JPH06166551A - Laminated glass - Google Patents

Abstract

PURPOSE:To obtain a laminated glass excellent in impact resistance and penetration resistance. CONSTITUTION:A thermosetting resin comprising ethylene-vinyl acetate copolymer and an organic peroxide is applied between glass plates and integrated. The resin layer is thermally cured to give an adhesive force of 0.3-3.5kg/inch between the thermosetting resin and glass plates of the laminated glass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass used for windshields and side windows of automobiles, window glass for buildings, soundproof glass and the like.

[0002]

2. Description of the Related Art Conventionally, polyvinyl butyral resin has been most commonly used as an intermediate layer of laminated glass, but since polyvinyl butyral resin is a thermoplastic resin, it has the following problems.

(1) Since the softening point is relatively low, the glass plate may be displaced or bubbles may be generated by heat after laminating.

(2) Since it is easily affected by moisture, when left in a high humidity atmosphere for a long period of time, whitening gradually occurs from the peripheral portion and a decrease in adhesive strength with glass is recognized.

(3) Impact puncture resistance depends on temperature, and especially in a temperature range exceeding room temperature, that is, at about 30 ° C. or higher, the puncture resistance is sharply reduced.

In order to solve the above problems of the polyvinyl butyral type resin, the present inventors interpose a thermosetting resin in which an ethylene-vinyl acetate copolymer is mixed with an organic peroxide between glass plates. A laminated glass in which the thermosetting resin layer is integrally cured by thermosetting is proposed, and a patent application has been previously filed (for example, JP-A-57-196747).

It has been conventionally known that the impact fracture resistance and penetration resistance of laminated glass are related to the adhesive force between the resin layer and the glass interposed between the glass plates, and the adhesive force is strong. If it is too much, shock cannot be absorbed at the interface between the glass and the resin layer, so the impact fracture resistance and penetration resistance as laminated glass are insufficient, and if the adhesive strength is too weak, the glass peels from the resin layer at the time of impact. However, there is a problem that the function as a safety glass is not fulfilled.

In the case of the above-mentioned thermosetting resin in which an ethylene-vinyl acetate copolymer is blended with an organic peroxide, it is difficult to appropriately control the adhesive force between the thermosetting resin and the glass, and therefore, the resistance to fracture is high. The characteristics were insufficient. Conventionally, the adhesive strength improver used in this system was a silane coupling agent represented by the following general formula (I).

[0009]

[Chemical 1] (In the formula, A represents a reactive functional group such as a vinyl group, an epoxy group, an amino group, and a methacryloxy group, and OR represents an alkoxy group.)

The silane coupling agent has a trifunctional alkoxy group in order to firmly adhere the silanol group on the glass surface to the resin layer, and the reactive functional group is also reactive with the above copolymer. The high one was used. Therefore, it is difficult to effectively control the adhesive force.

[0011]

As described above, impact resistance and penetration resistance cannot be said to be sufficient when considering safety, which is one of the great required characteristics of laminated glass.

The object of the present invention is to improve the impact resistance and penetration resistance of conventional laminated glass by controlling the adhesive force between the resin layer and the glass, and to be safe even if it is damaged by the action of external force. To provide a laminated glass.

[0013]

The laminated glass of the present invention comprises a thermosetting resin in which an ethylene-vinyl acetate copolymer is mixed with an organic peroxide, and the thermosetting resin is integrated between the glass plates.
In a laminated glass obtained by thermosetting this resin layer, the adhesive force between the thermosetting resin and the glass is 0.3 kg / inch.
It is characterized by being ~ 3.5 Kg / inch.

That is, the present inventors achieved the object by controlling the adhesive force between the thermosetting resin and the glass within the above range in order to improve the impact resistance and penetration resistance of the laminated glass. Then, the present invention has been completed.

The present invention will be described in detail below. The present inventors effectively adjust the adhesive force between the thermosetting resin and the glass by selecting an adhesive force adjusting agent, and the adhesive force is 0.3 Kg / inch to 3.5 Kg / inch. Within the range, it was possible to obtain a laminated glass exhibiting excellent performance in which impact resistance, penetration resistance, and glass peelability under impact were balanced.

In the present invention, the adhesive strength means that measured by a 180-degree peeling test method using a tensile tester. That is, the resin test piece was adjusted to have a width of 1 inch and a thickness of 0.4 mm, and the glass was washed with a 3 mm float glass to be the bottom surface (the surface that comes into contact with tin in the float glass manufacturing process).
The glass bottom surface and the resin test piece are adhered by using, and the adhesion force between the glass surface and the resin test piece is measured by a 180-degree peel test method at a pulling speed of a tensile tester of 100 mm /
The adhesive strength is measured in minutes.

In the present invention, if the adhesive force between the thermosetting resin and the glass is controlled within the range of 0.3 Kg / inch to 3.5 Kg / inch, the control method is not limited. Examples of the effective control method include a method of appropriately selecting the type and / or the addition amount of the adhesiveness adjusting agent in the thermosetting resin, a method of applying a liquid to the glass surface and adjusting the activity of the glass surface, and the like. be able to.

The method of adjusting the activity of the glass surface is to apply a liquid to the surface of the glass to adjust the reactivity with the thermosetting resin, and then produce laminated glass.
As the liquid, a silane compound such as tetramethoxysilane or tetraethoxysilane that reacts only with the glass surface, or a release agent such as a fluorine compound can be preferably used.

The method of using an adhesive strength adjusting agent is to add a suitable adhesive strength adjusting agent to a resin and to produce a laminated glass using the resin. The adhesive strength adjusting agent is added to the resin. As long as it is a compound capable of effectively controlling the adhesive strength, at least one selected from coupling agents other than silane coupling agents such as silane coupling agents and titanium coupling agents, aluminum coupling agents. A compound can be used, and a silane coupling agent is preferably used. As the silane coupling agent, the number of (1) alkoxy groups (OR) should be reduced as compared with the conventional silane coupling agent represented by the general formula (I). (2) The reactive functional group (A) contains a resin having a weak reactivity with the resin. A compound satisfying at least one of the above two points is preferably used.

Specific examples of the above-mentioned silane coupling agent include trimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, diethoxysilane, methyltrimethoxysilane, methoxy (dimethyl) vinylsilane, ethoxytrimethylsilane, Diethoxymethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, diethoxydimethylsilane, triethoxysilane, diethoxy (methyl) vinylsilane, butyltrimethoxysilane, methyltriethoxysilane, 3-aminopropyldimethylethoxy Silane, diethoxydivinylsilane, diethoxydiethylsilane, ethyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3- (2-aminoethylaminopropyl) dimethoxy Methylsilane, triethoxy silane, hexyl trimethoxy silane, 3-methacryloxypropyl dimethoxymethyl silane, dimethylethoxy-3-glycidoxypropyl silane, methoxy tripropyl silane, methyl tripropoxysilane, 3
-Dimethylaminopropyldiethoxymethylsilane, dimethyl-p-anisylvinylsilane, diethoxy-3-
Glycidoxypropylmethylsilane, pentyltriethoxysilane, diethoxydodecylmethylsilane, diethoxymethyloctadecylsilane, octadecyltriethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane and the like. To be Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditrityl). Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl virophosphate) oxyacetate titanate, bis (dioctyl virophosphate) ethylene titanate, isopropyl Trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylate Titanate, isopropyl tri (dioctyl phosphate)
Examples thereof include titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, and the like. Examples of the aluminum coupling agent include compounds represented by acetoalkoxyaluminum isopropylate.

The blending amount of the adhesiveness regulator used in the present invention is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 10 to 50.
It is preferably in the range of 15% by weight, in particular 15-40% by weight.
If the vinyl acetate content is less than 10% by weight, the transparency of the resin obtained when it is crosslinked and cured at high temperature is not sufficient, and conversely if it exceeds 50% by weight, the impact resistance and the resistance to resistance when laminated glass is used. Penetration tends to be insufficient.

As the organic peroxide used as a curing agent for the ethylene-vinyl acetate copolymer in the production of the laminated glass of the present invention, any organic peroxide can be decomposed at a temperature of 100 ° C. or higher to generate radicals. It can be used.
In consideration of stability during blending, it is preferable that the decomposition temperature with a half-life of 10 hours is 70 ° C. or higher.
5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t-butylperoxide, t-butylcumylperoxide , 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4
-Bis (t-butylperoxy) valerate, 2,2-
Bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxy Examples thereof include benzate and benzoyl peroxide. As the organic peroxide, at least one of them is selected, and the blending amount thereof is ethylene-vinyl acetate copolymer 1
It is preferably 0.1 to 5 parts by weight with respect to 00 parts by weight.

In the present invention, in order to improve the initial modulus of the ethylene-vinyl acetate resin and enhance the penetration resistance,
At least one compound selected from the group consisting of acryloxy group-containing compounds, methacryloxy group-containing compounds and allyl group-containing compounds can be added as a curing aid.

Among these compounds, as the acryloxy group-containing compound and the methacryloxy group-containing compound, an acrylic acid derivative or a methacrylic acid derivative, for example, an ester thereof can be used. In this case, as the alcohol residue of the ester, in addition to alkyl groups such as methyl group, ethyl group, dodecyl group, stearyl group and lauryl group, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group Group, 3-hydroxypropyl group, 3-chloro-2-hydroxypropyl group and the like. In addition, ethylene glycol,
Esters with polyfunctional alcohols such as triethylene glycol and polyethylene glycol can also be used in the same manner.

As the allyl group-containing compound, diallyl phthalate, diallyl fumarate, diallyl maleate, triallyl isocyanurate and triallyl cyanurate are preferably used.

The compounding amount of these compounds is ethylene-
It is preferably 50 parts by weight or less with respect to 100 parts by weight of the vinyl acetate copolymer.

In the present invention, a hydrocarbon resin can be added to the ethylene-vinyl acetate copolymer as a resin hardness adjusting agent.

The hydrocarbon resin used in the present invention may be either a natural resin type or a synthetic resin type. As the natural resin type, rosin, rosin derivative, terpene type resin and the like are preferably used. Among these, gum resins, tall oil resins, wood resins and the like can be used as the rosin. As the rosin derivative, those obtained by hydrogenating, disproportionating, polymerizing, esterifying, or metallizing the above rosin can be used. As a terpene resin, α-
In addition to terpene resins such as pinene and β-pinene, terpene phenol resins and the like can be used. Further, other natural resins such as dammar, copal and shellac may be used.

On the other hand, petroleum-based resins, phenol-based resins, xylene-based resins and the like are preferably used as synthetic resin-based resins. Of these, petroleum-based resins include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, hydrogenated petroleum resins, pure monomer petroleum resins, and coumarone indene resins. Can be used. As the phenol resin, an alkylphenol resin, a modified phenol resin or the like can be used. As the xylene-based resin, a xylene resin, a modified xylene resin, or the like can be used.

The amount of the hydrocarbon resin added in the present invention is
1 to 100 parts by weight of ethylene-vinyl acetate copolymer
To 100 parts by weight, preferably 2 to 80 parts by weight.

As the hydrocarbon resin, those having a weight average molecular weight of 200 to 50,000 can be used, and those having a weight average molecular weight of 200 to 10,000 are preferably used.

In the present invention, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone or methylhydroquinone is added to ethylene-vinyl acetate copolymer for the purpose of improving the stability of the resin layer. It can be added in an amount of 5 parts by weight or less based on 100 parts by weight of the coalescence. In addition to these additives, a colorant, an ultraviolet absorber, an antiaging agent, a discoloration preventing agent, etc. can be added if necessary.

Further, in the present invention, an antioxidant can be used for the purpose of further improving light stability and heat stability. Examples of this antioxidant include phenols, sulfur, phosphorus, amines, hindered phenols, hindered amines, and hydrazines, with hindered amines being particularly preferred.

[0035]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

[Examples] (Adhesive force measuring method) A 180-degree peel test is conducted by a tensile tester. The resin layer of the adhesive strength measurement sample was cut into a width of 1 inch, and a glass part and a resin layer were pulled out at a pulling speed of 100 mm / min using a tensile tester: Autograph AG-10TB manufactured by Shimadzu Corporation. 180 degree peeling test is performed to obtain the adhesive force (Kg / inch).

(Impact resistance evaluation method) JIS R3205
According to the (1983) shotback test method, a drop height of 75 cm was used to perform a shotback test using four test pieces per sample to confirm the presence or absence of cracks.

(Preparation and Evaluation of Samples) The respective components were blended in the proportions shown in Table 1 and mixed by a roll mill heated to 80 ° C. to prepare thermoplastic resins for Products 1 to 3 of the present invention. This resin composition was made into a 0.76 mm thick sheet and a 0.4 mm thick sheet by using a press. A 0.76 mm thick sheet is sandwiched between two 3 mm thick float glasses that have been washed and dried in advance to form a laminate for laminated glass. A 0.4 mm thick sheet is prepared in advance. The resin sheet is laminated on the bottom surface side of the float glass having a thickness of 3 mm that has been washed and dried to form a laminate for measuring the adhesive strength,
Then, these were put in a rubber bag, deaerated under vacuum, and pre-bonded at a temperature of 80 ° C. Next, the pre-bonded sample was placed in an oven and treated at 130 ° C. for 30 minutes.

Table 1 shows the results of measuring the adhesive force of the laminates for measuring the adhesive force of the products 1 to 3 of the present invention according to the above-mentioned adhesive force measuring method.

According to the above shot-back test method,
Table 1 shows the results of evaluating the obtained laminated glasses of the present invention products 1 to 3.

(Adjustment and Evaluation of Comparative Product) A thermosetting resin for a comparative product was prepared in the same manner as the product of the present invention except that 3-methacryloxypropylmethoxysilane was used as an adhesive force adjusting agent, and the comparison product was combined. A glass and a sample for measuring the adhesive strength were produced and evaluated. The results are shown in Table 1.

(Results) As shown in Table 1, the products of the present invention 1 to
The laminated glass of 3 showed good impact resistance and penetration resistance with no cracks observed in all four specimens, but the comparative example product had a crack of 60 mm in length and lacked impact resistance. Was confirmed.

[0043]

[Table 1]

[0044]

Since the laminated glass of the present invention has the above-mentioned constitution, it has an excellent effect that it is excellent in impact resistance and penetration resistance and is safe even if it is broken by the action of external force.

Claims (1)

[Claims] 1. A laminated glass in which a thermosetting resin containing an ethylene-vinyl acetate copolymer and an organic peroxide is interposed and integrated between glass plates, and the resin layer is heat-cured. The adhesive force between the resin and the glass is 0.
Laminated glass characterized in that it is 3 kg / inch to 3.5 kg / inch.