JPH0635334B2 - Laminated glass - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminated glass having a modified ethylene-unsaturated ester copolymer as an intermediate film.

More specifically, the present invention relates to a laminated glass having a modified product obtained by heating and reacting an ethylene-unsaturated ester copolymer, an unsaturated alkyd, and an organic peroxide as an intermediate film.

[Prior Art] Laminated glass is obtained by laminating a plurality of glasses through an adhesive intermediate film for the purpose of imparting strength.

As materials for laminated glass interlayer films, polyvinyl butyral and modified products of saponified ethylene-vinyl acetate copolymer are usually used.

However, polyvinyl butyral is expensive, and a modified product of a saponified ethylene-vinyl acetate copolymer is expensive, and it has problems such as lack of heat resistance.

[Problems to be Solved by the Invention] Laminated glass has strength by laminating a plurality of glass sheets through a transparent adhesive layer, and at the same time prevents glass fragments from scattering at the time of breakage by impact. It has a function and is widely used for automobile windshields and building windowpanes.

The adhesive used for the adhesive layer (intermediate film) of glass is required to have transparency, adhesive strength to glass, heat resistance to withstand high temperatures, penetration resistance against impact, and the like.

An object of the present invention is to provide a laminated glass having an interlayer film for laminated glass which has the above-mentioned various properties and is cheaper and superior in properties to those conventionally used for interlayer films.

[Means for Solving the Problem] The inventors of the present invention have determined that a certain type of ethylene-unsaturated ester modified product has excellent properties such as heat resistance, penetration resistance and transparency as an interlayer film for laminated glass. I found it.

That is, the present invention provides (1) an ethylene-unsaturated ester copolymer, (2) an unsaturated alkyd obtained from a polybasic acid / polyhydric alcohol, and (3) an organic peroxide as an interlayer film of laminated glass. The feature is that a modified product obtained by heating and reacting the product is used.

[Structure of the Invention] Examples of the unsaturated ester used as a copolymerization monomer of the ethylene-unsaturated ester copolymer used in the present invention include vinyl esters such as vinyl butyrate, vinyl propionate, vinyl acetate and vinyl benzoate. And methyl acrylate, ethyl acrylate, propyl acrylate,
There are unsaturated carboxylic acid esters such as ethyl methacrylate and methyl methacrylate. Among these ethylene-unsaturated ester copolymers, ethylene-vinyl acetate copolymers are particularly preferable in terms of adhesiveness to glass.

Similarly, the unsaturated alkyl is produced by a conventional production method, for example, α, β-unsaturated dibasic acid or a mixture of the same with a saturated dibasic acid and a polyhydric alcohol in an inert gas stream of 80 to 250.
It is obtained by a method of heating at ℃, causing a condensation reaction, distilling the generated water out of the reaction system and gradually raising the temperature according to the degree of reaction progress. It is 100 to 10 mol%, preferably 80 to 30 mol% of the acid component. Further, in this reaction, the polyhydric alcohol is used in excess in an amount substantially equivalent to 20 mol% with respect to the acid component.

The molecular weight of the unsaturated alkyd is preferably 500 to 5,000 in terms of number average molecular weight calculated from the terminal quantification of hydroxyl group and base, from the viewpoint of compatibility and handling.

As the unsaturated acid used, maleic anhydride, fumaric acid, itaconic acid and the like, as the saturated acid, phthalic anhydride,
Isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, adipic acid, sebacic acid, head acid and the like, and polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, Hydrogenated bisphenol or the like is used.

The organic peroxide used in the present invention is an initiator used in general radical polymerization, for example, benzoyl peroxide, lauroyl peroxide, 1,1-di-t-butylperoxy -3,3,5- Trimethylcyclohexane, t-butylperbenzoate, di-t-butylperoxide, or dicumylperoxide can be used, and the organic peroxide to be used is appropriately selected depending on the synthesis temperature of the adhesive composition, the processing temperature, and the adhesion temperature. Thereby, excellent adhesive strength can be exhibited.

The ethylene-unsaturated ester copolymer, unsaturated alkyd, the compounding ratio of the organic peroxide is not particularly limited, processability of the film used as a laminated glass interlayer, adhesiveness to glass, heat resistance, Considering penetration resistance, ethylene-unsaturated ester copolymer 99.7〜
80 parts by weight, 0.3 to 20 parts by weight of unsaturated alkyd, and 0.01 to 5 parts by weight of organic peroxide are preferable.

The procedure for modifying and processing the modified product used as the interlayer film of the laminated glass of the present invention is as follows, for example.

First, the base resin (ethylene-unsaturated ester copolymer) to be used, unsaturated alkyd, and organic peroxide are mixed in an appropriate ratio, and the mixture of the organic peroxide is removed with an extruder, an open roll, a Banbury mixer, or the like. Knead and denature at temperatures around the decomposition temperature (half-life of 10 hours). Further, if necessary, suitable amounts of a plasticizer, an antioxidant, a weather resistance improver, a slip agent, a tackifying resin, an antiblocking agent and the like are added to the modified resin and pelletized by an extruder or the like. The kneading time at this time varies depending on the amount of the organic peroxide used, but is generally a short time of several minutes to several tens of minutes.

The pelletized adhesive composition obtained here is processed into a film by an inflation method, a T-die method, a calendering method, a pressing method or the like depending on the processability of the base resin and used as an interlayer film of laminated glass. At this time, the film thickness is 0.1 to 2 mm.

The modified product used as the interlayer film of the laminated glass of the present invention is an unsaturated alkyd partially chemically bonded to the base resin,
Some of the others are believed to be mixed in a shorter blend. Further, when heat-bonding the glass to each other, the organic peroxide causes a binding reaction of unsaturated alkyd / unsaturated alkyd, unsaturated alkyd / base resin and base resin / base resin, while acting with unsaturated alkyd and base resin. It is believed that this results in strong adhesion.

An example of the method for producing the laminated glass of the present invention is as follows.

Cut the interlayer film so that it is 1 to 2 cm larger than the shape of the glass plate at the periphery, and sandwich it between two clean glass plates without wrinkles. The two glass sheets sandwiching the interlayer film are gradually compressed between 60 to 80 ° C while being compressed between several sets of rubber rolls.
Heat to, and increase compression pressure gradually. In this way, the air interposed between the intermediate film and the glass is expelled, and at the same time, the glass is bonded with the softened intermediate film. Roll pressure
Use at least 5 kg / cm ² .

The integrated glass plate is then placed in an autoclave and heated under pressure. Heating is performed by circulating heated mineral oil in the autoclave, and the pressure is about 10-15 kg /
multiply by cm ² . A heating temperature of 120 to 180 ° C and a heating time of 10 to 20 minutes are sufficient for the oil bath. Indirect heating with steam can also be used.

After cooling, the laminated glass is washed, the excess film protruding to the periphery is cut off, and the periphery is chamfered to obtain a product.

EFFECTS OF THE INVENTION The present invention uses a modified product obtained by heating and reacting an ethylene-unsaturated ester copolymer, an unsaturated alkyd, and an organic peroxide as an intermediate film, and has penetration resistance, transparency, and heat resistance. It is an excellent laminated glass.

This laminated glass is effectively used as a window glass for automobiles, vehicles and buildings, and since the interlayer film is relatively inexpensive, the laminated glass using this is therefore low in price and used in a wide range of applications.

Next, the present invention will be described in more detail with reference to Examples. The parts in the examples are parts by weight.

Example 1 Vinyl acetate content 20% by weight, melt flow rate 150 g / 10
Minutes ethylene-vinyl acetate copolymer 97 parts, unsaturated alkyd (use maleic anhydride 147 parts, phthalic anhydride 74 parts, propylene glycol 160 parts, the one having a molecular weight of 1000 made by dehydration condensation reaction) 3 parts, The composition obtained by mixing and reacting 1 part of benzoyl peroxide with a hot roll at 100 ° C. for 3 minutes was pelletized, and the pellet was extruded at a resin temperature of 90 ° C. using a 40 mmφ extruder to obtain a 0.76 mm thick sheet. The sheet was sandwiched between 2 mm-thick glass and pressed at 150 ° C. for 5 minutes to adhere the glass to each other. The laminated glass thus obtained was excellent in transparency. A heat resistance test was conducted using this laminated glass. As a result, no bubbles or other defects were found in the laminated glass after the test. Further, a penetration resistance test was conducted using this laminated glass. As a result, the steel ball did not penetrate.

As described above, the laminated glass using the present composition as an intermediate film was excellent in transparency, heat resistance and penetration resistance.

The test was conducted by the following method.

Transparency test: The laminated glass was visually observed and passed if there was no haze.

Heat resistance test: Based on JIS R 3212, the pass / fail judgment was made according to JIS R 3211. However, the glass plate used had a thickness of 75 × 150 × 2 mm.

Penetration resistance test: Based on JIS R 3212, pass / fail judgment was made according to JIS R 3211. However, the glass plate is 200 × 200 × 2 mm
Using the thickness, the drop height of the steel ball was 2 m and the load was 2 kg.

Example 2 Vinyl acetate content 28% by weight, melt flow rate 150 g / 10
Of ethylene-vinyl acetate copolymer (94 parts), unsaturated alkyd (6 parts prepared in the same manner as in Example 1), and 1 part of benzoyl peroxide were mixed and reacted for 3 minutes on a hot roll at 100 ° C. The composition was pelletized, and the pellets were extruded at a resin temperature of 90 ° C. using a 40 mmφ extruder to obtain a 0.76 mm thick sheet. This sheet is sandwiched between 2mm thick glass and 150 ℃
Then, pressurizing for 5 minutes to bond the glass to each other. The laminated glass thus obtained was excellent in transparency. A heat resistance test was conducted using this laminated glass.
As a result, no bubbles or other defects were found in the laminated glass after the test. Further, a penetration resistance test was conducted using this laminated glass. As a result, the steel ball did not penetrate.

As described above, the laminated glass using the present composition as an intermediate film was excellent in transparency, heat resistance and penetration resistance.

Example 3 Vinyl acetate content 26% by weight, melt flow rate 4 g / 10 min ethylene-vinyl acetate copolymer 97 parts, unsaturated alkyd (made by the same method as in Example 1) 3 parts, 1 part The 140
The composition obtained by mixing and reacting for 3 minutes with a hot roll at ℃ is pelletized, and the pellets are heated at the resin temperature using a 40 mmφ extruder.
A sheet having a thickness of 0.76 mm was extruded at 120 ° C. The sheet was sandwiched between 2 mm-thick glass and pressed at 150 ° C. for 5 minutes to adhere the glass to each other. The laminated glass thus obtained was excellent in transparency. A heat resistance test was conducted using this laminated glass. As a result, no bubbles or other defects were found in the laminated glass after the test. Further, a penetration resistance test was conducted using this laminated glass. As a result, the steel ball did not penetrate.

As described above, the laminated glass using the present composition as an intermediate film was excellent in transparency, heat resistance and penetration resistance.

Example 4 Vinyl acetate content 10% by weight, melt flow rate 9 g / 10
Of ethylene-vinyl acetate copolymer (99 parts), unsaturated alkyd (made by the same method as in Example 1), and dicumyl peroxide (0.04 part) were mixed with a hot roll at 140 ° C. for 10 minutes to react. The composition obtained was pelletized, and the pellets were extruded at a resin temperature of 120 ° C using a 40 mmφ extruder.
A mm thick sheet was obtained. The sheet was sandwiched between 2 mm-thick glass and pressed at 150 ° C. for 5 minutes to adhere the glass to each other. The laminated glass thus obtained was excellent in transparency. A heat resistance test was conducted using this laminated glass. As a result, no bubbles or other defects were found in the laminated glass after the test. Further, a penetration resistance test was conducted using this laminated glass. As a result, the steel ball did not penetrate.

As described above, the laminated glass using the present composition as an intermediate film was excellent in transparency, heat resistance and penetration resistance.

[Example 5] Ethyl acrylate content 20% by weight, melt flow rate
97 parts of 20 g / 10 min ethylene-ethyl acrylate copolymer,
Unsaturated alkyd (made by the same method as in Example 1) 3
Part and benzoyl peroxide (1 part) were mixed and reacted on a hot roll at 100 ° C for 3 minutes to pelletize the composition, which was extruded at a resin temperature of 90 ° C using a 40 mmφ extruder.
A thick sheet was obtained. The sheet was sandwiched between 2 mm-thick glass and pressed at 150 ° C. for 5 minutes to bond the glass sheets together. The laminated glass thus obtained was excellent in transparency. A heat resistance test was conducted using this laminated glass. As a result, no bubbles or other defects were found in the laminated glass after the test. Further, a penetration resistance test was conducted using this laminated glass. As a result, the steel ball did not penetrate.

As described above, the laminated glass using the present composition as an intermediate film was excellent in transparency, heat resistance and penetration resistance.

Claims (1)

[Claims] 1. An ethylene-unsaturated ester copolymer, (2)
A laminated glass using an unsaturated alkyd obtained from a polybasic acid / polyhydric alcohol and a modified product obtained by heating (3) an organic peroxide as an interlayer film.