JPH0280354A - Middle layer composition for laminated glass - Google Patents

Abstract

PURPOSE:To form a middle layer compsn. for laminated glass having superior penetration resistance, satisfactory adhesion work efficiency and bonding strength by adding a plasticizer to vinyl chloride-based resin contg. vinyl chloride, an epoxy group-contg. monomer and an allyl compd. as essential monomer components and having a specified epoxy group content. CONSTITUTION:This compsn. is formed by adding a plasticizer to vinyl chloride- based resin contg. at least 3 monomers of vinyl chloride, an epoxy group-contg. monomer and an allyl compd. as essential monomer components and having >=0.5wt.% epoxy group content. The epoxy group-contg. monomer may be selected among glycidyl ethers of unsatd. alcohols, glycidyl esters of unsatd. acids and epoxide olefins. Allyl chloride is preferably used as the allyl compd. because it is easily available. The pref. amt. of the allyl compd. in the vinyl chloride-based resin is 0.5-10wt.%.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a safety laminated glass interlayer film composition. The present invention relates to a composition for providing an improved interlayer film for laminated glass having good properties and adhesive strength.

(Prior Art) It is widely known to use a film made of plasticized polyvinyl butyral as an interlayer film for bonding safety laminated glass. The plasticized porvinyl butyral film has excellent adhesive strength, light stability, transparency, and low-temperature flexibility, and is widely used today as safety glass for automobiles, aircraft, and construction.

However, this plasticized polyvinyl butyral film has a problem in that the films stick to each other when being rolled up after film formation due to the strong adhesiveness of the film surface.The film surface is embossed to prevent such adhesion. In addition, anti-blocking agents such as bicarbonate of soda are sprayed. Therefore, when bonding a polyvinyl butyral film and glass, there is a problem in that a washing step and a drying step must be performed in advance to remove the anti-blocking agent.

Although it is effective to use a plasticized polyvinyl chloride film to prevent such adhesion between interlayer films, it is not practical as a safety laminated glass interlayer film because it does not have adhesion to glass. On the other hand, approximately 40% plasticizer was added for the purpose of imparting adhesive properties.
It is known to use vinyl chloride-glycidyl methacrylate copolymer membranes containing % by weight. JP-A-52-1
According to Publication No. 21016, by using the membrane,
It is stated that the adhesive force with the glass plate is, for example, 4 to 10 pumel units. However, JP-A-52-12101
The interlayer film for safety laminated glass described in Publication No. 6, Fig. 3, lacks penetration resistance. Even if the content of glycidyl methacrylate in the copolymer is changed, the adhesive strength is slightly improved, but the penetration strength is hardly improved. or,
Even if the amount of plasticizer is further increased to increase the flexibility of the membrane itself for the same purpose, the mechanical strength will decrease even more, and it will not exhibit sufficient penetration resistance. Since the plasticizer bleeds between the glass plates, the adhesive strength decreases when used for a long period of time, which is undesirable.

Furthermore, the interlayer film using the vinyl chloride-glycidyl methacrylate copolymer has poor thermal stability (sometimes the laminated glass becomes discolored).

In view of the shortcomings of conventional safety laminated glass interlayer films, the present inventors have conducted intensive research on resin compositions containing vinyl chloride resin, and have found that they have excellent penetration resistance and adhesive strength required for safety laminated glass interlayer films. We have now invented a new interlayer film composition for safety laminated glass that has excellent adhesive processing and workability.

(Means for Solving the Problems) That is, the object of the present invention is to make at least three monomers of vinyl chloride, an epoxy group-containing monomer, and an allyl compound as essential components, and the content of the epoxy group is at least 0. 5
This can be achieved by using an interlayer film composition for laminated glass, characterized in that a plasticizer is added to the vinyl chloride resin in a weight percent or more.

(Effects of the Invention) The content of epoxy groups in the vinyl chloride resin used in the present invention is preferably 0.5% by weight to 5% by weight. If a resin with an epoxy group content of less than 0.5% by weight is used, the adhesive strength of the resulting interlayer film will be insufficient;
If it exceeds % by weight, the obtained laminated glass will have insufficient penetration resistance, which is not preferable. Epoxy group-containing monomers for introducing epoxy groups into the resin include glycidyl ethers of unsaturated alcohols such as allyl glycidyl ether and methacryl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, chrycidyl-P-vinylbenzoate, and methylglycidyl itaco. Glycidyl esters of unsaturated acids such as ester, glycidyl ethyl maleate, glycidyl vinyl sulfonate, glycidyl (meth)allylsulfonate, epoxides such as butadiene monooxide, vinylcyclohexene monooxide, 2-methyl-5,6-epoxyhexene Examples include olefins.

Further, the allyl compound in the vinyl chloride resin used in the present invention is preferably 0.5% by weight or more to 10% by weight. If a resin with an allyl compound content of less than 0.5% by weight is used, the thermal stability of the resulting interlayer film will be low;
Resins containing 10% by weight or more of allyl compounds are not preferred because the laminated glass obtained using the interlayer film lacks penetration resistance, and it is difficult to obtain a resin with a high degree of polymerization. Since the strength is low, sufficient penetration resistance strength as a laminated glass cannot be obtained, which is not preferable.

Allyl compounds used in copolymerization include allyl halides such as allyl chloride and allyl bromide, alkyl ethers of furyl alcohol such as methyl allyl ether and ethyl allyl ether, ethylene glycol monoallyl ether, and propylene glycol monoallyl. Allyl alcohol (poly)oxyalkylene ethers such as ether, polyethylene glycol monoallyl ether, and polypropylene glycol monoallyl ether; allyl carboxylic acids such as vinyl acetic acid and undecenoic acid; esters of allyl alcohol such as allyl acetate and allyl butyrate; Allylphenols such as eugenol and isoeugenol, allylthiol and its ethers and esters, N
, N-dimethylallylamine, allylamine, and salts thereof, etc. can be used. Among these allyl compounds, allyl chloride is easily used because of its easy availability.

It is also possible to use epoxy group-containing monomers and allyl compounds as well as vinyl chloride and monomers copolymerizable with these monomers. Examples of these monomers include fatty acid vinyls such as vinyl acetate and vinylnato propionate, olefins such as ethylene and propylene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, isobutyl vinyl ether, methyl vinyl ether, and cetyl vinyl ether. Compatible with vinyl ethers.

In order to obtain the 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 adopted. The most suitable polymerization method may be adopted depending on the manufacturing method. For example, if a sheet-like interlayer film is created by adding resin, plasticizer, and other compounding agents and heating and kneading, which is then sandwiched between glass plates, deaerated, and compressed, as is generally done, it is not economical. Suspension polymerization is preferred from the viewpoint of properties. Suspension stabilizers used in suspension polymerization include:
Any material used for suspension polymerization of vinyl chloride may be used, including partially saponified polyvinyl alcohol polyvinyl pyrrolidone, polyvinyl methyl ether methyl cellulose, hydroxypropyl cellulose, and polyethylene glycol. On the other hand, film-forming plastisol is coated on one or both sides of glass and then heated, and film-forming glass plates obtained by heating the film-forming plastisol are laminated via the film surface and heated, or film-forming plastisol is applied between at least two glass plates. When using the manufacturing method of laminated glass, which is disclosed in Japanese Patent Laid-Open No. 63-134539, in which laminated glass is obtained by filling plastisol and heating, emulsion polymerization, which has been praised as a manufacturing method of vinyl chloride resin for paste processing, or micro Suspension polymerization is preferred. As the emulsifier used in these emulsion polymerizations and microsuspension polymerizations, those known to have been used in the polymerization of vinyl chloride for paste processing can be used.

The average degree of polymerization of the vinyl chloride resin used in the present invention is
It needs to be 500 or more, and in order to obtain a laminated glass with particularly good penetration resistance, it is desirable to have a polymerization degree as high as possible. However, when employing the method disclosed in Japanese Patent Publication No. 134539/1984 as a method for manufacturing laminated glass, the degree of polymerization is preferably 3000 or less, preferably 2000 or less, from the viewpoint of productivity during the process.

Line absorbers, antioxidants, fillers, and colorants can be mixed. Furthermore, it is also possible to use a resin that is compatible with vinyl chloride, such as vinyl chloride resin, acrylic resin, and epoxy resin, which do not contain epoxy groups. As the stabilizer to be mixed, a wide variety of stabilizers that generally belong to polyvinyl chloride stabilizers can be used. For example, metal soaps, organic tin compounds, etc. can be used. The amount of these stabilizers added is 10% of the thermoplastic resin.
1-10 parts by weight is suitable for 0 parts by weight.

When forming the copolymer used in the present invention into a film, various plasticizers are mixed. As the plasticizer to be blended, those generally referred to as plasticizers for polyvinyl chloride can be widely used. For example, esters of phthalic acid, adipic acid, and sepatic acid, epoxy derivatives, polyester derivatives, etc. can be widely used. Specific examples include phthalate esters such as dioctyl phthalate, dibutyl phthalate, and diisobutyl phthalate, and adipate esters such as di-2-ethylhexyl adipate and diisodecyl adipate. Examples of epoxy derivatives include epoxidized soybean oil and epoxy fatty acid monoester. The amount of plasticizer in the interlayer film composition is preferably 10 to 40% by weight.

If it exceeds 40% by weight, the mechanical strength of the membrane will drop significantly and the excellent property of puncture resistance will be lost.

The interlayer film composition of the present invention can be formed into a film by using the above-mentioned copolymer by a known processing method, such as a calender roll method, an extrusion sheet casting method, an inflation method, or the like. In order to use this resin film as an interlayer film to produce a safety laminated glass, the interlayer film may be placed between glasses and heat-fused and pressure-bonded under heat and pressure. In this case, the heating temperature is 80
-200°C1 Usually 100-180°C is suitable.

The pressure is the pressure necessary to maintain close contact between the interlayer film and the glass plate, and to remove air bubbles at the interface and within the interlayer film layer, and is preferably 5 to 15 kg/cff.
l is preferred. For heat-press bonding, after hot press molding, a bonding device used for conventional plasticized polyvinyl butyral films, such as a heating furnace, a pressure roll, or a hydraulic or pneumatic autoclave, can be used.

Since the interlayer film composition for safety laminated glass of the present invention has the above-mentioned structure, when it is formed as an interlayer film, the films do not show stickiness to each other at room temperature, so it is necessary to spray an anti-stick agent. It is possible to shorten the adhesion process between the interlayer film and the glass, and the adhesion to the safety laminated glass is sufficient, and the film composition also improves the penetration resistance of the safety laminated glass used as the interlayer film. The strength is much improved compared to safety laminated glass in which conventional vinyl chloride resin is used for the interlayer film.

The above describes the characteristics of the composition of the present invention when the conventional method for manufacturing laminated glass called the sheet method is used. Since the sheet method itself eliminates the work of adhering glass and membrane, the effect of using the composition of the present invention is to lower the temperature for gelation of plastisol applied to glass, and to lower the temperature during lamination. This can be seen in the fact that the productivity of laminated glass can be further improved by reducing the time required for both.

When such plastisol is used as an embodiment of the composition of the present invention, it is possible to use thickeners, diluents, and thinners that adjust the fluidity of plasdecyl, as well as crosslinking agents and coupling agents. etc. can also be used together.

The present invention will be explained 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 1 200 parts of deionized water was placed in a 1000E stainless steel autoclave, degassed under reduced pressure, and 0.1% of methyl cellulose was added.
parts, 0.3 parts of di-2-ethylhexyl dicarbonate,
84 parts of vinyl chloride, 4 parts of glycidyl methacrylate, 4 parts of allyl chloride, and 8 parts of vinylidene chloride were charged and polymerized at 52° C. for 13 hours with stirring. The results of component analysis of the resin after dehydrating and drying the product were as follows: 84% vinyl chloride, 1.5% epoxy group, 3% allyl chloride, 9% vinylidene chloride.
%Met. Moreover, the average degree of polymerization was 1060.

To 100 parts of this product, 1.5 parts of dinorshiroctyltin bis(isooctylthioglycolic acid ester) salt, 2 parts (
Add 0.3 parts of 2'-hydroxy-5'-methylphenyl)benzotriazole, 0.3 parts of 2.6-tert-butyl-p→cresol, 30 parts of di-2-ethylhexyl adipate, and 10 parts of dioctyl phthalate. After mixing thoroughly in a beaker, the
Mixed for a minute to obtain a clear, flexible, non-stick sheet 1 inch thick. This sheet is 305mm long, 305mm wide,
The laminate was sandwiched between two glass plates with a thickness of 2.5 mm and placed in a rubber bag. After evacuating the inside of the rubber bag, the laminate was heated at 105°C for 30 minutes while maintaining the vacuum for pre-press bonding. After obtaining the glass, 13 kg in the autoclave
A laminated glass was obtained by pressure bonding at 140° C. for 30 minutes under a pressure of /c+fl.

Example 2 The same vinyl chloride resin used in Example 1 was used as 60 parts, and the average degree of polymerization of 40 parts was 1000 and the ethylene content was 7%.
A laminated glass was obtained in the same manner as in Example 1 except that the vinyl chloride-ethylene copolymer was used.

Examples 3 to 5 and Comparative Examples 1 and 2 Same as Example 1 except that instead of the vinyl chloride resin used in Example 1, a vinyl chloride resin obtained by changing the type and composition of monomers was used. A laminated glass was obtained.

Example 6 A 1000A stainless steel autoclave was charged with 160 parts of deionized water, 0.2 parts of styrene-maleic acid copolymer ammonium salt, 1 part of lauryl alcohol, and 0.4 parts of lauroyl peroxide, degassed under reduced pressure, and then chlorinated. 90 parts of vinyl and 3 parts of allyl chloride were absorbed to obtain an emulsion with stirring. This mixture was transferred via a homogenizer into another degassed 1000f autoclave at 54°C.
The temperature was raised to C to initiate polymerization. Immediately after raising the temperature, a mixture of 7 parts of glycidyl methacrylate, 10 parts of deionized water, and 0.2 parts of sodium dioctyl sulfosuccinate was continuously injected into the autoclave in the 4-cup container for 10 hours. Polymerization was terminated after 12 hours.

After recovering unreacted vinyl chloride under reduced pressure, the reaction solution was dried using a spray dryer and pulverized to obtain a resin.

To 100 parts of this resin, 1.5 parts of diptyltin malate, 2 (
0.3 parts of 2"-hydroxy-5'-methylphenyl)benzotriazole, 0.3 parts of 2.2"-methylenebis(4-methyl-6-tert-butylphenol), 10 parts of dioctyl adipate, 40 parts of C9+C11 mixed phthalate were mixed in a Hobart mixer and defoamed under reduced pressure to obtain a plastisol.The mixture was heated with a trowel at 120°C for 5 minutes to obtain two glass plates having a gel layer of 0.5 wa in thickness.

The glass plates having the gel layers were stacked on top of each other so that the gel layers faced each other, and the glass plates were moved back and forth between rubber rolls and a heating furnace at 200°C to obtain a transparent laminated glass.

In order to investigate the performance of the laminated glass obtained in the Examples and Comparative Examples, visible light transmittance,
The penetration resistance strength and adhesiveness were evaluated, and the color of the laminated glass was also visually evaluated.

1. Visible light transmittance spectrophotometer (newly manufactured by Hitachi) from 380 mμ to 750 m
The transmittance (%) up to μ was measured.

2. Penetration resistance After the laminated glass obtained by each of the above methods was left in an atmosphere of 20°C, four steel balls of 2.26 glare were placed in the center of the laminated glass.
It was dropped from a height of m and measured whether it penetrated.

3. Adhesion The laminated glass obtained by each method above was heated to 23°C ± 2”C.
After being left in a room for 4 hours, a 227 grO 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.

The evaluation results are shown in Table-1. As shown in Table 1, the composition of the present invention can satisfy the performance of laminated glass.

Claims (1)

[Claims] A plasticizer is added to a vinyl chloride resin that contains at least three monomers: vinyl chloride, an epoxy group-containing monomer, and an allyl compound as essential components, and has an epoxy group content of at least 0.5 percent by weight. An interlayer film composition for laminated glass, characterized in that: