JP2001031937A - Bonding material for reinforced glass and method for preparing reinforced glass using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bonding material for a reinforced glass capable of forming a firm bond between laminated plate-shaped units, at least one of which is a plastic, without distorting the plastic, and to provide a method for manufacturing a reinforced glass using the same. SOLUTION: There is provided a plate-shaped bonding material for a reinforced glass which is arranged between plate-shaped units, at least one of which being a plastic, and thermally set thereby effecting interlaminar bonding, which bonding material comprises a thermosetting resin comprising an ethylene/vinyl acetate copolymer(EVA), and incorporated therein, an organic peroxide, a crosslinking auxiliary and an adhesion accelerator and is characterized in that the organic peroxide has a 10-hr half-life temperature of 105 deg.C or below, which permits to obtain a plate-shaped bonding material for a reinforced glass excellent in bonding strength, transparency and heat resistance even when heating is carried out at a temperature as low as 130 deg.C or below or the heating time is reduced down to 10 min or less at a heating temperature of 130-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plate-like tempered glass adhesive which is interposed between plate-like units each of which at least one is made of plastic and is heated and cured to bond between layers, and a method of forming tempered glass using the same. Things.

[0002]

2. Description of the Related Art Ethylene-vinyl acetate copolymer (EV)
A), a thermosetting resin in which an organic peroxide is blended has excellent adhesion, heat resistance, and transparency, and is excellent in glass (G).
It is widely used for adhesion between L) / glass (GL).

[0003]

However, the above E
A thermosetting resin in which an organic peroxide is blended with VA needs to be heated at 130 to 150 ° C. for 10 minutes or more when thermosetting, and thus has the following various problems.

That is, when a tempered glass containing plastic is formed, the plastic is deformed and loses its commercial value. If the curing temperature is lowered or the time is shortened to prevent thermal deformation of the plastic, the curing reaction is not sufficient, the transparency is deteriorated, the adhesive strength is reduced, and the plastic cannot be used. From the viewpoint of energy saving, there is a problem that the loss of energy consumption is large, and so on.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and an object thereof is to achieve a heating temperature of 130 ° C.
Even at a low temperature below, or a heating temperature of 130 to 150
Even if the heating time is shortened within 10 minutes at ° C, the curing reaction of EVA occurs, and at least one of the laminated plate-like units containing plastic has high strength and can be bonded without deforming plastic. It is an object of the present invention to provide a material and a method for forming a tempered glass using the same.

[0006]

In order to achieve the above object, the adhesive for tempered glass according to the present invention comprises at least one adhesive.
One is a plate-shaped adhesive material that is interposed between plate-shaped single bodies made of plastic and is heat-cured to bond between layers,
It is composed of a thermosetting resin obtained by blending an organic peroxide, a crosslinking aid, and an adhesion promoter with an ethylene-vinyl acetate copolymer (EVA), and the 10-hour half-life temperature of the organic peroxide is 105 °.
C or lower, and the heating temperature is 130 ° C. or lower, or the heating temperature is 130 to 150 ° C.
Even if the heating time was shortened to 10 minutes or less at C, a plate-like adhesive for tempered glass excellent in adhesive strength, transparency and heat resistance was obtained.

[0007] The laminate-forming adhesive according to the second aspect of the invention is characterized in that the plastic plate-shaped simple substance is polycarbonate (PC), and a part of the structure of the laminate has transparency. Even when a plate-like simple substance made of high PC is included, it can be bonded with high strength without thermal deformation.

Further, in the adhesive for forming a laminate according to the third aspect of the present invention, the plastic plate-shaped simple substance is made of polyethylene terephthalate (PET), and a part of the structure of the laminate has transparency. Even when a plate-shaped simple substance made of PET having a high PET is included, it can be bonded with high strength without thermal deformation.

Further, the method for forming a laminate according to the invention according to claim 4 is a method for forming an organic peroxide which is prepared by blending an ethylene-vinyl acetate copolymer with a crosslinking aid and an adhesion promoter.
A plate-like object made of a thermosetting resin having a 0-hour half-life temperature of 105 ° C. or less is interposed between at least one plate-like single piece of plastic and heated and cured, and a heating temperature of 130 ° C. Even at the following low-temperature energy savings, the heating temperature is 130 to 150 ° C and the heating time is 10
Cured with energy savings shortened within minutes, and
It was configured such that a laminate having high adhesive strength, transparency and heat resistance could be efficiently formed without deforming the plastic contained in one of the laminates.

Further, in the method of forming a laminate according to the present invention, the plastic is polycarbonate (PC), and a part of the structure of the laminate comprises PC having high transparency. Even when a plate-like simple substance is included, it is configured such that it can be bonded as high strength without thermal deformation to form a laminate.

Further, in the method of forming a laminate according to the present invention, the plastic plate-like simple substance is made of polyethylene terephthalate (PET), and a part of the structure of the laminate has transparency. Even when a plate-shaped simple substance made of high PET is included, it is configured to be bonded as high strength without thermal deformation to form a laminate.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments shown in the accompanying drawings. FIG. 1 is a schematic enlarged cross-sectional view of a laminate formed using the adhesive of the present application, FIG. 2 is a diagram showing a table of test results of a temperature rise test according to an example, and FIG. FIG.

The adhesive 1 of the present invention is used to form a tempered glass S by being interposed between the laminated GLs, plastics and other plate-like units 2 and 3 and heat-cured to form a tempered glass S. It is made of a thermosetting resin containing a crosslinking aid and an adhesion promoter. In addition, the plate-shaped simple substance may be an inorganic substance other than GL (eg, a calcical plate), an organic substance other than plastic (eg, paper), or a metal. In addition, not only between the plate-shaped simple substances, but also between the plate-shaped simple substance and the adhesive or between the adhesives, a material other than the plate-shaped (for example, a mesh-like or irregular-shaped thing) may be interposed.

Of course, the EVA includes an organic peroxide, a crosslinking assistant, an adhesion promoter, a weather stabilizer, an antioxidant,
An ultraviolet absorber or the like may be added. The organic peroxide added here has a 10-hour half-life temperature of 105 ° C. or less.

The plate-like units 2 and 3 may be made of only plastic, but FIG. 1 shows the case of GL alone and plastic alone (PC or PET). Of course, it is not necessary to limit to these two kinds of plastics of PC or PET, and the tempered glass S is not limited to the case of three layers as shown in FIG.

The EVA has a vinyl acetate content of 13 to
35%, MFR (metro flow rate) 3-30g /
10 min is preferable. Of course, EVA having different values of vinyl acetate content and MFR may be used.

The crosslinking agent peroxide has a half-life of 1
The decomposition temperature at 0 hours is 105 ° C. or less, but from the viewpoint of safety, the maximum storage temperature of dilauroyl peroxide or 1,1,3,3-tetramethylbutylperoxy is 10 ° C. or more. 2-ethylhexanoate, dibenzoyl peroxide, t-amyl peroxy-2-
Ethyl hexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3, 3,5-trimethylcyclohexane, 1,1-di (t-amylperoxy) cyclohexane, t-amylperoxyisononanoate, t-amylperoxy normal octoate, 1,
1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2- Ethylhexyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-amyl-peroxybenzoate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxy At least one kind from benzoate etc.
The peroxide is preferably added in an amount of 5 parts by weight or less based on 100 parts by weight of EVA.

As the cross-linking aid, an allyl group-containing compound such as triallyl isocyanurate and trimethallyl isocyanurate can be used, and the amount of the cross-linking aid is preferably 10 parts by weight or less based on 100 parts by weight of EVA.

The adhesion promoters include vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxy-ethoxy) silane, γ-glycidoxypropyl-tripyltri-methoxysilane, β- (3,4 epoxycyclohexyl)- Ethyltrimethoxysilane, γ-
Glycidoxypropyl-trimethoxysilane, γ-aminopropyltriethoxysilane and the like can be used.
The amount of the adhesion promoter is preferably 5 parts by weight or less based on 00 parts by weight.

The EVA made of a thermosetting resin containing the above-mentioned organic peroxide, a crosslinking aid and an adhesion promoter is formed into a plate (including a sheet and a film) to improve usability. For forming into a plate, it can be performed by molding at a temperature not higher than the decomposition temperature of the peroxide by a known means such as a press molding machine, a calendar molding machine, an extruder with a T-die, and an extruder with a round die. . In this case, an embossed pattern may be provided on the plate-like molded product. That is, it is effective for preventing blocking of the molded product and for enhancing the degassing effect at the time of forming the laminate.

[0021]

Example 1 EVA (V made by DuPont-Mitsui Polychemicals)
523, vinyl acetate content 33%, MFR 15 g / 10
min) 100 parts by weight, peroxide 1,1-di (t-butylperoxy) -3 having a half-life temperature of 96 ° C. for 10 hours.
3,5-trimethylcyclohexane (DBPOTMCH
1 part by weight of Lupazole 231) manufactured by Atochem Yoshitomi,
Crosslinking aid triallyl isocyanurate (Nippon Kasei) 2
Parts by weight, silane coupling agent 3-methacryloxypropyltrimethoxysilane (KMB50 manufactured by Shin-Etsu Chemical Co., Ltd.)
3) Blend 1 part by weight and use an extruder with a T die to obtain a thickness of 8
A plate-shaped adhesive of the present invention having a thickness of 0 μm was prepared. At this time, molding was performed at a temperature of 90 ° C. or less at which the organic peroxide did not decompose.

The above-mentioned adhesive of the present invention, 30 cm × 30 cm, is made of two GLs each having a thickness of 2 mm, a length of 30 cm and a width of 30 cm, and a GL having a thickness of 1 mm, a length of 30 cm and a width of 30 cm inserted therebetween.
C sample (GL / EVA / PC / E
VA / GL) was placed in an oven-type vacuum chamber, and the temperature was raised from room temperature to 120 ° C. and the pressure was reduced to 70 cmHg. The results are as shown in the table of FIG.

According to the table of FIG.
It takes 12 minutes (heating time) for the temperature to rise to 120
After heating for 15 minutes (crosslinking time) at ° C (crosslinking temperature),
The appearance of the sample taken out of the oven-type vacuum chamber was good without bubbles and distortion. The gel fraction, which is an indicator of the degree of crosslinking, was 80%. This was measured by the following method.

That is, 1 g of the charged sample was precisely weighed, and
ml of xylene, and allowed to stand at 110 ° C. for 12 hours.
C for 10 hours. This was weighed and the gel fraction was calculated by the following equation. Gel fraction = [weight of undissolved component / amount of sample charged] × 100
(%)

Further, as shown in FIG. 2, the heat resistance was evaluated by observing the state of peeling after being placed in an oven at 90 ° C. for 24 hours. The sample taken out of the oven was good without peeling.

[0026]

Example 2 The procedure was the same as in Example 1 except that EVA (EV550 manufactured by DuPont-Mitsui Polychemicals) having an MFR of 15 g / 10 min and a vinyl acetate content of 14% was used. The results are as shown in the table shown in FIG.

[0027]

Example 3 EVA having an MFR of 6 g / 10 min and a vinyl acetate content of 28% (EVA manufactured by DuPont-Mitsui Polychemicals)
V260P), except that V260P) was used. The results are as shown in the table shown in FIG.

[0028]

Example 4 The procedure was the same as in Example 1 except that EVA (EV150P manufactured by DuPont-Mitsui Polychemicals) having an MFR of 30 g / 10 min and a vinyl acetate content of 33% was used. The results are as shown in the table shown in FIG.

[0029]

Example 5 The procedure of Example 1 was repeated except that the structure of the sample (tempered glass) of Example 1 was changed to GL / EVA / PET / EVA / GL. PET is 1m thick
m, length 30 cm, width 30 cm. The results are as shown in the table shown in FIG.

[0030]

Example 6 The procedure was the same as in Example 1, except that the crosslinking temperature was 150 ° C. and the crosslinking time was 5 minutes. The results are as shown in the table shown in FIG.

[0031]

Example 7 The procedure of Example 5 was repeated except that the crosslinking temperature was 150 ° C. and the crosslinking time was 5 minutes. The results are as shown in the table shown in FIG.

[0032]

Comparative Example 1 The procedure was the same as in Example 1, except that EVA containing no peroxide was used. The results are as shown in the table shown in FIG.

[0033]

Comparative Example 2 The peroxide used in Example 1 was heated for 10 hours by half-life at a temperature of 120 ° C. in 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (DMDBPOH).
All procedures were performed in the same manner as in Example 1 except that Lupazole 101) manufactured by Atochem Yoshitomi was changed. The results are as shown in the table shown in FIG.

[0034]

COMPARATIVE EXAMPLE 3 The peroxide used in Example 5 was heated for 10 hours to a half-life temperature of 120 ° C. in 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (DMDBPOH,
All procedures were performed in the same manner as in Example 5, except that Lupazole 101) manufactured by Atochem Yoshitomi was changed. The results are as shown in the table shown in FIG.

[0035]

Comparative Example 4 The procedure of Comparative Example 1 was repeated except that the crosslinking temperature was 150 ° C. and the crosslinking time was 5 minutes. The results are as shown in the table shown in FIG.

[0036]

Comparative Example 5 The peroxide used in Example 6 was heated for 10 hours by half-life at a temperature of 120 ° C. in 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (DMDBPOH,
All procedures were performed in the same manner as in Example 6, except that Lupazole 101) manufactured by Atochem Yoshitomi was changed. The results are as shown in the table shown in FIG.

[0037]

COMPARATIVE EXAMPLE 6 The peroxide used in Example 5 was heated for 10 hours by half-life at a temperature of 120 ° C. in 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (DMDBPOH,
All procedures were performed in the same manner as in Example 5, except that Lupazole 101) manufactured by Atochem Yoshitomi was changed. The results are as shown in the table shown in FIG.

[0038]

Comparative Example 7 The same procedure was performed as in Comparative Example 5 except that the crosslinking time in Comparative Example 5 was changed to 20 minutes. The results are as shown in the table shown in FIG.

[0039]

Comparative Example 8 Comparative Example 3 was carried out in the same manner as in Comparative Example 3 except that the crosslinking time was changed to 20 minutes. The results are as shown in the table shown in FIG.

[0040]

As described above, the adhesive for tempered glass according to the present invention is a plate-like adhesive which is interposed between plate-like single bodies, at least one of which is made of plastic, and is heated and cured for interlayer bonding. Is composed of a thermosetting resin containing an organic peroxide, a crosslinking assistant, and an adhesion promoter, and is characterized in that the 10-hour half-life temperature of the organic peroxide is 105 ° C. or less. Excellent bonding strength and transparency without deforming the plastic contained in one of the tempered glasses with energy saving of 130 ° C or less, or heating temperature of 130-150 ° C and heating time of 10 minutes or less And an excellent effect of obtaining heat resistance.

Further, the adhesive for tempered glass according to the second aspect of the present invention is characterized in that the plastic plate-shaped simple substance is polycarbonate (PC).
Even when a part of the structure of the tempered glass includes a plate-shaped simple substance made of PC having high transparency, an excellent effect that it can be bonded with high strength without thermal deformation can be obtained.

Furthermore, the adhesive for tempered glass according to the third aspect of the present invention is characterized in that the plastic plate-shaped simple substance is polyethylene terephthalate (PET). Even when a plate-shaped simple substance made of PET having high transparency is included, an excellent effect is obtained in that it can be bonded with high strength without thermal deformation.

Further, in the method for forming a tempered glass according to the present invention, the organic peroxide blended with EVA together with a crosslinking aid and an adhesion promoter has a 10-hour half-life temperature of 10%.
Since a plate-like object made of a thermosetting resin having a temperature of 5 ° C. or less is interposed between at least one plate-like unit made of plastic and heated and cured, the heating temperature is 130 ° C. or less, or , Heating temperature is 130 ~ 150
It is possible to harden the plastic contained in one of the tempered glasses without deforming it with energy saving of heating time within 10 minutes at ° C and efficiently form a tempered glass with high adhesive strength, transparency and heat resistance. This is an excellent effect.

Further, in the method for forming a tempered glass according to the invention of claim 6, since the plastic plate-like element is made of polyethylene terephthalate (PET), a part of the structure of the tempered glass is provided. Even when a plate-like simple substance made of PET having a high transparency is included, it is possible to obtain an excellent effect that it can be bonded as high strength without thermal deformation to form a laminate.

[Brief description of the drawings]

FIG. 1 is a schematic enlarged cross-sectional view of a tempered glass formed using an adhesive of the present application.

FIG. 2 is a diagram showing a table of a temperature rise test result according to an example.

FIG. 3 is a diagram showing a table of a temperature rise test result according to a comparative example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Adhesive of this application 2 Plate-like simple substance (GL) 3 Plate-like simple substance (PC or PET) S Tempered glass GL Glass PC Polymethyl methacrylate PET Polyethylene terephthalate

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Shizuo Shimizu 4-2-16-1 Nihonbashi Muromachi, Chuo-ku, Tokyo Inside High Seat Industry Co., Ltd. (72) Inventor Yutaka Kanagawa 4-2-16-1 Nihonbashi Muromachi, Chuo-ku, Tokyo No. High Seat Industries Co., Ltd. (72) Inventor Izumi Komatsuzaki 4-2-1 Nihonbashi Muromachi, Chuo-ku, Tokyo High Seat Industry Co., Ltd. F-term (reference) 4F211 AA10 AA24 AA28 AA36 AB03 AB04 AD04 AD05 AD08 AG01 AG03 AH47 TA04 TC02 TD11 TH06 TH22 TN42 TN49 TN52 TN56 TQ07 4J040 DA051 DE031 FA062 FA102 FA202 GA03 GA08 HB41 HD35 HD36 JA08 JA09 JB02 KA16 LA01 LA05 LA06 LA08 LA10 MA05 MB05

Claims (6)

[Claims] 1. A plate-like adhesive for tempered glass, which is interposed between plate-like single bodies, at least one of which is plastic, and heat-cured to bond between layers, comprising ethylene-
It is made of a thermosetting resin in which an organic peroxide, a crosslinking assistant, and an adhesion promoter are blended with a vinyl acetate copolymer, and the 10-hour half-life temperature of the organic peroxide is 105 ° C. or less. Adhesive for tempered glass. 2. The tempered glass adhesive according to claim 1, wherein the plastic plate-shaped simple substance is polycarbonate. 3. The plastic plate-shaped simple substance is polyethylene terephthalate.
3. The adhesive for tempered glass according to 1.). 4. A plate made of a thermosetting resin having a 10-hour half-life temperature of 105 ° C. or less of an organic peroxide compounded with an ethylene-vinyl acetate copolymer together with a crosslinking aid and an adhesion promoter, A method for forming a tempered glass, wherein at least one of the plastics is interposed between plate-like single bodies and is cured by heating. 5. The method for forming a tempered glass according to claim 4, wherein the plastic plate-shaped simple substance is polycarbonate. 6. The plastic plate-shaped simple substance is polyethylene terephthalate.
3. The method for forming a tempered glass according to item 1.