JPH04362045A - Laminated glass - Google Patents

Abstract

PURPOSE:To improve the shock and piercing resistances of laminated glass, to reduce a shock given to a man by hitting against the glass and to render sound insulating performance. CONSTITUTION:An org. resin sheet is interposed between middle layers of thermosetting resin prepd. by blending an ethylene-vinyl acetate copolymer with a hydrocarbon resin and an org. peroxide and the resulting laminate is held between glass sheets and integrated by curing. Since the hydrocarbon resin is added, laminated glass having improved shock and piercing resistances, reducing a shock given by hitting and also having satisfactory sound insulating property can be obtd. Since the org. resin sheet is interposed, high funcition can be rendered.

Description

[Detailed description of the invention]

0001

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

0002

[Prior Art] Conventionally, polyvinyl butyral resin has been most commonly used as the intermediate layer of laminated glass, but since polyvinyl butyral resin is a thermoplastic resin, it has had the following problems. . ■ Because the softening point is relatively low, the glass plates may shift due to heat or bubbles may form after lamination. ■ Because it is easily affected by moisture, if it is left in a high humidity atmosphere for a long period of time, it will gradually turn white from the periphery and the adhesive strength with glass will decrease. (2) Impact resistance to fracture depends on temperature, and in particular, in a temperature range exceeding room temperature, that is, above about 30° C., penetration resistance decreases rapidly.

[0003] In order to solve the above-mentioned problems with polyvinyl butyral resins, the present inventors integrated a thermosetting resin made of ethylene-vinyl acetate copolymer with an organic peroxide by interposing it between glass plates. proposed a laminated glass made by thermosetting a thermosetting resin layer, and filed a patent application (for example, Japanese Patent Application Laid-open No. 57-196747).

[0004] The present inventors also inserted a film made of organic resin between the intermediate layers of laminated glass to improve the impact resistance and penetration resistance of the laminated glass, and also added a design to the organic resin film. He proposed a laminated glass that was coated with heat rays and colored to give it properties of reflecting and absorbing heat rays, and filed a patent application earlier (Japanese Unexamined Patent Publication No. 60-226436).
. This laminated glass utilizes the property that the intermediate layer made of ethylene-vinyl acetate copolymer adheres not only to glass but also to organic resin films with very good adhesion.

[0005]

[Problems to be Solved by the Invention] However, the problem with conventional laminated glass is that, first, when a strong impact that would break the glass is applied to the laminated glass, the repulsive force as a laminated glass structure is It has been pointed out that because it is so strong, when it is used, for example, on the windshield of a car, it causes a large impact on the head of an occupant.

Second, when an organic resin film is inserted into the intermediate layer of laminated glass, it is expected to block out sound, that is, to function as soundproof glass, but in reality, this effect is insufficient. It was also pointed out that The soundproofing performance of laminated glass is such that when used in automobile glass, it blocks out external noise such as engine noise to create a comfortable driving environment, and when used in building windows, it blocks out external noise such as engine noise and creates a comfortable driving environment. Recently, it has become particularly important to ensure a comfortable living environment by blocking noise as well as sounds generated from inside the room.

The present invention has been made in view of the above-mentioned conventional circumstances, and when used for automobile window glass or building window glass, there is little impact when a person collides with it, and
The aim is to provide high-performance laminated glass with excellent sound insulation and soundproofing performance.

[0008]

[Means for Solving the Problems] The laminated glass according to claim 1 has a laminate formed by interposing an organic resin film between at least two intermediate layers made of thermosetting resin, interposed between glass plates, The laminated glass in which the intermediate layer is hardened and integrated is characterized in that the thermosetting resin is a mixture of an ethylene-vinyl acetate copolymer, a hydrocarbon resin, and an organic peroxide.

The present invention will be explained in detail below. Materials for the organic resin film used in the present invention include polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polymethyl methacrylate, and polyvinyl butyral. , ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, metal ion crosslinked ethylene-methacrylic acid copolymer,
Examples include polystyrene, polyurethane, polycarbonate, cellophane, etc., but polyester is most preferred from the viewpoints of film smoothness, surface gloss (required for forming thin metal films by vapor deposition, etc.), strength, workability, etc. It's a film.

[0010] In the present invention, in order to improve decorativeness, designs such as various patterns, pictures, photographs, characters, symbols, etc. are applied to the whole or part of such an organic resin film to impart heat ray absorption properties. It is possible to apply a thin film of metal or metal oxide by vapor deposition or other means to add color to the laminated glass, or to apply a thin film of metal or metal oxide to provide heat ray reflective effect or conductivity. Because of its presence in the intermediate layer, the designs, colors, and thin films applied are extremely durable.

In the present invention, methods for forming a thin film of metal or metal oxide on an organic resin film include methods such as vapor deposition, sputtering, and ion plating. The main components are indium oxide, chromium oxide, gold, palladium, tin, cadmium oxide, silver, platinum, aluminum, copper,
Copper iodide, tin oxide, antimony tin oxide, titanium oxide, etc. are used, and two or more of these may be used in combination.

In the present invention, the glass plate used may be directly coated with a thin film of the metal or metal oxide described above in order to impart a heat ray reflecting or absorbing function. In this case, a transparent film can be used as the organic resin film.

Next, the thermosetting resin forming the intermediate layer will be explained. The thermosetting resin according to the present invention is made by blending an ethylene-vinyl acetate copolymer with a hydrocarbon resin and an organic peroxide.

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

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

On the other hand, as synthetic resins, petroleum-based resins, phenol-based resins, xylene-based resins, etc. are preferably used. Among these, petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, hydrogenated petroleum resins, pure monomer petroleum resins, coumaron indene resins, etc. can be used. As the phenolic resin, alkylphenol resin, modified phenol resin, etc. can be used. As the xylene resin, xylene resin, modified xylene resin, etc. can be used.

The hydrocarbon resin preferably has a weight average molecular weight of 200 to 50,000, particularly 200 to 10,000.

Such hydrocarbon resin is preferably added in an amount of 1 to 100 parts by weight, particularly 2 to 80 parts by weight, per 100 parts by weight of the ethylene-vinyl acetate copolymer.

[0019] The organic peroxide is used as a curing agent for ethylene-vinyl acetate copolymer.
Any material that decomposes at the above temperature to produce radicals can be used. When considering the stability during blending, it is preferable that the decomposition temperature at a half-life of 10 hours is 70°C or higher. Specifically, 2,5-dimethylhexane-2
, 5-dihydroperoxide, 2,5-dimethyl-
2,5-di(t-butylperoxy)hexane-3, di-t-butylperoxide, t-butylcumyl peroxide, 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-butyl peroxybenzoate, benzoyl peroxide and the like. These organic peroxides can be used alone or in combination of two or more, and the amount added is 0.1 to 5 parts by weight per 100 parts by weight of the ethylene-vinyl acetate copolymer. It is preferable that

In the present invention, at least one compound selected from the group consisting of an acryloxy group-containing compound, a methacryloxy group-containing compound, and an aryl group-containing compound is used in order to improve the initial modulus of the obtained resin and enhance the penetration resistance.
Seed compounds may be added as curing aids. Among these compounds, acrylic acid or methacrylic acid derivatives, such as esters thereof, can be used as the acryloxy group-containing compound and the methacryloxy group-containing compound. In this case, alcohol residues in the ester include alkyl groups such as methyl, ethyl, dodecyl, stearyl, and lauryl, as well as cyclohexyl, tetrahydrofurfuryl, aminoethyl, and 2-hydroxyethyl groups. group, 3-hydroxypropyl group, 3-chloro-
Examples include 2-hydroxypropyl group. Furthermore, ethylene glycol, triethylene glycol,
Esters with polyfunctional alcohols such as polyethylene glycol can be used as well.

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

[0022] The blending amount of these compounds is ethylene-
The amount is preferably 50% by weight or less based on the vinyl acetate polymer.

Furthermore, in the present invention, a silane coupling agent may be added as an adhesive force improver in order to further enhance the adhesive force between the ethylene-vinyl acetate resin and glass. In this case, known silane coupling agents are used, such as γ-chloropropylmethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-methacryloxypropyl trimethoxysilane,
β-(3,4-ethoxycyclohexyl)ethyl-trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl)-γ-aminopropyltrimethoxysilane and the like can be mentioned. It is sufficient that the amount of these silane coupling agents is 5% by weight or less based on the ethylene-vinyl acetate copolymer.

In the present invention, if necessary, for the purpose of improving the stability of the resin, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, or methylhydroquinone is added to the ethylene-vinyl acetate copolymer. It can also be added in an amount of 5% by weight or less. Furthermore, colorants, ultraviolet absorbers, anti-aging agents, anti-discoloration agents, etc. can also be added to these additives as necessary.

The thermosetting resin used in the present invention is easily prepared by mixing predetermined amounts of each of the above components in accordance with a conventional method.

In order to produce the laminated glass of the present invention using the thermosetting resin thus produced, a sheet of the thermosetting resin is formed according to a conventional method, and the above-mentioned layer is formed between the two sheets. An organic resin film is interposed to form a laminate, this laminate is interposed between glasses, and is cured at the curing temperature of the thermosetting resin to integrate the glass and the organic resin film.

[0027] The laminated glass of the present invention is a high-performance laminated glass that has excellent impact resistance and penetration resistance, and has little impact when collided with objects such as humans, and has excellent soundproofing performance. It is extremely useful as windshields and side glasses for automobiles, window glass for buildings, etc.

[0028]

[Function] When used in laminated glass, the thermosetting resin obtained by blending ethylene-vinyl acetate copolymer with a hydrocarbon resin and an organic peroxide has extremely high resistance due to the effect of the addition of the hydrocarbon resin. Shows impact resistance and penetration resistance.

Furthermore, according to the present invention, the impact on the human body upon collision with an object can be reduced, and the soundproofing and sound insulation functions are also improved. Furthermore, by adding a design, coloring, metal thin film, etc. to this organic resin film, a multifunctional laminated glass having decorative properties, heat ray absorption or reflection function, electrical conductivity, etc. can be obtained.

[0030]

[Example] Example 1 Thermosetting resins were prepared by mixing each component in the proportions shown in Table 1 in a roll mill heated to 80°C.

Two sheets each having a thickness of 0.4 mm were produced from the obtained thermosetting resin using a press. A 100 μm thick transparent polyester film was sandwiched between these two sheets to form a laminate. This laminate was sandwiched between two pieces of 3 mm thick float glass that had been previously washed and dried. Place this in a rubber bag and vacuum degas it to 80°C.
Preliminary pressure bonding was carried out at a temperature of . Thereafter, this pre-press bonded laminated glass was placed in an oven and treated at 130° C. for 30 minutes. All of the obtained laminated glasses had high transparency and no optical distortion.

The following tests were conducted on each laminated glass, and the results are shown in Table 2 and FIG. ■ Drop ball test Based on JIS R 3025, a 2.25 kg steel ball was dropped onto the surface of the laminated glass from the height shown in Table 2, and the state of fracture was observed. The presence or absence of steel balls penetrating the laminated glass and the occurrence of cracks in the membrane were investigated. In addition, the height of the steel ball flying up after it collided with the laminated glass was measured.

[0033] Soundproofing test A sample of 300 mm x 25 mm was cut out from the laminated glass, and the loss coefficient was measured. The device used for the measurement was a loss coefficient measurement device manufactured by Toyo Technica Co., Ltd., and the measurement frequencies were 500 Hz, 1000 Hz, and 2000 Hz.
The temperature was measured from -20°C to +60°C, and the results are illustrated. Note that the frequency band from 500 hertz to 2000 hertz is a frequency band that humans can identify as sound in a living environment, and the larger the loss coefficient, the higher the soundproofing effect.

[0034]

[Table 1]

*1: Ethylene-vinyl acetate copolymer (vinyl acetate content = 26% by weight) (manufactured by Tosoh Corporation (trademark)) *2: Hydrocarbon resin (alicyclic hydrocarbon with a weight average molecular weight of 700) Resin) (manufactured by Arakawa Chemical Industry Co., Ltd. (trademark))

[
0036

[Table 2]

Comparative Example 1 A laminated glass was obtained in the same manner as in Example 1 except that the formulation shown in Table 1 was used, and the tests were conducted in the same manner. The results are shown in Table 2.
and shown in Figure 2.

[0038] As is clear from Tables 1 and 2, the laminated glass of the present invention has excellent fracture resistance when colliding with an object, and has a small spring-up height, so it can reduce the impact on the human body when colliding with an object. can do. In addition, looking at the loss coefficient measurement results in Figures 1 and 2, Example 1 has a larger loss coefficient at a living environment temperature of around 20°C at any frequency, and is also less effective in terms of soundproofing performance. It is clear that the laminated glass of the invention is highly effective.

[0039]

[Effects of the Invention] As detailed above, the laminated glass of the present invention not only has excellent impact resistance and penetration resistance, but also has less impact when objects such as humans collide with it, and has excellent soundproofing performance. We also offer superior high-performance laminated glass.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the measurement results of the loss coefficient of the laminated glass of Example 1.

FIG. 2 is a graph showing the measurement results of the loss coefficient of the laminated glass of Comparative Example 1.

Claims (1)

[Claims] 1. A laminated glass comprising a laminate formed by interposing an organic resin film between at least two intermediate layers made of a thermosetting resin, interposed between glass plates, and the intermediate layers being cured and integrated. In, the thermosetting resin is
A laminated glass characterized by blending an ethylene-vinyl acetate copolymer with a hydrocarbon resin and an organic peroxide.