JPH08319140A - Production of laminated glass - Google Patents

Abstract

PURPOSE: To relatively readily produce laminated glass having resistance to plasticizer and capable of preventing peeling of an end part of the laminated glass. CONSTITUTION: In production of laminated glass by using an intermediate film of a thermoplastic resin having 0.01-15 kg/cm peeling adherence to float glass or 0.5-30 melt flow rate, the laminated glass is re-heated at 50-200 deg.C after cancelling vacuum in vacuum laminate processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminated glass using a thermoplastic resin as an intermediate film.

[0002]

2. Description of the Related Art When incorporating glass into a metal sash or the like, a soft plastic glass bead or the like is used as a cushioning material. When a laminated glass produced by a conventional vacuum degassing method is applied by this method, there is a drawback that the plasticizer in the glass beads migrates into the interlayer film and induces peeling at the edge of the laminated glass.

In order to solve this drawback, a glass bead using a non-migrating plasticizer is used, or a specific tape is attached to the end of the laminated glass to prevent the migration of the plasticizer. There have been methods such as suppressing peeling of the peripheral portion of the laminated glass. (Actual Kaihei 6-12443 bulletin)

[0004]

However, the glass beads using the non-migratory plasticizer are more expensive than the conventional products, and the limitation of the kind of the beads to be used cannot be indicated to the end user in the field. Also, the actual Kaihei 6-124
The method described in Japanese Patent Publication No. 43 is also not practical in industrialization because it involves a complicated manual work process after the production of laminated glass.

Further, in the laminated glass using the polyvinyl acetal resin interlayer film, since the plasticizer is contained in the interlayer film, the migration of the glass beads to the plasticizer is not a problem, but the interlayer film can be stored and laminated at the same time. It has the drawback of being very complex.

As a result of intensive studies in view of the above problems, the present inventors have found that the peel adhesive strength with float glass is 0.0.
1 to 15 kg / cm or a method for producing a laminated glass using a thermoplastic resin intermediate film having a melt flow rate of 0.5 to 30 inclusive, in which the laminated glass is heated to 50 ° C. or more and 200 ° C. or less after releasing the vacuum during vacuum lamination processing. It was found that a laminated glass having a plasticizer resistance and capable of preventing peeling at the edges of the laminated glass can be relatively easily produced by carrying out the reheating treatment with the above method, and completed the present invention.

An object of the present invention is to provide a relatively easy method for producing a laminated glass having a plasticizer resistance and capable of preventing peeling at the edges of the laminated glass.

[0008]

That is, according to the present invention, the peel adhesive strength with float glass is 0.01 to 15 kg /
A method for producing a laminated glass using a thermoplastic resin intermediate film having a numerical value of cm, wherein the laminated glass is reheated at 50 ° C. or higher and 200 ° C. or lower after releasing the vacuum during vacuum bonding. A method for manufacturing glass is provided.

Further, the present invention is a method for producing a laminated glass using a thermoplastic resin intermediate film having a melt flow rate of 0.5 or more and 30 or less. 200 ° C
The present invention provides a method for producing a laminated glass, which is characterized by performing reheating treatment.

The present invention will be described in detail below. The method for producing a laminated glass of the present invention is as follows. First, the intermediate film 1
Then, the laminated body 3 (laminated glass) is produced from the float glass 2.

The intermediate film used in the present invention may be any as long as it can be combined by a usual vacuum degassing method or the like. For example, ethylene-vinyl acetate copolymer, ethylene-
Examples thereof include (meth) acrylic acid ester copolymers and polyacetal resins, or resins obtained by subjecting them to plasticization, partial saponification, acid modification, partial crosslinking and the like may be used.

However, in the first aspect of the present invention,
In any case, an interlayer film having a peel adhesive force for float glass of 0.01 to 15 kg / cm is used. If the peel adhesive strength is lower than 0.01 kg / cm, peeling or the like occurs after the laminated glass is produced, and if higher than 15 kg / cm, the penetration resistance, that is, the shock absorption is poor and the glass is unsuitable as a safety glass.

In the second aspect of the present invention, an interlayer film having a melt flow rate (hereinafter abbreviated as MFR) of 0.5 or more and 30 or less is used in any case. If the MFR is lower than 0.5, residual air and the like will occur during the production of laminated glass, and if it is higher than 30, the resin will flow during reheating and the appearance will be poor. The measurement of MFR is a numerical value measured according to JIS K7210.

The constituent resin of the intermediate film used is as described above, but if necessary, an ultraviolet absorber, an antioxidant, a clarifying agent, an adhesive strength adjusting agent and the like may be added.

Further, when the above laminated body is produced, for example,
A rigid body other than a glass plate and a synthetic resin plate, such as a metal or an inorganic material; a polymer having low rigidity such as a polyester film or a polyurethane film, or paper may be laminated to form a multilayer type.

Examples of the layer structure of the above-mentioned multi-layered transparent laminate include (1) glass plate / intermediate film / polymer film / intermediate film / glass plate (2) glass plate / intermediate film / metal plate / intermediate film / Glass plate /
Polymer film (3) Glass plate / intermediate film / paper / intermediate film / glass plate (4) Synthetic resin plate / intermediate film / polymer film / intermediate film / synthetic resin plate (5) Synthetic resin plate / intermediate film / metal Plate / intermediate film / synthetic resin plate / polymer film (6) Combinations of synthetic resin plate / intermediate film / paper / intermediate film / synthetic resin plate and the like can be mentioned.

Next, the above laminated body was introduced into a vacuum bag,
Degas at a vacuum degree of 100 torr or less. It may be heated immediately after this, but may be kept at room temperature for about 10 minutes in order to increase the degree of vacuum. Next, the vacuum bag is transferred to the oven while maintaining the deaerated state, and heat treatment is performed for a predetermined time. The temperature at this time is 50 ° C. to 200 ° C., and the heating time is not particularly specified, but is usually about 10 minutes. If the laminating temperature is 50 ° C. or lower, degassing failure of the laminated glass occurs, and if it is 200 ° C. or higher, the resin deteriorates and the appearance of the laminated glass becomes poor. Further, in order to sufficiently deaerate the laminated glass, the heating may be performed in two or more steps to raise the temperature.

This laminated glass manufacturing process is not limited to the vacuum bag system, and may be a system using a simple laminating device manufactured by Hitec Engineering Co., Ltd., a vacuum ring or the like.

Next, as a feature of the present invention, it is essential to release the vacuum and perform reheat treatment in order to remove the distortion of the laminated glass. Reheat temperature is 50 ℃ or more 200
It is below ℃. If the temperature is lower than 50 ° C., the internal stress of the resin and the strain of the laminated glass cannot be sufficiently removed, and if the temperature exceeds 200 ° C., the interlayer resin deteriorates and the laminated glass has a poor appearance. A cooling process may be performed before or after releasing the vacuum. Pressurization is not particularly required, but may be applied to each part of the laminated glass as long as it is uniform. No decompression is required, but decompression may be done as long as it is uniform in each part of the laminated glass.

[0020]

[Function] For peeling laminated glass with glass beads,
The glass strain generated at the time of manufacture is closely related. Laminated glass produced by the conventional vacuum degassing method has a distortion in the entire glass so that the thickness of the peripheral portion becomes thinner than the thickness of the central portion because excessive pressure is concentrated on the peripheral portion. . If the glass beads containing a plasticizer are used in this state, the plasticizer in the beads causes peeling at the glass edge. However, when the laminated glass is reheated to remove the distortion of the laminated glass, it is possible to significantly suppress the peeling due to the glass beads and to provide the laminated glass having excellent plasticizer resistance.

[0021]

Example 1 (1) Production of laminated glass 100 parts by weight of an ethylene-vinyl acetate copolymer (“EVAFLEX460” manufactured by Mitsui DuPont Polychemical Co., Ltd.) and 0.2 parts by weight of a silane coupling agent were placed in a roll mill. The resin composition was supplied and melt-kneaded at a temperature of 200 ° C. to obtain a resin composition. The obtained resin composition was sandwiched between two sheets of polyethylene terephthalate film having a thickness of 0.1 mm, and the sandwiched body was press-molded by a press molding machine at 150 ° C. and 120 kgf / cm ² The polyethylene terephthalate film was peeled off to obtain a resin sheet having a thickness of 0.4 mm. A laminate was prepared by sandwiching the above resin sheet as an intermediate film between two pieces of 8 cm square float glass (thickness 3 mm). The obtained laminate is put in a vacuum bag and the degree of vacuum is 2 to 10 torr.
After degassing for 0 minutes, the vacuum bag containing the laminate was transferred to an oven while maintaining the degassed state, and kept at 100 ° C. for 30 minutes. Then, it was cooled to room temperature and the vacuum state was released to obtain a laminated glass.

(2) Reheating of laminated glass The laminated glass prepared by the above method was placed in an oven preheated to 100 ° C and reheated for 10 minutes.

(3) Production of Peel Adhesion Strength Measuring Glass Between two pieces of 8 cm square float glass (thickness 3 mm),
A laminated body is prepared by sandwiching one sheet of polyethylene terephthalate film having a thickness of 0.1 mm and one sheet of the intermediate film. The obtained laminated body is put in a vacuum bag and deaerated for 20 minutes at a vacuum degree of 10 torr. The vacuum bag containing the laminated body is transferred to an oven while keeping the deaerated state, and kept at 100 ° C. for 30 minutes.
Then, after cooling to room temperature and releasing the vacuum state to produce a laminated glass, it was cut into a width of 2 cm and a length of 10 cm to obtain a glass for peel strength measurement.

[Example 2] (1) Production of laminated glass Between two pieces of 8 cm square float glass (thickness 3 mm),
"Dumilan Film F" manufactured by Takeda Pharmaceutical Co., Ltd. as an intermediate film
-100 "(thickness 0.4 mm) is sandwiched to prepare a laminated body. The obtained laminate is put in a vacuum bag and the degree of vacuum is 10 t.
Degas for 20 minutes at orr, transfer the vacuum bag containing the laminated body to the oven while keeping the degassed state, and at 100 ° C. for 3 minutes.
Hold for 0 minutes. Then, it was cooled to room temperature and the vacuum state was released to obtain a laminated glass.

(2) Reheating of laminated glass The same procedure as in Example 1 was carried out.

(3) Production of Peel Adhesion Strength Measuring Glass The same procedure as in Example 1 was carried out.

Example 3 (1) Production of laminated glass The same procedure as in Example 1 was carried out.

(2) Reheating of laminated glass The laminated glass prepared by the above method was placed in an oven preheated to 70 ° C. and reheated for 10 minutes.

(3) Production of Glass for Peel Adhesion Strength Measurement was carried out in the same manner as in Example 1.

[Example 4] (1) Production of laminated glass The same procedure as in Example 1 was carried out.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 150 ° C. and reheated for 10 minutes.

(3) Production of Peel Adhesion Strength Measuring Glass The same procedure as in Example 1 was carried out.

Comparative Example 1 (1) Production of laminated glass An ethylene-vinyl acetate copolymer (“EVAFLEX460” manufactured by Mitsui DuPont Polychemical Co., Ltd.) having a thickness of 0.1 mm
Sandwiched between two sheets of polyethylene terephthalate film, and the resulting sandwich is pressed by a press molding machine at 150 ° C. and 120 kgf /
After press molding with cm ² and cooling, the polyethylene terephthalate film on both sides of the resin was peeled off to obtain a resin sheet having a thickness of 0.4 mm. A laminated glass was obtained in the same manner as in Example 1 except that the resin sheet was used as an intermediate film.

(2) Reheating of laminated glass The same procedure as in Example 1 was carried out.

(3) Production of Peel Adhesion Strength Measuring Glass The same procedure as in Example 1 was carried out.

Comparative Example 2 (1) Production of laminated glass 100 parts by weight of ethylene-vinyl acetate copolymer (“EVAFLEX460” manufactured by Mitsui DuPont Polychemical Co., Ltd.) and 5 parts by weight of a silane coupling agent were supplied to a roll mill, Melt kneading was performed at a temperature of 200 ° C. to obtain a resin composition. The obtained resin composition was sandwiched between two sheets of polyethylene terephthalate film having a thickness of 0.1 mm, and the sandwiched body was press-molded with a press molding machine at 150 ° C. and 120 kgf / cm ² , and the resin was cooled. The polyethylene terephthalate film on both sides was peeled off to obtain a resin sheet having a thickness of 0.4 mm. A laminated glass was obtained in the same manner as in Example 1 except that the resin sheet was used as an intermediate film.

(2) Reheating of laminated glass The same procedure as in Example 1 was carried out.

(3) Production of Peel Adhesion Strength Measuring Glass The same procedure as in Example 1 was carried out.

Comparative Example 3 (1) Production of laminated glass The same procedure as in Example 1 was carried out.

(2) Reheating of laminated glass No reheating was performed.

(3) Production of Peel Adhesive Strength Measurement Glass The same procedure as in Example 1 was carried out.

Comparative Example 4 (1) Production of laminated glass The same procedure as in Example 1 was carried out.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 40 ° C. and reheated for 10 minutes.

(3) Production of Peel Adhesion Strength Measuring Glass The same procedure as in Example 1 was carried out.

Using the laminated glass and the glass for peel adhesion measurement obtained in Examples 1 to 4 and Comparative Examples 1 to 4, a laminated glass was evaluated by conducting a plasticizer resistance test and an impact resistance test. The glass for peel strength measurement was evaluated by performing an adhesion test with a float glass plate, and the obtained results are shown in Table 1. In the above-mentioned plasticizer resistance test, di-2-ethylhexyl phthalate (hereinafter referred to as DOP) is put in a stainless steel vat, and the entire laminated glass for evaluation is dipped in the vat to be heated in an oven at 50 ° C. for 100%.
The peeling state of the laminated glass end portion when the time acceleration test was performed was observed (the numerical value in Table 1 is the ratio of the peeled area to the total area of the laminated glass). DOP is the most frequently used plasticizer for regular glass beads. The adhesive strength test with the float glass plate was performed at a temperature of 23 ° C. and a humidity of 50% RH.
Using a glass for peel adhesion measurement that was held for a period of time, a constant speed tensile tester ("Tensilon UCE50" manufactured by Orientec Co., Ltd.
0 "), the 90 ° peel adhesive force (kg / cm) was measured at a pulling speed of 500 mm / min. The test is n = 10
I went in. The above impact resistance test is performed according to JIS R 3205.
It was carried out in accordance with the above, and the grade III was evaluated as ◯ and the failure was evaluated as x.

[0046]

[Table 1]

From the results shown in Table 1, Examples 1 to 4 produced by the production method of the present invention show superior results to the Comparative Examples in the plasticizer resistance test and the impact resistance test.

Example 5 (1) Production of laminated glass Ethylene-vinyl acetate copolymer (“EVAFLEX 260” manufactured by Mitsui DuPont Polychemical Co., Ltd., MFR = 6 g / 1)
0 min) 100 parts by weight and silane coupling agent 0.1
Part by weight was supplied to a roll mill and melt-kneaded at a temperature of 200 ° C. to obtain a resin composition. The resin composition thus obtained has a thickness of 0.
It is sandwiched between two 1 mm polyethylene terephthalate films,
The obtained sandwich is pressed by a press molding machine at 150 ° C for 120k.
After press-molding at gf / cm ² , after cooling, the polyethylene terephthalate film on both sides of the resin was peeled off to obtain a resin sheet having a thickness of 0.4 mm. 8cm square float glass (thickness 3m
m) A laminate was produced by sandwiching the above resin sheet as an intermediate film between two sheets. The obtained laminated body was put in a vacuum bag and deaerated for 20 minutes at a vacuum degree of 10 torr. The vacuum bag containing the laminated body was transferred to an oven while keeping the deaerated state, and kept at 100 ° C. for 30 minutes. Then, it was cooled to room temperature and the vacuum state was released to obtain a laminated glass.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 100 ° C. and reheated for 10 minutes.

Example 6 (1) Manufacture of laminated glass As resin, "Ultrasen 631" manufactured by Tosoh Corporation (MFR =
The same procedure as in Example 5 was carried out except that 1.5 g / 10 min) was used.

(2) Reheating of laminated glass The same procedure as in Example 5 was carried out.

Example 7 (1) Manufacture of laminated glass As resin, "Ultrasen 750" manufactured by Tosoh Corporation (MFR = 3)
The same procedure as in Example 5 was carried out except that 0 g / 10 min) was used.

(2) Reheating of laminated glass The same procedure as in Example 5 was carried out.

Example 8 (1) Production of laminated glass The same procedure as in Example 5 was carried out.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 70 ° C. and reheated for 10 minutes.

Example 9 (1) Production of laminated glass The same procedure as in Example 5 was carried out.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 150 ° C. and reheated for 10 minutes.

[Comparative Example 5] (1) Production of laminated glass As a resin, "Petrosene 172" manufactured by Tosoh Corporation (MFR = 0.
The same procedure as in Example 5 was carried out except that 3 g / 10 min) was used.

(2) Reheating of laminated glass The same procedure as in Example 5 was carried out.

[Comparative Example 6] (1) Manufacture of laminated glass Resin "Mersen H6960" (MFR = 3) manufactured by Tosoh Corporation
The same procedure as in Example 5 was carried out except that 8 g / 10 min) was used.

(2) Reheating of laminated glass The same procedure as in Example 5 was carried out.

Comparative Example 7 (1) Production of laminated glass The same procedure as in Example 5 was carried out.

(2) Reheating of laminated glass No reheating was performed.

Comparative Example 8 (1) Production of laminated glass The same procedure as in Example 5 was carried out.

(2) Reheating of laminated glass The laminated glass produced by the above method was placed in an oven preheated to 40 ° C. and reheated for 10 minutes.

The laminated glasses of Examples 5 to 9 and Comparative Examples 7 and 8 had good appearance even after reheating. The laminated glass of Comparative Example 6 had a good appearance at the time of producing the laminated glass, but when reheated, the resin flowed out from the edge of the glass, resulting in a remarkable poor appearance.

Using the laminated glass obtained in Examples 5 to 9 and Comparative Examples 7 and 8, a plasticizer resistance test was conducted and evaluated, and the obtained results are shown in Table 2. In the plasticizer resistance test, di-2-ethylhexyl phthalate (hereinafter referred to as DOP) is put in a stainless steel vat, and the entire laminated glass for evaluation is immersed therein and accelerated in a 50 ° C. oven for 100 hours. The peeled state of the edge of the laminated glass at the time of the test was observed (the numerical values in Table 2 are the ratio of the peeled area to the total area of the laminated glass). DOP is the most frequently used plasticizer for regular glass beads. For Comparative Examples 5 and 6, a plasticizer resistance test was not performed because good laminated glass could not be obtained.

[0068]

[Table 2]

From the results shown in Table 2, Examples 5 to 9 produced by the production method of the present invention were tested in the plasticizer resistance test.
The result is superior to that of the comparative example.

[0070]

According to the manufacturing method of the present invention, a laminated glass using an interlayer film having an adhesive strength with respect to float glass of 0.01 to 15 kg / cm is used to prevent the influence of a sealing material or the like used during construction, It is possible to manufacture a laminated glass in which peeling of the interlayer film-glass edge does not occur.

Further, according to the manufacturing method of the present invention, the laminated glass using the intermediate film having the melt flow rate of 0.5 or more and 30 or less can be prevented from being affected by the sealing material used at the time of construction, and the interlayer film can be used for a long period of time. It is possible to manufacture a laminated glass in which peeling of the glass edge does not occur.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a laminated body of laminated glass.

[Explanation of symbols]

 1: Intermediate film 2: Float glass 3: Laminated body (laminated glass)

Claims (2)

[Claims] 1. The peel adhesion to float glass is 0.
In the method for producing a laminated glass using a thermoplastic resin interlayer film of 01 to 15 kg / cm, the laminated glass is heated to 50 ° C. or higher at 200 ° C. or higher after releasing the vacuum during vacuum alignment processing.
A method for producing a laminated glass, which comprises performing a reheat treatment at a temperature of not higher than ° C. 2. A method for producing a laminated glass using a thermoplastic resin intermediate film having a melt flow rate of 0.5 or more and 30 or less, wherein the laminated glass is heated to 50 ° C. or more and 200 ° C. or less after releasing the vacuum during vacuum lamination processing. A method for producing laminated glass, which comprises performing reheating treatment.