JPH04362044A - Uv absorbing sandwich glass - Google Patents

Abstract

PURPOSE:To provide sandwich glass having UV absorbing ability as well as excellent shock and piercing resistances and high safety. CONSTITUTION:Thermosetting resin prepd. by blending an ethylene-vinyl acetate copolymer with a hydrocarbon resin, an org. peroxide, a compd. contg. an acryloyl group, a silane coupling agent and a UV absorber is held between glass sheets and integrated by curing to obtain UV absorbing sandwich glass having excellent UV absorbing performance as well as excellent shock and piercing resistances proper to sandwich glass.

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 and 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 the following problems. Was. ■
Since 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 particularly in a temperature range exceeding room temperature, that is, above about 30° C., penetration resistance deteriorates 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] After further study, we developed a new laminated glass that completely avoids and overcomes the defects of conventional laminated glass, which is a thermosetting glass made by blending hydrocarbon resin and organic peroxide with ethylene-vinyl acetate resin. We proposed a laminated glass using resin (Japanese Patent Application No. 1-318921 (hereinafter referred to as the "prior application")).

[0005]

[Problems to be solved by the invention] The laminated glass of the above-mentioned prior application has the original performance of laminated glass, such as being difficult to penetrate by impact objects, being highly safe, being resistant to scattering of fragments, and being useful in preventing intrusion and theft. However, in recent years, as buildings and residences have become more sophisticated and intelligent, there has been a need for anti-stain performance due to ultraviolet rays, which is required to prevent fading of furniture, curtains, carpets, tatami mats, etc., and to prevent display products such as show windows from fading. It was not possible to expect ultraviolet absorption performance for the purpose of protection.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminated glass having excellent impact resistance and penetration resistance as well as ultraviolet absorption performance.

[0007]

[Means for Solving the Problems] The ultraviolet absorbing laminated glass according to claim 1 is a laminated glass made by integrally curing a thermosetting resin interposed between glass plates, wherein the thermosetting resin is ethylene- A vinyl acetate copolymer, one or more selected from the group consisting of a hydrocarbon resin, an organic peroxide, an acryloxy group-containing compound, a methacryloxy group-containing compound, and an aryl group-containing compound, a silane coupling agent, and It is characterized by containing an ultraviolet absorber.

The present invention will be explained in detail below. First, the thermosetting resin interposed between the glasses will be explained. The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 10 to 50% by weight, particularly 1
It is preferably 5 to 40% by weight. If the vinyl acetate content is less than 10% by weight, the resin obtained will not have sufficient transparency when crosslinked and cured at high temperatures;
If the weight percentage exceeds the impact resistance of laminated glass,
It tends to lack penetration resistance.

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.

[0012] Such a 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.

[0013] 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 are 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, the alcohol residue of the ester is a methyl group,
In addition to alkyl groups such as ethyl, dodecyl, stearyl, and lauryl, cyclohexyl, tetrahydrofurfuryl, aminoethyl, 2-hydroxyethyl, 3-hydroxypropyl, and 3-chloro-2- Examples include hydroxypropyl group. Furthermore, esters with polyfunctional alcohols such as ethylene glycol, triethylene glycol, and polyethylene glycol can also be used.

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

[0016] 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 is 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)- Examples include γ-aminopropyltrimethoxysilane. 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, any known ultraviolet absorber can be used to impart ultraviolet absorbing properties, but it is possible to use any known ultraviolet absorber without impairing the adhesiveness of the resulting resin to glass. Benzophenone-based and benzotriazole-based ultraviolet absorbers are preferred because they cause extremely little yellowing. As ultraviolet absorbers, 2-hydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2,2
'-dihydroxy-4-methoxybenzophenone, 2-
Benzophenones such as hydroxy-4-n-octoxybenzophenone, 2-[2'-hydroxy-3'-(
3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 2
Benzotriazole-based compounds such as -(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole are particularly preferred. The amount of the ultraviolet absorber added is preferably 5 parts by weight or less per 100 parts by weight of the ethylene-vinyl acetate copolymer. If the amount added exceeds 5 parts by weight, surface bleeding may occur in the resin, resulting in poor adhesion to glass.

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 the above-mentioned components according to a conventional method.

[0021] In order to produce the ultraviolet absorbing laminated glass of the present invention using the thermosetting resin thus produced, a predetermined amount of the thermosetting resin is interposed between the glasses according to a conventional method. It is cured at the curing temperature of the resin and integrated with the glass.

The ultraviolet absorbing laminated glass of the present invention has excellent impact resistance and penetration resistance, and is extremely safe even if it is broken by external force. When used as a window in a house, etc., it can prevent fading of furniture, curtains, carpets, tatami mats, etc., and when used as a show window, it can protect displayed products.

[0023]

[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.

Moreover, in the present invention, since the resin also contains an ultraviolet absorber, it is possible to impart ultraviolet absorbing performance to the laminated glass. In particular, as a UV absorber,
When benzophenone-based or benzotriazole-based products are used, they do not cause yellowing of the resin over time or poor adhesion, and can ensure transparency comparable to glass and sufficient adhesion to glass. , is extremely advantageous.

[0025]

[Examples] The present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. The ethylene-vinyl acetate copolymer and hydrocarbon resin used are as follows. Ethylene-vinyl acetate copolymer: "Ultracene 634"
” (manufactured by Tosoh Corporation (trademark)) Vinyl acetate content = 2
6% by weight Hydrocarbon resin: "Alcon M-100" (manufactured by Arakawa Chemical Co., Ltd. (trademark)) Alicyclic hydrocarbon resin with a weight average molecular weight of 700 In addition, the ultraviolet absorbers ■ to ■ are the following compounds . ■: 2-hydroxy-4-methoxybenzophenone ■:
2,2'-dihydroxy-4,4'-dimethoxybenzophenone ■: 2-hydroxy-4-n-doderoxybenzophenone ■: 2,4-dihydroxybenzophenone ■: 2,2'
-dihydroxy-4-methoxybenzophenone ■: 2-hydroxy-4-n-octoxybenzophenone ■: 2-[2'-hydroxy-3'-(3", 4", 5
",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole ■: 2-(2'-hydroxy-3',5'-t-amylphenyl)benzotriazole Examples 1 to 8 Table 1 shows Each component was mixed in a roll mill heated to 80° C. in the ratio shown to prepare a thermosetting resin.

A sheet with a thickness of 0.76 mm was produced using a press using the obtained thermosetting resin, and the sheet was sandwiched between two pieces of float glass with a thickness of 3 mm that had been previously washed and dried. This product was placed in a rubber bag, degassed under vacuum, and pre-pressed at a temperature of 80°C. 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. ■ Impact resistance test: As a result of shot-back testing of laminated glass in accordance with JIS R3205 (1983), the drop height was 1.
Those in which no cracks were observed in any of the four samples at 20 cm were designated as "no cracks." ■ Transparency Test The haze value was measured using a haze meter manufactured by Suga Test Instruments Co., Ltd. (2) Ultraviolet Absorption Characteristics As shown in Figure 1, the UV cut wavelength was determined from the ultraviolet absorption spectrum. ■ Change in degree of coloration due to heat aging Each sample whose haze value was measured was divided in half, and one half was
Heat in an oven set at 50°C for 5 hours, and after cooling,
The samples before and after heating were arranged on white paper, and the progress of yellowing was visually observed. Comparative Example 1 A laminated glass was obtained in the same manner as in Example 1, except that no ultraviolet absorber was used and the formulation shown in Table 1 was used, and the test was conducted in the same manner. The results are shown in Table 1.

As is clear from Tables 1 and 2, the product of Comparative Example 1, which does not contain an ultraviolet absorber, cannot block ultraviolet rays.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

Effects of the Invention As detailed above, according to the ultraviolet absorbing laminated glass of the present invention, the ultraviolet absorbing laminated glass has excellent impact resistance and penetration resistance, which are the inherent properties of laminated glass, and also has excellent ultraviolet absorbing performance. is provided.

[Brief explanation of drawings]

FIG. 1 is a graph showing a method of extrapolating a UV cut wavelength using an ultraviolet absorption spectrum.

Claims (1)

[Claims] Claim 1: A laminated glass made by integrally curing a thermosetting resin interposed between glass plates, wherein the thermosetting resin contains an ethylene-vinyl acetate copolymer, a hydrocarbon resin, and an organic peroxide. , an acryloxy group-containing compound, a methacryloxy group-containing compound, and an aryl group-containing compound, one or more selected from the group consisting of a silane coupling agent, and an ultraviolet absorber. Laminated glass.