JPH09263429A - Interlayer for laminated glass and laminated glass using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an interlayer for a laminated glass having no autohesion property and moisture absorption in the interlayer, capable of executing laminating work at relatively low temp. without using an autoclave, good in adhesion between a glass plate and the interlayer and in clarity and also improved in resistance to plasticizer, UV screening property and resistance to light and durability of the laminated glass and to produce the laminated glass. SOLUTION: The interlayer is composed of 100 pts.wt. ethylene-vinyl acetate copolymer or ethylene-(meth)acrylate copolymer. 0.01-4 pts.wt. clarity improving agent, 0.01-4 pts.wt. silane coupling agent having more than one kind functional group selected from a group consisting of amino, glycidyl and mercapto group, 1-40 pts.wt. petroleum resin and 0.01-2 pts.wt. 2,2'-dihydroxybenzophenone based UV absorber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer film for laminated glass containing an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer as a main component, and a laminated glass using the same.

[0002]

2. Description of the Related Art As an interlayer film for laminated glass, a polyvinyl butyral interlayer film containing a plasticizer is widely used. However, this type of polyvinyl butyral interlayer film and a laminated glass using this interlayer film still have problems particularly in terms of film self-adhesiveness, hygroscopicity, heat resistance, and bleeding of a plasticizer, and they are sufficiently satisfactory. Not going.

As an interlayer film and a laminated glass in which the above-mentioned drawbacks have been improved, Japanese Patent Publication No. 2-53381 discloses that an ethylene-vinyl acetate copolymer is mixed with an organic peroxide and a silane coupling agent and heated. Form a crosslinkable interlayer film,
A technique is disclosed in which the interlayer film is interposed between glass plates, and the interlayer film is thermally crosslinked and integrated by heating and pressing the glass plate in an autoclave to form a laminated glass.

In this case, if it is heated and pressed at a relatively high temperature (about 130 ° C. or higher) in the autoclave, a good crosslinking reaction is not carried out and the transparency is not improved. Actually, it is heated and pressed in an autoclave at about 160 ° C. for 20 minutes.

However, the autoclave is expensive,
The operation has the disadvantage that the number of steps is increased and the manufacturing cost is increased. Further, when an organic glass plate such as polycarbonate or polymethylmethacrylate is used as the glass plate, the organic glass plate is thermally deformed, so that there is a drawback that it is limited to an inorganic glass plate.

Further, when a decorative laminated glass is produced by using the above-mentioned intermediate film, a polyester film or the like having a decorative pattern printed thereon is interposed between the intermediate films, and the printing ink of this film requires a heat-resistant dye. Therefore, the cost is also high.

Further, Japanese Patent Publication No. 47-2103 discloses that
An intermediate film is formed by using a resin of a specific component in which a partially saponified ethylene-vinyl acetate copolymer is partially esterified with phthalic anhydride, and the intermediate film is interposed between glass plates and heated with a press or the like. A technique is disclosed in which a laminated glass is integrated by applying pressure.

In this case, a press machine or the like can be used in addition to the autoclave, which is advantageous in this respect. However, in practice, press machine at 130 ℃ or 140 ℃ 30
Since it is heated and pressed for a minute, there is a drawback that the glass plate is limited to the inorganic glass plate as described above. Although it is possible to heat and pressurize at a relatively low temperature, for example, about 100 ° C. to integrate them, the adhesiveness and the transparency decrease at such a temperature.

As an interlayer film and laminated glass from which these various drawbacks have been removed, JP-A-7-2551 discloses an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer 100. 0 to 4 parts by weight of a transparency modifier (transparency improver), and a silane coupling agent having one or more functional groups selected from the group consisting of amino groups, glycidyl groups and mercapto groups. An interlayer film composed of 0.01 to 4 parts by weight and a laminated glass using the interlayer film have been proposed.

[0010]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The interlayer film and laminated glass proposed in Japanese Patent No. 1 do not have self-adhesiveness and hygroscopicity, and can be laminated at a relatively low temperature without using an autoclave. The transparency is good, but there is still room for improvement.

That is, this kind of laminated glass is usually used by being set on a frame body such as a metal sash, and in this case, a bead made of soft plastic is used.
However, the plasticizer in this bead migrates from the end face of the laminated glass to the intermediate film, and the interface between the glass plate and the intermediate film at the end face partly peels off. That is, there is still room for improvement in terms of plasticizer resistance.

Further, this type of laminated glass is used for window glass of vehicles and buildings, and in order to prevent fading and discoloration of interiors and equipment of vehicles and buildings, it is required to have a high ultraviolet ray cutting performance. . At the same time, an intermediate film having excellent light resistance and weather resistance is required. In this respect, there is still room for improvement.

The present invention is intended to solve the above problems, and an object of the present invention is to provide an interlayer film having neither self-adhesiveness nor hygroscopicity, without using an autoclave, and performing a bonding process at a relatively low temperature. It is possible, and in addition to having good adhesion and transparency between the glass plate and the interlayer film, it is an interlayer film for laminated glass with improved plasticizer resistance, UV blocking property, light resistance and weather resistance of the laminated glass. And providing laminated glass.

[0014]

Means for Solving the Problems The above-mentioned objects are 100 parts by weight of an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer, and a transparency improving agent of 0.1.
01 to 4 parts by weight, 0.01 to 4 parts by weight of a silane coupling agent having one or more functional groups selected from the group consisting of an amino group, a glycidyl group and a mercapto group, and 1 to 40 parts by weight of a petroleum resin. This can be achieved by an interlayer film for laminated glass comprising 0.01 to 2 parts by weight of a 2,2′-dihydroxybenzophenone-based ultraviolet absorber and a laminated glass using the interlayer film.

The ethylene-vinyl acetate copolymer used in the present invention preferably contains 18 to 35% by weight of vinyl acetate as its constituent component. The ethylene- (meth) acrylic acid ester copolymer used in the present invention preferably contains 18 to 35% by weight of (meth) acrylic acid ester as a constituent component thereof. Here, as the (meth) acrylic acid ester constituting the ethylene- (meth) acrylic acid ester copolymer, for example, methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate can be used. Etc.

When the content of vinyl acetate or (meth) acrylic acid ester is increased, the transparency of the obtained intermediate film is improved, but the tensile strength is decreased. Conversely, when the content of vinyl acetate or (meth) acrylic acid ester decreases,
The tensile strength of the resulting interlayer film is sufficient, but the transparency decreases.

The melt index (MI) of the ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer is preferably 1 to 200 g / 10 minutes. When the MI is small, the fluidity of the obtained intermediate film is lowered, and the workability of combining (deaeration and processing time) is lowered.
On the other hand, when the MI becomes large, the viscosity of the obtained intermediate film decreases, the intermediate film protrudes from the end portion and the thickness decreases after the laminating process, and the impact resistance of the obtained laminated glass decreases. The above copolymers preferably have a weight average molecular weight of 30,000 to 300,000.

The transparency improver added to the above ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer improves the transparency of the resulting interlayer film. -Transparent modifiers (transparency improvers) such as those described in JP-2551-, for example, dibenzylidene sorbitol compound, dibenzylidene xylitol compound, dibenzylidene dulcitol compound, dibenzylidene mannitol compound and calixarene compound. Is used. These transparency improving agents may be used alone or in combination of two or more kinds. Among them, the dibenzylidene sorbitol compound and the calixarene compound are particularly preferable.

Examples of the dibenzylidene sorbitol compound include dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (ethylbenzylidene) sorbitol, bis (propylbenzylidene) sorbitol, bis (butylbenzylidene) sorbitol, bis (pentylbenzylidene). Sorbitol,
Examples thereof include bis (hexylbenzylidene) sorbitol and bis (chlorobenzylidene) sorbitol.

The above-mentioned calixarene compound includes 4-t-butylcalix [4] arene and 4-t-butylcalix [4] arene.
t-Butylcalix [5] arene, 4-t-butylcalix [6] arene, 4-t-butylcalix [7] arene, 4-t-butylcalix [8] arene 4-t-butylcalix

[9] arenes, 4-t
-Butylcalix [10] arene, 4-t-butylcalix [11] arene, 4-t-butylcalix [12] arene, 4-t-butylcalix [1]
3] arenes, t-butyl calix [14] arenes, 4-t-butyl calix [15] arenes, 4-
Examples include t-butyl calix [16] arene.
In the above calixarene compound, the number in parentheses indicates the degree of polymerization of the calixarene compound.

The above-mentioned transparency improver used in the present invention is 0.1% by weight per 100 parts by weight of an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer.
The amount is 0.01 to 4 parts by weight, preferably 0.02 to 1 part by weight. The blending amount of the transparency improver is 0.01
When the amount is less than the weight part, the transparency of the obtained interlayer film or laminated glass becomes insufficient. On the contrary, the blending amount of the transparency improver is 4
If it exceeds the amount by weight, the compatibility with the above-mentioned copolymer is deteriorated and the transparency of the obtained interlayer film or laminated glass is lowered.

The silane coupling agent added to the above ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer improves the adhesiveness of the resulting interlayer film, and has amino groups and glycidyl groups. A silane coupling agent having at least one functional group selected from the group consisting of a group and a mercapto group is used.
A silane coupling agent as described in JP-A-551 is used.

As the silane coupling agent having an amino group, 3-aminopropyldimethylethoxysilane,
3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) And -3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having a glycidyl group include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltrimethoxysilane. .

Further, as the silane coupling agent having a mercapto group, mercaptomethyldimethylethoxysilane, mercaptomethylmethyldiethoxysilane, 3
-Mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and the like can be mentioned.

Such a silane coupling agent is used in an amount of 0.0 to 100 parts by weight of an ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer.
It is compounded in the range of 1 to 4 parts by weight. If the blending amount of the silane coupling agent is less than 0.01 parts by weight, the adhesiveness of the resulting interlayer film or laminated glass will be insufficient. On the other hand, when the amount of the silane coupling agent is more than 4 parts by weight, the obtained intermediate film may turn yellow, and the transparency of the obtained intermediate film or laminated glass is deteriorated.

Further, in the present invention, a petroleum resin is blended with the above ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer. This petroleum resin improves the decrease in the adhesiveness between the glass plate and the interlayer film during long-term storage of the obtained laminated glass, and particularly, the end face portion due to the plasticizer in the bead (rim) during long-term use. The improvement of the adhesiveness between the glass plate and the interlayer film (long-term plasticizer resistance) is improved, and this point is significantly different from the interlayer film and laminated glass proposed in JP-A-7-2551.

As the above-mentioned petroleum resin, cracked oil fractions (C ₅ , C ₉₎ produced as a by-product from a plant for producing ethylene, propylene and the like by steam cracking of petroleum are mainly used.
Aliphatic (C ₅ ) petroleum resin, aromatic (C ₉ ) petroleum resin, alicyclic (hydrogenated C ₉ ) petroleum resin, C ₅ -C ₉ obtained by polymerizing cracked oil fraction) Copolymer petroleum resin is used. Further, a pure monomer petroleum resin such as a styrene oligomer is also used. In general, these petroleum-based resins preferably have a softening point of 60 to 150 ° C.

These petroleum resins are in the range of 1 to 40 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the ethylene-vinyl acetate copolymer or the ethylene- (meth) acrylic acid ester copolymer. It is mixed in the range of parts. If the blending amount of the petroleum resin is less than 1 part by weight, the effect of improving the plasticizer resistance becomes insufficient. On the contrary, the blending amount of petroleum resin is 40
When it exceeds the weight part, the dispersibility in the copolymer is deteriorated and the transparency of the obtained interlayer film or laminated glass is lowered.

Further, in the present invention, a 2,2'-dihydroxybenzophenone type ultraviolet absorber is blended with the above ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer. This 2, 2 '
The dihydroxybenzophenone-based UV absorber improves the UV blocking property of the laminated glass obtained and the light resistance and weather resistance of the interlayer film.
This is significantly different from the interlayer film and laminated glass proposed in Japanese Patent No. 551.

The 2,2'-dihydroxybenzophenone-based UV absorber is a benzophenone-based UV absorber having a hydroxyl group at each of the 2-position and the 2'-position of benzophenone or a derivative thereof. For example, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4 , 4'-
Dibutoxybenzophenone, 2,2'-dihydroxy-
4-ethoxybenzophenone, 2,2'-dihydroxy-4-butoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethylbenzophenone, 2,2'-dihydroxy-4,4'-dipentylbenzophenone,
2,2'-dihydroxy-4-methoxy-4'-hydroxybenzophenone, 2,2'-dihydroxy-4-hydroxybenzophenone and the like can be mentioned.

These 2,2'-dihydroxybenzophenone type ultraviolet absorbers are used in an amount of 0.01 to 2 with respect to 100 parts by weight of ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer. It is compounded in the range of parts by weight, preferably 0.05 to 1 part by weight. If the amount of these ultraviolet absorbers is less than 1 part by weight, the effect of improving the ultraviolet cut property of the obtained laminated glass becomes insufficient.
On the other hand, if the amount of these ultraviolet absorbers blended exceeds 2 parts by weight, the dispersibility in the copolymer becomes poor and the transparency of the resulting interlayer film or laminated glass deteriorates.

In addition to the above-mentioned various compounding agents, known additives such as heat stabilizers and antioxidants may be compounded, if necessary.

Examples of the heat stabilizer include calcium stearate, dialkanol aliphatic tertiary amine and the like. Antioxidants include t-butylhydroxytoluene (BHT) and tetrakis [methylene-3-
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Irganox 1010 manufactured by Ciba-Geigy) and the like can be mentioned.

In order to obtain the interlayer film for laminated glass of the present invention, a conventionally known method is adopted. For example, the above-mentioned ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer is blended with the above-mentioned various additives in a predetermined amount, or various additives are blended at a high concentration. A method in which a composition obtained by mixing a predetermined amount of a masterbatch is melt-kneaded with an extruder and extruded into a sheet, or a method in which the composition is melt-kneaded with a roll and molded into a sheet is used. The thickness of the intermediate film is appropriately determined depending on the use, but a thickness of 0.2 to 1.2 mm is generally preferable.

To produce a laminated glass using the thus obtained interlayer film for laminated glass, generally, the above-mentioned intermediate film is provided between transparent inorganic glass plates such as float glass or transparent organic glass plates such as polycarbonate and polymethylmethacrylate. After sandwiching it, put this sandwich in a rubber bag, degas it at a vacuum degree of about 20 Torr or less for a certain period of time, then transfer it to an oven at about 80 ° C or more in the degassed state and hold it at this temperature for a certain period of time A method of adhering the plate and the intermediate film is adopted.

The above sandwich was heated to about 100 ° C.
After passing through the above pressure rubber roll for a certain period of time, about 80
It is also possible to adopt a method in which the glass plate and the interlayer film are adhered by transferring the glass plate to an oven at a temperature of not less than 0 ° C. and holding at this temperature for a certain period of time.

The laminated glass is composed of a glass plate /
The multilayer structure is not limited to the interlayer film / glass plate, but may be a multilayer structure such as glass plate / intermediate film / glass plate / intermediate film / glass plate. Further, between the intermediate film and the intermediate film, a film or a sheet such as a polyester film, a polyurethane film, paper, or a metal sheet on which various patterns are printed is interposed to form a multilayered interlayer film or a decorative interlayer film. A laminated glass can also be manufactured using such an intermediate film.

[0039]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention will be described below. Examples 1-5, Comparative Examples 3-6 As ethylene-vinyl acetate copolymer (EVA), vinyl acetate content 28% by weight, melt index (MI)
6 Ultracen 751 (manufactured by Tosoh Corporation), vinyl acetate content 33% by weight, MI1 Evaflex 170
(Mitsui DuPont Chemical Co., Ltd.), vinyl acetate content 28
Evaflex 270 (manufactured by Mitsui DuPont Chemical Co., Ltd.) having a weight percentage of MI1 was prepared.

As an ethylene- (meth) acrylic acid ester copolymer (EEA), the content of methyl methacrylate is 20% by weight, MI3 Acryft WH202 (manufactured by Sumitomo Chemical Co., Ltd.), the content of methyl methacrylate is 20% by weight,
MI20 DPDJ 9169 (manufactured by Nippon Unicar Co., Ltd.) was prepared. Used.

As the transparency improver, dibenzylidene sorbitol, dibenzylidene xylitol and dibenzylidene mannitol were prepared by synthesizing by the following method.

(1) Synthesis of dibenzylidene sorbitol In a 3 liter flask equipped with a reflux condenser and a stirrer, 182 g (1 mol) of D-sorbitol, 212 g (2 mol) of benzaldehyde, 800 cc of toluene and 2 cc of concentrated sulfuric acid were placed. And reacted at 80 ° C. for 3 hours. afterwards,
Toluene was distilled off, neutralized with potassium hydroxide, washed with hot water, filtered and dried to give dibenzylidene sorbitol 3
47 g (yield 97% by weight) was obtained.

(2) Synthesis of dibenzylidene xylitol Using 152 g (2 mol) of xylitol instead of D-sorbitol, 320 g of dibenzylidene xylitol (yield 95% by weight) was synthesized in the same manner as in the above (1).

(3) Synthesis of dibenzylidene mannitol D-mannitol 182 g instead of D-sorbitol
Using (1 mol), 269 g of dibenzylidene mannitol (yield 75% by weight) was synthesized in the same manner as in the above (1).

As a silane coupling agent, N- (2-
Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane were prepared.

As the petroleum resin, alicyclic petroleum resin (Alcon P-115: Arakawa Chemical Co., Ltd.), alicyclic petroleum resin (Alcon P-70: Arakawa Chemical Co., Ltd.), alicyclic petroleum resin ( Alcon M-100: Arakawa Chemical Co., Ltd., pure monomer-based petroleum resin (styrene-based oligomer) (FTR 810)
0: manufactured by Mitsui Petrochemical Co., Ltd.) was prepared.

As 2,2'-dihydroxybenzophenone type ultraviolet absorber, 2,2'-dihydroxy-4,
4'-dimethoxybenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethylbenzophenone and 2,2'-dihydroxy-4-methoxy-5-methylbenzophenone were prepared.

As other ultraviolet absorbers, 2-
Hydroxy-5-butoxybenzophenone (benzophenone type), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (benzotriazo type), p
-Octylphenyl salicylate (salicylate type) was prepared.

The above various materials are used, and these materials are shown in Table 1.
And mixing in the proportions shown in Table 2, and mixing this mixture
It is supplied to Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at 200 ° C., sandwiched with polyester film, molded into a sheet with a press machine, and allowed to stand until room temperature, and then the polyester film is peeled off to a thickness 400
Various μm interlayer films for laminated glass were manufactured.

The obtained interlayer film for laminated glass was made to have a thickness of 3
It is sandwiched between transparent float glass plates of 300 mm (300 mm x 300 mm) and the sandwich body is put in a rubber bag.
After degassing at a vacuum degree of torr for 20 minutes, transfer to an oven at 100 ° C in the degassed state and hold at this temperature for 30 minutes to bond the glass plate and the intermediate film to produce various laminated glass. did.

Comparative Example 1 100 parts by weight of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 25% by weight and MI2 (Evaflex 360: manufactured by Mitsui DuPont Chemical Co.) were added with 1,1-bis (as an organic peroxide. 1 part by weight of t-butylperoxy) 3,3,5-trimethylcyclohexane (Perhexa 3M: manufactured by NOF CORPORATION), 3 parts by weight of triallyl isocyanurate (Tyke: manufactured by Nippon Kasei Co., Ltd.) as a crosslinking aid, and silane. 0.3 parts by weight of γ-methacryloxypropyltrimethoxysilane as a coupling agent and 2- as an ultraviolet absorber
0.2 parts by weight of hydroxy-4-methoxybenzophenone were mixed.

This mixture was melt-kneaded with a roll mill at 100 ° C., sandwiched between polyester films, formed into a sheet by a press machine, and allowed to stand at room temperature, and then the polyester film was peeled off to prepare various 400 μm thick films. An interlayer film for laminated glass was manufactured.

The obtained interlayer film for laminated glass was made to have a thickness of 3
It is sandwiched between transparent float glass plates of 300 mm (300 mm x 300 mm) and the sandwich body is put in a rubber bag.
After degassing at a vacuum degree of torr for 20 minutes, it was transferred to an oven at 130 ° C. in the degassed state and kept at this temperature for 30 minutes to bond the glass plate and the intermediate film to each other to manufacture a laminated glass.

Comparative Example 2 In a 5 liter flask equipped with a reflux condenser and a stirrer, 200 parts by weight of ethylene-vinyl acetate copolymer having a vinyl acetate content of 32% by weight and MI30 (Ultrasen 751: manufactured by Tosoh Corporation). 300 parts by weight of a 10% by weight aqueous sodium hydroxide solution and 1500 parts by weight of xylene were added and hydrolyzed under reflux to obtain a partially saponified product having a saponification degree of 90%.

180 parts by weight of the obtained partially saponified product, 104 parts by weight of phthalic anhydride and 40 parts by weight of pyridine were placed in a 5 liter flask equipped with a reflux condenser and a stirrer.
The mixture was reacted at 110 ° C for 4 hours under reflux.

The composition of the partially esterified product of phthalic anhydride obtained was examined by infrared analysis and elemental analysis. As a result, 3.2% by weight of vinyl acetate component, 16.1% by weight of vinyl alcohol component, vinyl phthalate were obtained. Ingredient 12.7% by weight
The balance consisted of 68.0% by weight of ethylene component.

This partial esterified product of phthalic anhydride is
It is supplied to Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) and melt-kneaded at 200 ° C., sandwiched with polyester film, molded into a sheet with a press machine, and allowed to stand until room temperature, and then the polyester film is peeled off to a thickness 400
A μm interlayer film for laminated glass was fabricated.

The obtained interlayer film for laminated glass was made to have a thickness of 3
It is sandwiched between transparent float glass plates of 300 mm (300 mm x 300 mm) and the sandwich body is put in a rubber bag.
After deaeration at a vacuum degree of torr for 20 minutes, the degassed state was transferred to an oven at 100 ° C., and this temperature was maintained for 30 minutes to bond the glass plate and the intermediate film to each other to produce a laminated glass.

With respect to the laminated glass thus obtained,
By the following method, transparency test, adhesion test, impact resistance test, cold heat test, humidity resistance test, boiling test, plasticizer resistance test,
A weather resistance test and an ultraviolet protection test were conducted. Table 3 shows the results.

Transparency test For laminated glass, an integrating turbidimeter (manufactured by Tokyo Denshoku Co., Ltd.)
Was used to measure the total light transmittance (%) and the haze (cloudiness value) (%) under the conditions of a temperature of 23 ° C. and a relative humidity of 50%.

Adhesion Test A transparent float glass was used on one side and a polyester film was used on the opposite side, and an intermediate film was sandwiched between them, and they were adhered under the same conditions as those for the production of the above laminated glass. The sample was cut to 100 mm. The intermediate film at the end of this sample was peeled off, and the end of the peeled intermediate film was pulled at a pulling speed of 500 mm / min by using a tensile tester (Tensilon UCE500: manufactured by Orientec Co., Ltd.).
The peel strength was measured by pulling at 0 degree. Impact resistance test Based on JIS R3205, temperature 23 ° C, relative humidity 5
A shot bag test was conducted under the condition of 0% by freely dropping a hitting body having a weight of 45 kg and a maximum of 75 mm filled with lead shot in a laminated glass from a height of 30 cm in a pendulum manner. The case where an opening through which the above-mentioned attacking body freely passes occurs is marked with X, and the case where it does not occur is marked with ○.

Cold Heat Test The laminated glass was left at 70 ° C. for 2 hours, cooled from 70 ° C. to −20 ° C. over 2 hours, and further cooled at −20 ° C. for 2 hours.
After leaving it for an hour, it is heated from −20 ° C. to 70 ° C. for 2 hours. This was set as one cycle, and after a total of 10 cycles of tests, the presence or absence of layer delamination was observed.

Moisture resistance test A laminated glass was allowed to stand at a temperature of 55 ° C. and a relative humidity of 98% for 2 weeks, and then the presence or absence of layer delamination was observed.

Boiling test After the laminated glass was left in boiling water for 2 hours, the presence or absence of delamination was observed.

Plasticizer resistance test A stainless steel bat was used as a plasticizer and di-2-phthalic acid was used.
Ethylhexyl (DOP) was put, the laminated glass was immersed therein, and this was left in an oven at 50 ° C. for 300 hours, and then the layer peeling area of the peripheral edge of the laminated glass was measured.
The ratio of the delaminated area to the total area is shown.

Weather resistance test According to JIS A1415, a sunshine weatherometer was used to measure a laminated glass with a black panel temperature of 63 ° C. and a spray cycle of 120 minutes for 18 minutes for 100 minutes.
Irradiation is performed for 0 hours, and the yellowness (Y) after irradiation is measured under the conditions of a reflection method, a C light source, and a 2 degree visual field based on JIS A7103.
I) and the yellowness index (YI ₀ ) before irradiation are measured, and the difference between them is shown by the yellowing index (ΔYI).

Ultraviolet ray cut property test Based on DIN 67507, the ultraviolet ray cut rate of the laminated glass was calculated using a spectrophotometer.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

From this result, it is understood that the plasticizer resistance is remarkably improved by blending the petroleum resin, as compared with the laminated glass described in JP-A-7-2551. Further, by blending a 2,2′-dihydroxybenzophenone type ultraviolet absorber, the above-mentioned JP-A-7-2
It can be seen that the weather resistance and the ultraviolet ray blocking property are remarkably improved as compared with the laminated glass described in Japanese Patent No. 551.

[0072]

As described above, the interlayer film for laminated glass of the present invention comprises 100 parts by weight of ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid ester copolymer and 0.01% transparency improver. 1 to 4 parts by weight and 1 selected from the group consisting of an amino group, a glycidyl group and a mercapto group.
Silane coupling agent having at least one functional group 0.01
~ 4 parts by weight, 1-40 parts by weight of petroleum resin, 2,2 '
-Dihydroxybenzophenone UV absorber 0.01
In addition, the laminated glass of the present invention uses the above-mentioned intermediate film, whereby the intermediate film does not have self-adhesiveness or hygroscopicity, and is excellent in heat resistance, transparency, and adhesiveness. Moreover, the plasticizer resistance of the laminated glass is improved. Therefore, it is possible to prevent the adhesiveness between the glass plate and the interlayer film at the end face portion from being deteriorated by the plasticizer in the bead (edge) during long-term use. In addition, the deterioration of the adhesiveness between the glass plate and the interlayer film during long-term storage is also improved.

Further, the interlayer film for laminated glass of the present invention is excellent in the processability of laminating, and after degassing with, for example, a rubber bag or a pressure rubber roll, without using an expensive autoclave, it is comparatively conducted by an oven or a press. Since the laminating process can be easily performed at a low temperature, for example, 100 ° C., the manufacturing cost of the laminated glass becomes low.

Furthermore, a relatively low temperature, for example 100 ° C.
Since it can be laminated with, it can be used not only as an inorganic glass plate as a glass plate, but also as an organic glass plate such as polycarbonate or polymethylmethacrylate without being thermally deformed. No need to use heat-resistant dyes in ink,
Lower costs.

Therefore, the laminated glass of the present invention is
Set on a frame such as a metal sash and press it with a soft plastic bead (rim) to use it for vehicle window glass, building window glass, glazing material for exercise facilities and public facilities, partition, crime prevention door Can be suitably used.

Claims (2)

[Claims] 1. An ethylene-vinyl acetate copolymer or an ethylene- (meth) acrylic acid ester copolymer 100 parts by weight, a transparency improver 0.01 to 4 parts by weight, an amino group,
Silane coupling agent having one or more functional groups selected from the group consisting of glycidyl group and mercapto group 0.0
1-4 parts by weight, petroleum resin 1-40 parts by weight, 2,2 '
-Dihydroxybenzophenone UV absorber 0.01
An interlayer film for laminated glass consisting of ˜2 parts by weight. 2. A laminated glass using the interlayer film for laminated glass according to claim 1.