JP3990782B2 - Laminated glass intermediate film forming resin composition, laminated glass interlayer film and laminated glass - Google Patents

Description

【００３５】
上記で得られた樹脂組成物を、２枚のポリエチレンテレフタレートフィルムの間に挟んで、１２０℃、５分の条件でプレス成形し、放冷後、得られた中間膜をフィルムより剥離して、厚み０．８ｍｍの中間膜を得た。
【００３６】
＜合わせガラスの作製＞
予め洗浄乾燥しておいた２枚の３ｍｍ厚のフロートガラス板の間に、上記中間膜を挟み、これをゴム袋に入れて真空脱気し、約８０℃の温度で予備圧着する。次いで、この予備圧着ガラスをオートクレーブの中に入れ、圧力５kg/cm²、１５０℃の条件で３０分間加圧処理を行った。
【００３７】
上記のようにして、実施例１〜３及び比較例１の合わせガラスを得た。いずれの合わせガラスも着色が少なく、光学的ゆがみの少ないものであった。
【００３８】
［合わせガラスの評価］
（１）ヘイズ（％）
ＪＩＳ−Ｒ３２１２に記載の方法に従って測定した。その際、ヘイズメータ（スガ試験機（株）製）を用いた。
（２）透過率（％）
上記（１）と同様に測定した。
（３）ＹＩ値
カラーコンピュータ（スガ試験機（株）製）を用いて測定した。
（４）接着力(kgf）
【００３９】
得られた合わせガラスを２５ｍｍ幅の短冊状に裁断し１８０゜ピーリング試験と同様にして引張試験機にて、１００ｍｍ／分の引張速度で剥離強度を測定した。
【００４０】
上記で得られた結果を表２に示す。
【００４１】
【表２】

【００４２】
【発明の効果】
本発明の樹脂組成物から形成される中間膜をガラス板間に挟持してなる合わせガラスは、ガラス板との適度な接着力を有すると共に、耐湿性、透明性に優れ、かつ広い温度範囲で優れた耐貫通性を示す。これは、可塑化されたポリビニルアセタール樹脂系に、有機過酸化物を導入することにより、中間膜の着色が減少し、また有機過酸化物を導入によりポリビニルアセタール樹脂の硬化が促進され接着力の改善、耐貫通性の温度依存性の改善の効果が得られるためと、考えられる。
【００４３】
特に、シランカップリング剤、アクリロキシ基等含有化合物をさらに可塑化されたポリビニルアセタール樹脂系に導入することにより、架橋が行われるため、より一層、接着力、耐貫通性の温度依存性が改善される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a laminated glass, particularly a laminated glass used for a windshield or side glass of an automobile or an aircraft or a window glass of a building, a laminated glass intermediate film, and a resin suitably used for forming a laminated glass intermediate film. Relates to the composition.
[0002]
[Prior art]
Conventionally, laminated glass has been widely used for windshields and side glasses of automobiles, aircraft, and window glass of buildings. Laminated glass usually has a structure in which a resin film (intermediate film) is sandwiched between two glass plates, and has high safety against impacts, etc., and thus is used as safety glass as described above. . That is, when an impact is applied from the outside to the laminated glass, the glass portion is broken, but the interlayer film between the glass plates is not easily broken, and therefore the broken glass is stuck to the interlayer film. Until then, glass fragments are hardly scattered around.
[0003]
In order for the laminated glass to exhibit the function as the safety glass as described above, it is necessary to adjust the adhesion between the glass plate and the interlayer film within a certain range. That is, when the adhesive force between the glass plate and the intermediate film is small, the glass plate damaged by an external impact is easily peeled off and scattered, and when the adhesive force is large, the glass plate and the intermediate film are shocked. At the same time, both tend to break and scatter.
[0004]
Therefore, the interlayer film of the laminated glass has the above-mentioned function, and also requires high transparency itself so as not to lower the transparency of the glass. As an interlayer film of such a laminated glass, a film mainly composed of polyvinyl acetal and a plasticizer is representative, but an interlayer film satisfying the above characteristics at a high level has not been obtained yet.
[0005]
Furthermore, the intermediate film mainly composed of polyvinyl acetal and a plasticizer has the following problems because polyvinyl acetal is a thermoplastic resin. That is, (1) Since it is easy to soften, the glass plate is likely to be displaced or bubbles are likely to be generated due to heat after being bonded to the glass plate. (2) When left in a high humidity atmosphere for a long time, the resin swells due to moisture Therefore, mechanical strength and weather resistance are likely to decrease. (3) Impact resistance is likely to change depending on temperature, and penetration resistance (penetration of laminated glass such as flying objects) is particularly high in the high temperature range exceeding room temperature. There is a problem that a decrease in ease is likely to occur.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a laminated glass having an intermediate film that has an appropriate adhesive force with a glass plate, is excellent in moisture resistance and transparency, and exhibits excellent penetration resistance in a wide temperature range. .
[0007]
Another object of the present invention is to provide an interlayer film of laminated glass that has an appropriate adhesive force with a glass plate, is excellent in moisture resistance and transparency, and exhibits the above characteristics and penetration resistance in a wide temperature range. There is to do.
[0008]
Furthermore, the objective of this invention is providing the resin composition for intermediate film formation of said laminated glass.
[0009]
[Means for Solving the Problems]
The present inventor has repeatedly studied to obtain an interlayer film of laminated glass having an appropriate adhesive force with a glass plate, excellent in moisture resistance and transparency, and having excellent penetration resistance in a wide temperature range. It was. As a result, it has been found that by introducing an organic peroxide into a plasticized polyvinyl acetal resin system, not only adhesive strength, transparency and moisture resistance, but also the temperature dependence of penetration resistance is improved. The invention has been reached. The reason for this is not clear, but is estimated as follows. Transparency is improved by reacting with the introduced organic peroxide and impurities (polymerization catalyst, etc.) that cause color development to change to a non-colored substance. Also, improved adhesion and temperature dependency of penetration resistance. The improvement is considered to be because some cross-linked structure is formed in the polyvinyl acetal resin by the introduction of the organic peroxide, or the curing is accelerated.
[0010]
The present invention relates to a resin composition for forming an interlayer film of laminated glass containing a polyvinyl acetal resin, a plasticizer and an organic peroxide; an interlayer film for laminated glass formed from the resin composition; and an interlayer film comprising a glass plate And a laminated glass sandwiched between a glass plate and a plastic sheet.
[0011]
In the above resin composition, the weight ratio of the polyvinyl acetal resin, the plasticizer and the organic peroxide is preferably in the range of 100: 20 to 50: 0.1 to 10 (resin: plasticizer: peroxide). . Moreover, it is preferable that the said resin composition contains 0.01-5 weight part of silane coupling agents with respect to 100 weight part of polyvinyl acetal resins. Furthermore, the resin composition is at least one selected from the group consisting of an acryloxy group (acryloyloxy group) -containing compound, a methacryloxy group (methacryloyloxy group) -containing compound, and an epoxy group-containing compound with respect to 100 parts by weight of the polyvinyl acetal resin. It is preferable that 0.5-80 weight part is included.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The resin composition for forming an interlayer film of the laminated glass of the present invention contains a polyvinyl acetal resin, a plasticizer, and an organic peroxide as main components.
[0013]
A polyvinyl acetal resin is a thermoplastic resin obtained by condensing a part or all of hydroxyl groups of polyvinyl alcohol with an aldehyde (eg, formaldehyde, acetaldehyde, butyraldehyde). Accordingly, the polyvinyl acetal resin usually has a vinyl alcohol unit, a vinyl acetate unit and a vinyl acetal unit (or a vinyl formal unit or a vinyl butyral unit). Those having a vinyl formal unit as a main component are generally called polyvinyl formal, those having a vinyl acetal unit as a main component are generally called polyvinyl acetal, and those having a vinyl butyral unit as a main component are generally called polyvinyl butyral. There is almost no resin of one composition.
[0014]
In the present invention, a polyvinyl acetal resin (generally referred to as polyvinyl butyral) having a vinyl butyral unit as a main component is preferable, and the composition thereof is 50 to 70 mol% of vinyl butyral units and 15 to 50 of vinyl alcohol units. A range of mol% and vinyl acetate units of 20 mol% or less (particularly 0.5 to 20 mol%) is preferred. When the vinyl butyral unit is less than the above range, the compatibility with the plasticizer is lowered, and when it exceeds the above range, the penetration resistance is deteriorated. When the vinyl acetate unit exceeds the above range, the transparency is lowered.
[0015]
The degree of polymerization of the resin is preferably in the range of 600 to 2000. When the degree of polymerization is less than 600, the strength of the film is lowered and the impact resistance is not sufficient. When the degree of polymerization exceeds 2000, the viscosity is too high, the workability is lowered, and the work of forming the intermediate film becomes difficult.
[0016]
Although it does not specifically limit as a plasticizer contained in the said resin composition, Generally the ester of a polybasic acid and the ester of a polyhydric alcohol are used. Examples thereof include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethylbutyrate, butyl sebacate, tetraethylene glycol diheptanoate, and triethylene glycol dipelargonate. One type of plasticizer may be used, or two or more types may be used in combination. The content of the plasticizer is preferably in the range of 20 to 50 parts by weight with respect to 100 parts by weight of polyvinyl acetal.
[0017]
The said resin composition of this invention contains the organic peroxide as glass of an intermediate film, and an adhesive control agent. Since the resin composition containing the organic peroxide has improved curability by heating, the film strength of the resulting intermediate film is also improved.
[0018]
Any organic peroxide can be used as long as it decomposes at a temperature of 70 ° C. or higher to generate radicals. The organic peroxide is generally selected in consideration of the film formation temperature, the adjustment conditions of the composition, the curing (bonding) temperature, the heat resistance of the adherend, and the storage stability. In particular, those having a decomposition temperature of 50 hours or more with a half-life of 10 hours are preferred.
[0019]
Examples of organic peroxides include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di-t. -Butyl peroxide, 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, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3, 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide 2,5-dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide Oxide, Decanoyl peroxide, Lauroyl peroxide, Cumyl peroxy octoate, Succinic acid peroxide, Acetyl peroxide, t-butyl peroxy (2-ethylhexanoate), m-toluoyl peroxide, t-butyl Mention may be made of peroxyisobutylene and 2,4-dichlorobenzoyl peroxide . One kind of organic peroxide may be used, or two or more kinds may be used in combination. The content of the organic peroxide is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of polyvinyl acetal.
[0020]
The resin composition for forming an interlayer film of the present invention is an improvement or adjustment of various physical properties of the interlayer film (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, crosslinking speed, etc.) In particular, in order to improve mechanical strength, it is preferable that an acryloxy group-containing compound, a methacryloxy group-containing compound and / or an epoxy group-containing compound are included.
[0021]
The acryloxy group-containing compound and the methacryloxy group-containing compound are generally acrylic acid or methacrylic acid derivatives, and examples thereof include acrylic acid or methacrylic acid esters and amides. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl Group, 3-chloro-2-hydroxypropyl group. In addition, polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, and esters of acrylic acid or methacrylic acid can also be used.
[0022]
Examples of amides include diacetone acrylamide.
[0023]
Examples of the polyfunctional compound include esters obtained by esterifying a plurality of acrylic acids or methacrylic acids with glycerin, trimethylolpropane, pentaerythritol, or the like.
[0024]
Examples of epoxy-containing compounds include triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and phenol. -Glycidyl ether , pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether of ethylene oxide 5 mol adduct can be mentioned.
[0025]
The above compounds may be used alone or in combination of two or more. The content of the compound is preferably in the range of 0.5 to 80 parts by weight, particularly preferably in the range of 0.5 to 70 parts by weight with respect to 100 parts by weight of the polyvinyl acetal. If it exceeds 80 parts by weight, workability such as adjustment of the composition and film forming property may be deteriorated.
[0026]
The resin composition for forming an intermediate film of the present invention preferably contains a silane coupling agent in order to further improve the adhesiveness. Examples of silane coupling agents include vinyl ethoxy silane, vinyl tris (β-methoxy ethoxy) silane, γ-methacryloxypropyl trimethoxy silane, vinyl triacetoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycid Xylpropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl)- γ-aminopropyltrimethoxysilane can be mentioned.
[0027]
The above silane coupling agents may be used alone or in combination of two or more. The content of the compound is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of polyvinyl acetal.
[0028]
The laminated glass of the present invention can be obtained by forming an intermediate film between glass plates using the above resin composition. The method for producing this laminated glass can be carried out in the same manner as the method for producing a laminated glass having a conventional polyvinyl butyral interlayer film (for example, JP-A-5-186250).
[0029]
The interlayer film of the laminated glass of the present invention can be produced, for example, by a method for obtaining a sheet-like material by ordinary extrusion molding, calendar molding, or the like. Alternatively, the resin composition can be dissolved in a solvent, and this solution can be coated on a suitable support with a suitable coating machine (coater) and dried to form a coating film to obtain a sheet.
[0030]
The laminated glass of the present invention uses the above-mentioned sheet-like intermediate film, for example, by sticking a glass plate on both surfaces of the intermediate film, degassing the sandwich structure, and then pressing under heating. Obtainable.
[0031]
If the thickness of the interlayer film is too thin, the penetration resistance of the resulting laminated glass is lowered, and if it is too thick, the transparency is lowered. Therefore, the range of 0.2 to 1.6 mm is preferable, and particularly 0.3 to 1. A range of 3 mm is preferred.
[0032]
A transparent conductive layer made of metal and / or metal oxide may be provided on the glass plate surface of the laminated glass.
[0033]
【Example】
[Examples 1 to 3 and Comparative Example 1]
<Production of interlayer film>
The materials shown in Table 1 were supplied to a roll mill and melt kneaded at 95 ° C. to prepare a resin composition.
[0034]
[Table 1]

[0035]
The resin composition obtained above was sandwiched between two polyethylene terephthalate films, press molded at 120 ° C. for 5 minutes, allowed to cool, and then the obtained interlayer film was peeled off from the film. An intermediate film having a thickness of 0.8 mm was obtained.
[0036]
<Production of laminated glass>
The intermediate film is sandwiched between two 3 mm thick float glass plates that have been washed and dried in advance, put in a rubber bag, vacuum degassed, and pre-pressed at a temperature of about 80 ° C. Next, this pre-pressed glass was put in an autoclave and subjected to pressure treatment for 30 minutes under conditions of a pressure of 5 kg / cm ² and 150 ° C.
[0037]
As described above, laminated glasses of Examples 1 to 3 and Comparative Example 1 were obtained. All the laminated glasses had little coloration and little optical distortion.
[0038]
[Evaluation of laminated glass]
(1) Haze (%)
It measured according to the method of JIS-R3212. At that time, a haze meter (manufactured by Suga Test Instruments Co., Ltd.) was used.
(2) Transmittance (%)
It measured similarly to said (1).
(3) YI value It measured using the color computer (made by Suga Test Instruments Co., Ltd.).
(4) Adhesive strength (kgf)
[0039]
The obtained laminated glass was cut into a 25 mm width strip, and the peel strength was measured with a tensile tester at a tensile rate of 100 mm / min in the same manner as in the 180 ° peeling test.
[0040]
The results obtained above are shown in Table 2.
[0041]
[Table 2]

[0042]
【The invention's effect】
A laminated glass obtained by sandwiching an interlayer film formed from the resin composition of the present invention between glass plates has an appropriate adhesive force with the glass plate, and is excellent in moisture resistance and transparency, and in a wide temperature range. Excellent penetration resistance. This is because the introduction of an organic peroxide into the plasticized polyvinyl acetal resin system reduces the coloration of the intermediate film, and the introduction of the organic peroxide accelerates the curing of the polyvinyl acetal resin, resulting in an adhesive strength. This is thought to be due to the effect of improving the temperature dependency of the improvement and penetration resistance.
[0043]
In particular, by introducing a compound containing a silane coupling agent, an acryloxy group or the like into a further plasticized polyvinyl acetal resin system, crosslinking is performed, so that the temperature dependency of adhesive strength and penetration resistance is further improved. The

Claims (6)

  A resin composition for forming an interlayer film of laminated glass containing a polyvinyl acetal resin, a plasticizer, and an organic peroxide.   The resin composition according to claim 1, wherein a weight ratio of the polyvinyl acetal resin, the plasticizer, and the organic peroxide is in the range of 100: 20 to 50: 0.1 to 10.   Furthermore, the resin composition of Claim 1 or 2 which contains 0.01-5 weight part of silane coupling agents with respect to 100 weight part of polyvinyl acetal resin.   Furthermore, 0.5 to 80 parts by weight of at least one selected from the group consisting of an acryloxy group-containing compound, a methacryloxy group-containing compound, and an epoxy group-containing compound is included with respect to 100 parts by weight of the polyvinyl acetal resin. A resin composition according to claim 1.   The intermediate film for laminated glasses formed from the resin composition in any one of Claims 1-4.   Laminated glass in which the interlayer film according to claim 5 is sandwiched between a glass plate and a glass plate or a plastic sheet.