomethyl)phenol, 4 parts of dibutyltin polymercaptide, hindered amine light stabilizer ( Asahi Denka (
0.3 part of MARK LA-62) manufactured by Co., Ltd. was placed in a vacuum high-speed defoaming mixer, mixed and defoamed to obtain Pustisol.

The above-mentioned plastisol was used instead of the plastisol of Meishiteiko, and the procedure was repeated in the same manner as in Example 1, except that the heating temperature was 180°C, and the adhesive strength measurement sample ``■'' and 02 transparent laminated glass samples were The adhesive strength and physical property test values are as shown.

The laminated glass production time was 18 minutes.

Comparative Example 1 Example 4 except that a straight vinyl chloride resin (Zeon 22 manufactured by Nippon Zeon Co., Ltd., average degree of polymerization 1100) was used instead of the epoxy group-containing vinyl chloride resin of Example 4.
In the same manner as above, 102 sheets of transparent laminated glass and samples for adhesive strength measurement ■' were prepared.

For this sample, the obtained adhesive strength, physical property test values, and laminated glass production time were as shown.

Comparative Example 2 Two transparent laminated glass samples and an adhesive strength measurement sample ■' were prepared in the same manner as in Example 1 except that 2.4.6-tris(dimethylaminomethyl)phenol in Example 1 was removed. did.

The adhesive strength, physical property test values, and preparation time obtained for this sample were as shown.

Comparative Example 3 Bisphenol A type epoxy resin (Adeka Resin EP-4340 manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent weight 23) was used instead of the bisphenol A type liquid epoxy resin of Example 4.
0-270.25℃, viscosity 200,000 cps or more, gel-like)
The procedure was the same as in Example 4 except that the laminated glass 1
02 sheets and adhesive strength measurement sample ■' were prepared.

For this sample, the obtained adhesive strength, physical property test values, and laminated glass production time were as shown.

Comparative Example 4 Example 4 except that the liquid epoxy resin of Example 4 was not used.
In the same manner as above, two pieces of laminated glass and a sample for measuring adhesive strength ■' were prepared.

For this sample, the obtained adhesive strength, physical property test values, and laminated glass production time were as shown.

Comparative Example 5 Commercially available polyvinyl butyral interlayer film for backing glass (
The humidity was adjusted to 0.5% moisture.

150m * 50 stories, on top of a glass plate with a thickness of 3 pieces,
The above interlayer film, a 20 μm thick polyethylene terephthalate film, and a cover glass (thickness: 2 ml) were laminated in this order. Next, the above interlayer film was sandwiched between two glass plates of 300 mm x 300 mm and 3 mm thick to obtain a laminate. I created two of these. These were passed between rubber rollers at 70 to 75°C to perform preliminary pressure bonding. 130°C% 13~
30 in a 15 kg7 cm” pneumatic autoclave.
After heating and pressure bonding for several minutes, the cover glass was finally removed to obtain two transparent laminated glass samples and a sample for adhesive strength measurement.

The laminated glass production time and the adhesive strength and physical property test values measured using this sample were as shown.

The adhesive strength, transparency, penetration strength, and impact resistance of the laminated glasses obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were measured by the following methods.

(1) Transparency (visible light transmittance) Laminated glass ■～■ was measured with a spectrophotometer (newly manufactured by Hitachi).
The transmittance was measured from 80 parts m to 750 parts m.

(2) After leaving the laminated glass ■~■ whose penetration resistance strength and transparency were measured in an atmosphere of 20°C for 2 hours, the center of the laminated glass with 2.2
Drop steel balls No. 7 and No. 9 from a height of 3 m to see if they penetrate.

(3) Impact resistance Another sheet of laminated glass ■～■ is heated to 2.
After standing for a period of time, a 227 g steel ball was dropped from a height of 9 m, and the total weight of the glass peeled off from the opposite side of the impact surface was measured.

(4) Adhesive strength Pylayer glass ■′～■゛ under 23℃ atmosphere
After standing for a period of time, 4 cuts were made with a razor at intervals of 10111 m parallel to the long side of the film to prepare a total of 5 short strip-shaped films in the shape of glass plates.

Approximately 5 pieces of each inner edge of these three strip-like membranes are peeled off and held in a chuck, and the T-beer adhesive strength is measured and the average value is determined.

The evaluation results are shown in Table 1. From Table 1, according to the present invention, a laminated glass that satisfies the performance can be manufactured with high productivity.

(Left below) At a speed of 300 am/im at a 90 degree angle , it is possible to obtain laminated glass with high penetration resistance and impact resistance without impairing the transparency of the glass, and it also eliminates the series of operations associated with handling the membrane, such as cleaning, drying, cutting, and humidity conditioning. This reduces work time and enables the production of highly productive and inexpensive laminated glass.

Procedural amendment November 7, 1990

Claims (1)

[Scope of Claims] 1. A plastisol containing an epoxy group-containing vinyl chloride resin, a liquid epoxy resin, a curing agent, and a plasticizer as essential components, wherein the plastisol film is 2K on the glass surface.
A method for producing laminated glass, which comprises filling the space between two pieces of glass with a material having an adhesive strength of g/cm or more, and then heating the mixture. 2. Claim 1: 1 to 20 parts by weight of liquid epoxy resin is used per 100 parts by weight of epoxy group-containing vinyl chloride resin.
The method for manufacturing the laminated glass described.