JP2003285042A - Method for treating waste laminated glass and method for recycling glass and polyvinyl butyral resin for intermediate film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating waste laminated glass which can recycle glass and intermediate film. <P>SOLUTION: The waste laminated glass is disassembled from an automobile body and the disassembled glass is crushed to obtain intermediate glass pieces with fine glass pieces 5. The intermediate film pieces with fine glass pieces 5 are immersed into an organic solvent 11 for dissolving the intermediate film pieces 6 to obtain an intermediate film solution containing the fine glass pieces 12. The fine glass pieces 7 are separated from the intermediate film solution 12 to obtain an intermediate film solution 14. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for treating waste laminated glass composed of two glass plates and an interlayer film made of polyvinyl butyral resin sheets sandwiched between these two glass plates, and The present invention relates to a method for regenerating polyvinyl butyral resin for intermediate films.

[0002]

2. Description of the Related Art For example, most of the waste laminated glass for automobile windshield, which has been removed from the main body of a scrapped vehicle, is reused, but most of it is landfilled as shredder dust.

In this way, the waste laminated glass must be landfilled in such a manner that when the waste laminated glass removed from the automobile body is crushed by a crusher, fine glass particles of glass are intermediate films. This is because an interlayer film piece with glass particles attached to the piece is generated, and it is extremely difficult to appropriately separate the glass particles from the generated interlayer film piece with glass particles. About 10 kg of waste laminated glass for automobile windshield is used for each scrap car, and the waste laminated glass that was landfilled in 2000 is
It is said that it was estimated to be about 45,000 tons.

[0004]

Therefore, in recent years, it is possible to properly separate and recover the glass and the intermediate film from the waste laminated glass without the need to reclaim the waste laminated glass that has become unnecessary as shredder dust. There has been a long-awaited demand for a method for treating abandoned laminated glass that can be reused.

The present invention has been made in view of the above points, and can appropriately separate and recover glass and an intermediate film from waste laminated glass that is no longer needed, and can reuse the glass and the intermediate film. An object of the present invention is to provide a method for treating a laminated glass and a method for regenerating a polyvinyl butyral resin for an interlayer film.

[0006]

A method for treating waste laminated glass according to claim 1 is characterized in that two glass plates and an interlayer film made of a polyvinyl butyral resin sheet sandwiched between these two glass plates are used. A method for treating waste laminated glass constituted by, immersing an intermediate film piece with glass particles obtained from the waste laminated glass in an organic solvent, the intermediate film piece of the interlayer film piece with glass particles is the organic solvent. And a step of obtaining a glass particle-containing intermediate film solution by dissolving in glass, and a step of separating glass particles from the glass particle-containing intermediate film solution to obtain an interlayer film solution.

[0007] Further, the waste laminated glass can be properly separated and recovered from the waste laminated glass without landfilling waste waste laminated glass as shredder dust, and the glass and the intermediate film can be reused. Becomes

According to a second aspect of the present invention, there is provided a method for treating waste laminated glass, which comprises an automobile front comprising two glass plates and an interlayer film made of a polyvinyl butyral resin sheet sandwiched between the two glass plates. A method for treating waste laminated glass for glass, the step of removing the waste laminated glass from an automobile body, the step of crushing the removed waste laminated glass to obtain an interlayer film piece with glass particles, The step of dipping the piece of interlayer film with an organic solvent into an organic solvent, the step of dissolving the piece of interlayer film of the piece of interlayer film with glass particles into the organic solvent to obtain a glass particle-containing interlayer film solution, and the glass particle-containing interlayer film solution From the glass to obtain an interlayer film solution.

The glass and the intermediate film can be properly separated and recovered from the waste laminated glass for automobile windshields without the need to bury the waste laminated glass for automobile windshields as shredder dust. It is possible to reuse the intermediate film.

The method for treating waste laminated glass according to claim 3 is the same as the method for treating waste laminated glass according to claim 1 or 2, wherein the organic solvent is a lower alcohol having 4 or less carbon atoms, chloroform, or a cyclic ether. , N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide.

An organic solvent containing at least one of lower alcohols having 4 or less carbon atoms, chloroform, cyclic ethers, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide. By using, it becomes possible to appropriately dissolve the interlayer film piece in the organic solvent.

The method for reclaiming polyvinyl butyral resin for interlayer film according to claim 4 is composed of two glass plates and an interlayer film made of polyvinyl butyral resin sheet sandwiched between these two glass plates. A method for recycling polyvinyl butyral resin for interlayer film from waste laminated glass, in which the glass particle-attached interlayer film piece obtained from the waste laminated glass is immersed in an organic solvent to remove the glass particle-attached interlayer film piece. A step of dissolving an interlayer film piece in the organic solvent to obtain a glass particle-containing interlayer film solution; a step of separating glass particles from the glass particle-containing interlayer film solution to obtain an interlayer film solution; and the interlayer film solution And removing the organic solvent to obtain the polyvinyl butyral resin for interlayer film.

Then, the interlayer film piece of the glass particle-attached interlayer film piece is dissolved in an organic solvent to obtain a glass particle-containing interlayer film solution, and the glass particle is separated from the glass particle-containing interlayer film solution. By obtaining an interlayer film solution and then removing the organic solvent from the obtained interlayer film solution to obtain a polyvinyl butyral resin for interlayer film, the polyvinyl butyral resin for interlayer film is appropriately regenerated from waste laminated glass.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of the present invention will be described below with reference to the drawings.

A waste laminated glass 1 shown in FIG. 1 is, for example, a waste laminated glass for an automobile windshield attached to the front portion of an automobile body of a scrap car (not shown), two glass plates 2 and 2 and these two glass plates. Intermediate film 3 made of polyvinyl butyral resin sheet sandwiched between glass plates 2 and 2
It consists of and.

The polyvinyl butyral resin sheet forming the intermediate film 3 for preventing glass scattering is made of polyvinyl butyral resin (PVB) and triethylene glycol.
A plasticized polyvinyl butyral sheet manufactured by melt-extruding a mixture of ester plasticizers such as di2-ethyl butyrate into a sheet.

The intermediate film piece 5 with glass particles shown in FIG.
Is obtained by crushing, for example, a waste laminated glass 1 for an automobile windshield removed from a car body of a scrap car, and an intermediate film piece 6 and a number of fine glass pieces attached to the surface of the intermediate film piece 6. It is composed of fine pieces 7.

Next, with reference to FIG. 3, a method for treating the waste laminated glass 1 for automobile windshield will be described.

When treating the waste laminated glass 1 shown in FIG. 1, first, the waste laminated glass 1 is removed from the front part of the automobile body of the waste vehicle.

Next, this removed laminated glass 1
Is crushed by a crusher (not shown) to obtain the glass film-attached interlayer film piece 5 shown in FIG. When the waste laminated glass 1 is crushed, a predetermined amount of the glass film-attached interlayer film piece 5 is obtained, and at the same time, a predetermined amount of the glass piece is obtained. Unlike the interlayer film piece 5, it can be reused without performing the processing described below.

Next, as shown in FIG. 3 (a), a piece of intermediate film piece 5 with glass particles obtained by crushing the waste laminated glass 1 is stored in the melting tank 10 as a predetermined storage liquid in a liquid state. It is immersed in a solvent (organic solvent) 11 and the interlayer film piece 6 of the interlayer film piece 5 with glass particles is dissolved in the organic solvent 11 to obtain a glass particle-containing interlayer film solution 12 shown in FIG. 3 (b).

That is, the intermediate film piece 5 with glass particles is immersed in the organic solvent 11 for a predetermined period of time to completely dissolve the intermediate film piece 6 in the intermediate film piece 5 with glass particles in the organic solvent 11 and the remaining The solid glass particles 7 are suspended or precipitated in a solution in which the interlayer film 6 is dissolved to obtain a glass particle-containing interlayer film solution 12.

Here, since the glass particle-attached interlayer film piece 5 obtained by crushing the waste laminated glass 1 has a water content of about 5%, it is preferable to sufficiently dry it before immersing it in the organic solvent 11. Further, in order to promote the dissolution of the interlayer film piece 6 in the organic solvent 11, the organic solvent 11 is stirred by the stirring means while the organic solvent 11 is stirred by the heating means at a predetermined temperature (for example, 40 ° C. to organic solvent). It is preferable to heat so as to maintain the boiling point of 11).

On the other hand, the organic solvent 11 is a lower alcohol having a carbon number of 4 or less (eg, methanol, ethanol,
Propyl alcohol, isopropyl alcohol, butyl alcohol), chloroform, cyclic ethers (eg, tetrahydrofuran, 1,4-dioxane), N, N-
It contains at least one of dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide. That is, for example, the organic solvent 11 may be mainly composed of one kind of substance selected from these six kinds of substances, or may be mainly composed of two or more kinds of substances selected from these six kinds of substances. .

In order to evaluate the dissolution state of the interlayer film piece 6, 0.2 g of the glass film-attached interlayer film piece 5 was used as 16 kinds of 2 pieces.
The film was immersed in ml of solvent (about 20 ° C.), and the solubility, viscosity and complete dissolution days of the interlayer film piece 6 were examined. The results are shown in Table 1 below.

[0026]

[Table 1]

From Table 1, as a solvent for dissolving the interlayer film piece 6, an organic solvent of methanol, ethanol, propyl alcohol, isopropyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide or dimethylsulfoxide is used. It turns out to be suitable.

Next, as shown in FIG. 3 (c), the glass particle-containing interlayer film solution 12 is filtered under reduced pressure using a filtering means 13 such as a glass filter to remove the glass particle-containing interlayer film solution 12 from the glass. Separation and removal of fine pieces 7 to remove interlayer film solution
Get 14

According to such a method for treating waste laminated glass 1, a part of the intermediate film piece 5 with glass particles produced by the crushing treatment of the waste laminated glass 1 for an automobile windshield which has become unnecessary is formed. By dissolving the interlayer film piece 6 in a predetermined organic solvent (for example, ethanol) 11, the glass particles 7 can be properly separated from the interlayer film piece 5 with glass particles, so that the waste laminated glass 1 is shredded with dust. As an abandoned laminated glass without landfill treatment 1
The glass and the intermediate film can be completely separated and recovered in a predetermined state, and the glass and the intermediate film can be reused.

That is, for example, the glass collected as the glass fragments 7 can be used as glass wool by subjecting it to a predetermined treatment, for example.

The intermediate film recovered as the intermediate film solution 14, for example, is subjected to a predetermined treatment, if necessary, to make use of the properties of polyvinyl butyral resin (PVB), such as a protective sheet material (film sheet), It can be used as a sealant, adhesive, liquid glue, and paint such as undercoat paint.

The protective sheet material is used for the purpose of preventing scratches, scattering at the time of breakage, dirt adhesion prevention, dew condensation prevention, deterioration prevention, and the like. For example, storage materials, stored products, ventilation fans with severe oil stains, airtightness Used for windows of tall houses. The characteristic of this protective sheet is that it can form a transparent protective film that adheres to the surface of various materials such as glass, wood, metal, tiles, plastics, etc. It is easy to clean up after leaving without sticking the material. As the handling of this protective sheet, for example, brush painting, casting, dipping, etc. can be considered.

The sealing material is used for the purpose of preventing water permeation, preventing the formation of mold, etc., and is used, for example, in a water area of a bathroom, kitchen or the like. The characteristic of this sealing material is that a white pigment, an antifungal agent, etc. are mixed and overcoated along the tile joints, and when dried, it exhibits a sealing effect like an adhesive tape and is easy to peel off. For handling the sealing material, for example, a tube may be considered.

Further, the adhesive / liquid glue is particularly excellent in adhering paper and wallpaper, suitable for sick house measures, and environmentally friendly. In addition, this adhesive / liquid glue is not limited to the material, is excellent in temporary adhesion, and does not leave a trace of peeling. For handling the adhesive / liquid glue, for example, a tube or the like can be considered.

The coating material can be colored by adding a pigment, has excellent gloss, has a beautiful finish, and may be overcoated with a curable resin, if necessary.
As a method of handling this paint, brush painting or the like can be considered.

On the other hand, the organic solvent 11 such as methanol or ethanol is removed from the intermediate film solution 14 obtained by filtering and separating the glass particles 7 by, for example, natural evaporation or heating, and PVB for an intermediate film (automobile windshield). It is possible to obtain a PVB for interlayer film of laminated glass for commercial use.
That is, the PVB for interlayer film can be appropriately regenerated by utilizing the method for treating the waste laminated glass 1.

It should be noted that FIGS. 4, 5 and 6 show PVB (intermediate film PVB) for interlayer films of laminated glass for automobile windshields obtained by collecting using the processing method of the above embodiment.
The measurement data regarding B) are shown.

The one shown in FIG. 4 is a recovered PVB for interlayer film recovered by using an organic solvent 11 made of methanol (a film-shaped or sheet-shaped PVB obtained by drying and removing methanol from the interlayer film solution 14). And the new PVB for interlayer film are the infrared absorption spectra (IR spectra) measured data.

The one shown in FIG. 5 is a recovered product P for intermediate film recovered by using an organic solvent 11 made of tetrahydrofuran.
It is the data which measured the gel permeation chromatogram (GPC profile) about VB and the new PVB for interlayer films.

From both data, it can be seen that the recovered PVB for interlayer film is in good agreement with the new PVB and there is no significant difference between the two. In particular, in the IR spectrum of FIG.
Judging from the appearance of the absorption band of C = 0 stretching vibration around 1740 cm ⁻¹ and the low molecular weight peak around 20 ml in the GPC profile of FIG. 5, the presence of the ester plasticizer is strong. It can be seen that the amount of the plasticizer that can be supported and is the same as that of a new product is contained in the recovered PVB for interlayer film.

Further, the one shown in FIG. 6 is a PV for interlayer film which is a recovered product recovered by using the organic solvent 11 consisting of methanol.
B (film-like or sheet-like PVB obtained by removing methanol from the interlayer solution 14 by drying) and new P for interlayer film
Thermal analysis was performed on VB and the heating rate was 10 ° C / mi.
n is a thermogravimetric curve measured under a nitrogen atmosphere.

From this thermogravimetric curve, it can be seen that the recovered PVB for interlayer film is in good agreement with the new PVB and there is no significant difference between the two. In both cases, the weight loss due to thermal decomposition progresses in two stages, and it can be judged that the first stage is the loss of the contained plasticizer and the second stage is the loss due to thermal decomposition of PVB itself. It is considered that similar data can be obtained even when an organic solvent 11 other than methanol or tetrahydrofuran is used.

In the above embodiment, the abandoned laminated glass 1 is not limited to the one for automobile windshields, for example, for safety glass for vehicles other than automobiles, for window glass of buildings, etc. But it's okay.

[0044]

According to the invention described in claim 1, the glass and the intermediate film can be properly separated and recovered from the waste laminated glass without the need for landfilling the waste waste laminated glass as shredder dust. The interlayer film can be reused.

According to the second aspect of the present invention, the glass and the intermediate film are removed from the waste laminated glass for the automobile windshield without the need for landfilling the waste waste laminated glass for the automobile windshield as shredder dust. It can be properly separated and recovered, and the glass and interlayer film can be reused.

According to the invention of claim 3, the number of carbon atoms is 4
By using an organic solvent containing at least one of the following lower alcohols, chloroform, cyclic ethers, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethylsulfoxide, an organic solvent can be obtained. The interlayer film piece can be melted properly.

According to the invention as set forth in claim 4, the interlayer film piece of the interlayer film piece with glass particles is dissolved in an organic solvent to obtain a glass particle-containing interlayer film solution, and then this glass particle-containing interlayer film solution is obtained. From the waste laminated glass, polyvinyl butyral for interlayer film is obtained by separating glass fragments from the glass plate to obtain interlayer film solution, and then removing the organic solvent from the obtained interlayer film solution to obtain polyvinyl butyral resin for interlayer film. The resin can be recycled properly.

[Brief description of drawings]

FIG. 1 is a view showing a waste laminated glass for an automobile windshield.

FIG. 2 is a view showing an interlayer film piece with glass particles obtained from the same waste laminated glass.

[Fig. 3] Fig. 3 is an explanatory diagram for explaining a method for treating waste laminated glass.

FIG. 4 shows IR spectrum measurement data of recovered PVB for interlayer film and new PVB for interlayer film.

FIG. 5 shows GPC profile measurement data of collected PVB for interlayer film and new PVB for interlayer film.

FIG. 6 is a thermogravimetric measurement curve of the recovered PVB for interlayer film and a new PVB for interlayer film.

[Explanation of symbols]

1 abandoned laminated glass 2 glass plates 3 Intermediate film 5 Interlayer film piece with glass particles 6 pieces of interlayer film 7 glass pieces 11 Organic solvent 12 Intermediate film solution containing glass particles 14 Interlayer solution

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 29:00 B09B 5/00 ZABZ C08L 29:00 3/00 Z 304P (72) Inventor Kazumi Odabe 1085 Kayahashi, Oyama City, Tochigi Prefecture Tsuruoka Oyama Factory (72) Inventor Takao Kimura 6-21-1 F Term, Kiyoharadai, Utsunomiya City, Tochigi Prefecture (reference) 4D004 AA18 BA07 CA04 CA13 CA41 CC04 4F301 AA13 BF08 BF11 BF27 BF31 CA09 CA12 4G059 AA01 AB19 AC30

Claims (4)

[Claims] 1. A method for treating waste laminated glass, which comprises two glass plates and an interlayer film made of a polyvinyl butyral resin sheet sandwiched between these two glass plates, the method comprising: A step of immersing the glass particle-attached interlayer film piece obtained from glass in an organic solvent, and dissolving the glass particle-attached interlayer film piece in the organic solvent to obtain a glass particle-containing interlayer film solution; And a step of separating glass pieces from the glass piece-containing interlayer film solution to obtain an interlayer film solution. 2. A method for treating waste laminated glass for an automobile windshield, which comprises two glass plates and an interlayer film made of polyvinyl butyral resin sheets sandwiched between these two glass plates. A step of removing the waste laminated glass from the automobile body, a step of crushing the removed waste laminated glass to obtain an interlayer film piece with glass particles, and immersing the interlayer film piece with glass particles in an organic solvent, A step of dissolving the interlayer film piece of the glass particle-attached interlayer film piece in the organic solvent to obtain a glass particle-containing interlayer film solution, and separating the glass particle from the glass particle-containing interlayer film solution to form an interlayer film solution. The method for treating waste laminated glass, comprising: 3. The organic solvent includes lower alcohols having 4 or less carbon atoms, chloroform, cyclic ethers, N, N-dimethylformamide, N, N-dimethylacetamide,
And at least any one of dimethyl sulfoxide
3. The method for treating waste laminated glass according to claim 1 or 2, further comprising: 4. A polyvinyl butyral resin for interlayer film is reclaimed from waste laminated glass composed of two glass plates and an interlayer film made of polyvinyl butyral resin sheets sandwiched between these two glass plates. A method of recycling, wherein the glass piece with an interlayer film piece obtained from the waste laminated glass is immersed in an organic solvent, and the interlayer film piece of the glass piece with an interlayer film piece is dissolved in the organic solvent to contain a glass particle piece. A step of obtaining an interlayer film solution; a step of separating glass particles from the glass particle-containing interlayer film solution to obtain an interlayer film solution; a step of removing the organic solvent from the interlayer film solution and the polyvinyl butyral for interlayer film A method of regenerating a polyvinyl butyral resin for interlayer film, comprising the step of obtaining a resin.